CA2466366C - Preparation of lithium-containing materials - Google Patents

Abstract

The invention provides novel lithium-mixed metal materials which, upon electrochemical interaction, release lithium ions, and are capable of reversibly cycling lithium ions and a method of making such materials. The disclosed method comprises a method of making a lithium mixed metal compound by reaction of starting material which comprises mixing starting materials in particle form with a volatile solvent or binder to form a wet mixture. The starting materials comprise at least one metal containing compound, a lithium compound having a melting point greater than 450°C, and carbon, where said carbon is present in an amount sufficient to reduce the oxidation state of at least one metal ion of said starting materials without full reduction to an elemental state. The method comprises heating said wet mixture in a non-oxidizing atmosphere at a temperature sufficient to form a reaction product which comprises lithium and said reduced metal ion.

Description

PREPARATION OF LITHIUM-CONTAINING MATERIALS
This application is a divisional of Canadian Application Serial No.: 2,395,115, filed December 22, 2000 (division of Canadian Application Serial No. 2,394,318, filed December 22, 2000).
Field of the Invention This invention relates to improved materials usable as electrode active materials and to their preparation.
Background of the Invention Lithium batteries are prepared from one or more lithium electrochemical cells containing electrochemically active (electroactive) materials. Such cells typically include an anode (negative electrode), a cathode (positive electrode), and an electrolyte interposed between spaced apart positive and negative electrodes. Batteries with anodes of metallic lithium and containing metal chalcogenide cathode active material are known. The electrolyte typically comprises a salt of lithium dissolved in one or more solvents, typically nonaqueous (aprotic) organic solvents. Other electrolytes are solid electrolytes typically called polymeric matrixes that contain an ionic conductive medium, typically a metallic powder or salt, in combination with a polymer that itself may be sonically conductive which is electrically insulating. By convention, during discharge of the cell, the negative electrode of the cell is defined as the anode. Cells having a metallic lithium anode and metal chalcogenide cathode are charged in an initial condition. During discharge, lithium ions from the metallic anode pass through the liquid electrolyte to the electrochemical active (electroactive) material of the cathode whereupon they release electrical energy to an external circuit.

2 It has recently been suggested to replace the lithium metal anode with an insertion anode, such as a lithium metal chalcogenide or lithium metal oxide.
Carbon anodes, such as coke and graphite, are also s insertion materials. Such negative electrodes are used with lithium- containing insertion cathodes, in order to form an electroactive couple in a cel7_. Such cells, in an initial condition, are not charged. In order to be used to deliver electrochemical energy, such cells must to be charged in order to transfer lithium to the anode from the lithium- containing cathode. During discharge the lithium is transferred from the anode back to the cathode. During a subsequent recharge, the lithium is transferred back to the anode where it re-inserts. Upon 15 subsequent charge and discharge, the lithium ions (Li+) are transported between the electrodes. Such rechargeable batteries, having no free metallic. species are called rechargeable ion batteries or rocking chair batteries. See U.S. Patent Nos. 5,418,090; 4,464,447;
20 4,194,062; and 5,130,211.
Preferred positive electrode active materials include LiCo02, LiMn204, and LiNi02. The cobalt compounds are relatively expensive and the nickel compounds are 2~ difficult to synthesize. A relatively economical positive electrode is LiMn204, for which methods of synthesis are known. The lithium cobalt oxide (LiCo02), the lithium manganese oxide (LiMn204), and the lithium nickel oxide (LiNi02) all have a common disadvantage in so that the charge capacity of a cell comprising such cathodes suffers a significant loss in capacity. That is, the initial capacity available (amp hours/gram) from LiMn204, LiNiOz, and LiCo02 is less than the theoretical capacity because significantly less than 1 atomic unit of 35 lithium engages in the electrochemical reaction: Such an initial capacity value is s~_gnificantly diminished during ~ 02466366 2004-05-28 - ~.... _. ... . ..._. _ the first cycle operation and such capacity further diminishes on every successive cycle of operation. For LiNi02 and LiCo02 only about 0.5 atomic units of lithium is reversibly cycled during cell operation. Many s attempts have been made to reduce capacity fading, for example, as described in U.S. Patent Na. 4,828,834 by Nagaura et al. However, the presently l~nown arid commonly used, alkali transition metal oxide compounds suffer from relatively low capacity. Therefore, there remains the 1o difficulty of obtaining a lithium-containing electrode material having acceptable capacity without disadvantage of significant capacity loss when used in a cell.

Summary of the Invention The invention provides novel lithium-mixed metal materials which, upon electrochemical interaction, release lithium ions, and are capable of reversibly s cycling lithium ions. The invention provides methods for the preparation of materials useful ire manufacturing a rechargeable lithium battery which comprises an electrode formed from the novel lithium-mixed metal materials.
Methods for making the novel lithium-mixed metal so materials and methods for using such lithium-mixed metal materials in electrochemical cells are also provided.
The lithium-mixed metal materials comprise lithium and at least one other metal besides lithium. Preferred materials are lithium--mixed metal phosphates which z5 contain lithium and two other metals besides a_ithium.
Accordingly, the invention provides a rechargeable lithium battery which comprises an electrolyte; a first electrode having a compatible active material,o and a second electrode comprising the nove7_ materials. In one 2o aspect, the novel materials are lithium-mixed metal phosphates which preferably used as a positive electrode active material, reversibly cycle lithium ions with the compatible negative electrode active material. Desirably, the lithium-mixed metal phosphate is represented by the 25 nominal general formula LiaMI~MIIC (P04) d. Such compounds include LiIMIaMIIbP09 and Li3MIaMIIb (POD) 3; therefore, in an initial condition 0 <_ a _< 1 or 0 _< a _< 3, respectively.
During cycling, x quantity of lithium is released.where 0 <_ x <_ a. In the general formula, the sum of b plus c so is up to about 2. Specific examples axe LilMIl_yMII},P04 and Li3MI2_yMIIy (P04) 3, where '~y" is defined hereinafter.
In one aspect, MI and MII are the same. In a 35 preferred aspect, MI and MII are different from one another. At least one of MI and MII is an element ~J
capable of an oxidation state higher than that initially present in the lithium-mixed metal phosphate compound.
Correspondingly, at least one of MI and MII has more than one oxidation state in the phosphate compound, and more than one oxidation state above the ground state M°. The term oxidation state and valence state are used in the art interchangeably.
In another aspect, both MI and MII may have zo more than one oxidation state and both may be oxidizable from the state initially present in the phosphate compound. Desirably, MTI is a metal or semi-metal having a +2 oxidation state, and is selected from Groups 2, 12 and 14 of the Periodic Table. Desirably, MII is selected Z5 from non-transition metals and semi-metals. In one embodiment, MII has only one oxidation state and is nonoxidizable from its oxidation state in the lithium-mixed metal compound. Tn another embodiment, MII has more than one oxidation state. Bxamples of semi-metals 2o having more than one oxidation state are selenium and tellurium; other non-transition metals with more than one oxidation state are tin and Lead. Preferably, MII is selected from Mg (magnesium), Ca (calcium), Zn (zinc), Sr (strontium), Pb (lead), Cd (cadmium), Sn (tin), Ba 25 (barium), and Be (beryllium), and mixtures thereof. In another preferred aspect, MII is a metal having a +2 oxidation state and having more than one oxidation state, and is oxidizable from its oxidation state in lithiurn-mixed metal compound.
Desirably, MI is selected from Fe (iron), Co (cobalt), Ni (nickel), Mn (manganese), Cu (copper.), V
(vanadium), Sn (tin), Ti (titanium), Cr (chromium), and mixtures thereof. As can be seen, MI is preferably selected from the first row of transition metals and further includes tin, and MI preferably initially has a +2 oxidation state.
In one aspect, the product LiMI,_y,MTIyP04 may have an olivine structure and the product Zi3MI~_Y(P04)3 is a rhombohedral or monoclinic Nasicon structure. Tn another aspect, the term "nominal formula'° refers to the fact that the relative proportion of atomic species may vary slightly on the order of 2 percent to 5 percent, or 1o more typically, 2 percent to 3 percent. In still another aspect, any portion of P (phosphorous) may be substituted by Si (silicon), S (sulfur), and/or As (arsenic); and any portion of O (oxygen) may be substituted by halogen, preferably F (fluorine). These aspects are also disclosed in U.S. Patent Application Serial Numbers 09/105,748 issued as U.S. 6,136,4'72 on October 24, 2000, 09/274,371 issued as U.S. 6,153,333 on November 28, 2000 and in U.S. Patent No. 5,871,866 issued February 16, 1999; each of the listed applications and patents are co-owned by the assignee of the present invention.
The metal phosphates are alternatively represented by the nominal general formulas such as Lil_XMZ1_yMI IYPOQ ( 0 S x <_ 1 ) , and Li3_xMT2_yMI Iy ( PO4 ) 3 2s signifying capability to release and reinsert lithium.
The term °°general" refers to a family of campounds, with M, x and y representing variations therein. The expressions 2-y and 1-y each signify that the relative amount of MI and MIT may vary. In addition, as stated so above, MI may be a mixture of metals meeting the earlier stated criteria for MI. In addition, MII may be a mixture of metallic elements meeting the stated criteria for MII. Preferably, where MIT is a mixture, it is a mixture of 2 metallic elements and where MT is a s5 mixture, it is a mixture of 2 metals. Preferably, each such metal and metallic element has a +2 oxidation state in the initial phosphate compound.
The active material of the counter electrode is s any material compatible with the lithium-mixed metal phosphate of the invention. Where the lithium-mixed metal phosphate is used as a positive electrode active material, metallic lithium, lithium-containing material, or non-lithium-containing material ma.y be used as the to negative electrode active material. The negative electrode is desirably a nonmetallic insertion material.
Desirably, the negative electrode comprises an active material from the group consisting of metal oxide, particularly transition metal oxide, metal chalcogenide, carbon, graphite, and mixtures thereof. It is preferred that the anode active material comprises a carbonaceous material such as graphite. The lithium-mixed metal phosphate of the invention may also he used as a negative electrode material.
In another embodiment, the present invention provides a method of preparing a compound of the nominal general formula LiaMI~MII~ (P04) d where 0 < a <_ 3; the sum of b plus c is greater than zero and up to about 2; and 2s 0 < d <_ 3. Preferred compounds include Li3MIbMII~ (POQ) 3 where b plus c is about 2 ~ and LiMI,,MI I~P04 where b plus c is about 1. The method comprises providing starting materials in particle form. The starting (precursory materials include a lithium-containing compound, one or 3o more metal containing compounds, a compound capable of providing the phosphate (PO9)-3 anion., and carbon.
Preferably, the lithium-containing compound is in particle form, and an example is lithium salt.
Preferably, the phosphate-containing anion compound is in 35 particle form, and examples include metal phosphate salt and diammonium hydrogen phosphate (D.AHP) and arnmanium ~ 02466366 2004-05-28 dihydrogen phosphate (ADHP). The lithium compound, one or more metal compounds, and phosphate compound are included in a proportion which provides the stated nominal general formula. The starting materials are s mixed together with carbon, which is included in an amount sufficient to reduce the metal ion of one or more of the metal-containing starting materials without full reduction to an elemental metal state. Excess quantities of carbon and one or more other starting materials (i.e., 5 to loo excess) may be used to enhance product quality.
A small amount of carbon, remaining after the reaction, functions as a conductive constituent in the ultimate electrode formulation. This is an advantage since such remaining carbon is very intimately mixed with the 25 product active material. Accordingly, large quantities of excess carbon, on the order of 200$ excess carbon are useable in the process. The carbon present during compound formation is thought to be .i:ntimately dispersed throughout the precursor and product. This provides many 2o advantages, including the enhanced conductivity of the product. The presence of carbon particles in the starting materials is also thought to provide nucleation sites for the production of the product crystals.
2s According to a preferred embodiment, the invention provides a method of making a lithium mixed metal compound by reaction of starting materials which comprises:
mixing starting materials in particle form, 3o said starting materials comprising a metal compound, a lithium compound having a melting point greater than 450°C, and carbon, where said carbon is present in an amount sufficient to reduce the oxidation state of at least one metal ion of said starting materials without ss full reduction to an elemental state; and heating said starting materials in a non--oxidizing atmosphere at a temperature sufficient to form a reaction product comprising lithium and said reduced metal ion.
Another preferred embodiment of the invention provides a method of making a lithium. mixed metal compound by reaction of starting materials which comprises:
1o mixing starting materials i.n particle form, said starting materials comprising a metal cornpound, a lithium compound, and carbon, where said carbon is present in an amount s~.fficient to reduce the oxidation state of at least one metal ion of said starting materials without full reduction to an elemental state;
and heating said starting materials at a temperature sufficient to form a reactsion product comprising lithium and said reduced metal ion; wherein 2o said lithium compound is selected from the group consisting of lithium carbonate, lithium phosphate, lithium oxide, lithium wanadate, and mixtures thereof.
Still another preferred embodiment of the 2s invention is a method of making a lithium mixed metal compound by reaction of starling materials which comprises:
mixing starting materials in particle form, said starting materials comprising a metal compound: a so lithium compounds carbon present in an amount sufficient to reduce the oxidation state of at least one metal ion of said starting materials without full reduction to an elemental state; and a compound containing a polyanion capable of forming a crystal latticed and s5 heating said starting materials at a temperature sufficient to form a single phase reaction product comprising lithium, said reduced metal ion, and said polyanion.
In another aspect of the present invention, there is provided, in a preferred embodiment, a method of making a lithium mixed metal compound by reaction of starting materials which comprises:
mixing starting materials J.n particle farm, said starting materials comprising a metal oxide: lithium to carbonate; carbon present in an amount sufficient to reduce the oxidation state of at least one metal ion of said starting materials without full reduction to. an elemental state: and a compound containing a phosphate group; and heating said starting materials at a temperature sufficient to form a single phase reaction product comprising lithium, said reduced metal ion, and said phosphate group.
2o In another aspect of this invention there is provided a method of making a compound which comprises:
mixing starting materials in particle form, said starting materials comprising a metal compound, a lithium compound selected from the group consisting of lithium acetate (Li00CCH~), lithium nitrate (LzN03)~
lithium oxalate (Li2C204) , lithium oxide (Li20) , lithium phosphate (Li3POq), lithium dihydrogen phosphate (LiH2P04), lithium vanadate (LiV03), and lithium carbonate (Li2C03), and carbon present in an amount sufficient to so reduce the oxidation state of at least one metal ion of said starting materials without full reduction to an elemental state; and heating said starting materials at a temperature sufficient to form a single phase reaction product.

l Still another preferred embodiment of the invention, there is provided a method of making a lithium mixed metal compound by reaction of starting materials which comprises: mixing starting materials in particle s form, said starting materials comprising a first metal compound, a lithium compound, a second metal compound, and carbon, where said carbon is present in an amount sufficient to reduce the oxidation state of at least one metal ion of said starting materials without full 1o reduction to an elemental state; and heating said starting materials at a temperature sufficient to form a reaction product comprising lithium and said reduced metal ion, wherein the second metal compound has a second metal ion which is not reduced and which forms a part of 15 said reaction product.
In still another aspect of the present invention, there is provided in a preferred embodiment, a method of making a lithium mixed metal compound by 2o reaction of starting materials which comprises: mixing starting materials in particle form, said starting materials comprising a metal compound, a lithium compound, a phosphate compound, and carbon, where said carbon is present in an amount sufficient to reduce the 2s oxidation state of at least one metal ion of said starting materials without full reduction to an elemental state; and heating said starting materials at a temperature sufficient to form a reaction product comprising lithium and said reduced metal ion, wherein 3o said reaction product is a lithium metal phosphate.
In another aspect of this invention there is provided a two-stage method for making a lithium iron phosphate, wherein the first stage cromprises mixing ss starting materials comprising iron oxide, diammonium hydrogen phosphate and carbon, and heating said first stage mixed starting materials at a temperature sufficient to produce iron phosphate; and the second stage comprises mixing starting matE:rials comprising said iron phosphate and lithium phosphate, arid heating said second stage mixed starting materials at a 'temperature sufficient to form the lithium iron phosphate represented by the nominal formula LiFeP04.
According to another preferred embodiment, the Zo invention provides a method of making a lithium mixed metal compound by reaction of starting materials which comprises:
mixing starting materials in particle form, said starting materials consisting of lithium carbonate, iron phosphate, diammonium hydrogen phosphate, a hydroxide selected from the group consisting of magnesium hydroxide and calcium hydroxide, and carbon present in an amount sufficient to reduce the oxidation state of at least one metal ion of said starting materials without 2o full reduction to an elemental state; and heating said starting materials at a temperature sufficient to form a single phase reaction product comprising lithium, said reduced metal ion, and said phosphate group.
Still another preferred embodiment of the invention there is provided a method of making a lithium mixed metal compound by reaction of starting materials which comprises:
so mixing starting materials in particle form, said starting materials comprising an oxide of a transition metal selected from Groups 4 to 21 inclusive of the Periodic Table having a +2 valence state, a compound of a metal selected from Groups 2, 12, and 14 of the Periodic Table having a ~2 valence state; a lithium compound selected from the group consisting of lithium carbonate and lithium dihydrogen phosphate, a phosphate group containing compound selected from the group diammonium hydrogen phosphate, ammonium dihydrogen phosphate, lithium dihydrogen phosphate, and mixtures thereof; and carbon present in an amount sufficient to reduce the oxidation state of at least one metal ion of said starting materials without full reduction to an elemental stated and heating said starting materials at a 1o temperature sufficient to form a single phase reaction product comprising lithium, said reduced meta7_ ion, and said phosphate group.
The starting materials are intimately mixed and Z5 then reacted together where the reaction is initiated by heat and is preferably conducted in a nonoxidizing, inert atmosphere, whereby the lithium, metal from the metal compound(s), and phosphate combine to form the LiaMI~MII~ (POq) d product.. Before reacting the compounds, 2o the particles are intermingled to form an essentially homogeneous powder mixture of the precursors. Tn one aspect, the precursor powders are dry-mixed using a ball mill, such as zirconia media. Then the mixed powders are pressed into pellets. In another aspect, the precursor 25 powders are mixed with a binder. The binder is selected so as to not inhibit reaction between particles of the powders. Therefore, preferred binders decompose or evaporate at a temperature less than the reaction temperature. Examples include mineral ails (i.e., 3o glycerol, or C-18 hydrocarbon mineral oil) anal polymers which decompose (carbonize] to form a carbon residue before the reaction starts, or which evaporate before the reaction starts. In still another aspect, intermingling is conducted by forming a wet mixture using a volatile 35 solvent and then the intermingled particles are pressed together in pellet form to provide good grain-to-grain contact.
Although it is desired that the precursor compounds be present in a proportion which provides the stated general formula of the product, the lithium compound may be present in an excess amount on the order of 5 percent excess lithium compared to a stoichiometric mixture of the precursors. And the carbon may be present ~.o at up to 1000 excess compared to the stoichiometric amount. The method of the invention may also be used to prepare other novel products, and to prepare known products. A number of lithium compounds are available as precursors, such as lithium acetate (Li00CCH3), lithium hydroxide, lithium nitrate (LiN03), lithium oxalate (Li2C204) , lithium oxide (Li20} , lithium phosphate (Li3P04) , lithium dihydrogen phosphate (LiH2P04) , lithium vanadate (LiV03) , and lithium carbonate (Li2C03) . The lithium carbonate is preferred for the solid state 2o reaction since it has a very high melting point and commonly reacts with the other precursors before melting.
Lithium carbonate has a melting poini~ over 600°C and it decomposes in the presence of the other precursors and/or effectively reacts with the other precursors before 2s melting. In contrast, lithium hydroxide melts at about 400°C. At some reaction temperatures preferred herein of over 450°C the lithium hydroxide will melt before any significant reaction with the other precursors occurs to an effective extent~ This melting renders the reaction so very difficult to control. In addition, anhydrous LiOH
is highly hygroscopic and a significant quantity of water is released during the reaction. Such water needs to be removed from the oven and the resultant product may need to be dried. In one preferred aspect, the solid state 3s reaction made possible by the present invention is much preferred since it is conducted at temperatures at which the lithium-containing compound reacts with the other reactants before melting. Therefore, lithium hydroxide is useable as a precursor in the method of the invention in combination with some precursors, particularly the s phosphates. The method of the invention is able to be conducted as an economical carbothermal--based process with a wide variety of precursors and. over a relatively broad temperature range.
1o The aforesaid precursor compounds (starting materials) are generally crystals, granules, and powders and are generally referred to as being in particle form.
Although many types of phosphate salts are known, it is preferred to use diammonium hydrogen phosphate (NH4)2HP04 15 (DAHP) or ammonium dihydrogen phosphate (NH4) HZP04 (ADHP) .
Both ADHP and DAHP meet 'the preferred criteria that the precursors decompose in the presence of one another or react with one another before melting of such precursor.
Exemplary metal compounds are Fe203, F e3O4, V205, V02, 2o LiV03, NHQV03, Mg (OH) 2, Cao, MgO, Ca (OH) 2, Mn02, Mn203, Mn3 (P04) 2, CuO, SnO, Sn02, Ti02, Ti203, Cr203, Pb02, PbO, Ba(OH)2, BaO, Cd(OH)2. In addition, some starting materials serve as both the source of metal ion and phosphate, such as FeP04, Fe3 (P04) 2, Zn3 (P04) 2, and 2s Mg3(PO~)2. Still others contain both lithium ion and phosphate such as LiaP04 and LiH2P04. Other exemplary precursors are H3PO4 (phosphoric acid) ; and P205 (P401o) phosphoric oxide; and HP03 meta phosphoric acid, which is a decomposition product of P205. If i.t is desired to so replace any of the oxygen with a halogen, such as fluorine, the starting materials further include a fluorine compound such as LiF. If i.t is desired to replace any of the phosphorous with silicon, then the starting materials further include silicon oxide (Si02).
35 Similarly, ammonium sulfate in the starting materials is useable to replace phosphorus with sulfur.

The starting materials are available from a number of sources. The following are typical. Vanadium pentoxide of the formula V205 is obtainable from any number of suppliers including Kerr McGee, Johnson s Matthey, or Alpha Products of Davers, Massachusetts.
Vanadium pentoxide has a CAS number of 1314-62-1. Iron oxide Fe303 is a common and very inexpensive material available in powder form from the same suppliers. The other precursor materials mentioned above are also 1o available from well known suppliers, such as those listed above.
The method of the invention may also be used to react starting materials in the presence of carbon to i5 form a variety of other novel products, such as gamma-LiV205 and also to produce known products. Here, the carbon functions to reduce metal ion of a starting metal compound to provide a product containing such reduced metal ion. The method is particularly useful to also add 20 lithium to the resultant product, which thus contains the metallic element ions, namely, the lithium ion and the other metal ion, thereby forming a mixed metal product.
An example is the reaction of vanadium pentoxide (V205) with lithium carbonate in the presence of carbon to form 25 gamma-LiV205. Here the starting metal ion V~SV+5 is reduced to V+9V+5 in the final product. A single phase gamma-LiV205 product is not known to have been directly and independently formed before.
3o As described earlier, it is desirable to conduct the reaction at a temperature where the lithium compound reacts before melting. The temperature should be about 400°C or greater, and desirably 450°C or greater, and preferably 500°C or greater, and generally 35 W111 proceed at a faster rate at higher temperatures.
The various reactions involve production of CO or C02 as an effluent gas. The equilibrium at higher temperature favors CO formation. Some of the reactions are more desirably conducted at temperatures greater thin 600°C;
most desirably greater than 650°C; preferably 700°C or greater; more preferably 750°C or greater. Suitable ranges for many reactions are about 700 to 950°C, or about 700 to 800°C.
Generally, the higher temperature reactions Zo produce CO effluent and the stoichiometry requires more carbon be used than the case where CO~ effluent is produced at lower temperature. This is because the reducing effect of the C to C02 reaction is greater than the C to CO reaction. The C to C02 reaction involves an z5 increase in carbon oxidation state of. +4 (from 0 to 4) and the C to CO reaction involves an increase in carbon oxidation state of +2 (from ground state zero to 2).
Here, higher temperature generally refers to a range of about 650°C to about 2000°C and lower temperature refers 2o to up to about 650°C. Temperatures higher than 1200°C
are not thought to be needed.
In one aspect, the method of the invention utilizes the reducing capabilities of carbon in a unique 25 and controlled manner to produce des.i.red products having structure and lithium content suitable for electrode active materials. The method of the invention makes it possible to produce products containing lithium, metal and oxygen in an economical and convenient process. The so ability to lithiate precursors, and change the oxidation state of a metal without causing abstraction of oxygen from a precursor is heretofore unexpected. These advantages are at least in part achieved by the reductant, carbon, having an oxide whose free energy of 35 formation becomes more negative as temperature increases.
Such oxide of carbon is more stable at high temperature than at low temperature. This feature is used to produce products having one or more metal ions in a reduced oxidation state relative to the precursor metal ion oxidation state. The method utilizes an effective s combination of quantity of carbon, time and temperature to produce new products and to produce known products ir~
a new way.
Referring back to the discussion of 1o temperature, at about 700°C both the carbon to carbon monoxide and the carbon to carbon dioxide reactions are occurring. At closer to 600°C the C to C02 reaction is the dominant reaction. At closer to 800°C the C to CO
reaction is dominant. Since the reducing effect of the C
15 to Co2 reaction is greater, the result is that less carbon is needed per atomic unit of metal to be reduced.
In the case of carbon to carbon monoxide, each atomic unit of carbon is oxidized from ground state zero to plus 2. Thus, for each atomic unit of metal ion (M) which is 2o being reduced by one oxidation state, one half atomic unit of carbon is required. In the case of the carbon to carbon dioxide reaction, one quarter atomic unit of carbon is stoichiometrically required for each atamic unit of metal ion (M) which a_s reduced by one oxidation 25 state, because carbon goes from ground state zero to a plus 4 oxidation state. These same :relationships apply for each such metal ion being reduced and for each unit reduction in oxidation state desired.
3o It is preferred to heat the starting materials at a ramp rate of a fraction of a degree to 10°C per minute and preferably about 2°C per minute. Cnce the desired reaction temperature is attained, the reactants (starting materials) are held at the reaction temperature 3s for several hours. The heating is preferably conducted under non-oxidizing or inert gas such as argon or vacuum.

Advantageously, a reducing atmosphere is not required, although it may be used if desired. .After reaction, the products are preferably cooled from the elevated temperature to ambient (room) temperature (i.e., 10°C to s 40°C). Desirably, the cooling occurs at a rate similar to the earlier ramp rate, and preferably 2°C/minute cooling. Such cooling rate has been found to be adequate to achieve the desired structure of the final product.
zt is also possible to quench the products at a cooling 1o rate on the order of about 100°C/minute. In some instances, such rapid cooling (quench) may be preferred.
The present invention resolves the capacity problem posed by widely used cathode active material. It 1~ has been found that the capacity and capacity retention of cells having the preferred active material of the invention are improved over conventional materials.
Optimized cells containing lithium-mixed metal phosphates of the invention potentially have performance improved 20 over commonly used lithium metal oxide compounds.
Advantageously, the new method of making the novel lithium-mixed metal phosphate compounds of the invention is relatively economical and readily adaptable to commercial production.
Another feature of one embodiment of the invention includes an electrochemical cell or battery based on lithium-mixed metal phosphates. Still another feature is to provide an electrode active material which so combines the advantages of good discharge capacity and capacity retention. It is also a desirable feature of the present invention to provide electrades which can be manufactured economically. Yet another feature of one embodiment is to provide a method for farming electrode 3s active material which lends itself to commercial scale production for preparation of large quantities.

CA 02466366 2004-05-28 _. . . _ ..... . .. . .
2 C~
Another embodiment of the method of the present invention comprises of a method of making a lithium mixed metal polyanion compound by reacting a mixture of a lithium compound and at least one metal containing s compound, said compounds in particle form, the improvement comprising of an incorporating carbon into said mixture in an amount sufficient to reduce the oxidation state of at least one metal ion of t:he metal containing compound without full reduction to an ~.o elemental state and carrying out the reaction in the presence of said carbon.
Another embodiment of the method of the present invention consists of a method of making a lithium mixed metal compound by reaction of starting materials which s5 comprises: (a) in a first stage, mixj_ng starting materials in particle form, the stari:ing materials consisting of iron oxide, diammonium hydrogen phosphate and carbon, said carbon being present in an amount sufficient to reduce the oxidation state of the iron 20 oxide without full reduction to an elemental state, and heating said starting materials in a non°oxidizing atmosphere at a temperature sufficient to produce iron phosphate; and(b) in a second stage, mixing starting materials consisting o.f said iron phosphate and lithium 25 phosphate and heating said second stage mixed starting materials at a temperature sufficient to form lithium iron phosphate represented by the nominal formula LiFeP04.
A further aspect of the method of the present 3o invention relates to an improvement in a method of making a lithium mixed metal compound by reaction of starting materials in which the reaction, in a first stage comprises heating in a non-oxidizing atmosphere and at a temperature sufficient to form iron phosphate, a mixture 35 Of starting materials in particle form, said starting materials being - 20 a -iron oxide and diammonium hydrogen phosphate, and in a second stage, mixing starting materials consisting of said iron phosphate and lithium phosphate and heating said second stage mixed starting materials at a temperature sufficient to farm lithium iron phosphate represented by the nominal formula i~iFeP04, the improvement which comprises incorporating, in the starting materials of the first stage, and prior to said zo heating of said starting materials of said first stage, carbon in an amount sufficient to reduce the oxidation state of the iron ion of said iron oxide withaut full reduction to an elemental state.
~.5 Yet another aspect of the method of the present invention relates to a method of making a lithium mixed metal compound by reaction of starting materials comprising mixing starting materials in particle form, said starting materials comprising a metal oxide; a zo lithium compound selected from lithium carbonate and lithium dihydrogen phosphateo and a compound containing a phosphate group; and in which the reaction involves heating said starting materials at a temperature sufficient to form a single phase reaction product z5 comprising lithium, said reduced. metal ion, and said phosphate group, the improvement comprising incorporating into said starting materials carbon in an amount sufficient to reduce the oxidation state of at least one metal ion of said starting materials without full so reduction to an elemental state.
The present invention also includes a method of making a lithium mixed metal compound by reaction of starting materials which comprises mixing starting 35 materials in particle form, said starting materials consisting of iron oxide, a hydroxide selected from the group consisting of magnesium hydroxide and calcium hydroxides lithium carbonateo a phosphate selected from CA 02466366 2004-05-28 ..
- 20 b -the group consisting of diammonium hydrogen phosphate and ammonium dihydrogen phosphate; and carbon, said carbon being present in an amount sufficient to reduce the s oxidation state of the iron ion of said iron oxide without full reduction to an elemental state; and heating said starting materials at a temperature sufficient to form a single phase reaction product comprising lithium, reduced iron ion, and said phosphate group.
io An additional embodiment of the invention includes a method of making a lithium mixed metal compound by reaction of starting materials which comprises mixing starting materials in particle form, said starting 15 materials being lithium carbonate; iron phosphate;
diammonium hydrogen phosphate; a hydroxide selected from the group consisting of magnesium hydroxide and calcium hydroxide; and heating said starting materials at a temperature sufficient to form a single phase reaction 2o product comprising lithium, the reduced iron ion; and said phosphate group, the impravement which comprises incorporating carbon into said starting materials in an amount sufficient to reduce the oxidation state of the iron ion of said iron phosphate without full reduction to 25 an elemental state.
Further aspects of the present invention include a method of making a compound which comprises mixing starting materials in particle form, said starting 3o materials comprising at least one metal containing compound and a lithium compound selected from the group consisting of lithium.acetate (Li00CCH3), lithium nitrate (LiN03) , lithium oxalate (Li2C209) , lithium oxide (Li20) , lithium phosphate (Li3P09), lithium dihydrogen phosphate s5 (LiH2P04) , lithium vanadate (LiV03) , and lithium carbonate (Li2C03); and heating said starting materials at a temperature sufficient to form a single phase reaction product, the - 20 c -improvement which comprises incorparating carbon into said starting materials in an amount sufficient to reduce the oxidation state of at least one metal ion of said s starting materials without full reduction to an elemental state.
According to a further aspect of the present invention, there is provided a reactive composition ~.o comprising a mixture of starting materials in particle form, said starting materials comprising at least one metal containing compound, a lithium compound and carbon, said carbon being present in at least an amount sufficient to reduce the oxidation state of at least one i5 metal ion of said starting materials without full reduction to an elemental state upon heating of the mixture.
Tn the above composition the .Lithium compound 2o preferably has a melting point greater than 450°C. Still further, most desirably the lithium compound is selected from the group consisting of lithium carbonate, lithium phosphate, lithium oxide, lithium vanadate, and mixtures thereof. In a preferred composition, the metal of said 2s metal containing compound is selected from the group consisting of Fe, Co, Ni; Mn, Cu, V, Sn, Ti, Cr, and mixtures thereof. More desirably, the metal containing compound is selected from the group consisting of Fe203, V205, FeP04, VO2, Fe309, ZiV03, NH4VC)3, and mixtures 3o thereof.
In other preferred embodiments of the invention, the above composition starting materials which include a second metal containing campound having a second metal ion which is not reduced and which is adapted to form a part of a reaction product of said composition:
Desirably, such starting materials include a second metal containing compound which is a compound of a metal - 20 d -selected from the group consisting of Mg, Ca, Vin, Sr, Pb, Cd, Sn, Ba, Be, and mixtures thereof.
s In another embodiment of the above composition of the present invention, the said second metal containing compound is selected from the group consisting of magnesium hydroxide and calcium hydroxide. In addition, desirably the starting materials include a phosphate Zo compound and said composition when reacted forms a reaction product which is a lithium metal phosphate. In other embodiments, the phosphate compound may be selected from the group consisting of diammor~.ium hydrogen phosphate, ammonium dihydrogen phosphate, lithium 35 dihydrogen phosphate, and mixtures thereof.
In another embodiment of this invention the above composition, said. metal compound is a metal oxide or a metal phosphate. Desirably, the metal compound is V2o5, 2o and said lithium compound is lithium carbonate.
According to another aspect of the present invention, there is provided a reactive composition in particle form for forming a lithium iron phosphate 25 represented by the nominal formula ~iFeP04, wherein said reactive mixture consists of an iron phosphate and lithium phosphate, in which the iron phosphate is the reaction product of iron oxide, diammonium hydrogen phosphate and carbon, the carbon being present in said 3o reactive composition in at least an amount sufficient to reduce the oxidation state of the iron ion of said iron oxide without full reduction to an elemental state.
In a still further aspect of the present invention, ss there is provided a reactive composition for forming a single phase reaction product comprising 1~_thium~ reduced iron ion, and a phosphate group, said composition - 20 a -comprising a mixture of starting materials in particle form, said starting materials consisting of iron oxide, a hydroxide selected from the group consisting of magnesium hydroxide and calcium hydroxide; lithium carbonate; a phosphate selected from the group consisting of diammonium hydrogen phosphate and ammonium dihydrogen phosphate; and carbon, said carbon being present in at least an amount sufficient to reduce the oxidation state to of the iron ion of said iron oxide without full reduction to an elemental state.
In yet a further embodiment of the present invention there is also provided a reactive composition for making i5 a single phase reaction product comprising lithium, reduced iron ion, and a phosphate group, said composition comprising a mixture of starting materials in particle form, said starting materials consisting of: lithium carbonate; iron phosphate; diammonium hydrogen phosphate;
2o a hydroxide selected from the group consisting of magnesium hydroxide and calcium hydroxide; arid carbon, said carbon being present in at least an amount sufficient to reduce the oxidation state of the iron ion of said iron phosphate without full reduction to an 2s elemental state.
Another embodiment of the present invention involves a reactive composition comprising a mixture of starting materials in particle form, wherein said starting 3o materials comprise carbon, at least one metal oxide and one further metal compound, the metal of said metal oxide being selected from (a) Ca; (b) Sn; and (c) a transition metal selected from Groups ~1 to 11 inclusive of the Periodic I°able having a +2 valence estate, and the further 3s metal compound being a compound of a metal selected from Groups 2, 12, and s~ of the Periodic Table hav~.ng a +2 valence state; a lithium compound selected from the group - 20 f -consisting of lithium carbonate and lithium dihydrogen phosphate; and a phosphate compound selected from the group consisting of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, lithium dihydrogen phosphate, and mixtures thereof, said carbon being present in an amount sufficient to reduce the oxidation state of at least one metal ion of said starting materials without full reduction to an elemental state.
In a preferred composition of the present invention, desirably the starting materials consist of carbon, lithium carbonate, iron oxide and a phosphate of a metal selected from the group consisting of Mg, Ca, Zn, Sr, Pb, i5 Cd, Sn, Ba, Be, and mixtures thereof.
A still further embodiment of the present invention involves a reactive composition suitable for making a single phase compound which comprises mixed starting 2o materials in particle form, said starting materials comprising at least one metal containing compound, a lithium compound selected from the group consisting of lithium acetate (Li00CCH3), lithium nitrate (LiN03), lithium oxalate (L12C2Oq) , lithium oxide (Li20) , lithium 25 phosphate (Li3P0~), lithium dihydrogen phosphate (LiH2P0~) , lithium vanadate (LiVO~) , and lithium carbonate (Li2C03), and carbon present in an amount at least sufficient to reduce the oxidation state of at least one metal ion of said starting materials without full 3o reduction to an elemental statee Tn the preceding composition, desirably the metal of said metal containing compound is a metal selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Sn, Ti, 35 Cr, and mixtures thereofo A further preferred feature of such a composition is where the metal containing compound is _ 20 g selected from the group consisting of Fe203, V205, ~'eP04, VO2, Fe3Og, LiV03, NHQV03, and mixtures thereof ..
Other preferred forms of the above composition include embodiments where the starting materials include a second metal compound having a second metal ion not capable of being reduced and which will form a part of a reaction product~ Desirably, the sec=and metal compound to is a compound of a metal selected from the group consisting of Mg, Ca, 2n, Sr, Pb, Cd, Sn, Ba, Be, and mixtures thereof. Most preferably, the second metal compound is selected from the group c=onsisting of magnesium hydroxide and calcium hydroxide.
In the preceding compositions, preferably the starting materials include a phosphat=a compound which is selected from the group consisting of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, and mixtures 2o thereof~ Another preferred embodiment of the above compositions is where the metal containing compound is a metal oxide or a metal phosphate. Preferably, the metal containing compound is V205, and said lithium compound is lithium carbonate.
In yet another embodiment of the present invention, there is provided a reactive composition for making a lithium mixed metal compound comprising a mixture of starting materials in particle form, said starting 3o materials comprising a first metal compound, a lithium compound, a second metal compound., ar.~d carbon,. where said carbon is present in an amount sufficient to reduce the oxidation state of at least one metal. ion of said starting materials without full reduction to an elemental state, said second metal compound having a second metal ion which is nonreducable and which is adapted to form a part of a reaction product.

- 20 h -The present invention also provides another embodiment of a reactive composition suitable for making a lithium mixed metal reaction product comprising lithium and a reduced metal ion, said composition comprising a mixture of starting materials in particle form, said starting materials comprising one or more metal containing compounds, a lithium compound, a phosphate compound, and carbon, where said carbon is present in an ~o amount at least sufficient to reduce the oxidation state of at least one metal ion of said starting materials without full reduction to an elemental state"
Another form of the present invention involves a z5 reactive composition for forming a lithium iron phosphate represented by the nominal formula LiFeP04, said composition being a mixture of starting materials in particle form comprising iron oxide, diammonium hydrogen phosphate and carbon.
In the preceding embodiments, desirably the second metal compound comprises a compound of a metal selected from the group consisting of Mg, Ca, Vin, Sr, Pb, Cd, Sn, Ba, Be, and mixtures thereof. Preferably the above compositions are compositions which have the second metal compound chosen from the group consisting of magnesium hydroxide and calcium hydroxide.
In a further desirable embodiment of the above 3o compositions, the phosphate compound is selected from the group consisting of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, lithium dihydrogen phosphate, and mixtures thereof. Also~ desirably, the first metal compound is selected from the group consisting of Fe203, V205, FePO4, V02, Fe304, LiV03, 1~H4VO3, and mixtures thereof. Preferably, the composition is one where - 20 i -the metal of said first metal compound is a compound of a metal selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Ti and Cr. The above compositions may be compositions where the second metal compound is a compound of a metal selected from th.e group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba and Be.
A particularly preferred embodiment according to one so aspect of the present invention is where any of the above compositions have carbon present in a stoichiometric excess, which is desirably up to i00o stoichiometric excess.
~5 In another embodiment of the present invention, there is provided as a novel productr a reaction product produced by any one of the previously described methods.
In such a reaction product obtained by the previously described methods, the product can contain residual 2o carbon from the reaction, and in which the residual carbon is in intimate admixture with the components of the reaction product. The reaction product obtained by the previously described methods can be a product which comprises crystals of lithium material, wherein the 25 crystals are nucleated onto the carbon particles.
In another embodiment of the present invention, there is also provided a composition comprising a lithium mixed metal polyanion compouncl~ arid a carbon dispersed so throughout the lithium mixed metal polyanion compound, wherein the composition is prepared by a process comprising the step of reacting, in particle form, a lithium compound and at least one metal compound in the presence of carbon wherein the carbon is present in an s5 amount sufficient to reduce the oxidation state of at least one metal ion of the metal compound without full reduction to an elemental state.

20 j -Desirably, the preceding composition is obtained by a reaction step which comprises providing as starting materials a lithium compound, a metal compound, and carbon, in powder form, mixing the powders, and heating the mixture for a time and at a temperature sufficient to produce the reaction product. Desirably, carbon is present in stoichiometric excess during the reaction step. Preferably, the to reaction step comprises reacting a finely divided mixture of a lithium compound, a metal compound and carbon.
In the preceding compositions, desirably the lithium mixed metal polyanion compound comprises a mixed metal 1s phosphate of general formula ZiaMTbMII~ (P04~ d wherein 0 < a < 3, 0< b+c ~2, 0 < d s 3, and wherein MI
2o and 8. MII are the same or different, and at least one of MI and MII has more than one oxidation state above the ground state. Preferably, MI and MII are the same. In other cases, MI and MIT have more than one oxidation state above the ground state. A preferred embodiment is 2s where MII has a +2 oxidation state. In such an embodiment desirably MII comprises an element from groups 2, l2,or 14 of the periodic table. A particularly preferred embodiment is where MII is selected from the group consisting of magnesium, calcium, zinc, strontium, 30 lead, cadmium, tin, barium, beryllium, and mixtures thereof.
In the preceding compositions preferably MI is selected from the group consisting of iron, cobalt, 3s nickel, manganese, copper, vanadium, tin, titanium, chromium, and mixtures thereof. In another embodiment, MT comprises one or more metals selected from the group consisting of first - 20 k -row transition metals and tin, and wherein MII is selected from the group consisting of magnesium, calcium, zinc, strontium, lead, cadmium, tin, barium, beryllium, and mixtures thereof.
A still further aspect of the present invention relates to a composition comprising a lithium mixed metal material represented by general formula hiMll_,,MIIyPO~
and carbon particles dispersed throughout the lithium mixed metal material in particle form, wherein the composition is prepared by a process comprising the step of reacting a lithium compound and at least one metal compound in the presence of carbon wherein the carbon is present in an amount sufficient to reduce at least one metal ion of the metal compound without full reduction to 2o elemental state, wherein 0 s y 5 l, MI and MIT are the same or different and each comprise a. metal or. mixture of metals, and at least one of MI and MII has more than one oxidation state abo~re the ground state.
2s In the preceding composition, the lithium mixed metal material may have an olivine structure. As preferred embodiments, MI is selected from the group consisting of iron, cobalt, manganese, copper, vanadium, tin, titanium, chromium, and mixture thereof, and MII is so selected from the group consisting of magnesium, calcium, zinc, strontium, lead, cadmium, tin barium, beryllium, and mixtures thereof. Another embodiment is where MI has more than one oxidation state above the ground state, and MII has an oxidation state of +2. Desirably, MI
35 comprises iron or cobalt. Another embodiment is where MI
comprises iron, cobalt or mixtures thereof and where MII
comprises magnesium, ~ 02466366 2004-05-28 calcium, zinc or mixtures thereof.
In the above formula, preferably the composition is one in which 0 < y 5 0.5, desirably 0 < y s 0.2.
The present invention also provides an embodiment of a composition i~. which the composition comprises a lithium mixed metal material represented by formula Li Fel_YMgYP04 wherein 0 < y s 0.2r and carbon particles dispersed throughout the lithium mixed metal material, the material being in particle form, wherein the composition is prepared by a process comprising the step of reacting a lithium compound and at least one metal compound in the presence of carbon wherein the carbon is present in an amount sufficient to reduce the oxidation state of at least one metal ion of the metal compound without full reduction to an elemental state. In. this composition~
desirably the lithium mixed metal material is a compound of the general formula Li Fel_yCayP09 wherein 0 < y ~ 0.2. .Another embodiment of the invention is a composition wherein the lithium mixed metal material is a compound of the general formula 3n LiFel_yZnYPOq wherein 0 < y s 0.2.
Yet a further aspect of the presemt inve:ntior.~
provides a composition of the type outlined above, wherein the - 20 m -lithium mixed metal material is a compound of the general formula LiCol_yMgYPG4 wherein 0 < y _< 0.2.
Another embodiment of the invention wherein the lithium mixed metal material is a compound of the general formula LiCol_yCayPO~
1s wherein 0 < y <_ 0.2.
A further embodiment of the invention is where the lithium mixed metal material is a compound of the general farmula LiCol_yZnyPO,~
wherein 0 < y < 0.2.
2s Yet another aspect of the invention is a composition compr~.sing carbon particles and crystals of a lithium mixed metal material in particle form, wherein the crystals are nucleated onto the particles, wherein the composition is made by a process comprising the step of reacting a lithium compound and a. metal compound in the presence of carbon.
In a further embodiment the invention provides a composition comprising carbon particles and crystals of a 3s lithium mixed metal material in particle form, wherein the crystals are nucleated onto the particles, wherein the ~ 02466366 2004-05-28 - 20 n -composition is made by a process comprising the step of reacting a lithium compound and a metal compound in the presence of a stoichiometric exces:~ of carbon.
In yet another embodiment the invention includes a composition comprising a lithium mixed. metal material in particle form represented by general formula 1o Li3MIs,MI I2_~, i P0~ ) 3, and carbon particles dispersed throughout the lithium mixed metal material, wherein the composition is prepared by a process comprising the step of reacting a lithium s5 compound and a metal compound in the presence of carbon, wherein 0 <_ y < 2, MI and MII are the same or different and each comprise a metal or mixture of metals and at least one of MI and MII has more than one oxidation state above the ground state~
In the preceding embodiment, the lithium mixed metal material may have a nasicon structu.re~ preferably MI and MII are different. Further, in preceding embodiments, MI
is desirably selected from the group consisteing of iron, cobalt, nickel, manganese, copper, vanadium, tin~
titanium, chromium and mixtures thereof, and wherein MII
is selected from the group consisting of magnesium, calcium, zinc, strontium, lead, cadmium, tin, barium, beryllium, and mixtures thereaf.
These and other aspects, :features, and advantages will become apparent from the following description of the preferred embodiments, claims, and accompanying drawings.

According to one aspect of the present invention there is provided a method of making a lithium mixed metal compound by reaction of starting materials which comprises:
mixing starting materials in particle form with a volatile solvent or binder to form a wet mixture, the starting materials comprising at least one metal containing compound, a lithium compound having a melting point greater than 450°C, and carbon, where the carbon is present in an amount sufficient to reduce the oxidation state of at least one metal ion of the starting materials without full reduction to an elemental state; and heating the wet mixture in a non-oxidizing atmosphere at a temperature sufficient to form a reaction product comprising lithium and the reduced metal ion.
According to another aspect of the present invention there is provided a method of making a lithium mixed metal compound by reaction of starting materials which comprises:
mixing starting materials in particle form with a volatile solvent or binder to form a wet mixture, the starting materials comprising at least one or more metal containing compound, a lithium compound, and carbon, where the carbon is present in an amount sufficient to .reduce the oxidation state of at least one metal ion of the starting materials without full reduction to an e1_emental state; and heating the wet mixture at a temperature sufficient to form a reaction product comprising lithium and the reduced metal ion; wherein the lithium compound is selected from the group consisting of lithium carbonate, lithium phosphate, lithium oxide, lithium vanadate, and mixtures thereof.

According to yet another aspect of the present invention there is provided a method of making a 1_ithium mixed metal compound by reaction of starting materials which comprises: mixing starting materials in particle form with a volatile solvent or binder to form a wet mixture, the starting materials comprising at least one metal containing compound; a lithium compound; carbon present in an amount sufficient to -red_uce the oxidation state of at least one metal ion of the starting materials without full reduction to an elemental state; and a compound containing a polyanion capable of forming a crystal lattice; and heating the wet mixture at a temperature sufficient to form a single phase reaction product comprising lithium, the reduced metal ion, and the polyanior_.
According to still yet another aspect of the present invention there is provided a method of making a lithium mixed metal compound by reaction of starting materials which comprises: mixing starting materials in particle form with a volatile solvent cr binder to form a wet mixture, the starting materials comprising a first metal compound, a lithium compound, a second metal compound, and carbon, where the carbon is present in an amount sufficient to reduce the oxidation state of at least one metal ~_on of the starting materials without full reduction to an e~_emental state; and heating the wet mixture at a temperature sufficient to form a reaction product comprising e_ithium and the reduced metal ion, wherein the second metal compound has a second metal ion which is not reduced and which forms a part of the reaction product.
According to still yet another aspect of the present invention there is provided a reactive composition comprising: a wet mixture of starting materials irz particle 20 ~ _ form and a volatile solvent or binder, the starting materials comprising at least one metal containing compound, a lithium compound and carbon, the carbon being present in at least an amount sufficient to reduce the oxidation state of at least one metal ion of the starting materials without full reduction to an elemental :M ate upon heating of the wet mixture According to still yet another aspect of the present invention there is provided a reactive composition for making a lithium mixed metal compound comprising a wet mixture of starting materials in particle form and a volatile solvent or binder, the starting materials comprising a first metal comioound, a lithium compound, a second metal compound, and carbon, where the carbon is present in an amount sufficient to reduce the oxidation state of at least one metal i.on of the starting materials without full reduction to an elemental state, the second metal compound having a second metal ion which is nonreducable and which is adapted to form a part of a reaction product.
According to still yet another aspect of the present invention there is provided a composition. comprising: a lithium mixed metal polyanion compound; a:nd carbon dispersed tr.roughout the lithium mixed metal material, wherein the composition is prepared by a process comprising mixing a lithium compound, a volatile solvent or binder and at least one metal compound in the presence of carbon, wherein the carbon is present in an amount sufficient to reduce the oxidation state of at least one metal ion of the metal compound without full- reduction to an elemental state, to form a wet mixture; and heating the wet mixture at a temperature and for a time sufficient to produce the lithium mixed metal polyanion.
According to still yet another aspect of the present invention there is provided a composition comprising a lithium mixed metal material represented by general formula Z=~MI~ _~,MI I~PO
and carbon dispersed throughout the lithium mixed metal material, wherein the composition is prepared by a process comprising the step of mixing a lithium compound, a volatile, and at least one metal compound in the presence of carbon wherein the carbon is present z.n an amount sufficient to reduce at least one metal ion of the metal compound without full reduction to elemental state, wherein 0 <_ y <_ 1, MI and MII are the same or different and each comprise a metal or mixture of metals, and at least one of MI and MII has more than one oxidation state above the ground state.

_21 Brief Description of the Drawincts Figure 1 shows the results of an x-ray diffraction analysis, of the LiFeP04 prepared according s to the invention using CuKcx radiation, r~ = 1.5405A. Bars refer to simulated pattern from refined cell parameters, Space Group, SG = Pnma (62). The values are a = 10.2883A
(0.0020), b = 5.9759A (0.0037), c = 4.6717A (0.0012) 0.0072, cell volume = 287.2264A~ (O.O~a85). Density, p =
so 3.605 g/cc, zero = 0.452 (0.003). Peak at full width half maximum, PFWHM = 0.21. Crystallite size from XRD
data = 704A.
Figure 2 is a voltage/capacity plot of LiFeP09-1s containing cathode cycled with a lithium metal anode using constant current cycling at ~ 0.2 milliamps per square centimeter in a range of 2.5 t:o 4.0 volts at a temperature of about 23°C. The cathode contained l9.Omg of the LiFeP04 active material, prepared by the method of 2o the invention. The electrolyte comprised ethylene carbonate (EC) and dimethyl carbonate (DMC) in a weight ratio of 2:1 and included a 1 molar concentration of LiPF6 salt. The lithium-metal-phosphate containing electrode and the lithium metal counter electrode are 2s maintained spaced apart by a glass f~.ber separator which is interpenetrated by the solvent and the salt.
Figure 3 shows multiple constant current cycling of LiFeP04 active material cycled with a lithium so metal anode using the electrolyte as described in connection with Figure 2 and cycled, charge and discharge at ~ 0.2 milliamps per square centimeter, 2.5 to 4.0 volts at two different temperature conditions, 23°C and 60°C. Figure 3 shows the excellent rechargeability of ss the lithium iron phosphate/lithium metal cell, and also shows the excellent cycling and specific capacity (mAh/g) of the active material.

~ 02466366 2004-05-28 _.....,... _. .... _ Figure 4 shows the results of an x-ray diffraction analysis, of the LiFeo_gMgo,lPOq prepared according to the invention, using CuKCC radiation, A =
1.5405A. Bars refer to simulated pattern from refined s cell parameters SG = Pnma (62). The values are a =
10.2688A (0.0069), b =,5.9709A (0.0072), c = 4.6762A
(0.0054), cell volume = 286.7208A (0.04294), p = 3.617 g/cc, zero = 0.702 (0.003), PFWHM = 0.01, and crystallite - 950A.
Figure 5 is a voltage/capacity plot of LiFeo,9Mgo.1P09-containing cathode cycled with a lithium metal anode using constant current cycling at ~ 0.2 milliamps per square centimeter in a range of 2.5 to 4.0 z5 volts. Other conditions are as described earlier with respect to Figure 2. The cathode contained 18.9mg of the LiFeo,9Mgo.lPOq active material prepared by the :method of the invention.
2o Figure 6 shows multiple coxastant current cycling of LiFeo.~Mgo,1P04 cycled with .a lithium metal anode using the electrolyte as described in. connection with Figure 2 and cycled, charge and discharge at 1- 0.2 milliamps per square centimeter, 2.5 to 4.0 volts at two 2s different temperature conditions, 23°C and 60°C. Figure 6 shows the excellent rechargeability of the lithium-metal-phosphate/lithium metal cell, and also shows the excellent cycling and capacity of the cell.
3o Figure 7 is a voltage/capacity plot of LiFeo.BMgo.2P04-containing cathode cycled with a lithium metal anode using constant current cycling at -!- 0.2 milliamps per square centimeter in a range of 2.5 to 4.0 volts at 23°C. Other conditions are as described earlier 35 with respect to Figure 2. The cathode contained l6mg of the LiFeo.~Mgo.2P0~ active material prepared by the method of the invention.

Figure 8 shojis the results of an x-x~ay diffraction analysis, of the LiFeo.9Cao.1P04 prepared according to the invention, using CuKcx radiation, 1~ =
1.5405A. Bars refer to simulated pattern front refined cell parameters 3G = Pnma (62). The values are a =
10.3240A (0.0045), b = 6.0042A (0.0031), c = 4.6887A
(0.0020), cell volume = 290.6370A (0.1807), zero = 0.702 (0.003), p = 3.62 g/cc, PFWHM = 0.18, and crystallite =
680A.
to Figure 9 is a voltage/capacity plot of LiFeo,BCao.2P0a'containing cathode cycled with a lithium metal anode using constant current cycling at ~ 0.2 milliamps per square centimeter in a range of 2:5 to 4.0 volts at 23°. Other conditions are as described earlier with respect to Figure 2. The cathode contained 18.5mg of the LiFeo,eCao.2P04 active material prepared by the method of the invention.
2o Figure 10 is a voltage/capacity plot of LiFeo,eZno.2P04'containing cathode cycled with a lithium metal anode using constant current cycling at ~ 0.2 milliamps per square centimeter in a range of 2.5 to 4.0 volts at 23°C. Other conditians are as described earlier with respect to Figure 2. The cathode contained 18.9mg of the LiFeo,eZno.2P0q active material prepared by the method of the invention.
Figure 11 shows the results of an x~-ray 3o diffraction analysis of the gamma-LiXV205 (x = _L, gamma LiV205) prepared according to the invention using CuKOc radiation A = 1.5405A. The values are a = 9.687A (1), b

- 3.603A (2), and c = 10.677A (3); phase type is gamma-LiXV205 (x = 1); symmetry is orthorhombic; and space group is Pnma.
Figure I2 is a voltage/capacity plot of gamma-LiV205-containing cathode cycled with a lithium metal anode using constant current cycling at ~ 0.2 milliamps per square centimeter in a range of 2.5 to 3.8 volts at 23°C. Other conditions are as described earlier with s respect to Figure 2. The cathode contained 2lmg of the gamma-LiV205 active material prepared by the method of the invention.
Figure 13 is a two-part graph based on multiple 1o constant current cycling of gamma-LiV205 cycled with a lithium metal anode using the electrolyte as described in connection with Figure 2 and cycled, charge and discharge at ~ 0.2 milliamps per square centimE:ter, 2.5 to 3.8 volts . In the two-part graph, Figure: 13 show s the 15 excellent rechargeability of the lithium-meta:l-oxide/lithium metal cell. Figure 13 shows the excellent cycling and capacity of the cell.
Figure 14 shows the result:y of an x-ray 2o diffraction analysis of the Li3V2(P09)a prepared according to the invention. The analysis is based on CuKcX
radiation, A = 1.5405A. The values a.re a = 12.184A (2), b = 8. 679A (2) , c = 8. 627A (3) , and ~i = 90.457° (4) .
25 Figure 15 shows the results of an x-ray diffraction analysis of L i3V2 {PO9) 3 prepared according to a method described in U.S. Patent No. 5,871,806. The analysis is based on CuKcx radiation, A = 1.5405A. The values are a = 12.155A {2), b = 8.711A (2), c = 8.645A
so (3); the angle beta is 90.175 (6); symmetry is Monoclinic; and space group is P2,/n.
Figure 1~ is an EVS (Electrochemical Voltage Spectroscopy) voltage/capacity profile for a cell with s5 cathode material formed by the carbot:.hermal reduction method of the invention. The cathode material is 13.8mg of Li3V2(POq)3. The cell includes a lithium metal counter electrode in an electrolyte comprising ethylene carbonate (EC) and dimethyl carbonate (DMC) in a weight ratio of 2:1 and including a 1 molar concentration of hiPF6 salt.
The lithium-metal-phosphate containing electrode and the lithium metal counter electrode are maintained spaced apart by a fiberglass separator which is interpenetrated by the solvent and the salt. The conditions are ~ 10 mV
steps, between about 3.0 and 4.2 volts, and the critical limiting current density is less than or equal to 0.1 1 o mA/ cm2 .
Figure 17 is an EVS differential capacity versus voltage plot for the cell as described in connection with Figure 16.
Figure 18 shows multiple canstant current cycling of LiFe~.QMgo.2POQ cycled with a lithium metal anode using the electrolyte as described in connection with Figure 2 and cycled, charge and discharge at ~ 0.2 2o milliamps per square centimeter, 2.5 to 4.0 volts at two different temperature conditions, 23°C and 60°C. Figure l~ shows the excellent rechargeability of the lithium-metal-phosphate/lithiurn metal cell, and also ;shows the excellent cycling and capacity of the cell.
Figure 19 is a graph of potential over time for the first four complete cycles of the LiMgo,lFeo.gPO~/MCMB
graphite cell of_ the invention.
3o Figure ~0 is a two-part graph based on multiple constant current cycling of LiFeo,9Mgo,1P09 cycled with an MCMB graphite anode using the electrolyte as described in connection with Figure 2 and cycled, charge and discharge at ~ 0.2 milliamps per square centimeter, 2.5 to 3.6 s5 volts, 23°C and based on a C/10 (10 hour) rate. In the two-part graph, Figure 2tJ shows the excellent rechargeability of the lithium-metal-phosphate/graphite ~ 02466366 2004-05-28 ..
cell. Figure 20 shows the excellent cycling and capacity of the cell.
Figure 21 is a graph of potential over time for s the first three complete cycles of the gamma-LiV205/MCMB
graphite cell of the invention.
Figure 22 is a diagrammatic representation of a typical laminated lithium-ion battery cell structure.
~o Figure 23 is a diagrammatic representation of a typical mufti-cell battery cell structure.

Detailed Desori~tion of the Preferred Eanl~odiments The present invention provides lithium-mixed metal-phosphates, which are usable as electrode active materials, for lithium (Li-~) ion removal and insertion.
Upon extraction of the lithium ions from the lithium-mixed-metal-phosphates, significant capacity is achieved.
In one aspect of the invention, electrochemical energy is provided when combined with a suitable counter electrode to by extraction of a quantity x of lithium from lithium-mixed-metal-phosphates Lia_XMI,,NIII~ (POg) d. When a quantity x of lithium is removed per formula unit of the lithium-mixed-metal phosphate, metal MI is oxidized. In another aspect, metal MII is also oxidized. Therefore, at least one of MI and MII is oxidizable from its initial condition in the phosphate compound as Li is removed.
Consider the (allowing which illustrate the mixed metal compounds of the invention: LiFe~_YSn~,P09, has two oxidizable elements, Fe and Sn~ in contrast, 2o LiFe1_yNIgYPOq has one oxidizable metal, the metal Fe.
In another aspect, the invention provides methods for preparation of materials useful in a lithium ion battery; typically such a battery comprises an 2s electrolyte; a negative electrode having an insertion active material; and a. positive electrode comprising a lithium-mixed-metal-phosphate active material characterized by an ability to release lithium ions for insertion into the negative electrode active material.
3o The lithium-mixed-metal-phosphate is desirably represented by the nominal general formula LiaMIbMII~ (POq) d. Although the metals MI and M.II may be the same, it is preferred that the metals MI and MII
are different. Desirably, in the phosphate compound 35 MI is a metal selected from the group: Fe, Co, Ni, Mn, Cu, V, Sn, Ti, Cr and mixtures thereof, and MI is most desirably a transition metal or mixture thereof ~ 02466366 2004-05-28 -2~-selected from said group. Mast preferably, MI has a +2 valence or oxidation state.
In another aspect, MII is selected from Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, and mixtures thereof. Most preferably, MII has a +2.valence or oxidation state. The lithium-mixed-metal-phosphate is preferably a compound represented by the nominal general formula Lia_XMIbMII~ (P09) d, signifying the preferred composition and so its capability to release x lithium. Accordingly, during cycling, charge and discharge, the value of x varies as x greater than or equal to 0 and less than or equal to a.
The present invention resolves a capacity problem posed by conventional cathode active mater_~als. Such problems ~.5 with conventional active materials are described by Tarascon in U.S. Patent No. 5,425,932, using LiMn204 as an example. Similar problems are observed with LiCo02, LiNi02, and many, if not all, lithium metal chalcogenide materials. The present invention dernonstrates.that 2o significant capacity of the cathode active material is utilizable and maintained.
A preferred novel procedure for forming th.e lithium-mixed-metal-phosphate LiaMIbMITC (PO9) d compound 25 active material will now be described. In addition, the preferred novel procedure is also applicable to formation of other lithium metal compounds, and will be described as such. The basic procedure will be described with reference to exemplary starting materials but is riot 30 limited thereby. The basic process comprises conducting a reaction between a lithium compound, preferably lithium carbonate (Li2C03), metal compound(s), for example, vanadium pentoxide (V205) , iron oxide (Fe203) , and/or manganese hydroxide, and a phosphoric: acid derivative, 35 preferably the phosphoric acid ammonium salt, diammonium hydrogen phosphate, (NHq) 2H (P04) . Each of the precursor starting materials are available frorr~ a number of -z~-chemical outfits including Aldrich Chemical Company and Flukes. Using the method described herein, LiFePOn and LiFeo.s~'~go.iPOa. Li~V2 (P04) 3 were prepared with approximately a stoichiometric amount of Li2C03, the respective metal s compound, and (NHq)ZHPO~. Carbon powder was included with these precursor materials. The precursor materials were initially intimately mixed and dry ground for about 30 minutes. The intimately mixed compounds were then pressed into pellets. Reaction was conducted by heating so in an oven at a preferred ramped heating rate to an elevated temperature, and held at such elevated temperature far several hours to com~alete formation of the reaction product. The entire reaction was conducted in a non-oxidizing atmosphere, under flowing pure argon 15 gas. The flow rate will depend upon the size of the oven and the quantity needed to maintain 'the atmosphere. The oven was permitted to cool down at the end of the reaction period, where cooling occurred at a desired rate under argon. Exemplary and preferred ramp rates, 2o elevated reaction temperatures and reaction times are described herein. In one aspect, a :ramp rate of ~°/minute to an elevated temperature in a range of 750°C
to 800°C was suitable along with a dwell (reaction time) of 8 hours. Refer to Reactions 1, 2, 3 and 4 herein. In 2s another variation per Reaction 5, a reaction temperature of 600°C was used along with a dwell time of about one hour. In still another variation, as per Reaction 6, a two-stage heating was conducted, first to a temperature of 300°C and then to a temperature of 850°.
The general aspects of the above synthesis route are applicable to a variety of starting materials.
Lithium-containing compounds include Li20 (lithium oxide), LiH2P0~ (lithium hydrogen phosphate), Li2C204(lithium oxalate), LiOH (lithium hydroxide), Li0H.H20 (lithium hydroxide m.onohydride), and LiHC03 (lithium hydrogen carbonate). The metal compounds(s) are reduced in the presence of the reducing agent, carbon.
The same considerations apply to other lithium-metal- and phosphate-containing precursors. The thermodynamic considerations such as ease of reduction, of the selected s precursors, the reaction kinetics, and the melting point of the salts will cause adjustment in the general procedure, such as, amount of carbon reducing agent, and the temperature of reaction.
io Figures 1 through 21 which will be described more particularly below show characterization data and capacity in actual use for the cathode materials (positive electrodes) of the invention. Some tests were conducted in a cell comprising a lithium metal counter z5 electrode (negative electrode) and other tests were conducted in cells having a carbonaceous counter electrode. All of the cells had an ECeDMC-LiPF6 electrolyte.
2o Typical cell configurations will now be described with reference to Figures 22 and 2~; and such battery or cell utilizes the novel active material of the invention. Note that the preferred cell arrangement described here is illustrative and the invention is not 2s limited thereby. Experiments are often performed, based on full and half cell arrangements, as per the following description. For test purposes, test cells are often fabricated using lithium metal electrodes. then forming cells for use as batteries, it is preferred to use an so insertion positive electrode as per the invention and a graphitic carbon negative electrode.
A typical laminated battery cell structure 10 is depicted in Figure ~~. It comprises a negative s5 electrode side 12, a positive electrode side 14, and an electrolyte/separator 16 there between. Negative electrode side 12 includes current collector 18, and positive electrcde side 24 includes current collector 22.
A copper collector foil. 18, preferably in the form of an open mesh grid, upon which is laid a negative electrode membrane 20 comprising an insertion material such as s carbon or graphite or low-voltage lithium insertion compound, dispersed in a polymeric binder matrix. An electrolyte/separator film 16 membrane is preferably a plasticized copolymer. This electrolyte/separator preferably comprises a polymeric separator and a suitable 1o electrolyte for ion transport. The electrolyte/separator is positioned upon the electrode element and is covered with a positive electrode membrane 24 comprising a composition of a finely divided lithium insertion compound in a polymeric binder matrix. An aluminum 15 collector foil or grid 22 completes the assernbly.
Protective bagging material 40 covers the cell and prevents infiltration of air and moisture.
In another embodiment, a multi-cell battery 2o configuration as per Figure 23 is prepared with copper current collector 51, negative electrode 53, electrolyte/separator 55, positive electrode 57, and aluminum current collector 59. Tabs 52 and 58 of the current collector elements form respective terminals for z5 the battery structure As used herein, the terms "cell"
and "battery" refer to an individual cell comprising anode/electrolyte/cathode and also :refer to a mufti-cell arrangement in a stack.
so The relative weight proportions of the components of the positive electrode are generally: 50-g0o by weight active material; 5-30o carbon black as the electric conductive diluent; and 3-20o binder chosen to hold all particulate materials in contact with one 35 another without degrading ionic conductivity. Stated ranges are not critical, and the amount of active material in an electrode may range from 25-95 weight percent. The negative electrode comprises about 50-95%
by weight of a preferred graphite, with the balance constituted by the binder. A typical electrolyte separator film comprises approximately two parts polymer s for every one part of a preferred fumed silica. The conductive solvent comprises any number of suitable solvents and salts. Desirable solvents and salts are described in U.S. Patent Nos. 5,643,695 and 5,418,091.
One example is a mixture of EC:DMC:LiPF6 in a weig~.t 1o ratio of about 6C:30:1Ø
Solvents are selected to be used individually or in mixtures, and include dimethyl carbonate (DMC), diethylcarbonate (DEC), dipropylcarbonate (DPC), 15 ethylmethylcarbonate (EMC), ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate, lactones, esters, glymes, sulfoxides, sulfolanes, etc. The preferred solvents are EC/DMC, EC/DEC, EC/DPC and EC/EMC.
The salt content ranges from 5° to 65~ by weight, 2o preferably from 8o to 35o by weight.
Those skilled in the art will understand that any number of methods are used to form films from the casting solution using conventional meter bar or doctor 25 blade apparatus. Tt is usually sufficient to air-dry the films at moderate temperature to yield self-supporting films of copolymer composition. Lamination of assembled cell structures is accomplished by conventional means by pressing between metal plates at a temperature of about so 120-160°C. Subsequent to lamination, the battery cell material may be stored either with the retained plasticizes or as a dry sheet after extraction of the plasticizes with a selective low-boiling point solvent.
The plasticizes extraction solvent is not critical, and 35 methanol or ether are often used.
Separator membrane element 16 is generally polymeric and prepared from a composition comprising a copolymer. A preferred composition is the 75 to 920 vinylidene fluoride with 8 to 25o hexafluoropropylene copolymer (available commercially from Atochem North America as KYNAR FLEX) and an organic solvent plasticizer. Such a copolymer composition is also preferred for the preparation of the electrode membrane elements, since subsequent laminate interface compatibility is ensured. The plasticizing solvent may 1o be one of the various organic compounds commonly used as solvents for electrolyte salts, e.g., propylene carbonate or ethylene carbonate, as well as mixtures of these compounds. Higher-boiling plasticizer compounds such as dibutyl phthalate, dimethyl phthalate, diethyl phthalate, i5 and tris butoxyethyl phosphate are particularly suitable.
Inorganic filler adjuncts, such as fumed alumina or silanized fumed silica, may be u~;ed to enhance 'che physical strength and melt viscosity of a separator membrane and, in some compositions, to increase the 2o subsequent level of electrolyte solution absorption.
In the construction of a lithium-ion battery, a current collector layer of aluminum foil or grid is overlaid with a positive electrode film, or membrane, 2s separately prepared as a coated layer of a dispersion of insertion electrode composition. This is typically an insertion compound such as LiMn209 (LMO), LiCoO2, or LiNi02, powder in a copolymer matrix solution, which is dried to form the positive electrode. An so electrolyte/separator membrane is formed as a dried coating of a composition comprising a solution containing VdF:HFP copolymer and a plasticizer solvent as then overlaid on the positive electrode film. A negative electrode membrane formed as a dried coating of a 35 powdered carbon or other negative electrode material dispersion in a VdF:HFP copolymer matrix solution is similarly overlaid on the separator membrane layer. A

copper current collector foil or grid is laid upon the negative electrode layer to complete the cell assembly.
Therefore, the VdFoHFP copolymer composition is used as a binder in all of th.e major cell components, positive s electrode film, negative electrode film, and electrolyte/separator membrane. The assembled components are then heated under pressure to achieve heat-fusion bonding between the plasticized copolymer matrix electrode and electrolyte components, and to the to collector grids, to thereby form an effective laminate of cell elements. This produces an essentially unitary and flexible battery cell structure.
Examples of forming cells containing metallic 15 lithium anode, insertion electrodes, solid electrolytes and liquid electrolytes can be found in U.S. Patent Nos.

4, 668, 595; 4, 830, 939; 4, 935, 317; 4, 990, 413; 4, 792, 504;

5, 037, 712; 5, 262, 253; 5, 300, 373; 5, 435, 054; 5, 463, 279;
5,399,447; 5,482,795 and 5,411,820. Note that the older 2o generation of cells contained organic polymeric and inorganic electrolyte matrix materials, with the polymeric being most preferred. The polyethylene oxide of 5,411,820 is an example. More modern examples are the VdF:HFP polymeric matrix. Examples of casting, 2s lamination and formation of cells using VdF:HFP are as described in U.S. Patent Nos. 5,418,091; 5,460,904;
5, 456, 000; and 5, 540, 741; assigraed to Bell Communications Research.
so As described earlier, the electrochemical cell operated as per the invention, may be prepared in a variety of ways. In ane embodiment, the negative electrode may be metal~_ic lithium. In more desirable embodiments, the negative electrode is an insertion 35 active material, such as, metal oxides and graphite.
When a metal oxide active material is used, the components of the electrode are the metal oxide, electrically conductive carbon, and binder, in proportions similar to that described above for the positive electrode. In a preferred embodiment, the negative electrode active material is graphite particles.
s For test purposes, test cells are often fabricated using lithium metal electrodes. When forming cells for use as batteries, it is preferred to use an insertion metal oxide positive electrode and a graphitic carbon negative electrode. Various methods for fabricating to electrochemical cells and batteries and for forming electrode components are described herein. The invention is not, however, limited by any particular fabrication method.

- 3t -Formation of Active Materials EXAMPLE I
Reaction 1 (a) < LiFePOQ formed from FeP04 FeP04 + 0.5 Li2C03 + 0.5 C --~ LiFeP04 + 0. 5 C02 + 0. 5 CO
(a) Pre-mix reactants in the following proportions 1o using ball mill. Thus, 1 mol FeP04 150.828 0.5 mol Li2C03 36.958 0.5 mol. carbon 6.Og (but use 1000 excess carbon -~ 12.008) (b) Pelletize powder mixture (c) Heat pellet to 750°C at a rate of 2°/minute in flowing inert atmosphere (e. g. argon). Dwell for 8 hours at 750°C under. argon.
(d) Cool to room temperature at 2°/minute under argon .
(e) Powderize pellet.
Note that at 750°C this is predominantly a CO
3o reaction. This reaction is able to be conducted at a temperature in a range of about 700°C to about 950°C in argon as shown, and also under other inert atmospheres such as nitrogen or vacuum.
EXAMPLE II

Reaction 1 (b) . LiFeP04 formed from Fe203 0. 5 Fe203 + 0 . 5 Li2C03 + (NH4) ZHP04 + 0. 5 C -~ LiFeP04 +
0 . 5 C02 + 2 NH3 + 3 / 2 H20 + 0 . 5 CO
s (a) Premix powders in the following proportions 0 . 5 mo l Fe203 7 9 . 8 58 0 . 5 mol Li2C03 3 6 . 958 1 mol (NH4) 2HP04132. 068 0.5 mol carbon 6.008 (use 100 o excess carbon -~ 12 . 008) (b) Pelletize polder mixture (c) Heat pellet to 750°C at a rate of 2°/minute in flowing inert atmosphere (e. g. argon). Dwell for 8 hours at 750°C under_ argon.
(d) Cool to room temperature at 2°/minute under argon.
(e) Powderize EX1~MPIsE III
Reaction 1 (c) . LiFeP09 - from Fe3 (P04) 2 3o Two stepse Part I. Carbothermal preparation of Fe3(P04)2 3 / 2 Fe203 -ø- 2 ( NH4 ) zHPO~ + 3 / 2 C -~ Fe3 ( PO4 ) 2 +
3/2 CO + 4NH3 + 5/2 Hz0 (a) Premix reactants in the following proportions 3/2 mol Fe203 239.548 2 mol (NH4) 2 HP04 264.128 3/2 mol carbon 18.008 (use 100 excess carbon -~ 36.008) (b) Pelletize powder mixture (c) Heat pellet to 800°C at a rate of 2°/minute in flowing inert atmosphere (e. g. argon). Dwell to for 8 hours at 750°C under argon.
(d) Cool to room temperature at 2°C/minute under argon.
15' (e) Powderize pellet.
Part II. Preparation of LiFePO~ from the Fe3(POq)2of Part I.
2o Li3POq + Fe ( POq ) 2 --~ 3 LiFeP04 (a) Premix reactants in the following proportions 1 mol Li3P09 115.798 1 mol Fe3 ( POq ) 2 357 . 4 88 (b) Pelletize powder mixture (c) Heat pellet to 750°C at a rate of 2°/minute in flowing inert atmosphere (e. g~ argon). Dwell 3o for 8 hours at 750°C 'under argon.
(d) Cool to room temperature at 2°C/minute under argon.
(e) Powderize pellet.
EXAMPLE hI

Reaction 2 (a) . LiFeo.9Mgo,zP04 (LiFel_~,MgYP04) formed from FeP09 0 . 5 Zi2C03 + 0 . 9 FeP04 + 0.1 Mg (OH) 2 + 0.1 (NH4) 2HP04 +
0.45C ---~ LiFeo.9Mgo,1P0~ + 0.5C02 + 0.45C0 + 0.2NH3 +
0.25 H20 (a) Pre-mix reactants in the following proportions 1o 0.50 mol Li2C03 = 36.95g 0.90 mol Fe~'O9 - 135.748 0.10 mol Mg(OH)2 - 5.838 0 . 10 mol (NH4) 2HP04- 1 .:328 0.45 mol carbon - 5.408 (use 200 a excess carbon --~ 10. SOg) (b) Pelletize powder mixture (c) Heat to 750°C at a rate of 2°/minute in argon.
Hold for 8 hours dwell at 750°C in argon (d) Cool at a rate of 2°/minute (e) Powderize pellet.
EXAMPLE V
Reaction 2 (b) . LiFe~,9Mg~,1P04 (LiFel_yMgyP04) formed from Fe203 0 . 50 Li2C03 + 0 . 45 Fe203 + 0 . 10 Mg (OH) 2 + (NH4 ) 2HP04 +
0.45C > LiFeo,9Mgo,1P09 + 0.5 C02 + 0.45 CO + 2 NH3 +
2 . 6 Hz0 (a) Pre-mix reactants in following ratio 0.50 mol Li2C03 = 3o.95g 0.45 mol Fe203 - 71.868 0.10 mol Mg(OH)Z - 5.838 1 . 00 mol (NH9) 2HP09- 132. 068 0.45 mol carbon - 5.408 (use 100 excess carbon --~10.80g) (b) Palletize powder"mixture (c) Heat to 750°C at a rate of 2°/minute in argon.
Hold for 8 hours dwell at 750°C in. argon (d) Cocl at a rate of 2°/minute (e) Powderize pellet.

EXAMPLE VI
Reaction 2 (c) . LiFeo,gMgo.1P09 (LiFel_yMgYPOq) formed from LiH2POq 1 . 0 LiH2POQ + 0. 45 Fe203 + 0. 10 Mg (OH) 2 + 0 . 45C -LiFeo.sMgo.iP04 + 0.45 CO + 1.I H20 (a) Pre-mix reactants in the following proportions 1.00 mol LiH2P0~, - 103.938 0.45 mol Fe203 - 71.868 0.10 mol Mg(OH)2 - 5.838 0.45 mol carbon - 5.408 (use 100 o excess carbon --~ 10 . 808) (b) Pelletize powder mixture (c) Heat to 750°C at a rate of 2°/minute in argon.
Hold for 8 hours dwell at ?50°C in argon (d) Cool at a rate of 2°/minute (e) Powderize pellet.
EXAMPLE VIII
Reaction 3. Formation of LiFeo,9Cao,1P04 (LiFe2_yCayPOq) from Fe203 0. 50 Li2COj + 0. 45 Fe203 + 0. 1 Ca (OH) 2 + (NH4) 2HP04 +
0.45C ~ LiFeo,9Cao,1P04 + 0.5 C02 + 0.45 CO + 2 NH3 +
1.6 H20 (a) Pre-mix reactants in the following proportions 0.50 mol Li2C03 - 36.958 0.45 mol Fe203 - 71.868 0.10 mol CadOH)~ - 7.418 1 mol (NH9) ZHPO~ 132 .068 . -0.45 mol carbon - 5.408 (1000 excess carbon -~ 10.808) (b) Pelletize powder mixture (c) Heat to 750°C at a rate of 2°/minut~e in argon.
Hold for 8 hours dwell at 750°C in argon (d) Cool at a rate of 2°/minute (e) Powderize pellet.
EXAMPLE VIII
2o Reaction 4. Formation of LiFe~,9Gno,1P04 (LiFe,_YZnYP04) from Fe203.
0. 50 Li2C0; + 0. 45 Fe203 + 0. 033 Zn3 (POQ) 2 +
0.933 (NHS) 2HP0q + 0. 45 C --~ LiFeo,9Zno,1P04 + 0.50 C02 +
0.45 CO + 1.866 NH3 + 1.2 H20 Pre-mix reactants in the following proportions 0.50 mol Li2C0~ = 36.958 0.45 mol Fe203 - 71.868 0. 033 mol Zn3 (POQ) ~ - 12.748 0. 933 mol (NH4) 2HP0ø - 123.218 0.45 mol carbon - 5.408 ss (100$ excess carbon --~ 10.808}
(b) Pelletize powder mixture _43_ (c) Heat to 750°C at a rate of 2°/minute in argon.
Hold for 8 hours dwell at 750°C in argon (d) Cool at a rate of 2°/minute (e) Powderize pellet.
EXAMPLE IX
Reaction 5. Formation of gamma-LiV205 (Y) V205 + 0.5 Li2C0~ + 0.25 C -~ LiV205 + 3/4 C02 (a) Pre-mix alpha V205, Li2C03 and Shiwinigan Black (carbon) using ball mix with suitable media.
Use a 25~ weight excess of carbon over the reaction amounts above. For example, according 2o to reaction above:
Need: 1 mol V205 181.888 0.5 mol Li.2C03 36.958 0.25 mol carbon 3.008 (but use 25o excess carbon -> 3.758) (b) Pelletize powder mixture (c) Heat pellet to 600°C in flowing argon (or other inert atmosphere) at a heat rate of approximately 2°/minute. Hold at 600°C for about 60 minutes.
(d) Allow to cool to room temperature in argon at cooling rate of about 2°fminute.

(e) Powderize pellet using mortar and pestle This reaction is able to be conducted at a temperature in a range of about 400°C to about 650°C in argon as shown, and also under other inert atmospheres such as nitrogen or vacuum. This reaction at this temperature range is primarily C -~ C02. Note that the reaction C --~ CO primarily occurs at a temperature over 1o about 650°C (HT, high temperature); and the reaction C
C02 primarily occurs at a temperature of under about 650°C (LT, low temperature). The reference to about 650°C is approximate and the designation °'primarily"
refers to the predominant reaction thermodynamically favored although the alternate reaction may occur to some extent.
EXAMPLE X
Reaction 6 . Formation of Li3V2 ( PO9 ) 3 V205 + 3 / 2 LizC03 + 3 ( NHS ) 2HP0g + C -~ Li3V2 ( P04 ) 3 + 2 CO
+ 3/2 C0~ -~- 6 NH3 + ~j2 H20 (a) Pre-mix reactants above using ball mill with suitable media. Use a 25o weight: excess of carbon. Thus, s o 1 mo 1 V205 181 . 8 8 g 3/2 mol Li2C03 110.848 3 mol (NH4) 2HP04 396. 188 1 mol carbon 12.018 (but use 25~ excess carbon ---~ 15.018) (b) Pelletize powder mixture (c) Heat pellet at 2°/minute to 300°C to remove C02 ( from Li2C03) and to remove NH3, H20. Heat in an inert atmosphere (e. g. argon). Cool to room temperature.
(d) Powderize arid repelletize (e) Heat pellet in inert atmosphere at a rate of 2°C/minute to 850°C. Dwell for 8 hours at 850°C
(f) Cool to room temperature at a rate of 2°/minute ~n argon.
(e) Powderize This reaction is able to be conducted at a temperature in a range of about 700°C to about 950°C in argon as shown, and also under other inert atmospheres such as nitrogen or vacuum. A reaction temperature 2o greater than about 670°C ensures C ~ CO reaction is primarily carried out.
Characterization of Active t~iaterials and Formation and meeting of Cells Referring to Figure 1, the .final product LiFePU4, prepared from Fe203 metal compound per Reaction 1(b), appeared brown/black in color. This olivine material product included carbon that remained after so reaction. Its CuKoc x-ray diffraction pattern contained all of the peaks expected for this material as shown in Figure 1. The pattern evident in Figure 1 is consistent with the single phase olivine phosphate, LiFePU4. This is evidenced by the position of the peaks in terms of the ss scattering angle 2 8 (theta), x axis. The x-ray pattern showed no peaks due to the presence of precursor oxides indicating that the solid state reaction is essentially entirely completed. Here the space group SG = pnma (62) and the lattice parameters from XRD refinement are consistent with the olivine structure. The values are a - 10.2883A (0.0020), b = 5.9759 (0.0037), c = 4.6717A
(0.0012) 0.0072, cell volume = 287.2264A3 (0.0685).
Density, p = 3.605 g/cc, zero = 0.452 (0.003). Peak at full width half maximum, PFWHM = 0.21. Crystallite size from XRD data = 704A.
1o The x-ray pattern demonstrates that the product of the invention was indeed the nominal formula LiFeP09.
The term °'nominal formula°' refers to the fact that the relative proportion of atomic species may vary slightly on the order of 2 percent to 5 percent, or more typically, 1 percent to 3 percent. and that some portion of P may be substituted by Si, S or As; and some portion of O may be substituted by halogen, preferably F.
The LiFeP04, prepared as described immediately 2o above, was tested in an electrochemical cell. The positive electrode was prepared as described above, using l9.Omg of active material. The positive electrode contained, on a weight o basis, 85o active material, 10~
carbon black, and 5o EPDM. The negative electrode was metallic lithium. The electrolyte was a 2:1 weight ratio mixture of ethylene carbonate and dimethyl carbonate within which was dissolved 1 molar LiPFs. Th.e cells were cycled between about 2.5 and about 4.0 volts with performance as shown in Figures 2 arad 3.
Figure 2 shows the results of the first constant current cycling at 0.2 milliamps per square centimeter between about 2.5 and 4.0 volts based upon about 19 milligrams of the LiFeP04 active material in the s5 cathode (positive electrode). In an as prepared, as assembled, initial condition, the positive electrode active material is LiFePOY. The lithium is extracted -4'7-from the LiFePO~ during charging of the cell. When fully charged, about 0.72 unit of lithium had been removed per formula unit. Consequently, the positive electrode active material corresponds to Lil_xFeP04 where x appears s to be equal to about 0.72, when the cathode material is at 4.0 volts versus Li/Li+. The extraction represents approximately 123 milli_amp hours per gram corresponding to about 2.3 milliamp hours based on 19 milligrams active material. Next the cell is discharged whereupon a to quantity of lithium is re-inserted into the LiFeP04. The re-insertion corresponds to approximately 121 milliamp hours per gram proportional to the insertion. of essentially all of the lithium. The bottom of the curve corresponds to approximately 2.5 volts. The total cumulative capacity demonstrated during the entire extraction-insertion cycle is 244mAh/g.
Figure 3 presents data obtained by multiple constant current cycling at 0.2 mil.liamp hours per square 2o centimeter of the LiFeP04 versus lithium metal counter electrode between 2.5 and 4.0 volts. Data is shown for two temperatures, 23°C and 60°C. Figure 3 shows the excellent rechargeability of the LiFeP04 cell, and also shows good cycling and capacity of the cell. The 2s performance shown after about 190 to 200 cycles is good and shows that electrode formulation is very desirable.
Referring to Figure 4, there is shown data far the final product LiFeo.gMgo.lPO9, prepared from the metal 3o compounds Fe20~ and Mg (OH) 2 ~ Mg (OH) 2, per Reaction 2 (b) .
Its CuKcx x-ray diffraction pattern contained all of the peaks expected for this material as shown in Figure 4.
The pattern evident in Figure 4 is consistent with the single phase olivine phosphate compound, LiFeo.9Mgo.1P09.
35 This is evidenced by the position of the peaks in terms of the scattering angle 2 B (theta), x axis. The x-ray pattern showed no peaks due to the presence of precursor oxides indicating that the solid state reaction is essentially entirely completed. Here the space group SG
- Pnma (62) and the lattice parameters from XRD
refinement are consistent with the olivine structure.
s The values are a = 10.2688A (0.0069), b = 5.9709A
(0.0072), c = 4.6762A (0.0054), cell volume = 286.7208A
(0.04294), p = 3.617 g/cc, zero = 0~702 (0.003), PFWHM =
0.01, and crystallite = 950A.
1o The x-ray pattern demonstrates that the product of the invention was indeed the nominal forrnula LiFeo.9Mgo.1P04. The term "nominal formula'° refers to the fact that the relative proportion of atomic species may vary slightly on the order of 2 percent to 5 percent, or 15 more typically, 1 percent to 3 percent, and that some substitution of P and G may be made while maintaining the basic olivine structure.
The LiFeo,9Mgo.~P04, Prepared as described 2o immediately above, was tested in an electrochemical cell.
The positive electrode was prepared as described above, using 18.9mg of active materials. The positive electrode, negative electrode and electrolyte were prepared as described earlier and in connection with 25 Figure 1. The cell was between about 2.5 and about 4.0 volts with performance as shown in 1~igures 4, 5 and 6.
Figure 5 shows the results of the :First constant current cycling at 0.2 milliamps per square 3o centimeter between about 2.5 and 4.0 volts based upon about 18.9 milligrams oz the LiFeo.~.Mgo.IPOQ active material in the cathode (positive electrode). In an as prepared, as assembled, initial condition, the positive electrode active material is Li.Feo_9Mgo.1P04. The lithium 35 is extracted from the Li Feo_9Mgo.1P09 during charging of the cell. When fully charged, about 0.87 units of lithium have been removed per formula unit.

Consequently, the positive electrode active material corresponds to Lil_xFeo.~Mgo.rP04 where x appears to be equal to about 0.87, when the cathode material is at 4.0 volts versus Li/Li+. The extraction represents approximately s 150 milliamp hours per gram corresponding to about 2.8 milliamp hours based on 18.9 milligrams active material.
Next, the cell is discharged whereupon a quantity of lithium is re-inserted into the LiFeo.~Mgo.lPC>4 . The re-insertion corresponds to approximately 146 milliamp hours 1o per gram proportional to the insertion of essentially all of the lithium. The bottom of the curve corresponds to approximately 2.5 volts. The total cumulat~_ve specific capacity over the entire cycle is 296 mAhr/g. This material has a much better cycle profile than the 1s LiFeP09. Figure 5 (LiFeo.gMgo.1P04) shows a very well defined and sharp peak at about 150 mAh/g. In contrast, Figure 2 (LiFeP04) shows a very shallow slope leading to the peak at about 123 mAh/g. The Fe-phosphate (Figure 2) provides 123 mAh/g compared to its theoretical capacity 20 of 170 mAh/g. This ratio of 123/170, 72o is relatively poor compared to the Fe/Mg-phosphate. The Fe/Mg-phosphate (Figure 5) provides 150 m~lh/g compared to a theoretical capacity of 160, a ratio of 150/160 or 940.
25 Figure 6 presents data obtained by multiple constant current cycling at 0.2 milliamp hours per square centimeter of the LiFeo.gMgo.1P04 versus lithium metal counter electrode between 2.5 and 4.0 volts. Figure 6 shows the excellent rechargeability of the 3o Li/LiFeo.9Mgo.1P0~ cell, and also shows good cycling and capacity of the cell. The performance shown after about 150 to 160 cycles is very good and shows that electrode formulation LiFeo.9Mgo.iP04 performed significantly better than the LiFePO~. Comparing Figure 3 (LiFeP04) to Figure 35 5 (LiFeo,9Mg~_1P04) it can be seen that. the Fe/Mg-phosphate maintains its capacity ever prolonged cycling, whereas the Fe-phosphate capacity fades significantly.

Figure 7 shows the results of the first constant current cycling at 0.2 milliamps per square centimeter between about 2.5 and 4.0 volts based upon about 16 milligrams of the LiFeo,aMgc,2P0Q active material s in the cathode (positive electrode;- Tn an as prepared, as assembled, initial condition, the positive electrode active material is LiFeo,aMgo,2P0-0. The lithium is extracted from the LiFeo,aMgo.2p04 during charging of the cell. When fully charged, about 0.79 units of lithium 1o have been removed per formula unit. Consequently, the positive electrode active material corresponds to LiFeo,aMgo,2P04 where x appears to be equal to about 0.79, when the cathode material is at 4.0 volts versus Li/Li+.
The extraction approximately 140 milliamp hours per gram 1s corresponding to about 2.2 milliamp hours based on 16 milligrams active material. Next, the cell is discharged whereupon a quantity of lithium is re-inserted into the LiFeo,aMgo,2PO4. The re-insertion corresponds to approximately 122 milliamp hours per gram proportional to 2o the insertion of essentially all of the lithium. The bottom of the curve corresponds to approximately 2.5 volts. The total cumulative specific capacity over the entire cycle is 262 mAhr/g.
2s Referring to Figure 8, there is shown data for the final product LiFeo,aCaoe1P04, prepared from Fe20a and Ca(OH)2 by Reaction 3. Its CuKC~ x-ray diffraction pattern contained all of the peaks expected for this material as shown in Figure 8. The pattern evident in 3o Figure 8 is consistent with the single phase olivine phosphate compound, LiFeo,9Cao.iP04 ~ This is evidenced by the position of the peaks in terms of the scattering angle 2 8 (theta)a x axis. The x-ray pattern showed no peaks due to the presence of precursor oxides indicating 35 that the solid state reaction is essentially entirely completed. Here the space group SG = puma (62) and the lattice parameters from XRD refinement are consistent with olivine. The values are a = 10.3240A (0.0045), b =

6.0042A (0.0031), c = 4.6887A (0.0020), cell volume =
290.6370A (0.1807), zero = 0.?02 (0.003), p = 3.62 g/cc, PFWHM = 0.18, and crystallite = 680A. The :~-ray pattern demonstrates that the product of the invention was indeed the nominal formula LiFeo,9Cao.1P04.
Figuxe 9 shows the results of the first constant current cycling at 0.2 miZ.liamps per square so centimeter between about 2.5 and 4.0 volts based upon about 18.5 milligrams of t'he LiFeo,aCao,2P04 active material in the cathode (positive electp-ode). In an as prepared, as assembled, initial condition, the positive electrode active material is LiFeo.aCao.2PO9. The lithium is extracted from the LiFeo.aCao.2P09 during charging of the cell. When fully charged, about 0.71 units of lithium have been removed per formula unit.
Consequently, the positive electrode active material corresponds to LiFe~.aCao.2P09 where x appears to be equal 2o to about 0.71, when the cathode material is at 4.0 volts versus Li/Li+. The extraction represents approximately 123 milliamp hours per gram corresponding to about 2.3 milliamp hours based on 18.5 milligrams active material.
Next, the cell is discharged whereupon a quantity of lithium is re-inserted into the LiFeo.eCao.2POQ . The re-insertion corresponds to approximately 110 milliamp hours per gram proportional to the insertion of nearly all of the lithium. The bottom of the curve corresponds to approximately 2.5 volts. The total specific cumulative 3o capacity over the entire cycle is 233 mAhr/g.
Figure 10 shows the results of the first constant current cycling at 0.2 milliamps per_ square centimeter between about 2.5 and 4.0 volts based upon 3s about 18.9 milligrams of the LiFeo.aZ~'to.zPOa olivine active material in the cathode (positive electrode),. In an as prepared, as assembled, initial condition, the positive electrode active material is LiFeo,aZno,2P04, prepared from Fe203 and Zn3 (P04) 2 by Reaction 4. The lithium is extracted from the LiFeo,gZno,2P04 during charging of the cell. When fully charged, about 0.74 units of lithium s have been removed per formula unit. Consequently, the positive electrode active material corresponds to Li,..
xFe0.8Zn0.2P04 T,ahere x appears to be equal to about 0.74, when the cathode material is at 4.0 volts versus Li/Li+.
The extraction represents approximately 124 milliamp Zo hours per gram corresponding to about 2.3 milliamp hours based on 18.9 milligrams active material. Next, the cell is discharged whereupon a quantity of lithium is re-inserted into the LiFeo,eZna,2P04. The re-insertion corresponds to approximately 108 milliamp hours per gram 15 proportional to the insertion of nearly all of the lithium. The bottom of the curve corresponds to approximately 2.5 volts.
Referring to Figure 11, the final product 2o LiV205, prepared by Reaction 5, appeared black in color.
Its CuKcc x-ray diffraction pattern contained all of the peaks expected for this material as shown in Figure 11.
The pattern evident in Figure l~, is consistent with a single oxide compound gamma-LiV205, 'his is evidenced by 2s the position of the peaks in terms of the scattering angle 2 8 (theta), x axis. The x-ray pattern showed no peaks due to the presence of precursor oxides indicating that the solid state reaction is essentially entirely completed.
The x-ray pattern demonstrates that the product of the invention was indeed the nominal formula gamma-LiV205. The term "nominal formula'° refers to the fact that the relative proportion of atomic species may vary 3s slightly on the order of 2 percent t:o 5 percent, or more typically, 1 percent to 3 percent.

_ ~~j _ The LiV2~5 prepared as described immediately above, was tested in an electrochemical cell. The cell was prepared as described above and cycled with performance as shown in Figures I2 and 13.
Figure 12 shows the results of the first constant current cycling at 0.2 milliamps per square centimeter between about 2.8 and 3.,8 volts based upon about 15.0 milligrams of the LiV205 active material in 1o the cathode (positive electrode). In an as prepared, as assembled, initial condition, the positive electrode active material is LiV205. The lithium is extracted from the hiV205 during charging of the cell. When fully charged, about 0.93 unit of lithium had been removed per 1s formula unit. Consequently, the positive e_Lectrode active material corresponds to Lil_~'VZO~ where x appears to be equal to about 0.93, when the cathode mai~erial is at 3.8 volts versus Li/Lii. The extraction represents approximately 132 milliamp hours per gram corresponding 2o to about 2.0 milliamp hours based on 15.0 milligrams active material. Next, the cell is discharged whereupon a quantity of lithium is re-inserted into the LiV205. The re-insertion corresponds to approximately 130 milliamp hours per gram proportional to the insertion of 25 essentially all of the lithium. The bottom of the curve corresponds to approximately 2.8 volts.
Figure 13 presents data obtained by multiple constant current cycling at 0.4 milliamp hours per square 3o centimeter (C/2 rate) of the LiV205 versus lithium metal counter electrode between 3~0 and 3.75 volts. Data for two temperature conditions are shown, 23°C and 60°C.
Figure 13 is a two part graph with Figure 13A showing the excellent rechargeability of the LiV205. Figure 13B
35 shows good cycling and capacity of the cell. The performance shown up to about 300 cycles is good.

Referring to Figure 14, t;he final product Li3V2(P04)3, prepared by Reaction 6, appeared green/black in color. Its CuKcx x-ray diffraction pattern contained all of the peaks expected for this material as shown in Figure 14. The pattern evident in Figure I4 is consistent with a single phosphate compound Li3V2(P04)3 of the monoclinic, Nasicon phase. This is evidenced by the position of the peaks in terms of the scattering angle 2 8 (theta), x axis. The x-ray pattern showed no peaks due 1o to the presence of precursor oxides indicating that the solid state reaction is essentially entirely completed.
The x-ray pattern demonstrates that the product of the invention was indeed the nominal formula Li3V2 (P04) 3 . The term "nominal formula" refers to the fact that the relative proportion of atomic species may vary slightly on the order of 2 percent to 5 percent, or more typically, 1 percent to 3 percent; and that substitution of P and O may occur.
The Li3V2 (PO.,) 3 prepared as described immediately above, was tested in an electrochemical ce7_1. The cell was prepared as described above, using 13.8mg of active material. The cell was prepared as described above and cycled between about 3.0 and about 4.2 volts using the EVS technique with performance as shown in Figures 16 and 17. Figure 16 shows specific capacity versus electrode potential against Li. Figure 17 shows dif:Eerential capacity versus electrode potential against Li.
A comparative method was used to form Li3V2(P04)3. Such method was reaction without carbon and under H2-reducing gas as described in U.S. Patent No.
5,871,86. The final product, prepared as per U.S.
Patent No. 5,871,866, appeared green in color. Its CuKoc x-ray diffraction pattern contained all of the peaks expected for this material as shown in Figure 15. The .. 5 5 _ pattern evident in Figure 15 is consistent with a monoclinic Nasicon single phase phosphate compound Li3V2 (PO9) 3. This is evidenced by th.e position of the peaks in terms of the scattering angle 2 8 (theta), x axis. The x-ray pattern showed no peaks due to the presence of precursor oxides indicating that the solid state reaction is essentially entirely completed.
Chemical analysis for lithium and vanadium by atomic absorption spectroscopy showed, on ~;. percent by weight 1o basis, 5.17 percent lithium and 26 percent vanadium. This is close to the expected result of 5.11 percent lithium and 25 percent vanadium.
The chemical analysis and x-ray patterns of Figures 14 and 15 demonstrate that the product of Figure 14 was the same as that of Figure 15. The product of Figure 14 was prepared without the undesirable H2 atmosphere and was prepared by the novel carbothermal solid state synthesis of the invention.
Figure 16 shows a voltage profile of the test cell, based on the Li3V2(POq)3 positive electrode active material made by the process of the invention and as characterized in Figure 14. It was cycled against a 2s lithium metal counter electrode. The data shown in Figure 16 is based on the Electrochemical Vo:Ltage Spectroscopy (EVS) technique. Electrochemical and kinetic data were recorded using the Electrochemical Voltage Spectroscopy (EVS) technique. Such i~echnique is 3o known in the art as described by J. Barker in Synth, Met 28, D217 (1989); Synth. Met. 32, 43 (1989); :T. Power Sources, 52, 185 ( 1994 ) ,~ and. Electrochemica Acta, Vol .
40, No. 11, at 1603 (1995). Figure 16 clearly shows and highlights the reversibility of the product. The positive s5 electrode contained about 13.8 milligrams of the Li3V2(POq)3 active material. The positive electrode showed a performance of about 133 milliamp hours per gram on the first discharge. zn Figure ~.6, the capacity in, and the capacity out are essentially the same, resulting in essentially no capacity loss. E'igure 17 is an EVS
differential capacity plot based on Figure 7_6. .~s can be seen from Figure 17, the relatively symmetrical nature of peaks indicates good electrical reversibility, there are small peak separations (charge/discharge), and good correspondence between peaks above and below the zero axis. There are essentially no peaks that can be related so to irreversible reactions, since all peaks above the axis (cell charge) have corresponding peaks below the axis (cell discharge), and there is essentially no separation between the peaks above and below the axis. This shows that the carbothermal method of the invention produces 25 high quality electrode material.
Figure 1~ presents data obtained by multiple constant current cycling at 0.2 milliamp hours per square centimeter of the LiFeo.$Mgo.2P04 versus lithium metal 2o counter electrode between 2.5 and 4.0 volts. Figure 18 shows the excellent rechargeability of the Li/LiFeo.eMgo,2P04 cell, and also shows good cycling and capacity of the cell. The performance shown after about 110 to 120 Cycles at 23°C is very good and shows that 25 electrode formulation LiFe~,BMgo,2P0,~ performE=d significantly better than the LiFeP09. The cell cycling test at 60°C was started after the 23°C test and was ongoing. Comparing F~.gure 3 (LiFeP04) to Figure 18 (LiFeo_$Mgo.zPO~) , it can be seen that the Fe/Mg-phosphate 3o maintains its capacity over prolonged cycling, whereas the Fe-phosphate capacity fades significantly.
In addition to the above cell tests, the active materials of the invention were also cycled against s5 insertion anodes in non-metallic, lithium ion, rocking chair cells.

The lithium mixed metal phosphate and 'the lithium metal oxide were used to formulate a cathode electrode. The electrode was fabricated by solvent casting a slurry of the treated, enriched lithium manganese oxide, conductive carbon, binder, plasticizer and solvent. The conductive carbon used was Super P (MMM
Carbon)'. Kynar Flex 2801~ was used as the binder and electronic grade acetone was used as a solvent. The preferred plasticizer was dibutyl phthalate (DPB). The to slurry was cast onto glass and a free-standing electrode was formed as the solvent was evaporated. In this example, the cathode had 23.1mg LiFeo,9Mgo 1P04 active material. Thus, the proportions are as follows on a percent weight basis: 80o active material; 8~ Super P
z5 carbon; and 12o Kynar binder.
A graphite counter electrode was prepared for use with the aforesaid cathode. The graphite counter electrode served as the anode in the electrochemical 2o cell. The anode had 10.8 mg of the MCMB graphite active material. The graphite electrode was fabricated by solvent casting a slurry of MCMB2528 graphite, binder, and casting solvent. MCMB2528 is a mesocarbon microbead material supplied by Alumina Trading, which is the U.S.
25 distributor for the supplier, Osaka Gas Company of Japan.
This material has a density of about 2.24 grams per cubic centimeter; a particle size maximum for at least 95o by weight of the particles of 37 microns; median size of about 22.5 microns and an interlayer distance of about 30 0.336. As in the case of the cathode, the binder was a copolymer of polyvinylidene difluoride (PVdF) and hexafluoropropylene (HFP) in a wt. :ratio of PVdF to HFP
of 88:12. This binder is sold under the designation of Kynar Flex 28010, showing it's a registered trademark.
35 Kynar Flex is available from Atochem Corporation. An electronic grade solvent was used. The slurry was cast onto glass and a free standing eleci~rode was formed as _5$-the casting solvent evaporated. The electrode composition was approximately as follows on a dry weight basis: 85o graphite; 12o binder; and 3% conductive carbon.
A rocking chair battery was prepared comprising the anode, the cathode, and an electrolyte. The ratio of the active cathode mass to the active anode mass was about 2.14:1. The two electrode layers were arranged to with an electralyte layer in between, and the layers were laminated together using heat and pressure as per the Bell Comm. Res. patents. In a preferred method, the cell is activated with EC/DMC solvent in a weight ratio of 2:1 in a solution containing 1 M LiPF6 salt.
Figures 19 and 20 show data for the first four complete cycles of the lithium ion cell having the LiFeo.~Mgo.~P04 cathode and the MCMB2528 anode. The cell comprised 23.Im.g active LiFeo.9Mgo.1P04 arAd 10.8mg active 2o MCMB2528 for a cathode to anode mass ratio of 2.14. The cell was charged and discharged at 23°C at an approximate C/10 (10 hour) rate between voltage limits of 2.50 V and 3.60 V. The voltage profile plot Figure 19) shows the variation in cell voltage versus time for the LiFeo.9Mgo.~P09/MCMB2528 lithium ion cell. The symmetrical nature of the charge-discharge is clearly evident. The small degree of voltage hysteresis between the charge and discharge processes is evidence far the low overvoltage in the system, which is very good. Figure 20 shows the 3o variation of LiFeo.~go.~P04 specific capacity with cycle number. Clearly, over the cycles shown, the material demonstrates good Cycling stability.
Figure 21 shows data for the first three 3s complete cycles of the lithium ion cell having the gamma-LiV205 cathode and the MCMB2528 anode. The cell prepared was a rocking chair, lithium ion cell as described above.

The cell comprised 29.1mg gamma-LiV'205 cathode active material and 12.2mg MCMB2528 anode active material, for a cathode to anode mass ratio of 2.39. As stated earlier, the liquid electrolyte used was EC/DMC (2a1) and 1M
LiPF6. The cell was charged and discharged at 23°C at an approximate C/IO (10 hour) rate between voltage limits of 2.50 V and 3.65 V. The voltage profile plot (Figure 21) shows the variation in cell voltage versus time for the LiV20~/MCMB2528 lithium ion cell. The symmetrical nature of the charge-discharge is clearly evident. The small degree of voltage hysteresis between the charge and discharge processes is evidence for the low overvoltage in the system, which is very good.
is In summary, the invention provides new compounds Li~MI;,MI I~ ( PO9 ) d and gamma-LiV205 by new methods which are adaptable to commercial scale production. The LilMI1-"MIIYPO-0 compounds are isostructural olivine compounds as demonstrated by XRD analysis. Substituted 2o compounds, such as LiFel_YMgYP04 show better performance than LiFeP09 unsubstituted compounds when used as electrode active materials. The method of the invention utilizes the reducing capabilities of carbon along with selected precursors and reaction conditions to produce 2s high quality products suitable as e7_ectrode active materials or as ion conductors. The reduction capability of carbon over a broad temperature range is selectively applied along with thermodynamic and kinetic considerations to provide an energy-efficient, economical 3o and convenient process to produce compounds of a desired composition and structure. This is in contrast to known methods.
Principles of carbothermal reduction have been s5 applied to produce pure metal from metal oxides by removal of oxygen~ See, for example, U.S. Patent Nos.
2, 580, 878, 2, 570, 232, 4, 177, 060, arid 5, 803, 974.

Principles of carbothermal and thermal reduction have also been used to form carbides. See, for example, LJ.S.
Patent Nos. 3,865,745 and 5,384,291 and non-oxide ceramics (see U.S. Patent No. 5,607,.297). Such methods are not known to have been applied to form lithiated products or to form products without oxygen abstraction from the precursor. The methods described with respect to the present invention provide high quality products which are prepared from precursors which are lithiated during 1o the reaction without oxygen abstraction. This is a surprising result. The new methods of the invention also provide new compounds not known to have been made before.
For example, alpha-VzOs is conventionally lithiated electrochemically against metallic lithium.
Thus, alpha-V.~OS is not suitable as a source of lithium for a cell. As a result, alpha-V20s is not used in an ion cell. In the present invention, alpha-V20s is lithiated by carbothermal reduction using a simple lithium-containing compound and the reducing capability of carbon to form a gamma-LiV205. The single phase compound, gamma-LiV~05 is not known to have been directly and independently prepared before. There is not known to be a direct synthesis route. Attempts to form it as a single phase resulted in a mixed phase product containing one or more beta phases and having the formula LiXV20s with 0 < x 5 0.49. This is far different from the present single phase gamma-LixV20s with x equal to one, or very close to one. The flexibility of the process of the 3o present invention is such that~it can be conducted over a wide temperature range. The higher the temperature, the more quickly the reaction proceeds. For example, at 650°C, conversion of alpha-V20s to gamma-LiV20s occurs in about one hour, and at 500° it takes about 8 hours.
Here, about one quarter (1I4) atomic unit of carbon is used to reduce one atomic unit of 'vanadium, that is, V+5V+s to V+sV+4 a The predominate reaction is C to COZ

-~?1 where for each atomic unit of carbon at ground state zero, a plus 4 oxidation state results. Correspondingly, for each 1/4 atomic unit of carbon, one atomic unit of vanadium is reduced from V~5 to V"9. (See Reaction 5) .
The new product, gamma-LiV205 is air-stable and suitable as an electrode material for an ion cell ar racking chair battery.
The convenience and energy efficiency of the 1o present process can also be contrasted to known methods for forming products under reducing atmosphere such as H2 which is difficult to controlr and from complex and expensive precursors. In the present invention, carbon is the reducing agent, and simple, inexpensive and even naturally occurring precursors are useable. For example, it is possible to produce LiFeP04 from Fe203, a simple common oxide. (See Reaction 1b). The production of LiFeP04 provides a good example of the thermodynamic and kinetic features of the method. Iran phosphate is 2o reduced by carbon and lithiated over a broad temperature range. At about 600°C, the C to C02 reaction predominates and takes about a week to complete. At about 750°C, the C to CO reaction predominates and takes about 8 hours to complete. The C to C02 reaction 2s requires less carbon reductant but takes longer due to the low temperature kinetics. The C to CO reaction requires about twice as much carbon, but due to the high temperature reaction kinetics, it proceeds relatively fast. In both cases, the Fe in the precursor Fe203 has so oxidation state +3 and is reduced to oxidation (valence) state +2 in the product LiFeP04. The C to CO reaction requires that =~ atomic unit of carbon be used for each atomic unit of Fe reduced by one valence state. The CO
to C02 reaction requires that 1/4 atomic unit of carbon 35 be used for each atomic unit of Fe reduced by one valence state.

The active materials of the invention are also characterized by being stable in an as-prepared condition, in the presence of air and particularly humid air. This is a striking advantage, because it facilitates preparation of and assembly of battery cathodes and cells, without the requirement for controlled atmosphere. This feature is particularly important, as those skilled in the art will recognize that air stability, that is, lack of degradation on to exposure to air, is very important for commercial processing. Air-stability is known in the art to more specifically indicate that a material does not hydrolyze in presence of moist air. Generally, air-stable materials are also characterized by Li being extracted therefrom above about 3.0 volts versus lithium. The higher the extraction potential, the more tightly bound the lithium ions are to the host lattice. This tightly bound property generally confers air stability on the material. The air-stability of the materials of the 2o invention is consistent with the stability demonstrated by cycling at the conditions stated herein. This is in contrast to materials which insert Li at lower voltages, below about 3.0 volts versus lithium, and which are not air-stable, and which hydrolyze in moist air.
While this invention has been described in terms of certain embodiments thereof, it is not intended that it be limited to the above description, but rather only to the extent set forth in the following claims.
The embodiments of the invention i.n which an exclusive property or privilege is claimed are defined in the following claims.

Claims (82)

WHAT IS CLAIMED IS:

1. A method for synthesis of a Li metal compound of the formula Li a MI1-y MII y(XO4)d wherein a is greater than 0 but less than or equal to 3, and y is greater than or equal to 0 and less than or equal to 1, d is greater than 0 and less than or equal to 3, X is P, S or Si, MI is a transition metal or a mixture of transition metals selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Ti, and Cr, and MII is an element with fixed valency selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, and mixtures thereof, by bringing into equilibrium, a mixture containing at least one precursor of:
a) a source of the element MI, at least part of said transition metal or metals that constitute MI being in an oxidation state greater than that of the metal in the compound of the above formula;
b) a source of the element MII;
c) a compound that is a source of the element lithium; and, d) a compound that is a source of the XO4 if the element X is not present in another compound or source;
said at least one precursor of said sources (a) to (d) being present in the mixture in proportions required to form the lithium metal compound, and said at least one precursor having one or more additional elements other than the elements of (a) to (d), said method comprising effecting a reduction step to reduce the valency of the transition metal or metals whereby the oxidation state of at least one metal ion of the precursor or precursors is reduced to form the compound of said formula.

2. The method according to claim 1, the method being carried out in a gaseous reducing atmosphere.

3. The method according to claims 1 or 2, in which at least one of the following conditions apply: the source of MI is also the source of X; the source of MII is also the source of X; the source of lithium is also the source of X; and the source of X is also the source of lithium.

4. The method according to any one of claims 1 to 3, in which the step of bringing the precursors in the mixture of at least one precursor (a) to (d) into equilibrium is carried out by forming an intimate and/or homogeneous mixture of the source compounds.

5. The method according to any one of claims 1 to 4, in which the transition metal or metals comprise a metal from the group constituted by iron, manganese and vanadium.

6. The method according to any one of claims 1 to 5, in which the compound that is the source of MI is a compound wherein the oxidation state of MI varies from 3 to 7.

7. The method according to any one of claims 1 to 6, in which the compound which is the source of MI is iron (III) oxide or magnetite, manganese dioxide, di-vanadium pentoxide, a ferric phosphate, or a mixture of the compounds.

8. The method according to claim 7, wherein the ferric phosphate is trivalent ferric phosphate.

9. The method according to any one of claims 1 to 8, in which the compound that is the source of lithium is selected from the group consisting of lithium oxide, lithium carbonate, lithium phosphate, LiH2PO4, lithium acetate, lithium nitrate, lithium oxalate, lithium vanadate, and mixtures thereof.

10. The method according to claim 9, in which the lithium source compound is lithium carbonate of the formula Li2CO3.

11. The method according to any one of claims 1 to 10, in which the source of X is selected from the group consisting of sulfuric acid, lithium sulfate, phosphoric acid and its esters, Li3PO4, LiH2PO4, a monoammonium or diammonium phosphate, trivalent ferric phosphate, manganese and ammonium phosphate (NH4MnPO4), silica, lithium silicates, alkoxysilanes or their partial hydrolysis products, and mixtures of the latter.

12. The method according to claim 11, in which the precursor compound for the source of element X is ferric phosphate.

13. The method according to any one of claims 1 to 12, wherein said Li metal compound has the formula LiFePO9.

14. The method according to any one of claims 1 to 12, wherein MI is selected from the group consisting of Fe and Mn, and MII is Mg, X is PO4 and y is greater than 0 and less than 1.

15. The method according to any one of claims 1 to 12, wherein MI is Fe, MII is Mg or Ca, X is PO4 and y is greater than 0 and less than 1.

16. The method according to any one of claims 1 to 12, wherein MI is Fe or a mixture of Fe and Mn, MII is Mg, X is PO4 and y is greater than 0 and less than 1.

17. The method according to any one of claims 1 to 16, in which the compounds of said formula have an olivine or Nasicon structure, including a monoclinic form.

18. The method according to any one of claims 1 to 17, wherein the synthesis is carried out in the presence of the reducing atmosphere wherein the reducing atmosphere contains carbon monoxide or a mixture of carbon monoxide and carbon dioxide, optionally in the presence of water vapor and optionally in the presence of a neutral gas.

19. The method according to claim 18, wherein said neutral gas is nitrogen or argon.

20. The method according to claim 19, in which the reducing atmosphere includes a mixture of carbon monoxide and carbon dioxide.

21. The method according to any one of claims 18 to 20, in which the reducing atmosphere includes a mixture of carbon monoxide and carbon dioxide, the synthesis temperature being up to 1200°C., and the time of contact between the reaction mixture and the gaseous phase being up to 8 hours.

22. The method according to claim 21, wherein said temperature is between about 500 to about 800°C.

23. The method according to any one of claims 1 to 22, in which the compounds of said formula are obtained in the form of particles.

24. The method according to any one of claims 1 to 23, in which there is included a source of carbon in the reaction medium whereby the carbon is present in an amount so as to be nucleated or bound to particles of the compound of said formula.

25. The method according to any one of claims 1 to 24, in which the method is carried out above a minimum temperature at which the reaction is capable of reducing the transition element or elements to their oxidation state required in the compound of said formula and under reaction conditions leading to a reduction of the transition element or elements without full reduction to a metallic state.

26. A method for the synthesis of a Li metal compound of the formula Li a MI1-y MII y (XO4)d wherein the lithium of the metal compound is linked by being nucleated or bound to carbon, a is greater than 0 but less than or equal to 3, and y is greater than or equal to 0 and less than or equal to 1, d is greater than 0 and less than or equal to 3, X is P, S or Si, MI is a transition metal or a mixture of transition metals selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Ti, and Cr, and MII is an element with fixed valency selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, and mixtures thereof, by bringing into equilibrium for a thermal synthesis, a mixture containing at least one precursor of a) a source of the element MI, at least part of said transition metal or metals that constitute MI being in an oxidation state greater than that of the metal in the compound of the above formula;
b) a source of the element MII;
c) a compound that is a source of the element lithium;
d) a compound that is a source of the element XO4 if the element X is not present in another compound or source;
e) a source of carbon, said at least one precursor of said sources (a) to (d) being present in the mixture in proportions required to form the lithium metal compound, and said at least one precursor having one or more additional elements other than the elements of (a) to (d), said method comprising effecting the thermal synthesis reaction between said at least one precursor of said mixture in a gaseous atmosphere to reduce the valency of the transition metal or metals to a desired valency and including the step of controlling the composition of the gaseous atmosphere, the temperature of the reaction and the relative amount of the source of lithium proportionately to the sources of (a), (b) and (d), said method comprising at least one thermal step to heat said source of carbon and to decompose or transform the same, and to obtain said mixed metal compound having electrical conductivity.

27. The method according to claim 26, in which the synthesis between the source compounds a) to d) is carried out simultaneously with heating and degradation of the source compound e).

28. The method according to claim 26, in which the synthesis is carried out in a two step reaction.

29. The method according to claim 27 or 28, the synthesis being carried out in a reducing or neutral gas atmosphere.

30. The method according to any one of claims 27 to 29, in which the compounds of said formula are obtained in the form of particles.

31. The method according to any one of claims 26 to 30, in which the source of carbon is present in the synthesis in an amount so as to be present in a residual amount in the reaction product to thereby coat particles of the compound obtained.

32. The method according to any one of claims 26 to 31, in which the mixture of the at least one precursor has a final form comprising pellets.

33. The method according to any one of claims 26 to 32, in which the source of the carbon is carbon or a precursor thereof.

34. The method according to any one of claims 26 to 33, in which the carbon source contains a source of oxygen and hydrogen which are chemically bound.

35. The method according to any one of claims 26 to 34, in which the carbon source compound comprises at least one carbon source capable of degradation at temperatures above 400°C., said carbon source compound being a polymer or a mineral oil.

36. The method according to any one of claim 26 to 35, in which the carbon source comprises a polymer.

37. The method according to any one of claims 26 to 36, in which the sources a) to d) are in the form of compressed pellets prior to the to thermal synthesis being carried out.

38. The method according to any one of claims 26 to 37, in which the carbon source is present as part of the mixture.

39. The method according to claim 37 to 38, wherein the carbon source forms part of said compressed pellets.

40. The method according to claim 39, said synthesis being carried out at a temperature of between 650 -800° C., and for a dwell time up to 8 hours.

41. The method according to claim 26, 27 or 28, said synthesis being carried out in the presence of a reducing gaseous atmosphere.

42. The method according to any one of claims 29 to 39 or 41, wherein the gas atmosphere is a reducing gas atmosphere containing carbon monoxide.

43. The method according to claim 42, wherein the reducing gas atmosphere contains carbon monoxide in the presence of water vapor.

44. The method according to claim 42 or 43, wherein the reducing gas atmosphere contains carbon monoxide in the presence of a neutral gas.

45. The method according to claim 44, wherein said neutral gas is nitrogen or argon.

46. The method according to any one of claims 42 to 45, in which the reducing gas atmosphere includes a mixture of carbon monoxide and carbon dioxide.

47. The method according to any one of claims 42 to 46, in which the reducing gas atmosphere includes a mixture of carbon monoxide and carbon dioxide, the synthesis temperature being up to 1200°C., and the time of contact between the reaction mixture and the gaseous phase being up to 8 hours.

48. The method according to claim 47, wherein said temperature is between about 500 to about 800°C.

49. The method according to any one of claims 42 to 48, in which the reducing gas atmosphere is obtained by thermal decomposition of said source of carbon, and wherein the reaction under heating or thermal conditions generates carbon monoxide or a mixture of carbon dioxide and carbon monoxide, said synthesis further generating water vapor, the synthesis being carried out to react the source compounds to obtain a compound of said formula.

50. The method according to any one of claims 42 to 47, in which the gaseous reducing gas atmosphere is obtained by partial oxidation of oxygen or air, and of the source of carbon, optionally in the presence of water vapor, said synthesis being carried out at an elevated temperature, whereby there is formed during the synthesis, carbon monoxide or a mixture of carbon monoxide and carbon dioxide.

51. The method according to claim 50, in which the synthesis is carried out at a temperature of between 400 - 1200°C.

52. The method according to claim 50 or 51, wherein the thermal synthesis is carried out under elevated temperatures sufficient to react the source compounds, said elevated temperatures comprising heating said source compounds at a temperature in the range of from 500 to 1100°C.

53. The method according to claim 52, in which the temperature is between 500 and 800°C.

54. The method according to any one of claims 4 to 53, in which the dwell time of the source compounds in the thermal processing step is up to 8 hours.

55. The method according to any one of claims 26 to 53, in which at least one of the following conditions apply: the source of MI is also the source of X; the source of MII is also the source of X; and the source of lithium is also the source of X; and the source of X is also the source of lithium.

56. The method according to any one of claims 26 to 53 and 5S, in which bringing the mixture of precursors a) to d) into equilibrium is carried out by forming an intimate and/or homogeneous mixture of the source compounds.

57. The method according to any one of claims 26 to 53, 55 and 56, in which the transition metal or metals comprise the metal selected from the group consisting of iron, manganese, cobalt, nickel, vanadium, titanium, chromium, copper, and a mixture thereof.

58. The method according to any one of claims 26 to 53 and 55 to 57, in which the compound that is the source of MI has an oxidation state that varies from 3 to 7.

59.The method according to any one of claims 26 to 53 and 55 to 58, in which the compound which is the source of MI is iron (III) oxide or magnetite, manganese dioxide, di-vanadium pentoxide, a ferric phosphate, or a mixture of the compounds.

60.The method according to claim 59, wherein the ferric phosphate is trivalent ferric phosphate.

61.The method according to any one of claims 26 to 60, in which the compound that is the source of lithium is selected from the group consisting of lithium oxide, lithium carbonate, lithium phosphate, acid phosphate LiH 2P0 4, lithium acetate, lithium nitrate, lithium oxalate, lithium vanadate, and mixtures thereof.

62.~The method according to claim 61, in which the lithium source compound is lithium carbonate of the formula Li 2C0 3.

63. ~The method according to any one of claims 26 to 62, in which the source of X is selected from the group consisting of sulfuric acid, lithium sulfate, phosphoric acid and its esters, neutral phosphate Li 3PO 4 or acid phosphate LiH 2PO 4, monoammonium or diammonium phosphates, trivalent ferric phosphate, manganese and ammonium phosphate (NH 4MnPO 4), silica, lithium silicates, alkoxysilanes, or their partial hydrolysis products, and mixtures of the latter.

64.~The method according to claim 63, in which the precursor compound for the source of element X is ferric phosphate.

65. ~The method according to claim 61, wherein said compound of said formula has the formula LiFePO 4.

66. ~The method according to claim 57, wherein MI is Fe, MII is Mg, X is PO 4 and y is greater than 0 and less than 1.

67. ~The method according to claim 57, wherein MI is Fe, MII is Mg or Ca, X is PO 4 and y is greater than 0 and less than 1.

68. ~The method according to claim 57, wherein MI is Fe, MII is Mg, X is PO 4 and y is greater than 0 and less than 1.

69. ~The method according to any one of claims 26 to 68, in which the compounds of said formula have an olivine or Nasicon structure, including a monoclinic form.

70.~The method according to any one of claims 26 to 69, wherein the mixed metal compounds contain residual carbon.

71. ~The method according to claim 70, in which the amount of the carbon source, present in the reactants, is below about 9% based on the total weight of the reaction mixture.

72. ~The method according to claim 71, wherein said amount of the carbon source is below about 1.6%.

73.~The method of synthesis according to any one of claims 26 to 72, in which the compound of said formula is a compound of the formula C-LiaMI 1-y MII y(XO4) n and in which the reaction product includes carbon remaining after the reaction is completed.

74. ~The method according to any one of claims 26 to 73, in which the source of carbon is dispersed in a pre-mix of reactants to form an intimate mixture of precursors a) to d) with the source of carbon.

75. ~The method according to any one of claims 26 to 72 and 74, in which the compound of said formula obtained has the formula LiFePO 4.

76.~The method of synthesis according to any one of claims 26 to 75, in which the particles of the compound obtained are substantially constituted by said compound of said formula, and in which the compound obtained includes an amount of carbon in association with said particles.

77. ~A composition of particles comprised of particles of at least one compound of said formula of any one of claims 26 to 76, the lithium of the mixed metal compound being linked by nucleation or bound to carbon, said composition having electrical conductivity.

78.~An electrochemical cell comprising at least two electrodes and at least one electrolyte, wherein at least one of said electrodes contains at least one composition as defined in claim 77.

79.~The cell according to claim 78, wherein the electrolyte includes at least one lithium salt.

80. ~The cell according to claim 78 or 79, wherein the cell has at least one negative electrode comprised of metallic lithium or a lithium-containing material.

81.~The cell according to claim 78, 79 or 80, wherein the cell includes at least one positive electrode, said at least one positive electrode comprising one or more compounds obtained by the method of any one of claims 1 to 76.

82. ~The method according to any one of claims 1 to 25, in which the source of said compounds are in the form of compressed pellets prior to the thermal synthesis being carried out.