CN101438434B - Electrode active material with high stability and the electrochemical appliance using the material - Google Patents

Electrode active material with high stability and the electrochemical appliance using the material Download PDF

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Publication number
CN101438434B
CN101438434B CN200780016026.3A CN200780016026A CN101438434B CN 101438434 B CN101438434 B CN 101438434B CN 200780016026 A CN200780016026 A CN 200780016026A CN 101438434 B CN101438434 B CN 101438434B
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active material
electrode active
compound
electrode
acidic site
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CN101438434A (en
Inventor
张诚均
房义龙
朴熙祥
李琪永
朴盛镛
黄璄圭
张钟山
金德奎
郑成和
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Korea Research Institute of Chemical Technology KRICT
LG Energy Solution Ltd
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Korea Research Institute of Chemical Technology KRICT
LG Chemical Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/38—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

Make the electrode active material that stability is improved by the regulation of surface acid site disclosed herein is a kind of；A kind of electrode for including the electrode active material, the electrode surface is coated with the compound with acidic site or is mixed with the compound with acidic site；With a kind of electrochemical appliance, the device includes the electrode so that its efficiency is improved.Side reaction with electrolyte, the structural stability of holding electrode active material are reduced by adjusting the acidic site on the electrode active material surface, so as to improve battery efficiency.

Description

Electrode active material with high stability and the electrochemical appliance using the material
Technical field
Make the electrode active material that stability is improved by the regulation of surface acid site the present invention relates to a kind of； A kind of electrode for including the electrode active material, the electrode surface is coated with the compound with acidic site or is mixed with Compound with acidic site；And it is a kind of including the electrode so that the electrochemical appliance that efficiency is improved, such as lithium is secondary Battery.
Background technology
Because lithium secondary battery has been commercialized, the exploitation of this battery is a kind of with such as capacity mainly for preparing The active material of cathode of the electrochemical properties such as height, long lifespan.Except electrochemical properties, also need exploitation stability-enhanced really Active material of cathode with ensure stability of the battery system under exceptional condition (such as, exposed to thermal environment, burn or overcharge) and Reliability.
LiMO2(M is a kind of transition metal, including Ni, Mn, Co etc.) is widely used as the cathode active material of lithium secondary battery Material, in the state of charging or overcharging, the structure that it can be with electrolysis qualitative response generation accessory substance, or destruction electrode active material, So as to cause battery efficiency to reduce.Therefore, many scientific workers have carried out many by using stable oxide process Surface of active material improves the research of active material efficiency, but these researchs can not increase the steady of electrode active material simultaneously Qualitative and efficiency.
The content of the invention
Technical problem
Meanwhile, inventor has found, if using conventional surface-modification method, will the low compound of reactivity be coated in electricity The particle surface of pole active material, it is ensured that the stability of electrode active material, but battery efficiency inevitably declines. Therefore, instead of conventional surface-modification method, with the electrode coated surface of active material of compound with adjusted acid strength not But the structural stability of electrode active material can be improved, but also the change of its physical characteristic can be prevented.Therefore, the present inventor tastes Pilot production is with a kind of reactivity significantly reduced with electrolyte so as to improve the new surface modifications method of battery efficiency.
Technical scheme
It is an object of the present invention to provide a kind of electrode active material for including acidic site, the acidic site part Or fully it is formed at the electrode active material surface；A kind of electrode comprising the electrode active material and one kind have institute State the electrochemical appliance of electrode, such as lithium secondary battery.
One aspect of the present invention provides a kind of following electrode, and the electrode has one and is coated with containing acidic site Compound surface or contain the compound；With a kind of electrochemical appliance with the electrode, such as lithium secondary battery.
A kind of electrode activity for the coat being conditioned with acid strength is produced another aspect provides a kind of The method of material, the described method comprises the following steps：(i) by a kind of (a) compound or one kind that can be provided or receive proton It can provide or receive compound and a kind of (b) compound reaction with acidic site of electronics pair；And (ii) is by step (i) Product be coated on the electrode active material surface and dry the coat.
It is a feature of the present invention that acidic site be partly or wholly formed at can be embedded in/deintercalate lithium ions or It is inserted into/takes off to insert the particle surface of the electrode active material of lithium ion, thus changes the electrochemistry of the electrode active material Physical characteristic.
Commonly known acidic site is the reactivity site being present on the solid acid catalyst of such as zeolite, solid Acid catalyst can induced chemical reaction, such as decomposition reaction.But in the present invention, acidic site, which is meant, may indicate that surface is modified The active region of partial specific acid strength, the acidic site is partly or entirely formed at by new surface-modification method The surface of the active material.
How acid strength is according to readily supplying proton or how easily to receive electronics to determining.Therefore, acidic site The feature of point is generally uncorrelated to surface texture, but related to the interatomic characteristic electron for constituting surface.
Due to positive charge or there is electronegativity difference, the electrode active material of acidic site is formed with surface such as Equally reacted with the partly general acidic material with positive charge.Therefore, because with the Bu Langsi as proton donor Platform moral acid (Acid) or as the reaction of the lewis acid (Lewis acid) of electron pair acceptor substantially reduce, therefore electricity Pole active material can improve battery efficiency, can make following presumption to this.
1) first, common electrode active material surface shows alkalescent by lithium accessory substance or Hydrophilic Surface Treatment.Cause This, almost recognizes less than acidic site.
Battery for utilizing common electrode active material --- being particularly active material of cathode ---, electrode or electrolyte Present in moisture can be with lithium salts (such as LiPF6) reaction generation strong acid HF.The HF of generation is spontaneously with showing weakly alkaline electrode Active material reacts, with the electrode active material composition that dissolves and degrade.In addition, LiF and electrode can be produced on cathode surface Resistance increase, thus produces gas and therefore shortens battery life.Specifically, the electrode dissolution speed caused by HF is in height It can increase under temperature, therefore HF becomes influence battery life and the principal element safeguarded.
By contrast, because the electrode active material of the present invention on its surface carries acidic site, therefore it can be used as acid Property material.So, the reaction with HAX (AX represents halogen) is reduced, so that above mentioned problem is substantially achieved solution, it is ensured that electricity The structural stability of pole active material and the efficiency for improving battery.
In addition, 2) second, the nonaqueous solvents based on carbonate is used as electrolyte in conventional batteries.Following article equation Disclosed in 1, due to dipole moment, the nonaqueous solvents based on carbonate has positively charged carbon and negatively charged oxygen.Herein In example, if the presence of electrode active material surface can provide the lewis base of localization of the unshared electron pair, lewis base will be attacked Carbon with positive charge, so as to further activate the electrophilic decomposition reaction of electrolyte.
Comparatively speaking, the electrode active material of the present invention with acidic site is can not to provide localization of the unshared electron pair but can Receive the lewis acid of localization of the unshared electron pair.Therefore, the above-mentioned side reaction occurred with electrolyte is significantly reduced, so that electric Pond efficiency deterioration minimizes.
[reaction equation 1]
Partly or entirely be formed at the present invention electrode active material surface acidic site refer to it is well known in the art Conventional acid site.For example, it can be carried protogenic Bronsted acid (i.e. proton donor) or can receive non-common The lewis acid (i.e. electron pair acceptor) of electronics pair.
Acid strength can use H0(Hammett (Hammett) indicator) is indicated, and can model known in the art --- such as -20 to 20 scopes --- are enclosed inside to be adjusted.H0Preferred scope is -10 to 10, so that by adjusting acidic site Put to prevent the degraded of electrode active material, and suppress the side reaction with electrolyte.
The method that acidic site is formed on electrode active material surface is unrestricted；It will hereafter retouch by way of example State two embodiments.
1) embodiment 1
In this embodiment, electrode active material surface is handled with inorganic matter.
Due to different metal (hetero-metal) element and/or the part or all of proton donor for being present in mineral surfaces The inorganic matter handled on the electronegativity difference of functional group, electrode active material surface can change the electronics on electrode active material surface Distribution, so as to form acidic site on electrode active material surface.
The inorganic matter is known in the art, for example ceramics, metal or its compound.The inorganic matter is unrestricted, only When working as electrode active material surface in the presence of the inorganic matter, the electrochemical properties on the surface are changed.In particular it is preferred to contain The compound of 13rd, 14,15 race's elements (such as B, Al, Ga, In, Ti) or their mixture, the compound can pass through The embedded of Li improves the structural stability of electrode, and this is due to that Li atom sizes make it that easily electrode active material can be mixed Surface.
Available inorganic matter example may include the 13rd race's element, the 13rd race's element and at least one element for being selected from following group Compound：Alkaline-earth metal, alkali metal, the 14th race's element, the 15th race's element, transition metal, lanthanide series metal and actinide metals, this The scope of invention is not limited to this.For example, the inorganic matter can be M1-xSixO2(M is at least one member selected from transition metal Element；0≤x ＜ 1).
Inorganic matter with the acidic site can be by forming to the modified heat treatment in electrode active material surface. In this example, there is no particular restriction for heat treatment temperature, or even also may be used more than the temperature for forming the acidic site.If hydroxyl Base is still in the surface, it is then not possible to form strong lewis acid site.It is therefore preferable that temperature is at 400 DEG C or higher to disappear Hydroxyl-removal.
There is no particular restriction for above-mentioned inorganic matter granularity and content, and they can be fitted in normal ranges known in the art When regulation.
2) embodiment 2
In this embodiment, with organometalloid (organic metalloid) compound or organo-metallic compound The surface of the electrode active material is handled with the compound of inorganic matter.
Due to electronegativity difference between compound and inorganic matter of the organometalloid (metal) that bonds together and/or with having The organic matter of machine metalloid (metal) compound bonding, the organometalloid compound or organo-metallic compound and electrode active Property material surface processing the compound of inorganic matter can change the electrochemistry physical characteristic on the surface, so as in the electrode Surface of active material formation acidic site.
In the compound, organometalloid (metal) compound and inorganic matter are bonded together by chemical bond, The form and species of chemical bond are unrestricted.For example, it can be covalent bond or co-ordinate covalent bond.
If the compound using the organometalloid compound or organo-metallic compound and inorganic matter is used as electrode The surface modifier of active material or electrode, then can reduce the hydrolysis rate of inorganic constituents (such as inorganic alkoxide).In addition, it is not It is only capable of producing the surface produced by more homogeneous surface, but also sustainable maintenance.Therefore, it can reduce to battery efficiency deterioration Minimum, the deterioration is due to the rupture knot of the reduction of electrode active material structural stability and the material during charging and discharging Caused by structure.In addition, it can introduce surface reforming layer by using inorganic compound contained in organic-inorganic composition, from And effectively increase the electrical conductivity of electrode active material.
The organic-inorganic composition that the electrode active material surface is introduced into can be with moisture or titanium dioxide contained in air Carbon reacts, and Li accessory substances is generated, so as to prevent from causing the aging character of side reaction.Specifically, the nickel seriously changed by moisture The active material of cathode of base is more effective.
In addition, the side reaction that it can reduce in the battery being made up of common electrode active material between negative electrode and electrolyte connects Surface is touched, its surface is not changed, so as to improve the stability of battery.
As described above, can make acidic site partly or entirely result from the electrode active material particles surface it is organic- One of inorganic composite can be the conventional organometalloid compound or organo-metallic compound of this area likewise known.In order to Enhancing adjusts acid strength and prevents the effect of aging character, preferably comprises for increasing the electron-donating group of bronsted acid sites Group.The electron-donating group is not particularly limited on structural formula, substituent and carbon atom number range.For example can be hydrogen or hydrocarbon.
The example of available organometalloid compound or organo-metallic compound may include the 14th race's element or the 14th race Element and at least one compound selected from following group of element：Alkaline-earth metal, alkali metal, the 13rd race's element, the 15th race's element, Transition metal, lanthanide series metal and actinide metals, the scope of the present invention are not limited to this.The organometalloid compound or organic Metallic compound is preferably silicon-containing compound (for example, silane, silanizing agent (silylizing agent), silane coupler, hydrogen SiClx, single silane, silane polymer or their mixture).
The organometalloid compound can be represented by one of following formula 1-7.To the organometalloid compound or have Machine metallic compound is not limited.
[formula 1]
SiH4
[formula 2]
Si(OR)4-xRx(0.1≤x≤3)
[formula 3]
Si(OR)4-(x+y)RxZy(0.1≤x+y≤3.9)
[formula 4]
Si(OR)4-xRxSi(0.1≤x≤3)
[formula 5]
Si(OR)4-(x+y)RxZySi(0.1≤x+y≤3.9)
[formula 6]
RxM(OR)4-x(1≤x≤3)
[formula 7]
RxMZy(OR)4-(x+y)(0.1≤x+y≤3.9)
Wherein, Z is a kind of element selected from halogen atom；
M is at least one element selected from alkaline-earth metal, alkali metal, transition metal, lanthanide series metal and actinide metals；And
R is a kind of substituent, selected from being optionally substituted by halogen or unsubstituted C1-C20Alkyl, alkenyl, alkynyl, vinyl, Amino and sulfydryl.
Another organic-nothing that acidic site can be made partly or entirely to result from the electrode active material particles surface Machine compound can be a kind of conventional inorganic matter for producing acidic site, and the generation of the acidic site is due to above-mentioned organic Metal (metal) is between compound and inorganic matter caused by the difference of chemical number of keys.Any compound containing inorganic matter can make With to this and without concrete restriction.For example, above-mentioned inorganic constituents can be used.In this example, in order to prevent electrode active material because Caused by the introducing of organic-inorganic composition electrical conductivity reduction, it is preferred to use conducting metal, the oxide containing conducting metal, Hydroxide or their mixture containing conducting metal.
The organic-inorganic composition being made up of the organometalloid (metal) compound and inorganic matter be not organic matter and The simple mixtures of inorganic matter, but their chemical bonding mixture.For example, it may include metal-organometalloid (gold Category) compound, metal oxide-organometalloid (metal) compound (Al2O3-SiOCH3) and hydroxide-organometalloid (metal) compound (AlOOH-Si-CH3)。
In the compound for forming acidic site, the component ratio of organometalloid (metal) compound and inorganic matter is in 0 weight In the range of %-95 weight % is measured than 5 weight %-100 weight %.
In addition, the organic and inorganic compound of the present invention may also include well known in the art add in addition to including said components Plus agent.
For the method for producing the electrode active material comprising Organic-inorganic composite coat, there is no particular restriction. In one embodiment, the surface portion of electrode active material or fully by containing acidic site compound coat.
According to preferred embodiment, methods described may include following steps：(i) by the compound containing inorganic matter or contain The compound of machine thing is mixed with organometalloid (metal) compound, or they are scattered in a kind of solvent, and (ii) to Electrode active material is added in the mixture or dispersion soln, is stirred for and dries.
The compound containing inorganic matter used can be that conventional containing at least one above-mentioned element is dissolved in water or insoluble In the compound (for example, alkoxide, nitrate, acetate containing above-mentioned inorganic matter etc.) of water.
The solvent may include Conventional solvents well known in the art (for example, organic solvent, such as water, alcohol or its mixture).
The used coated electrode active material with compound obtained above can be well known in the art conventional cloudy Pole active material and typical anode active material.
In this example, it is electrode coated with the complex solution for being mixed with inorganic matter and organometalloid (metal) compound The method of surface of active material may include solvent evaporated method, coprecipitation, the precipitation method, sol-gel process, absorbing and filtering method, splash Penetrate method, CVD etc..In these methods, preferred spraying process.
When adding the organometalloid (metal) compound and inorganic matter in electrode active material or containing inorganic matter During the mixed solution of compound, the electrode active material of preferably every 100 parts by weight adds the mixed solution of 0.05 to 20 parts by weight, The scope of the present invention is not limited to the number range.If mixed solution is excessive, electrode active material surface will exist a large amount of Surface-treated layer, so that lithium can not be free to migrate to electrode active material, so that the electrochemistry of electrode active material Feature is deteriorated.If in addition, mixed solution is very not enough, then the effect of acidic site will be very weak.By the electrode active of coating Property material and then can be dried by conventional method.
If it is necessary, can add the process of the electrode active material annealing obtained by drying.In this example, it is heat-treated Temperature range is not especially limited this more than 100 DEG C.Preferably, the scope is 100 DEG C to 600 DEG C.In addition, the heat Processing can be carried out under air or inert gas conditions.
Required effect can not be obtained by conventional method, because at ignition process (hotfiring process) In, the organic matter is that thermally labile and/or part are burned.Therefore, firing temperature is restricted.By contrast, In the present invention, the thermal instability of organic matter is compensated by inorganic constituents, therefore can provide the electrode activity with heat endurance Material.Further, since the electrode active material can be prepared by Conventional drying methods or low-temperature ignition method, therefore letter can be passed through Change preparation method to improve economic benefit and increase yield.
The surface of the electrode active material prepared by the above method has inorganic or Organic-inorganic composite layer, wherein described Inorganic or Organic-inorganic composite layer can produce acidic site.
It can verify that and obtain by experiment, the table of obtained electrode active material is modified by inorganic or organic-inorganic composition Face has acidic site (see Fig. 9).Specifically, the organic-inorganic composition not only shows organic matter and inorganic matter Bonding state (see Fig. 7), but also inorganic matter is relatively increased by electron-donating group present in the organic matter in compound Bronsted acid sites, so as to increase the acid strength of electrode active material (see Fig. 9).
The present invention provides a kind of electrode containing above-mentioned electrode active material.In this example, the electrode is preferably one kind The negative electrode significantly changed by HF or moisture.
In addition, the present invention also provides a kind of following electrode, the surface of the electrode is coated with the acidic site Compound or the electrode contain the compound with the acidic site.
Prepare and had no particularly as the method for the electrode of the constituent of electrode comprising the compound with acidic site Limitation, the electrode can be made by conventional method.In a preferred embodiment, by the compound containing organic/inorganic substance or contain The compound of machine thing is mixed with organometalloid (metal) compound, or is dispersed in solvent, and by the electrode active Property material add in the solution of mixing or scattered gained to form electrode slurry.Then, slurry is added to and electricity is prepared on current-collector Pole, and by pole drying.
In this example, in mixed process, mixed solution or dispersion soln are mixed with electricity with electrode active material After the slurry of pole, the slurry is added on current-collector.
The method of pole is produced electricity by the way that the organic-inorganic composition to be used as to the coating composition next life of electrode of the present invention to lead to Cross conventional method implementation.For example, the compound containing inorganic matter or the compound containing organic matter and the organometalloid is (golden Category) compound mixing, the mixture is added into preformed electrode surface, then again by pole drying.In this example, institute Stating preformed electrode can be prepared by the conventionally known method in this area.
In addition, the present invention also provides a kind of containing anode, negative electrode, spacer and electrolyte electrochemical device, wherein described The either or both of anode and/or negative electrode contains above-mentioned electrode active material or above-mentioned electrode.
The electrochemical appliance includes all devices being electrochemically reacted, and their instantiation includes all kinds One-shot battery and secondary cell, fuel cell, solar cell and capacitor.For secondary cell, preferably lithium is secondary Battery, including lithium metal secondary cell, lithium rechargeable battery, lighium polymer secondary battery and the secondary electricity of lithium ion polymer Pond.
The electrochemical appliance of the present invention can be made according to any conventional method known in the art.In an embodiment In, the electrochemical appliance can be by inserting a porous separator and then will be electrolysed between the negative electrode and anode in battery case Matter injects the electrochemical appliance case to prepare.
For the electrolyte and spacer in electrode, there is no particular restriction, can use the electricity for being usually used in electrochemical appliance Solve matter and spacer.
By electrochemical appliance produced by the present invention (such as lithium secondary battery) can be made into cylindric, coin, prism-shaped or It is bag-shaped, but it is not limited to the shape.
In addition, the present invention also provides a kind of production method for the electrode active material that surface acid strength is conditioned.At one In embodiment, it the described method comprises the following steps：(i) a kind of (a) compound that can be provided or receive proton is provided, or it is a kind of It can provide or receive compound and a kind of (b) compound reaction with acidic site of electronics pair；And (ii) is by step (i) Product is coated to the surface of the electrode active material, and dries the coat.But the present invention is not limited to such scheme.
The described compound that can be provided proton (or electronics to) or receive proton (or electronics to) can be used as conventional chemical combination Regulatory factor of the thing acid strength in particular range.In this example, the content for controlling the compound, the chemical combination can be passed through Functional group present in thing with and combinations thereof adjust the acid strength.
Had no for the compound that can be provided proton (or electronics to) or receive proton (electronics to) available for the present invention Especially limitation, as long as the compound can provide proton (or electronics to) or receive proton (electronics to).Preferably adjust described The modulated acid strength in electrode active material surface is -20 to 20 (i.e. -20<H0<20), preferably -10 to 10 (i.e. -10<H0< 10) in the range of.
Brief description of the drawings
Take the following drawings into consideration, foregoing and other objects, features and advantages of the invention will by it is described below more It is clear.
Fig. 1 is the charging/discharging capacity for showing the lithium secondary battery produced using the active material of cathode of embodiment 1 Curve map；
Fig. 2 is the charging/discharging capacity for showing the lithium secondary battery produced using the active material of cathode of embodiment 2 Curve map；
Fig. 3 is the charging/discharging capacity for showing the lithium secondary battery produced using the active material of cathode of embodiment 3 Curve map；
Fig. 4 is that the charge/discharge for showing the lithium secondary battery produced using the active material of cathode of comparing embodiment 1 is held The curve map of amount；
Fig. 5 is that the charge/discharge for showing the lithium secondary battery produced using the active material of cathode of comparing embodiment 2 is held The curve map of amount；
Fig. 6 is that the charge/discharge for showing the lithium secondary battery produced using the active material of cathode of comparing embodiment 3 is held The curve map of amount；
Fig. 7 is to show that obtained active material of cathode is with temperature and the surface characteristics of measuring condition generation in embodiment 1 The IR spectrograms of change；
Fig. 8 is to show that obtained active material of cathode is with temperature and the surface of measuring condition generation in comparing embodiment 1 The IR spectrograms of changing features；
Fig. 9 is the acidic site and its acid strength for the active material of cathode for showing embodiment 1-3 and comparing embodiment 1-3 IR spectrograms.
Embodiment
With reference to embodiment and comparing embodiment, the present invention is detailed further below.It is to be understood, however, that these are implemented Example is merely to illustrate, and non-limiting the scope of the present invention.
Embodiment 1
The preparation of 1-1. active material of cathode
By 0.8mol% aluminium isopropoxides and 0.8mol%CH3Si(OCH3)3It is placed in 200ml absolute ethyl alcohols, and it is small to stir 18 When.Then, 100g LiCoO are added into mixture2, then stir the mixture for 80 minutes.This is filtered with vacuum filter to mix Compound is to obtain electrode active material.With vacuum drying chamber drying at 130 DEG C by the electrode active material of gained, so as to be made Active material with the surface through processing.
The production of 1-2. negative electrodes
By obtained active material of cathode, conductive agent and adhesive with 95：2.5：2.5 ratio add in nmp solvent with Prepare cathode slurry.After slurries are added on 20 μm of aluminium foils, then the aluminium foil is set to be dried in vacuum drying chamber at 130 DEG C, from And negative electrode is made.
The production of the secondary half-cell of 1-3. lithiums
The electrode of acquisition is subjected to the porosity that rolling process obtains 25%, is then struck out coin to form button Detain battery.Now, relative electrode is made up of Li metals, and uses following electrolyte, i.e., the 1M LiPF in the electrolyte6 It is 1 to be dissolved in containing ratio：In 2 EC and EMC solvent.
Embodiment 2
Except again by dry active material in addition to 300 DEG C are annealed, negative electrode is obtained with the same procedure of such as embodiment 1 Active material.Then, with the same procedure of such as embodiment 1, produce active material of cathode, used the active material of cathode Negative electrode and the button cell with the negative electrode.
Embodiment 3
Except will only use active material of cathode made from aluminium isopropoxide in addition to 400 DEG C are annealed again, with the phase of such as embodiment 1 Active material of cathode is obtained with method.Then, with the same procedure of such as embodiment 1, produce active material of cathode, used this The negative electrode of active material of cathode and the button cell with the negative electrode.
Comparing embodiment 1
Except by conventional LiCoO2Replaced as active material of cathode the active material of cathode with treated surface with Outside, negative electrode and the button cell with the negative electrode are produced with the same procedure of such as embodiment 1.
Comparing embodiment 2
In addition to only preparing active material of cathode with aluminium isopropoxide, negative electrode is obtained with the same procedure of such as embodiment 1 Active material.Then, to produce active material of cathode such as the same procedure of embodiment 1, use the active material of cathode Negative electrode and the button cell with the negative electrode.
Comparing embodiment 3
Except only using CH3Si(OCH3)3Prepare beyond active material of cathode, negative electrode is obtained with the same procedure of such as embodiment 1 Active material.Then, active material of cathode produced with the same procedure of such as embodiment 1, used the moon of the active material of cathode Pole and the button cell with the negative electrode.
EXPERIMENTAL EXAMPLE 1：The surface physical characteristic analysis of electrode active material
The physical characteristic for the electrode active material being modified for the surface of the analysis present invention carries out following test.
The active material of cathode with the surface being modified through organic-inorganic composition that embodiment 1 is obtained is used as sample, And with common electrode active material (i.e. LiCoO2) it is used as control.
Above-mentioned active material of cathode is observed under following state respectively using IR spectrometers：In room temperature and air, room temperature and Vacuum, 50 DEG C and vacuum, 100 DEG C and vacuum, 200 DEG C and vacuum and 300 DEG C and vacuum.As a result show, the He of comparing embodiment 1 2 active material of cathode does not occur 2800 to 3000cm-1Neighbouring alkyl (- CH2CH3) (see Fig. 8), but the negative electrode work of the present invention Property material occurs in that alkyl (see Fig. 7).Therefore, it can be verified that surface modifying material present in active material of cathode of the invention The middle compound that there is the organic matter and inorganic matter.
EXPERIMENTAL EXAMPLE 2：The acidic site analysis of electrode active material
Following test is carried out for the surface characteristic of the surface modified electrodes active material of the analysis present invention.
Following material is used as sample：The negative electrode with the surface being modified by organic-inorganic composition obtained by embodiment 1 Active material, and there is the active material of cathode through the mineral-modified surface containing acidic site by what embodiment 3 was obtained；With Lower material is used as control：Conventional cathode active material (the i.e. LiCoO obtained by comparing embodiment 12), and by comparing embodiment 2 With 3 active material of cathode with the surface only through inorganic matter or organics modifications obtained.
Make above-mentioned active material of cathode absorption compound CH3CN, then measures their acidic site respectively with IR spectrometers Point.As reference, due to compound CH3CN is a kind of alkali compounds with localization of the unshared electron pair, and therefore can by with The compound of acidic site is neutralized and the change at peak occurs by Surface absorption, therefore in IR spectrums.Thus it is measurable to have The acid strength of the compound of acidic site.
Experimental result is shown, is employed the active material of cathode of the comparing embodiment 1 of conventional cathode active material, is employed The active material of cathode of comparing embodiment 2 with the active material of cathode only through mineral-modified surface and employing has The active material of cathode of the only comparing embodiment 3 of the active material of cathode on the surface through organics modifications does not show IR data Special change.Comparatively speaking, the cathode active material with the embodiment 3 for only passing through the mineral-modified surface containing acidic site Material, and the embodiment 1 with the surface being modified through organic and inorganic compound complex active material of cathode, 2200 to 2400cm-1Nearby there is cyano group peak.Therefore, it can be verified that, acidic site is formed with the electrode activity surface (see Fig. 9).
Specifically, will have in embodiment 3 only by the active material of cathode on identical mineral-modified surface with being compared Active material of cathode in embodiment 2 is compared, although the active material of cathode of comparing embodiment 2 can prevent secondary anti-with electrolyte Should occur, but the active material of cathode can not promote the formation of acidic site, therefore can still make battery efficiency deterioration (see Fig. 5). However, being strengthened (see Fig. 3) using the battery efficiency of the active material of cathode with acidic site of embodiment 3.Therefore, The formation of susceptible of proof acidic site is a factor related to battery efficiency.
EXPERIMENTAL EXAMPLE 3：The efficiency evaluation of lithium secondary battery
For the effect for the lithium secondary battery for evaluating the electrode active material production that there is acidic site using the surface of the present invention Following test can be carried out.
The button cell of embodiment 1-3 to being produced using the active material of cathode with acidic site is tested. It is tested simultaneously using comparing embodiment 1-3 button cell as corresponding sample, wherein the corresponding sample surfaces It is unmodified, or surface is only through inorganic matter or organics modifications.
It is that 0.5C, charge/discharge scope are progress under conditions of 3-4.5V in current density at 50 DEG C to make each sample Constant current and constant voltage (CC/CV) charge/discharge cycle.Acquired results such as Fig. 1-6 each cycle charging/discharge curve Shown in figure.
Test result is shown, for the embodiment 1-3 produced using the active material of cathode with acidic site battery For, charge/discharge efficiency is maintained in cyclic process.In other words, it is known that its cycle characteristics is significantly improved (Fig. 1-3).Together When, for the comparing embodiment 1-3 produced using the active material of cathode in the no acidic site in surface battery, it is known that it fills Electricity/discharge characteristic is deteriorated (Fig. 4-6).
Although the present invention has been described for be presently believed to be reality the most and preferred embodiment, it will be appreciated that, The invention is not restricted to disclosed embodiment and accompanying drawing.On the contrary, it is contemplated that be covered in appended claims purport and In the range of various modifications and alterations scheme.
Industrial applicability
From foregoing teachings, by adjusting the acidic site on electrode active material surface, electrode active material can be reduced With the side reaction of electrolyte, it is ensured that the structural stability of electrode active material, so as to improve battery efficiency.

Claims (3)

1. a kind of method for being used to prepare the electrode active material containing acidic site, wherein the acidic site is partly or entirely The surface of the electrode active material is formed at, be the described method comprises the following steps：
(i) by the way that aluminium isopropoxide and a kind of organometalloid compound or a kind of organo-metallic compound are mixed in a solvent and Prepare a kind of solution；
(ii) a kind of mixture is prepared by adding electrode active material into the solution；
(iii) stir and dry the mixture including electrode active material to form the drying with the surface through processing Electrode active material；And
(iv) electrode active material of the drying is annealed within the temperature range of 300-600 DEG C in addition,
And wherein described electrode active material is LiCoO2；
Wherein described organometalloid compound or organo-metallic compound are represented with one of following formula 1-7：
Formula 1
SiH4；
Formula 2
Si(OR)4-xRx, wherein 0.1≤x≤3；
Formula 3
Si(OR)4-(x+y)RxZy, wherein 0.1≤x+y≤3.9；
Formula 4
Si(OR)4-xRxSi, wherein 0.1≤x≤3；
Formula 5
Si(OR)4-(x+y)RxZySi, wherein 0.1≤x+y≤3.9；
Formula 6
RxM(OR)4-x, wherein 1≤x≤3；With
Formula 7
RxMZy(OR)4-(x+y), wherein 0.1≤x+y≤3.9,
Wherein, Z is a kind of element selected from halogen atom；
M is selected from following element to be at least one：Alkaline-earth metal, alkali metal, transition metal, lanthanide series metal and actinide metals；And And
R is a kind of substituent, selected from being optionally substituted by halogen or unsubstituted C1-C20Alkyl, alkenyl, alkynyl, amino and sulfydryl.
2. the method for claim 1 wherein the alkenyl is vinyl.
3. the method for claim 1 wherein the acidic site is Bronsted acid or lewis acid.
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