CN102070199B - Method for preparing micron frame-shaped manganese series lithium ion battery cathode material - Google Patents
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Abstract
The invention belongs to the field of energy sources, particularly relating to a method for preparing a micron frame-shaped manganese series lithium ion battery cathode material. The method is characterized by comprising the following steps of: alternately processing a MnCO3 micron square block by utilizing low-temperature calcining and pickling to form amorphous manganese dioxide with a micron frame structure, reducing at a low temperature by utilizing LiI, calcining in vacuum and crystallizing to form a micron frame of LiMn2O4. By means of the method, the prepared material has a hollow structure so shat a stress generated during the intercalation/de-intercalation of Li is weakened and the stability of the material is high and has a porous structure to provide electron/ion channels; a distance of the Li intercalation/de-intercalation is shortened by utilizing a nanoscale frame wall, thereby enhancing dynamic rate of Li intercalation/de-intercalation, improving multiplying power and cycle performances of the material, and effectively preventing phenomena that nanometer materials aggregate, pass through diaphragm and the like in a reaction; and the size and the distribution of pore diameter can be controlled by utilizing differences of calcining conditions and pickling conditions so that the lithium ion battery cathode materials suitable for different needs are easy to prepare. The method for preparing the micron frame-shaped manganese series lithium ion battery cathode material has the characteristics of simple operation, low energy consumption and the like and is suitable for large-scale preparation and production.
Description
Technical field
The invention belongs to energy field, particularly the preparation method of a kind of micron frame shape manganese series lithium ion battery cathode electrode material.
Background technology
Lithium ion battery is high because of its voltage, and energy density is high, and output rating is big, and self-discharge is little, and advantages such as long service life are widely used in fields such as all kinds of portable electronic products, medical treatment device, power storage system, aerospace.Its environmental protection simultaneously is applied to it can significantly reduce emission of carbon-dioxide in all kinds of vehicles, alleviates environmental problem.Current, the cathode material LiCoO of lithium ion battery
2Cost an arm and a leg, toxicity is big, and laminate structure is destroyed easily during heavy-current discharge, makes lithium ion battery be difficult for developing into power energy supply device.And LiMn
2O
4Cheap, to cross and do not have the gas generation when discharging and recharging, three-dimensional tunnel texture ratio laminate structure is more conducive to the ionic embedding and takes off, and it is become substitute LiCoO
2, the important cathode material of motive force of development ionization cell.
But LiMn
2O
4Not good with the consistency of organic electrolyte, because disproportionation reaction manganese constantly dissolves, lithium ion embeds and the conversion (Jahn-Teller distortion) mutually of cubes/tetrahedron takes place when deviating from, and the lattice volume is changed, and makes the cell container decay soon, and the life-span is lower.Improve LiMn at present
2O
4The performance main path be to mix and finishing, particularly mixing, some provide [Y.Shin, A.Manthiram, the Chem.Mater.2003 such as element such as Ni, Co, Al of the average Oxidation Number of manganese; 15,2954] and surperficial coating can remove [Y.-K.Sun, the K.-J.Hong such as MOX such as ZnO of remaining HF in the electrolytic solution; J.Prakash, J.Electrochem.Soc., 2003; 150, A970], but these all can reduce LiMn
2O
4Specific storage, make the preparation process more complicated simultaneously, condition is more harsh, is unfavorable for LiMn
2O
4Application in power lithium-ion battery.Designing and preparing has the LiMn of special nanostructure
2O
4, utilize structural advantage to improve dissolving and the thaumatropy that embeds and deviate from manganese in the lithium ion process, improvement becomes development novel high-energy LiMn with the consistency of electrolytic solution
2O
4The important channel.
It is big that hollow porous structure has specific surface area, and the duct is abundant, and the good characteristics of resistive connection structure stress are adapted to solve LiMn
2O
4Existing problem.But general solid reaction process prepares LiMn
2O
4The time, need be difficult to control pattern calcining several hours more than 600 ℃, the product grain size is big, wider distribution, and often different because of reducing degree, contain impurity, therefore need to seek a kind of appropriate preparation method, prepare hollow porous LiMn
2O
4, utilize the advantage of structure, it is high to obtain electrochemical activity, the high performance lithium ion battery cathode electrode material that the doff lithium structural stability is good.
Summary of the invention:
The objective of the invention is to prepare hollow porous LiMn in order to solve
2O
4, utilize the advantage of structure, it is high to obtain electrochemical activity; The high performance lithium ion battery cathode electrode material that the doff lithium structural stability is good; The preparation method of a kind of micron frame shape manganese series lithium ion battery cathode electrode material is provided, it is characterized in that, utilize low temperature calcination and pickling alternate treatment MnCO
3The micron square forms the amorphous Manganse Dioxide with micron mount structure, with LiI low-temperature reduction and vacuum calcining crystallization, forms LiMn
2O
4The micron frame, the step of preparation micron frame shape manganese series lithium ion battery cathode electrode material is:
1) prepares amorphous MnO
2The micron frame:
Press KMnO
4With the mol ratio of sucrose is 2.5～3.0 to take by weighing the KMnO of aequum
4And sucrose, fully dissolve KMnO respectively with deionized water
4And sucrose, obtain the KMnO that concentration is 30～32g/L
4The sucrose solution of solution and 20～27g/L;
Above-mentioned two kinds of solution are mixed stirring after 10～30 minutes, the gained mixing solutions is transferred in the water heating kettle of polytetrafluoroethylliner liner, seal tight kettle cover;, temperature reacted 12～48 hours in being 150～160 ℃ baking oven; Take out reaction kettle naturally cooling in air,, colourless through suction filtration to elutant with deionized water repetitive scrubbing deposition; In temperature is 30～50 ℃ of oven dry throw outs down, obtains MnCO
3The micron square;
To above-mentioned MnCO
3The micron square will be through heat treated MnCO 290 ℃ of following thermal treatments of temperature 2～10 hours
3Micron square and concentration are that the hydrochloric acid (HCl) of 0.1 mol is made into the suspension liquid that concentration is 5g/L, mix to stir to obtain suspension liquid in 4 hours;
With above-mentioned suspension by dispersed with stirring in deionized water; The volume of deionized water is 1～2 times of above-mentioned used hydrochloric acid volume; The dilution suspension; Reduce acid concentration; Cessation reaction makes product even immediately, under 500～2000 rev/mins of rotating speeds, isolates sediment with centrifuge; Repeated washing, precipitation and separate 3～5 times obtain spending the sediment of deionised water;
Above-mentioned throw out with deionized water wash is passed through dispersed with stirring in ethanol; The alcoholic acid volume is 1～2 times of above-mentioned used hydrochloric acid volume; Under 500～2000 rev/mins of rotating speeds, isolate throw out with whizzer; Repeated washing, deposition and separate 2～5 times obtain the throw out with washing with alcohol;
The throw out of above-mentioned use washing with alcohol is dried in temperature is 30～50 ℃ baking oven, obtain the amorphous MnO of black
2The micron frame.
2) preparation LiMn
2O
4The micron frame:
Configuration concentration is the LiI acetonitrile solution of 0.05～0.06 mol, presses MnO
2Concentration be that the requirement of 6.0～6.5g/L adds the amorphous MnO of the prepared black of step 1) in said LiI acetonitrile solution
2The micron frame is 60～75 ℃ of refluxed reactions 12～18 hours in temperature, and the cooling back is isolated precipitated product with whizzer under 500～2000 rev/mins of rotating speeds;
Again precipitated product is distributed in the acetonitrile; The volume of acetonitrile is 1～2 times of above-mentioned used LiI acetonitrile solution volume; Under 500～2000 rev/mins of rotating speeds, isolate sediment with centrifuge; Repeated washing, precipitation and separate 5～10 times; Dilution washing repeatedly; For removing iodide ion, prevent that the disproportionation of too much iodine in weak solution from decomposing the generation accessory substance, obtain sediment with the acetonitrile washing;
Is 20～50 ℃ of following vacuum-dryings with the throw out of above-mentioned use acetonitrile washing in temperature, is to calcine 2～3 hours in the vacuum under 300～400 ℃ of conditions in temperature again, and gained black product is LiMn
2O
4The micron frame is a micron frame shape manganese series lithium ion battery cathode electrode material.
The LiMn for preparing with the present invention
2O
4Micron frame shape manganese series lithium ion battery cathode electrode material is hollow porous structure; Has bigger specific surface area; Vesicular structure has improved the consistency of material and electrolytic solution, has improved the transfer rate of lithium ion and electronics, has improved the heavy-current discharge performance of cathode material; Nano level frame wall wall has shortened the electrons/ions transmission route, has reduced polarization, has improved the doff lithium kinetic rate, improves the material high rate performance; Hollow structure has been alleviated the material stress that the Jahn-Teller inversion of phases produces in the doff lithium process, has stablized the structure of material; Micron frame and current material such as static eliminator, tackiness agent etc. have consistency preferably, and the electrode of preparation is stable; Simultaneously, the micron mount structure has prevented that the material that diffuses out from passing through battery diaphragm, has reduced self-discharge and short circuit phenomenon, has improved battery security and work-ing life; Utilize the different of calcination condition and pickling condition, can control the size and the distribution in aperture, be easy to prepare the lithium ion battery cathode electrode materials that is fit to different demands.
Beneficial effect of the present invention is: utilize the method for low-temperature heat treatment and pickling, obtain the amorphous MnO with hollow porous structure simply and easily
2, method simple controllable, easy handling; Utilize the amorphous MnO of excessive LiI acetonitrile solution low-temperature reduction vesicular structure
2, kept the structure of material; Calcining is to obtain the LiMn of higher crystallinity under the vacuum
2O
4, required time is short, and temperature is low; Simple to operate, energy consumption is little, is suitable for scale operation micron frame shape manganese series lithium ion battery cathode electrode material.
Description of drawings:
Fig. 1 is with the observed LiMn of JSM 7401F type field emission microscope
2O
4ESEM (SEM) picture of micron frame;
Fig. 2 uses metal lithium sheet to be anode material, LiMn
2O
4The micron frame is the battery of cathode material preparation, constant current charge curve and discharge curve under different multiplying.
Fig. 3 uses metal lithium sheet to be anode material, LiMn
2O
4The micron frame is the battery of cathode material preparation, 250 circle cycle performances under discharge-rate changes.
Embodiment
The invention provides the preparation method of a kind of micron frame shape manganese series lithium ion battery cathode electrode material, the present invention is further specified below in conjunction with description of drawings and embodiment.
Preparation LiMn
2O
4The embodiment of micron frame shape manganese series lithium ion battery cathode electrode material:
(1) with 4.42 gram KMnO
4Fully dissolve with the 140mL deionized water respectively with 3.5 gram sucrose, obtain the KMnO that concentration is 31.5g/L
4The sucrose solution of solution and 25g/L;
(2) above-mentioned two kinds of solution were mixed stirring after 20 minutes, gained solution is transferred in the water heating kettle of polytetrafluoroethylliner liner, compactedness is 80%; Sealing tight kettle cover, is reaction 24 hours in 150 ℃ the baking oven in temperature, takes out reaction kettle naturally cooling in air; Precipitate with the deionized water repetitive scrubbing through suction filtration; Colourless to elutant, be 50 ℃ of oven dry throw outs down in temperature, obtain MnCO
3The micron square;
(3) to MnCO
3The micron square is 290 ℃ of following thermal treatments 2 hours in temperature, and getting 0.5 gram is that the hydrochloric acid (HCl) of 0.1 mol is made into the suspension liquid that concentration is 5g/L through 290 ℃ of thermal treatment products and 100mL concentration, mixes stirring and obtaining suspension liquid in 4 hours;
(4) above-mentioned suspension liquid is distributed in the 100mL deionized water through magnetic agitation, under 2000 rev/mins of rotating speeds, isolates throw out with whizzer, repeated washing, deposition and separate 3～5 times obtain the throw out with deionized water wash;
(5) above-mentioned throw out with deionized water wash is distributed in the 100mL ethanol through magnetic agitation, under 2000 rev/mins of rotating speeds, isolates throw out with whizzer, repeated washing, deposition and separate 3～5 times obtain the throw out with washing with alcohol;
(6) throw out with above-mentioned use washing with alcohol is to dry in 30～50 ℃ of baking ovens in temperature, obtains the amorphous MnO of black
2The micron frame;
(7) 0.65 gram LiI is dissolved in the 90mL acetonitrile solution, adds the amorphous MnO of black of 0.56 gram step (6) gained afterwards
2The micron frame; In temperature is 70 ℃ of refluxed reactions 12 hours; The cooling back is isolated precipitated product with whizzer under 2000 rev/mins of rotating speeds, precipitated product is distributed in the 100mL acetonitrile again, under 2000 rev/mins of rotating speeds, isolates throw out with whizzer; Repeated washing, deposition and separate 5 times obtain the throw out with the acetonitrile washing;
(8) throw out with above-mentioned use acetonitrile washing is 50 ℃ of following vacuum-dryings in temperature,, be to calcine 2 hours in the vacuum under 350 ℃ of conditions in temperature again, gained black product is LiMn
2O
4Micron frame shape manganese series lithium ion battery cathode electrode material.
Use JSM 7401F type field emission microscope to test above-mentioned gained black product and be LiMn
2O
4The micron frame, the ESEM of test result (SEM) picture is as shown in Figure 1, and the micron edge is about 2 microns, even size distribution.The illustration in the upper right corner is the sample SEM picture after ultra-sonic dispersion is handled 30 minutes among the figure, has seen LiMn
2O
4The hollow structure of micron frame.
With LiMn
2O
4The micron frame is charging capacity, loading capacity, cycle life and the capability retention test of cathode material battery.
LiMn with above-mentioned gained
2O
4The micron frame is made cathode material, and metal lithium sheet is assembled into lithium ion battery as anode material, carries out the constant current charge-discharge test.LiMn with 80wt%
2O
4Micron frame electrode active material, the acetylene black of 10wt% and the PVDF powder of 10wt%; Dissolve with N-methyl-pyrrolidone (NMP); In mortar, fully grind, after thing to be mixed becomes glue, use scraper that it evenly is coated on the circular copper sheet collector electrode of diameter as 10mm; Drying is 12 hours under temperature is 120 ℃, depresses to electrode at 10MPa pressure then.Electro-chemical test adopts two electrode systems to carry out; Pour lithium slice with same diameter is a counter electrode; Capillary polypropylene (Ceigard-2402) is as barrier film; Measure NSC 11801 (EC), methylcarbonate (DMC), diethyl carbonate (DEC) at 1: 1: 1 and mix according to volume ratio, add LiPF again as solvent
6, make LiPF
6Concentration in above-mentioned solvent is 1.0 mol preparing electrolyte, in being full of the glove box of nitrogen, is assembled into battery.Adopt the LAND battery test system at room temperature respectively with 0.5C, 1C, 2C, the current density of 5C is carried out the constant current charge-discharge test.1C is equivalent to accomplish in 1 hour the current density ratio of unit mass (test current with) of charge or discharge, for LiMn
2O
4, 1C=148mA g
-1Charging capacity, loading capacity, cycle life and capability retention to sample in 3.0～4.3V voltage range are tested.The PARSTAT 2273Potentiostat/Galvanostat electrochemical analyser of employing United States advanced measuring technology company comes the impedance spectrum of recording cell, and bias voltage is 5mV, and range of frequency is 100KHz-100mHz.Test result as shown in Figures 2 and 3.
Fig. 2 is with LiMn
2O
4The micron frame is a negative electrode, and metal lithium sheet is the charging curve and the discharge curve of the different C values of anodic battery, show the battery of surveying discharge platform under the discharge-rate of different C stablize, under the 5C discharging current, specific discharge capacity still reaches 60mAh g
-1About (mAh g
-1The electric weight of representing 1 gram active substance to emit).Fig. 3 by the survey battery constantly change 250 circle cyclic curves down at discharging current, flow down charge and discharge cycles at least 10 times in different electric, can find out that the average specific capacity of different C values correspondences is respectively: 95mAhg
-1(0.5C), 87mAh g
-1(1C), 80mAh g
-1(2C), 60mAh g
-1(5C), after 250 circulations, under the 0.5C discharge-rate, specific storage still has 82mAh g
-1
Experimental result shows: the wellability of material and electrolytic solution has been improved in this duct that utilizes acid etch to go out, and passage is provided for electronics and ion transport; Hollow structure has been alleviated the inversion of phases stress that doff lithium produces; Thin wall thickness has shortened the electrons/ions transmission route, has reduced polarization process, has improved the kinetic rate of doff lithium; Micron frame and current material static eliminator, tackiness agent etc. have consistency preferably, and the preparation electrode is stable; The micron mount structure has prevented that the material that diffuses out from passing through battery diaphragm, has reduced self-discharge and short circuit phenomenon, has improved battery security and work-ing life.Through organically combining these nano effects, it is high to have obtained specific storage, and the heavy-current discharge capacity is high, the cathode material for lithium ion battery of good cycle.
The present invention is applicable to micron preparation of frame shape manganese series lithium ion battery cathode electrode material.
Claims (1)
1. the preparation method of a micron frame shape manganese series lithium ion battery cathode electrode material is characterized in that, utilizes low temperature calcination and pickling alternate treatment MnCO
3The micron square forms the amorphous Manganse Dioxide with micron mount structure, with LiI low-temperature reduction and vacuum calcining crystallization, forms LiMn
2O
4The micron frame, the step of preparation micron frame shape manganese series lithium ion battery cathode electrode material is:
1) prepares amorphous MnO
2The micron frame:
Press KMnO
4With the mol ratio of sucrose is 2.5～3.0 to take by weighing the KMnO of aequum
4And sucrose, fully dissolve KMnO respectively with deionized water
4And sucrose, obtain the KMnO that concentration is 30～32g/L
4The sucrose solution of solution and 20～27g/L;
Above-mentioned two kinds of solution are mixed stirring after 10～30 minutes, the gained mixing solutions is transferred in the water heating kettle of polytetrafluoroethylliner liner, seal tight kettle cover;, temperature reacted 12～48 hours in being 150～160 ℃ baking oven; Take out water heating kettle naturally cooling in air,, colourless through suction filtration to elutant with deionized water repetitive scrubbing deposition; In temperature is 30～50 ℃ of oven dry throw outs down, obtains MnCO
3The micron square;
To above-mentioned MnCO
3The micron square is 290 ℃ of following thermal treatments 2～10 hours in temperature, will be through heat treated MnCO
3Micron square and concentration are that the hydrochloric acid of 0.1 mol is made into the suspension liquid that concentration is 5g/L, mix to stir to obtain suspension liquid in 4 hours;
Above-mentioned suspension liquid is passed through dispersed with stirring in deionized water; The volume of deionized water is that the above-mentioned concentration that is made into is that the used concentration of suspension liquid of 5g/L is 1～2 times of hydrochloric acid volume of 0.1 mol; Under 500～2000 rev/mins of rotating speeds, isolate throw out with whizzer; Repeated washing, deposition and separate 3～5 times obtain the throw out with deionized water wash;
Above-mentioned throw out with deionized water wash is passed through dispersed with stirring in ethanol; The alcoholic acid volume is that the above-mentioned concentration that is made into is that the used concentration of suspension liquid of 5g/L is 1～2 times of hydrochloric acid volume of 0.1 mol; Under 500～2000 rev/mins of rotating speeds, isolate throw out with whizzer; Repeated washing, deposition and separate 2～5 times obtain the throw out with washing with alcohol;
The throw out of above-mentioned use washing with alcohol is dried in temperature is 30～50 ℃ baking oven, obtain the amorphous MnO of black
2The micron frame;
2) preparation LiMn
2O
4The micron frame:
Compound concentration is the LiI acetonitrile solution of 0.05～0.06 mol, presses MnO
2Concentration be that the requirement of 6.0～6.5g/L adds the amorphous MnO of the prepared black of step 1) in said LiI acetonitrile solution
2The micron frame is 60～75 ℃ of refluxed reactions 12～18 hours in temperature, and the cooling back is isolated precipitated product with whizzer under 500～2000 rev/mins of rotating speeds;
Again precipitated product is distributed in the acetonitrile; The volume of acetonitrile is 1～2 times of above-mentioned used LiI acetonitrile solution volume; Under 500～2000 rev/mins of rotating speeds, isolate throw out with whizzer, repeated washing, deposition and separate 5～10 times obtain the throw out with the acetonitrile washing;
Is 20～50 ℃ of following vacuum-dryings with the throw out of above-mentioned use acetonitrile washing in temperature, is to calcine 2～3 hours in the vacuum under 300～400 ℃ of conditions in temperature again, and gained black product is LiMn
2O
4The micron frame is a micron frame shape manganese series lithium ion battery cathode electrode material.
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| CN103682339B (en) * | 2013-12-24 | 2016-08-24 | 中南大学 | A kind of preparation method of lithium vanadyl phosphate anode material |
| CN104538581B (en) * | 2014-12-31 | 2017-01-04 | 江苏锋驰绿色电源有限公司 | A kind of three-dimensional porous LiMn2O4 membrane electrode and its preparation method and application |
| CN104779384B (en) * | 2015-03-19 | 2017-02-01 | 广西大学 | Preparation method of lithium ion battery negative electrode materials |
| CN111620378B (en) * | 2020-01-16 | 2022-10-11 | 太原科技大学 | Preparation method of porous cubic lithium manganate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5955052A (en) * | 1998-05-21 | 1999-09-21 | Carus Corporation | Method for making lithiated manganese oxide |
| CN1490250A (en) * | 2002-10-18 | 2004-04-21 | 北京圣比和科技有限公司 | Preparing method for spinel potassium manganate as lithium ion battery anode of electric vehicle |
| CN1562771A (en) * | 2004-04-07 | 2005-01-12 | 中信国安盟固利电源技术有限公司 | Spherical shaped lithium manganate and preparation method |
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| JPS5515922A (en) * | 1978-07-15 | 1980-02-04 | Nippon Chem Ind Co Ltd:The | Stabilizing method for aqueous solution of permanganate |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5955052A (en) * | 1998-05-21 | 1999-09-21 | Carus Corporation | Method for making lithiated manganese oxide |
| CN1490250A (en) * | 2002-10-18 | 2004-04-21 | 北京圣比和科技有限公司 | Preparing method for spinel potassium manganate as lithium ion battery anode of electric vehicle |
| CN1562771A (en) * | 2004-04-07 | 2005-01-12 | 中信国安盟固利电源技术有限公司 | Spherical shaped lithium manganate and preparation method |
Non-Patent Citations (2)
| Title |
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| JP昭55-15922A 1980.02.04 |
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