CN1585161A - Potassium manganate modifying technology of secondary lithium ion battery - Google Patents

Potassium manganate modifying technology of secondary lithium ion battery Download PDF

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Publication number
CN1585161A
CN1585161A CNA2004100273626A CN200410027362A CN1585161A CN 1585161 A CN1585161 A CN 1585161A CN A2004100273626 A CNA2004100273626 A CN A2004100273626A CN 200410027362 A CN200410027362 A CN 200410027362A CN 1585161 A CN1585161 A CN 1585161A
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lithium
nitrate
limn
cobalt
acrylic copolymer
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王洪
郭春泰
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Huizhou TCL Jinneng Battery Co Ltd
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Huizhou TCL Jinneng Battery 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
    • H01M4/13—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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The modification technology is to cover a layer of metallic oxide film to the lithium manganate particle. Cover the uniform and dense layer of the usher film on the lithium manganate particle, then cover an uniform and dense layer of lithium cobalt film onto the usher film. The usher film is formed by painting the complex generated by the stearic acid usher or generated by acrylic acid copolymer and the usher to the surface of lithium manganate particle. The excellent solubility simple processing technology and low cost supply the method for industrial production.

Description

The secondary lithium battery modification technology of LiMn2O4
Technical field
Invention relates to the secondary lithium battery positive pole and uses lithium manganate material, refers to that especially LiMn2O4 is used for the modification technology of anodal manufacturing process.
Background technology
Fast development along with present information and mechanics of communication, portable audio-visual devices of mobile communication and laptop computer are popularized, demand to high-energy battery is strong day by day, countries in the world are all at the develop actively volume is little, in light weight, energy is high battery thus, lithium battery is exactly the important representative of this battery, particularly uses the lithium ion battery of non-aqueous electrolyte to obtain to use widely on various electric terminal machines.
Lithium (lithium ion) battery is a kind of electrochemical appliance, its basic functional principle is in charge and discharge process, shuttle back and forth between the positive pole of battery and negative pole by a kind of ionic conduction material from lithium metal or the lithium ion that contains the lithium intercalation compounds, electronics is done corresponding motion by external circuit between positive pole and negative pole simultaneously.In the production and processing, the anodal used lithium intercalation compounds material that contains of high energy lithium ion cell, employing be transition metal oxide, existing available have a cobalt acid lithium LiCoO 2, lithium manganate having spinel structure LiMn 2O 4, layered lithium manganate LiMnO 2, lithium nickelate LiNiO 2, nickel manganese cobalt acid complex LiCo xMn yNi zO 2, nickel cobalt acid complex LiCo 1～xNi xO 2, LiFePO4 LiFePO 4Deng.In these materials, LiFePO 4It is ripe to make that is that all right, LiNiO 2Poor safety performance but price height, LiMn 2O 4Cycle performance instability, high-temperature behavior are poor; Available material only has LiCoO in the present in fact industry 2One, but also there is the problem of several aspects in it, the one, expensive, the 2nd, cobalt resource lacks (in recent years, LiCoO 2Price rises steadily, and makes LiCoO 21075 dollar every pound 2450 dollars of increasing to now of price at the beginning of the last year of raw material cobalt metal, arrived the stage that the lithium battery manufacturer is difficult to bear), the 3rd, LiCoO 2Still there is certain potential safety hazard, therefore seeks LiCoO 2Substitute be very urgent thing.
LiMn2O4 LiMn 2O 4Most possibly to become cobalt acid lithium LiCoO 2The candidate of substitute is because produce LiMn 2O 4Raw material MnO 4Aboundresources, LiMn 2O 4Cost only have LiCoO 2About 1/5th.But LiMn 2O 4The cycle performance instability, high-temperature behavior is poor, through a large amount of studies confirm that, this mainly is because LiMn 2O 4In electrolyte, produce due to the dissolved destruction, more serious when this dissolved destruction acts on high temperature.For this reason, people are at synthetic LiMn 2O 4The time to add metal or nonmetalloid mainly be the components such as metal or transition metal such as iron, cobalt, nickel, aluminium, fluorine, magnesium, calcium, namely in its structure, mix, try hard to send its performance, but effect is unsatisfactory.People also pass through the method for chemistry or physics at LiMn 2O 4The surface of particle coats the last layer transition metal oxide to improve basic performance, namely adopts the way of direct or low molecular complex, at LiMn 2O 4Surface Creation one deck modifier plasma membrane, but there is a major defect in this method, and the presoma that namely coats process begins to be difficult at LiMn 2O 4The surface form the film of one deck even compact, therefore coat the modification body that comes out and also just be difficult at LiMn 2O 4The surface forms the uniform coating of one deck, and because uniformity is bad, and film forming is relatively poor, the thickness of clad also is difficult to control.
Summary of the invention
The purpose of this invention is to provide a kind of LiMn2O4 LiMn 2O 4Method of modifying, the problem of cycle performance instability, high-temperature behavior difference when being used for lithium ion battery to solve it.
It is anodal with the modification technology of lithium manganate material in anodal manufacturing process to have designed a kind of secondary lithium battery according to above-mentioned purpose, and this technology is at LiMn2O4 LiMn 2O 4The surface of particle coats one deck transition metal oxide film, namely earlier at LiMn2O4 LiMn 2O 4The surface of particle is coated with the precursor film of one deck even compact, is the cobalt acid lithium LiCoO of one deck even compact the surface coated of precursor film 2Coating film, this precursor film is to be applied to LiMn2O4 LiMn by the complex compound that stearic acid and modification predecessor lithium nitrate and cobalt nitrate (lithium nitrate and cobalt nitrate are with 2: 2～2: 3 ratio, the equivalent proportion of stearic acid and metal ion lithium and cobalt 3: 2～3: 1.5) reaction generates 2O 4Particle surface forms, or by acrylic copolymer and modification predecessor lithium nitrate and cobalt nitrate (lithium nitrate and cobalt nitrate be with 2: 2～2: 3 ratio, and the complex compound that carboxyl in the acrylic acid (COOH) with the equivalent proportion of metal ion lithium and cobalt 3: 2～3: 1.5) reaction generates is applied to LiMn2O4 LiMn 2O 4Particle surface and forming.
The implementation method one of aforementioned modification technology is,
At first, with lithium nitrate LiNO 3With moisture cobalt nitrate Co (NO 3) 26H 2O mixes in ball mill and grinds with 3: 2～3: 1.5 mol ratio;
Secondly, with the lithium nitrate LiNO that grinds and mix 3With moisture cobalt nitrate Co (NO 3) 26H 2O adds fully stirring in the stearic acid;
Its three, to lithium nitrate LiNO 3, moisture cobalt nitrate Co (NO 3) 26H 2O and stearic acid mixture add LiMn2O4 (LiMn 2O 4) and the dispersed with stirring mixing; (first three step process is namely with stearic acid and lithium nitrate LiNO 3, cobalt nitrate Co (NO 3) 26H 2O forms presoma, and at LiMn2O4 LiMn 2O 4The surface forms precursor film and finishes generation and the deposition of organic lithium salt)
Its four, to lithium nitrate LiNO 3, moisture cobalt nitrate Co (NO 3) 26H 2O, stearic acid and LiMn2O4 LiMn 2O 4Add in the mixture and be equivalent to lithium nitrate LiNO 3The lithium hydroxide LiOH aqueous solution of half left and right sides mole, and stirring is mixed; (in acid-base reaction at LiMn 2O 4Surface Creation one deck CoOOH film)
Its five, 130～150 ℃ of high-speed mixing after 2～3 hours with products therefrom in 600～800 ℃ of sintering in air.Wherein, stearic temperature is 80～110 ℃, stearic acid and lithium nitrate LiNO 3, moisture cobalt nitrate Co (NO 3) 26H 2The ratio of O is 1: 1～1: 2, mixes the back mixing time 0.5～2 hour; Whipping temp behind the adding lithium hydroxide LiOH aqueous solution is 80～110 ℃, mixing time 2～6 hours; Sintering time is 5～8 hours.
The implementation method two of aforementioned modification technology is,
At first, acrylic copolymer is dissolved in the deionized water;
Secondly, in acrylic acid aqueous solution, add cobalt carbonate CoCO 3Powder, (COOH) equivalent proportion with lithium metal and cobalt is 3: 2～3: 1.5 to carboxyl in the acrylic copolymer, is stirred at normal temperatures fully dissolving;
Its three, at acrylic acid CoCO 3The adding particle mean size is 8～15 microns LiMn2O4 LiMn in the aqueous solution 2O 4Powder and stir after, slowly add again the lithium hydroxide LiOH aqueous solution, the concentration of LiOH is 5～20%, it adds mole is LiNO 3About 1/2nd; At this moment with cobalt carbonate CoCO 3With the presoma of acrylic copolymer generation, at LiMn2O4 LiMn 2O 4The surface forms growth and the deposition that precursor film is finished organic lithium salt, then in the acid-base neutralization reaction also at Surface Creation one deck CoOOH of organolithium salt deposit film.
Its four, aforementioned solution through alkali neutralization is mixed under 2000 rev/mins high-speed stirred, and after about 150 ℃ of high temperature go down except that moisture, with products therefrom in 600～800 ℃ of sintering in air.Wherein, high temperature of putting in order when mixing is 70～110 ℃; Temperature when removing moisture is 130～180 ℃; Sintering time is 5～8 hours.
The present invention adopts polymer substance acrylate copolymer or stearic acid, generates earlier the complex compound of big molecule shape with the modification predecessor, is applied to LiMn2O4 LiMn with physics and chemical mode then 2O 4Particle surface, because high molecular polymer has extraordinary facial mask, and acrylate copolymer or stearic acid have the reactive side chain group the same with low molecule, and it has again goodish dissolubility in water or polar solvent, therefore treatment process is very simple, and processing cost is also very low.And because adopting the basic salt neutralization, no acidic material generates in the process, and post processing work formality is simplified greatly, directly just provides the method that can be used for suitability for industrialized production, makes suitability for industrialized production become feasible.
Specific embodiments
Thinking of the present invention is to adopt the polymer substance elder generation of screening and the complex compound that the modification predecessor generates big molecule shape, is applied to LiMn with physics and chemical mode then 2O 4Particle surface, utilize the good facial mask that this high molecular polymer has and the reactive side chain group the same with low molecule arranged again, and this polymer substance has again goodish dissolubility in water or polar solvent, even treatment process is very simple, cost is not high yet, is beneficial to suitability for industrialized production.
The first step of the present invention adopts low-temp reaction.Cobalt at first forms oxide, because of crystal structure and the LiMn2O4 LiMn of cobalt/cobalt oxide 2O 4Identical, the LiMn of cell parameter and spinel-type 2O 4Again very close, and according to the Crystallization principle, in the situation identical at crystal structure, that component is close, a kind of crystal can connect growth on the surface of another crystal.Therefore, when low temperature cobalt oxide just at the LiMn of spinel structure 2O 4The surface continued growth, and then cobalt oxide and lithium salts are reacted, at last at uniform, the nano level lithium and cobalt oxides of Surface Creation one deck, to LiMn 2O 4The surface play a protective role, thereby greatly improved LiMn 2O 4Performance.The present invention is the method by chemistry, at LiMn 2O 4The surface on form from level to level fine and close LiCoO 2The nanometer bag is carried out film, has so just overcome electrolyte to LiMn 2O 4Dissolving.Make LiMn 2O 4Cycle performance stablized.
After now non-limiting embodiment of the present invention being specified in, the variation of design parameter in the interval that sets can not produce substantial effect to the present invention.
Method one: with LiNO 3With Co (NO 3) 26H 2O mixes in grinding in ball grinder with 1: 1 mol ratio, adds then in 95 ℃ the stearic acid, and the ratio of slaine and acid is 1: 1～2: 1; Fully stir after 1 hour, add LiMn 2O 4, mixing; Add again and be equivalent to LiNO 3The aqueous solution of the LiOH of mole 1/2nd, 90 ℃ of lower stirrings 4 hours.At last 150 ℃ of high-speed mixing 2～3 hours, products therefrom is at 700 ℃ of sintering 6～8 hours in air.
Method two, acrylic copolymer are dissolved in the deionized water, rear adding CoCO 3Stir under the powder, normal temperature; After treating dissolve complete, the LiMn about the 10 μ m that the adding particle mean size is 2O 4Powder, and make it fully behind the Uniform Dispersion, slowly add again the water-soluble solution of LiOH; Then 90 ℃ of high-speed mixing about 4 hours, remove moisture in 150 ℃, products therefrom is at 700 ℃ of sintering 6～8 hours in air.
Wherein, the ratio of Co ion and Mn ion is 1～10: 90～99, preferably 3～5: 95～97.The content of Co is too big, and then cost rises, and the clad structure is comparatively loose, and is unfavorable to properties of product; The content of Co is too little, then LiMn 2O 4Plane of crystal can not be by LiCoO 2Particulate all coats, and forms bigger slit, to LiMn 2O 4Modification do not reach expected effect.LiMn 2O 4Average grain diameter remain on about 10 μ m and be advisable, too big, battery is more on the low side than molten amount; Too little, then cycle performance is not good enough.
Example 1 is dissolved in the deionized water rear adding CoCO with the acrylic copolymer 220g of carboxyl-content 0.0045mole/g 3Stir the LiMn of the 10 μ m that treat to add behind the dissolve complete particle mean size and be under the powder 120g, normal temperature 2O 4Powder 2000g fully disperses, and reaches even.Slowly add the water-soluble 240g of separating of 10%LiOH again, then 50 ℃ of high-speed mixing 4 hours, remove moisture in 150 ℃, products therefrom is at 700 ℃ of sintering 6～8 hours in air.
Example 2, other is with example 1, it is the content difference of carboxyl in the acrylic copolymer, be respectively 0.0045mole/g (A), 0.0040mole/g (B), 0.0035mole/g (C), 0.0030mole/g (D), 0.0025mole/g (E), 0.0020mole/g (F), but keep the total amount of carboxyl to equate.Experimental result is in table 2.
Example 3, other is with example 2, and just the ratio of Co ion and Mn ion is 5: 95 (A), 4: 96 (B), 3: 97 (C), 4.5: 95.5 (D), 3.5: 96.5 (E), 2.5: 97.5 (F), 6: 94 (G), 7: 93 (H).Experimental result is in table 3.
The test data of utilizing after lithium manganate material after the above-mentioned modification is made battery below:
Example 1: anodal with PVDF (Kynoar) 9g, be dissolved in 70g NMP (1-METHYLPYRROLIDONE), rear adding conductive agent SperP 3g and the present invention make LiCoO 2The LiMn that film coats 2O 488g, mixing is made slurry.After coat on the thick aluminium foil of the 0.015mm one side, 170 ℃ of oven dry form the pole piece of thick 0.15mm, prick sheet at twin rollers and become 0.10mm thickness, cut into pole plate.
Negative pole PVDF 8g is dissolved in 60g NMP, and the back adds MCMB (carbonaceous mesophase spherules) and Super p mixes, MCMB 90g, and electrically conductive graphite 2g makes slurry.Slurry is coated on the thick Copper Foil of 0.015mm, and 170 ℃ of oven dry form the pole piece of thick 0.16mm, and back pair roller is cut into pole plate to 0.11mm.
The system battery
The pole plate made and PP (polypropylene), PE (polyethylene) barrier film are made battery by the mode of reeling, after changing into 0.2C (battery capacity number 20%) electric current, discharge and recharge its cycle performance of evaluation with 1C (battery capacity number 100%) electric current; High-temperature behavior is measured and to be carried out the cycle performance test discharge and recharge on the instrument at ARBIN (Ah the third) and carry out in climatic chamber.
Example 2: all the other just adopt the LiMn that does not coat modification such as example 1 2O 4As positive electrode active materials.After make battery, test performance, evaluation method is identical with example one.
Example 3: all the other just adopt LiCoO as example 1 2As positive electrode active materials.After make battery, test performance, evaluation method is identical with example one.
(4) implement test result:
Table 1
The battery numbering Cycle performance under the normal temperature (cycle-index of battery capacity decline 20%) 60 ℃ of lower cycle performances (cycle-index of battery capacity decline 20%)
Example 1 389 268
386 255
375 257
Example 2 150 105
155 112
143 89
Example 3 500 458
485 451
496 437
Table 2
Example Carboxyl-content (mole/g) Initial capacity mAh/g The capacity mAh/g in 50 weeks circulates Capability retention, %
??2-A ??0.0045 ??126 ??121 ??96.0
??2-B ??0.0040 ??125 ??122 ??97.6
??2-C ??0.0035 ??126 ??123 ??97.6
??2-D ??0.0030 ??127 ??122 ??96.1
??2-E ??0.0025 ??125 ??123 ??98.4
??2-F ??0.0020 ??125 ??122 ??97.6
Table 3
Example Cobalt coating weight (g) Initial capacity mAh The capacity mAh in 50 weeks circulates Capability retention, %
??3-A ??5 ??123 ??119 ??96.7
??3-B ??4 ??125 ??122 ??97.6
??3-C ??3 ??126 ??123 ??98.0
??3-D ??4.5 ??127 ??123 ??96.8
??3-E ??3.5 ??125 ??120 ??97.6
??3-F ??2.5 ??123 ??119 ??96.7
??3-G ??6 ??126 ??120 ??95.2
??3-H ??7 ??128 ??121 ??94.5

Claims (9)

1, a kind of secondary lithium battery modification technology of LiMn2O4, this technology is at LiMn2O4 LiMn 2O 4The surface of particle coats one deck transition metal oxide film, it is characterized in that at LiMn2O4 LiMn 2O 4The surface of particle is coated with the precursor film of one deck even compact, is the cobalt acid lithium LiCoO of one deck even compact the surface coated of precursor film 2Coating film,
Described precursor film is to be applied to LiMn2O4 LiMn by the complex compound that stearic acid and lithium nitrate and cobalt nitrate reaction generate 2O 4Particle surface and forming, perhaps
Described precursor film is by acrylic copolymer and lithium nitrate and cobalt nitrate, and the complex compound that reaction generates is applied to LiMn2O4 LiMn 2O 4Particle surface and forming.
2, modification technology according to claim 1, it is characterized in that and lithium nitrate and the ratio between the cobalt nitrate that the reaction of stearic acid or acrylic copolymer generates precursor film are 2: 2～2: 3 the equivalent proportion 3: 2～3: 1.5 of carboxyl-COOH and metal ion lithium and cobalt in the acrylic copolymer.
3, a kind of method of implementing the described modification technology of claim 1 is characterized in that
At first, with lithium nitrate LiNO 3With moisture cobalt nitrate Co (NO 3) 26H 2O mixes in ball mill and grinds with 3: 2～3: 1.5 mol ratio,
Secondly, with the lithium nitrate LiNO that grinds and mix 3With moisture cobalt nitrate Co (NO 3) 26H 2O adds fully stirring in the stearic acid,
Its three, to lithium nitrate LiNO 3, moisture cobalt nitrate Co (NO 3) 26H 2Add LiMn2O4 LiMn in O and the stearic acid mixture 2O 4And stir and evenly mix,
Its four, to lithium nitrate LiNO 3, moisture cobalt nitrate Co (NO 3) 26H 2O, stearic acid and LiMn2O4 LiMn 2O 4Add in the mixture and be equivalent to lithium nitrate LiNO 3The lithium hydroxide LiOH aqueous solution about half mole, and stir and to be mixed,
Its five, 130～150 ℃ of following high-speed mixing after 2～3 hours with products therefrom in 600～800 ℃ of sintering in air.
4, method according to claim 3 is characterized in that described stearic acid temperature is 80～110 ℃, stearic acid and lithium nitrate LiNO 3, moisture cobalt nitrate Co (NO 3) 26H 2The ratio of O is 2: 2～2: 3, mixes the back mixing time 0.5～2 hour; Whipping temp behind the adding lithium hydroxide LiOH aqueous solution is 80～110 ℃, mixing time 2～6 hours.
5, method according to claim 3 is characterized in that sintering time is 5～8 hours.
6, a kind of method of implementing the described modification technology of claim 1 is characterized in that
At first, acrylic copolymer is dissolved in the deionized water,
Secondly, in the acrylic copolymer aqueous solution, add CoCO 3Powder, carboxyl and CoCO in the acrylic copolymer 3Equivalent proportion be 2.0～2.3: 1.0, be stirred at normal temperatures fully dissolving,
Its three, at acrylic copolymer and CoCO 3The adding particle mean size is 8～15 microns LiMn2O4 LiMn in the reacted aqueous solution 2O 4Powder and stir after, slowly add again the lithium hydroxide LiOH aqueous solution, the LiOH concentration of aqueous solution is that the equivalent proportion of carboxyl-COOH in 5～20%, LiOH and the acrylic copolymer is 1: 4～1: 3.5,
Its four, aforementioned solution through alkali neutralization is mixed under 2000 rev/mins high speed, and goes down except that moisture for 150 ℃ in high temperature, after with products therefrom in 600～800 ℃ of sintering in air.
7, method according to claim 6 is characterized in that high temperature of putting in order when mixing is 50～110 ℃.
8, method according to claim 6, the temperature when it is characterized in that removing moisture are 130～180 ℃.
9, method according to claim 6 is characterized in that sintering time is 5～8 hours.
CNA2004100273626A 2004-05-25 2004-05-25 Potassium manganate modifying technology of secondary lithium ion battery Pending CN1585161A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1319192C (en) * 2005-05-31 2007-05-30 中国科学院广州化学研究所 Method for processing positive pole material of lithium cobalt acid in lithium ion battery
CN100502100C (en) * 2005-09-02 2009-06-17 鸿富锦精密工业（深圳）有限公司 Lithium secondary anode, its preparing method and lithium secondary anode using same
CN1855587B (en) * 2005-04-28 2010-05-05 比亚迪股份有限公司 Battery anode preparation method and preparation method of lithium ion batteries using the battery anode
CN101659448B (en) * 2009-09-23 2011-09-28 北京师范大学 Preparation method of spinel type lithium manganate
CN103022484A (en) * 2012-12-15 2013-04-03 华中科技大学 Lithium iron conductive complex modified lithium iron phosphate anode material and preparation method thereof
CN104282902A (en) * 2014-10-20 2015-01-14 安徽师范大学 Lithium manganate of core-shell structure and preparation method of lithium manganate

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1855587B (en) * 2005-04-28 2010-05-05 比亚迪股份有限公司 Battery anode preparation method and preparation method of lithium ion batteries using the battery anode
CN1319192C (en) * 2005-05-31 2007-05-30 中国科学院广州化学研究所 Method for processing positive pole material of lithium cobalt acid in lithium ion battery
CN100502100C (en) * 2005-09-02 2009-06-17 鸿富锦精密工业（深圳）有限公司 Lithium secondary anode, its preparing method and lithium secondary anode using same
CN101659448B (en) * 2009-09-23 2011-09-28 北京师范大学 Preparation method of spinel type lithium manganate
CN103022484A (en) * 2012-12-15 2013-04-03 华中科技大学 Lithium iron conductive complex modified lithium iron phosphate anode material and preparation method thereof
CN104282902A (en) * 2014-10-20 2015-01-14 安徽师范大学 Lithium manganate of core-shell structure and preparation method of lithium manganate
CN104282902B (en) * 2014-10-20 2016-09-14 安徽师范大学 Nucleocapsid structure LiMn2O4 and preparation method thereof

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