CN1148818C - Positive electrode material of lithium ion cell and its preparation method - Google Patents

Positive electrode material of lithium ion cell and its preparation method Download PDF

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CN1148818C
CN1148818C CNB001173472A CN00117347A CN1148818C CN 1148818 C CN1148818 C CN 1148818C CN B001173472 A CNB001173472 A CN B001173472A CN 00117347 A CN00117347 A CN 00117347A CN 1148818 C CN1148818 C CN 1148818C
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lithium
preparation
limn
powder
ion batteries
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CN1282113A (en
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周震涛
李新生
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South China University of Technology SCUT
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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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • 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
    • 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
    • H01M4/48—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention relates to a positive pole material of a lithium ion battery. A LiCoO2 layer with a layered crystal structure is evenly coated on the surface of LiMn2O4. A preparation method of the positive pole material of a lithium ion battery comprises the following steps: respectively preparing a soluble lithium salt and a soluble cobalt salt into a water solution; blending and mixing the water solution; adding the LiMn2O4 to be dispersed by ultrasonic waves to form a suspension system; completely infiltrating the surfaces of LiMn2O4 particles by a solution containing a modifying agent; preparing powder; hot treating the powder to obtain the positive pole material of a lithium ion battery. The LiCoO2 layer is coated on the surfaces of the LiMn2O4 particles by a liquid phase coating technique, which efficiently prevents the dissolution of Mn <3+> in the LiMn2O4 in an electrolytic solution and the generation of Jahn-Teller effect caused by the dissolution, and thus, the circulation reversibility and the high-temperature performance of the LiMn2O4 are efficiently improved.

Description

Anode material for lithium-ion batteries and preparation method thereof
Technical field
The present invention relates to lithium ion battery, more particularly relate to the used positive electrode LiMn of polymer Li-ion battery and lithium rechargeable battery 2O 4Preparation and modification thereof.
Background technology
LiCoO 2, LiNiO 2, LiMn 2O 4It all is the positive electrode of lithium ion battery.With the LiCoO with layer structure 2, LiNiO 2Compare, have the LiMn of spinel structure 2O 4Owing to low price, nontoxic, raw material is easy to get, preparation technology is simple etc., and advantage has more wide application prospect.But restriction LiMn 2O 4The main problem of extensive industrialization is that its cycle performance and high-temperature behavior are poor.This mainly is because at LiMn 2O 4In, the Mn of part 3+Can be dissolved in electrolyte on the one hand, can cause on the other hand to cause LiMn 2O 4The generation of structural unstable Jahn-Teller effect has destroyed the stability of crystal structure.
In order to improve LiMn 2O 4Cycle performance, have many people to do deep research work, mainly be to adopt metallic element to replace the manganese of part, as being doped to LiMn with Co, Ni, Cr, Cu, Fe, Li, Al etc. 2O 4In, having synthesized chemical formula is LiMn 2-xM xO 4(M=Co, Ni, Al, Cr; 0.001＜x＜1.999) have the compound of spinel structure.But this method is when improving the cycle performance of material, and the specific capacity of material has but all correspondingly descended.
Ellgen LiMn 2-bM bO 4(M=Al, Ti, V, Cr, Fe, Co, Ni, Cu) and lithium salts form the mixture that mixes in liquid phase medium, add to carry out thermal synthesis behind the reducing agent and obtain product (United States Patent (USP) 5639438 and United States Patent (USP) 5605773) again.This method can be improved the cycle performance of material, but complex manufacturing.
It is Li that Relmers has synthesized chemical formula xMn 2O 4The compound with tetrahedron crystal structure, can partly improve LiMn 2O 4Overcharging resisting over-discharge property (U.S. Patent application 5882218), but the specific capacity of its cycle performance and material is lower.
As seen, above-mentionedly improve LiMn by doped metallic elements 2O 4The mechanism of circulating and reversible performance is the stoichiometric Mn that replaces part with metallic element 3+, prevent or thereby LiMn is stablized in the generation that weakens the Jahn-Teller effect 2O 4Crystal structure.But improving LiMn 2O 4Cycle performance the time but reduced widely LiMn 2O 4Reversible specific capacity.
Jaephil Cho etc.[Electrochemical and Solid-state Letters.2 (12), 1999] reported and utilized sol-gel process, at LiMn 2O 4Coat one deck cycle performance, LiCoO that high-temperature behavior is good on the surface 2, to LiMn 2O 4Carry out finishing, can improve LiMn 2O 4The cycle performance of material in the time of 55 ℃, the specific capacity of material does not descend basically simultaneously, but its technology that adopts is comparatively complicated, can increase the manufacturing cost of material.
Summary of the invention
The objective of the invention is to the shortcoming for the prior art existence, a kind of anode material for lithium-ion batteries is provided, use the liquid phase technique for packing at LiMn 2O 4The surface of particle superscribes one deck LiCoO 2, effectively prevent LiMn 2O 4In Mn 3+Dissolving in electrolyte and cause the generation of Jahn-Teller effect makes LiMn 2O 4Distortion of lattice be difficult for to take place in charge and discharge process, directly do not contact with electrolyte and prevented Mn 3+Be dissolved in the electrolyte, thereby effectively improved LiMn 2O 4Circulating and reversible performance and high-temperature behavior.
The present invention also aims to provide a kind of preparation method of anode material for lithium-ion batteries, utilize the liquid phase technique for packing at LiMn 2O 4The surface of particle superscribes the superior LiCoO of one deck circulating and reversible performance 2, the technology simple possible is easy to suitability for industrialized production.
Anode material for lithium-ion batteries of the present invention is at LiMn 2O 4The surface superscribe one deck LiCoO 2
The preparation method of anode material for lithium-ion batteries of the present invention comprises the steps:
1. solubility lithium salts, solubility cobalt salt are made into the aqueous solution of 0.01～1mol/L respectively;
2. with above-mentioned two kinds of solution Li in molar ratio +: Co 2+=1 sampling mixes, and Co: Mn=0.005～0.15: 1 adds LiMn in system in molar ratio 2O 4, disperse to make it to form suspension system in 5--30 minute through ultrasonic wave, make the solution that contains modifier at LiMn 2O 4Particle surface forms the complete wetting state;
3. spray-dried technology or Freeze Drying Technique, or after adding sagging inhibitor (carboxymethyl cellulose, cellulose acetate, polyethylene glycol) makes it to form pastel, carry out slowly dry dry technology again and make powder;
4. with powder under 100-1000 ℃ temperature heat treatment 0.5-16 hour, obtain anode material for lithium-ion batteries.
Above-mentioned lithium salts can be solubility lithium salts and composition thereof arbitrarily; Cobalt salt is solubility cobalt salt and composition thereof arbitrarily.
The present invention can not destroy LiMn 2O 4Crystal structure.Improving LiMn 2O 4The circulating and reversible performance and high-temperature behavior the time, can not reduce significantly LiMn 2O 4The initial discharge specific capacity.At first synthesize high performance LiMn 2O 4, then with LiMn 2O 4Join in the solution that contains lithium salts and cobalt salt, through disperseing fully, make each LiMn 2O 4The surface of particle all forms completely wetting, and the material that obtains modification is heat-treated in recycling spray-drying or freeze drying or add the technology powder process of sagging inhibitor drying at last under certain conditions.
The basic principle of liquid phase technique for packing is as follows: with synthetic LiMn 2O 4Powder joins in the soluble-salt solution that contains modifier, through ultrasonic disperser the powder of reuniting is disperseed fully, make solution (being liquid phase) around each powder granule, form completely wetting after, recycling spray-drying or freeze drying, water in the solution around each particle is evaporated, thereby make soluble-salt crystallization on each powder granule surface, pass through again the heat treatment of uniform temperature, can form on the surface of each particle the integument of one deck soluble-salt, thereby by changing LiMn 2O 4Grain boundary structure reach the purpose of particle surface modification.
Wrap up resulting material owing to wrapped up the LiCoO that one deck very thin same electrolyte has excellent compatibility on the surface by liquid phase 2, make LiMn 2O 4In charge and discharge process, be difficult for directly contacting, make Mn on the one hand with electrolyte 3+Can not be dissolved in the electrolyte, prevent on the other hand yet by Mn 3+The generation of the Jahn-Teller effect that causes, thus LiMn protected 2O 4The stability of crystal structure has improved the circulating and reversible performance and the high-temperature behavior of material.Particularly, its advantage is as follows:
By this liquid phase technique for packing to LiMn 2O 4Carry out the resulting material of surface modification, still have good spinel crystal structure.
2. at room temperature the first discharge specific capacity of material is pure LiMn 2O 498% of first discharge specific capacity reaches 133.4mAh/g (0.2C leads); First discharge specific capacity under 60 ℃ is the LiMn that does not carry out finishing 2O 494%, reach 132.2mAh/g.
3. at 60 ℃ of material circulating and reversible performance description of tests that carried out down, after 100 charge and discharge cycles, also have 94% of initial reversible specific capacity by the resulting material of modification, after 100 circulations, do not have only 48% of initial reversible specific capacity and carry out surface modified material.
4. this by the resulting material of liquid phase technique for packing, LiCoO 2At LiMn 2O 4Surface distributed even.
5. utilize the liquid phase technique for packing at LiMn 2O 4Parcel one deck LiCoO on the surface of particle 2Method of modifying, carry out modification with doped metallic elements and compare, resulting material can not reduce LiMn on the one hand significantly 2O 4Initial reversible specific capacity, can also more effectively improve LiMn on the other hand 2O 4High-temperature behavior; This modification technology is compared with the technology of carrying out finishing with sol-gel process, and technical process is simpler, is easier to carry out large-scale industrial production.
The invention will be further described below by embodiment.
Embodiment
Embodiment one:
Get the CH of 200 milliliters of 0.03mol/L 3COOLi solution is poured rapidly (the CH of 200 milliliters of 0.03mol/L of vigorous stirring into 3COO) 2In the Co solution, continue to stir after 30 minutes, add 112.8g LiMn 2O 4, spray-dried technology makes powder again after ultrasonic wave disperses to make it to form suspension in 10 minutes.This powder is placed in the high temperature furnace obtained product in 8 hours 500 ℃ of following roastings.
Be that positive pole is made Experimental cell with resulting material, lead with 0.2C and carry out charge-discharge test that test result is as follows: the reversible specific capacity that discharges first under the room temperature is 133.4mAh/g, is pure LiMn 2O 4Capability retention after 98%, 100 circulation of first discharge specific capacity is 97.5% of its initial reversible specific capacity; First reversible specific discharge capacity in the time of 60 ℃ is 132.2mAh/g, and the capability retention after 100 circulations is 94.3% of its initial reversible specific capacity.
Embodiment two:
Get the CH of 100 milliliters of 0.01mol/L 3COOLi solution is poured rapidly (the CH of 100 milliliters of 0.01mol/L of vigorous stirring into 3COO) 2In the Co solution, continue to stir after 5 minutes, add 18.8g LiMn 2O 4, after ultrasonic wave disperses to make it to form suspension in 30 minutes, make powder through Freeze Drying Technique again.This powder is placed in the high temperature furnace obtained product in 16 hours 100 ℃ of following roastings.
Be that positive pole is made Experimental cell with resulting material, lead with 0.2C and carry out charge-discharge test that test result is as follows: the first discharge reversible specific capacity under the room temperature is 102mAh/g, only has pure LiMn 2O 4The capability retention that discharges first after 75%, 100 time of the reversible specific capacity circulation is 80.4% of its initial reversible specific capacity; First discharge reversible specific capacity under 60 ℃ is 105mAh/g, and the capability retention after 100 circulations is the 79.2%. of its initial reversible specific capacity
Embodiment three:
Get the CH of 100 milliliters of 1mol/L 3COOLi solution is poured rapidly (the CH of 100 milliliters of 1mol/L of vigorous stirring into 3COO) 2In the Co solution, continue to stir after 60 minutes, add 62.67g LiMn 2O 4, spray-dried technology makes powder again after powerful ultrasonic wave disperses to make it to form suspension in 5 minutes.This powder is put into high temperature furnace obtained product in 0.5 hour 1000 ℃ of following roastings.
Be that positive pole is made Experimental cell with resulting material, lead with 0.2C and carry out charge-discharge test that test result is as follows: the first discharge reversible specific capacity under the room temperature is 112mAh/g, only has pure LiMn 2O 4The capability retention that discharges first after 82.4%, 100 time of the reversible specific capacity circulation is 80.4% of its initial reversible specific capacity; First discharge reversible specific capacity under 60 ℃ is 113mAh/g, and the capability retention after 100 circulations is 79.2% of its initial reversible specific capacity.
Embodiment four
Get the CH of 100 milliliters of 0.05mol/L 3COOLi solution is poured rapidly (the CH of 100 milliliters of 0.05mol/L of vigorous stirring into 3COO) 2In the Co solution, continue to stir after 10 minutes, add 15.67g LiMn 2O 4With 0.5g carboxymethyl cellulose (CMC), again through slowly dry, grinding makes powder behind the suspension of ultrasonic wave dispersion formation pasty state.This powder is put into high temperature furnace obtained product in 10 hours 800 ℃ of following roastings.
Be that positive pole is made Experimental cell with resulting material, lead with 0.2C and carry out charge-discharge test that test result is as follows: the first discharge reversible specific capacity under the room temperature is 108mAh/g, only has pure LiMn 2O 479.4% of reversible specific capacity first discharges; First discharge reversible specific capacity under 60 ℃ is 106mAh/g.
Embodiment five:
Get the CH of 100 milliliters of 0.1mol/L 3COOLi solution is poured rapidly (the CH of 100 milliliters of 0.1mol/L of vigorous stirring into 3COO) 2In the Co solution, continue to stir after 30 minutes, add 15.67g LiMn 2O 4Disperse to form through ultrasonic wave behind the suspension of pasty state again through slowly dry with the polyethylene glycol of 1 gram, grind and make powder.This powder is put into high temperature furnace obtained product in 10 hours 600 ℃ of following roastings.
Be that positive pole is made Experimental cell with resulting material, lead with 0.2C and carry out charge-discharge test that test result is as follows: the first discharge reversible specific capacity under the room temperature is 124.8mAh/g, only has pure LiMn 2O 4The capability retention that discharges first after 91.7%, 100 time of the reversible specific capacity circulation is 93.4% of its initial reversible specific capacity; First discharge reversible specific capacity under 60 ℃ is 126mAh/g, and the capability retention after 100 circulations is 88.4% of its initial reversible specific capacity.
Embodiment six
Get the CH of 200 milliliters of 0.03mol/L 3COOLi solution is poured rapidly (the CH of 200 milliliters of 0.03mol/L of vigorous stirring into 3COO) 2In the Co solution, continue to stir after 15 minutes, add 56.4g LiMn 2O 4With the cellulose acetate of 1.2 grams, again through slowly dry, grinding makes powder behind the suspension of ultrasonic wave dispersion formation pasty state.This powder is put into high temperature furnace obtained product in 6 hours 650 ℃ of following roastings.
Be that positive pole is made Experimental cell with resulting material, lead with 0.2C and carry out charge-discharge test that test result is as follows: the first discharge reversible specific capacity under the room temperature is 120.3mAh/g, only has pure LiMn 2O 4The capability retention that discharges first after 88.5%, 100 time of the reversible specific capacity circulation is 91.4% of its initial reversible specific capacity; First discharge reversible specific capacity under 60 ℃ is 118mAh/g, and the capability retention after 100 circulations is 85.4% of its initial reversible specific capacity.

Claims (7)

1, a kind of anode material for lithium-ion batteries is characterized in that at LiMn 2O 4The surface on parcel one deck have uniformly the LiCoO of layered crystal structure 2
2, a kind of preparation method of anode material for lithium-ion batteries is characterized in that comprising the steps:
(1) solubility lithium salts, solubility cobalt salt are made into the aqueous solution of 0.01-1mol/L respectively;
(2) with above-mentioned two kinds of solution Li in molar ratio +: Co 2+=1 sampling mixed 5～60 minutes;
(3) Co: Mn=0.005-0.15 in molar ratio: 1 adds LiMn 2O 4, disperse to form suspension system in 5--30 minute through ultrasonic wave, make the solution that contains lithium salts and cobalt salt at LiMn 2O 4Particle surface forms complete wetting;
(4) preparation powder with the powder that makes under 100-1000 ℃ of temperature heat treatment 0.5-16 hour, obtains anode material for lithium-ion batteries.
3, the preparation method of anode material for lithium-ion batteries according to claim 2 is characterized in that above-mentioned solubility lithium salts is LiOH, Li 2CO 3, LiNO 3, CH 3One or more mixtures among the COOLi.
4,, it is characterized in that above-mentioned solubility cobalt salt is (CH according to the preparation method of claim 2 or 3 described anode material for lithium-ion batteries 3COO) 2Co4H 2O, Co (NO 3) 26H 2O.
5, the preparation method of anode material for lithium-ion batteries according to claim 2 is characterized in that adopting the spray drying method for preparation powder.
6, the preparation method of anode material for lithium-ion batteries according to claim 2 is characterized in that adopting freeze-drying to prepare powder.
7, the preparation method of anode material for lithium-ion batteries according to claim 2 is characterized in that adding sagging inhibitor carboxymethyl cellulose or cellulose acetate or polyethylene glycol and forms pastel, carries out slow drying again and makes powder.
CNB001173472A 2000-08-14 2000-08-14 Positive electrode material of lithium ion cell and its preparation method Expired - Fee Related CN1148818C (en)

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Publication number Priority date Publication date Assignee Title
CN100377391C (en) * 2004-12-29 2008-03-26 深圳市比克电池有限公司 Method for modified cladding composite, anode material LiCoO* of lithium ion battery, and batteries
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
JP2009537936A (en) * 2006-05-18 2009-10-29 中信国安盟固利新能源科技有限公司 Small and medium capacity high power lithium ion battery
CN103247796B (en) * 2013-05-14 2018-04-10 东莞新能源科技有限公司 Lithium ion battery more crystalline phase positive electrodes and preparation method thereof
KR20190003110A (en) * 2017-06-30 2019-01-09 삼성전자주식회사 Composite cathode active material, Cathode and Lithium battery containing composite cathode active material and Preparation method thereof
CN107863525A (en) * 2017-10-23 2018-03-30 兰州金川新材料科技股份有限公司 A kind of preparation method of grade doping cobalt acid lithium
CN107863526A (en) * 2017-10-23 2018-03-30 兰州金川新材料科技股份有限公司 A kind of preparation method for adulterating cobalt acid lithium
CN107946578B (en) * 2017-11-27 2020-07-17 中南大学 Lithium cobaltate-coated nickel cobalt lithium aluminate cathode material and preparation method thereof
CN108807964B (en) * 2018-06-29 2021-11-05 桑顿新能源科技(长沙)有限公司 Coating method and application of nickel-cobalt-aluminum ternary cathode material
CN109860582B (en) * 2018-12-28 2022-04-19 蜂巢能源科技股份有限公司 Positive electrode material of lithium ion battery and preparation method thereof

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