CN1945876A - Method for preparing lithium ion battery positive electrode composite material - Google Patents
Method for preparing lithium ion battery positive electrode composite material Download PDFInfo
- Publication number
- CN1945876A CN1945876A CNA2006101140635A CN200610114063A CN1945876A CN 1945876 A CN1945876 A CN 1945876A CN A2006101140635 A CNA2006101140635 A CN A2006101140635A CN 200610114063 A CN200610114063 A CN 200610114063A CN 1945876 A CN1945876 A CN 1945876A
- Authority
- CN
- China
- Prior art keywords
- lithium ion
- ion battery
- composite material
- positive active
- anode composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 24
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 24
- 239000002131 composite material Substances 0.000 title claims description 20
- 238000000034 method Methods 0.000 title description 2
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000013543 active substance Substances 0.000 claims abstract description 5
- 238000005516 engineering process Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000007774 positive electrode material Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 9
- 229910013716 LiNi Inorganic materials 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 6
- WCOATMADISNSBV-UHFFFAOYSA-K diacetyloxyalumanyl acetate Chemical compound [Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WCOATMADISNSBV-UHFFFAOYSA-K 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000009938 salting Methods 0.000 claims description 6
- 159000000013 aluminium salts Chemical class 0.000 claims description 5
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 abstract 4
- 239000011365 complex material Substances 0.000 abstract 2
- 239000012266 salt solution Substances 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910004186 Li(NiCoMn)1/3O2 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910011695 LiNi0.7Co0.3O2 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
This invention discloses a preparation method for the positive complex material of Li ionic cells, which applies a surface covering technology to cover an Al2O film of amorphous structure on a positive active substance surface of the Li ionic cells, confects the Al salt and a solvent to a soluble Al salt solution then mixes it with the positive active substance in proportion and mix them uniformly then to get a positive complex material of Li ionic cell with an amorphous structure Al2O film covered on the surface after filtration, sinter and cool naturally, which improves the interface state of the electrolyte and positive active substance and suppresses the badness reaction between the two.
Description
Technical field
The invention belongs to functional ceramic and technical field of chemical power, particularly utilize surface coating technology to synthesize the preparation method of a kind of anode composite material of lithium ion battery of composite material powder with nucleocapsid structure.
Background technology
Lithium ion battery is widely used in mobile electronic electrical equipment, as mobile phone, camera, notebook computer etc., along with lithium ion battery is expected to apply at electric automobile or electric power redundant electrical power etc., positive electrode becomes one of critical elements of the restriction lithium ion battery ratio of performance to price.The positive electrode of present commercial extensive use mainly is LiCoO
2, the about 140-150mAh/g of its actual capacity, and resource shortage cost an arm and a leg.LiCoO
2The circulation volume performance is stablized when 3.8V vs.Li, and the discharge capacity decay is very fast when 4.2V vs.Li.Because HF, the CH of coming out are decomposed in non-aqueous eletrolyte easy spontaneous decomposition under high voltage and high temperature
4, CO etc., these catabolites not only can corrode positive electrode, and can worsen the bad reaction of electrolyte and positive electrode, cause cycle performance of battery to worsen, even the safety issue that jeopardizes battery; Other positive electrodes such as LiNi
0.7Co
0.3O
2Li (NiCoMn)
1/3O
2, LiMn
2O
4Deng all there being shortcomings such as the anti-ability of filling, high temperature (as 60 ℃) unstable properties.For overcoming the above problems, Chinese scholars has been carried out finishing work, coat one deck charcoal or metal oxide as surface at positive active material, to improve the state of interface of electrolyte and positive active material, suppress bad reaction between the two, reach the purpose that strengthens the anti-ability of filling and improve cyclical stability under the high temperature.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of anode composite material of lithium ion battery, adopt surface coating technology to coat the aluminum oxide film that one deck has impalpable structure, to prepare anode composite material of lithium ion battery with the high cyclical stability of high power capacity on the active substance of lithium ion battery anode surface.
It is characterized in that aluminium salt and solvent are mixed with the soluble aluminum salting liquid that concentration is 0.1～0.3g/ml in the ratio of g/ml, mixed in the ratio of g/ml with positive active material again, mixed ratio is a positive active material: soluble aluminum salting liquid=0.2～0.5; And stir, after filtering, 350～750 ℃ of sintering, insulation 3～7h in air behind the natural cooling, obtain the surface and coat the anode composite material of lithium ion battery that one deck has the aluminum oxide film of impalpable structure.
Described aluminium salt is aluminum nitrate, aluminum sulfate or aluminium acetate.
Described solvent is ethanol or deionized water.
Described positive active material is a lithium-containing transition metal oxide, and its chemical general formula is LiNi
1-x-yCo
xM
yO
2M is Mg in the formula, Al, Cr or Mn, 0≤x≤1,0≤y≤1.
The invention has the beneficial effects as follows the state of interface that improves electrolyte and positive active material, suppress bad reaction between the two, reach the purpose that strengthens the anti-ability of filling and improve cyclical stability under the high temperature.Under the condition of 25 ℃ of cut-ff voltage 3.0-4.5V of room temperature, surface plating Al
2O
3The capability retention of 50 circulations of positive electrode has improved 10% behind the film; Under the test condition of 55 ℃ of cut-ff voltage 3.0-4.5V of temperature, the capability retention of 50 circulations of positive electrode has improved 17% behind the surface coating.
Embodiment
The invention provides a kind of preparation method of anode composite material of lithium ion battery.This method is that aluminium salt and solvent are mixed with the soluble aluminum salting liquid that concentration is 0.1～0.3g/ml in the ratio of g/ml, and mixed in the ratio of g/ml with positive active material again, mixed ratio is a positive active material: soluble aluminum salting liquid=0.2～0.5; And stir, after filtering, 350～750 ℃ of air atmosphere sintering, insulation 3～7h behind the natural cooling, obtain the surface and coat the anode composite material of lithium ion battery that one deck has the aluminum oxide film of impalpable structure, enumerate embodiment below and are illustrated.
Embodiment 1
Be that the ratio of 1g: 10ml is dissolved in the absolute ethyl alcohol according to concentration at first, continue stirring until dissolving fully, positive active material LiNi with aluminum nitrate
1/3Co
1/3Mn
1/3O
2According to concentration is that ratio and the aluminum nitrate ethanolic solution of 1g: 5ml mixes, continue to stir fully mix the back to its filter, drying, at 500 ℃ of sintering 5h, then products therefrom pulverizing, classification are promptly obtained coating the anode composite material of lithium ion battery of one deck aluminum oxide film then.
Embodiment 2
Be that the ratio of 1g: 5ml is dissolved in the deionized water according to concentration at first, continue stirring until dissolving fully, positive active material LiNi with aluminum nitrate
0.7Co
0.25Mn
0.05O
2According to concentration is that ratio and the aluminum nitrate aqueous solution of 1g: 3ml mixes, continue to stir fully mix the back to its filter, drying, at 400 ℃ of sintering 3h, then products therefrom pulverizing, classification are promptly obtained coating the anode composite material of lithium ion battery of one deck aluminum oxide film then.
Embodiment 3
Be that the ratio of 1g: 10ml is dissolved in the deionized water according to concentration at first, continue stirring until dissolving fully, positive active material LiNi with aluminum sulfate
0.7Co
0.25Mg
0.05O
2According to concentration is that ratio and the aluminum sulfate aqueous solution of 1g: 3ml mixes, continue to stir fully mix the back to its filter, drying, at 500 ℃ of sintering 4h, then products therefrom pulverizing, classification are promptly obtained coating the anode composite material of lithium ion battery of one deck aluminum oxide film then.
Embodiment 4
Be that the ratio of 1g: 10ml is dissolved in the ethanol according to concentration at first, continue stirring until dissolving fully, positive active material LiNi with aluminum sulfate
0.7Co
0.25Al
0.05O
2According to concentration is that ratio and the aluminum sulfate ethanolic solution of 1g: 5ml mixes, continue to stir fully mix the back to its filter, drying, at 600 ℃ of sintering 5h, then products therefrom pulverizing, classification are promptly obtained coating the anode composite material of lithium ion battery of one deck aluminum oxide film then.
Embodiment 5
Be that the ratio of 1g: 5ml is dissolved in the deionized water according to concentration at first, continue stirring until dissolving fully, positive active material LiNi with aluminium acetate
0.7Co
0.25Cr
0.05O
2According to concentration is that the ratio and the aluminium acetate aqueous solution of 1g: 5ml mixes, continue to stir fully mix the back to its filter, drying, at 500 ℃ of sintering 5h, then products therefrom pulverizing, classification are promptly obtained coating the anode composite material of lithium ion battery of one deck aluminum oxide film then.
Embodiment 6
Be that the ratio of 1g: 5ml is dissolved in the ethanol according to concentration at first, continue stirring until dissolving fully, positive active material LiNi with aluminium acetate
0.6Co
0.2Mn
0.2O
2According to concentration is that ratio and the aluminium acetate ethanolic solution of 1g: 5ml mixes, continue to stir fully mix the back to its filter, drying, at 600 ℃ of sintering 5h, then products therefrom pulverizing, classification are promptly obtained coating the anode composite material of lithium ion battery of one deck aluminum oxide film then.
Claims (4)
1. the preparation method of an anode composite material of lithium ion battery, adopt surface coating technology to coat the aluminum oxide film that one deck has impalpable structure on the active substance of lithium ion battery anode surface, it is characterized in that, aluminium salt and solvent are mixed with the soluble aluminum salting liquid that concentration is 0.1～0.3g/ml in the ratio of g/ml, mixed in the ratio of g/ml with positive active material again, mixed ratio is a positive active material: soluble aluminum salting liquid=0.2～0.5; And stir, after filtering, 350～750 ℃ of sintering, insulation 3～7h in air behind the natural cooling, obtain the surface and coat the anode composite material of lithium ion battery that one deck has the aluminum oxide film of impalpable structure.
2. according to the preparation method of the described anode composite material of lithium ion battery of claim 1, it is characterized in that described aluminium salt is aluminum nitrate, aluminum sulfate or aluminium acetate.
3. according to the preparation method of the described anode composite material of lithium ion battery of claim 1, it is characterized in that described solvent is ethanol or deionized water.
4. according to the preparation method of the described anode composite material of lithium ion battery of claim 1, it is characterized in that described positive active material is a lithium-containing transition metal oxide, its chemical general formula is LiNi
1-x-yCo
xM
yO
2M is Mg in the formula, Al, Cr or Mn, 0≤x≤1,0≤y≤1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101140635A CN100521299C (en) | 2006-10-26 | 2006-10-26 | Method for preparing lithium ion battery positive electrode composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101140635A CN100521299C (en) | 2006-10-26 | 2006-10-26 | Method for preparing lithium ion battery positive electrode composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1945876A true CN1945876A (en) | 2007-04-11 |
| CN100521299C CN100521299C (en) | 2009-07-29 |
Family
ID=38045150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101140635A Expired - Fee Related CN100521299C (en) | 2006-10-26 | 2006-10-26 | Method for preparing lithium ion battery positive electrode composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100521299C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102947985A (en) * | 2010-06-21 | 2013-02-27 | 锂电池科技有限公司 | Lithium-ion battery with amorphous electrode materials |
| CN103515611A (en) * | 2012-06-29 | 2014-01-15 | 河南科隆集团有限公司 | Lithium ion positive electrode material cladded by nanometer alumina membrane and preparation method thereof |
| CN106972167A (en) * | 2011-09-30 | 2017-07-21 | 旭硝子株式会社 | Positive electrode active material for lithium ion secondary battery and its manufacture method |
| CN107146875A (en) * | 2017-04-20 | 2017-09-08 | 中航锂电（洛阳）有限公司 | A kind of heat chemistry blocking-up type composite positive pole, anode pole piece and preparation method thereof, lithium ion battery |
-
2006
- 2006-10-26 CN CNB2006101140635A patent/CN100521299C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102947985A (en) * | 2010-06-21 | 2013-02-27 | 锂电池科技有限公司 | Lithium-ion battery with amorphous electrode materials |
| CN106972167A (en) * | 2011-09-30 | 2017-07-21 | 旭硝子株式会社 | Positive electrode active material for lithium ion secondary battery and its manufacture method |
| US10326127B2 (en) | 2011-09-30 | 2019-06-18 | Sumitomo Chemical Co., Ltd. | Cathode active material for lithium ion secondary battery, and process for its production |
| US10910640B2 (en) | 2011-09-30 | 2021-02-02 | Sumitomo Chemical Co., Ltd | Cathode active material for lithium ion secondary battery, and process for its production |
| CN103515611A (en) * | 2012-06-29 | 2014-01-15 | 河南科隆集团有限公司 | Lithium ion positive electrode material cladded by nanometer alumina membrane and preparation method thereof |
| CN103515611B (en) * | 2012-06-29 | 2017-09-26 | 河南科隆集团有限公司 | A kind of lithium ion anode material of nano oxidized aluminium film cladding and preparation method thereof |
| CN107146875A (en) * | 2017-04-20 | 2017-09-08 | 中航锂电（洛阳）有限公司 | A kind of heat chemistry blocking-up type composite positive pole, anode pole piece and preparation method thereof, lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100521299C (en) | 2009-07-29 |
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| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
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Granted publication date: 20090729 Termination date: 20121026 |