CN102394304A - Preparing technology of wrapping anode material on surface of lithium ion battery - Google Patents
Preparing technology of wrapping anode material on surface of lithium ion battery Download PDFInfo
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- CN102394304A CN102394304A CN2011103672276A CN201110367227A CN102394304A CN 102394304 A CN102394304 A CN 102394304A CN 2011103672276 A CN2011103672276 A CN 2011103672276A CN 201110367227 A CN201110367227 A CN 201110367227A CN 102394304 A CN102394304 A CN 102394304A
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- anode material
- ion battery
- lithium ion
- preparation technology
- positive electrode
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to a preparing technology of wrapping an anode material on the surface of a lithium ion battery, which comprises the following steps: inputting the anode material containing lithium carbonate and lithium into a solvent A, and continuously stirring the solvent A to obtain dispersion liquid containing lithium carbonate and the anode material; inputting a salt compound or a solution of the compound containing one or more metal M into the dispersion liquid for sediment, and absorbing a sediment product M(OH)n or M(CO3)n/2 or the mixture of the two on the surface of the anode material, wherein when M=Mg and Zn, n=2, when M=AL, Ce and La, n=3, and when M=Si, Sn, Ti and Zr, n=4; drying the anode material absorbed with the sediment product; and roasting the dried material to obtain the anode material coated by metallic oxide. The method is simple in practical operation, and is suitable for mass production.
Description
Technical field
The present invention relates to a kind of lithium ion battery, is a kind of preparation technology of lithium ion battery surface clad anode material.
Background technology
Lithium rechargeable battery has that specific capacity height, operating voltage are high, operating temperature range is wide, self-discharge rate is low, has extended cycle life, memory-less effect, pollution-free, in light weight, advantage such as security performance is good, thereby is widely used in mobile devices such as mobile phone, digital camera, notebook computer and portable DVD player.
Lithium ion battery generally is made up of positive pole, barrier film, negative pole and electrolyte.Positive electrode commonly used at present has LiCoO
2, LiNiO
2, LiMn
2O
4, LiNi
xCo
yMn
(1-x-y)O
2Deng, various positive electrodes all have corresponding shortcoming, like LiCoO
2Poor safety performance, LiNiO
2Structural instability, LiMn
2O
4High-temperature behavior is poor, LiNi
xCo
yMn
(1-x-y)O
2Platform is low, therefore need carry out modification to these materials and handle.It is the most effective one of modification processing method that positive electrode is carried out that the surface coats.Oxide is coated on the surface of positive active material, stops positive active material to contact, can effectively improve the fail safe of lithium ion battery, cycle performance etc. with the direct of electrolyte.
The method that more surface of positive electrode active material coats is disclosed at present both at home and abroad; Like the U.S. Pat of announcing on November 4th, 2,008 7; 445,871 disclose: prepare clad material through liquid phase method, then with dried clad material and positive active material mixed sintering; Reach surface coated purpose, there is the coating problem of non-uniform in this method.
The application number 201010119172.2 of Chinese patent document publication and for example; On February 11 2010 applying date, denomination of invention is " lithium ion battery surface clad anode material and preparation method thereof ", and it discloses: will contain the salt compounds that coats material earlier and add in the solvent and obtain hydrolyzate; Adding active material then stirs; Regulate PH and make the hydrolysate homogeneous precipitation and be adsorbed on the active material surface, then active material is dried roasting, obtain oxide coated positive electrode.
Make and have defective in this way: general active material all is alkalescence; Join in the solvent; Promptly changed the pH value of solvent, a large amount of active materials contains in the solution process of a small amount of coating material in adding, coats material and just possibly precipitate the part active material surface that formerly adds fully.Coat uneven problem it is thus clear that above-mentioned coating mode all exists, influenced energy density, fail safe and the cycle performance of lithium ion battery.
Summary of the invention
For overcoming above-mentioned deficiency, the objective of the invention is provides a kind of anode material for lithium-ion batteries surface cladding tech to this area, makes it solve existing cladding process and has defective, coats uneven technical problem.Its objective is and realize through following technical scheme.
The preparation technology of this lithium ion battery surface clad anode material may further comprise the steps:
(1) lithium carbonate and the positive electrode that contains lithium are put in the solvent orange 2 A, constantly stirred the dispersion liquid that obtains lithium carbonate and positive electrode.
Salt compounds or its solution that (2) will contain one or more clad metals M are put in the dispersion liquid and are precipitated precipitated product M (OH)
nOr M (CO
3)
N/2Or both mixtures are adsorbed on the positive electrode surface, wherein when M=Mg, Zn, and n=2; When M=Al, Ce, La, n=3; When M=Si, Sn, Ti, Zr, n=4.
(3) will be adsorbed with the positive electrode oven dry of precipitated product.
(4) material after will drying carries out roasting, obtains the positive electrode that is covered by metal oxide.
In above-mentioned steps, solvent orange 2 A is a water described in the said step (1), or the organic solvent that can dissolve each other with water, or the mixture of water and the organic solvent that can dissolve each other with water.
In the said step (1), said volume A is a water and the mixture of the organic solvent that can dissolve each other with water, and the weight ratio of organic solvent and water is between 0～100, and the weight of said solvent orange 2 A is 0.5～50 times of the positive electrode weight that added.
Alcohols or the ketone of said organic solvent for dissolving each other by arbitrary proportion with water.
Precipitation temperature is 0～100 ℃ in the said step (2), and the deposition adsorption time is 0.1～1000 minute.
Oven dry described in the said step (3) is carried out under 50～200 ℃, and drying time is 1～24 hour.
Cure the burning temperature described in the said step (4) and under 300～1000 ℃, carry out, roasting time is 1～24 hour.
The said general formula that contains the lithium positive electrode active materials is LiCo
(1-x-y)M
xN
yO
2, M, N are selected from a kind of among Al, Ce, Ca, Ge, La, Mg, Mn, Ni, Si, Sn, Ti, W, the Zn respectively in the formula, and M, N are inequality, 0≤x＜1,0≤y＜1.
The salt compounds of said clad metal M is Zn (NO
3)
26H
2O, Mg (NO
3)
26H
2O, MgCl
26H
2O, La (NO
3)
36H
2O, Ce (NO
3)
36 H
2O, Al (NO
3)
39H
2O, SnCl
4, Si (OC
2H
5)
4, Zr (NO
3)
45H
2O or metatitanic acid dimethyl ester.
The weight of said clad metal salt compounds and the said weight ratio that contains lithium anode material are 0.1～10.Saidly contain the weight of clad metal salt compounds and the weight ratio of said lithium carbonate is 0.1～20.
The present invention compared with prior art; The present invention adopts lithium carbonate to regulate the PH of positive electrode dispersion liquid; Make the PH of dispersion liquid remain on low relatively level, more help precipitated product and evenly be adsorbed on the active material surface, and use lithium carbonate can not introduce other metal cation impurity.Resulting hydroxide or the carbonate of being precipitated as all can change into metal oxide behind high temperature sintering.Practical operation of the present invention is simple, is fit to produce in enormous quantities use.
Description of drawings
Fig. 1 is that the embodiment of the invention adopts LiCoO
2Coat Al
2O
3SEM figure (amplifying 5k) before.
Fig. 2 is that the embodiment of the invention adopts LiCoO
2Coat Al
2O
3SEM figure (amplifying 5k) afterwards.
Fig. 3 is that the embodiment of the invention adopts LiCoO
2Coat Al
2O
3SEM figure (amplifying 10k) before.
Fig. 4 is that the embodiment of the invention adopts LiCoO
2Coat Al
2O
3SEM figure (amplifying 10k) afterwards.
Fig. 5 is a technological process block-diagram of the present invention.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the present invention is described in further detail.
Embodiment 1: get 3.78g lithium carbonate and 2500g LiCoO
2,Join in the 1L water and fully and stir, in the process that stirs, in dispersion liquid, drip 170ml and contain 13.10g Mg (NO
3)
26H
2The solution of O after dripping in 30 minutes, continues to stir 1 minute; Stop to stir and filter, the positive electrode that will be coated is 150 ℃ of bakings 24 hours, then with dried mixture 500 ℃ of following roastings 6 hours; Slowly cool to room temperature, obtain coating Mg and Co mol ratio and be 0.2% positive electrode.
Embodiment 2: take by weighing 5.56g lithium carbonate and 2500g LiCoO
2,Join in the 1L water and fully and stir, in the process that stirs, in dispersion liquid, drop into 19.17g Al (NO
3)
39H
2O stops after 30 minutes stirring and filters, and the positive electrode that will be coated is 150 ℃ of bakings 24 hours, then with dried mixture 700 ℃ of following roastings 6 hours, slowly cool to room temperature, obtain coating Al and Co mol ratio and be 0.2% positive electrode.
Embodiment 3: take by weighing 9.34g lithium carbonate and 2500g LiCoO
2,Join in the 1L water and fully and stir, in the process that stirs, in dispersion liquid, drip 170ml and contain 13.15g Mg (NO
3)
26H
2O and 19.24g Al (NO
3)
39H
2The solution of O; After dripping in 30 minutes, continue to stir 1 minute, stop to stir and filtering; The positive electrode that will be coated was 150 ℃ of bakings 24 hours; Then with dried mixture 700 ℃ of following roastings 6 hours, slowly cool to room temperature, coated Mg and Al simultaneously and the Co mol ratio is 0.2% positive electrode.
According to the announcement and the description of above-mentioned specification, the technical staff in field according to the invention can also change and revise above-mentioned execution mode.Therefore, the specific embodiment that discloses and describe above the present invention is not limited to also should fall in the protection domain of claim of the present invention modifications and changes more of the present invention.
Claims (10)
1. the preparation technology of a lithium ion battery surface clad anode material is characterized in that this preparation technology may further comprise the steps:
(1) lithium carbonate and the positive electrode that contains lithium are put in the solvent orange 2 A, constantly stirred the dispersion liquid that obtains lithium carbonate and positive electrode;
Salt compounds or its solution that (2) will contain one or more clad metals M are put in the dispersion liquid and are precipitated precipitated product M (OH)
nOr M (CO
3)
N/2Or both mixtures are adsorbed on the positive electrode surface, wherein when M=Mg, Zn, and n=2; When M=Al, Ce, La, n=3; When M=Si, Sn, Ti, Zr, n=4;
(3) will be adsorbed with the positive electrode oven dry of precipitated product;
(4) material after will drying carries out roasting, obtains the positive electrode that is covered by metal oxide.
2. the preparation technology of lithium ion battery surface clad anode material according to claim 1 is characterized in that solvent orange 2 A is a water described in the said step (1), or the organic solvent that can dissolve each other with water, or the mixture of water and the organic solvent that can dissolve each other with water.
3. the preparation technology of lithium ion battery surface clad anode material according to claim 2; It is characterized in that in the said step (1); Said solvent orange 2 A is a water and the mixture of the organic solvent that can dissolve each other with water; The weight ratio of organic solvent and water is between 0～100, and the weight of said solvent orange 2 A is 0.5～50 times of the positive electrode active materials weight that added.
4. according to the preparation technology of claim 2 or 3 described lithium ion battery surface clad anode materials, it is characterized in that alcohols or the ketone of said organic solvent for dissolving each other by arbitrary proportion with water.
5. the preparation technology of lithium ion battery surface clad anode material according to claim 1 is characterized in that precipitation temperature is 0～100 ℃ in the said step (2), and the deposition adsorption time is 0.1～1000 minute.
6. the preparation technology of lithium ion battery surface clad anode material according to claim 1 is characterized in that oven dry is carried out described in the said step (3) under 50～200 ℃, and drying time is 1～24 hour.
7. the preparation technology of lithium ion battery surface clad anode material according to claim 1 is characterized in that curing described in the said step (4) the burning temperature and under 300～1000 ℃, carries out, and roasting time is 1～24 hour.
8. the preparation technology of lithium ion battery surface clad anode material according to claim 1 is characterized in that the said general formula that contains the positive electrode active materials of lithium is LiCo
(1-x-y)M
xN
yO
2, M, N are selected from a kind of among Al, Ce, Ca, Ge, La, Mg, Mn, Ni, Si, Sn, Ti, W, the Zn respectively in the formula, and M, N are inequality, 0≤x＜1,0≤y＜1.
9. the preparation technology of lithium ion battery surface clad anode material according to claim 1, the salt compounds that it is characterized in that said clad metal M is Zn (NO
3)
26H
2O, Mg (NO
3)
26H
2O, MgCl
26H
2O, La (NO
3)
36H
2O, Ce (NO
3)
36 H
2O, Al (NO
3)
39H
2O, SnCl
4, Si (OC
2H
5)
4, Zr (NO
3)
45H
2O or metatitanic acid dimethyl ester.
10. the preparation technology of lithium ion battery surface clad anode material according to claim 1; The weight and the said weight ratio that contains lithium anode material that it is characterized in that said clad metal salt compounds are 0.1～10, and the weight of said clad metal salt compounds and said lithium carbonate weight ratio are 0.1～20.
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|---|---|---|---|
| CN2011103672276A CN102394304A (en) | 2011-11-18 | 2011-11-18 | Preparing technology of wrapping anode material on surface of lithium ion battery |
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| CN2011103672276A CN102394304A (en) | 2011-11-18 | 2011-11-18 | Preparing technology of wrapping anode material on surface of lithium ion battery |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103456946A (en) * | 2013-09-12 | 2013-12-18 | 刘志航 | Anode material for lithium ion battery |
| CN103647059A (en) * | 2013-12-17 | 2014-03-19 | 惠州亿纬锂能股份有限公司 | Lithium ion battery anode material with coating layer and preparation method thereof |
| CN104078670A (en) * | 2013-03-29 | 2014-10-01 | 北京当升材料科技股份有限公司 | Composite lithium battery positive electrode material and preparation method thereof |
| US8900751B2 (en) | 2012-11-26 | 2014-12-02 | Industrial Technology Research Institute | Electrode powder and electrode plate for lithium ion battery |
| CN106025214A (en) * | 2016-06-07 | 2016-10-12 | 山东齐星新材料科技有限公司 | Post-processing process for aluminium oxide-coated lithium cobalt oxide |
| CN108390065A (en) * | 2018-01-25 | 2018-08-10 | 湖北师范大学 | A method of in li-ion electrode materials surface coating cerium oxide |
| CN114784278A (en) * | 2022-04-22 | 2022-07-22 | 天津巴莫科技有限责任公司 | Surface modification method of high-nickel anode material |
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| CN101777647A (en) * | 2010-02-11 | 2010-07-14 | 东莞新能源科技有限公司 | Lithium ion battery surface clad anode material and preparation method thereof |
| CN101834289A (en) * | 2010-04-28 | 2010-09-15 | 东莞新能源科技有限公司 | Preparation method of lithium-ion battery anode material with oxide coated on surface |
| CN102195034A (en) * | 2010-03-09 | 2011-09-21 | 深圳市比克电池有限公司 | Preparation method of anode material for lithium ion batteries and prepared battery |
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2011
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Patent Citations (3)
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| CN101777647A (en) * | 2010-02-11 | 2010-07-14 | 东莞新能源科技有限公司 | Lithium ion battery surface clad anode material and preparation method thereof |
| CN102195034A (en) * | 2010-03-09 | 2011-09-21 | 深圳市比克电池有限公司 | Preparation method of anode material for lithium ion batteries and prepared battery |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8900751B2 (en) | 2012-11-26 | 2014-12-02 | Industrial Technology Research Institute | Electrode powder and electrode plate for lithium ion battery |
| CN104078670A (en) * | 2013-03-29 | 2014-10-01 | 北京当升材料科技股份有限公司 | Composite lithium battery positive electrode material and preparation method thereof |
| CN103456946A (en) * | 2013-09-12 | 2013-12-18 | 刘志航 | Anode material for lithium ion battery |
| CN103456946B (en) * | 2013-09-12 | 2017-07-11 | 湖南立方新能源科技有限责任公司 | Anode material for lithium-ion batteries |
| CN103647059A (en) * | 2013-12-17 | 2014-03-19 | 惠州亿纬锂能股份有限公司 | Lithium ion battery anode material with coating layer and preparation method thereof |
| CN106025214A (en) * | 2016-06-07 | 2016-10-12 | 山东齐星新材料科技有限公司 | Post-processing process for aluminium oxide-coated lithium cobalt oxide |
| CN106025214B (en) * | 2016-06-07 | 2019-05-24 | 山东齐星新材料科技有限公司 | The aftertreatment technology of alumina-coated cobalt acid lithium |
| CN108390065A (en) * | 2018-01-25 | 2018-08-10 | 湖北师范大学 | A method of in li-ion electrode materials surface coating cerium oxide |
| CN114784278A (en) * | 2022-04-22 | 2022-07-22 | 天津巴莫科技有限责任公司 | Surface modification method of high-nickel anode material |
| CN114784278B (en) * | 2022-04-22 | 2024-05-31 | 天津巴莫科技有限责任公司 | Surface modification method of high-nickel positive electrode material |
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Owner name: NINGBO JINHE LITHIUM BATTERY MATERIAL CO., LTD. Free format text: FORMER OWNER: NINGBO JINHE NEW MATERIALS CO., LTD. Effective date: 20141118 |
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Effective date of registration: 20141118 Address after: Jia Ling Road 315400 Yuyao City, Zhejiang province Ningbo City No. 39 Applicant after: NINGBO JINHE LITHIUM BATTERY MATERIAL CO., LTD. Address before: Jia Ling Road high tech Zone of Yuyao City, Zhejiang province Ningbo city 315400 Applicant before: Ningbo Jinhe New Materials Co., Ltd. |
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Application publication date: 20120328 |