CN104795541B - Lithium-ion battery negative electrode slurry preparation method - Google Patents
Lithium-ion battery negative electrode slurry preparation method Download PDFInfo
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- CN104795541B CN104795541B CN201410018017.XA CN201410018017A CN104795541B CN 104795541 B CN104795541 B CN 104795541B CN 201410018017 A CN201410018017 A CN 201410018017A CN 104795541 B CN104795541 B CN 104795541B
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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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
- 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
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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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
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- 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
Abstract
The present invention discloses a lithium-ion battery negative electrode slurry preparation method, which comprises adopting 90-95 parts by weight of a mixture comprising artificial graphite and soft carbon as a negative electrode active substance, adding 0.5-1 part by weight of CMC, 1-2 parts by weight of a water-based adhesive LA133, 0.5-1.5 parts by weight of an electric conduction agent SP, and 2-3 parts by weight of SBR, and uniformly stirring in a stirrer to obtain the negative electrode slurry. According to the present invention, the CMC, SBR and LA133 combined adhesive is adopted, such that the adhesion of the negative electrode is enhanced, the dusting phenomenon is not easily generated, the use of the fibrous electric conduction agent is eliminated, and the cost is reduced.
Description
Technical field
The present invention relates to cell size preparation field, more particularly, to a kind of lithium ion battery cathode slurry preparation method.
Background technology
Lithium ion battery is because with higher specific energy density, high battery operating voltage, length storage life, self-discharge rate
Low advantage is widely used in hybrid-electric car (HEV), electric automobile (EV) and notebook computer, mobile phone sum code-phase
In the electronics and IT products such as machine market.Binding agent is the important component part of lithium ion battery plus-negative plate, current binding agent
Mainly there are oiliness and aqueouss, oiliness binding agent mainly has Kynoar（PVDF）, PVDF can provide good electrochemically stable
Property, there is higher adhesion to electrode material and collector.But fluorine-containing binding agent have the shortcomings that it is certain, it is easily molten by electrolyte
It is swollen so that electrode material is bondd variation on a current collector.And PVDF is needed using suitable organic solvent as dispersant, is made
With during, most of organic solvent is directly volatized into environment, has both been unfavorable for that organic solvent is reclaimed, has also been unfavorable for environmental conservation.
Aqueous binders typically adopt sodium carboxymethyl cellulose（CMC）And SBR emulsion（SBR）, but in some negative pole systems,
Such as graphite, CMC and SBR system can not play good bond effect, and its viscosity can be reduced with the rising of temperature, hold
The easy moisture absorption, or even there is the problem of negative pole dry linting.Meanwhile, easily there is roll banding phenomenon in CMC and SBR system, and just cannot be used for
Pole, use range are restricted.
Such as Chinese patent Authorization Notice No.：CN102916166A, the authorized announcement date patent document of on 02 06th, 2013
In, a kind of preparation method of pulp of lithium ion battery is disclosed, is comprised the steps：（1）It is prepared by glue：By deionized water and
CMC is proportionally added in agitator tank, and opening revolution carries out stirring at low speed, and glue is taken out stand-by after the completion of aerofluxuss；（2）Slurry system
It is standby：Graphite and conductive agent are proportionally added into in slurry tank carries out low speed revolution stirring, after dry powder is all wetted simultaneously
Rotation stirring is opened, is added and the same amount of SBR binding agents of CMC if viscosity is qualified；（3）Discharging：To obtaining before discharging
Slurry carries out evacuation process, by sand net filtration of the slurry less than 150 mesh during discharging.The paste composition that the present invention is obtained
Stable, quality is high.But the slurry of the CMC and SBR system equally exists following defect：Its viscosity can be with the rising of temperature
Reduce, the easy moisture absorption, or even the problem of negative pole dry linting occur.
The content of the invention
The present invention is that dry linting occur for the negative pole for solving the problems, such as lithium ion battery water-based binder system, there is provided one
Plant the more preferable lithium ion battery cathode slurry preparation method of caking property.
To achieve these goals, the present invention is employed the following technical solutions：
A kind of lithium ion battery cathode slurry preparation method, the preparation method are comprised the following steps：
（1）In agitator, add the deionized water stirring of the CMC and 50 weight portions of 0.5～1 weight portion that CMC glue is obtained
Liquid；
（2）The aqueous binder LA133 of 1～2 weight portion is added in CMC glues, is stirred；It is subsequently adding 0.5～
The conductive agent SP of 1.5 weight portions, stirs；
（3）Then the mixture of the Delanium and soft carbon of 90～95 weight portions is added in agitator, is disperseed at a high speed
Uniformly；
（4）Deionized water is added to adjust viscosity to 5000～6000cp；
（5）The SBR of 2～3 weight portions is added, is stirred；
（6）Cathode size is obtained through strainer filtering.
Compared with prior art, one is the negative pole for employing the big soft carbon mixture of Delanium and specific surface area to the present invention
System, is useful on high power type battery；Two is in the bonding system CMC-SBR of existing cathode size to add LA133, is improved
The cohesive force of the big negative pole system of specific surface area；Three is only to have used granular conductive agent SP just keep very in negative pole system
Good electric conductivity, eliminates the use of fibrous conductive agent, reduces cost.
LA133 is the aqueous binders of acrylonitrile multiple copolymer, with good caking property.Its addition, on the one hand
Improve its caking property, on the other hand, using compound conductive agent more than the conductive agent of present lithium ion battery, will graininess lead
Electric agent and fibrous conductive agent collaboration are used, and LA133 polyacrylonitrile therein（PAN）Segment has ionic conductivity, it
Addition can save the use of fibrous conductive agent, while the electric conductivity of whole system is unaffected, so reducing cost.
In this system, LA133 and CMC plays a part of bonding jointly, but pole piece is more crisp after LA133 is added, and
SBR is that, by 1,3-butadiene and styrene copolymerized obtained elastomer, its emulsion is good as elasticity during binding agent, and percentage elongation is high,
It is mainly used in increasing the pliability of electrode slice.If not using CMC using LA133+SBR systems, so obtained slurry is solid
Containing higher, during slurry is easier dry doubling and coating process, pole piece easily has little particle.The deployed CMC of the present invention,
The formula proportion of LA133 and SBR threes, makes obtained slurry be uniformly dispersed, and without granule, after coating, pole piece is without cracking, pole
Piece pliability is good, stands multiple winding process, and pole piece active substance stripping is that dry linting phenomenon is not susceptible to.
The present invention is compared with prior art LA133+SBR system, and LA133+SBR systems are used in Delanium and soft carbon
In negative pole system, the slurry for preparing contains very high admittedly, and the pole piece being coated with is coarse, has decorative pattern, and reason is possibly due to
LA133 has captured the water in SBR as the very strong material of polarity, makes SBR breakdowns of emulsion cause pole piece coarse.In addition, above-mentioned
The binding agent of LA133+SBR systems is all used in the negative pole system of graphite or admixed graphite, and in some specific surface area ratios
Larger negative pole for example, in soft carbon, as the specific area of soft carbon is than larger, cohesive force is poor, and LA133+SBR can not be solved
Its dry linting phenomenon.
The present invention in terms of preparation technology the characteristics of starching can first prepare CMC glues on a small quantity using CMC, improve viscous
Degree, adds LA133 and conductive agent, the species precipitate added after preventing using CMC glues, beneficial to dispersion afterwards.Be conducive to strengthening system
The electric conductivity and the dispersing uniformity of obtained slurry of the pole piece for obtaining.Scattered active substance, after adjusting viscosity, adds SBR, and
CMC, LA133 constitute water base class compound binding agent, strengthen the electric conductivity and cycle performance of battery, while further enhancing slurry
Caking property.
Preferably, in step（1）And step（4）Deionized water in be mixed into ethanol, obtain participating in after ethanol water
The preparation of slurry.The addition of ethanol can reduce the surface tension of water so that binding agent and negative material wellability are more preferable, material
Mix evenly, while prevented also from the slurry shrinkage phenomenon being likely to occur when pole piece is scratched.
Preferably, step（3）The scattered rotating speed of high speed is 800～1000rpm.Disperse at a high speed, beat by shearing force
Scattered material.
Preferably, step（3）Equivalent is added the mixture of middle Delanium and soft carbon at twice.Powder is impregnated with progressively,
Prevent solid content too high, damage agitator.
Preferably, vacuum condition is arranged in whipping process, pressure is -0.09～-0.098MPa.Vacuum froth breaking, prevents
During dispersed material, a large amount of bubbles of generation are difficult to remove so that mixed material expands, distension agitator.
Preferably, the particle diameter of the Delanium is 4～7 μm, soft carbon specific surface area is 2.6～3.6m2/g.Soft carbon ratio
Surface area is larger, the addition of soft carbon, is easier to insert lithium, can be suitable for lithium electricity than relatively similar with the crystallinity of graphite due to it
The high current charge-discharge condition that pond needs, safety is also better, also, its is high temperatures relatively good, with some manganese systems just
When pole matches, the high-temperature behavior of battery can be improved.
Beneficial effect：The present invention uses the mixture of Delanium and soft carbon as negative electrode active material, using CMC+SBR
The aqueous binders of+LA133 combinations, enhance the caking property of negative pole, are not susceptible to dry linting phenomenon；Eliminate fibrous conductive agent
Use, reduce cost.
Specific embodiment
With reference to specific embodiment, the present invention will be further described.
Embodiment 1：
The deionized water of the CMC and 50 weight portions of 0.7 weight portion is added in agitator, be evacuated i.e. pressure for-
After 0.095MPa, stirring 30min is obtained CMC glues, and follow-up whipping process keeps this vacuum condition.（2）Add in CMC glues
The aqueous binder LA133 of 1.5 weight portions, stirs 30min；The conductive agent SP of 1 weight portion is subsequently adding, 30min is stirred.（3）
Then two parts that the mixture of the Delanium and soft carbon of 92 weight portions is divided into equivalent are added sequentially in agitator, it is artificial
The particle diameter of graphite is 5 μm, and soft carbon specific surface area is 3m2/g.Start rotating speed 300rpm during mixing, mixture and glue tentatively merge
Disperse at a high speed 120min afterwards, the scattered rotating speed of high speed is 900rpm.（4）Deionized water is added to adjust viscosity to 5500cp.（5）Plus
Enter the SBR of 2.5 weight portions, stir 30min.（6）Cathode size is obtained through strainer filtering.
Embodiment 2：
10% ethanol water of the CMC and 50 weight portions of 0.5 weight portion is added in agitator, be evacuated i.e. pressure
For, after -0.09MPa, stirring 30min is obtained CMC glues, and follow-up whipping process keeps this vacuum condition.（2）Add in CMC glues
Enter the aqueous binder LA133 of 1 weight portion, stir 30min；The conductive agent SP of 0.5 weight portion is subsequently adding, 30min is stirred.
（3）Then two parts that the mixture of the Delanium and soft carbon of 90 weight portions is divided into equivalent are added sequentially in agitator,
The particle diameter of Delanium is 4 μm, and soft carbon specific surface area is 2.6m2/g.Start at the beginning of rotating speed 300rpm during mixing, mixture and glue
Disperse at a high speed 120min after step fusion, the scattered rotating speed of high speed is 800rpm.（4）Add 10% ethanol water adjust viscosity to
5000cp.（5）The SBR of 2 weight portions is added, 30min is stirred.（6）Cathode size is obtained through strainer filtering.
Embodiment 3：
10% ethanol water of the CMC and 50 weight portions of 0.7 weight portion is added in agitator, be evacuated i.e. pressure
For, after -0.095MPa, stirring 30min is obtained CMC glues, and follow-up whipping process keeps this vacuum condition.（2）In CMC glues
The aqueous binder LA133 of 1.5 weight portions is added, 30min is stirred；The conductive agent SP of 1 weight portion is subsequently adding, 30min is stirred.
（3）Then two parts that the mixture of the Delanium and soft carbon of 92 weight portions is divided into equivalent are added sequentially in agitator,
The particle diameter of Delanium is 5 μm, and soft carbon specific surface area is 3m2/g.Start rotating speed 300rpm during mixing, mixture and glue are preliminary
Disperse at a high speed 120min after fusion, the scattered rotating speed of high speed is 900rpm.（4）Add 10% ethanol water adjust viscosity to
5500cp.（5）The SBR of 2.5 weight portions is added, 30min is stirred.（6）Cathode size is obtained through strainer filtering.
Embodiment 4：
10% ethanol water of the CMC and 50 weight portions of 1 weight portion is added in agitator, be evacuated i.e. pressure for-
After 0.098MPa, stirring 30min is obtained CMC glues, and follow-up whipping process keeps this vacuum condition.（2）Add in CMC glues
The aqueous binder LA133 of 2 weight portions, stirs 30min；The conductive agent SP of 1.5 weight portions is subsequently adding, 30min is stirred.（3）
Then two parts that the mixture of the Delanium and soft carbon of 95 weight portions is divided into equivalent are added sequentially in agitator, it is artificial
The particle diameter of graphite is 7 μm, and soft carbon specific surface area is 3.6m2/g.Start rotating speed 300rpm during mixing, mixture and glue tentatively melt
Disperse at a high speed 120min after conjunction, the scattered rotating speed of high speed is 1000rpm.（4）Add 10% ethanol water adjust viscosity to
6000cp.（5）The SBR of 3 weight portions is added, 30min is stirred.（6）Cathode size is obtained through strainer filtering.
Claims (6)
1. a kind of lithium ion battery cathode slurry preparation method, it is characterised in that the preparation method is comprised the following steps：
（1）In agitator, add the deionized water stirring of the CMC and 50 weight portions of 0.5～1 weight portion that CMC glues are obtained；
（2）The aqueous binder LA133 of 1～2 weight portion is added in CMC glues, is stirred；It is subsequently adding 0.5～1.5 weight
The conductive agent SP of amount part, stirs；
（3）Then the mixture of the Delanium and soft carbon of 90～95 weight portions is added in agitator, is uniformly dispersed at a high speed；
（4）Deionized water is added to adjust viscosity to 5000～6000cp；
（5）The SBR of 2～3 weight portions is added, is stirred；
（6）Cathode size is obtained through strainer filtering.
2. a kind of lithium ion battery cathode slurry preparation method according to claim 1, it is characterised in that by step（1）
And step（4）Deionized water substituted with the ethanol water of identical weight part respectively after participate in the preparation of slurry.
3. a kind of lithium ion battery cathode slurry preparation method according to claim 1 and 2, it is characterised in that step（3）
The scattered rotating speed of high speed is 800～1000rpm.
4. a kind of lithium ion battery cathode slurry preparation method according to claim 1 and 2, it is characterised in that step（3）
Equivalent is added the mixture of middle Delanium and soft carbon at twice.
5. a kind of lithium ion battery cathode slurry preparation method according to claim 1 and 2, it is characterised in that stirred
Vacuum condition is set in journey, and pressure is -0.09～-0.098MPa.
6. a kind of lithium ion battery cathode slurry preparation method according to claim 1, it is characterised in that the artificial stone
The particle diameter of ink is 4～7 μm, and soft carbon specific surface area is 2.6～3.6m2/g。
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105206804A (en) * | 2015-08-31 | 2015-12-30 | 无锡市嘉邦电力管道厂 | Lithium ion battery and preparing method thereof |
| CN106384816A (en) * | 2016-10-28 | 2017-02-08 | 深圳拓邦股份有限公司 | High-nickel ternary lithium ion battery positive electrode slurry and preparation method thereof |
| CN108075103A (en) * | 2016-11-17 | 2018-05-25 | 深圳格林德能源有限公司 | A kind of pollution-free anode plate for lithium ionic cell manufacturing process |
| CN108807997A (en) * | 2018-08-27 | 2018-11-13 | 上海力信能源科技有限责任公司 | Lithium ion battery anode slurry preparation process |
| CN109758960B (en) * | 2019-03-07 | 2020-09-29 | 广东宏工物料自动化***有限公司 | Lithium ion battery positive and negative electrode slurry mixing production system and slurry preparation process |
| CN109888175B (en) * | 2019-03-11 | 2021-07-02 | 珠海冠宇电池股份有限公司 | Preparation method of lithium ion battery for improving high-voltage low-temperature discharge and cycle performance |
| CN109817985A (en) * | 2019-03-25 | 2019-05-28 | 福建冠城瑞闽新能源科技有限公司 | A kind of lithium ion battery anode slurry stabilizer and preparation method thereof, application |
| CN111180659B (en) * | 2019-12-30 | 2021-03-12 | 江西安驰新能源科技有限公司 | Preparation method of lithium ion battery cathode slurry |
| CN113130856B (en) * | 2019-12-30 | 2022-12-02 | 江西格林德能源有限公司 | Silicon-carbon-graphite cathode slurry for polymer lithium ion battery and preparation method thereof |
| CN111554937A (en) * | 2020-05-26 | 2020-08-18 | 苏州凌威新能源科技有限公司 | Negative electrode slurry, negative electrode sheet and preparation method thereof |
| CN111509231B (en) * | 2020-05-26 | 2021-08-10 | 苏州凌威新能源科技有限公司 | Negative electrode slurry, negative electrode sheet and preparation method thereof |
| CN113013372A (en) * | 2021-02-22 | 2021-06-22 | 江西省允福亨新能源有限责任公司 | Preparation method of aqueous anode and cathode slurry of lithium ion battery |
| CN113257584B (en) * | 2021-05-08 | 2023-03-17 | 贵州梅岭电源有限公司 | Preparation method of hard carbon slurry for lithium ion capacitor |
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|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
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| CB02 | Change of applicant information |
Address after: 311215 Xiaoshan economic and Technological Development Zone, Zhejiang District, No. two road, building No. 855, No. Applicant after: Wanxiang 123 Co Ltd Applicant after: Wanxiang Electric Vehicle Co., Ltd. Applicant after: Wanxiang Group Corporation Address before: 311215 Xiaoshan economic and Technological Development Zone, Zhejiang, No. two road, building No. 118, No. Applicant before: Universal A 1 System Co., Ltd Applicant before: Wanxiang Electric Vehicle Co., Ltd. Applicant before: Wanxiang Group Corporation |
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| COR | Change of bibliographic data | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211111 Address after: 311215 No. 855, Jianshe Second Road, economic and Technological Development Zone, Xiaoshan District, Hangzhou City, Zhejiang Province Patentee after: Wanxiang 123 Co., Ltd Address before: 311215 No. 855, Jianshe Second Road, economic and Technological Development Zone, Xiaoshan District, Hangzhou City, Zhejiang Province Patentee before: Wanxiang 123 Co., Ltd Patentee before: WANXIANG EV Co.,Ltd. Patentee before: WANXIANG GROUP Co.,Ltd. |