CN108923020A - A kind of preparation method of the lithium ion battery water system anode sizing agent containing VGCF - Google Patents
A kind of preparation method of the lithium ion battery water system anode sizing agent containing VGCF Download PDFInfo
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- CN108923020A CN108923020A CN201810732561.9A CN201810732561A CN108923020A CN 108923020 A CN108923020 A CN 108923020A CN 201810732561 A CN201810732561 A CN 201810732561A CN 108923020 A CN108923020 A CN 108923020A
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- slurry
- lithium ion
- vgcf
- sizing agent
- ion battery
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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
- H01M4/04—Processes of manufacture in general
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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
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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 relates to technical field of lithium ion to include the following steps more particularly, to a kind of preparation method of lithium ion battery water system anode sizing agent containing VGCF：（1）Water-base cement and deionized water are mixed, gluing is carried out；（2）Step is added in conductive black SP（1）In glue mixed solution in, carry out infiltration stirring, stir and VGCF composite mortar is added after a period of time is mixed；（3）Iron phosphate powder is added into the slurry after infiltrated stirring, carries out high-speed stirred；（4）It continuously adds deionized water, slurry is adjusted into its viscosity to 2000 ~ 4000mPas after high-speed stirred.Solvent of the present invention is deionized water, at low cost and environmentally friendly, and the present invention is stirred using wet process, slurry good dispersion, the electric conductivity of slurry is improved, and then reduces the internal resistance of cell, improves high rate performance, in addition, slurry viscosity is low under the conditions of identical solid content compared with dry method, it is effectively improved the processing performance of slurry.
Description
Technical field
The present invention relates to technical field of lithium ion, more particularly, to a kind of lithium ion battery water system anode containing VGCF
The preparation method of slurry.
Background technique
Lithium ion battery is during charge and discharge cycles, and when positive and negative anodes pole piece has electric current to pass through, electrode potential can deviate flat
The current potential that weighs generates polarization.If polarization phenomena cannot improve the precipitation that can accelerate cathode lithium metal for a long time, can if things go on like this pierce
Wearing diaphragm leads to battery short circuit, causes safety problem.How to improve lithium battery electric conductivity by design becomes the class for needing to pay close attention to
Topic.But the electric conductivity for relying solely on active material is unable to satisfy electron transfer rate requirement, it is therefore desirable to which conductive agent adds
Enter.
Conductive agent can play the role of collecting micro-current between active material, between active material and collector, this
Effect can be reduced electrode contact internal resistance, so that improving electronic conductivity reduces battery polarization.
Nano carbon fiber (VGCF) has the structure of linear hollow multi-pipe wall, can be with as the conductive agent in electrode
Good conductive network is formed, compared to the connection type of the point and point of conductive black and electrically conductive graphite, the point of VGCF and line
The way of contact is more advantageous to raising electric conductivity, reduces battery polarization.Simultaneously structural pipe wall can receive more electrolyte, be lithium from
Sub smooth, quick insertion or deintercalation provide convenience, are conducive to high power charging-discharging.But VGCF specific surface is big, easy to reunite, only by passing
The mechanical stirring of system, is not easy evenly dispersed in a solvent, while most of solvent uses NMP in the market, is harmful to the human body, pollutes
Environment.
The slurry technology of preparing of existing lithium ion battery is by simple mechanical stirring, and this stirring is difficult to make various
Component is uniformly dispersed, and this specific surface of especially VGCF is big, easy to reunite in solvent dispersion process, especially in water solvent
It is bigger to disperse difficulty.
Summary of the invention
Present invention aim to address above-mentioned the deficiencies in the prior art, improve the dispersibility of water system anode sizing agent, improve lithium
Ion battery electronic conductivity reduces its polarization, reduces its internal resistance, provides a kind of lithium ion battery aqueous positive-pole slurry containing VGCF
The preparation method of material makes VGCF obtain fine dispersion and stability height in water system anode sizing agent.
The present invention is achieved by the following technical solutions：
A kind of preparation method of the lithium ion battery water system anode sizing agent containing VGCF, includes the following steps：
(1) water-base cement and deionized water are mixed, carries out gluing；
(2) conductive black SP is added in the glue mixed solution in step (1), infiltration stirring is carried out, when stirring one section
Between after be added VGCF composite mortar be mixed；
(3) iron phosphate powder is added into the slurry after infiltrated stirring, carries out high-speed stirred；
(4) it continuously adds deionized water, slurry is adjusted into its viscosity to 2000~4000mPas after high-speed stirred.
Preferably, the mass ratio of the anode sizing agent is LiFePO4 LFP：Conductive black SP：Carbon nano-fiber VGCF=
94~96：0.5~1.5：0.5~1.5.
Preferably, gluing described in step (1) stirring revolution be 15~25rmp, dispersion revolving speed be 2000~
4000rmp；15~30min of mixing time.
Preferably, infiltrated described in step (2) stirring revolution be 10~45rmp, dispersion revolving speed be 1000~
4500rmp；Mixing time is 120~180min, and fineness is down to 12-15 μm.
Preferably, the conductivity of deionized water described in step (1)≤3 μ s/cm, amount of water are to make step (2) slurry afterwards
Solid content be 67~73wt%.
Preferably, the solute of water-base cement described in step (1) is polyacrylonitrile, and the content that solute accounts for water-base cement is
15wt%, solute account for 3~4wt% of all solids content in slurry.
Preferably, the revolution of high-speed stirred described in step (3) be 10~45rmp, dispersion revolving speed be 1000~
4500rmp；Mixing time is 10~90min, and fineness is down to 8~12 μm.
The beneficial effects of the present invention are：
Solvent of the present invention is deionized water, at low cost and environmentally friendly, and the present invention is stirred using wet process, and slurry good dispersion mentions
The electric conductivity of high slurry, and then the internal resistance of cell is reduced, high rate performance is improved, in addition, the identical solid content condition compared with dry method
Lower slurry viscosity is low, is effectively improved the processing performance of slurry.
Specific embodiment
To be best understood from the present invention, the present invention will be further described below with reference to examples, and following embodiment is only pair
The present invention is illustrated rather than is limited to it.
Embodiment 1
1, it mixes, is put into double using 1228g LA132 (solid content 15wt%) and 724g as the water of solvent first
Star blender stirs 15min with revolution speed 20rpm/min, rate of dispersion 3000rpm/min；Surveying its viscosity is 3100mPa
s。
2, then 26.3g SP is added in above-mentioned solution；Then with revolution speed 10rpm/min, rate of dispersion
1000rpm/min stirs 50min；Its fineness is surveyed lower than 15 μm.Again by 877.2g VGCF composite mortar after fineness is lower than 15 μm
(solid content 6wt%) is added in above-mentioned mixed liquor, then again with revolution speed 40rpm/min, rate of dispersion 4500rpm/min
High-speed stirred 100min；This stage solid content is 67%.
3, then the iron phosphate powder of 5000g is added in above-mentioned solution to the stirring for carrying out two stages；First to revolve
Speed 10rpm/min, rate of dispersion 1000rpm/min stirring 10min achieve the effect that infiltration, then with revolution speed 40rpm/
Min, rate of dispersion 4500rpm/min high-speed stirred 90min.
4, the water of 1438.1g is taken to be added thereto again, with revolution speed 40rpm/min, rate of dispersion 4500rpm/min high speed
60min is stirred, so that final solid content is 57%, viscosity 3300mPas.
Embodiment 2
1, it is mixed first using 1430g LA132 and 576g as the water of solvent, is put into double star blender with the speed that revolves
It spends 20rpm/min, rate of dispersion 3000rpm/min and stirs 15min；Surveying its viscosity is 3100mPas.
2, then 80g SP is added in above-mentioned solution；With revolution speed 10rpm/min, rate of dispersion 1000rpm/min
Stir 50min；Its fineness is surveyed lower than 15 μm.1166.6g VGCF composite mortar (solid content 6wt%) is added again above-mentioned mixed
It closes in liquid, then again with revolution speed 40rpm/min, rate of dispersion 4500rpm/min high-speed stirred 100min；This stage is solid
Content is 65%.
3, then the iron phosphate powder of 5000g is added in above-mentioned solution to the stirring for carrying out two stages；First to revolve
Speed 10rpm/min, rate of dispersion 1000rpm/min stirring 10min achieve the effect that infiltration, then with revolution speed 40rpm/
Min, rate of dispersion 4500rpm/min high-speed stirred 90min.
4, the water of 1326.9g is taken to be added thereto again, with revolution speed 40rpm/min, rate of dispersion 4500rpm/min high speed
60min is stirred, so that final solid content is 56%, viscosity 3100mPas.
Comparative example
1,5000g LiFePO4,52gSP, 700gVGCF composite mortar (solid content 6wt%) is taken to be added to double-planet and stir
It mixes in machine, 25min is stirred with revolution speed 25rpm/min, dispersion revolving speed 500rpm/min；
2,1123g polyacrylonitrile glue and 992g deionized water is taken to be added in double planetary mixer, with revolution speed
35rpm/min, dispersion revolving speed 4300rpm/min stir 150min；
3,1793g deionized water is taken to be added in double planetary mixer, revolution speed 35rpm/min, dispersion revolving speed
4300rpm/min stirs 60min, so that solid content is 55%, viscosity 4100.
Slurry prepared by Examples 1 to 2 and comparative example is tested for the property analysis, as a result as shown in table 1 below：
1 embodiment of table and comparative example size performance are analyzed
Lithium battery prepared by Examples 1 to 2 and comparative example is tested for the property analysis, as a result as shown in table 2 below：
2 embodiment of table and the performance evaluation of comparative example lithium battery
By the analysis of embodiment and comparative example as can be seen that being better than using the performance of the slurry of the stirring means of embodiment
The stability of the slurry of comparative example, i.e. slurry is improved, while improving the cycle performance of battery and reducing the internal resistance of cell.
Embodiment described above is only that preferred embodiments of the present invention will be described, not to model of the invention
It encloses and is defined, without departing from the spirit of the design of the present invention, those of ordinary skill in the art are to technical side of the invention
The various changes and improvements that case is made, should fall within the scope of protection determined by the claims of the present invention.
Claims (7)
1. a kind of preparation method of the lithium ion battery water system anode sizing agent containing VGCF, which is characterized in that include the following steps：
（1）Water-base cement and deionized water are mixed, gluing is carried out；
（2）Step is added in conductive black SP（1）In glue mixed solution in, infiltration stirring is carried out, after stirring a period of time
VGCF composite mortar is added to be mixed；
（3）Iron phosphate powder is added into the slurry after infiltrated stirring, carries out high-speed stirred；
（4）It continuously adds deionized water, slurry is adjusted into its viscosity to 2000 ~ 4000mPas after high-speed stirred.
2. a kind of preparation method of lithium ion battery water system anode sizing agent containing VGCF according to claim 1, feature
It is：The mass ratio of the anode sizing agent is LiFePO4 LFP：Conductive black SP：Carbon nano-fiber VGCF=94 ~ 96：0.5~
1.5：0.5~1.5.
3. a kind of preparation method of lithium ion battery water system anode sizing agent containing VGCF according to claim 1, feature
It is：Step（1）Described in gluing stirring revolution be 15 ~ 25rmp, dispersion revolving speed be 2000 ~ 4000rmp；Mixing time 15 ~
30min。
4. a kind of preparation method of lithium ion battery water system anode sizing agent containing VGCF according to claim 1, feature
It is：Step（2）Described in infiltrate stirring revolution be 10 ~ 45rmp, dispersion revolving speed be 1000 ~ 4500rmp；Mixing time is
120 ~ 180min, fineness are down to 12-15 μm.
5. a kind of preparation method of lithium ion battery water system anode sizing agent containing VGCF according to claim 1, feature
It is：Step（1）Described in deionized water conductivity≤3 μ s/cm, amount of water be make step（2）The solid content of slurry is afterwards
67~73wt%。
6. a kind of preparation method of lithium ion battery water system anode sizing agent containing VGCF according to claim 1, feature
It is：Step（1）Described in the solute of water-base cement be polyacrylonitrile, the content that solute accounts for water-base cement is 15wt%, and solute accounts for slurry
3 ~ 4wt% of middle all solids content.
7. a kind of preparation method of lithium ion battery water system anode sizing agent containing VGCF according to claim 1, feature
It is：Step（3）Described in high-speed stirred revolution be 10 ~ 45rmp, dispersion revolving speed be 1000 ~ 4500rmp；Mixing time is
10 ~ 90min, fineness are down to 8 ~ 12 μm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109860604A (en) * | 2019-01-28 | 2019-06-07 | 中盐安徽红四方锂电有限公司 | A kind of lithium iron phosphate dynamic battery and its manufacturing method |
| CN112447969A (en) * | 2019-09-04 | 2021-03-05 | 深圳市拓邦锂电池有限公司 | Water-based positive electrode slurry of lithium iron phosphate battery and preparation method thereof |
| CN112599715A (en) * | 2020-12-10 | 2021-04-02 | 浙江浙能中科储能科技有限公司 | Water-based battery positive electrode slurry for water-based battery and preparation process and method of pole piece |
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| CN102145329A (en) * | 2011-03-14 | 2011-08-10 | 中航锂电（洛阳）有限公司 | Slurry mixing process of lithium ion battery electrode slurry |
| CN103618063A (en) * | 2013-09-26 | 2014-03-05 | 奇瑞汽车股份有限公司 | Lithium ion power battery positive electrode slurry and slurry mixing method |
| CN104600246A (en) * | 2013-10-30 | 2015-05-06 | 上海悦达墨特瑞新材料科技有限公司 | Lithium ion battery electrode based on graphene and preparation method thereof |
| CN104681811A (en) * | 2013-11-27 | 2015-06-03 | 万向A一二三系统有限公司 | Preparation method of lithium iron phosphate positive electrode material slurry |
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2018
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102145329A (en) * | 2011-03-14 | 2011-08-10 | 中航锂电（洛阳）有限公司 | Slurry mixing process of lithium ion battery electrode slurry |
| CN103618063A (en) * | 2013-09-26 | 2014-03-05 | 奇瑞汽车股份有限公司 | Lithium ion power battery positive electrode slurry and slurry mixing method |
| CN104600246A (en) * | 2013-10-30 | 2015-05-06 | 上海悦达墨特瑞新材料科技有限公司 | Lithium ion battery electrode based on graphene and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109860604A (en) * | 2019-01-28 | 2019-06-07 | 中盐安徽红四方锂电有限公司 | A kind of lithium iron phosphate dynamic battery and its manufacturing method |
| CN112447969A (en) * | 2019-09-04 | 2021-03-05 | 深圳市拓邦锂电池有限公司 | Water-based positive electrode slurry of lithium iron phosphate battery and preparation method thereof |
| CN112599715A (en) * | 2020-12-10 | 2021-04-02 | 浙江浙能中科储能科技有限公司 | Water-based battery positive electrode slurry for water-based battery and preparation process and method of pole piece |
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Application publication date: 20181130 |