CN106299247A - A kind of lithium ion battery aqueous silicon-base negative plate and preparation method thereof - Google Patents
A kind of lithium ion battery aqueous silicon-base negative plate and preparation method thereof Download PDFInfo
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- CN106299247A CN106299247A CN201610851257.7A CN201610851257A CN106299247A CN 106299247 A CN106299247 A CN 106299247A CN 201610851257 A CN201610851257 A CN 201610851257A CN 106299247 A CN106299247 A CN 106299247A
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- silicon
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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
- H01M4/134—Electrodes based on metals, Si or alloys
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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
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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 invention discloses a kind of lithium ion battery aqueous silicon-base negative plate and preparation method thereof, including battery cathode collector and silicon-based anode, it is provided with conductive coating between described battery cathode collector and silicon-based anode, described conductive coating includes following raw material by mass percentage: SBR emulsion 5% 40%, carboxymethyl cellulose 1% 15%, conductive carbon black 10% 90%, solvent 20% 80%；The mass percent sum of above-mentioned raw materials is 100%.The aqueous silicon-base negative plate of the present invention is provided with coating between Copper Foil and silicon-based anode, by designing brand-new coating formula and optimizing preparation technology, silicon-based anode sheet is made not affect active material lithium ion deinsertion, prevention active substance contacts with collector, alleviate silicon-based anode pole piece during charge and discharge battery splash rise after negative plate and collector peel off, and then solve to lose electrical contact, alleviate and cause capacity to be decayed rapidly and the situation of cycle performance deterioration.
Description
Technical field
The present invention relates to a kind of lithium ion battery aqueous silicon-base negative plate and preparation method thereof, belong to lithium ion battery technology
Field.
Background technology
At present, whole world lithium cell cathode material is still based on native graphite and Delanium, and within 2015, accounting reaches 80%
Above.New material such as silicon-carbon (Si/C) negative material yield is also quickly increasing, the high speed of Portable movable electronic equipment
Development have stimulated the demand of market lithium ion battery higher to lightweight low capacity and energy density greatly.Business at present
Industry lithium ion battery is all using carbon-based material as negative pole, but owing to the reversible capacity of graphite cathode only has 372mAh/g
(LiC6), the development of following lithium ion battery is seriously limited, so research and development lithium ion battery negative material of future generation becomes new
Focus.It is found that the constant current theoretical capacity of silicon in Li22Si5 has reached 4200mAh/g, be the lithium of great exploitation potential
Ion negative material.But the shortcoming of this material is the most prominent: can expand at embedding and removing process in which materials volume, silicon
Removal lithium embedded reaction by with big change in volume (～300%), cause destruction and the machinery efflorescence of material structure, cause electrode
Storeroom and electrode material separate with collector, and then lose electrical contact, cause capacity to be decayed rapidly, and cycle performance deteriorates.
While obtaining high power capacity, how to improve the cycle performance of Si base negative material, be the research emphasis of Si sill.
Summary of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of lithium ion battery aqueous silicon-base negative plate and
Its preparation method, this aqueous silicon-base negative plate is while obtaining high power capacity, it is possible to increase the cycle performance of Si base negative material.
Realize the purpose of the present invention to reach by adopting the following technical scheme that:
A kind of lithium ion battery aqueous silicon-base negative plate, including battery cathode collector and silicon-based anode, it is characterised in that
Being provided with conductive coating between described battery cathode collector and silicon-based anode, described conductive coating includes by mass percentage
Following raw material: SBR emulsion 5%-40%, carboxymethyl cellulose 1%-15%, conductive carbon black 10%-90%, solvent
20%-80%；The mass percent sum of above-mentioned raw materials is 100%.
As preferably, described conductive coating includes following raw material by mass percentage: SBR emulsion 5%-
40%, carboxymethyl cellulose 1%-11%, conductive carbon black 10%-74%, solvent 20%-70%；The percent mass of above-mentioned raw materials
It is 100% than sum.
As preferably, described conductive coating includes following raw material by mass percentage: SBR emulsion 6%-
11%, carboxymethyl cellulose 2%-11%, conductive carbon black 25%-35%, solvent 45%-60%；The percent mass of above-mentioned raw materials
It is 100% than sum.
As preferably, described conductive coating includes following raw material by mass percentage: SBR emulsion 11%, carboxylic
Methylcellulose 11%, conductive carbon black 33%, solvent 45%.
As preferably, the solid content of described SBR emulsion is 50%.
As preferably, the thickness of described coating is 2-5 μm.
As preferably, described solvent is deionized water.
As preferably, described battery cathode collector is Copper Foil.
The preparation method of a kind of lithium ion battery aqueous silicon-base negative plate, it is characterised in that comprise the following steps:
1) carboxymethyl cellulose of formula ratio is dissolved in the solvent of formula ratio, stirs 1-10h under vacuum, obtain
Uniform first solution；
2) conductive carbon black of formula ratio is added step 1) in the first solution of obtaining, stir 1-12h under vacuum,
Obtain uniform first mixture；
3) SBR emulsion of formula ratio is added step 2) in the first mixture of obtaining, stir under vacuum
0.5-2h, obtains uniform second mixture；
4) by step 3) the second mixture of obtaining is coated in the surface of battery cathode collector uniformly, consolidated after drying
The conductive coating of state, the thickness of conductive coating is 2-5 μm；
5) in step 4) obtain one layer of silicon based anode material of surface-coated of conductive coating, obtain half with silicon-based anode
Finished product negative plate；
6) roll squeezer is used by 5) semi-finished product negative plate entirety pressing one-time that step obtains, i.e. obtain lithium-ion electric water
Property silicon-based anode sheet.
As preferably, step 5) in the coating processes of silicon based anode material be according to 18650-3000mAh lithium ion battery
The requirement of energy density of preparation technology carry out.
The beneficial effects of the present invention is:
The aqueous silicon-base negative plate of the present invention is provided with coating between Copper Foil and silicon-based anode, by designing brand-new coating
Formula and optimization preparation technology so that silicon-based anode sheet does not affect active material lithium ion deinsertion, stops active substance and afflux
The contact of body, alleviate silicon-based anode pole piece during charge and discharge battery splash rise after negative plate and collector peel off, and then solve to lose
Go electrical contact, alleviate and cause capacity to be decayed rapidly and the situation of cycle performance deterioration.The aqueous silicon-base negative plate of the present invention is used for
18650-3000mAh battery process makes 0.3C and fills 0.5C discharge cycles 1000 weeks, and capability retention is up to more than 80%.
Accompanying drawing explanation
Fig. 1 is the battery cycle life figure of the embodiment of the present invention 1；
Fig. 2 is the battery dissection and analysis picture of the embodiment of the present invention 1；
Fig. 3 is the battery cycle life figure of comparative example 1 of the present invention；
Fig. 4 is the battery dissection and analysis picture of comparative example 1 of the present invention；
Fig. 5 is the battery cycle life figure of comparative example 2 of the present invention；
Fig. 6 is the battery dissection and analysis picture of comparative example 2 of the present invention.
Detailed description of the invention
Below, in conjunction with accompanying drawing and detailed description of the invention, the present invention is described further:
Embodiment 1-4:
A kind of lithium ion battery aqueous silicon-base negative plate, including battery cathode collector and silicon-based anode, described battery is born
Being provided with conductive coating between pole collector and silicon-based anode, described conductive coating includes following raw material by mass percentage:
Solid content is the SBR emulsion of 50%, carboxymethyl cellulose, conductive carbon black, deionized water.Described battery cathode collector
For Copper Foil, concrete formula composition is shown in Table 1.
Table 1
The preparation method of a kind of lithium ion battery aqueous silicon-base negative plate, comprises the following steps:
1) carboxymethyl cellulose of formula ratio is dissolved in the solvent of formula ratio, stirs 1-10h under vacuum, obtain
Uniform first solution；
2) conductive carbon black of formula ratio is added step 1) in the first solution of obtaining, stir 1-12h under vacuum,
Obtain uniform first mixture；
3) SBR emulsion of formula ratio is added step 2) in the first mixture of obtaining, stir under vacuum
0.5-2h, obtains uniform second mixture；
4) by step 3) the second mixture of obtaining is coated in the surface of battery cathode collector uniformly, consolidated after drying
The conductive coating of state, the thickness of conductive coating is 2-5 μm；
5) in step 4) obtain one layer of silicon based anode material of surface-coated of conductive coating, obtain half with silicon-based anode
Finished product negative plate；The coating processes of silicon based anode material is the energy of the preparation technology according to 18650-3000mAh lithium ion battery
The requirement of metric density is carried out；
6) roll squeezer is used by 5) semi-finished product negative plate entirety pressing one-time that step obtains, i.e. obtain lithium-ion electric water
Property silicon-based anode sheet.
Lithium ion battery aqueous silicon-base negative plate embodiment 1 obtained uses 18650-3000mAh technique to make
Become experimental cell to carry out test comparison: 0.3C charging 0.5C discharge cycles data and see Fig. 1 and Fig. 2 as follows.Battery charging and discharging circulates
1000 conservation rates, more than 80% (such as Fig. 1), find negative active core-shell material and collector adhesive property after dissecting cycle battery
Well, without dropping situations (such as Fig. 2).
The lithium ion battery aqueous silicon-base negative plate that embodiment 2-4 obtains uses 18650-3000mAh technique to make
Becoming experimental cell to carry out test comparison, result is similar with the test result of embodiment 1, does not repeats them here.
Comparative example 1-2:
A kind of lithium ion battery aqueous silicon-base negative plate, including battery cathode collector and silicon-based anode, described battery is born
Being provided with conductive coating between pole collector and silicon-based anode, described conductive coating includes following raw material by mass percentage:
Solid content is the SBR emulsion of 50%, carboxymethyl cellulose, conductive carbon black, deionized water.Described battery cathode collector
For Copper Foil, concrete formula composition is shown in Table 2.
Table 2
The preparation method of a kind of lithium ion battery aqueous silicon-base negative plate, comprises the following steps:
1) carboxymethyl cellulose of formula ratio is dissolved in the solvent of formula ratio, stirs 1-10h under vacuum, obtain
Uniform first solution；
2) conductive carbon black of formula ratio is added step 1) in the first solution of obtaining, stir 1-12h under vacuum,
Obtain uniform first mixture；
3) SBR emulsion of formula ratio is added step 2) in the first mixture of obtaining, stir under vacuum
0.5-2h, obtains uniform second mixture；
4) by step 3) the second mixture of obtaining is coated in the surface of battery cathode collector uniformly, consolidated after drying
The conductive coating of state, the thickness of conductive coating is 2-5 μm；
5) in step 4) obtain one layer of silicon based anode material of surface-coated of conductive coating, obtain half with silicon-based anode
Finished product negative plate；The coating processes of silicon based anode material is the energy of the preparation technology according to 18650-3000mAh lithium ion battery
The requirement of metric density is carried out；
6) roll squeezer is used by 5) semi-finished product negative plate entirety pressing one-time that step obtains, i.e. obtain lithium-ion electric water
Property silicon-based anode sheet.
Lithium ion battery aqueous silicon-base negative plate comparative example 1 obtained uses 18650-3000mAh technique to carry out
Be fabricated to experimental cell carry out test comparison: 0.3C charging 0.5C discharge cycles data see Fig. 3 and Fig. 4 as follows.Battery charge and discharge follows
300 conservation rates of ring are less than 80% (such as Fig. 3), are the discovery that negative active core-shell material comes off (such as Fig. 4) after dissecting cycle battery, electricity
After the circulation of pond, internal resistance rises, and causes cycle performance poor.
Lithium ion battery aqueous silicon-base negative plate comparative example 2 obtained uses 18650-3000mAh technique to carry out
Be fabricated to experimental cell carry out test comparison: 0.3C charging 0.5C discharge cycles data see Fig. 5 and Fig. 6 as follows.Battery charging and discharging
Circulate 180 conservation rates and be less than 80% (such as Fig. 5), after cycle battery is dissected, be the discovery that negative active core-shell material comes off (such as Fig. 6),
The internal resistance of cell rises, and causes cycle performance of battery poor.
For a person skilled in the art, can technical scheme as described above and design, make other each
Plant corresponding change and deformation, and all these changes and deforms the protection model that all should belong to the claims in the present invention
Within enclosing.
Claims (10)
1. a lithium ion battery aqueous silicon-base negative plate, including battery cathode collector and silicon-based anode, it is characterised in that institute
State and between battery cathode collector and silicon-based anode, be provided with conductive coating, described conductive coating include by mass percentage as
Lower raw material: SBR emulsion 5%-40%, carboxymethyl cellulose 1%-15%, conductive carbon black 10%-90%, solvent 20%-
80%；The mass percent sum of above-mentioned raw materials is 100%.
Lithium ion battery aqueous silicon-base negative plate the most according to claim 1, it is characterised in that described conductive coating includes
Following raw material by mass percentage: SBR emulsion 5%-40%, carboxymethyl cellulose 1%-11%, conductive carbon black
10%-74%, solvent 20%-70%；The mass percent sum of above-mentioned raw materials is 100%.
Lithium ion battery aqueous silicon-base negative plate the most according to claim 2, it is characterised in that described conductive coating includes
Following raw material by mass percentage: SBR emulsion 6%-11%, carboxymethyl cellulose 2%-11%, conductive carbon black
25%-35%, solvent 45%-60%；The mass percent sum of above-mentioned raw materials is 100%.
Lithium ion battery aqueous silicon-base negative plate the most according to claim 3, it is characterised in that described conductive coating includes
Following raw material by mass percentage: SBR emulsion 11%, carboxymethyl cellulose 11%, conductive carbon black 33%, solvent
45%.
Lithium ion battery aqueous silicon-base negative plate the most according to claim 1, it is characterised in that described SBR emulsion
Solid content be 50%.
Lithium ion battery aqueous silicon-base negative plate the most according to claim 1, it is characterised in that the thickness of described coating is
2-5μm。
Lithium ion battery aqueous silicon-base negative plate the most according to claim 1, it is characterised in that described solvent is deionization
Water.
Lithium ion battery aqueous silicon-base negative plate the most according to claim 1, it is characterised in that described battery cathode afflux
Body is Copper Foil.
9. according to the preparation method of the lithium ion battery aqueous silicon-base negative plate described in claim 1-8 any one, its feature
It is, comprises the following steps:
1) carboxymethyl cellulose of formula ratio is dissolved in the solvent of formula ratio, stirs 1-10h under vacuum, obtain uniformly
The first solution；
2) conductive carbon black of formula ratio is added step 1) in the first solution of obtaining, stir 1-12h under vacuum, obtain
Uniform first mixture；
3) SBR emulsion of formula ratio is added step 2) in the first mixture of obtaining, stir 0.5-under vacuum
2h, obtains uniform second mixture；
4) by step 3) the second mixture of obtaining is coated in the surface of battery cathode collector uniformly, obtains solid-state after drying
Conductive coating, the thickness of conductive coating is 2-5 μm；
5) in step 4) obtain one layer of silicon based anode material of surface-coated of conductive coating, obtain the semi-finished product with silicon-based anode
Negative plate；
6) roll squeezer is used by 5) semi-finished product negative plate entirety pressing one-time that step obtains, i.e. obtain lithium ion battery aqueous silicon
Base negative plate.
The preparation method of lithium ion battery aqueous silicon-base negative plate the most according to claim 9, it is characterised in that step
5) in, the coating processes of silicon based anode material is the energy density of the preparation technology according to 18650-3000mAh lithium ion battery
Requirement is carried out.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109638223A (en) * | 2018-12-05 | 2019-04-16 | 宁波维科新能源科技有限公司 | A kind of silicon-based anode of lithium ion battery and its preparation method and application |
| CN111224057A (en) * | 2018-11-23 | 2020-06-02 | 广州汽车集团股份有限公司 | Current collector for silicon-based negative electrode, preparation method of current collector and silicon-based negative electrode piece |
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| CN101373826A (en) * | 2007-08-24 | 2009-02-25 | 比亚迪股份有限公司 | Silicium cathode and lithium ion secondary battery containing the same, and method for preparing the same |
| CN105870400A (en) * | 2015-01-20 | 2016-08-17 | 深圳市比克电池有限公司 | Lithium ion battery negative pole piece, production method thereof, and lithium ion battery |
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2016
- 2016-09-26 CN CN201610851257.7A patent/CN106299247A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101373826A (en) * | 2007-08-24 | 2009-02-25 | 比亚迪股份有限公司 | Silicium cathode and lithium ion secondary battery containing the same, and method for preparing the same |
| CN105870400A (en) * | 2015-01-20 | 2016-08-17 | 深圳市比克电池有限公司 | Lithium ion battery negative pole piece, production method thereof, and lithium ion battery |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111224057A (en) * | 2018-11-23 | 2020-06-02 | 广州汽车集团股份有限公司 | Current collector for silicon-based negative electrode, preparation method of current collector and silicon-based negative electrode piece |
| CN109638223A (en) * | 2018-12-05 | 2019-04-16 | 宁波维科新能源科技有限公司 | A kind of silicon-based anode of lithium ion battery and its preparation method and application |
| CN109638223B (en) * | 2018-12-05 | 2022-08-19 | 宁波维科新能源科技有限公司 | Silicon-based negative electrode of lithium ion battery and preparation method and application thereof |
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