CN108199002A - A kind of high specific energy negative electrode of lithium ion battery and preparation method thereof - Google Patents
A kind of high specific energy negative electrode of lithium ion battery and preparation method thereof Download PDFInfo
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- CN108199002A CN108199002A CN201711264558.0A CN201711264558A CN108199002A CN 108199002 A CN108199002 A CN 108199002A CN 201711264558 A CN201711264558 A CN 201711264558A CN 108199002 A CN108199002 A CN 108199002A
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- negative electrode
- conductive agent
- copper foil
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- 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
- H01M4/13—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
- 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
- H01M4/1395—Processes of manufacture of 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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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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- 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 a kind of high specific energy negative electrode of lithium ion battery, include the component of following mass ratio：Negative electrode active material 70 98%, conductive agent one 0 5%, conductive agent 20 5% and bonding agent surplus, while the preparation method that cathode of lithium battery is prepared by the component is proposed, include the following steps：Negative electrode active material, conductive agent one, conductive agent two and bonding agent are added in deionized water by S1, are sufficiently stirred, obtain negative electrode slurry；It is 4 12um that above-mentioned negative electrode slurry coating machine is coated on thickness by S2, and porosity is 0% 50%, in 0 200um copper foil current collectors of pore size, and is dried；S3 by step S2 dry after copper foil current collector roll-in, cathode pole piece is made.Utilize the combination of different type conductive agent, and porous current collector, improve the adhesion strength of electrode, the effective adverse effect for counteracting volume expansion in silicium cathode charge and discharge process, simultaneously, the porous design of collector, improving silicium cathode expansion leads to pole piece buckling problems, reduces the dangerous risk of silicium cathode.
Description
Technical field
The present invention relates to technical field of lithium ion, it particularly relates to a kind of high specific energy negative electrode of lithium ion battery and
Preparation method.
Background technology
With the demand of fast development and consumer to its long course continuation mileage of new-energy automobile in recent years, high specific energy lithium
Ion battery becomes the inexorable trend of power battery development.Since high-energy-density lithium-ion-power cell needs to use newly
Battery system and new technique are higher than energy to provide, and therefore, matched manufacturing process is needed in existing lithium
Optimized on the basis of the manufacture craft of ion battery, with improve the safety of high specific energy lithium-ion-power cell,
Electrical property, and then meet the needs of high mileage, long-life new-energy automobile.
In terms of negative material, since the theoretical capacity of traditional business graphite is 372mAhg-1, it is difficult to meet high ratio
The demand of energy lithium ion battery, therefore searching higher seems especially urgent than energy material cathode.The theoretical of silicium cathode material holds
It measures as 4200mAhg-1, it is 10 times of business graphite or more, and de-/intercalation potential (0-0.45V) is approached with Graphite platform, because
This, is counted as the most potential high specific energy cathode alternative materials of commercial graphite.But the expansion issues of silicon itself, in charge and discharge
Volume change is 300% in the process, electrodes collapse can be caused to come off, in being designed in negative electrode, taken in,
Successfully manage the adverse effect that its expansion is brought.
For the problems in the relevant technologies, currently no effective solution has been proposed.
Invention content
For the above-mentioned technical problem in the relevant technologies, the present invention proposes a kind of high specific energy negative electrode of lithium ion battery and its system
Preparation Method can solve problems of the prior art.
To realize the above-mentioned technical purpose, the technical proposal of the invention is realized in this way：
A kind of high specific energy negative electrode of lithium ion battery includes the component of following mass ratio：Negative electrode active material 70-98%, conductive agent
One 0-5%, two 0-5% of conductive agent and bonding agent surplus.
Further, the negative electrode active material is nano-silicon, silica carbon, aoxidizes sub- silicon, graphite, silicon alloy, metal oxygen
One or more of compound, tin alloy.
Further, the conductive agent one and conductive agent two are carbonaceous material, the graphite type material of sheet, linear carbon fibre
Tie up one or more of material, graphene, metal powder, metallic fiber material and conducting polymer species material.
Further, the bonding agent is sodium carboxymethylcellulose, sodium alginate, pectin, polyacrylic acid, carboxyl butyronitrile rubber
One or more of glue and carboxyl polyimides.
The invention also provides a kind of preparation methods of high specific energy negative electrode of lithium ion battery, include the following steps：
Negative electrode active material, conductive agent one, conductive agent two and bonding agent are added in deionized water by S1, are sufficiently stirred, obtained
Negative electrode slurry；
Above-mentioned negative electrode slurry is 4-12um, porosity 0%-50%, pore size 0- coated on thickness with coating machine by S2
In 200um copper foil current collectors, and dried；
S3 by step S2 dry after copper foil current collector roll-in, cathode pole piece is made.
Further, the copper foil current collector is rolled copper foil, electrolytic copper foil；In surface smooth foils, rough surface foil
It is one or more of.
Further, the copper foil current collector thickness of the coating negative electrode slurry is 100-300um.
Further, the copper foil current collector thickness after the roll-in is 10-80um.
Beneficial effects of the present invention：Combination and porous current collector using different type conductive agent, on the one hand improve
The adhesion strength of electrode effectively counteracts the adverse effect of volume expansion in silicium cathode charge and discharge process, on the other hand, afflux
The porous design of body, effectively improving silicium cathode expansion leads to pole piece buckling problems, reduces the uneasiness of silicium cathode to a certain degree
Full blast danger.
Specific embodiment
The technical solution in the embodiment of the present invention will be clearly and completely described below, it is clear that described implementation
Example is only part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's all other embodiments obtained, shall fall within the protection scope of the present invention.
A kind of high specific energy negative electrode of lithium ion battery according to embodiments of the present invention includes the component of following mass ratio：
Negative electrode active material 70-98%, one 0-5% of conductive agent, two 0-5% of conductive agent and bonding agent surplus.
In one particular embodiment of the present invention, the negative electrode active material be nano-silicon, silica carbon, the sub- silicon of oxidation,
One or more of graphite, silicon alloy, metal oxide, tin alloy.
In one particular embodiment of the present invention, the conductive agent one and conductive agent two be carbonaceous material, the stone of sheet
One in black class material, linear carbon fibre material, graphene, metal powder, metallic fiber material and conducting polymer species material
Kind is several.
In one particular embodiment of the present invention, the bonding agent for sodium carboxymethylcellulose, sodium alginate, pectin,
One or more of polyacrylic acid, carboxy nitrile rubber and carboxyl polyimides.
The invention also provides a kind of preparation methods of high specific energy negative electrode of lithium ion battery, include the following steps：
Negative electrode active material, conductive agent one, conductive agent two and bonding agent are added in deionized water by S1, are sufficiently stirred, obtained
Negative electrode slurry；
Above-mentioned negative electrode slurry is 4-12um, porosity 0%-50%, pore size 0- coated on thickness with coating machine by S2
In 200um copper foil current collectors, and dried；
S3 by step S2 dry after copper foil current collector roll-in, cathode pole piece is made.
In one particular embodiment of the present invention, the copper foil current collector is rolled copper foil, electrolytic copper foil；Surface is smooth
One or more of foil, rough surface foil.
In one particular embodiment of the present invention, the copper foil current collector thickness of the coating negative electrode slurry is 100-
300um。
In one particular embodiment of the present invention, the copper foil current collector thickness after the roll-in is 10-80um.
In order to facilitate the above-mentioned technical proposal for understanding the present invention, below by way of specific embodiment and comparative example to the present invention's
Above-mentioned technical proposal is described in detail.
Embodiment one
Negative electrode active material is silica carbon, and conductive agent one and conductive agent two are SP and VGCF, and bonding agent is CMC and SBR.
By silica carbon, SP, VGCF, CMC, SBR according to 88：3：3：3.5：2.5 mass ratio adds in appropriate amount of deionized water,
It is sufficiently stirred, prepares slurry, slurry solid content 35-50%, slurry viscosity 4000-6000mPas, the slurry that will be prepared
Material coating machine, it is thick coated on 8um with gap 150um, it in the calendered surface smooth copper foil of porosity 0%, and dries, will apply
The copper foil roll-in covered is made cathode pole piece, measures its peel force, the full batteries of 2Ah, anode is made with this pole piece to 60um thickness
With tertiary cathode, it is formulated as NCM523：sp：KS-6：PVDF=88：2：2：8, electrolyte selects 1MLiPF6inEC/EMC/DEC
(1:1:1v/v)+2%VC, diaphragm select 25umPP diaphragms.The electrochemical Characterizations such as loop test are carried out to full battery.
Embodiment two
Negative electrode active material is silica carbon, and conductive agent one and conductive agent two are SP and SFG, and bonding agent is CMC and SBR.
By silica carbon, SP, SFG, CMC, SBR according to 88：3：3：3.5：2.5 mass ratio adds in appropriate amount of deionized water,
It is sufficiently stirred, prepares slurry, slurry solid content 35-50%, slurry viscosity 4000-6000mPas, the slurry that will be prepared
Material coating machine, with gap 150um, coated on 8um thickness, porosity 20%, in the calendered surface smooth copper foil of aperture 30um, and
Drying by coated copper foil roll-in to 60um thickness, is made cathode pole piece, measures its peel force, it is entirely electric that 2Ah is made with this pole piece
Pond, anode matching tertiary cathode, is formulated as NCM523：sp：KS-6：PVDF=88：2：2：8, electrolyte is selected
1MLiPF6inEC/EMC/DEC(1:1:1v/v)+2%VC, diaphragm select 25umPP diaphragms.Loop test etc. is carried out to full battery
Electrochemical Characterization.
Embodiment three
Negative electrode active material is silica carbon, and conductive agent one and conductive agent two are SP and CNT, and bonding agent is CMC and SBR.
By silica carbon, SP, CNT, CMC, SBR according to 88：3：3：3.5：2.5 mass ratio adds in appropriate amount of deionized water,
It is sufficiently stirred, prepares slurry, slurry solid content 35-50%, slurry viscosity 4000-6000mPas, the slurry that will be prepared
Material coating machine, with gap 150um, coated on 6um thickness, porosity 10%, in the calendered surface smooth copper foil of aperture 30um, and
Drying by coated copper foil roll-in to 60um thickness, is made cathode pole piece, measures its peel force, it is entirely electric that 2Ah is made with this pole piece
Pond, anode matching tertiary cathode, is formulated as NCM523：sp：KS-6：PVDF=88：2：2：8, electrolyte is selected
1MLiPF6inEC/EMC/DEC(1:1:1v/v)+2%VC, diaphragm select 25umPP diaphragms.Loop test etc. is carried out to full battery
Electrochemical Characterization.
Comparative example one
Negative electrode active material is silica carbon, and conductive agent one and conductive agent two are SP and KS-6, and bonding agent is CMC and SBR.
By silica carbon, SP, KS-6, CMC, SBR according to 88：3：3：3.5：2.5 mass ratio adds in appropriate amount of deionized water,
It is sufficiently stirred, prepares slurry, slurry solid content 35-50%, slurry viscosity 4000-6000mPas, the slurry that will be prepared
Material coating machine, it is thick coated on 10um with gap 150um, it in the calendered surface smooth copper foil of porosity 0%, and dries, will apply
The copper foil roll-in covered is made cathode pole piece, measures its peel force, the full batteries of 2Ah, anode is made with this pole piece to 60um thickness
With tertiary cathode, it is formulated as NCM523：sp：KS-6：PVDF=88：2：2：8, electrolyte selects 1MLiPF6inEC/EMC/DEC
(1:1:1v/v)+2%VC, diaphragm select 25umPP diaphragms, and the electrochemical Characterizations such as loop test are carried out to full battery.
Comparative example two
Negative electrode active material is silica carbon, and conductive agent one and conductive agent two are SP and VGCF, and bonding agent is CMC and SBR.
By silica carbon, SP, VGCF, CMC, SBR according to 88：3：3：3.5：2.5 mass ratio adds in appropriate amount of deionized water,
It is sufficiently stirred, prepares slurry, slurry solid content 35-50%, slurry viscosity 4000-6000mPas.The slurry that will be prepared
Material coating machine, with gap 150um, coated on 8um thickness, porosity 20%, in the calendered surface smooth copper foil of aperture 100um,
And it dries.By coated copper foil roll-in to 60um thickness, cathode pole piece is made, measures its peel force, it is complete that 2Ah is made with this pole piece
Battery, anode matching tertiary cathode, is formulated as NCM523：sp：KS-6：PVDF=88：2：2：8, electrolyte is selected
1MLiPF6inEC/EMC/DEC(1:1:1v/v)+2%VC, diaphragm select 25umPP diaphragms, and loop test etc. is carried out to full battery
Electrochemical Characterization.
Comparative example three
Negative electrode active material is silica carbon, and conductive agent one and conductive agent two are SP and SFG, and bonding agent is CMC and SBR.
By silica carbon, SP, SFG, CMC, SBR according to 88：3：3：3.5：2.5 mass ratio adds in appropriate amount of deionized water,
It is sufficiently stirred, prepares slurry, slurry solid content 35-50%, slurry viscosity 4000-6000mPas, the slurry that will be prepared
Material coating machine, it is thick coated on 8um with gap 150um, porosity 30%, in the calendered surface smooth copper foil of aperture 30um,
And dry, by coated copper foil roll-in to 60um thickness, cathode pole piece is made, measures its peel force, it is complete that 2Ah is made with this pole piece
Battery, anode matching tertiary cathode, is formulated as NCM523：sp：KS-6：PVDF=88：2：2：8, electrolyte is selected
1MLiPF6inEC/EMC/DEC(1:1:1v/v)+2%VC, diaphragm select 25umPP diaphragms.Loop test etc. is carried out to full battery
Electrochemical Characterization.
Embodiment and comparative example test result is subjected to Macro or mass analysis, is listed in Table 1 below:
Table 1：Results of property summary sheet
From 1 data of table it is found that a kind of high specific energy negative electrode of lithium ion battery of the present invention, utilizes different type conductive agent
Combination and porous current collector, on the one hand improve the adhesion strength of electrode, effectively counteract silicium cathode charge and discharge process
The adverse effect of middle volume expansion.On the other hand, the porous design of collector, effectively improving silicium cathode expansion leads to pole piece pleat
Wrinkle problem reduces the dangerous risk of silicium cathode to a certain degree.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
With within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention god.
Claims (8)
1. a kind of high specific energy negative electrode of lithium ion battery, which is characterized in that include the component of following mass ratio：Negative electrode active material
70-98%, one 0-5% of conductive agent, two 0-5% of conductive agent and bonding agent surplus.
A kind of 2. high specific energy negative electrode of lithium ion battery according to claim 1, which is characterized in that the negative electrode active material
For one or more of nano-silicon, silica carbon, the sub- silicon of oxidation, graphite, silicon alloy, metal oxide, tin alloy.
3. a kind of high specific energy negative electrode of lithium ion battery according to claim 1, which is characterized in that the conductive agent one and lead
Electric agent two is carbonaceous material, the graphite type material of sheet, linear carbon fibre material, graphene, metal powder, metallic fiber material
One or more of with conducting polymer species material.
4. a kind of high specific energy negative electrode of lithium ion battery according to claim 1, which is characterized in that the bonding agent is carboxylic first
One or more of base sodium cellulosate, sodium alginate, pectin, polyacrylic acid, carboxy nitrile rubber and carboxyl polyimides.
5. a kind of preparation method of high specific energy negative electrode of lithium ion battery, which is characterized in that include the following steps：
Negative electrode active material, conductive agent one, conductive agent two and bonding agent are added in deionized water by S1, are sufficiently stirred, obtained
Negative electrode slurry；
Above-mentioned negative electrode slurry is 4-12um, porosity 0%-50%, pore size 0-200um coated on thickness with coating machine by S2
In copper foil current collector, and dried；
S3 by step S2 dry after copper foil current collector roll-in, cathode pole piece is made.
A kind of 6. preparation method of high specific energy negative electrode of lithium ion battery according to claim 5, which is characterized in that the copper
Foil collector is rolled copper foil, electrolytic copper foil；One or more of surface smooth foils, rough surface foil.
A kind of 7. preparation method of high specific energy negative electrode of lithium ion battery according to claim 6, which is characterized in that the painting
The copper foil current collector thickness for covering negative electrode slurry is 100-300um.
A kind of 8. preparation method of high specific energy negative electrode of lithium ion battery according to claim 7, which is characterized in that the roller
Copper foil current collector thickness after pressure is 10-80um.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109599532A (en) * | 2018-12-10 | 2019-04-09 | 江苏天鹏电源有限公司 | A kind of pulping process of silicium cathode material ternary lithium battery |
| CN110767872A (en) * | 2019-10-30 | 2020-02-07 | 桑德新能源技术开发有限公司 | Silicon-carbon negative plate, preparation method thereof and battery |
| CN111525136A (en) * | 2020-04-30 | 2020-08-11 | 青岛科技大学 | Composite binder and application thereof in silicon cathode of lithium ion battery |
| CN112331832A (en) * | 2020-11-06 | 2021-02-05 | 珠海冠宇电池股份有限公司 | Silicon negative plate, preparation method thereof and lithium ion battery |
| CN113497224A (en) * | 2020-04-01 | 2021-10-12 | 深圳格林德能源集团有限公司 | Silicon-carbon negative pole piece of lithium ion battery |
| CN114551877A (en) * | 2021-10-09 | 2022-05-27 | 万向一二三股份公司 | Lithium battery negative plate and preparation method thereof |
| CN117239064A (en) * | 2023-11-16 | 2023-12-15 | 瑞浦兰钧能源股份有限公司 | Silicon negative electrode piece and preparation method and application thereof |
-
2017
- 2017-12-05 CN CN201711264558.0A patent/CN108199002A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109599532A (en) * | 2018-12-10 | 2019-04-09 | 江苏天鹏电源有限公司 | A kind of pulping process of silicium cathode material ternary lithium battery |
| CN110767872A (en) * | 2019-10-30 | 2020-02-07 | 桑德新能源技术开发有限公司 | Silicon-carbon negative plate, preparation method thereof and battery |
| CN113497224A (en) * | 2020-04-01 | 2021-10-12 | 深圳格林德能源集团有限公司 | Silicon-carbon negative pole piece of lithium ion battery |
| CN111525136A (en) * | 2020-04-30 | 2020-08-11 | 青岛科技大学 | Composite binder and application thereof in silicon cathode of lithium ion battery |
| CN112331832A (en) * | 2020-11-06 | 2021-02-05 | 珠海冠宇电池股份有限公司 | Silicon negative plate, preparation method thereof and lithium ion battery |
| CN114551877A (en) * | 2021-10-09 | 2022-05-27 | 万向一二三股份公司 | Lithium battery negative plate and preparation method thereof |
| CN114551877B (en) * | 2021-10-09 | 2023-07-07 | 万向一二三股份公司 | Lithium battery negative plate and preparation method thereof |
| CN117239064A (en) * | 2023-11-16 | 2023-12-15 | 瑞浦兰钧能源股份有限公司 | Silicon negative electrode piece and preparation method and application thereof |
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