CN104953124A - Binder of silicon-carbide negative electrode material, negative electrode plate of silicon-carbide battery, manufacturing method of negative electrode plate, and silicon-carbide battery - Google Patents
Binder of silicon-carbide negative electrode material, negative electrode plate of silicon-carbide battery, manufacturing method of negative electrode plate, and silicon-carbide battery Download PDFInfo
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- CN104953124A CN104953124A CN201410115297.6A CN201410115297A CN104953124A CN 104953124 A CN104953124 A CN 104953124A CN 201410115297 A CN201410115297 A CN 201410115297A CN 104953124 A CN104953124 A CN 104953124A
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- 239000011230 binding agent Substances 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title abstract 10
- 229910010271 silicon carbide Inorganic materials 0.000 title abstract 10
- 239000007773 negative electrode material Substances 0.000 title abstract 3
- 229920000642 polymer Polymers 0.000 claims abstract description 37
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 35
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 24
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 69
- 239000010406 cathode material Substances 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 25
- 239000007767 bonding agent Substances 0.000 claims description 23
- 239000006258 conductive agent Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 229920002125 Sokalan® Polymers 0.000 claims description 10
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 9
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 9
- 239000004584 polyacrylic acid Substances 0.000 claims description 9
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 9
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 9
- 230000032050 esterification Effects 0.000 claims description 8
- 238000005886 esterification reaction Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 6
- 235000010413 sodium alginate Nutrition 0.000 claims description 6
- 239000000661 sodium alginate Substances 0.000 claims description 6
- 229940005550 sodium alginate Drugs 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052744 lithium Inorganic materials 0.000 abstract description 17
- 239000002245 particle Substances 0.000 abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 11
- 229910052710 silicon Inorganic materials 0.000 abstract description 11
- 239000010703 silicon Substances 0.000 abstract description 11
- 230000008859 change Effects 0.000 abstract description 3
- 229920003023 plastic Polymers 0.000 abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 12
- 238000000227 grinding Methods 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910013872 LiPF Inorganic materials 0.000 description 6
- 101150058243 Lipf gene Proteins 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 6
- 230000004087 circulation Effects 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- -1 ethyl carbonate ester Chemical class 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910004691 OPF3 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000003660 carbonate based solvent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a binder of a silicon-carbide negative electrode material, a negative electrode plate of the silicon-carbide battery, a manufacturing method of the negative electrode plate, and the silicon-carbide battery. The binder of the silicon-carbide negative electrode material comprises polymer containing hydroxyl groups and polymer containing carboxyl groups. According to the negative electrode plate of the silicon-carbide battery, the binder of the negative electrode plate is cross-linked to form a net-shaped structure by utilizing the characteristic that the hydroxyl groups and the carboxyl groups dehydrate under high temperature, and the negative electrode plate has excellent rigidity and excellent caking property. The stable specific capacity of the negative electrode plate of the silicon-carbide battery prepared by the binder is greater than 600mAh/g, the initial efficiency is greater than 75%, silicon-based active particles in the silicon-carbide battery are uniformly distributed in a three-dimensional network of the binder, and the change of the thickness of the plate is inhibited by the rigid structure of the binder. The volume of the silicon-based active particles in the plate can increase during a lithium embedding process, the increased volume is mainly positioned in the original gap of the plate, and the process is realized mainly depending on the plastic deformation of the silicon-based active particles.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of binding agent of silicon-carbon cathode material, the cathode pole piece and preparation method thereof of silicon-carbon battery, silicon-carbon battery.
Background technology
At present, the lithium ion battery of production and application mainly adopts graphite negative electrodes material, but the embedding lithium capacity of the theory of graphite is 372mAh/g, and reality reaches 370mAh/g, therefore, graphite negative electrodes material on capacity almost without room for promotion.
The nearly more than ten years, various novel high power capacity and high magnification negative material are developed, wherein silica-base material becomes study hotspot due to its high specific discharge capacity (theoretical specific capacity of silicon is 4200mAh/g), but this material in doff lithium process along with serious volumetric expansion and contraction, cause the electroactive material powder of detached on electrode, finally cause capacity attenuation.Due to the composite construction of the complexity that the pole piece of lithium ion battery is made up of active material, binding agent and conductive agent, therefore, the performance difference of raw material and preparation technology can affect the performance of final pole piece.In order to overcome the special capacity fade of silicon based anode material, research in the past mainly concentrates on the microstructure of regulation activity material to optimize the performance of material, a small amount of research is only had to report binding agent and conductive agent to the impact of electrode performance, result shows: a lot of very important performance of electrode, comprise cyclical stability and irreversible capacity first, be all strongly depend on the performance of binding agent.
Recent research shows: the polymer (as polyacrylic acid (PAA)) with carboxyl is compared traditional binding agent such as Kynoar (PVDF) and is more suitable for doing the binding agent of silicon based anode material.Such as, the silicon-based anode pole piece (as silicon-carbon cathode material) adopting these binding agents to prepare, its cycle life is compared and is adopted the pole piece of PVDF to extend decades of times.But, the pole piece that these binding agents are made is after the drying still containing a large amount of carboxyls, the meeting of these carboxyls and electrolyte reaction generate trifluoro oxygen phosphorus (OPF3), and the decomposition of OPF3 meeting catalysis carbonate-based solvent, thus cause the silica-based rapid decay of pole piece specific capacity and the increase of internal resistance.
Summary of the invention
Technical problem to be solved by this invention is for above shortcomings in prior art, cathode pole piece of a kind of binding agent of silicon-carbon cathode material, silicon-carbon battery and preparation method thereof, silicon-carbon battery are provided, by the polymer containing hydroxyl and the polymer containing carboxyl being shared the binding agent as silicon-carbon cathode material, the cathode pole piece of silicon-carbon battery utilizes carboxyl and hydroxyl at high temperature to dewater and forms the characteristic of ester group, binding agent in pole piece is cross-linked into network structure, and there is good rigidity and caking property.
The technical scheme that solution the technology of the present invention problem adopts is to provide a kind of binding agent of silicon-carbon cathode material, comprises the polymer containing hydroxyl and the polymer containing carboxyl.
Preferably, described is (0.5:1) ~ (2:1) containing the hydroxyl in the polymer of hydroxyl and the described mol ratio containing the carboxyl in the polymer of carboxyl.
Preferably, the described polymer containing hydroxyl is one or more in polyvinyl alcohol, sodium carboxymethylcellulose, sodium alginate.
Preferably, the described polymer containing carboxyl is polyacrylic acid and/or polymethylacrylic acid.
The present invention also provides a kind of manufacture method of cathode pole piece of silicon-carbon battery, comprises the following steps:
(1) will coat on negative current collector after silicon-carbon cathode material and auxiliary material mixing, dry, wherein, described auxiliary material comprises conductive agent and above-described binding agent;
(2), after heating makes the polymer containing hydroxyl in described bonding agent and contains the polymer generation esterification of carboxyl, the cathode pole piece of silicon-carbon battery is obtained.
Preferably, the described silicon-carbon cathode material in described step (1) and the mass ratio of described auxiliary material are (90:10) ~ (70:30).
Preferably, the described conductive agent in described step (1) and the mass ratio of described binding agent are (1:2) ~ (1:1).
Preferably, the described heating-up temperature in described step (2) is 100 ~ 200 DEG C, and described heating time is 1 ~ 10 hour.
The present invention also provides a kind of cathode pole piece of silicon-carbon battery, and it is prepared by said method.
The present invention also provides a kind of silicon-carbon battery, and it comprises above-mentioned cathode pole piece.
It is kept to have superiority in order to overcome the inherent defect of rich carboxylic binding agent, polymer containing hydroxyl and the polymer containing carboxyl are shared the binding agent as silicon-carbon cathode material by the present invention, the cathode pole piece of silicon-carbon battery utilizes carboxyl and hydroxyl at high temperature to dewater and forms the characteristic of ester group, binding agent in pole piece is cross-linked into network structure, and there is good rigidity and caking property.
After tested: the stabilization ratio capacity of the cathode pole piece of silicon-carbon battery prepared by the bonding agent employing silicon-carbon cathode material of the present invention is greater than 600mAh/g, efficiency is greater than 75% first, silicon-based active uniform particles in silicon-carbon battery is distributed in the three-dimensional network of binding agent, and the rigid structure of binding agent inhibits the change of pole piece thickness.Silicon-based active particle in this pole piece volume in embedding lithium process still can increase, but the volume increased mainly is filled in the hole of original silicon-carbon cathode material in pole piece (because pole piece is made up of a large amount of micron particles, can not be completely tightly packed between particle, generally can have an appointment 40 ~ 60% porosity), this process realizes mainly through the plastic deformation of particle itself.The present invention raw materials used cheap and easy to get, preparation technology is simple, flow process is short, process easily controls, easily realize suitability for industrialized production.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
The present embodiment provides a kind of manufacture method of cathode pole piece of silicon-carbon battery, comprises the following steps:
(1) silicon-carbon cathode material is (homemade by prior art, efficiency 75% first, embedding lithium specific capacity 800mAh/g first) and auxiliary material according to after the mass ratio mixing of 88:12, in agate mortar, grinding is evenly, wherein auxiliary material comprises the conductive agent and bonding agent that mass ratio is 5:7, bonding agent comprises sodium alginate and polyacrylic acid, and the mol ratio of the hydroxyl in sodium alginate and the carboxyl in polyacrylic acid is 4:3.Add water again after grinding evenly and grind to form the slurry with viscosity, slurry is coated in copper foil current collector, 80 DEG C of vacuumizes 24 hours.
(2) at 120 DEG C heat 12 hours, make in described bonding agent containing hydroxyl polymer and containing carboxyl polymer generation esterification after, obtain the cathode pole piece of silicon-carbon battery.
With above-mentioned pole piece for positive pole, be to electrode with lithium sheet, electrolyte is the LiPF of 1mol/L
6solution, solvent is EC(ethyl carbonate ester)+DMC(dimethyl carbonate) (volume ratio 1:1) solution, barrier film is celgard2400 film, is assembled into CR2025 type button cell in the glove box being full of argon gas atmosphere.
The charge-discharge performance test of the button cell that composite cathode material for lithium ion cell prepared by the present embodiment is made: first discharge specific capacity reaches 852mAh/g, first efficiency 76%, still remains on 605mAh/g after 100 circulations.
The present embodiment also provides a kind of silicon-carbon battery, and it comprises above-mentioned cathode pole piece.
It is kept to have superiority in order to overcome the inherent defect of rich carboxylic binding agent, polymer containing hydroxyl and the polymer containing carboxyl are shared the binding agent as silicon-carbon cathode material by the present embodiment, the cathode pole piece of silicon-carbon battery utilizes carboxyl and hydroxyl at high temperature to dewater and forms the characteristic of ester group, binding agent in pole piece is cross-linked into network structure, and there is good rigidity and caking property.And the cathode pole piece in the present embodiment is when to avoid in bonding agent only containing carboxyl, carboxyl can react with electrolyte and generate trifluoro oxygen phosphorus, avoid the decomposition of trifluoro oxygen phosphorus for carbonate-based solvent, avoid the rapid decay of silicon-carbon cathode pole piece specific capacity and the increase of internal resistance.
After tested: the stabilization ratio capacity of the cathode pole piece of silicon-carbon battery prepared by the bonding agent employing the silicon-carbon cathode material of the present embodiment is 605mAh/g, efficiency is 76% first, silicon-based active uniform particles in silicon-carbon battery is distributed in the three-dimensional network of binding agent, and the rigid structure of binding agent inhibits the change of pole piece thickness.Silicon-based active particle in this pole piece volume in embedding lithium process still can increase, but the volume increased mainly is filled in the hole of original silicon-carbon cathode material in pole piece (because pole piece is made up of a large amount of micron particles, can not be completely tightly packed between particle, generally can have an appointment 40 ~ 60% porosity), this process realizes mainly through the plastic deformation of particle itself.The present embodiment raw materials used cheap and easy to get, preparation technology is simple, flow process is short, process easily controls, easily realize suitability for industrialized production.
Embodiment 2
The present embodiment provides a kind of manufacture method of cathode pole piece of silicon-carbon battery, comprises the following steps:
(1) by silicon-carbon cathode material (self-control, efficiency 75% first, embedding lithium specific capacity 800mAh/g first) and auxiliary material according to after the mass ratio mixing of 85:15, in agate mortar, grinding is evenly, wherein auxiliary material comprises the conductive agent acetylene black and bonding agent that mass ratio is 5:10, bonding agent comprises sodium alginate and polymethylacrylic acid, and the mol ratio of the hydroxyl in sodium alginate and the carboxyl in polymethylacrylic acid is 5:5.Add water again after grinding evenly and grind to form the slurry with viscosity, slurry is coated in copper foil current collector, 80 DEG C of vacuumizes 24 hours.
(2) when heating 6 at 150 DEG C, make in described bonding agent containing hydroxyl polymer and containing carboxyl polymer generation esterification after, obtain the cathode pole piece of silicon-carbon battery.
With above-mentioned pole piece for positive pole, be to electrode with lithium sheet, electrolyte is the LiPF of 1mol/L
6solution, solvent is EC(ethyl carbonate ester)+DMC(dimethyl carbonate) (volume ratio 1:1) solution, barrier film is celgard2400 film, is assembled into CR2025 type button cell in the glove box being full of argon gas atmosphere.
The charge-discharge performance test of the button cell that composite cathode material for lithium ion cell prepared by the present embodiment is made: first discharge specific capacity reaches 847mAh/g, first efficiency 78%, still remains on 618mAh/g after 100 circulations.
The present embodiment also provides a kind of silicon-carbon battery, and it comprises above-mentioned cathode pole piece.
Embodiment 3
The present embodiment provides a kind of manufacture method of cathode pole piece of silicon-carbon battery, comprises the following steps:
(1) by silicon-carbon cathode material (self-control, efficiency 75% first, embedding lithium specific capacity 800mAh/g first) and auxiliary material according to after the mass ratio mixing of 74:26, in agate mortar, grinding is evenly, wherein auxiliary material comprises the conductive agent and bonding agent that mass ratio is 10:16, bonding agent comprises sodium carboxymethylcellulose, polyacrylic acid, polymethylacrylic acid (wherein, the mass ratio of polyacrylic acid and polymethylacrylic acid is 1:1), the mol ratio of the carboxyl in the mixture of the hydroxyl in sodium carboxymethylcellulose and polyacrylic acid and polymethylacrylic acid is 10:6.Add water again after grinding evenly and grind to form the slurry with viscosity, slurry is coated in copper foil current collector, 80 DEG C of vacuumizes 24 hours.
(2) at 160 DEG C heat 4 hours, make in described bonding agent containing hydroxyl polymer and containing carboxyl polymer generation esterification after, obtain the cathode pole piece of silicon-carbon battery.
With above-mentioned pole piece for positive pole, be to electrode with lithium sheet, electrolyte is the LiPF of 1mol/L
6solution, solvent is EC(ethyl carbonate ester)+DMC(dimethyl carbonate) (volume ratio 1:1) solution, barrier film is celgard2400 film, is assembled into CR2025 type button cell in the glove box being full of argon gas atmosphere.
The charge-discharge performance test of the button cell that composite cathode material for lithium ion cell prepared by the present embodiment is made: first discharge specific capacity reaches 887mAh/g, first efficiency 80%, still remains on 671mAh/g after 100 circulations.
The present embodiment also provides a kind of silicon-carbon battery, and it comprises above-mentioned cathode pole piece.
Embodiment 4
The present embodiment provides a kind of manufacture method of cathode pole piece of silicon-carbon battery, comprises the following steps:
(1) by silicon-carbon cathode material (self-control, efficiency 75% first, embedding lithium specific capacity 800mAh/g first) and auxiliary material according to after the mass ratio mixing of 72:28, in agate mortar, grinding is evenly, wherein auxiliary material comprises the conductive agent and bonding agent that mass ratio is 10:18, bonding agent comprises sodium carboxymethylcellulose and polymethylacrylic acid, and the mol ratio of the hydroxyl in sodium carboxymethylcellulose and the carboxyl in polymethylacrylic acid is 10:8.Add water again after grinding evenly and grind to form the slurry with viscosity, slurry is coated in copper foil current collector, 80 DEG C of vacuumizes 24 hours.
(2) at 180 DEG C heat 1 hour, make in described bonding agent containing hydroxyl polymer and containing carboxyl polymer generation esterification after, obtain the cathode pole piece of silicon-carbon battery.
With above-mentioned pole piece for positive pole, be to electrode with lithium sheet, electrolyte is the LiPF of 1mol/L
6solution, solvent is EC(ethyl carbonate ester)+DMC(dimethyl carbonate) (volume ratio 1:1) solution, barrier film is celgard2400 film, is assembled into CR2025 type button cell in the glove box being full of argon gas atmosphere.
The charge-discharge performance test of the button cell that composite cathode material for lithium ion cell prepared by the present embodiment is made: first discharge specific capacity reaches 873mAh/g, first efficiency 79%, still remains on 643mAh/g after 100 circulations.
The present embodiment also provides a kind of silicon-carbon battery, and it comprises above-mentioned cathode pole piece.
Embodiment 5
The present embodiment provides a kind of manufacture method of cathode pole piece of silicon-carbon battery, comprises the following steps:
(1) by silicon-carbon cathode material (self-control, efficiency 75% first, embedding lithium specific capacity 800mAh/g first) and auxiliary material according to after the mass ratio mixing of 90:10, in agate mortar, grinding is evenly, wherein auxiliary material comprises the conductive agent acetylene black and bonding agent that mass ratio is 5:5, bonding agent comprises polyvinyl alcohol, sodium carboxymethylcellulose (wherein, the mass ratio of polyvinyl alcohol and sodium carboxymethylcellulose is 1:2) and polyacrylic acid, the mol ratio of the hydroxyl in the mixture of polyvinyl alcohol and sodium carboxymethylcellulose and the carboxyl in polyacrylic acid is 6:3.Add water again after grinding evenly and grind to form the slurry with viscosity, slurry is coated in copper foil current collector, 50 DEG C of vacuumizes 24 hours.
(2) at 100 DEG C heat 10 hours, make in described bonding agent containing hydroxyl polymer and containing carboxyl polymer generation esterification after, obtain the cathode pole piece of silicon-carbon battery.
With above-mentioned pole piece for positive pole, be to electrode with lithium sheet, electrolyte is the LiPF of 1mol/L
6solution, solvent is EC(ethyl carbonate ester)+DMC(dimethyl carbonate) (volume ratio 1:1) solution, barrier film is celgard2400 film, is assembled into CR2025 type button cell in the glove box being full of argon gas atmosphere.
The charge-discharge performance test of the button cell that composite cathode material for lithium ion cell prepared by the present embodiment is made: first discharge specific capacity reaches 893mAh/g, first efficiency 81%, still remains on 694mAh/g after 100 circulations.
The present embodiment also provides a kind of silicon-carbon battery, and it comprises above-mentioned cathode pole piece.
Embodiment 6
The present embodiment provides a kind of manufacture method of cathode pole piece of silicon-carbon battery, comprises the following steps:
(1) by silicon-carbon cathode material (self-control, efficiency 75% first, embedding lithium specific capacity 800mAh/g first) and auxiliary material according to after the mass ratio mixing of 70:30, in agate mortar, grinding is evenly, wherein auxiliary material comprises the conductive agent and bonding agent that mass ratio is 10:18, bonding agent comprises polyvinyl alcohol and polymethylacrylic acid, and the mol ratio of the hydroxyl in polyvinyl alcohol and the carboxyl in polymethylacrylic acid is 6:12.Add water again after grinding evenly and grind to form the slurry with viscosity, slurry is coated in copper foil current collector, 80 DEG C of vacuumizes 24 hours.
(2) at 200 DEG C heat 10 hours, make in described bonding agent containing hydroxyl polymer and containing carboxyl polymer generation esterification after, obtain the cathode pole piece of silicon-carbon battery.
With above-mentioned pole piece for positive pole, be to electrode with lithium sheet, electrolyte is the LiPF of 1mol/L
6solution, solvent is EC(ethyl carbonate ester)+DMC(dimethyl carbonate) (volume ratio 1:1) solution, barrier film is celgard2400 film, is assembled into CR2025 type button cell in the glove box being full of argon gas atmosphere.
The charge-discharge performance test of the button cell that composite cathode material for lithium ion cell prepared by the present embodiment is made: first discharge specific capacity reaches 869mAh/g, first efficiency 77%, still remains on 634mAh/g after 100 circulations.
The present embodiment also provides a kind of silicon-carbon battery, and it comprises above-mentioned cathode pole piece.
Be understandable that, the illustrative embodiments that above execution mode is only used to principle of the present invention is described and adopts, but the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement are also considered as protection scope of the present invention.
Claims (10)
1. a binding agent for silicon-carbon cathode material, is characterized in that, comprises the polymer containing hydroxyl and the polymer containing carboxyl.
2. the binding agent of silicon-carbon cathode material according to claim 1, is characterized in that, described is (0.5:1) ~ (2:1) containing the hydroxyl in the polymer of hydroxyl and the described mol ratio containing the carboxyl in the polymer of carboxyl.
3. the binding agent of silicon-carbon cathode material according to claim 1, is characterized in that, the described polymer containing hydroxyl is one or more in polyvinyl alcohol, sodium carboxymethylcellulose, sodium alginate.
4. the binding agent of silicon-carbon cathode material according to claim 1, is characterized in that, the described polymer containing carboxyl is polyacrylic acid and/or polymethylacrylic acid.
5. a manufacture method for the cathode pole piece of silicon-carbon battery, is characterized in that, comprises the following steps:
(1) will coat on negative current collector after silicon-carbon cathode material and auxiliary material mixing, dry, wherein, described auxiliary material comprises conductive agent and the binding agent described in Claims 1 to 4 any one;
(2), after heating makes the polymer containing hydroxyl in described bonding agent and contains the polymer generation esterification of carboxyl, the cathode pole piece of silicon-carbon battery is obtained.
6. the manufacture method of the cathode pole piece of silicon-carbon battery according to claim 5, is characterized in that, the described silicon-carbon cathode material in described step (1) and the mass ratio of described auxiliary material are (90:10) ~ (70:30).
7. the manufacture method of the cathode pole piece of silicon-carbon battery according to claim 5, is characterized in that, the described conductive agent in described step (1) and the mass ratio of described binding agent are (1:2) ~ (1:1).
8. the manufacture method of the cathode pole piece of silicon-carbon battery according to claim 5, is characterized in that, the described heating-up temperature in described step (2) is 100 ~ 200 DEG C, and described heating time is 1 ~ 10 hour.
9. a cathode pole piece for silicon-carbon battery, is characterized in that, it is prepared by method described in claim 5 ~ 8 any one.
10. a silicon-carbon battery, is characterized in that, it comprises cathode pole piece according to claim 9.
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