CN114122316A - Negative electrode and use thereof - Google Patents
Negative electrode and use thereof Download PDFInfo
- Publication number
- CN114122316A CN114122316A CN202111389342.3A CN202111389342A CN114122316A CN 114122316 A CN114122316 A CN 114122316A CN 202111389342 A CN202111389342 A CN 202111389342A CN 114122316 A CN114122316 A CN 114122316A
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- Prior art keywords
- negative electrode
- conductive agent
- parts
- sulfonic acid
- anode
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Links
- 239000006258 conductive agent Substances 0.000 claims abstract description 59
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 27
- 239000007773 negative electrode material Substances 0.000 claims abstract description 22
- 239000006183 anode active material Substances 0.000 claims abstract description 13
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 40
- 239000011970 polystyrene sulfonate Substances 0.000 claims description 28
- 229960002796 polystyrene sulfonate Drugs 0.000 claims description 28
- 239000006229 carbon black Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 15
- 239000002041 carbon nanotube Substances 0.000 claims description 13
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 13
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 7
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 7
- 230000035699 permeability Effects 0.000 claims description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 12
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 238000002156 mixing Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000011267 electrode slurry Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000001035 drying Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 8
- 239000011889 copper foil Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 230000001678 irradiating effect Effects 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 241000872198 Serjania polyphylla Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 241000287828 Gallus gallus Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 239000010242 baoji Substances 0.000 description 1
- GXONETWXEOOVHM-UHFFFAOYSA-N buta-1,3-diene;hydrate Chemical compound O.C=CC=C GXONETWXEOOVHM-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides an anode and use thereof, the anode includes an anode active material layer including an anode active material and a sulfonic acid group-containing compound. Due to the existence of the sulfonic acid group, the activated conductive agent is connected to the sulfonic acid group-containing compound by the negative electrode through the sulfonic acid ester bond, so that the conductive agent and the sulfonic acid group-containing compound are well combined together, the dispersion is more uniform, and the using amount of the conductive agent is reduced; meanwhile, through the synergistic effect of the sulfonic acid group-containing compound and the conductive agent, the problem of volume expansion of the negative active material can be solved, so that the negative electrode has low volume resistivity, and an electrochemical device comprising the negative electrode has high cycle capacity retention rate.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a negative electrode and application thereof.
Background
The lithium ion battery has the advantages of high specific capacity, high working voltage, long cycle life, no memory effect and the like, is widely applied to various fields of communication, traffic, energy storage and the like, and is a green and environment-friendly battery.
In order to improve the energy density of lithium ion batteries, people are eagerly expected to find new materials with higher specific capacity to replace the traditional materials of lithium batteries, and silicon is more and more popular to use as a negative electrode material due to the advantages of high specific capacity, wide distribution, low cost and the like. However, the volume of the silicon-containing material changes in the battery cycle process, so that the negative electrode material is damaged, and the conductivity, stability and battery capacity of the battery are affected.
The prior art discloses a zinc oxide coated silicon negative electrode material, which includes a conductive agent, a binder, silicon nanoparticles, and zinc oxide. The problem of volume expansion of the silicon negative electrode material is effectively prevented through zinc oxide coating, so that the cycle performance and the charge-discharge capacity of the lithium ion battery are improved. However, the silicon negative electrode material has a non-uniform dispersion of the conductive agent, a high amount of the conductive agent, and a slightly poor conductive property.
The common defects of the prior art are that the adopted coating material has high cost, the coating is incomplete or the conductive agent in the cathode material is not uniformly dispersed, so that the dosage of the conductive agent is higher, and the cycle performance and the rate performance of the lithium ion battery are influenced.
Therefore, the development of a negative electrode with small volume change and good conductivity, which can improve the cycle performance and rate performance of a battery, is an urgent problem to be solved in the field.
Disclosure of Invention
In view of the disadvantages of the prior art, an object of the present invention is to provide a negative electrode and use thereof, in which the dispersibility of a conductive agent can be improved by coating a sulfonic acid group-containing compound on a negative electrode active material, which contributes to solving the problem of volume expansion of the negative electrode active material, and an electrochemical device including the negative electrode has excellent rate capability.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an anode including an anode active material layer including an anode active material and a sulfonic acid group-containing compound.
In the present invention, by coating a sulfonic acid group-containing compound on a negative active material, it is helpful to solve the problem of volume expansion of the negative active material, and an electrochemical device including the negative electrode has excellent rate performance.
Preferably, the negative electrode further includes a negative electrode current collector.
Preferably, the negative electrode current collector includes a copper foil.
Preferably, the copper foil has a thickness of 9 μm to 11 μm, and may be, for example, 9 μm, 10 μm, 11 μm, or the like.
Preferably, the negative active material includes a silicon oxygen material and/or a silicon carbon material.
Preferably, the sulfonic acid group-containing compound comprises a compound having the structure shown in formula I;
Preferably, the sulfonic acid group-containing compound includes polystyrene sulfonate.
Preferably, the polystyrene sulfonate has a number average molecular weight of 5000 to 50000, and may be, for example, 5000, 10000, 15000, 20000, 25000, 30000, 35000, 40000, 45000, 50000, or the like.
Preferably, the polystyrene sulfonate comprises sodium polystyrene sulfonate and/or potassium polystyrene sulfonate.
Preferably, the anode active material layer further includes a conductive agent.
Preferably, the conductive agent is a surface-treated conductive agent.
In the invention, the reagent for surface treatment comprises aqua regia, and the aqua regia is prepared by concentrated nitric acid and concentrated sulfuric acid according to the volume ratio of 1: 3; the purpose of the surface treatment is to expose more hydroxyl groups on the surface of the conductive agent, and to form sulfonic acid ester by the reaction of the hydroxyl groups with sulfonic acid groups, thereby linking the conductive agent to the surface of the sulfonic acid group-containing compound.
Preferably, the conductive agent includes at least one of carbon black, graphite, carbon nanotubes, or carbon fibers.
Preferably, the conductive agent includes carbon black and/or carbon nanotubes.
Preferably, the negative electrode further comprises a binder including at least one of polyvinylidene fluoride, styrene butadiene rubber, polyimide, or carboxymethyl cellulose.
As a preferable aspect of the present invention, the negative electrode includes, in parts by weight, 95 to 99 parts of a negative electrode active material, 1 to 5 parts of a sulfonic acid group-containing compound, 1 to 5 parts of a conductive agent, and 1 to 3 parts of a binder.
Preferably, the anode includes 95 to 99 parts of the anode active material, which may be, for example, 95 parts, 96 parts, 97 parts, 98 parts, 99 parts, or the like.
Preferably, the negative electrode includes 1 to 5 parts of the sulfonic acid group-containing compound, and may be, for example, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, or the like.
In the invention, the excessive content of the sulfonic acid group-containing compound can cause the pH value of the slurry to increase, cause the slurry to flocculate and gel, and influence the homogenization process; if the content is too small, the negative active material cannot be coated well, and the function of a dispersant cannot be achieved.
Preferably, the negative electrode includes 1 part to 5 parts of the conductive agent, and may be, for example, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, or the like.
In the invention, the content of the conductive agent is too much, which causes poor dispersion of slurry, fine particles during coating and overlarge fineness; if the content is too low, the conductive network is insufficient, and the internal resistance of the battery is affected.
Preferably, the negative electrode includes 1 to 3 parts of binder, which may be, for example, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, etc.
According to the invention, polystyrene sulfonate is coated on the surface of a negative active material, through pi-pi conjugation, meanwhile, a conductive agent reacts with aqua regia, the surface of the conductive agent is oxidized to generate hydroxyl, and the hydroxyl can generate sulfonate with a sulfonic group, so that the conductive agent and the polystyrene sulfonate are well combined together, and due to the existence of phenyl on the polystyrene sulfonate, the conductive agent is dispersed more uniformly by using a steric effect, and the using amount of the conductive agent is reduced; through the synergistic effect of the polystyrene sulfonate and the conductive agent, the volume resistivity of the negative electrode is low, and an electrochemical device comprising the negative electrode has excellent rate performance.
In the present invention, the surface-treated conductive agent is prepared by a method comprising:
mixing a conductive agent and aqua regia, washing and drying to obtain the conductive agent.
Preferably, the time for mixing the conductive agent and the aqua regia is 1h to 3h, and for example, 1h, 1.5h, 2h, 2.5h, 3h and the like can be given.
Preferably, the washed solvent comprises water.
Preferably, the number of washing is 3 to 5, for example, 3, 4, 5, etc.
In the invention, the preparation method of the negative electrode comprises the following steps:
mixing a negative electrode active material, a sulfonic group-containing compound, a conductive agent, a binder and a solvent according to the formula ratio to obtain negative electrode slurry; and then coating the negative electrode slurry on a negative electrode current collector, drying and cold-pressing to obtain the negative electrode.
Preferably, the binder has a solids content of 5% to 50%, for example, may be 5%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, etc.
Preferably, the solvent comprises water.
Preferably, the solid content of the anode slurry is 50% to 70%, for example, may be 50%, 52%, 54%, 56%, 58%, 60%, 62%, 64%, 66%, 68%, 70%, and the like.
Preferably, the mixing time is 30min to 240min, for example, 30min, 35min, 40min, 45min, 50min, 55min, 60min, 80min, 100min, 120min, 140min, 160min, 180min, 200min, 220min, 240min, etc.
Preferably, the mixing device is a stirred tank.
Preferably, the rotation speed of the agitation tank is 100rpm to 300rpm, and for example, may be 100rpm, 120rpm, 140rpm, 160rpm, 180rpm, 200rpm, 220rpm, 240rpm, 260rpm, 280rpm, 300rpm, or the like.
Preferably, the step of irradiating with ultraviolet light is further included after the mixing.
Preferably, the time of the ultraviolet irradiation is 30min to 60min, for example, 30min, 35min, 40min, 45min, 50min, 55min, 60min, etc.
Preferably, the rotation speed at the time of the ultraviolet light irradiation is 100rpm to 300rpm, and may be, for example, 100rpm, 120rpm, 140rpm, 160rpm, 180rpm, 200rpm, 220rpm, 240rpm, 260rpm, 280rpm, 300rpm, or the like.
Preferably, the ultraviolet irradiation is followed by a stirring step.
Preferably, the time for stirring after the ultraviolet irradiation is 60min to 240min, for example, 60min, 80min, 100min, 120min, 140min, 160min, 180min, 200min, 220min, 240min and the like.
Preferably, the rotation speed of the stirring after the ultraviolet irradiation is 300rpm to 500rpm, and for example, may be 300rpm, 320rpm, 350rpm, 380rpm, 400rpm, 420rpm, 450rpm, 480rpm, 500rpm, or the like.
As a preferable technical solution of the present invention, the method for preparing the negative electrode includes:
mixing a negative electrode active material and a compound containing sulfonic groups in a stirring tank at the rotating speed of 100-300 rpm for 30-60 min according to the formula amount, adding a solvent, continuously stirring for 60-240 min, adding a conductive agent, irradiating for 30-60 min by ultraviolet light, adding a binder and the solvent, and continuously stirring for 60-240 min at the rotating speed of 300-500 rpm to obtain negative electrode slurry; and then coating the negative electrode slurry on a negative electrode current collector, drying and cold-pressing to obtain the negative electrode.
In a second aspect, the present invention provides an electrochemical device comprising the anode according to the first aspect, an electrolytic solution, a separator, and a cathode.
Preferably, the electrolyte includes a lithium salt and a non-aqueous solvent.
Preferably, the lithium salt comprises lithium hexafluorophosphate.
Preferably, the content of the lithium salt in the electrolyte is 1% to 20% by mass, and may be, for example, 1%, 2%, 4%, 8%, 12%, 16%, 20%, or the like.
Preferably, the non-aqueous solvent includes any one of Ethylene Carbonate (EC), dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC), Propylene Carbonate (PC), or diethyl carbonate (DEC), or a combination of at least two thereof.
Preferably, the electrolyte includes, in parts by weight, 0.1 to 5 parts of ethylene carbonate, 0.1 to 5 parts of dimethyl carbonate, 0.1 to 8 parts of ethyl methyl carbonate, 0.1 to 5 parts of propylene carbonate, and 0.1 to 8 parts of diethyl carbonate.
Preferably, the electrolyte includes ethylene carbonate 0.1 to 5 parts by weight, for example, may be 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, etc.
Preferably, the electrolyte comprises dimethyl carbonate 0.1 to 5 parts by weight, for example, 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, etc.
Preferably, the electrolyte includes ethyl methyl carbonate 0.1 to 8 parts by weight, for example, may be 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 7, 8, etc.
Preferably, the electrolyte comprises 0.1 to 5 parts by weight of propylene carbonate, for example, 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, etc.
Preferably, the electrolyte includes 0.1 to 8 parts by weight of diethyl carbonate, and may be, for example, 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 7, 8, etc.
In a third aspect, the present invention provides an electrochemical device in which the separator has a permeability value of 140 to 160, and may be, for example, 140, 142, 144, 146, 148, 150, 152, 154, 156, 158, 160, etc.
Preferably, the separator includes a polyethylene-based film and ceramic layers coated on upper and lower surfaces of the polyethylene-based film.
Preferably, the thickness of the polyethylene-based film is 9 μm to 11 μm, and may be, for example, 9 μm, 10 μm, 11 μm, or the like.
Preferably, the ceramic layer has a thickness of 2 μm to 5 μm, and may be, for example, 2 μm, 3 μm, 4 μm, 5 μm, or the like.
Preferably, the positive electrode includes a positive electrode current collector, 92 to 97 parts by weight of a positive electrode active material, 2 to 4 parts by weight of a conductive agent, and 1 to 2 parts by weight of polyvinylidene fluoride.
Preferably, the positive electrode current collector includes an aluminum foil.
Preferably, the thickness of the aluminum foil is 15 μm to 17 μm, and may be, for example, 15 μm, 16 μm, 17 μm, or the like.
Preferably, the positive electrode includes 92 to 97 parts by weight of the positive electrode active material, and may be, for example, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts, and the like.
Preferably, the positive electrode includes 2 parts to 4 parts of the conductive agent by weight, and may be, for example, 2 parts, 3 parts, 4 parts, or the like.
Preferably, the positive electrode includes 1 to 2 parts by weight of polyvinylidene fluoride, for example, may be 1 part, 1.5 parts, 2 parts, etc.
Preferably, the positive active material includes a lithium iron phosphate and/or a nickel cobalt manganese ternary positive material.
Preferably, the conductive agent includes carbon black and/or carbon nanotubes.
According to the electrochemical device, the negative electrode, the electrolyte, the specific diaphragm and the positive electrode are in synergistic action, so that the electrochemical device has excellent rate performance.
In a fourth aspect, the invention provides an electronic device comprising a cathode according to the first aspect and/or an electrochemical device according to the second or third aspect.
The recitation of numerical ranges herein includes not only the above-recited values, but also any values between any of the above-recited numerical ranges not recited, and for brevity and clarity, is not intended to be exhaustive of the specific values encompassed within the range.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a negative electrode, which is beneficial to improving the dispersibility of a conductive agent and reducing the volume resistivity by coating a sulfonic acid group-containing compound on a negative electrode active material, and an electrochemical device has excellent cycle retention rate by the synergistic use of the negative electrode, an electrolyte, a specific diaphragm and a positive electrode.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The scheme in the prior art is that materials such as single-walled carbon nanotubes are adopted to coat silicon-containing cathode materials, the coating is incomplete, the cost is high, and the cycle performance and the charge rate performance of the lithium ion battery are affected; in addition, the conductive agent is not uniformly dispersed in the solvent, and the conductivity is poor.
In order to solve the above problems, the present invention provides an anode including an anode active material layer including an anode active material and a sulfonic acid group-containing compound; according to the cathode provided by the invention, the sulfonic acid group-containing compound is coated on the cathode active material, so that the dispersibility of the conductive agent is improved, the volume resistivity is reduced, and the cycle retention rate of an electrochemical device comprising the cathode is high.
In some embodiments, the negative active material includes a silicon oxygen material and/or a silicon carbon material.
In some embodiments, the sulfonic acid group containing compound comprises a compound having the structure shown in formula I;
In some embodiments, the sulfonic acid group-containing compound comprises polystyrene sulfonate.
In some embodiments, the polystyrene sulfonate has a number average molecular weight of 5000 to 50000.
In some embodiments, the polystyrene sulfonate comprises sodium polystyrene sulfonate and/or potassium polystyrene sulfonate.
In some embodiments, the anode active material layer further includes a conductive agent.
In some embodiments, the conductive agent is a surface treated conductive agent.
In some embodiments, the conductive agent comprises at least one of carbon black, graphite, carbon nanotubes, or carbon fibers.
In some embodiments, the conductive agent comprises carbon black and/or carbon nanotubes.
In some embodiments, the negative electrode further comprises a binder comprising at least one of polyvinylidene fluoride, styrene butadiene rubber, polyimide, or carboxymethyl cellulose.
In some embodiments, the negative electrode includes 95 to 99 parts of a negative electrode active material, 1 to 5 parts of a sulfonic acid group-containing compound, 1 to 5 parts of a conductive agent, and 1 to 3 parts of a binder, in parts by weight.
The present invention provides an electrochemical device comprising the negative electrode, an electrolyte, a separator, and a positive electrode.
The present invention provides an electrochemical device in which a separator has a gas permeation value of 140 to 160.
The present invention provides an electronic device including the negative electrode and/or the electrochemical device.
Unless otherwise specified, various materials used in the examples and comparative examples of the present invention are commercially available or prepared according to a conventional method in the art.
Example 1
This example provides a negative electrode comprising copper foil (Guangdong Yuan, 10 μm), silicone material (97 parts by weight, Cabot, SSO-C420B), sodium polystyrene sulfonate (2.5 parts by weight, Guokang Biotech Co., Ltd., Bao chicken, purity 98%, molecular weight 25000) coated on the silicone material, carbon black (2.5 parts by weight, SP of Yiruite) attached to the sodium polystyrene sulfonate by a sulfonate ester bond, and carboxymethyl cellulose (2 parts by weight, Japan paper, MAC ° 500 LC).
The embodiment provides a preparation method of the cathode, which comprises the following specific steps:
mixing a silica material and sodium polystyrene sulfonate in a stirring tank with the rotation speed of 200rpm for 45min according to the formula amount, adding water, continuously stirring for 180min at the rotation speed of 300rpm, adding carbon black, irradiating for 45min under a 360nm ultraviolet lamp light source with the rotation speed of 200rpm, adding carboxymethyl cellulose and water, and continuously stirring for 180min at the rotation speed of 400rpm to obtain negative electrode slurry (the solid content is 60%); then coating the negative electrode slurry on a copper foil, drying and cold pressing to obtain the negative electrode; wherein the preparation method of the carbon black comprises the following steps: mixing carbon black with aqua regia for 2h, filtering, washing with water for 4 times, filtering, and drying to obtain the carbon black.
The present embodiment provides an electrochemical device, which includes the negative electrode, a separator (made of a star-source material, including a polyethylene base film and a ceramic layer coated on the upper and lower surfaces of the polyethylene base film), an electrolyte (TC-E123), and a positive electrode; the permeability value of the membrane is 150; the positive electrode includes a positive electrode current collector (south mountain aluminum, 16 μm), 95 parts by weight of a positive electrode active material (volitan, RL05-S6), 1.5 parts by weight of carbon black (yirui stone SP), 1.5 parts by weight of carbon nanotubes (tianaiwei, LB107-44), and 1.5 parts by weight of polyvinylidene fluoride (solvay, PVDF 5130).
Example 2
This example provides a negative electrode comprising copper foil (Guangdong Jiayuan, 10 μm), silicone material (95 parts by weight, Cabot, SSO-C420B), sodium polystyrene sulfonate (5 parts by weight, Guokang Biotech Co., Ltd., Bao Ji, purity 98%, molecular weight 25000) coated on the silicone material, carbon black (1 part by weight, SP of Yiruite) attached to the sodium polystyrene sulfonate through a sulfonate ester bond, and styrene butadiene rubber (3 parts by weight, ZEON, BM 451B).
The embodiment provides a preparation method of the cathode, which comprises the following specific steps:
mixing a silicon oxygen material and sodium polystyrene sulfonate in a stirring tank with the rotation speed of 300rpm for 30min according to the formula amount, adding water, continuously stirring for 60min at the rotation speed of 300rpm, adding carbon black, irradiating for 30min under a 360nm ultraviolet lamp light source with the rotation speed of 300rpm, adding butadiene styrene rubber and water, and continuously stirring for 60min at the rotation speed of 500rpm to obtain negative electrode slurry (the solid content is 50%); then coating the negative electrode slurry on a copper foil, drying and cold pressing to obtain the negative electrode; wherein the preparation method of the carbon black comprises the following steps: mixing carbon black with aqua regia for 1h, filtering, washing with water for 3 times, filtering, and drying to obtain the carbon black.
This example provides an electrochemical device which differs from example 1 only in that the permeability value of the separator is 140, and other components and parameters are the same as those of example 1.
Example 3
This example provides a negative electrode comprising copper foil (Guangdong Jiayuan, 10 μm), silicone material (99 parts by weight, Cabot, SSO-C420B), potassium polystyrene sulfonate (1 part by weight, Guokang Biotech Co., Ltd., Baoji, purity 98%, molecular weight 25000) coated on the silicone material, carbon nanotubes (5 parts by weight, Tiannai, LB107-44) attached to the potassium polystyrene sulfonate by a sulfonate ester bond, and carboxymethyl cellulose (1 part by weight, Japan paper, MAC ° 500 LC).
The embodiment provides a preparation method of the cathode, which comprises the following specific steps:
mixing a silicon oxygen material and potassium polystyrene sulfonate in a stirring tank with the rotation speed of 100rpm for 60min, adding water, continuously stirring at the rotation speed of 100rpm for 240min, adding carbon nano tubes, irradiating for 60min under a 360nm ultraviolet lamp light source with the rotation speed of 100rpm, adding carboxymethyl cellulose and water, and continuously stirring at the rotation speed of 300rpm for 240min to obtain negative electrode slurry (the solid content is 70%); then coating the negative electrode slurry on a copper foil, drying and cold pressing to obtain the negative electrode; the preparation method of the carbon nano tube comprises the following steps: mixing the carbon nano tube with aqua regia for 3h, filtering, washing for 5 times with water, filtering and drying to obtain the carbon nano tube.
This example provides an electrochemical device which differs from example 1 only in that the permeability value of the separator is 160, and other components and parameters are the same as those of example 1.
Example 4
This example provides a negative electrode, which is different from example 1 only in that the polystyrene sodium sulfonate is 15 parts by weight, and other components and amounts are the same as example 1.
The present example provides a method for preparing the negative electrode, and the specific steps are the same as those in example 1.
This example provides an electrochemical device, which is the same as in example 1.
Example 5
This example provides a negative electrode, which is different from example 1 only in that the polystyrene sodium sulfonate is 0.4 parts by weight, and other components and amounts are the same as example 1.
The present example provides a method for preparing the negative electrode, and the specific steps are the same as those in example 1.
This example provides an electrochemical device, which is the same as in example 1.
Example 6
This example provides a negative electrode which differs from example 1 only in that the carbon black is present in 15 parts by weight, and the other components and amounts are the same as in example 1.
The present example provides a method for preparing the negative electrode, and the specific steps are the same as those in example 1.
This example provides an electrochemical device, which is the same as in example 1.
Example 7
This example provides a negative electrode which differs from example 1 only in that the carbon black is present in an amount of 0.4 parts by weight, and the other components and amounts are the same as in example 1.
The present example provides a method for preparing the negative electrode, and the specific steps are the same as those in example 1.
This example provides an electrochemical device, which is the same as in example 1.
Example 8
This example provides a negative electrode which differs from example 1 only in that the carbon black is not linked to sodium polystyrene sulfonate via a sulfonate ester bond, but simply mixed, and the other components and amounts are the same as in example 1.
This example provides a method for preparing the negative electrode, which is different from example 1 only in that the method has no step of ultraviolet irradiation, and other steps and parameters are the same as those of example 1.
This example provides an electrochemical device, which is the same as in example 1.
Example 9
This example provides an anode having the same composition and amounts as in example 1.
The present example provides a method for preparing the negative electrode, and the specific steps are the same as those in example 1.
This example provides an electrochemical device which differs from example 1 only in that the permeability value of the separator is 170, and the other components and parameters are the same as those of example 1.
Comparative example 1
This comparative example provides a negative electrode which is different from example 1 only in that the sodium polystyrene sulfonate is replaced with polyacrylonitrile in an equal weight part, and the other components and amounts are the same as example 1.
The comparative example provides a preparation method of the negative electrode, and the specific steps are the same as those of example 1.
This comparative example provides an electrochemical device, which is the same as in example 1.
Comparative example 2
This comparative example provides a negative electrode which differs from example 1 only in that the negative electrode does not have sodium polystyrene sulfonate, and the other components and amounts are the same as in example 1.
The comparative example provides a preparation method of the negative electrode, and the specific steps are the same as those of example 1.
This comparative example provides an electrochemical device, which is the same as in example 1.
Performance testing
(1) The fineness of the negative electrode slurry is as follows: taking about 1mL of sample of the negative slurry above the scale line of a fineness plate by adopting a fineness meter with the measuring range of 100 mu m according to a GB1724-79 method, drawing the slurry by using a scraper, and observing particles in a groove in an instant manner, wherein the uniformly exposed part of the particles is the particle size value of the slurry; respectively testing the fineness of the slurry after standing for 2h and 24 h;
(2) volume resistivity: the negative electrodes provided in examples 1 to 9 and comparative examples 1 and 2 were included and tested using a hitachi film resistance meter RM 9003;
(3) cycle capacity retention ratio: adopt flourishing electronic apparatus share electric limited company battery capability test system (test cabinet), equipment model: BTS05/10C8D-HP, the electrochemical devices provided in examples 1 to 9, comparative examples 1 and 2 were placed in a test cabinet for testing, and capacity retention rates of 500 cycles after 1C/1C charge-discharge cycles were tested.
The specific test results are shown in table 1:
TABLE 1
As can be seen from the above table, according to the negative electrode provided by the invention, the polystyrene sulfonate is coated on the negative electrode active material, and the polystyrene sulfonate can react with the hydroxyl on the surface of the activated conductive agent due to the existence of the sulfonic acid group, so that not only can the dispersibility of the conductive agent be improved, but also the fineness of the prepared slurry is small, the volume resistivity of the negative electrode is low, and the retention rate of the cycle capacity of the electrochemical device is high through the synergistic effect of the negative electrode, the specific diaphragm, the electrolyte and the positive electrode.
As can be seen from the comparison between examples 1 to 3 and examples 4 to 7, the volume resistivity of the negative electrode is low and the retention rate of the cycle capacity of the electrochemical device including the negative electrode is high in the specific mixture ratio of the polystyrene sulfonate and the conductive agent; preferably, when the ratio of the two is 1: 1, the effect is best; too high or too low a content of the polystyrene sulfonate or the conductive agent causes uneven dispersion and large fineness of the conductive agent, and the retention rate of the cycle capacity is reduced.
As can be seen from comparison between examples 1 and 8, when the conductive agent is not connected to the polystyrene sulfonate via a sulfonate bond but simply mixed, the volume resistivity of the negative electrode increases and the cycle retention rate also decreases; as can be seen from comparison between example 1 and example 9, when the membrane permeability value in the electrochemical device is greater than 160, the cycle retention rate of the electrochemical device is reduced; as can be seen from comparison of example 1 with comparative examples 1 and 2, when the negative electrode is not substituted with polystyrene sulfonate or other polymers having no sulfonic acid group, the fineness of the slurry increases and the retention rate of the cycle capacity of the electrochemical device decreases.
In summary, according to the negative electrode provided by the invention, the polystyrene sulfonate is coated on the negative electrode active material, and the conductive agent is connected to the polystyrene sulfonate through the sulfonate bond, so that not only can the dispersibility of the conductive agent be improved, but also the negative electrode has low volume resistivity through the compounding of the polystyrene sulfonate and the conductive agent; the electrochemical device has high cycle capacity retention rate through the matched use of the negative electrode, the specific diaphragm, the electrolyte and the positive electrode.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. An anode, characterized in that the anode comprises an anode active material layer comprising an anode active material and a sulfonic acid group-containing compound.
2. The anode of claim 1, wherein the anode active material comprises a silicon oxygen material and/or a silicon carbon material;
preferably, the sulfonic acid group-containing compound comprises a compound having the structure shown in formula I;
wherein R is1、R2、R3Each independently selected from H, methyl or ethyl;
x is selected from metal ions.
3. The negative electrode according to claim 1 or 2, wherein the sulfonic acid group-containing compound comprises polystyrene sulfonate;
preferably, the polystyrene sulfonate has a number average molecular weight of 5000 to 50000;
preferably, the polystyrene sulfonate comprises sodium polystyrene sulfonate and/or potassium polystyrene sulfonate.
4. The anode according to any one of claims 1 to 3, wherein the anode active material layer further comprises a conductive agent;
preferably, the conductive agent is a surface-treated conductive agent.
5. The anode of claim 4, wherein the conductive agent comprises at least one of carbon black, graphite, carbon nanotubes, or carbon fibers;
preferably, the conductive agent includes carbon black and/or carbon nanotubes.
6. The negative electrode of any of claims 1 to 5, further comprising a binder comprising at least one of polyvinylidene fluoride, styrene butadiene rubber, polyimide, or carboxymethyl cellulose.
7. The negative electrode according to any one of claims 1 to 6, characterized in that the negative electrode comprises, in parts by weight, 95 to 99 parts of a negative electrode active material, 1 to 5 parts of a sulfonic acid group-containing compound, 1 to 5 parts of a conductive agent, and 1 to 3 parts of a binder.
8. An electrochemical device comprising the negative electrode according to any one of claims 1 to 7, an electrolyte, a separator, and a positive electrode.
9. An electrochemical device, wherein a gas permeability value of a separator in the electrochemical device is 140 to 160.
10. An electronic device, characterized in that it comprises a negative electrode according to any one of claims 1 to 7 and/or an electrochemical device according to claim 8 or 9.
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