CN116656277A - Adhesive, negative plate and sodium ion battery - Google Patents
Adhesive, negative plate and sodium ion battery Download PDFInfo
- Publication number
- CN116656277A CN116656277A CN202310406134.2A CN202310406134A CN116656277A CN 116656277 A CN116656277 A CN 116656277A CN 202310406134 A CN202310406134 A CN 202310406134A CN 116656277 A CN116656277 A CN 116656277A
- Authority
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- China
- Prior art keywords
- negative electrode
- adhesive
- binder
- derived repeating
- active material
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- 239000000853 adhesive Substances 0.000 title claims abstract description 57
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 57
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 40
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- VYFYYTLLBUKUHU-UHFFFAOYSA-N Dopamine Natural products NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229960003638 dopamine Drugs 0.000 claims abstract description 23
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 229920001577 copolymer Polymers 0.000 claims abstract description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims description 54
- 239000007773 negative electrode material Substances 0.000 claims description 22
- 239000011888 foil Substances 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 12
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 12
- 239000006258 conductive agent Substances 0.000 claims description 11
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 10
- 239000006229 carbon black Substances 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 239000006230 acetylene black Substances 0.000 claims description 4
- 229910021385 hard carbon Inorganic materials 0.000 claims description 4
- 239000002134 carbon nanofiber Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 229910021384 soft carbon Inorganic materials 0.000 claims description 3
- 239000013543 active substance Substances 0.000 abstract description 9
- 239000001257 hydrogen Substances 0.000 abstract description 9
- 230000003993 interaction Effects 0.000 abstract description 8
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 28
- 239000011149 active material Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 12
- 238000004806 packaging method and process Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- -1 polypropylene Polymers 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 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 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- 229920002125 Sokalan® Polymers 0.000 description 6
- 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 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 description 6
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 6
- 239000004584 polyacrylic acid Substances 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- 239000000661 sodium alginate Substances 0.000 description 6
- 235000010413 sodium alginate Nutrition 0.000 description 6
- 229940005550 sodium alginate Drugs 0.000 description 6
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 6
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 6
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 description 6
- 238000004804 winding Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DKQPXAWBVGCNHG-UHFFFAOYSA-N 2,2,4,4,6,6-hexafluoro-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound FP1(F)=NP(F)(F)=NP(F)(F)=N1 DKQPXAWBVGCNHG-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical group FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- JKUAHMKHSDOYKZ-UHFFFAOYSA-N FC(C(F)(F)F)(OP1N=PN=P[N]1)F Chemical compound FC(C(F)(F)F)(OP1N=PN=P[N]1)F JKUAHMKHSDOYKZ-UHFFFAOYSA-N 0.000 description 1
- QGUHMPOHPMAXBY-UHFFFAOYSA-N FC(C(OP1N=PN=P[N]1)=C(C(F)=C1F)F)=C1F Chemical compound FC(C(OP1N=PN=P[N]1)=C(C(F)=C1F)F)=C1F QGUHMPOHPMAXBY-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910020808 NaBF Inorganic materials 0.000 description 1
- 229910021201 NaFSI Inorganic materials 0.000 description 1
- 241001274216 Naso Species 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000005678 chain carbonates Chemical class 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/24—Homopolymers or copolymers of amides or imides
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The application belongs to the technical field of sodium ion batteries, and particularly relates to an adhesive, a negative plate and a sodium ion battery. The adhesive is a copolymer of acrylic monomer derived repeating units, acrylamide monomer derived repeating units and dopamine acrylic derived repeating units, has a carboxyl, amino and hydroxyl structure, can form hydrogen bonds and covalent bonds with negative electrode active substances, conductive carbon and negative electrode current collectors with strong interaction force, and the carboxyl has strong interaction with strong hydrogen bonds formed between functional groups on the surfaces of the active substances.
Description
Technical Field
The application belongs to the technical field of sodium ion batteries, and particularly relates to an adhesive, a negative plate and a sodium ion battery.
Background
In recent years, due to the scarcity of lithium resources, the continuous rising of raw materials and the burst of energy storage markets, the development of other related energy storage technologies capable of replacing lithium ion batteries at low cost is very critical. Meanwhile, the sodium ion battery is being developed into an emerging energy storage technical scheme, and has wide application prospects in the energy storage field due to the advantages of abundant sodium resources, low cost, good safety performance and the like; for sodium ion batteries, the negative electrode material plays an important role in loading and releasing sodium ions, which directly affects the overall kinetic properties of the battery, such as rate capability, power density, and the like.
Currently, practical use of sodium ion batteries is still limited by the lack of suitable binders, particularly binders with excellent adhesion and ionic conductivity. The common graphite carbon-based material for the negative electrode of the lithium ion battery has rich raw materials, low price and large reversible capacity, but because of large radius of sodium ions and thermodynamic instability of sodium and graphite compounds, the material cannot be used as the negative electrode material of the sodium ion battery; the unique structure of the non-graphite carbon-based material, although capable of exhibiting excellent electrochemical performance in sodium batteries, has low compaction density, more surface defects and pores, and can cause poor peel strength of the negative electrode sheet, which seriously affects the cycle life of the sodium ion battery.
Disclosure of Invention
The application aims at: aiming at the defects of the prior art, the adhesive is provided, which has strong hydrogen bond interaction formed between carboxyl and functional groups on the surface of an active substance, and dopamine of the adhesive has adsorption effect on the surface of the substance, so that the adhesive force among the negative electrode active substance layer, the current collector and each component of the negative electrode can be enhanced, and the peeling strength of the negative electrode plate is effectively improved.
In order to achieve the above purpose, the present application adopts the following technical scheme:
the adhesive is a copolymer of acrylic monomer derived repeating units, acrylamide monomer derived repeating units and dopamine acrylic derived repeating units, and the molecular formula of the adhesive is as follows:
wherein R is 1 Is H, -CH 3 、-COOH、-CH 2 COOH or-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 ，
R2 is H, li, na or K,
r3 is H,-CH 3 or-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 ，
R4 is H, -CH 3 、-COOH、-CH 2 COOH or-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 。
Preferably, in the molecular formula of the binder, x is an integer of 5 to 5000, y is an integer of 5 to 1000, and z is an integer of 5 to 1000.
The second object of the present application is to provide a negative electrode sheet, which comprises a negative electrode current collector and a negative electrode active material layer disposed on at least one surface of the negative electrode current collector, wherein the negative electrode active material layer comprises a negative electrode active material, a conductive agent, a dispersing agent and the binder.
Preferably, the mass percentages of the anode active material, the conductive agent, the dispersing agent and the binder are (90% -98%): (0.5 to 5 percent), 0.1 to 2 percent and 0.5 to 5 percent).
Preferably, the negative electrode active material is at least one of hard carbon and soft carbon.
Preferably, the peel strength of the negative electrode plate is D (N/m), wherein D is more than 2 and less than 40.
Preferably, the negative electrode active material layer has a resistivity E (Ω cm), wherein E.ltoreq.0.05.ltoreq.1.
Preferably, the conductive agent includes at least one of carbon black, activated carbon, carbon molecular sieve, acetylene black, carbon black, ketjen black, graphene, carbon nanotubes and carbon nanofibers.
Preferably, the negative electrode current collector comprises at least one of a carbon-coated foil, a metal foil or a composite foil.
The third object of the present application is to: the application provides a sodium ion battery, which comprises electrolyte, a positive plate, the negative plate and a diaphragm arranged between the positive plate and the negative plate.
The application has the beneficial effects that: the binder provided by the application has a carboxyl, amino and hydroxyl structure, not only can form a hydrogen bond and a covalent bond with strong interaction force with a negative electrode active substance, conductive carbon and a negative electrode current collector, but also can form a hydrogen bond and a covalent bond with strong interaction force among molecules of the binder, and the strong hydrogen bond interaction formed among carboxyl and functional groups on the surface of the active substance, and the dopamine in the binder has strong adsorption effect on the surface of the substance, so that the binding force among a negative electrode active substance layer, the current collector and each component of the negative electrode is favorably enhanced, the stripping capability of the negative electrode sheet is effectively improved, and the migration rate of sodium ions is favorably enhanced by the carboxyl component, so that the cycle performance, the stability performance and the multiplying power performance of a sodium ion battery are improved.
Detailed Description
In order to make the technical solution and advantages of the present application more apparent, the technical solution of the present application will be clearly and completely described in conjunction with specific embodiments, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
According to one aspect of the present application, there is provided a binder, wherein the binder is a copolymer of an acrylic monomer-derived repeating unit, an acrylamide monomer-derived repeating unit, and a dopamine acrylic-derived repeating unit, and the molecular formula of the binder is as follows:
wherein R is 1 Is H, -CH 3 、-COOH、-CH 2 COOH or-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 ，
R 2 Is H, li, na or K,
R 3 is H, -CH 3 or-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 ，
R 4 Is H, -CH 3 、-COOH、-CH 2 COOH or-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 。
The carboxyl, amino and hydroxyl structures not only can form hydrogen bonds and covalent bonds with strong interaction force with the negative electrode active material, conductive carbon and the negative electrode current collector, but also can form hydrogen bonds and covalent bonds with strong interaction force among molecules of the binder, and the strong hydrogen bonds formed between the carboxyl and the functional groups on the surface of the active material interact with each other.
In one embodiment of the present application, the binder has a formula wherein the number x of acrylic monomer derived repeating units is an integer from 5 to 5000, the number y of acrylamide monomer derived repeating units is an integer from 5 to 1000, and the number z of bazaar acrylic derived repeating units is an integer from 5 to 1000, which may be, for example, 5, 10, 20, 50, 80, 100, 500, 1000, 2000, 3000, 4000, 5000.
According to a second aspect of the present application, there is provided a negative electrode sheet comprising a negative electrode current collector and a negative electrode active material layer provided on at least one surface of the negative electrode current collector, the negative electrode active material layer comprising a negative electrode active material, a conductive agent, a dispersant and the binder described above.
In an embodiment according to the present application, the mass percentages of the anode active material, the conductive agent, the dispersant, and the binder are (90% to 98%): (0.5 to 5 percent), 0.1 to 2 percent and 0.5 to 5 percent).
The content of the components in the negative electrode active material layer can be adjusted according to performance requirements, for example, the negative electrode active material can be 90%, 91%, 92%, 93%, 94%, 96%, 98%; the conductive agent may be 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%; the dispersant may be 0.1%, 0.5%, 15, 1.5%, 2%; the binder may be 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%.
In an embodiment according to the present application, the anode active material is at least one of hard carbon and soft carbon.
In an embodiment according to the application, the peel strength of the negative electrode sheet is D (N/m), wherein 2 < D < 40, which may be, for example, 2N/m, 5N/m, 8N/m, 10N/m, 15N/m, 18N/m, 20N/m, 25N/m, 28N/m, 30N/m, 35N/m, 38N/m, 40N/m.
In one embodiment according to the present application, the negative electrode active material layer has a resistivity E (Ω·cm), wherein 0.05+.E+.ltoreq.1, and may be, for example, 0.05 Ω·cm, 0.06 Ω·cm, 0.08 Ω·cm, 0.1 Ω·cm, 0.3 Ω·cm, 0.5 Ω·cm, 0.81 Ω·cm, 0.85 Ω·cm, 1 Ω·cm.
In an embodiment according to the present application, the conductive agent includes at least one of carbon black, activated carbon, carbon molecular sieve, acetylene black, carbon black, ketjen black, graphene, carbon nanotube and carbon nanofiber, and a certain amount of conductive agent is added during the pole piece manufacturing to increase the conductivity of electrons and sodium ions, and the electron transmission rate is accelerated by forming a conductive network on the surface of the active material, and at the same time, the electrolyte can be absorbed and maintained, so as to provide more electrolyte interfaces for sodium ions, thereby improving the battery charging efficiency and cycle life.
In an embodiment according to the present application, the negative electrode current collector includes at least one of a carbon-coated foil, a metal foil or a composite foil, the current collector is a carbon-coated aluminum foil, and after the carbon-coated treatment is performed on the surface of the aluminum foil, the carbon-coated layer may function as a bridge, so that the negative electrode active material and the aluminum foil are tightly bonded, and the particles are embedded into each other, thereby improving the conductivity of the negative electrode sheet and finally reducing the internal resistance of the battery.
According to a third aspect of the present application, there is provided a sodium ion battery comprising an electrolyte, a positive electrode sheet, a negative electrode sheet as described in any one of the preceding claims, and a separator disposed between the negative electrode sheet and the positive electrode sheet.
The positive plate adopts N-methyl pyrrolidone (NMP) as a solvent to prepare active material slurry, conductive adhesive is added into the active material slurry to stir the active material slurry to prepare the positive plate, and then the positive plate is prepared into the pole plate through the procedures of coating, drying and the like.
The membrane adopts a single-layer or multi-layer membrane of at least one of polypropylene, polyethylene, polyester substrate, polyacrylonitrile, non-woven fabric, polyvinylidene fluoride and glass fiber.
The electrolyte comprises sodium salt, carbonate solvent and additive. Wherein the carbonate solvent comprises a cyclic carbonate solvent and a chain carbonate solvent; sodium salt is NaPF 6 、NaClO 4 、NaBF 4 、NaFSI、NaTFSI、NaSO 3 CF 3 And Na (CH) 3 )C 6 H 4 SO 3 At least one of (a) and (b); the additive comprises a first additive and a second additive, wherein the first additive is fluoroethylene carbonate or bifluoroethylene carbonate, and the second additive is at least one of fluorocyclotriphosphazene, hexafluorocyclotriphosphazene, pentafluoroethoxy cyclotriphosphazene and pentafluorophenoxy cyclotriphosphazene.
The technical scheme and beneficial effects of the present application will be described in detail with reference to specific examples and comparative examples.
Example 1
The adhesive provided in this embodiment is a copolymer of an acrylic monomer derived repeating unit, an acrylamide monomer derived repeating unit and a dopamine acrylic derived repeating unit, and the molecular formula of the adhesive is as follows:
wherein R is 1 ～R 3 All are H, R 4 -COOH, x 1023, y 408, z 415, the mass content of the binder in the active material layer being 4%;
the preparation method of the negative plate containing the adhesive comprises the following steps: and uniformly mixing hard carbon, a binder and carbon black in a proper amount of deionized water according to a weight ratio of 94:4:2 to obtain the negative electrode slurry. And then coating the negative electrode slurry on a negative electrode current collector aluminum foil, and baking and rolling to obtain a negative electrode plate. Wherein the thickness of the negative electrode current collector was 20 μm and the thickness of the negative electrode active material layer was 70 μm.
The preparation method of the positive plate comprises the following steps: uniformly mixing Prussian blue, nitrile rubber and acetylene black in a weight ratio of 92:4:4 in a proper amount of NMP to obtain anode slurry; and then coating the anode slurry on a carbon-coated aluminum foil of an anode current collector, and drying and rolling to obtain the anode sheet.
The preparation method of the sodium ion battery containing the binder comprises the following steps: sequentially stacking the above cathode pole piece, membrane (polyethylene film) and anode pole piece, or winding to obtain electric core, placing the electric core in packaging shell, adding electrolyte (ethylene carbonate+NaPF) 6 ) And packaging, and performing processes such as formation, hot and cold pressing, capacity division and the like to obtain the sodium ion battery.
Example 2
The values of the binder-related parameters are different from those of example 1.
The adhesive provided in this embodiment is a copolymer of an acrylic monomer derived repeating unit, an acrylamide monomer derived repeating unit and a dopamine acrylic derived repeating unit, and the molecular formula of the adhesive is as follows:
wherein R is 1 is-CH 3 ,R 2 Is Li, R 3 is-CH 3 ，R 4 is-CH 2 COOH, x being 2109, y being 542, z being 765, the mass content of the binder in the active substance layer being 3%;
the remainder is the same as embodiment 1 and will not be described in detail here.
Example 3
The values of the binder-related parameters are different from those of example 1.
The adhesive provided in this embodiment is a copolymer of an acrylic monomer derived repeating unit, an acrylamide monomer derived repeating unit and a dopamine acrylic derived repeating unit, and the molecular formula of the adhesive is as follows:
wherein R is 1 is-COOH, R 2 Is Na, R 3 is-CH 3 ，R 4 H, x is 821, y is 625, z is 356, the mass content of the binder in the active material layer is 3.5%;
the remainder is the same as embodiment 1 and will not be described in detail here.
Example 4
The values of the binder-related parameters are different from those of example 1.
The adhesive provided in this embodiment is a copolymer of an acrylic monomer derived repeating unit, an acrylamide monomer derived repeating unit and a dopamine acrylic derived repeating unit, and the molecular formula of the adhesive is as follows:
wherein R is 1 is-CH 2 COOH,R 2 Is K, R 3 Is H, R 4 is-CH 3 X is 3405, y is 385, z is 145, and the mass content of the binder in the active material layer is 2%;
the remainder is the same as embodiment 1 and will not be described in detail here.
Example 5
The values of the binder-related parameters are different from those of example 1.
The adhesive provided in this embodiment is a copolymer of an acrylic monomer derived repeating unit, an acrylamide monomer derived repeating unit and a dopamine acrylic derived repeating unit, and the molecular formula of the adhesive is as follows:
wherein R is 1 is-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 ,R 2 Is Na, R 3 is-CH 3 ，R 4 H, x is 4752, y is 143, z is 95, the mass content of the binder in the active material layer is 1.6%;
the remainder is the same as embodiment 1 and will not be described in detail here.
Example 6
The values of the binder-related parameters are different from those of example 1.
The adhesive provided in this embodiment is a copolymer of an acrylic monomer derived repeating unit, an acrylamide monomer derived repeating unit and a dopamine acrylic derived repeating unit, and the molecular formula of the adhesive is as follows:
wherein R is 1 Is H 3 ,R 2 Is Li, R 3 Is H, R 4 H, x 1615, y 717, z 232, the mass content of the binder in the active material layer being 1.2%;
the remainder is the same as embodiment 1 and will not be described in detail here.
Example 7
The values of the binder-related parameters are different from those of example 1.
The adhesive provided in this embodiment is a copolymer of an acrylic monomer derived repeating unit, an acrylamide monomer derived repeating unit and a dopamine acrylic derived repeating unit, and the molecular formula of the adhesive is as follows:
wherein R is 1 is-CH 3 ，R 2 Is Na, R 3 is-CH 3 ，R 4 is-CH 3 X is 4232, y is 633, z is 559, and the mass content of the binder in the active material layer is 0.6%;
the remainder is the same as embodiment 1 and will not be described in detail here.
Example 8
The values of the binder-related parameters are different from those of example 1.
The adhesive provided in this embodiment is a copolymer of an acrylic monomer derived repeating unit, an acrylamide monomer derived repeating unit and a dopamine acrylic derived repeating unit, and the molecular formula of the adhesive is as follows:
wherein R is 1 is-COOH, R 2 Is K, R 3 Is H, R 4 -COOH, x 485, y 725, z 624, the mass content of the binder in the active material layer being 2.3%;
the remainder is the same as embodiment 1 and will not be described in detail here.
Example 9
The values of the binder-related parameters are different from those of example 1.
The adhesive provided in this embodiment is a copolymer of an acrylic monomer derived repeating unit, an acrylamide monomer derived repeating unit and a dopamine acrylic derived repeating unit, and the molecular formula of the adhesive is as follows:
wherein R is 1 Is H, R 2 Is Li, R 3 is-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 ，R 4 is-CH 3 X is 977, y is 512, z is 428, the mass content of the binder in the active material layer is 3.9%;
the remainder is the same as embodiment 1 and will not be described in detail here.
Example 10
The values of the binder-related parameters are different from those of example 1.
The adhesive provided in this embodiment is a copolymer of an acrylic monomer derived repeating unit, an acrylamide monomer derived repeating unit and a dopamine acrylic derived repeating unit, and the molecular formula of the adhesive is as follows:
wherein R is 1 is-CH 2 COOH，R 2 Is H, R 3 is-CH 3 ，R 4 is-CH 2 COOH, x is 1456, y is 332, z is 216, the mass content of the binder in the active material layer is 4.6%; the method comprises the steps of carrying out a first treatment on the surface of the
The remainder is the same as embodiment 1 and will not be described in detail here.
Example 11
The values of the binder-related parameters are different from those of example 1.
The adhesive provided in this embodiment is a copolymer of an acrylic monomer derived repeating unit, an acrylamide monomer derived repeating unit and a dopamine acrylic derived repeating unit, and the molecular formula of the adhesive is as follows:
wherein R is 1 Is H, R 2 Is Na, R 3 Is H, R 4 H, x 2509, y 453, z 387, the mass content of the binder in the active material layer being 3.6%;
the remainder is the same as embodiment 1 and will not be described in detail here.
Example 12
The values of the binder-related parameters are different from those of example 1.
The adhesive provided in this embodiment is a copolymer of an acrylic monomer derived repeating unit, an acrylamide monomer derived repeating unit and a dopamine acrylic derived repeating unit, and the molecular formula of the adhesive is as follows:
wherein R is 1 is-CH 3 ，R 2 Is K, R 3 is-CH 3 ，R 4 is-CH 3 X is 3416, y is 785, z is 612, and the mass content of the binder in the active material layer is 2.5%;
the remainder is the same as embodiment 1 and will not be described in detail here.
Example 13
The values of the binder-related parameters are different from those of example 1.
The adhesive provided in this embodiment is a copolymer of an acrylic monomer derived repeating unit, an acrylamide monomer derived repeating unit and a dopamine acrylic derived repeating unit, and the molecular formula of the adhesive is as follows:
wherein R is 1 is-COOH, R 2 Is H, R 3 is-CH 3 ，R 4 -COOH, x 4135, y 264, z 826, the mass content of the binder in the active material layer being 1.8%;
the remainder is the same as embodiment 1 and will not be described in detail here.
Example 14
The values of the binder-related parameters are different from those of example 1.
The adhesive provided in this embodiment is a copolymer of an acrylic monomer derived repeating unit, an acrylamide monomer derived repeating unit and a dopamine acrylic derived repeating unit, and the molecular formula of the adhesive is as follows:
wherein R is 1 is-CH 2 OOH，R 2 Is Li, R 3 Is H, R 4 is-CH 2 OOH, x 658, y 768, z 494, the mass content of the binder in the active substance layer being 0.9%;
the remainder is the same as embodiment 1 and will not be described in detail here.
Example 15
The values of the binder-related parameters are different from those of example 1.
The adhesive provided in this embodiment is a copolymer of an acrylic monomer derived repeating unit, an acrylamide monomer derived repeating unit and a dopamine acrylic derived repeating unit, and the molecular formula of the adhesive is as follows:
wherein R is 1 Is H, R 2 Is K, R 3 Is H, R 4 is-CH 3 X is 1802, y is 156, z is 637, and the mass content of the binder in the active material layer is 1.6%;
the remainder is the same as embodiment 1 and will not be described in detail here.
Example 16
The values of the binder-related parameters are different from those of example 1.
The adhesive provided in this embodiment is a copolymer of an acrylic monomer derived repeating unit, an acrylamide monomer derived repeating unit and a dopamine acrylic derived repeating unit, and the molecular formula of the adhesive is as follows:
wherein R is 1 is-CH 3 ，R 2 Is H, R 3 Is H, R 4 is-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 X is 2318, y is 625, z is 738, the binder is in the activeThe mass content in the mass layer is 3.4%;
the remainder is the same as embodiment 1 and will not be described in detail here.
Comparative example 1
The adhesive provided in the comparative example comprises the following components in percentage by mass: 1.6%:0:0:0, sodium carboxymethyl cellulose, styrene-butadiene rubber, polyacrylic acid, sodium alginate and sodium polyacrylate;
the negative pole piece, the diaphragm (polyethylene film) and the positive pole piece containing the adhesive are sequentially stacked, or the battery core is obtained after winding, the battery core is arranged in a packaging shell, and electrolyte (ethylene carbonate+NaPF) is added 6 ) And packaging, and performing processes such as formation, hot and cold pressing, capacity division and the like to obtain the sodium ion battery.
Comparative example 2
The adhesive provided in the comparative example comprises the following components in percentage by mass: 2.1%:0%:0%:0% of sodium carboxymethyl cellulose, styrene-butadiene rubber, polyacrylic acid, sodium alginate and sodium polyacrylate;
the negative pole piece, the diaphragm (polyethylene film) and the positive pole piece containing the adhesive are sequentially stacked, or the battery core is obtained after winding, the battery core is arranged in a packaging shell, and electrolyte (ethylene carbonate+NaPF) is added 6 ) And packaging, and performing processes such as formation, hot and cold pressing, capacity division and the like to obtain the sodium ion battery.
Comparative example 3
The adhesive provided in the comparative example comprises the following components in percentage by mass: 0%:2.8%:0%:0% of sodium carboxymethyl cellulose, styrene-butadiene rubber, polyacrylic acid, sodium alginate and sodium polyacrylate;
the negative pole piece, the diaphragm (polyethylene film) and the positive pole piece containing the adhesive are sequentially stacked, or the battery core is obtained after winding, the battery core is arranged in a packaging shell, and electrolyte (ethylene carbonate+NaPF) is added 6 ) And packaging, and performing processes such as formation, hot and cold pressing, capacity division and the like to obtain the sodium ion battery.
Comparative example 4
The adhesive provided in the comparative example comprises the following components in percentage by mass: 0%:0%:3.2%:0% of sodium carboxymethyl cellulose, styrene-butadiene rubber, polyacrylic acid, sodium alginate and sodium polyacrylate;
the negative pole piece, the diaphragm (polyethylene film) and the positive pole piece containing the adhesive are sequentially stacked, or the battery core is obtained after winding, the battery core is arranged in a packaging shell, and electrolyte (ethylene carbonate+NaPF) is added 6 ) And packaging, and performing processes such as formation, hot and cold pressing, capacity division and the like to obtain the sodium ion battery.
Comparative example 5
The adhesive provided in the comparative example comprises the following components in percentage by mass: 0%:0%:0%:3.0% of sodium carboxymethyl cellulose, styrene-butadiene rubber, polyacrylic acid, sodium alginate and sodium polyacrylate;
the negative pole piece, the diaphragm (polyethylene film) and the positive pole piece containing the adhesive are sequentially stacked, or the battery core is obtained after winding, the battery core is arranged in a packaging shell, and electrolyte (ethylene carbonate+NaPF) is added 6 ) And packaging, and performing processes such as formation, hot and cold pressing, capacity division and the like to obtain the sodium ion battery.
The sodium ion batteries obtained in examples 1 to 16 and comparative examples 1 to 5 were subjected to electrochemical performance tests, and the experimental results are shown in table 1.
(1) And (3) testing the mechanical properties of the negative electrode plate:
and (3) attaching the double-sided adhesive tape to a flat steel plate, and attaching a negative pole piece with the length of 200mm and the width of 30mm to the double-sided adhesive tape. And then placing the steel plate of the bonding pole piece in a testing area of a pulling machine, and stripping the pole piece from the steel plate by the pulling machine at an angle of 180 degrees. Wherein the stripping length is 150mm and the stripping speed is 50mm/min.
(2) Cycling performance test of sodium ion battery:
and (3) charging the sodium ion battery to the upper limit of the cut-off voltage at the constant current of 1C, charging to the current of 0.2C by using the constant voltage, standing for 5min, discharging to the lower limit of the cut-off voltage by using the constant current of 1C, and standing for 5min, wherein the discharge capacity is the initial capacity of the sodium ion battery in the 1-cycle charge-discharge process. And (5) cycling the battery for 500 times according to the steps to obtain the 500 th cycle discharge capacity. The capacity retention rate of the sodium ion battery at 25 ℃ cycle 500 times = the discharge capacity of the 500 th cycle/the discharge capacity of the 1 st cycle x 100%.
(3) And (3) testing the multiplying power performance of the sodium ion battery:
at 25 ℃, the sodium ion battery is respectively charged and discharged at 0.2C and 1C multiplying power, wherein 1 C=160 mAh/g, and the cut-off voltage of charging and discharging is 1.5V-3.8V. The specific steps are that the sodium ion battery is charged to the upper limit of the cut-off voltage with a constant current of a set multiplying power, then is charged to the current of 0.05 ℃ with a constant voltage, then is kept stand for 5min, is discharged to the lower limit of the cut-off voltage with a constant current of the set multiplying power, is kept stand for 5min, and the above is a cyclic charging and discharging process. Repeating the above steps for 5 times of cyclic charge and discharge tests, and recording the discharge specific capacity of the 5 th time of the cycle. The ratio (%) =1c charge-discharge cycle 5 discharge specific capacity/0.2C charge-discharge cycle 5 discharge specific capacity×100% of the ratio of the rate discharge of the sodium ion battery for 5 cycles.
Wherein P is the peel strength of the negative electrode plate, C is the 500 th capacity retention rate of the sodium ion battery, and R is the 5 th rate discharge capacity ratio of the sodium ion battery.
TABLE 1 sodium ion battery Performance test Table
It can be seen from table 1 that when the binder is a copolymer of an acrylic monomer-derived repeating unit, an acrylamide monomer-derived repeating unit, and a dopamine acrylic acid-derived repeating unit, the negative electrode tab has good adhesion properties and ion-conducting properties, whereas when the negative electrode binder is sodium carboxymethyl cellulose, styrene-butadiene rubber, polyacrylic acid, sodium alginate, and sodium polyacrylate, the negative electrode tab has poor adhesion properties and ion-conducting properties, resulting in poor cycle properties and rate properties of the sodium ion battery.
Variations and modifications of the above embodiments will occur to those skilled in the art to which the application pertains from the foregoing disclosure and teachings. Therefore, the present application is not limited to the above-described embodiments, but is intended to be capable of modification, substitution or variation in light thereof, which will be apparent to those skilled in the art in light of the present teachings. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present application in any way.
Claims (10)
1. The adhesive is characterized in that the adhesive is a copolymer of acrylic monomer derived repeating units, acrylamide monomer derived repeating units and dopamine acrylic derived repeating units, and the adhesive has the following molecular formula:
wherein R is 1 Is H, -CH 3 、-COOH、-CH 2 COOH or-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 R2 is H, li, na or K,
r3 is H, -CH 3 or-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 R4 is H, -CH 3 、-COOH、-CH 2 COOH or-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 。
2. The binder of claim 1 wherein in the formula of the binder, x is an integer from 5 to 5000, y is an integer from 5 to 1000, and z is an integer from 5 to 1000.
3. A negative electrode sheet comprising a negative electrode current collector and a negative electrode active material layer provided on at least one surface of the negative electrode current collector, the negative electrode active material layer comprising a negative electrode active material, a conductive agent, a dispersant, and the binder of claim 1.
4. The negative electrode sheet according to claim 3, wherein the mass percentages of the negative electrode active material, the conductive agent, the dispersant and the binder are (90% -98%): (0.5 to 5 percent), 0.1 to 2 percent and 0.5 to 5 percent).
5. The negative electrode sheet according to claim 3, wherein the negative electrode active material is at least one of hard carbon and soft carbon.
6. The negative electrode sheet according to claim 3, wherein the peel strength of the negative electrode sheet is D (N/m), wherein 2 < D < 40.
7. The negative electrode sheet according to claim 3, wherein the negative electrode active material layer has a resistivity E (Ω -cm), wherein E.ltoreq.0.05.ltoreq.1.
8. The negative electrode sheet according to claim 3, wherein the conductive agent comprises at least one of carbon black, activated carbon, carbon molecular sieve, acetylene black, carbon black, ketjen black, graphene, carbon nanotubes, and carbon nanofibers.
9. The negative electrode tab of claim 3, wherein the negative current collector comprises at least one of a carbon-coated foil, a metal foil, or a composite foil.
10. A sodium ion battery comprising a positive plate, a negative plate, a diaphragm and electrolyte, wherein the negative plate is the negative plate of claims 3-9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117096268A (en) * | 2023-10-18 | 2023-11-21 | 瑞浦兰钧能源股份有限公司 | Negative electrode of sodium ion battery, negative electrode slurry and preparation method of negative electrode slurry |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117096268A (en) * | 2023-10-18 | 2023-11-21 | 瑞浦兰钧能源股份有限公司 | Negative electrode of sodium ion battery, negative electrode slurry and preparation method of negative electrode slurry |
| CN117096268B (en) * | 2023-10-18 | 2024-02-06 | 瑞浦兰钧能源股份有限公司 | Negative electrode of sodium ion battery, negative electrode slurry and preparation method of negative electrode slurry |
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