CN117913212A - Negative electrode plate, preparation method thereof and battery - Google Patents
Negative electrode plate, preparation method thereof and battery Download PDFInfo
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- CN117913212A CN117913212A CN202410319974.XA CN202410319974A CN117913212A CN 117913212 A CN117913212 A CN 117913212A CN 202410319974 A CN202410319974 A CN 202410319974A CN 117913212 A CN117913212 A CN 117913212A
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- negative electrode
- current collector
- binder
- active material
- material layer
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000011230 binding agent Substances 0.000 claims abstract description 66
- 239000011149 active material Substances 0.000 claims abstract description 49
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000003446 ligand Substances 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 5
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 40
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 40
- 229940112669 cuprous oxide Drugs 0.000 claims description 40
- 238000004070 electrodeposition Methods 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 21
- 239000006258 conductive agent Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- 229920002125 Sokalan® Polymers 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000004584 polyacrylic acid Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- 238000011065 in-situ storage Methods 0.000 claims description 5
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000661 sodium alginate Substances 0.000 claims description 4
- 235000010413 sodium alginate Nutrition 0.000 claims description 4
- 229940005550 sodium alginate Drugs 0.000 claims description 4
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 27
- 239000011889 copper foil Substances 0.000 description 21
- 239000010949 copper Substances 0.000 description 18
- 239000011888 foil Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- DCEMCPAKSGRHCN-UHFFFAOYSA-N oxirane-2,3-dicarboxylic acid Chemical compound OC(=O)C1OC1C(O)=O DCEMCPAKSGRHCN-UHFFFAOYSA-N 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000007770 graphite material Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical group [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000010399 physical interaction Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011530 conductive current collector Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005406 washing Methods 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
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention provides a negative electrode plate, a preparation method thereof and a battery, wherein the negative electrode plate comprises a current collector and an active material layer on at least one side surface of the current collector, an interface layer is arranged between the current collector and the active material layer, and the interface layer comprises a metal complex; the metal species in the metal complex is the same as the current collector, and the ligand in the metal complex includes a binder in the active material layer. According to the negative electrode plate, the interface layer containing the metal complex is formed between the current collector and the active material layer, so that the bonding strength between the current collector and the active material layer is enhanced, the stripping force and the cohesive force of the negative electrode plate are improved, and the negative electrode plate has excellent mechanical strength and electrochemical performance.
Description
Technical Field
The invention belongs to the technical field of batteries, and relates to a negative electrode plate, a preparation method thereof and a battery.
Background
Secondary batteries have been widely paid attention in recent years as rechargeable batteries because of their high energy density, smooth operating voltage, green environmental protection, and the like. In general, a secondary battery is composed of several parts, such as a negative electrode material, a positive electrode material, a separator, an electrolyte, and the like. In general, the positive and negative electrode materials cannot be formed into independent electrode sheets, and often need to be coated on a conductive current collector, wherein the common positive electrode current collector is aluminum foil, and the negative electrode current collector is copper foil. The negative electrode is a very critical part of the secondary battery, and is a main carrier of metals in the secondary battery (e.g., lithium in a lithium battery, sodium in a sodium battery, etc.), which has a great influence on intercalation and deintercalation of metals.
In the actual production process, the negative electrode is a water system, so that the conditions of poor stripping force between the current collector and the active material and the like often occur in the preparation process, thereby influencing the quality of the pole piece and causing the deterioration of the cycle performance and the multiplying power performance of the lithium ion battery. These deficiencies limit the development of high energy density lithium ion batteries, and in order to improve the mechanical strength of the negative electrode sheet, new carbon materials and binders are often developed to improve the peel strength between the current collector and the active material.
As disclosed in CN 116885180a, the adhesive comprises an epoxy succinic acid containing a catechol group and an acrylic acid copolymer, the epoxy succinic acid containing a catechol group and the acrylic acid copolymer have a plurality of active functional groups including hydroxyl groups, amine groups, carboxyl groups and the like, the active functional groups provide a plurality of active sites, and the adhesive has a self-repairing function, and can effectively enhance the adhesion between a current collector and a silicon negative electrode, so that the peeling strength of the negative electrode sheet and the cycle performance of a corresponding lithium ion battery can be improved.
However, the development of a novel carbon material or binder, such as the above-described method for improving the peel strength between the current collector and the active material by developing a novel binder having a higher viscosity, is relatively high in complexity and cost, and is not suitable for commercial and industrial production.
Based on the above research, it is necessary to provide a negative electrode sheet, which can still enable the negative electrode sheet to have higher stripping force and cohesion without adopting a novel binder or a negative electrode material, and has excellent mechanical strength and electrochemical performance.
Disclosure of Invention
The invention aims to provide a negative electrode plate, a preparation method thereof and a battery, wherein an interface layer containing a metal complex is formed between a current collector and an active material layer of the negative electrode plate, so that the bonding strength between the current collector and the active material layer is enhanced, the stripping force and cohesion of the negative electrode plate are improved, and the negative electrode plate has excellent mechanical strength and electrochemical performance.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
In a first aspect, the invention provides a negative electrode plate, which comprises a current collector and an active material layer on at least one side surface of the current collector, wherein an interface layer is further arranged between the current collector and the active material layer, and the interface layer comprises a metal complex;
the metal species in the metal complex is the same as the current collector, and the ligand in the metal complex includes a binder in the active material layer.
According to the invention, the interface layer is arranged between the current collector and the active material layer, wherein the interface layer is composed of the metal complex, the metal complex comprises the metal center and the ligand, the element types of the metal center are the same as those of the current collector, and the ligand is the binder in the active material layer, so that the interface layer can realize chemical bonding, and compared with the common physical interaction, the acting force of chemical bonding is stronger, the bonding strength between the current collector and the active material layer is greatly enhanced, and the stripping force and cohesive force of the negative electrode plate are improved, so that the negative electrode plate has excellent mechanical strength and electrochemical performance.
Preferably, the metal complex is obtained by in situ reaction of cuprous oxide with the binder in the active material layer.
The metal complex is obtained by in-situ coordination reaction of cuprous oxide (Cu 2 O) and a binder, and because a current collector of the negative electrode plate usually adopts copper foil or adopts a composite current collector with copper layers on both sides, the copper simple substance is difficult to carry out coordination reaction with the binder, and cuprous oxide is selected as a reactant to generate the metal complex.
Preferably, a cuprous oxide layer is further included between the current collector and the interface layer.
The metal complex of the present invention is not formed by copper and a binder in a current collector, but a cuprous oxide layer is formed on the surface of the current collector, and then an active material layer slurry is coated to coordinate the cuprous oxide and the binder, so that after an interface layer is formed, there is a possibility that a cuprous oxide layer which is not coordinated exists between the current collector and the interface layer.
Preferably, the binder comprises a polymer comprising carboxyl groups, preferably a polyolefin-based compound.
Preferably, the polyacrylic acid compound includes any one or a combination of at least two of polyacrylic acid, sodium lignin sulfonate, or Sodium Alginate (SA).
The binding agent which reacts with the cuprous oxide is preferably polyacrylic acid, and the PAA (polyacrylic acid) has higher modulus and interaction because of a water-soluble chain polymer structure, and has carboxyl functional groups on the molecular structure, so that the binding agent is more favorable for reacting with the cuprous oxide to form a coordination compound, and the performance of the negative electrode plate can be further improved when the binding agent adopts polyacrylic acid.
The metal complex formed by the coordination of the cuprous oxide and the PAA has the structural formula at the coordination position of
。
In a second aspect, the present invention provides a method for preparing the negative electrode sheet according to the first aspect, the method comprising the steps of:
And setting a cuprous oxide layer on at least one side surface of the current collector, coating active material layer slurry on the surface of the cuprous oxide layer, standing, and drying and rolling to obtain the negative electrode plate.
The preparation method is simple, and the electrochemical performance of the negative electrode plate can be greatly improved on the basis of not changing the original traditional process.
Preferably, the time of standing is 1-2h, for example, 1h, 1.25h, 1.5h, 1.75h or 2h, but not limited to the recited values, other non-recited values within the range of values are equally applicable.
According to the invention, the active material layer slurry is coated on the surface of the cuprous oxide layer, so that the binding agent in the active material layer slurry and the cuprous oxide carry out coordination reaction, therefore, the standing time can influence the amount of the generated metal complex, thereby influencing the mechanical property of the cathode pole piece, if the standing time is too short, more cuprous oxide which does not carry out coordination reaction with the binding agent can be remained on the surface of the copper foil, so that the binding force is low, and if the standing time is too long, more coordination compounds are generated, the binding force is better, and meanwhile, the internal resistance of the pole piece is increased.
Preferably, the current collector comprises copper foil.
Preferably, the method for setting the cuprous oxide layer comprises the following steps: and taking the current collector as a working electrode, and performing electrodeposition of a cuprous oxide layer on at least one side surface of the current collector.
According to the invention, the cuprous oxide layer is prepared by an electrodeposition method, and the copper foil current collector can be directly used as a working electrode to obtain the Cu-Cu 2 O foil, so that the bonding strength of copper and cuprous oxide is improved.
Preferably, the electrodeposition time is 60-180s, which may be, for example, 80s, 100s, 120s, 140s, 160s or 180s, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The electrodepositing time of the invention can influence the thickness of the produced cuprous oxide layer, thereby influencing the bonding strength of the current collector and the active material layer, if the electrodepositing time is too short, the cuprous oxide content on the surface of the copper foil is less, the subsequent reaction is not facilitated, and if the electrodepositing time is too long, the cuprous oxide is too thick, and the current conduction is not facilitated.
Preferably, the voltage of the electrodeposition is-0.2 to-0.8V, for example, -0.2V, -0.4V, -0.6V or-0.8V, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the electrodeposition liquid used for the electrodeposition includes copper salt and sodium salt.
Preferably, the copper salt comprises copper acetate.
Preferably, the sodium salt comprises sodium acetate.
Preferably, the electrodeposition is preceded by a power-on at a voltage of 0.6-1.2V, for example, 0.8V, 1.0V or 1.2V, for 30-60s, for example, 30s, 40s, 50s or 60s, but not limited to the values recited, other non-recited values within the range of values are equally applicable.
According to the invention, copper foil is used as a working electrode, foil Pt is used as a counter electrode, ag/AgCl is used as a reference electrode, and at room temperature, the current is firstly conducted for 30-60s under the voltage of 0.6-1.2V, copper ions on the surface of the copper foil can be dissolved in the solution, the quantity of the copper ions dissolved in the solution is controlled by controlling the voltage and the current conducting time, the quantity of Cu 2 O deposited later can be ensured, meanwhile, the excessive dissolving quantity of the copper foil is avoided, and then the modified Cu-Cu 2 O copper foil can be obtained by applying the voltage of-0.2-0.8V for 60-180 s.
Preferably, the electrodeposition is further washed and dried for a period of 6-12 hours, for example, 8 hours, 10 hours or 12 hours, but not limited to the recited values, and other non-recited values in the range are equally applicable.
Preferably, the active material layer slurry includes a negative electrode host material, a binder, a conductive agent, and a solvent.
Preferably, the binder accounts for 2-4wt% of the total mass of the negative electrode main material, the binder and the conductive agent, and may be, for example, 2.5wt%, 3wt%, 3.5wt% or 4wt%, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Because the binder plays a role in binding and can carry out coordination reaction, the addition of the binder can also influence the mechanical properties and the like of the negative electrode plate, if the addition of the binder is too small, most of the binder can carry out coordination reaction with cuprous oxide, the binding effect of active substances in the whole electrode plate and the active substances can be reduced, the process of the electrode plate is influenced, the material is easy to fall off in the use process of the battery, and if the addition of the binder is too large, the binding force of the electrode plate can be better, but a large amount of binder can influence the exertion of the capacity of the active materials, and meanwhile, the internal resistance of the electrode plate is increased.
Wherein, the cathode main material, the conductive agent and the solvent can reasonably select common materials in the prior art, and are not limited herein, and the exemplary cathode main material comprises any one or a combination of at least two of graphite materials, silicon oxygen materials and silicon carbon materials; the conductive agent comprises conductive carbon black; the solvent comprises water.
As a preferable technical scheme of the preparation method, the preparation method comprises the following steps:
(1) In the electro-deposition solution, a copper foil is used as a working electrode, current is firstly conducted for 30-60s under the voltage of 0.6-1.2V, then the voltage of-0.2 to-0.8V is maintained for 60-180s, the deposition of a cuprous oxide layer on the surface of the copper foil is realized, and then washing and 6-12h drying are carried out, so that a Cu-Cu 2 O foil is obtained;
(2) Coating active material layer slurry on the surface of a Cu-Cu 2 O foil, then standing for 1-2h, and finally drying and rolling to obtain the negative electrode plate;
the active material layer slurry comprises a negative electrode main material, a binder, a conductive agent and a solvent, wherein the binder accounts for 2-4wt% of the total mass of the negative electrode main material, the binder and the conductive agent.
In a third aspect, the present invention provides a battery comprising a negative electrode tab according to the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
According to the invention, the interface layer is arranged between the current collector and the active material layer, wherein the interface layer is composed of the metal complex, and the ligand of the metal complex is the binder in the active material layer, so that the interface layer can realize chemical bonding, compared with the common physical interaction, the acting force of the chemical bonding is stronger, the bonding strength between the current collector and the active material layer is greatly enhanced, and the stripping force and cohesive force of the negative electrode plate are improved, so that the negative electrode plate has excellent mechanical strength and electrochemical performance.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a negative electrode plate, which comprises a copper foil and active material layers on two side surfaces of the copper foil, wherein an interface layer is further arranged between a current collector and the active material layers, and a cuprous oxide layer is further arranged between the current collector and the interface layer;
the interface layer comprises a metal complex, wherein a metal center in the metal complex is copper, a ligand is a binder in the active substance layer, and the binder is polyacrylic acid (PAA-2906);
the metal complex is obtained by in-situ reaction of cuprous oxide and a binder in the active material layer;
The preparation method of the negative electrode plate comprises the following steps:
(1) Preparing an aqueous solution of 0.02M copper acetate ((CH 3COO)2 Cu) and 0.1M sodium acetate (CH 3 COONa) as electrodeposition liquid, placing clean copper foil as a working electrode in the electrodeposition liquid, taking foil Pt as a counter electrode, taking Ag/AgCl as a reference electrode, electrifying at room temperature under the voltage of 0.6V for 60s, maintaining the voltage of-0.2V for 60s to realize the deposition of a cuprous oxide layer on the surface of the copper foil, cleaning for 3 times by adopting deionized water, and drying in an oven at 50 ℃ for 6h to obtain a Cu-Cu 2 O foil;
(2) Coating active material layer slurry on the surface of a Cu-Cu 2 O foil, then standing for 1h, and finally drying and rolling to obtain the negative electrode plate;
The active material layer slurry comprises a negative electrode main material, a binder, a conductive agent and a solvent, wherein the binder accounts for 2wt% of the total mass of the negative electrode main material, the binder and the conductive agent, the negative electrode main material is a graphite material, the conductive agent is conductive carbon black, and the solvent is water.
Example 2
The embodiment provides a negative electrode plate, which comprises a copper foil and active material layers on two side surfaces of the copper foil, wherein an interface layer is further arranged between a current collector and the active material layers, and a cuprous oxide layer is further arranged between the current collector and the interface layer;
The interface layer comprises a metal complex, wherein a metal center in the metal complex is copper, a ligand is a binder in the active substance layer, and the binder is polyacrylic acid;
the metal complex is obtained by in-situ reaction of cuprous oxide and a binder in the active material layer;
The preparation method of the negative electrode plate comprises the following steps:
(1) Preparing an aqueous solution of 0.02M copper acetate ((CH 3COO)2 Cu) and 0.1 sodium acetate (CH 3 COONa) of M as electrodeposition liquid, placing clean copper foil as a working electrode in the electrodeposition liquid, taking foil Pt as a counter electrode, taking Ag/AgCl as a reference electrode, electrifying for 30s at a voltage of 1.2V at room temperature, then maintaining for 60s at a voltage of-0.8V to realize the deposition of a cuprous oxide layer on the surface of the copper foil, then adopting deionized water for 3 times, and then placing in an oven at 50 ℃ for drying for 12h to obtain a Cu-Cu 2 O foil;
(2) Coating active material layer slurry on the surface of a Cu-Cu 2 O foil, then standing for 2 hours, and finally drying and rolling to obtain the negative electrode plate;
The active material layer slurry comprises a negative electrode main material, a binder, a conductive agent and a solvent, wherein the binder accounts for 2wt% of the total mass of the negative electrode main material, the binder and the conductive agent, the negative electrode main material is a graphite material, the conductive agent is conductive carbon black, and the solvent is water.
Example 3
The present example provided a negative electrode sheet which was identical to example 1 except that in the preparation method thereof, when the electrodeposition was performed in step (1), the negative electrode sheet was maintained at a voltage of-0.2V for 120s so that the resultant negative electrode sheet was changed accordingly.
Example 4
The present example provided a negative electrode sheet which was identical to example 1 except that in the preparation method thereof, when the electrodeposition was performed in step (1), the negative electrode sheet was maintained at-0.2V for 180s so that the resultant negative electrode sheet was changed accordingly.
Example 5
The present example provided a negative electrode sheet which was identical to example 1 except that in the preparation method thereof, when the electrodeposition was performed in step (1), the negative electrode sheet was maintained at-0.2V for 40s so that the resultant negative electrode sheet was changed accordingly.
Example 6
The present example provided a negative electrode sheet which was identical to example 1 except that in the preparation method thereof, when the electrodeposition was performed in step (1), the negative electrode sheet was maintained at a voltage of-0.2V for 200s so that the resultant negative electrode sheet was changed accordingly.
Example 7
The present embodiment provides a negative electrode sheet, which is the same as that of embodiment 1 except that in the preparation method thereof, when the step (1) is performed with electrodeposition, the voltage of-0.2V is maintained for 120s, and the binder in the step (2) accounts for 3wt% of the total mass of the negative electrode main material, the binder and the conductive agent, so that the obtained negative electrode sheet is correspondingly changed.
Example 8
The present embodiment provides a negative electrode sheet, which is the same as that of embodiment 1 except that in the preparation method thereof, when the step (1) is performed with electrodeposition, the voltage of-0.2V is maintained for 120s, and the binder in the step (2) accounts for 4wt% of the total mass of the negative electrode main material, the binder and the conductive agent, so that the obtained negative electrode sheet is correspondingly changed.
Example 9
The present embodiment provides a negative electrode sheet, which is the same as that of embodiment 1 except that in the preparation method of the negative electrode sheet, the binder in step (2) accounts for 1wt% of the total mass of the negative electrode main material, the binder and the conductive agent, so that the obtained negative electrode sheet is correspondingly changed.
Example 10
The present embodiment provides a negative electrode sheet, which is the same as that of embodiment 1 except that in the preparation method thereof, the binder in step (2) accounts for 5wt% of the total mass of the negative electrode main material, the binder and the conductive agent, so that the obtained negative electrode sheet is correspondingly changed.
Example 11
The present embodiment provides a negative electrode sheet, which is the same as that of embodiment 1 except that in the preparation method thereof, the time of standing in step (2) is 0.5h, so that the obtained negative electrode sheet is correspondingly changed.
Example 12
The present embodiment provides a negative electrode sheet, which is the same as that of embodiment 1 except that in the preparation method thereof, the time of standing in step (2) is 3 hours, so that the obtained negative electrode sheet is correspondingly changed.
Example 13
The present embodiment provides a negative electrode sheet, which is the same as that of embodiment 1 except that the binder is sodium lignin sulfonate.
Example 14
The present embodiment provides a negative electrode sheet, which is the same as that of embodiment 1 except that the binder is sodium alginate.
Comparative example 1
This comparative example provides a negative electrode tab that is identical to example 1 except that it does not include a cuprous oxide layer and an interfacial layer;
The preparation method of the negative electrode sheet was the same as in example 1 except that the electrodeposition of step (1) was not performed, and the active material layer slurry was directly coated on the copper foil.
Comparative example 2
This comparative example provides a negative electrode sheet that is identical to example 1 except that the negative electrode sheet does not include an interface layer, and the binder in the active material layer is CMC (sodium carboxymethyl cellulose) and SBR (styrene butadiene rubber) in a mass ratio of 1:1.
The negative electrode plate, the positive electrode plate and the diaphragm are laminated and combined in the embodiment and the comparative example, are packaged in an aluminum plastic film, are subjected to hot pressing, drying and water removal, and are subjected to liquid injection and sealing to prepare the lithium ion soft package battery; the preparation process of the positive plate comprises the following steps: uniformly mixing lithium iron phosphate, PVDF, conductive carbon black and carbon nano tubes according to the mass ratio of 96.8:1.8:1.0:0.4, and preparing the positive plate with the compacted density of 2.4 g/cm 3 by coating and rolling.
Test conditions:
Peel force and cohesion test: the negative electrode sheets described in the above examples and comparative examples were cut to a size of 24 mm a wide and 150mm a long, and then tested in a tensile tester at a tensile angle of 180 °.
And (3) testing normal temperature cycle performance: and (3) circulating the prepared soft package battery at normal temperature, and performing charge and discharge circulation at the temperature of 0.5C for 500 circles, wherein the charge and discharge window of the lithium iron phosphate is 3.65-2.0V.
The test results were as follows:
TABLE 1
As can be seen from table 1:
According to the invention, the stripping force and the cohesive force of the pole piece can be effectively improved through the interface layer formed by the cuprous oxide and the binder, and meanwhile, the mechanical property of the pole piece is improved through the proper extension of the deposition time or the proper increase of the content of the binder, but according to the cyclic test result, the greater the stripping force and the cohesive force of the pole piece are, the better the cyclic property is, probably because the poor conductivity of the cuprous oxide and the binder is caused, the greater the contents of the cuprous oxide and the binder can have a great influence on the resistance of the pole piece; as can be seen from examples 1 and comparative examples 1-2, the mechanical properties and electrochemical properties of the pole piece were greatly reduced when no interfacial layer was present, and comparative example 2 could not be subjected to 500 cycles due to severe pole piece blanking; as is clear from examples 1, 5-6 and 9-14, the electrodeposition time, binder content, standing time and binder type of the present invention all affect the mechanical and electrochemical properties of the negative electrode sheet.
In summary, the invention provides a negative electrode plate, a preparation method thereof and a battery, wherein an interface layer containing a metal complex is formed between a current collector and an active material layer, so that the bonding strength between the current collector and the active material layer is enhanced, the stripping force and cohesion of the negative electrode plate are improved, and the negative electrode plate has excellent mechanical strength.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that fall within the technical scope of the present invention disclosed herein are within the scope of the present invention.
Claims (10)
1. The negative electrode plate is characterized by comprising a current collector and an active material layer on at least one side surface of the current collector, wherein an interface layer is further arranged between the current collector and the active material layer, and the interface layer comprises a metal complex;
the metal species in the metal complex is the same as the current collector, and the ligand in the metal complex includes a binder in the active material layer.
2. The negative electrode tab of claim 1, wherein the metal complex is obtained by in situ reaction of cuprous oxide with a binder in the active material layer.
3. The negative electrode tab of claim 2, further comprising a layer of cuprous oxide between the current collector and the interfacial layer.
4. The negative electrode tab of claim 1, wherein the binder comprises any one or a combination of at least two of polyacrylic acid, sodium lignin sulfonate, or sodium alginate.
5. A method of producing the negative electrode sheet according to any one of claims 1 to 4, comprising the steps of:
And setting a cuprous oxide layer on at least one side surface of the current collector, coating active material layer slurry on the surface of the cuprous oxide layer, standing, and drying and rolling to obtain the negative electrode plate.
6. The method according to claim 5, wherein the time for the standing is 1 to 2 hours.
7. The method of preparing according to claim 5, wherein the method of disposing the cuprous oxide layer comprises: using a current collector as a working electrode, and performing electrodeposition of a cuprous oxide layer on at least one side surface of the current collector;
the electrodeposition time is 60-180s;
the voltage of the electrodeposition is-0.2 to-0.8V.
8. The method of claim 7, wherein the electrodeposition is preceded by energizing at a voltage of 0.6-1.2V for 30-60s.
9. The method according to claim 5, wherein the active material layer slurry includes a negative electrode host material, a binder, a conductive agent, and a solvent;
The binder accounts for 2-4wt% of the total mass of the cathode main material, the binder and the conductive agent.
10. A battery comprising the negative electrode sheet according to any one of claims 1 to 4 or prepared according to the preparation method of any one of claims 5 to 9.
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