CN113193196A - Multifunctional aqueous binder for sodium ion battery and application thereof - Google Patents
Multifunctional aqueous binder for sodium ion battery and application thereof Download PDFInfo
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- CN113193196A CN113193196A CN202110450039.3A CN202110450039A CN113193196A CN 113193196 A CN113193196 A CN 113193196A CN 202110450039 A CN202110450039 A CN 202110450039A CN 113193196 A CN113193196 A CN 113193196A
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- Prior art keywords
- sodium
- ion battery
- aqueous binder
- multifunctional aqueous
- sodium ion
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 103
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000011230 binding agent Substances 0.000 title claims abstract description 77
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 25
- 239000011149 active material Substances 0.000 claims abstract description 15
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims description 25
- 239000011248 coating agent Substances 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 16
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 12
- 239000002041 carbon nanotube Substances 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 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 9
- 239000006258 conductive agent Substances 0.000 claims description 9
- 239000000661 sodium alginate Substances 0.000 claims description 9
- 235000010413 sodium alginate Nutrition 0.000 claims description 9
- 229940005550 sodium alginate Drugs 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 230000002441 reversible effect Effects 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003575 carbonaceous material Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 125000004185 ester group Chemical group 0.000 claims description 5
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 4
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 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 claims description 3
- 229960003351 prussian blue Drugs 0.000 claims description 3
- 239000013225 prussian blue Substances 0.000 claims description 3
- 230000001351 cycling effect Effects 0.000 abstract description 6
- 230000002427 irreversible effect Effects 0.000 abstract description 5
- 238000005886 esterification reaction Methods 0.000 abstract description 4
- 230000002829 reductive effect Effects 0.000 abstract description 2
- 239000002033 PVDF binder Substances 0.000 description 26
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 23
- 238000005303 weighing Methods 0.000 description 14
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 13
- OHVGNSMTLSKTGN-BTVCFUMJSA-N [C].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O Chemical compound [C].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O OHVGNSMTLSKTGN-BTVCFUMJSA-N 0.000 description 13
- 239000008103 glucose Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000010408 film Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 238000007373 indentation Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229910021385 hard carbon Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 102000020897 Formins Human genes 0.000 description 4
- 108091022623 Formins Proteins 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000010000 carbonizing Methods 0.000 description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000013507 mapping Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910002703 Al K Inorganic materials 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- -1 sodium hexafluorophosphate Chemical compound 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Images
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
-
- 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
- C09J101/00—Adhesives based on cellulose, modified cellulose, or cellulose derivatives
- C09J101/08—Cellulose derivatives
- C09J101/26—Cellulose ethers
- C09J101/28—Alkyl ethers
-
- 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
- C09J105/00—Adhesives based on polysaccharides or on their derivatives, not provided for in groups C09J101/00 or C09J103/00
- C09J105/04—Alginic acid; Derivatives thereof
-
- 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
- C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- 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
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/02—Polyalkylene oxides
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
Abstract
The invention relates to the field of sodium ion batteries, in particular to a multifunctional aqueous binder for a sodium ion battery and application thereof. The invention provides a multifunctional aqueous binder for a sodium ion battery, which comprises a sodium ion water-soluble polymer and polyethylene oxide. The multifunctional aqueous binder with a three-dimensional network structure is constructed through the esterification reaction of the water-soluble polymer containing sodium ions and polyethylene oxide, has strong mechanical property, can improve the binding property of the multifunctional aqueous binder, and improves the cycling stability of the electrode. The water-soluble polymer containing sodium ions can uniformly cover the surface of an active material to form a layer of passive film, so that the loss of irreversible capacity of a battery is reduced, and the first coulombic efficiency and rate capability are improved.
Description
Technical Field
The invention relates to the field of sodium ion batteries, in particular to a multifunctional aqueous binder for a sodium ion battery and application thereof.
Background
The sodium ions have the advantages of abundant reserves, wide distribution and low price, and can solve the problems of high price and limited resources of the lithium ion battery. Meanwhile, the lithium ion battery has rich research and development experience and can be directly applied to the field of sodium ion batteries. Therefore, sodium ion batteries are considered to be one of the most promising large-scale electrochemical energy storage systems at present.
The performance of sodium ion batteries varies depending on the manufacturing process of the electrodes and the raw materials (e.g., active materials, conductive agents, binders, etc.) selected. Among them, the addition amount of the binder is very low, but is an essential component in the preparation of an electrode of a sodium ion battery. At present, the development of the binder mainly focuses on alloy negative electrode materials and conversion negative electrode materials with serious volume expansion in the charging and discharging processes, and the development of the binder suitable for the hard carbon negative electrode materials with small volume expansion is neglected. Because the sodium ion battery and the lithium ion battery have similar physicochemical properties and working principles, polyvinylidene fluoride (PVDF) binder is generally used for hard carbon cathode materials of the sodium ion battery by directly taking the experience of the lithium ion battery as reference. However, hard carbon anodes have a larger specific surface area and more defects than graphite anodes, leading to the problem of lower first coulombic efficiency and rate capability. Therefore, it is not reasonable to apply the PVDF binder directly to the carbon negative electrode material of the sodium ion battery. In addition, although PVDF binder is widely used for the preparation of commercial lithium battery negative electrodes due to its good thermal and electrochemical stability, PVDF has high cost, low binding strength, and poor conductivity, and thus the development demand of high capacity electrode materials has not been met. Therefore, there is an urgent need to develop a multifunctional binder suitable for a hard carbon negative electrode, which can inhibit the occurrence of irreversible reactions and accelerate the diffusion of ions during charge and discharge, thereby effectively solving the problems of low first coulombic efficiency and rate capability of a sodium ion battery. In addition, the development of green and environmentally friendly and low-cost binders is also important in the commercialization of sodium ion batteries.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: the binder for the hard carbon cathode of the sodium ion battery in the prior art is an organic system, has high cost, low binding strength and poor conductivity, and has the problems of low first inventory efficiency, poor rate capability, poor battery cycle stability and the like when being applied to the sodium ion battery.
Aiming at the defects in the prior art, the invention aims to provide a multifunctional aqueous binder for a sodium-ion battery; the invention also aims to provide the application of the multifunctional aqueous binder for the sodium ion battery in the sodium ion battery; the invention also aims to provide a sodium ion battery electrode plate; the fourth purpose of the invention is to provide a preparation method of the sodium-ion battery electrode plate; the fifth purpose of the invention is to provide a sodium ion battery.
The technical scheme of the invention is as follows:
the invention provides a multifunctional aqueous binder for a sodium ion battery, which is prepared from a mixture of a sodium ion water-soluble polymer and polyethylene oxide and has a network structure formed by carboxyl and ester groups.
Preferably, the mass ratio of the sodium ion water-soluble polymer to the polyethylene oxide is 9-1: 1, preferably 5-9:1, and more preferably 7-9: 1.
Preferably, the sodium ion water-soluble polymer is one or more of sodium alginate, sodium carboxymethyl cellulose and sodium polyacrylate, and is preferably sodium alginate.
The invention also provides application of the multifunctional aqueous binder for the sodium ion battery in the sodium ion battery.
The invention also provides a sodium ion battery electrode plate, which comprises a current collector and a coating coated on the current collector, wherein the coating comprises an active material, a conductive agent and the multifunctional aqueous binder for the sodium ion battery.
Preferably, the multifunctional aqueous binder dry matter for the sodium-ion battery in the coating accounts for 2-20% of the total mass of the dry matter of the battery electrode plate, preferably 2-10% of the total mass of the dry matter of the battery electrode plate.
Preferably, the active material is one of a carbon-based material, an alloy material, a conversion material, a polyanionic compound, prussian blue, and an organic-based material, and is preferably a carbon-based material.
Preferably, the conductive agent is one of carbon nanotubes, carbon fibers, graphene, acetylene black, Super P and Super S.
The invention also provides a preparation method of the sodium-ion battery electrode plate, which comprises the following steps: and mixing the multifunctional water-based binder for the sodium ion battery with an active material to obtain slurry, coating the slurry on the current collector to obtain a coating, and then sequentially drying the coating at normal pressure and in vacuum to obtain the sodium ion battery electrode plate, wherein the vacuum drying temperature is 80-120 ℃, and preferably 100 ℃.
Preferably, the drying temperature under normal pressure is 40-60 ℃, the drying time under normal pressure is 1-3h, and the drying time under vacuum is 8-16 h.
The invention also provides a sodium ion battery, which comprises a positive electrode, a negative electrode, electrolyte and a diaphragm, wherein the positive electrode and/or the negative electrode are/is the sodium ion battery electrode plate or the electrode plate prepared by the preparation method.
Preferably, the sodium ion battery is at 0.02A g-1The reversible charging specific capacity is 230-340mAhg under the current density-1Preferably 330-340mAhg-1。
The invention has the beneficial effects that:
(1) the multifunctional aqueous binder with a three-dimensional network structure is constructed through the esterification reaction of the sodium ion water-soluble polymer and polyethylene oxide, the indentation force of the multifunctional aqueous binder can reach more than 8mN, the modulus can reach more than 5MPa, the hardness can reach more than 0.05GPa, the multifunctional aqueous binder has stronger mechanical property, can improve the binding property of the multifunctional aqueous binder to active material particles, a conductive agent and a current collector, relieve the problem of volume expansion of materials in the charging and discharging process, maintain the close contact of the whole electrode, improve the cycling stability of the electrode, and particularly for active materials with serious volume expansion in the sodium insertion/sodium removal process.
(2 the sodium ion water-soluble polymer of the invention has a large amount of carboxyl functional groups and hydroxyl functional groups, and can uniformly cover the surface of the active material by utilizing the hydrogen bond action formed on the surface of the active material to form a layer of passive film, thereby effectively inhibiting the decomposition reaction of the electrolyte in the first charge-discharge process, reducing the formation of a solid electrolyte film, reducing the loss of irreversible capacity and improving the first coulombic efficiency.
(3) The polyethylene oxide is an ionic adhesive, has rapid ion conducting capability, and improves the ion diffusion coefficient and the rate capability.
(4) Na in the multifunctional aqueous binder of the present invention+The first coulombic efficiency and rate capability of the electrode can be improved.
Drawings
FIG. 1 is a Fourier infrared spectrum of the multifunctional aqueous binder for sodium ion battery prepared in example 3 after vacuum drying at 25 ℃ and vacuum drying at 100 ℃;
FIG. 2 is an X-ray photoelectron spectrum of the multifunctional aqueous binder for sodium-ion battery prepared in example 3 after vacuum drying at 25 ℃;
FIG. 3 is an X-ray photoelectron spectrum of the multifunctional aqueous binder for sodium-ion battery prepared in example 3 after vacuum drying at 100 ℃;
FIG. 4 is a graph showing the variation of the indentation force and the indentation depth of the multifunctional aqueous binder for sodium ion batteries prepared in examples 1 to 3;
FIG. 5 is a graph showing the Young's modulus and indentation depth of the multifunctional aqueous binder for sodium-ion batteries prepared in examples 1 to 3;
FIG. 6 is a graph showing the hardness and indentation depth of the multifunctional aqueous binder for sodium ion batteries prepared in examples 1 to 3;
FIG. 7 is a Mapping chart of an electrode prepared in comparative example 2;
FIG. 8 is an SEM photograph of an electrode prepared in comparative example 2;
FIG. 9 is a Mapping diagram of the electrode prepared in example 4;
FIG. 10 is an SEM photograph of an electrode prepared according to example 4;
FIG. 11 is a graph of rate performance of the battery and BA-PVDF in Experimental examples 4-6;
FIG. 12 is an SEM image of the electrode EP-PVDF surface after the battery BA-PVDF long cycle in Experimental example 4;
FIG. 13 is an SEM image of the surface of the electrode EP-SA/PEO-1A after long cycling of the battery BA-SA/PEO-1A in Experimental example 4.
Detailed Description
The invention aims to provide a multifunctional aqueous binder for a sodium-ion battery.
Specifically, the multifunctional aqueous binder for the sodium-ion battery is prepared from a mixture of a sodium-ion water-soluble polymer and polyethylene oxide, and has a network structure formed by carboxyl and ester groups.
Preferably, the mass ratio of the sodium ion water-soluble polymer to the polyethylene oxide is 9-1: 1, preferably 5-9:1, and more preferably 7-9: 1.
Preferably, the sodium ion water-soluble polymer is one or more of sodium alginate, sodium carboxymethyl cellulose and sodium polyacrylate, and is preferably sodium alginate.
The invention also aims to provide the application of the multifunctional aqueous binder for the sodium-ion battery in the sodium-ion battery.
The invention also provides a sodium ion battery electrode plate, which comprises a current collector and a coating coated on the current collector, wherein the coating comprises an active material, a conductive agent and the multifunctional aqueous binder for the sodium ion battery.
Preferably, the multifunctional aqueous binder dry matter for the sodium-ion battery in the coating accounts for 2-20% of the total mass of the dry matter of the battery electrode plate, preferably 2-10% of the total mass of the dry matter of the battery electrode plate.
Preferably, the active material is one of a carbon-based material, an alloy material, a conversion material, a polyanionic compound, prussian blue, and an organic-based material, and is preferably a carbon-based material.
Preferably, the conductive agent is one of carbon nanotubes, carbon fibers, graphene, acetylene black, Super P and Super S.
The fourth purpose of the invention is to provide a preparation method of the sodium-ion battery electrode plate, which comprises the following steps: and mixing the multifunctional water-based binder for the sodium ion battery with an active material to obtain slurry, coating the slurry on the current collector to obtain a coating, and then sequentially drying the coating at normal pressure and in vacuum to obtain the sodium ion battery electrode plate, wherein the vacuum drying temperature is 80-120 ℃, and preferably 100 ℃. The multifunctional aqueous binder for the sodium ion battery completes the curing reaction process in the electrode drying process, the reaction conditions are mild, the whole process of electrode preparation also meets the requirements of green and safe production, the multifunctional aqueous binder is easy to control, high in feasibility and suitable for industrial mass production.
Preferably, the drying temperature under normal pressure is 40-60 ℃, the drying time under normal pressure is 1-3h, and the drying time under vacuum is 8-16 h.
The invention also provides a sodium ion battery, which comprises a positive electrode, a negative electrode, electrolyte and a diaphragm, wherein the positive electrode and/or the negative electrode is the sodium ion battery electrode plate or the electrode plate prepared by the preparation method.
Preferably, the sodium ion battery is at 0.02A g-1The reversible charging specific capacity is 230-340mAhg under the current density-1Preferably 330-340mAhg-1。
The multifunctional aqueous binder for sodium ion batteries and the application thereof will be specifically described below by specific examples and experimental examples.
The inventive examples and comparative examples used starting materials and equipment sources as shown in table 1.
TABLE 1 examples of the invention and comparative examples use sources of raw materials and equipment
Example 1
The embodiment provides a multifunctional aqueous binder for a sodium-ion battery, and the preparation method comprises the following steps: weighing 0.5g of sodium carboxymethylcellulose and 0.5g of polyethylene oxide, adding into a beaker, weighing 32.3mL of deionized water, adding into the beaker, stirring and dissolving to obtain the multifunctional aqueous binder for the sodium-ion battery, and marking as CMC/PEO.
Example 2
The embodiment provides a multifunctional aqueous binder for a sodium-ion battery, and the preparation method comprises the following steps: weighing 0.8g of sodium polyacrylate and 0.2g of polyethylene oxide, adding into a beaker, weighing 32.3mL of deionized water, adding into the beaker, stirring and dissolving to obtain the multifunctional aqueous binder for the sodium-ion battery, which is marked as SP/PEO.
Example 3
The embodiment provides a multifunctional aqueous binder for a sodium-ion battery, and the preparation method comprises the following steps: weighing 0.9g of sodium alginate and 0.1g of polyethylene oxide, adding the sodium alginate and the polyethylene oxide into a beaker, weighing 32.3mL of deionized water, adding the deionized water into the beaker, stirring and dissolving to obtain the multifunctional aqueous binder for the sodium-ion battery, which is marked as SA/PEO-1.
Example 4
The embodiment provides a sodium ion battery electrode plate, and the preparation method comprises the following steps: weighing 1g glucose, and heating at 3 deg.C for min under argon atmosphere-1Heating to 1500 ℃ and carbonizing for 4h to obtain glucose carbon, weighing 80mg of glucose carbon and 10mg of carbon nanotubes, adding into a mortar, mixing and grinding for 5min, transferring into a glass bottle, adding 333.3mg of the multifunctional aqueous binder for the sodium ion battery prepared in example 3, stirring for 12h to obtain uniform slurry, coating the slurry on a copper foil current collector by using a coater, drying for 2h at 50 ℃ in a forced air drying box, drying for 12h at 100 ℃ in a vacuum drying box, and cutting the dried electrode plate into a wafer with the diameter of 12mm, wherein the wafer is marked as EP-SA/PEO-1A.
Example 5
This example provides a sodium ion battery electrode plate, and its preparation methodThe following: weighing 1g glucose, and heating at 3 deg.C for min under argon atmosphere-1Heating to 1500 ℃ and carbonizing for 4h to obtain glucose carbon, weighing 85mg of glucose carbon and 13mg of carbon nanotubes, adding the glucose carbon and the 13mg of carbon nanotubes into a mortar, mixing and grinding for 5min, transferring the mixture into a glass bottle, adding 66.6mg of the multifunctional aqueous binder for the sodium ion battery prepared in the embodiment 3, stirring for 12h to obtain uniform slurry, coating the slurry on a copper foil current collector by using a coater, drying for 3h at 40 ℃ in a blast drying box, drying for 16h at 80 ℃ in a vacuum drying box, and cutting the dried electrode plate into a wafer with the diameter of 12mm, namely EP-SA/PEO-1B.
Example 6
The embodiment provides a sodium ion battery electrode plate, and the preparation method comprises the following steps: weighing 1g glucose, and heating at 3 deg.C for min under argon atmosphere-1Heating to 1500 ℃ and carbonizing for 4h to obtain glucose carbon, weighing 70mg of glucose carbon and 10mg of carbon nanotubes, adding the glucose carbon and the 10mg of carbon nanotubes into a mortar, mixing and grinding for 5min, transferring the mixture into a glass bottle, adding 666.6mg of the multifunctional aqueous binder for the sodium ion battery prepared in the embodiment 3, stirring for 12h to obtain uniform slurry, coating the slurry on a copper foil current collector by using a coater, drying at 60 ℃ for 1h in a blast drying box, drying at 120 ℃ for 8h in a vacuum drying box, and cutting the dried electrode plate into a wafer with the diameter of 12mm, namely EP-SA/PEO-1C.
Comparative example 1
0.2g of polyvinylidene fluoride was weighed and added to 3.8g of N-methylpyrrolidone to prepare a solution, which was noted as PVDF.
Comparative example 2
Weighing 1g glucose, and heating at 3 deg.C for min under argon atmosphere-1Heating to 1500 ℃ and carbonizing for 4h to obtain glucose carbon, weighing 80mg of glucose carbon and 10mg of carbon nanotubes, adding the glucose carbon and the 10mg of carbon nanotubes into a mortar, mixing and grinding for 5min, transferring the mixture into a glass bottle, adding 200mg of the binder PVDF prepared in the comparative example 1, stirring for 12h to obtain uniform slurry, coating the slurry on a copper foil current collector by using a coater, drying the copper foil current collector for 2h at 50 ℃ in a blast drying oven, drying the copper foil current collector for 12h at 100 ℃ in a vacuum drying oven, and cutting the dried electrode slice into a wafer with the diameter of 12mm, wherein the wafer is marked as EP-PVDF.
Experimental example 1
The multifunctional aqueous binder for sodium ion batteries prepared in example 3 was coated on a glass plate, vacuum-dried at 25 ℃ and 100 ℃ for 24 hours, respectively, and then scraped off, pulverized into powders by a pulverizer, designated as SA/PEO-1-25 ℃ and SA/PEO-1-100 ℃, and analyzed by Fourier infrared spectroscopy (test parameters: potassium bromide as a control, range 600--1Resolution of 4cm-1Scan 64 times) and X-ray photoelectron spectroscopy (XPS) analysis (test parameters: x-ray source Al K α, energy step 0.100eV, scan times 3), the results are shown in fig. 1-3.
As can be seen from FIG. 1, the infrared spectrum of the binder SA/PEO-1 is 1730cm-1A new absorption peak of the ester group (O-C ═ O) appears. This demonstrates that the carboxyl (-COOH) groups in sodium alginate and the hydroxyl (-OH) groups in polyethylene oxide (PEO) undergo esterification reactions to form a three-dimensional network structure.
As can be seen from FIGS. 2 and 3, the XPS C1s spectrum of SA/PEO-1 binder dried at 100 deg.C in vacuum showed new ester groups (-COOR) at 289.0eV, compared to the binder dried at 25 deg.C in vacuum, further demonstrating that the esterification reaction occurred during the drying of SA and PEO at 100 deg.C in vacuum.
Experimental example 2
Firstly, glucose carbon and carbon nanotubes are mixed and ground, then are respectively added into the binder prepared in the embodiment 1-3, wherein the mass ratio of the glucose carbon to the carbon nanotubes to the binder is 8:1:1, then the mechanical stirring is carried out to prepare uniform slurry, then the slurry is respectively coated on a 16mm gasket by using a coater and is transferred into a forced air drying oven to be dried for 2h at 50 ℃, and then is transferred into a vacuum drying oven to be dried for 12h at 100 ℃. Respectively marked as GC-SA/PEO, GC-CMC/PEO and GC-SP/PEO, then the mechanical properties of the samples are tested by adopting a nanoindentation instrument, and the constant strain is loaded for 0.05s in the test process-1The results are shown in FIGS. 4-6.
As can be seen from FIG. 4, the indentation force of the binder prepared by the invention can reach more than 8mN, the CMC/PEO binder prepared by the example 1 can reach more than 17mN, the SA/PEO-1 binder prepared by the example 3 can reach more than 42mN, and the binder prepared by the invention can enable the electrode to have stronger binding strength. The main reason is that the adhesive of the invention has a large amount of carboxyl and hydroxyl functional groups to form hydrogen bond with the functional groups (carboxyl and hydroxyl) on the surface of the active particles.
It can be known from fig. 5 and 6 that the modulus of the binder prepared by the invention can reach more than 5MPa, the modulus of the CMC/PEO binder prepared by example 1 reaches more than 15GPa, the modulus of the SA/PEO-1 binder prepared by example 3 reaches more than 25GPa, the hardness of the binder prepared by the invention reaches more than 0.05GPa, and the hardness of the CMC/PEO and SA/PEO-1 binders prepared by examples 1 and 3 reaches more than 0.45GPa, so that the electrode has stronger mechanical properties, the problem of poor conductive contact between the active particles and the conductive agent caused by the volume expansion and contraction behavior of the active particles in the charging and discharging process is alleviated, and the cycling stability of the electrode is improved.
Experimental example 3
SEM and mapping characterization analyses were performed on the electrode sheets prepared in example 4 and comparative example 2, respectively, and the test conditions of SEM are as follows: voltage 10Kv, current 10 μ a, mapping test conditions: the voltage was 5Kv and the current was 7. mu.A, and the results of the experiment are shown in FIGS. 7 to 10.
As can be seen from fig. 7, the F element was detected on the surface of the glucose char, indicating that PVDF was deposited on the surface of the glucose char. As can be seen from fig. 8, PVDF is adhered to the surface of the glucose char in the form of particles, and cannot uniformly cover the surface of the glucose char in the form of a film, and thus the electrolyte cannot be effectively prevented from contacting the surface of the glucose char. Therefore, the formation of SEI film of the EP-PVDF electrode cannot be inhibited, and the loss of irreversible capacity is reduced, resulting in low initial coulombic efficiency of the EP-PVDF electrode.
As can be seen from FIG. 9, Na element was detected on the surface of the glucose char, indicating that SA/PEO-1 was deposited on the surface of the glucose char. As can be seen from FIG. 10, SA/PEO-1 is uniformly coated on the surface of the glucose charcoal in the form of a thin film to form a passivation film, which prevents the electrolyte from contacting the surface of the glucose charcoal. Due to the formation of the passivation film, the EP-SA/PEO-1A electrode can suppress the formation of the SEI film, reduce the loss of irreversible capacity, and thus can obtain higher first coulombic efficiency than the EP-PVDF electrode.
Experimental example 4
The electrode sheets EP-SA/PEO-1A, EP-SA/PEO-1B, EP-SA/PEO-1C prepared in examples 4-6 and the electrode sheet EP-PVDF prepared in comparative example 2 were transferred into a glove box, respectively, and the electrode sheets prepared were used as working electrodes, ethylene carbonate and dimethyl carbonate (volume ratio 1:1) solutions containing 1mol/L sodium hexafluorophosphate were used as electrolytes, and Whatman F glass fiber membranes were used as membranes to assemble coin-cell batteries, which were designated as BA-SA/PEO-1A, BA-SA/PEO-1B, BA-SA/PEO-1C and BA-PVDF. Standing the assembled button cell for 24h, and performing charge and discharge test in a blue battery test system with cut-off voltage of 0.01-3.00V and current density of 0.02A g-1、0.05A g-1、0.1A g-1、0.2A g-1And 0.5A g-1The experimental results are shown in FIG. 11. And at a cut-off voltage of 0.01-3.00V and a current density of 0.1A g-1The cell was disassembled after 1000 cycles, and the results of the experiments were shown in FIGS. 12-13 by analyzing EP-SA/PEO-1A and EP-PVDF by scanning electron microscopy.
As can be seen from FIG. 11, the rate capability of BA-SA/PEO-1A, BA-SA/PEO-1B, BA-SA/PEO-1C and BA-PVDF was characterized at different current densities. BA-PVDF in the ranges of 0.02, 0.05, 0.10, 0.20 and 0.50A g-1The specific capacity of reversible charging is 307.6, 269.7, 196.7, 98.3 and 59.9mA h g-1BA-SA/PEO-1A at 0.02, 0.05, 0.10, 0.20 and 0.50A g-1Has a reversible capacity of 336.5, 308.5, 275.8, 193.0 and 75.9mA hr g-1BA-SA/PEO-1B at 0.02, 0.05, 0.10, 0.20 and 0.50A g-1Has a reversible capacity of 333.9, 300.0, 251.0, 154.3 and 64.9mA h g, respectively-1BA-SA/PEO-1C at 0.02, 0.05, 0.10, 0.20 and 0.50A g-1Has a reversible capacity of 232.5, 225.8, 205.8, 154.3 and 60.4mA h g, respectively-1. The results show that the addition of 2 wt%, 10 wt% and 20 wt% SA/PEO-1 binders all have good effects on improving the rate capability of the electrode of the material. Wherein the BA-SA/PEO-1A has a higher reversible capacity than BA-PVDF at the same binder level.
At 100mA g-1After 1000 times of circulation, the cell is disassembled and EP-SA is/are judged by a scanning electron microscopeThe electrode morphology was characterized after long cycling of PEO-1A and EP-PVDF as shown in FIGS. 12 and 13. Fig. 12 shows that after 1000 cycles, the EP-PVDF electrode delaminated from the Cu current collector and a large number of cracks appeared on the electrode surface. Fig. 13 shows that after 1000 cycles, the EP-SA/PEO-1A electrode remained tightly attached to the current collector with no cracks on the electrode surface. The results show that the SA/PEO-1 as binder electrode remains effectively intact during long cycling compared to conventional PVDF binders.
The foregoing is considered as illustrative and not restrictive in character, and that various modifications, equivalents, and improvements made within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (12)
1. The multifunctional aqueous binder for the sodium-ion battery is characterized by being prepared from a mixture of a sodium-ion water-soluble polymer and polyethylene oxide, and having a network structure formed by carboxyl and ester groups.
2. The multifunctional aqueous binder for sodium-ion batteries according to claim 1, wherein the mass ratio of the sodium-ion water-soluble polymer to the polyethylene oxide is 1-9:1, preferably 5-9:1, and more preferably 7-9: 1.
3. The multifunctional aqueous binder for sodium-ion batteries according to claim 1 or 2, wherein the sodium-ion water-soluble polymer is one or more of sodium alginate, sodium carboxymethylcellulose and sodium polyacrylate, and is preferably sodium alginate.
4. Use of the multifunctional aqueous binder for sodium ion batteries according to any one of claims 1 to 3 in sodium ion batteries.
5. An electrode plate for a sodium-ion battery, which is characterized by comprising a current collector and a coating coated on the current collector, wherein the coating comprises an active material, a conductive agent and the multifunctional aqueous binder for the sodium-ion battery of claims 1-3.
6. The sodium-ion battery electrode sheet according to claim 5, wherein the dry matter of the multifunctional aqueous binder for sodium-ion batteries in the coating accounts for 2-20%, preferably 2-10% of the total mass of the dry matter of the battery electrode sheet.
7. The sodium-ion battery electrode sheet according to claim 5 or 6, wherein the active material is one of a carbon-based material, an alloy material, a conversion material, a polyanionic compound, Prussian blue, and an organic-based material, preferably a carbon-based material.
8. The sodium-ion battery electrode sheet according to any one of claims 5 to 7, wherein the conductive agent is one of carbon nanotubes, carbon fibers, graphene, acetylene black, Super P, and Super S.
9. The preparation method of the sodium-ion battery electrode plate as defined in any one of claims 5 to 8, which is characterized by comprising the following steps: and mixing the multifunctional water-based binder for the sodium ion battery with an active material to obtain slurry, coating the slurry on the current collector to obtain a coating, and then sequentially drying the coating at normal pressure and in vacuum to obtain the sodium ion battery electrode plate, wherein the vacuum drying temperature is 80-120 ℃, and preferably 100 ℃.
10. The method according to claim 9, wherein the drying temperature under normal pressure is 40-60 ℃, preferably the drying time under normal pressure is 1-3h, and more preferably the drying time under vacuum is 8-16 h.
11. A sodium ion battery is characterized by comprising a positive electrode, a negative electrode, an electrolyte and a diaphragm, wherein the positive electrode and/or the negative electrode is the sodium ion battery electrode plate as defined in any one of claims 5 to 8 or the electrode plate prepared by the preparation method as defined in claim 9 or 10.
12. The sodium-ion battery of claim 11, wherein the sodium-ion battery is at 0.02Ag-1The reversible charging specific capacity is 230-340mAhg under the current density-1Preferably 330-340mAhg-1。
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