CN111600025A - Zinc cathode material with elastic protective layer and preparation and application thereof - Google Patents
Zinc cathode material with elastic protective layer and preparation and application thereof Download PDFInfo
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- CN111600025A CN111600025A CN202010327836.8A CN202010327836A CN111600025A CN 111600025 A CN111600025 A CN 111600025A CN 202010327836 A CN202010327836 A CN 202010327836A CN 111600025 A CN111600025 A CN 111600025A
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- negative electrode
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- 239000011701 zinc Substances 0.000 title claims abstract description 182
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 151
- 239000011241 protective layer Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000010406 cathode material Substances 0.000 title claims abstract description 7
- 239000002105 nanoparticle Substances 0.000 claims description 36
- 229920000642 polymer Polymers 0.000 claims description 34
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 32
- 239000003792 electrolyte Substances 0.000 claims description 29
- 239000010410 layer Substances 0.000 claims description 29
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 29
- 239000002002 slurry Substances 0.000 claims description 28
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 19
- 239000000725 suspension Substances 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 239000011787 zinc oxide Substances 0.000 claims description 13
- 229920002873 Polyethylenimine Polymers 0.000 claims description 11
- 229920001601 polyetherimide Polymers 0.000 claims description 11
- 229920000307 polymer substrate Polymers 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000007773 negative electrode material Substances 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000006182 cathode active material Substances 0.000 claims description 6
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 229910009848 Ti4O7 Inorganic materials 0.000 claims description 3
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 3
- 229920006184 cellulose methylcellulose Polymers 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 3
- 229940007718 zinc hydroxide Drugs 0.000 claims description 3
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims 4
- 239000000243 solution Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 19
- 238000012360 testing method Methods 0.000 description 17
- 210000004027 cell Anatomy 0.000 description 15
- 239000000843 powder Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000005303 weighing Methods 0.000 description 11
- 229910000368 zinc sulfate Inorganic materials 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 239000011686 zinc sulphate Substances 0.000 description 10
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 9
- 239000003365 glass fiber Substances 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000004070 electrodeposition Methods 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- 210000001787 dendrite Anatomy 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000001548 drop coating Methods 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000007373 indentation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 description 1
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 description 1
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- 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
- H01M4/623—Binders being polymers fluorinated 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
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a zinc cathode material with an elastic protective layer, and preparation and application thereof. Compared with the prior art, the elastic protective layer disclosed by the invention is simple to prepare, low in cost, light and thin, can prolong the service life of the zinc cathode by about 10 times under higher current density, has higher coulombic efficiency, and simultaneously ensures the energy density of a full battery assembled by adopting the zinc cathode.
Description
Technical Field
The invention belongs to the technical field of energy storage materials, and relates to a zinc cathode material with an elastic protective layer, and preparation and application thereof.
Background
In recent years, with the increasing demand for large-scale energy storage and the development of electric vehicles, the safety of secondary batteries has been receiving much attention. For the traditional lithium ion battery, the adopted organic electrolyte system and the high-activity metal lithium cause serious potential safety hazards in the use process of the lithium ion battery, and the problems limit the further development of the lithium ion battery in the field of large-scale energy storage. Therefore, aqueous zinc ion secondary batteries have attracted much attention because of their advantages such as high safety and low cost of aqueous electrolytes, and air-stable zinc negative electrodes. In addition, the metal zinc has higher theoretical specific capacity (820mAh g)1) And the high energy density of the water system zinc ion battery is ensured. However, due to its high metal activity, metallic zinc inevitably reacts with aqueous solutions in the electrolyte, causing corrosion and passivation of the zinc anode, resulting in a short life of the zinc anode during charge and discharge cycles. During charging and discharging, disordered electrodeposition of zinc ions often leads to zinc dendrites and zinc electrode pulverization, resulting in short circuit and low coulombic efficiency of the battery during cycling.
Some of the currently reported methods of improving corrosion and uneven deposition of zinc anodes mainly include: the high-salt electrolyte reduces the water activity and constructs a three-dimensional current collector and the like. Although these methods can alleviate the above problems to some extent, they have limited their large scale popularization due to their high cost. In a traditional lithium ion battery, a graphite cathode reacts with an electrolyte in a discharging process, and a layer of compact Solid Electrolyte Interface (SEI) film is generated on the surface of the graphite cathode, so that the SEI film can inhibit side reactions between the graphite cathode and the electrolyte, can help to stabilize the insertion/extraction of lithium ions in the graphite cathode, and realizes stable charge-discharge circulation. Therefore, the construction of an artificial protective layer on a zinc negative electrode has received a lot of attention. However, most of the current research on artificial protective layers focuses on the test of low current and low discharge surface capacity, which cannot meet the requirements of practical application on high energy density and power density. The invention patent CN 109980226A discloses a zinc cathode with a polyamide brightener layer and a preparation method thereof, and the process can only improve the service life of the zinc cathode under low current density and low surface capacity. The invention patent CN 108520985A discloses a method for prolonging the cycle life of a zinc electrode, the invention has simple process and low cost, but the cycle life of the zinc electrode prepared by the process is still less than 100h, and the chemical corrosion and the electrochemical corrosion of a zinc cathode can not be solved. Therefore, the zinc cathode which is stably circulated under high current density is obtained by adopting a process with low cost and simple preparation.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a zinc negative electrode material with an elastic protective layer, and preparation and application thereof. The inorganic nano-particles are anchored in the high molecular polymer by utilizing the high elastic modulus and viscosity of the high molecular polymer and are constructed on the zinc cathode to form a protective layer with high elastic modulus. The elastic protective layer can prevent the zinc cathode from directly contacting with the electrolyte, relieve the chemical corrosion and electrochemical corrosion of the zinc cathode in the electrolyte, and relieve zinc dendrite generated by the zinc cathode in the electrodeposition process; in addition, the uniformly dispersed nano particles in the elastic protective layer can regulate and control the electrodeposition of zinc ions.
The purpose of the invention can be realized by the following technical scheme:
one of the technical schemes of the invention provides a zinc cathode material with an elastic protection layer, which consists of a zinc cathode active material and the elastic protection layer coated on the zinc cathode active material, wherein the elastic protection layer comprises a high molecular polymer substrate and inorganic nano-particles anchored in the high molecular polymer substrate.
Furthermore, the zinc negative active material is selected from one or more of pure zinc foil, zinc alloy sheet, pure zinc powder, zinc oxide or zinc hydroxide and the like.
Furthermore, in the elastic protection layer, the mass ratio of the high molecular polymer substrate to the inorganic nanoparticles is 1: (1-20).
Further, the high molecular polymer substrate is selected from any one of PVDF, PVDF-HFP, PAA, PEI, CMC, PEI or PVC substrate, and the like, and the number average molecular weight of the high molecular polymer substrate is 10-500 ten thousand.
Further, the inorganic nanoparticles are selected from Al2O3、ZnO、TiO2、SiO2、BeO、Y2O3、Nb2O5、Ti4O7Or ZrO2One or more of them, the grain diameter is 10 nm-200 nm.
Furthermore, the thickness of the elastic restraint layer is not more than 50 μm, and the elastic modulus is 1 GPa-20 GPa, so that the function of the elastic restraint layer can be realized, and the energy density of the battery is not excessively lost.
In the invention, the substrate of the high molecular polymer in the elastic constraint layer can constrain loose hexagonal sheet-shaped objects formed by zinc ions in the electrodeposition process, inhibit the appearance change of the zinc cathode, reduce deactivated zinc metal, and reduce corrosion of electrolyte and dissolved oxygen in the electrolyte to the zinc cathode. And the inorganic nano-particles regulate the deposition of zinc ions and relieve zinc dendrites. Meanwhile, the mass ratio of the polymer substrate to the inorganic nanoparticles in the elastic constraint layer is 1: (1-20), which can ensure good film forming property and high elastic modulus of the elastic protective layer. The compact high-elasticity film can effectively prevent the corrosion of the metal zinc in the electrodeposition process, effectively restrain the shape change of the zinc cathode and reduce the inactivated zinc metal.
The second technical scheme of the invention provides a preparation method of a zinc cathode material with an elastic protective layer, which comprises the following steps:
(1) mixing a high molecular polymer with a solvent, and stirring to obtain a uniform and transparent high molecular solution;
(2) adding inorganic nano particles into the obtained polymer solution, and performing ultrasonic treatment to uniformly suspend the inorganic nano particles in the polymer solution to obtain suspension slurry;
(3) and uniformly coating the suspension slurry on the surface of the zinc cathode active material, and drying to evaporate the solvent to obtain the target product.
Further, in the step (1), the solvent is one or more selected from NMP, DMF, acetone, acetonitrile or diethyl ether.
Further, the mass ratio of the high molecular polymer to the solvent is 1: 2-1: 100. The solvent is required to ensure that the high molecular polymer can be fully dissolved and has certain viscosity so that the inorganic nano-particles can be uniformly dispersed in the subsequent preparation process. Too much solvent can cause agglomeration of the inorganic nanoparticles and formation of porous structures in the elastic constraining layer during baking.
Further, in the step (2), the added inorganic nanoparticles satisfy: the mass ratio of the high molecular polymer to the inorganic nanoparticles is 1: (1-20).
Further, in the step (3), the amount of the suspension slurry applied was 10. mu.L/cm2～100μL/cm2. When the coating amount is too small, a film is not easily formed, and when the coating amount is too large, the internal resistance of the battery is increased and the energy density of the battery is reduced.
Further, in the step (1), stirring is carried out at 50-100 ℃.
Further, in the step (3), the coating conditions are specifically as follows: the coating mode is one or two of spin coating, drop coating, blade coating and spray coating, the ambient temperature is 10-60 ℃, the ambient humidity is 10-80%, and the coating speed is 1-100 mu L/s. If the ambient temperature is too high, the solvent is easy to volatilize and the inorganic nano particles are easy to agglomerate in the coating process. The moisture content is high, so that the slurry is easy to absorb water in the coating process, and the film forming property is reduced. Too slow a coating speed can result in uneven dispersion of the inorganic nanoparticles within the elastic constraints.
Further, in the step (3), the drying conditions are as follows: the environment temperature is 25-100 ℃, and the environment pressure is-0.1 MPa. After drying, the residual quantity of the solvent evaporated is not higher than 1 percent by mass.
In the above steps, the high molecular polymer is dissolved in the solvent, so as to realize the dispersion of the high molecular polymer and ensure a certain viscosity. While the high molecular polymer solution with certain viscosity can effectively realize the dispersion and anchoring of the inorganic nano particles.
The third technical scheme of the invention provides a water-based secondary battery, which comprises a positive plate, a zinc negative plate made of the zinc negative material, a diaphragm and electrolyte, and is characterized in that the zinc negative plate and the positive plate are respectively positioned at two sides of the diaphragm, and an elastic protection layer on the surface of one side of the zinc negative plate is adjacent to the diaphragm.
Further, the positive electrode plate includes, but is not limited to, a manganese dioxide positive electrode plate, a vanadium pentoxide positive electrode plate, a prussian blue positive electrode plate, and a polyaniline positive electrode plate.
Further, the separator includes, but is not limited to, a glass fiber separator, a PP separator, a PE separator, and a filter paper separator.
Further, the solute of the electrolyte includes, but is not limited to, at least one of zinc sulfate, zinc trifluoromethanesulfonate, zinc perchlorate and zinc chloride; the solvent of the electrolyte is ultrapure water; the amount and concentration of the electrolyte can be the amount and concentration which are conventionally injected in the field.
Compared with the prior art, the invention has the following advantages:
(1) aiming at the water system electrolyte environment, in the large current density and current surface capacity charge and discharge test, the side reaction between the zinc electrode and the electrolyte is greatly inhibited, the stability is obviously improved, the deposition process of zinc ions on the zinc electrode is effectively regulated and controlled, and the pulverization of a zinc cathode and the generation of zinc dendrites are avoided, so that the coulomb efficiency and the cycle life of a symmetrical zinc ion battery are improved, and the capacity retention rate and the cycle life of a zinc-based secondary water system full battery are improved.
(2) The preparation process is simple, the cost is low, and the large-scale production is convenient.
Drawings
Fig. 1 is a picture of a zinc negative electrode having an elastic protective layer provided in example 1 of the present invention and a zinc negative electrode of comparative example 1 after being soaked in an electrolyte for 7 days.
Fig. 2 is an X-ray diffraction (XRD) pattern of the zinc cathode provided in example 2 of the present invention and the zinc cathode of comparative example 2 after 100 cycles.
Fig. 3 is an optical image of the electrodeposition morphology of the zinc negative electrode with the elastic protection layer provided in example 2 of the present invention and the zinc negative electrode of comparative example 2 after 100 cycles.
Fig. 4 is a scanning electron microscope image of the electrodeposition morphology of the zinc negative electrode with the elastic protective layer provided in example 2 of the present invention and the zinc negative electrode of comparative example 2 after 100 cycles.
Fig. 5 is a polarization voltage-cycle time diagram of a Zn | | | Zn battery assembled with a zinc negative electrode having an elastic protective layer provided in example 3 of the present invention and a zinc negative electrode of comparative example 3, respectively.
Fig. 6 is a polarization voltage-cycle time diagram of a Zn | | | Zn battery assembled by a zinc negative electrode having an elastic protective layer provided in example 3 of the present invention and a zinc negative electrode of comparative example 3 under deep discharge.
Fig. 7 is a coulombic efficiency-cycle time graph of a Zn | | | | Ti battery assembled by a zinc negative electrode having an elastic protective layer provided in example 4 of the present invention and a zinc negative electrode of comparative example 4.
FIG. 8 shows MnO assembled between the zinc negative electrode having an elastic protective layer provided in example 5 and the zinc negative electrode of comparative example 52And (4) a cyclic voltammogram of the | Zn full cell.
FIG. 9 shows MnO assembled between the zinc negative electrode having an elastic protective layer provided in example 5 and the zinc negative electrode of comparative example 52And | | Zn full battery capacity-cycle number graph.
Fig. 10 is a polarization voltage-cycle time diagram of a Zn | | | Zn battery assembled with the zinc negative electrode only with the polymeric protective layer and the zinc negative electrode of example 1 provided in this comparative example 6, respectively.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
The following examples are provided only for illustrating the present invention, and the specific implementation of the present invention is not limited to the descriptions, and any number of deductions, modifications or replacements made on the premise of the inventive concept should be considered as the protection scope of the claims submitted by the present invention.
Since the improvement of the invention only relates to the zinc negative electrode of the zinc-based battery, the positive electrode, the diaphragm and the electrolyte in the zinc secondary battery provided by the invention are all types of positive electrodes, diaphragms and water-based electrolytes used in the conventional zinc-based secondary battery. The person skilled in the art can very easily select and prepare the positive electrode, the separator and the electrolyte of the zinc secondary battery according to the present invention according to the guidance of the existing technology, and prepare the zinc secondary battery according to the present invention from the positive electrode, the zinc negative electrode, the separator and the electrolyte.
In the following examples, the number average molecular weight of the high molecular polymer PVDF-HFP used was about 50 ten thousand. The rest, if no specific material or processing technique is mentioned, indicates the conventional commercial material or conventional processing technique in this field.
Example 1
Weighing high molecular polymers PVDF-HFP and NMP according to the mass ratio of 1:50, and continuously stirring to fully dissolve the PVDF-HFP in the NMP to form a uniform and transparent solution. Adding TiO with average particle size of 100nm2Powder of PVDF-HFP with TiO2The mass ratio of the powder is 30: and 70, performing ultrasonic treatment by using an ultrasonic cell disruption instrument to uniformly suspend the inorganic nano particles in the solution to obtain suspension slurry for later use. Then according to 40ul/cm2The slurry was uniformly applied to the surface of the zinc sheet using a spin coater. Drying in a vacuum drying oven at 40 ℃ until the NMP solvent on the surface of the zinc sheet is completely volatilized to obtain the zinc sheet with the elastic protective layer. Soaking the obtained zinc sheet in 2mol/l ZnSO4Taking out the aqueous solution after seven days, and observing the surface appearance of the aqueous solution by using an optical microscope. As shown in fig. 1, corrosion was greatly mitigated on the zinc anode with the elastic protective layer as compared to the unprotected zinc anode of comparative example 1.
Comparative example 1
Soaking the zinc sheet which is not treated in any way in 2mol/l ZnSO4Taking out the aqueous solution after seven days, and observing the surface appearance of the aqueous solution by using an optical microscope.
Example 2
Weighing high molecular polymers PVDF-HFP and NMP according to the mass ratio of 1:20, and continuously stirring to fully dissolve the PVDF-HFP in the NMP to form a uniform and transparent solution. Adding an average particle diameter of100nm TiO2Powder of PVDF-HFP with TiO2The mass ratio is 30: and 70, performing ultrasonic treatment by using an ultrasonic cell disruption instrument to uniformly suspend the inorganic nano particles in the solution to obtain suspension slurry for later use. . Then according to 40ul/cm2The slurry is uniformly dripped on the surface of a zinc sheet by using a spin coater. Drying in a vacuum drying oven at 40 ℃ until the NMP solvent on the surface of the zinc sheet is completely volatilized to obtain the zinc sheet with the elastic protective layer.
At 2mol/l ZnSO4The aqueous solution is used as electrolyte, a glass fiber diaphragm is used, and the Zn symmetrical battery is assembled according to the conventional battery assembly mode in the field. At 0.885mA/cm2The charge and discharge test is carried out under the current density of (2), and after 100 cycles, the X-ray diffraction spectrum (XRD) test is carried out on the zinc sheet. As shown in fig. 2, the side reaction of the Zn | Zn symmetric battery assembled by using the zinc cathode with the elastic protection layer after 100 cycles is obviously inhibited. And (3) observing the appearance of the zinc sheet after circulation by using an optical microscope, wherein after circulation, a Zn | Zn symmetrical battery assembled by a zinc cathode with an elastic protective layer is adopted, the electrodeposited zinc is uniformly deposited on the zinc sheet, the zinc sheet without any protection is not protected, and the electrodeposited zinc is randomly accumulated on the surface of the zinc sheet, as shown in figure 3. The microscopic morphology of the zinc sheet after circulation is observed by a scanning electron microscope, as shown in figure 4, the Zn-Zn symmetrical battery assembled by the zinc cathode with the elastic protective layer has smooth and uniform zinc sheet surface, and the zinc sheet without any protection presents a disordered and piled sheet shape, so that the elastic protective layer can effectively regulate and control the electrodeposition of zinc ions and avoid zinc dendrites.
Comparative example 2
The zinc plate without any treatment is processed at 0.885mA/cm2The charge and discharge test was carried out at the current density of (1), and after 100 cycles, the zinc sheet was subjected to an X-ray diffraction spectrum (XRD) test, an optical microscope and a scanning electron microscope for observation.
Example 3
Weighing high molecular polymer PVDF-HFP and DMF according to the mass ratio of 1:20, and stirring to fully dissolve the PVDF-HFP in the DMF to form a uniform and transparent solution. Adding TiO with average particle size of 100nm2Powder of PVDF-HFP with TiO2The mass ratio of the powder is 20: and 80, performing ultrasonic treatment by using an ultrasonic cell disruption instrument to uniformly suspend the inorganic nanoparticles in the solution to obtain suspension slurry for later use. Then according to 40ul/cm2The slurry was uniformly applied to the surface of the zinc sheet using a spin coater. And drying in a vacuum drying oven at 40 ℃ until the DMF solvent on the surface of the zinc sheet is completely volatilized to obtain the zinc sheet with the elastic protective layer. At 2mol/l ZnSO4The water solution is used as electrolyte, a glass fiber diaphragm is used, the elastic protection layer is adopted, and the Zn symmetrical battery is assembled according to the conventional battery assembly mode in the field. At 0.885mA/cm2The current density of (A) was measured and the current density was measured at 8.85mA/cm2The deep charge and discharge test was performed at the current density of (1) as shown in fig. 5 and 6. The result proves that the Zn symmetrical battery assembled by the zinc cathode with the elastic protective layer can be stable for more than 2000 hours, while the Zn symmetrical battery assembled by the zinc electrode without any treatment can only circulate for less than 300 hours, so that the circulation service life of the zinc cathode is prolonged by nearly 6 times under the current density. Especially under deep charge and discharge conditions, the cycle life of the zinc negative electrode is improved more remarkably.
Comparative example 3
Assembling Zn symmetrical battery with untreated zinc sheet at 0.885mA/cm2The current density of (A) was measured and the current density was measured at 8.85mA/cm2Deep charge and discharge test was performed at the current density of (1).
Example 4
Weighing high molecular polymers PVDF-HFP and NMP according to the mass ratio of 1:20, and continuously stirring to fully dissolve the PVDF-HFP in the NMP to form a uniform and transparent solution. Adding TiO with average particle size of 100nm2Powder of PVDF-HFP with TiO2The mass ratio of the powder is 20:80, and the inorganic nano particles are uniformly suspended in the solution by adopting ultrasonic wave of an ultrasonic cell disruptor to obtain suspension slurry for later use. Then according to 40ul/cm2The slurry was uniformly applied to the surface of the zinc sheet using a spin coater. Drying in a vacuum drying oven at 40 deg.C until NMP solvent on the surface of the zinc sheet is completely volatilized to obtainA zinc sheet having an elastic protective layer. At 2mol/l ZnSO4The aqueous solution is used as electrolyte, a glass fiber diaphragm is used, and the Zn/Ti battery is assembled by adopting the elastic protection layer according to the conventional battery assembly mode in the field. At 1.77mA/cm2The charge and discharge tests are carried out under the current density of (1), as shown in figure 7, in 1000 cycles of the Zn & ltI & gt Ti battery assembled by adopting the zinc cathode with the elastic protection layer, the average coulombic efficiency of 99.4 percent can be realized; the zinc electrode without any protection can only be cycled for 300 circles, and the coulombic efficiency greatly fluctuates in the cycling process.
Comparative example 4
Assembling zinc sheets without any treatment into a Zn I Ti battery at 1.77mA/cm2The charge and discharge test was performed at the current density of (1).
Example 5
Weighing high molecular polymers PVDF-HFP and NMP according to the mass ratio of 1:20, and continuously stirring to fully dissolve the PVDF-HFP in the NMP to form a uniform and transparent solution. Adding ZnO powder with the average particle size of 100nm, wherein the mass ratio of PVDF-HFP to ZnO is 20:80, and ultrasonically treating with an ultrasonic cell disruption instrument to uniformly suspend inorganic nanoparticles in the solution to obtain suspension slurry for later use. Then according to 40ul/cm2The slurry is uniformly dripped on the surface of a zinc sheet by using a spin coater. Drying in a vacuum drying oven at 40 ℃ until the NMP solvent on the surface of the zinc sheet is completely volatilized to obtain the zinc sheet with the elastic protective layer. At 2mol/l ZnSO4The aqueous solution is used as electrolyte, a glass fiber diaphragm is used, the elastic protective layer is adopted, and Zn MnO is assembled according to the conventional battery assembly mode in the field2And (4) full cell. The full cell was subjected to cyclic voltammetry at a sweep rate of 0.1mV/S and charge-discharge testing at a current density of 2C (C ═ 308mAh/g), as shown in fig. 8 and fig. 9. The results showed that the zinc sheet-assembled full cell with the elastic protective layer and the zinc-assembled full cell without any protection had the same redox reaction, except that after the elastic protection, Zn | | MnO2The polarization voltage of the oxidation reaction and the reduction reaction of the whole battery is reduced by 0.02V on average; after 300 cycles of long circulation, Zn | MnO with elastic protection layer2The full battery has higher capacity retention (234mAh/g) than Zn MnO without any protection2The capacity retention of the full battery (103mAh/g) is 2 times.
Comparative example 5
Assembling Zn | MnO on zinc sheet without any treatment2And the battery is subjected to cyclic voltammetry test and charge-discharge test.
Comparative example 6
Weighing high molecular polymers PVDF-HFP and NMP according to the mass ratio of 1:50, and continuously stirring to fully dissolve the PVDF-HFP in the NMP to form a uniform and transparent solution. Then according to 40ul/cm2The slurry was uniformly applied to the surface of the zinc sheet using a spin coater. Drying in a vacuum drying oven at 40 ℃ until the NMP solvent on the surface of the zinc sheet is completely volatilized to obtain the zinc sheet with the elastic protective layer. At 2mol/l ZnSO4The water solution is used as electrolyte, a glass fiber diaphragm is used, the elastic protection layer is adopted, and the Zn symmetrical battery is assembled according to the conventional battery assembly mode in the field. At 0.885mA/cm2The long cycle test was performed at the current density of (1), as shown in fig. 10. Therefore, the addition of the inorganic nano particles can obviously prolong the cycle life of the zinc cathode.
Example 6
Weighing high molecular polymers PVDF-HFP and NMP according to the mass ratio of 1:20, and continuously stirring to fully dissolve the PVDF-HFP in the NMP to form a uniform and transparent solution. Adding Al with average particle size of 100nm2O3Powder of PVDF-HFP with Al2O3The mass ratio is 20:80, and the inorganic nano particles are uniformly suspended in the solution by adopting the ultrasonic of an ultrasonic cell disruptor to obtain suspension slurry for later use. Then according to 40ul/cm2The elastic protective layer is prepared on a polytetrafluoroethylene plate, and the elastic modulus of the elastic layer is tested by adopting a nano indentation technology, specifically as shown in attached table 1, the average elastic modulus of the 12 samples in the embodiment is 2.67GPa, and dendrite in the metal deposition process can be inhibited.
TABLE 1 elastic modulus data for the samples in example 6
Comparative example 7
Weighing high molecular polymers PVDF-HFP and NMP according to the mass ratio of 1:20, and continuously stirring to fully dissolve the PVDF-HFP in the NMP to form a uniform and transparent solution. Adding Al with average particle size of 100nm2O3Powder of PVDF-HFP with Al2O3The mass ratio is 1:25, and the inorganic nano particles are uniformly suspended in the solution by adopting the ultrasonic of an ultrasonic cell disruptor to obtain suspension slurry for later use. Then according to 40ul/cm2The elastic protective layer is prepared on a polytetrafluoroethylene plate, and the elastic modulus of the elastic layer is tested by adopting a nano indentation technology, specifically as shown in attached table 2, the average elastic modulus of the 12 samples in the embodiment is 0.23GPa, and dendrite in the metal deposition process can be inhibited.
TABLE 2 elastic modulus data for the samples in comparative example 7
Example 8
Weighing high molecular polymers PVDF-HFP and NMP according to the mass ratio of 1:20, and continuously stirring to fully dissolve the PVDF-HFP in the NMP to form a uniform and transparent solution. Adding ZnO powder with the average particle size of 100nm, wherein the mass ratio of PVDF-HFP to ZnO is 20:80, and ultrasonically treating with an ultrasonic cell disruption instrument to uniformly suspend inorganic nanoparticles in the solution to obtain suspension slurry for later use. Then according to the ratio of 100ul/cm2The slurry was uniformly applied to the surface of the zinc sheet using a spin coater. Drying in a vacuum drying oven at 40 ℃ until the NMP solvent on the surface of the zinc sheet is completely volatilized to obtain the zinc sheet with the elastic protective layer. At 2mol/l ZnSO4The water solution is used as electrolyte, a glass fiber diaphragm is used, the elastic protection layer is adopted, and the Zn symmetrical battery is assembled according to the conventional battery assembly mode in the field. At 0.885mA/cm2The current density of (A) was measured and the current density was measured at 8.85mA/cm2Deep charge and discharge test was performed at the current density of (1).
Example 9
Weighing high molecular polymer PEI and NMP according to the mass ratio of 1:20, and stirring continuously to enable the PEI to be fully dissolved in the NMP to form a uniform and transparent solution. Adding ZnO powder with the average particle size of 100nm, wherein the mass ratio of PEI to ZnO is 20:80, and ultrasonically treating with an ultrasonic cell disruption instrument to uniformly suspend inorganic nanoparticles in the solution to obtain suspension slurry for later use. Then according to 40ul/cm2The slurry was uniformly applied to the surface of the zinc sheet using a spin coater. Drying in a vacuum drying oven at 40 ℃ until the NMP solvent on the surface of the zinc sheet is completely volatilized to obtain the zinc sheet with the elastic protective layer. At 2mol/l ZnSO4The water solution is used as electrolyte, a glass fiber diaphragm is used, the elastic protection layer is adopted, and the Zn symmetrical battery is assembled according to the conventional battery assembly mode in the field. At 0.885mA/cm2The current density of (A) was measured and the current density was measured at 8.85mA/cm2Deep charge and discharge test was performed at the current density of (1).
Example 10
Weighing high molecular polymer PEI and NMP according to the mass ratio of 1:20, and stirring continuously to enable the PEI to be fully dissolved in the NMP to form a uniform and transparent solution. Adding ZnO powder with the average particle size of 100nm, wherein the mass ratio of PEI to ZnO is 20:80, and ultrasonically treating with an ultrasonic cell disruption instrument to uniformly suspend inorganic nanoparticles in the solution to obtain suspension slurry for later use. Then according to the ratio of 100ul/cm2The slurry was uniformly applied to the surface of the zinc sheet using a spin coater. Drying in a vacuum drying oven at 40 ℃ until the NMP solvent on the surface of the zinc sheet is completely volatilized to obtain the zinc sheet with the elastic protective layer. At 2mol/l ZnSO4The water solution is used as electrolyte, a glass fiber diaphragm is used, the elastic protection layer is adopted, and the Zn symmetrical battery is assembled according to the conventional battery assembly mode in the field. At 0.885mA/cm2The current density of (A) was measured and the current density was measured at 8.85mA/cm2Deep charge and discharge test was performed at the current density of (1).
Example 11 example 14
Compared with the embodiment 1, most of the active materials are the same except that the zinc negative active material in the embodiment is changed from a zinc sheet to a zinc alloy sheet, pure zinc powder, zinc oxide or zinc hydroxide.
Examples 15 to 19
Compared with example 1, most of them are the same except that the polymer in this example is changed to PVDF, PAA, CMC, PEI or PVC, respectively.
Examples 20 to 25
Compared with the embodiment 1, most of the inorganic nanoparticles are the same except that the inorganic nanoparticles in the embodiment are respectively changed to SiO2、BeO、Y2O3、Nb2O5、Ti4O7Or ZrO2。
Examples 26 to 28
Compared with example 1, most of the solvent is the same except that acetone, acetonitrile or diethyl ether is used as the solvent in the example.
Example 29
Compared with example 1, the polymer is mostly the same except that the mass ratio of the polymer to the solvent in this example is 1: 2.
Example 30
Compared with example 1, the polymer is mostly the same except that the mass ratio of the polymer to the solvent in this example is 1: 100.
Example 31
Compared with example 1, the coating amount of the suspension slurry in this example was 10. mu.L/cm2。
Example 32
Compared with example 1, the coating amount of the suspension slurry in this example was mostly the same except that the coating amount was 100. mu.L/cm2。
In the above embodiments, the stirring and dissolving of the high molecular weight polymer and the solvent are preferably performed at 50 to 100 ℃; the coating conditions may specifically be preferably: the coating mode is one or two of spin coating, drop coating, blade coating and spray coating, the ambient temperature is 10-60 ℃, the ambient humidity is 10-80%, and the coating speed is 1-100 mu L/s. The drying conditions may be specifically preferably: the environment temperature is 25-100 ℃, and the environment pressure is-0.1 MPa. After drying, the residual quantity of the solvent evaporated is not higher than 1 percent by mass.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The zinc cathode material with the elastic protection layer is characterized by consisting of a zinc cathode active material and the elastic protection layer coated on the zinc cathode active material, wherein the elastic protection layer comprises a high-molecular polymer substrate and inorganic nanoparticles anchored in the high-molecular polymer substrate.
2. The zinc negative electrode material with the elastic protective layer as claimed in claim 1, wherein the zinc negative active material is selected from one or more of pure zinc foil, zinc alloy sheet, pure zinc powder, zinc oxide or zinc hydroxide.
3. The zinc negative electrode material with the elastic protective layer as claimed in claim 1, wherein the elastic protective layer comprises the high molecular polymer substrate and the inorganic nanoparticles in a mass ratio of 1: (1-20).
4. The zinc negative electrode material with the elastic protection layer as claimed in claim 1, wherein the high molecular polymer substrate is selected from any one of PVDF, PVDF-HFP, PAA, PEI, CMC, PEI or PVC substrate, and the number average molecular weight is 10-500 ten thousand;
the inorganic nanoparticles are selected from Al2O3、ZnO、TiO2、SiO2、BeO、Y2O3、Nb2O5、Ti4O7Or ZrO2One or more of them, the grain diameter is 10 nm-200 nm.
5. The zinc negative electrode material with the elastic protective layer as claimed in claim 1, wherein the elastic constraining layer has a thickness of not more than 50 μm and an elastic modulus of 1GPa to 20 GPa.
6. The method for preparing a zinc anode material with an elastic protective layer according to any one of claims 1 to 5, comprising the steps of:
(1) mixing a high molecular polymer with a solvent, and stirring to obtain a uniform and transparent high molecular solution;
(2) adding inorganic nano particles into the obtained polymer solution, and performing ultrasonic treatment to uniformly suspend the inorganic nano particles in the polymer solution to obtain suspension slurry;
(3) and uniformly coating the suspension slurry on the surface of the zinc cathode active material, and drying to evaporate the solvent to obtain the target product.
7. The preparation method of the zinc anode material with the elastic protective layer according to claim 6, wherein in the step (1), the solvent is one or more selected from NMP, DMF, acetone, acetonitrile or diethyl ether;
the mass ratio of the high-molecular polymer to the solvent is 1: 2-1: 100.
8. The method for preparing a zinc anode material with an elastic protective layer according to claim 6, wherein in the step (2), the added inorganic nanoparticles satisfy the following conditions: the mass ratio of the high molecular polymer to the inorganic nanoparticles is 1: (1-20).
9. The method for preparing a zinc anode material with an elastic protective layer according to claim 6, wherein in the step (3), the coating amount of the suspension slurry is 10 μ L/cm2～100μL/cm2。
10. An aqueous secondary battery comprising a positive electrode sheet, a zinc negative electrode sheet made of the zinc negative electrode material having an elastic protective layer according to any one of claims 1 to 5, and a separator
And the electrolyte is characterized in that the zinc negative plate and the positive plate are respectively positioned at two sides of the diaphragm, and the elastic protective layer on the surface of one side of the zinc negative plate is close to the diaphragm.
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| CN112838211A (en) * | 2020-12-30 | 2021-05-25 | 中南大学 | Modification method of zinc metal negative electrode, product and application thereof |
| CN113097496A (en) * | 2021-02-25 | 2021-07-09 | 东华大学 | Zinc cathode with composite nanofiber protective layer and preparation and application thereof |
| CN113097496B (en) * | 2021-02-25 | 2022-04-29 | 东华大学 | Zinc cathode with composite nanofiber protective layer and preparation and application thereof |
| CN114361376A (en) * | 2022-01-17 | 2022-04-15 | 齐鲁工业大学 | Preparation and application of zinc cathode material of novel water-based zinc ion battery |
| CN114792775A (en) * | 2022-06-22 | 2022-07-26 | 北京航空航天大学 | Polymer coating modified zinc cathode and preparation method and application thereof |
| CN116387467A (en) * | 2023-06-05 | 2023-07-04 | 武汉理工大学三亚科教创新园 | Organic-inorganic interface as zinc negative electrode protective layer, zinc negative electrode, preparation method and battery |
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