CN117438741A - Inorganic oxide-based hydrophobic zinc ion battery diaphragm and application thereof in zinc battery - Google Patents
Inorganic oxide-based hydrophobic zinc ion battery diaphragm and application thereof in zinc battery Download PDFInfo
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- CN117438741A CN117438741A CN202311500271.9A CN202311500271A CN117438741A CN 117438741 A CN117438741 A CN 117438741A CN 202311500271 A CN202311500271 A CN 202311500271A CN 117438741 A CN117438741 A CN 117438741A
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000011701 zinc Substances 0.000 title claims abstract description 88
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 87
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 75
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052809 inorganic oxide Inorganic materials 0.000 title claims abstract description 25
- 239000012528 membrane Substances 0.000 claims abstract description 91
- 239000003365 glass fiber Substances 0.000 claims abstract description 53
- 239000003792 electrolyte Substances 0.000 claims abstract description 40
- 238000002360 preparation method Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000011521 glass Substances 0.000 claims abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 8
- 239000002033 PVDF binder Substances 0.000 claims abstract description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- PWPUKAKBNKSJSE-UHFFFAOYSA-N [O-2].[O-2].[V+5].[Zn+2] Chemical compound [O-2].[O-2].[V+5].[Zn+2] PWPUKAKBNKSJSE-UHFFFAOYSA-N 0.000 claims description 23
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 claims description 19
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 claims description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- QNDQILQPPKQROV-UHFFFAOYSA-N dizinc Chemical compound [Zn]=[Zn] QNDQILQPPKQROV-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 13
- 229960001763 zinc sulfate Drugs 0.000 claims description 13
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 13
- 229910001220 stainless steel Inorganic materials 0.000 claims description 12
- 239000010935 stainless steel Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 9
- 239000006229 carbon black Substances 0.000 claims description 8
- 238000005096 rolling process Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000001238 wet grinding Methods 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000009837 dry grinding Methods 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 47
- 238000012360 testing method Methods 0.000 description 44
- 230000000052 comparative effect Effects 0.000 description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000005611 electricity Effects 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 210000001787 dendrite Anatomy 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000012430 stability testing Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 230000032258 transport Effects 0.000 description 3
- 230000006978 adaptation Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a hydrophobic zinc ion battery diaphragm based on inorganic oxide and application thereof in a zinc battery, and belongs to the field of secondary zinc batteries. The hydrophobic separator is composed of an inorganic oxide and a binder. The preparation method is inorganic oxide (Ta 2 O 5 、Al 2 O 3 Or La (La) 2 O 3 Etc.) and binder (PVDF) in a mass ratio of (8-10): 1 stirring to mix them uniformly; placing the slurry on a glass plate, and uniformly coating the slurry by using a knife coater; drying; separating a membrane from a glass plate using deionized waterAnd (3) separating to obtain the hydrophobic membrane. The membrane has hydrophobicity, can isolate a large amount of free water, the surface of the membrane contains a porous structure, electrolyte ions can be freely transmitted, the membrane is self-assembled with a hydrophilic glass fiber membrane to form a hydrophobic-hydrophilic-hydrophobic membrane for a zinc ion battery with long service life, the hydrophilic membrane can store a large amount of electrolyte, the high-performance circulation of the zinc battery is ensured, and the hydrophobic membrane can isolate a large amount of free water to prevent electrode corrosion or dissolution.
Description
Technical Field
The invention belongs to the field of novel battery energy storage, and particularly relates to a hydrophobic zinc ion battery diaphragm based on inorganic oxide and application of the diaphragm in a zinc battery.
Background
The safety problem of the lithium battery is that a plurality of energy storage power station fires or explosion accidents occur in the electrochemical energy storage power station, so that the industry development is seriously hindered. Aqueous zinc ion batteries are considered to be one of the strongest competitors for the next generation of low cost energy storage devices. The development is rapid due to its high safety, rapid charge-discharge capability and high energy density. However, practical application of zinc ion batteries is limited by short circuits caused by the penetration of crazy dendrite growth through the separator, severe hydrogen evolution and corrosion side reactions shorten the cycle life of the battery, and capacity degradation caused by cathode dissolution. These problems are mainly determined by the electrode/electrolyte and electrolyte/separator interfaces.
Currently, in order to improve the stability of the electrode/electrolyte interface, researchers have tried a number of strategies or approaches to improve the life of zinc cells, but neglecting the interface effect of the electrolyte with the separator. The traditional hydrophilic diaphragms such as glass fiber, filter paper and the like cannot avoid direct contact between electrolyte and an electrode, so that the surface of a zinc negative electrode is severely corroded and has hydrogen evolution side reaction, and meanwhile, the anode is dissolved, so that the service life of the battery is rapidly reduced; the hydrophobic separator cannot transmit electrolyte through water, so that the battery has poor cycle performance due to insufficient electrolyte. Therefore, to thoroughly solve the interface problem of the battery electrode and the separator, it is necessary to study the combination of hydrophilic and hydrophobic separators to effectively avoid contact with a large amount of free water while transporting the electrolyte through the combined water.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a hydrophobic zinc ion battery diaphragm based on inorganic oxide and application thereof in a zinc battery, and when the hydrophobic diaphragm is used for assembling a hydrophobic-hydrophilic-hydrophobic diaphragm in the zinc battery, a large amount of free water can be isolated, a small amount of bound water can be used for transmitting electrolyte, more zinc ion transmission channels can be provided, and the cycle life of the zinc battery is prolonged.
In order to solve the technical problems of the invention, the adopted technical scheme is as follows:
an inorganic oxide-based hydrophobic zinc ion battery separator, obtained by the process of:
1) The inorganic oxide and the binder are mixed according to the mass ratio of (8-10): 1, dissolving the mixture in a proper amount of NMP, and stirring the mixture for 5 to 15 hours to uniformly mix the mixture; the inorganic oxide is Ta 2 O 5 、Al 2 O 3 And La (La) 2 O 3 At least one or a mixture of more than two of the above materials in any proportion, wherein the binder is PVDF;
2) Placing the slurry on a glass plate, uniformly coating the slurry by using a knife coater and drying;
3) The membrane was separated from the glass plate using deionized water to produce a hydrophobic zinc ion battery membrane.
And further, the drying is to dry the glass plate coated with the slurry in a drying oven or a vacuum oven at a drying temperature of 30-50 ℃, and the hydrophobic-hydrophilic-hydrophobic membrane is used for forming a hydrophobic-hydrophilic-hydrophobic structure by self-assembly of the hydrophobic membrane and the hydrophilic membrane in the process of assembling the battery.
Further, the membrane has hydrophobicity relative to the hydrophilic glass fiber membrane, and can isolate a large amount of free water; the thickness of the hydrophobic zinc ion battery diaphragm is 10-20 microns, and the surface of the hydrophobic zinc ion battery diaphragm is provided with a nanoscale porous structure.
The porous structure is that nano-scale porous is spread on the surface of the diaphragm, and the diaphragm porous structure transmits electrolyte through a small amount of bound water and a large amount of free water cannot pass through.
Further, the hydrophobic zinc ion battery separator is applied to zinc batteries.
Further, the zinc sheet is used as a negative electrode, vanadium dioxide or zinc sheet is used as a positive electrode, the hydrophobic zinc ion battery diaphragm, the glass fiber and the hydrophobic zinc ion battery diaphragm are assembled to form a hydrophobic-hydrophilic-hydrophobic diaphragm structure which is used as a battery diaphragm, and the zinc battery is assembled by taking 0.5-2 mol/L zinc sulfate solution as electrolyte.
Further, the zinc battery is a zinc vanadium dioxide full battery, a zinc symmetrical battery or a zinc vanadium dioxide soft package full battery.
Further, the zinc-zinc symmetrical battery has the structure that: positive electrode shell, zinc sheet, hydrophobic membrane, hydrophilic membrane, hydrophobic membrane, zinc sheet, gasket, negative electrode shell; the structure of the zinc vanadium dioxide full cell is as follows: the anode comprises an anode shell, a stainless steel mesh, a vanadium dioxide anode, a hydrophobic diaphragm, a hydrophilic diaphragm, a hydrophobic diaphragm, a zinc sheet, a gasket and a cathode shell; the structure of the zinc vanadium dioxide soft-package full battery is as follows: zinc sheet, hydrophobic membrane, hydrophilic membrane, hydrophobic membrane, vanadium dioxide positive electrode.
In the zinc cell, the stainless steel mesh is 400 mesh stainless steel mesh, and the thickness of the gasket is 500 μm.
The preparation process of the vanadium dioxide anode comprises the following steps: VO is to be provided with 2 Dry milling the powder and the carbon black powder for 5-15 minutes, then adding a proper amount of isopropanol and 55-65wt% of PTFE aqueous solution, and continuing wet milling until paste is formed; rolling the mixture into thin slices by using a roll squeezer, continuously adding isopropanol to keep PTFE sticky when rolling, slicing the long slices by using a slicer, and drying to obtain the VO in the positive plate 2 The load capacity of the catalyst is 5.4-6.2 mg cm -2 ，VO 2 The mass ratio of powder, carbon black and PTFE was 6:2:2.
Compared with the prior art, the beneficial effects are that:
first, improve electrode and diaphragm interface effect, improve battery life-span by a wide margin. Hydrophobic membrane assembly made of inorganic oxide "hydrophobic-hydrophilic-hydrophobic" membrane for zinc ion battery with high current density of 5mA cm -2 、10mA cm -2 Under test conditions, compared with the place without the placeThe cycle life of the zinc cathode is far longer than that of a battery using only a hydrophilic glass fiber diaphragm, and the average cycle life of the zinc cathode is improved by more than 15 times. The assembled full cell showed high specific capacity and excellent cycle performance with a capacity retention of 60.4% after 1000 cycles at 2C. The assembled soft package battery circulates 40 times under 0.5C, and the circulation time exceeds 240 hours, and shows 172.5mAh g -1 Is a high specific capacity of (a). Compared with other patents, the current density used by the technology is larger, and the service life is far longer than that of other patent methods.
Second, the "hydrophobic-hydrophilic-hydrophobic" structured separator has functionalization. By means of inorganic oxides (Ta 2 O 5 、Al 2 O 3 Or La (La) 2 O 3 Etc.) and a binder (PVDF) to form a surface nanoporous structure. The membrane and the hydrophilic glass fiber membrane self-assembled hydrophobic-hydrophilic-hydrophobic membrane are used for zinc batteries. The thickness of the hydrophobic layer diaphragm is only 10 micrometers, and the diaphragm is much thinner than thick glass fiber; has electrolyte transport, high free water blocking and Zn conditioning 2+ Ability to deposit uniformly. The middle hydrophilic glass fiber separator has the functions of storing electrolyte and ensuring free transport of electrolyte back and forth.
Thirdly, the preparation method is simple and effective, and the large-scale application is wide. First inorganic oxide (Ta) 2 O 5 、Al 2 O 3 Or La (La) 2 O 3 Etc.) and binder (PVDF) in a mass ratio of 9:1 stirring to mix them uniformly; the slurry was then placed on a glass plate, uniformly coated with a 120 micron knife coater and dried; finally, the membrane is separated from the glass plate by deionized water and dried to prepare the hydrophobic membrane. The preparation method is simple in process, the hydrophobic membrane can be prepared in a large quantity, and meanwhile, a hydrophobic-hydrophilic-hydrophobic structure is formed for the zinc ion battery, so that a new thought is provided for engineering application of the water-based battery membrane.
Drawings
FIG. 1 is a schematic illustration of a process for preparing a hydrophobic membrane based on an inorganic oxide;
FIG. 2 is an SEM image of the surface morphology of a hydrophobic separator and an assembled schematic of a "hydrophobic-hydrophilic-hydrophobic" separator applied to a zinc cell;
FIG. 3 is a graph of dynamic contact angle of glass fiber separator with hydrophobic separator surface;
FIG. 4 shows a zinc electrode and an inorganic oxide (Ta 2 O 5 ) An XRD pattern of (b);
FIG. 5 is an SEM image of the surface morphology of zinc after cycling of the zinc cells of comparative example 2 and example 1;
FIG. 6 is a graph of ion concentration of permeate from different membrane ion permeation experiments;
FIG. 7 is a graph of the long cycle test of the zinc-zinc symmetric cells of comparative example 2 and example 1;
FIG. 8 is a comparison of long cycle test results under different test conditions for a zinc-zinc symmetric cell with different separator applications;
FIG. 9 is a graph of the cycling of comparative example 3 and example 2 zinc vanadium dioxide full cells;
fig. 10 is a cycle graph of the soft pack full cell of comparative example 4 and example 3.
Detailed Description
The invention is further illustrated by the following comparative examples and examples in conjunction with the accompanying drawings.
Comparative example 1
Preparation and structural characterization of hydrophobic membranes.
Step 1, preparation of hydrophobic Membrane
First inorganic oxide (Ta) 2 O 5 、Al 2 O 3 Or La (La) 2 O 3 Etc.) and binder (PVDF) in a mass ratio of 9:1 in an appropriate amount of NMP, stirring for 8 hours to mix well, requiring about 1.5mLNMP per 100mg of solid (inorganic oxide+PVDF); then placing the slurry on a glass plate, uniformly coating the slurry by using a 120-micrometer knife coater, and drying the slurry in a vacuum oven at 40 ℃; finally, deionized water is used for separating the diaphragm from the glass plate and drying is carried out at 40 ℃ to prepare the hydrophobic diaphragm, wherein the thickness of the hydrophobic diaphragm is 10-20 mu m.
Step 2, characterization of hydrophobic Membrane Structure
The hydrophobicity of the membrane was verified using dynamic contact angles as shown in figure 3. When 1 mol.L -1 ZnSO 4 The contact angle of the electrolyte drop on the glass fiber diaphragm is 0 DEG, which indicates that the electrolyte drop hasSuper-hydrophilicity; the contact angle of the membrane prepared by the technology at 10s is 85.82 degrees, which shows that the membrane has hydrophobicity. However, with time, the contact angle slowly decreased to 73.15 ° at 60 s. This may be sufficient to explain that the hydrophobic membrane may isolate large amounts of free water and only transport the electrolyte through small amounts of bound water. Ta 2 O 5 The XRD results of (a) are shown in FIG. 4, and the inorganic oxide (Ta 2 O 5 ) The peak of the (B) is highly matched with the peak of a zinc (002) crystal face, so that zinc ions can be guided to be uniformly deposited. SEM as shown in fig. 2, the hydrophobic membrane is composed of a membrane with PVDF and inorganic oxide (Ta 2 O 5 ) The porous structure of the homogeneous mixture constitutes, which facilitates zinc ion transport.
Comparative example 2
And assembling the zinc-zinc symmetrical battery by utilizing the hydrophilic glass fiber diaphragm.
Step 1, preparation of zinc electrode
A200 μm thick pure zinc foil (purchased from Chinese medicinal chemical) was ultrasonically cleaned with ethanol (ultrasonic frequency 40kHz, power 300W, time 5 minutes) to form zinc sheets, and the zinc foil was cut into pieces having a diameter of 12mm and an area of about 1.13cm using an electrode microtome 2 Is cleaned again by ethanol with ultrasound (ultrasonic frequency 40kHz, power 300W, time 5 minutes) and then dried in a vacuum oven at 40 ℃ for 1 hour.
Step 2, zinc symmetrical battery assembly
The zinc electrode was assembled into a CR2016 type (cell diameter 20.0mm, thickness 1.6 mm) symmetrical cell for cycle stability testing. The components of the battery are a positive electrode shell, a pure zinc sheet, a glass fiber diaphragm, a pure zinc sheet, a stainless steel gasket (with the diameter of 16mm and the thickness of 500 mu m) and a negative electrode shell in sequence, and the sealing pressure is about 50 kilograms per cubic centimeter. The battery needs to stand at room temperature for not less than 2 hours before use. The membrane was glass fiber (manufactured by Whatman, inc., 110mm diameter, 260 μm thick, and cut into discs 19mm diameter for use). The electrolyte used was 1mol/L (or 1M) zinc sulfate solution, 100. Mu.L was added dropwise to each cell, and after the separator was placed, the electrolyte was added dropwise. The preparation method of the 1M zinc sulfate electrolyte comprises the steps of preparing ZnSO 4 ∙7H 2 O (analytically pure)Purchased from national pharmaceutical chemicals) are dissolved in pure water at a mass ratio of approximately 11.5024: 34.9556.
Step 3, zinc symmetrical battery test
The symmetrical cell long cycle test was performed in an incubator maintained at 25 ℃ to eliminate the effects of ambient temperature. Battery testing systems using the marchand blue electricity. As shown in FIG. 7, the test parameters were set to constant-current discharge and constant-current charge, and the current density based on the electrode area was 5mA/cm 2 The area capacity is 1mAh/cm 2 . Under this test condition, the symmetric battery using the hydrophilic glass fiber separator had a life of about 120 hours, and it was found that the battery using the hydrophilic glass fiber separator had a shorter life. In addition, at a higher test current density, as shown in FIG. 8, at 10mA/cm 2 、1mAh/cm 2 The symmetrical battery life was 163 hours under conditions.
Step 4, observing dendrite on surface of zinc symmetrical battery
The surface morphology of the zinc electrode after 120 hours of death was observed using a zeiss focused dual ion beam Scanning Electron Microscope (SEM). As shown in fig. 5, after long zinc deposition and stripping, the electrode surface is covered with disordered irregular dendrites, which is a main cause of short circuit of the battery.
Comparative example 3
Zinc vanadium dioxide full cell assembled by hydrophilic glass fiber diaphragm
And step 1, preparing a zinc electrode.
Step 1 was performed as in comparative example 2.
Step 2, preparation of vanadium dioxide positive electrode
VO 2 The powder was purchased from Taobao manufacturer. VO (VO) 2 The positive plate is prepared by adopting a rolling method without a current collector so as to increase the loading capacity of the active material. VO (VO) 2 The positive plate consists of VO with the mass ratio of 6:2:2 2 Powder, carbon black and PTFE. 150 mg of VO was first taken 2 The powder and 50mg carbon black powder were dry milled for 10 minutes, then the appropriate amount of isopropyl alcohol and 83.3 mg of 60wt% PTFE aqueous solution (PTFE mass 50 mg) were added and wet milling continued in a fume hood until a paste was formed. Next, the mixture was rolled into a sheet using a roll press. ScrollingWhen this is done, isopropanol is continuously added to keep the PTFE tacky. The long sheet was sliced using a microtome at a certain humidity. They were cut into discs of diameter 11. 11 mm (approximately 0.949. 0.949 cm in area 2 ) Then dried in an oven at 80 ℃ for 12 h and weighed for later use. Active material VO in positive plate 2 The loading was about 6.2mg cm -2 。
Step 3, full battery assembly
Zinc electrode and VO 2 The electrodes were assembled into a CR2016 type (20.0 mm diameter cell, 1.6mm thickness) full cell. The whole battery is assembled by a positive electrode shell, a stainless steel mesh (400 meshes, diameter 12 mm), a positive electrode plate, a glass fiber diaphragm, a negative electrode plate, a stainless steel gasket (thickness 500 μm) and a negative electrode shell. The sealing pressure is about 50 kg per cc. The battery needs to be left at room temperature for 2 hours before use. The membrane was glass fiber (manufactured by Whatman, inc., 110mm diameter, and cut into 19mm disks for use). The electrolyte used was 1mol/L (or 1M) zinc sulfate solution, 100. Mu.L was added dropwise to each cell, and after the separator was placed, the electrolyte was added dropwise.
Step 4, testing the zinc vanadium dioxide full cell
Full cell testing was performed in an incubator (25 ℃) to eliminate the effects of ambient temperature. Battery testing systems using the marchand blue electricity. The charge and discharge test under the 2C rate condition shows that the initial discharge specific capacity is 125mAh g as shown in FIG. 9 -1 Then a downward trend was seen, with a capacity drop of 35mAh g after about 1000 cycles -1 。
Comparative example 4
Preparation of zinc electrode and assembling soft package full cell with hydrophilic glass fiber diaphragm.
Step 1, preparation of a soft zinc-coated electrode
Pure zinc sheets (purchased from chinese medicinal chemical) 200 μm thick were ultrasonically cleaned (ultrasonic frequency 40kHz, power 300W, time 5 minutes) with ethanol, then zinc foil was cut into zinc sheets 4cm x 4cm, again ultrasonically cleaned with ethanol (ultrasonic frequency 40kHz, power 300W, time 5 minutes), and then dried in a vacuum oven at 40 ℃ for 1 hour.
Step 2, preparation of vanadium dioxide positive electrode
VO 2 The powder was purchased from Taobao manufacturer. VO (VO) 2 The positive plate is prepared by adopting a rolling method without a current collector so as to increase the loading capacity of the active material. VO (VO) 2 The positive plate consists of VO with the mass ratio of 6:2:2 2 Powder, carbon black and PTFE. 150 mg of VO was first taken 2 The powder and 50mg carbon black powder were dry milled for 10 minutes, then the appropriate amount of isopropyl alcohol and 83.3 mg of 60wt% PTFE aqueous solution (PTFE mass 50 mg) were added and wet milling continued in a fume hood until a paste was formed. Next, the mixture was rolled into a sheet using a roll press. During rolling, isopropanol was continuously added to maintain PTFE viscosity. The positive electrode sheet was cut into a positive electrode sheet of 4cm×4cm under a certain humidity, and then dried in an oven at 80 ℃ for 12 h, and weighed for use. Active material VO in positive plate 2 The loading was about 151.2mg.
Step 3, zinc vanadium dioxide soft package full battery assembly
And assembling the zinc electrode and the vanadium dioxide positive electrode into a 4cm multiplied by 4cm soft-packed full battery for cycle stability test. The battery needs to be left at room temperature for 2 hours before use. The membrane was glass fiber (manufactured by Whatman Co., cut to 4.2cm. Times.4.2 cm for use). The electrolyte used was 1mol/L (or 1M) zinc sulfate solution, 1mL was added dropwise to each cell, and the electrolyte was added dropwise before sealing.
Step 4, testing the zinc vanadium dioxide soft package full battery
The soft pack full cell test was performed in an incubator (25 ℃) to eliminate the effect of ambient temperature. Battery testing systems using the marchand blue electricity. Charge and discharge testing at 0.5C magnification. As shown in FIG. 10, the initial discharge specific capacity was 250mAh g -1 The capacity of the 40 th turn is reduced to 40mAh g -1 。
Example 1
The membrane with the 'hydrophobic-hydrophilic-hydrophobic' structure is formed by utilizing a hydrophobic membrane and is used for a zinc-zinc symmetrical battery.
Step 1, preparation of hydrophobic Membrane
The procedure was the same as in comparative example 1, step 1.
Step 2, zinc electrode preparation
The same as in step 1 of comparative example 2.
Step 3, assembling zinc-zinc symmetrical battery by 'hydrophobic-hydrophilic-hydrophobic' structure diaphragm
The zinc electrode was assembled into a CR2016 type (cell diameter 20.0mm, thickness 1.6 mm) symmetrical cell for cycle stability testing. The components of the battery are a positive electrode shell, a pure zinc sheet, a hydrophobic diaphragm, a glass fiber diaphragm, a hydrophobic diaphragm, a zinc sheet, a stainless steel gasket (with the diameter of 16mm and the thickness of 500 mu m) and a negative electrode shell in sequence, and the sealing pressure is about 50 kilograms per cubic centimeter. The battery needs to stand at room temperature for not less than 2 hours before use. The glass fiber membrane was glass fiber (manufactured by Whatman Co., ltd., diameter 110mm, thickness 260 μm, and cut into a disc having a diameter 19 mm). The electrolyte used was 1mol/L (or 1M) zinc sulfate solution, 100. Mu.L was added dropwise to each cell, and the electrolyte was added dropwise after placing the glass fiber membrane. The preparation method of the 1M zinc sulfate electrolyte comprises the steps of preparing ZnSO 4 ∙7H 2 O (analytically pure, purchased from national pharmaceutical chemicals) was dissolved in pure water at a mass ratio of approximately 11.5024: 34.9556.
As shown in fig. 1, a glass fiber membrane, a prepared hydrophobic membrane and a glass fiber membrane are assembled into a membrane with a 'hydrophobic-hydrophilic-hydrophobic' structure, and the two membranes are tested by an ion permeation device by using the glass fiber membrane as a comparison, and as a result, as shown in fig. 6, the membrane with the 'hydrophobic-hydrophilic-hydrophobic' structure can enable ZnSO to be formed 4 The electrolyte permeates, but a large amount of free water cannot pass through, and the hydrophilic glass fiber membrane cannot avoid a large amount of free water, so that the ion concentration of the permeate is reduced.
Step 4, "hydrophobic-hydrophilic-hydrophobic" structural membrane assembled zinc-zinc symmetrical battery test
And (3) carrying out a cycle test on the zinc-zinc symmetrical battery assembled by the 'hydrophobic-hydrophilic-hydrophobic' structure diaphragm obtained in the step (3). The reaction was carried out in an incubator at 25 ℃. Battery testing systems using the marchand blue electricity. As shown in FIG. 7, the test was conducted at a current density of 5mA cm -2 Area capacity 1mAh cm -2 Can effectively circulate for 2183 hours under the condition of (3); at a current density of 10mA cm -2 Area capacity 1mAh cm -2 Can be under the condition of (1)The effective cycle is more than 1800 hours.
Step 5, comparison of test results with Zinc symmetrical cells in comparative examples
Zinc-zinc symmetrical battery assembled by 'hydrophobic-hydrophilic-hydrophobic' structure diaphragm at 5mA cm -2 ,1mA h cm -2 And 10mA cm -2 ,1mA h cm -2 The test results under the test conditions are shown in fig. 8, and the service lives of the batteries respectively reach 2183 hours and 1800 hours or more, and are far from the comparative example of ultra-pure zinc. The membrane fully shows that the membrane with the 'hydrophobic-hydrophilic-hydrophobic' structure can obviously improve the battery performance and greatly prolong the cycle life.
Step 6, observing the surface morphology of the zinc electrode after long-term circulation by using SEM
After the zinc-zinc symmetrical battery assembled by the membrane with the 'hydrophobic-hydrophilic-hydrophobic' structure is subjected to cyclic test, the surface morphology of the zinc electrode is shown in figure 5, and the zinc surface is densely deposited without obvious dendrites. The deposition of zinc was significantly smoother and ordered than with the hydrophilic fiberglass membrane, which illustrates that the incorporation of a hydrophobic membrane can achieve dense deposition of zinc.
Step 7, elucidating the action mechanism of the membrane with the 'hydrophobic-hydrophilic-hydrophobic' structure in the zinc ion battery
FIG. 5 is a schematic view showing the deposition of zinc surface, wherein the hydrophobic membrane has a porous structure, and zinc ion transport channels are added, and inorganic oxide (Ta 2O 5 ) The crystal face is highly matched with the zinc (002) crystal face (figure 4), and zinc ions are induced to be uniformly deposited on the surface; because the hydrophilic glass fiber membrane can store a large amount of electrolyte, the hydrophobic membrane can block a large amount of free water, and further, the direct contact between the electrode and water is avoided, and thus, the hydrogen evolution and corrosion side reaction are reduced.
Example 2
The membrane with the 'hydrophobic-hydrophilic-hydrophobic' structure is formed by utilizing a hydrophobic membrane and is used for a zinc vanadium dioxide full cell.
Step 1, preparation of hydrophobic Membrane
The procedure was the same as in comparative example 1, step 1.
Step 2, zinc electrode preparation
The same as in step 1 of comparative example 2.
Step 3, preparation of vanadium dioxide anode
The same as in step 2 of comparative example 3.
And 4, assembling the zinc vanadium dioxide full cell by using the 'hydrophobic-hydrophilic-hydrophobic' structural diaphragm.
The zinc electrode was assembled into a CR2016 type (cell diameter 20.0mm, thickness 1.6 mm) full cell for cycle stability testing. The components of the battery are a positive electrode shell, a vanadium dioxide positive electrode plate, a hydrophobic diaphragm, a glass fiber diaphragm, a hydrophobic diaphragm, a zinc sheet, a stainless steel gasket (with the diameter of 16mm and the thickness of 500 mu m) and a negative electrode shell in sequence, and the sealing pressure is about 50 kilograms per cubic centimeter. The battery needs to stand at room temperature for not less than 2 hours before use. The glass fiber membrane was glass fiber (manufactured by Whatman Co., ltd., diameter 110mm, and cut into a disc having a diameter 19 mm). The electrolyte used was 1mol/L (or 1M) zinc sulfate solution, 100. Mu.L was added dropwise to each cell, and the electrolyte was added dropwise after placing the glass fiber membrane. The preparation method of the 1M zinc sulfate electrolyte comprises the steps of preparing ZnSO 4 ∙7H 2 O (analytically pure, purchased from national pharmaceutical chemicals) was dissolved in pure water at a mass ratio of approximately 11.5024: 34.9556.
Step 5, "hydrophobic-hydrophilic-hydrophobic" structural membrane assembled zinc vanadium dioxide full cell test
And (3) carrying out a cycle test on the zinc vanadium dioxide battery assembled by the 'hydrophobic-hydrophilic-hydrophobic' structure diaphragm assembled in the step (4). The battery test was performed in a 25 ℃ incubator using a battery test system with marchand blue electricity. Through testing, the lithium ion battery can effectively circulate for 1000 circles under the condition of 2C charge-discharge multiplying power, and the capacity is kept at 90.7mAh g -1 。
Step 6, comparing the performance of the zinc vanadium dioxide full battery assembled by using the glass fiber diaphragm with that of the comparative example
The performance of the assembled full cell using the "hydrophobic-hydrophilic-hydrophobic" structure separator, zinc as the negative electrode, vanadium dioxide as the positive electrode, and only hydrophilic glass fiber separator, zinc as the negative electrode, vanadium dioxide as the positive electrode was compared with the performance of the full cell using only hydrophilic glass fiber separator, and the results are shown in fig. 9, in contrast, the test was performed under the charge-discharge rate condition of 2C, after 1000 cycles, only glass fiber was usedFull cell capacity fade for dimensional separator is 35mAh g -1 While the initial discharge specific capacity of the full cell using the membrane with the 'hydrophobic-hydrophilic-hydrophobic' structure is 200mAh g -1 Then keeps stable, and the specific discharge capacity of the battery after 1000 th circle is still kept at 90.70mAh g -1 . This suggests that a "hydrophobic-hydrophilic-hydrophobic" structured separator can significantly improve the cycle life of a full cell.
Example 3
A zinc vanadium dioxide soft-packed full cell is assembled by a 'hydrophobic-hydrophilic-hydrophobic' structure diaphragm.
Step 1, preparation of hydrophobic Membrane
The procedure was the same as in comparative example 1, step 1.
Step 2, preparation of soft zinc-coated electrode
The same as in step 1 of comparative example 4.
Step 3, preparation of soft-package vanadium dioxide anode
The same as in step 2 of comparative example 4.
Step 4, a 'hydrophobic-hydrophilic-hydrophobic' structural diaphragm is assembled into the zinc vanadium dioxide soft-packed full battery
And assembling the zinc electrode and the vanadium dioxide positive electrode into a 4cm multiplied by 4cm soft-packed full battery for cycle stability test. The battery needs to be left at room temperature for 2 hours before use. Wherein the hydrophilic glass fiber membrane is glass fiber (manufactured by Whatman company and cut into 4.2cm multiplied by 4.2cm for use), and the hydrophobic membrane is prepared by the technology and cut into 4.2cm multiplied by 4.2cm. The electrolyte used was 1mol/L (or 1M) zinc sulfate solution, 1mL was added dropwise to each cell, and the electrolyte was added dropwise before sealing.
Step 5, "hydrophobic-hydrophilic-hydrophobic" structural membrane assembled zinc vanadium dioxide soft package full battery test
And (3) carrying out cycle test on the zinc vanadium dioxide soft-package battery assembled by the 'hydrophobic-hydrophilic-hydrophobic' structure diaphragm assembled in the step (4). The battery test was performed in a 25 ℃ incubator using a battery test system with marchand blue electricity. After being tested, the capacity is still kept at 172.5mAh g after the battery is circulated for 40 circles under the condition of 0.5C charge-discharge multiplying power -1 。
Step 6, comparing the performance of the zinc-vanadium dioxide soft-packaged full battery assembled by using the glass fiber diaphragm with that of the comparative example
The performance of the soft-packed full battery assembled by using the 'hydrophobic-hydrophilic-hydrophobic' structure diaphragm and zinc as the negative electrode and vanadium dioxide as the positive electrode and the hydrophilic glass fiber diaphragm and zinc as the negative electrode and vanadium dioxide as the positive electrode were compared and analyzed, and the result is shown in fig. 10, compared with the result, the full battery is tested under the condition of 0.5C charge-discharge multiplying power, and after 40 circles, the capacity attenuation of the full battery is 25mAh g by using the glass fiber diaphragm -1 While the initial discharge specific capacity of the full cell using the membrane with the 'hydrophobic-hydrophilic-hydrophobic' structure is 250mAh g -1 Then keeps stable, and the specific discharge capacity of the battery after the 40 th turn is still kept at 172.5mAh g -1 . This suggests that the "hydrophobic-hydrophilic-hydrophobic" structured separator can be applied in zinc cells on a large scale.
Example 4
By means of oxides (Al 2 O 3 Or La (La) 2 O 3 ) Preparation of a hydrophobic separator the "hydrophobic-hydrophilic-hydrophobic" structured separator was used in zinc-zinc symmetric cells.
Step 1, preparation of hydrophobic Membrane
The procedure was the same as in comparative example 1, step 1.
Step 2, zinc electrode preparation
The same as in step 1 of comparative example 2.
Step 3, assembling zinc-zinc symmetrical battery by 'hydrophobic-hydrophilic-hydrophobic' structure diaphragm
The zinc electrode was assembled into a CR2016 type (cell diameter 20.0mm, thickness 1.6 mm) symmetrical cell for cycle stability testing. The components of the battery are a positive electrode shell, a pure zinc sheet, a hydrophobic diaphragm, a glass fiber diaphragm, a hydrophobic diaphragm, a zinc sheet, a stainless steel gasket (with the diameter of 16mm and the thickness of 500 mu m) and a negative electrode shell in sequence, and the sealing pressure is about 50 kilograms per cubic centimeter. The battery needs to stand at room temperature for not less than 2 hours before use. The glass fiber membrane was glass fiber (manufactured by Whatman Co., ltd., diameter 110mm, thickness 260 μm, and cut into a disc having a diameter 19 mm). The electrolyte used was 1mol/L (or 1M) zinc sulfate solution, 100. Mu.L was added dropwise to each cell, after being placed in a glass fiber membraneAnd (3) an electrolyte. The preparation method of the 1M zinc sulfate electrolyte comprises the steps of preparing ZnSO 4 ∙7H 2 O (analytically pure, purchased from national pharmaceutical chemicals) was dissolved in pure water at a mass ratio of approximately 11.5024: 34.9556.
As shown in fig. 1, a glass fiber separator, a prepared hydrophobic separator, and a glass fiber separator were assembled into a "hydrophobic-hydrophilic-hydrophobic" structure separator, with the glass fiber separator as a comparison.
Step 4, "hydrophobic-hydrophilic-hydrophobic" structural membrane assembled zinc-zinc symmetrical battery test
And (3) carrying out a cycle test on the zinc-zinc symmetrical battery assembled by the 'hydrophobic-hydrophilic-hydrophobic' structure diaphragm obtained in the step (3). The reaction was carried out in an incubator at 25 ℃. Battery testing systems using the marchand blue electricity.
Step 5, comparison of test results with Zinc symmetrical cells in comparative examples
By means of oxides (Al 2 O 3 ) Preparation of hydrophobic Membrane composition "hydrophobic-hydrophilic-hydrophobic" Structure membrane assembled Zinc-Zinc symmetrical Battery at 5 mAcm -2 ,1mA h cm -2 The test results under the test conditions are shown in fig. 8, and the service life of the battery reaches more than 1500 hours, namely the comparative example of far ultra-pure zinc. By means of oxides (La 2 O 3 ) Preparation of hydrophobic Membrane composition "hydrophobic-hydrophilic-hydrophobic" Structure membrane assembled Zinc-Zinc symmetrical Battery at 5 mAcm -2 ,1mA h cm -2 The test results under the test conditions are shown in fig. 8, and the service life of the battery reaches more than 600 hours, namely the comparative example of far ultra-pure zinc. The membrane fully shows that the membrane with the 'hydrophobic-hydrophilic-hydrophobic' structure can obviously improve the battery performance and greatly prolong the cycle life.
Other embodiments of the disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the disclosure herein. This disclosure is intended to cover any adaptations, uses, or adaptations of the disclosure following the general principles of the disclosure and including such departures from the present disclosure as come within known or customary practice within the art to which the disclosure pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the disclosure being indicated by the following claims.
The present invention is not limited to the preferred embodiments, and the patent protection scope of the invention is defined by the claims, and all equivalent structural changes made by the application of the present invention are included in the scope of the invention.
Claims (9)
1. An inorganic oxide-based hydrophobic zinc ion battery separator, characterized by being obtained by the following process:
1) The inorganic oxide and the binder are mixed according to the mass ratio of (8-10): 1, dissolving the mixture in a proper amount of NMP, and stirring the mixture for 5 to 15 hours to uniformly mix the mixture; the inorganic oxide is Ta 2 O 5 、Al 2 O 3 And La (La) 2 O 3 At least one or a mixture of more than two of the above materials in any proportion, wherein the binder is PVDF;
2) Placing the slurry on a glass plate, uniformly coating the slurry by using a knife coater and drying;
3) The membrane was separated from the glass plate using deionized water to produce a hydrophobic zinc ion battery membrane.
2. The inorganic oxide-based hydrophobic zinc ion battery separator according to claim 1, wherein the drying is performed by placing the glass plate in a drying oven or a vacuum oven, and the drying temperature is 30-50 ℃.
3. The inorganic oxide-based hydrophobic zinc ion battery separator according to claim 1, wherein the thickness of the hydrophobic zinc ion battery separator is 10-20 microns, and the surface of the hydrophobic zinc ion battery separator is provided with a nanoscale porous structure.
4. Use of a hydrophobic zinc-ion battery separator according to claims 1 to 3 in a zinc battery.
5. The use according to claim 4, wherein the zinc sheet is used as a negative electrode, the vanadium dioxide or zinc sheet is used as a positive electrode, the hydrophobic zinc ion battery separator, the glass fiber and the hydrophobic zinc ion battery separator are assembled to form a hydrophobic-hydrophilic-hydrophobic separator structure which is used as a battery separator, and the zinc sulfate solution with the concentration of 0.5-2 mol/L is used as an electrolyte to form the zinc battery.
6. The use according to claim 5, wherein the zinc cell is a zinc vanadium dioxide full cell, a zinc symmetrical cell or a zinc vanadium dioxide soft pack full cell.
7. The use according to claim 6, wherein the zinc-zinc symmetrical cell has the structure: the cathode shell, the zinc sheet, the hydrophobic zinc ion battery diaphragm, the glass fiber, the hydrophobic zinc ion battery diaphragm, the zinc sheet, the gasket and the anode shell; the structure of the zinc vanadium dioxide full cell is as follows: the lithium ion battery comprises a positive electrode shell, a stainless steel mesh, a vanadium dioxide positive electrode, a hydrophobic zinc ion battery diaphragm, glass fibers, a hydrophobic zinc ion battery diaphragm, a zinc sheet, a gasket and a negative electrode shell; the structure of the zinc vanadium dioxide soft-package full battery is as follows: zinc sheet, hydrophobic zinc ion battery diaphragm, glass fiber, hydrophobic zinc ion battery diaphragm, vanadium dioxide positive electrode.
8. The use according to claim 7, wherein the preparation of the vanadium dioxide anode comprises: VO is to be provided with 2 Dry milling the powder and the carbon black powder for 5-15 minutes, then adding a proper amount of isopropanol and 55-65wt% of PTFE aqueous solution, and continuing wet milling until paste is formed; rolling the mixture into thin slices by using a roll squeezer, continuously adding isopropanol to keep PTFE sticky when rolling, slicing the long slices by using a slicer, and drying to obtain the VO in the positive plate 2 The load capacity of the catalyst is 5.4-6.2 mg cm -2 ，VO 2 The mass ratio of powder, carbon black and PTFE was 6:2:2.
9. The use according to claim 7, wherein the stainless steel mesh is a 400 mesh stainless steel mesh and the gasket has a thickness of 500 μm.
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