CN117525260A - High-stability water-system zinc ion battery cathode and preparation method and application thereof - Google Patents
High-stability water-system zinc ion battery cathode and preparation method and application thereof Download PDFInfo
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- CN117525260A CN117525260A CN202311474176.6A CN202311474176A CN117525260A CN 117525260 A CN117525260 A CN 117525260A CN 202311474176 A CN202311474176 A CN 202311474176A CN 117525260 A CN117525260 A CN 117525260A
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 239000011248 coating agent Substances 0.000 claims abstract description 69
- 238000000576 coating method Methods 0.000 claims abstract description 69
- 239000011701 zinc Substances 0.000 claims abstract description 54
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 59
- 239000011230 binding agent Substances 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 26
- 239000002033 PVDF binder Substances 0.000 claims description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 3
- 229910002113 barium titanate Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000007639 printing Methods 0.000 claims description 2
- 238000007761 roller coating Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims description 2
- 238000010345 tape casting Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000007086 side reaction Methods 0.000 abstract description 7
- 210000001787 dendrite Anatomy 0.000 abstract description 6
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 19
- 239000010949 copper Substances 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 7
- 238000007796 conventional method Methods 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 6
- 230000010287 polarization Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application discloses a high-stability water system zinc ion battery cathode and a preparation method and application thereof, and belongs to the field of water system zinc ion batteries. The negative electrode of the water-based zinc ion battery comprises a zinc-based current collector and a coating on the surface of the zinc-based current collector. The water system zinc ion battery cathode provided by the application has the advantages of cheap raw materials and simplicity in operation, inhibits the growth of dendrites on the surface of the zinc cathode, reduces side reactions on the surface of the zinc ion battery cathode, remarkably improves the cycle life, coulomb efficiency and cycle stability of the water system zinc ion battery, and has important significance for promoting commercialization of the water system zinc ion battery.
Description
Technical Field
The application relates to a high-stability water system zinc ion battery cathode, a preparation method and application thereof, and belongs to the field of water system zinc ion batteries.
Background
The water-based zinc ion battery has high theoretical value capacity (820 mAh g) -1 ) Low oxidation-reduction potential (-0.762V vs. SHE), abundant resources, no pollution, intrinsic safety, and environmental friendliness. Zinc anodes, however, present serious problems with zinc dendrites and side reactions such as corrosion and Hydrogen Evolution Reactions (HER). Dendrite growth may beCan damage the separator and short the battery. The side reactions reduce the coulombic efficiency of the cell and may increase the internal pressure of the cell rendering it ineffective. Therefore, control of dendrite growth and side reactions is of great importance for commercialization of aqueous zinc ion batteries.
Various strategies have been proposed to address the above problems, including electrode design engineering, electrolyte additives, interface engineering, and the like, however, the effect is not ideal.
Disclosure of Invention
In order to overcome the deficiencies of the prior art, according to one aspect of the present application, there is provided an aqueous zinc-ion battery anode comprising at least a zinc-based current collector and a coating on the surface of the zinc-based current collector.
The coating comprises at least a high dielectric constant material and a binder;
the cation of the high dielectric constant material is selected from at least one of barium, calcium and strontium, and the anion is selected from one of sulfate radical and titanate radical.
Optionally, the zinc-based current collector is obtained by pressing zinc foil, zinc plate or zinc powder.
Optionally, the mass ratio of the high dielectric constant material to the binder is (6-12): 1, a step of; preferably, the mass ratio of the high dielectric constant material to the binder is (7.5-9.5): 1.
optionally, the mass ratio of the high dielectric constant material and the binder is independently selected from any one or range of values of any two of 6:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, 10:1, 12:1.
Optionally, the binder is PVDF.
Alternatively, the high dielectric constant material coating has a loading of 0.6-1.8mg cm -2 。
Alternatively, the loading of the high dielectric constant material coating is independently selected from 0.6mg cm -2 、0.8mg cm -2 、1mg cm -2 、1.3mg cm -2 、1.5mg cm -2 、1.8mg cm -2 Any one or a range of values between any two of the above.
Alternatively, the thickness of the coating has an average value of 10-18 μm.
Alternatively, the thickness of the coating is independently selected from any one of 10 μm, 12 μm, 15 μm, 16 μm, 18 μm or a range between any two of the foregoing.
In this application, the thickness average of a coating refers to the average of the measured thicknesses of a plurality of locations.
Optionally, the porosity of the coating is 10% -50%; preferably, the porosity of the coating is 20% to 35%.
Alternatively, the average pore diameter of the coating is 100-1000nm.
In still another aspect, the present application provides a method for preparing the negative electrode of the aqueous zinc ion battery, including: and covering the surface of the zinc-based current collector with slurry containing a high dielectric constant material, a solvent and a binder, and drying to prepare the water-based zinc-ion battery cathode.
Optionally, the negative electrode of the water-based zinc ion battery at least comprises a zinc-based current collector and a coating on the surface of the zinc-based current collector, wherein the coating at least comprises a high dielectric constant material and a binder.
Optionally, the adhesive is PVDF and the solvent is N-methylpyrrolidone.
Optionally, the mass ratio of the high dielectric constant material to the binder is (7.5-9.5): 1.
optionally, the mass ratio of the high dielectric constant material and the binder is independently selected from any one of 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1 or a range of values therebetween.
Optionally, the drying temperature is 60-120 ℃; preferably, the temperature of drying is 70-90 ℃; more preferably, the temperature of the vacuum drying is 80 ℃.
Optionally, the coating is coated by at least one of coating, spraying, knife coating, printing and roller coating.
Optionally, the mass ratio of the high dielectric constant material to the binder is (6-12): 1, a step of; preferably, the mass ratio of the high dielectric constant material to the binder is (7.5-9.5): 1.
alternatively, the coating is loaded in an amount of 0.6-1.8mg cm -2 The average thickness of the coating is 10 mu m to the upper part18μm。
Optionally, the porosity of the coating is 10% -50%; preferably, the porosity of the coating is 20% to 35%.
In one embodiment, the method for preparing the negative electrode of the water-based zinc ion battery comprises the following steps: and mixing the high dielectric constant material, the binder and the solvent, magnetically stirring for 8-16 hours to obtain slurry, spreading the slurry on a zinc-based current collector, and vacuum drying at 80 ℃ to remove NMP, thereby obtaining the water-based zinc-ion battery cathode.
Yet another aspect of the present application provides an aqueous zinc-ion battery comprising the aqueous zinc-ion battery anode described above.
Optionally, the aqueous zinc-ion battery positive electrode is selected from Zn containing coating, cu containing coating and KV 3 O 8 At least one of the two layers is a coating @ Zn|coating @ Zn symmetrical battery, a coating @ Cu|coating @ Zn asymmetrical battery and a coating @ Zn|KV respectively 3 O 8 Any one of the full cells.
Optionally, the KV 3 O 8 The electrode is prepared by mixing KV 3 O 8 Mixing acetylene black and PVDF in N-methyl pyrrolidone solvent, coating on graphite paper, vacuum drying at 60-120deg.C for 8-16 hr to obtain KV 3 O 8 An electrode.
Optionally, the KV 3 O 8 KV in electrode 3 O 8 The loading is 1-5mg cm -2 。
Optionally, the KV 3 O 8 The synthesis method of (2) is as follows: will contain V 2 O 5 、CH 3 Mixing COOK water solution, washing, centrifuging to obtain precipitate, and drying to obtain KV 3 O 8 。
Alternatively, the temperature of mixing is 15-35℃and the time of mixing is 4-7 days.
Optionally, the solvent is a mixed solution of deionized water and ethanol in the mass ratio of 20:1-1:1 during washing.
Optionally, the V 2 O 5 、CH 3 The molar mass ratio of COOK is 1: (3-8).
Optionally, the temperature of the precipitate is 60-120 ℃ and the time is 2-48 h.
The beneficial effects that this application can produce include:
1) The water-based zinc ion battery cathode provided by the application is characterized in that the surface of a zinc-based current collector is covered with a coating which has a high-porosity structure and contains a high-dielectric-constant material. The porous structure of the coating improves wettability to induce a relatively uniform electrolyte flux, suppressing Zn 2+ Thereby inhibiting dendrite growth on the zinc anode.
2) The water system zinc ion battery cathode provided by the application is characterized in that a coating is coated on the surface of a zinc-based current collector, and the coating contains BaSO 4 、BaTiO 3 The equi-wide bandgap (6.03 eV) and high dielectric constant (9.42) materials result in "space charge polarization" to promote separation of positive and negative charge centers, electrostatic effects promote Zn 2+ And reduce the occurrence of side reactions.
3) The application provides a water system zinc ion battery cathode and a BaSO 4 @Zn、BaSO 4 @Cu、KV 3 O 8 Positive electrode matching, applied to BaSO 4 @Zn||BaSO 4 @ Zn symmetric battery, baSO 4 @Zn||BaSO 4 @ Cu asymmetric battery and BaSO 4 Any one of the all batteries of @ Zn KVO improves the cycle life and the cycle stability of the water-based zinc ion battery obviously. BaSO (Baso) 4 @Zn||BaSO 4 @ Zn cell at 2mA cm -2 The lower shows a longer lifetime (122 hours up to 1200 hours) and lower polarization (74.0 mV down to 47.2 mV). When it is in contact with KV 3 O 8 ·2H 2 At 5A g when O-cathode is coupled -1 The lower full cell shows an extended lifetime (3000 cycles) and stable coulombic efficiency.
4) The invention provides the negative electrode of the water-based zinc ion battery, which remarkably improves the cycle life, coulomb efficiency and cycle stability of the water-based zinc ion battery, has low cost and simple process, and has important significance for promoting commercialization of the zinc ion battery.
Drawings
FIG. 1 is a BaSO prepared in example 1 of the present application 4 @Zn||BaSO 4 The symmetric battery of @ Zn and bare Zn prepared in comparative example 1 was prepared at 2 mAcm -2 Constant current charge-discharge cycle curve;
FIG. 2 is a BaSO prepared in example 3 of the present application 4 @Zn||BaSO 4 The bare Zn bare Cu asymmetric battery prepared by @ Cu and comparative example 2 was prepared at 2mA cm -2 Constant current charge-discharge cycle curve;
FIG. 3 is a BaSO prepared in example 4 of the present application 4 The bare Zn KVO full cell prepared in comparative example 3 and @ Zn||KVO was 5A g -1 Constant current charge-discharge cycle curve.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
Example 1:
the mass ratio is 7.5:1 and a binder PVDF were added to 250mL of N-methylpyrrolidone (wherein the addition amount of barium sulfate was 0.75 g), magnetically stirred for 12 hours to obtain a slurry, then the slurry was spread on a zinc foil, and vacuum-dried at 80℃to remove NMP, thereby obtaining a zinc-based current collector (denoted as BaSO) with a barium sulfate coating on the surface 4 Cut disc (Φ=16mm) as negative electrode of aqueous zinc ion battery, wherein the loading of barium sulfate coating is 0.6mg cm -2 The thickness of the barium sulfate coating is 10-18 μm in average. Zinc-based current collector BaSO with positive electrode and negative electrode covered with barium sulfate coating 4 @Zn, electrolyte of 2M ZnSO 4 The solution and the diaphragm are glass fiber, and are assembled into a CR2025 button cell, namely BaSO, according to a conventional method 4 @Zn||BaSO 4 @ Zn symmetrical cell.
Example 2:
unlike example 1, barium sulfate was replaced with barium titanate (BaTiO 3 ). Otherwise, the same as in example 1 was used.
Example 3:
the mass ratio is 7.5:1 barium sulfate and Binder PVDF additionAdded into 250mL of N-methylpyrrolidone (wherein the addition amount of barium sulfate is 0.75 g), magnetically stirred for 12 hours to obtain a slurry, then the slurry was coated on a zinc foil, and vacuum-dried at 80 ℃ to remove NMP, thereby obtaining a zinc-based current collector (noted as BaSO) with a barium sulfate coating on the surface 4 @ Zn), cut into discs (Φ=16 mm) as the negative electrode of the aqueous zinc-ion battery, wherein the coating amount of the barium sulfate coating was 0.6mg cm -2 . The positive electrode was a copper foil (designated as BaSO) having a surface covered with a barium sulfate coating obtained by the same method as described above 4 @Cu) electrolyte of 2M ZnSO 4 The solution and the diaphragm are glass fiber, and are assembled into a CR2025 button cell, namely BaSO, according to a conventional method 4 @Zn||BaSO 4 @ Cu asymmetric cell.
Example 4:
the mass ratio is 7.5:1 and a binder PVDF were added to 250mL of N-methylpyrrolidone (wherein the addition amount of barium sulfate was 0.75 g), magnetically stirred for 12 hours to obtain a slurry, and then the slurry was coated on a zinc foil, and vacuum-dried at 80℃to remove NMP, thereby obtaining a zinc-based current collector (denoted as BaSO) with a barium sulfate coating on the surface 4 @ Zn), cut into discs (Φ=16 mm) as the negative electrode of the aqueous zinc-ion battery, wherein the coating amount of the barium sulfate coating was 0.6mg cm -2 。
Will be 1.5g V 2 O 5 And 22.5mL of 2M CH 3 The COOK solution was mixed in a beaker. The solution was then stirred at 25℃for 4 days. Subsequently, the product was centrifuged 2 times with deionized water and 1 time with absolute ethanol. After the centrifugation step, the precipitate was transferred to a forced air dryer at 80℃for drying for 12 hours to obtain the final product KV 3 O 8 。
KV is taken as the raw material 3 O 8 Acetylene black and PVDF in a weight ratio of 7:2:1 (wherein KV 3 O 8 The addition amount of (2) was 0.7 g) and was added to a 3g N-methylpyrrolidone solvent to prepare a cathode coating slurry. Coating the obtained slurry on graphite paper (controlling active material KV) 3 O 8 Is 1.5mg cm -2 ) Dried under vacuum at 80 ℃ for 12 hours, and then cut into discs (Φ=14mm) as positive electrode (denoted KVO)。
The electrolyte is 2M ZnSO 4 The solution and the diaphragm are glass fiber, and are assembled into a CR2025 button cell, namely BaSO, according to a conventional method 4 @ Zn||KVO full cell.
Example 5:
unlike example 4, the mass ratio of barium sulfate to binder PVDF was 6:1.
Example 6:
unlike example 4, the mass ratio of barium sulfate to binder PVDF is 8.5:1.
Example 7:
unlike example 4, the mass ratio of barium sulfate to binder PVDF was 9.0:1.
Example 8:
unlike example 4, the mass ratio of barium sulfate to binder PVDF was 10:1.
Example 9:
unlike example 4, the barium sulfate coating had a loading of 1.8mg cm -2 The thickness of the coating was 18 μm on average.
Example 10:
unlike example 4, the barium sulfate coating had a loading of 1mg cm -2 The thickness of the coating was 15 μm on average.
Example 11:
unlike example 4, barium sulfate (BaSO 4 ) Replacement with barium titanate (BaTiO) 3 ) The other steps are the same as in example 4.
Example 12:
unlike example 4, barium sulfate (BaSO 4 ) Replacement with calcium sulfate (CaSO) 4 ) The other steps are the same as in example 4.
Example 13:
unlike example 4, barium sulfate (BaSO 4 ) Is replaced by strontium sulfate (SrSO) 4 ) The other steps are the same as in example 4.
Example 14:
unlike example 4, barium sulfate (BaSO 4 ) Replacement with calcium titanate (CaTiO) 3 ) The other steps are the same as in example 4.
Example 15:
unlike example 4, barium sulfate (BaSO 4 ) Replacement with strontium titanate (SrTiO) 3 ) The other steps are the same as in example 4.
Comparative example 1:
the anode and the cathode are zinc-based current collectors without barium sulfate coating, and the electrolyte is 2M ZnSO 4 The solution and the diaphragm are glass fibers, and the CR2025 button battery, namely the bare Zn symmetric battery, is assembled according to a conventional method.
Comparative example 2:
unlike example 3, the negative electrode was a zinc-based current collector without a barium sulfate coating, the negative electrode was a copper foil without a barium sulfate coating, and the electrolyte was 2M ZnSO 4 The solution and the diaphragm are glass fibers, and the CR2025 button cell, namely the bare Cu and bare Zn asymmetric cell is assembled according to a conventional method.
Comparative example 3:
the difference to example 4 is that the negative electrode is a zinc-based current collector without a barium sulfate coating, and the electrolyte is 2M ZnSO 4 The solution and the diaphragm are glass fibers, and the CR2025 button cell, namely the bare Zn KVO full cell, is assembled according to a conventional method.
Test example:
the test was performed using a SU8010 field emission scanning electron microscope. The scanning acceleration voltage range is set to be 5-20 kV, and the vacuum degree of the sample chamber is 2.7X10 -5 Pa or below.
Examples 1 to 10, comparative examples 1 to 3 were tested for charge/discharge, polarization and cycle performance of aqueous zinc ion batteries using a New William battery tester CT-4008T-5V10 mA. Zn symmetry battery is at 2mA cm -2 And 1mAh cm -2 、5mA cm -2 And 1mAh cm -2 Constant current charge and discharge cycles are performed. Cu and Zn asymmetric battery is 2mA cm -2 Will Zn at the current density of (2) 2+ Plated on bare Cu or BaSO 4 Cu (fixed Capacity: 1mAh cm) -2 ) Then peeled to 0.6V. At 5A g -1 The full cell was tested for cyclic charge and discharge performance at constant current density with a test voltage of 0.3V to 1.5V.
The microscopic morphology of the barium sulfate coating was tested by scanning electron microscopy and its porosity by software fitting the volumetric method.
The cycling process of the symmetrical cells was analyzed using a constant current cycling method and the symmetrical cells were measured to evaluate reversibility at different current densities. FIG. 1 is a BaSO prepared in example 1 of the present application 4 @Zn||BaSO 4 The symmetric battery of @ Zn and bare Zn prepared in comparative example 1 was prepared at 2 mAcm -2 Constant current charge-discharge cycle curve; FIG. 2 is a BaSO prepared in example 3 of the present application 4 @Zn||BaSO 4 The bare Zn bare Cu asymmetric battery prepared by @ Cu and comparative example 2 was prepared at 2mA cm -2 Constant current charge-discharge cycle curve; FIG. 3 is a BaSO prepared in example 4 of the present application 4 The bare Zn KVO full cell prepared in comparative example 3 and @ Zn||KVO was 5A g -1 Constant current charge-discharge cycle curve.
TABLE 1 test results for examples 1-15, comparative examples 1-3
| Examples of the invention | Cycle time (h) | Electrode specific capacity mAh/g | Cycle times (times) |
| Example 1 | 1200 | —— | —— |
| Example 2 | 800 | —— | —— |
| Example 3 | —— | —— | 600 |
| Example 4 | —— | 144 | 3600 |
| Example 5 | —— | 146 | 3200 |
| Example 6 | —— | 148 | 3500 |
| Example 7 | —— | 147 | 4000 |
| Example 8 | —— | 146 | 3600 |
| Example 9 | —— | 143 | 3800 |
| Example 10 | —— | 145 | 3700 |
| Example 11 | —— | 142 | 3300 |
| Example 12 | —— | 146 | 3400 |
| Example 13 | —— | 143 | 3200 |
| Example 14 | —— | 142 | 3100 |
| Example 15 | —— | 140 | 3000 |
| Comparative example 1 | 122 | —— | —— |
| Comparative example 2 | —— | —— | 120 |
| Comparative example 3 | —— | 132 | 315 |
As shown in Table 1 and FIG. 1, baSO of example 1 4 @ Zn symmetric cell at 2mA cm -2 Lower pair 1mAh cm -2 Whereas the bare zinc symmetric cell of comparative example 1 was shorted after 122 hours with a cycle life exceeding 1200 hours, the polarization voltage was reduced from 74.0mV to 47.2mV, indicating a BaSO 4 The coating aids in forming a highly reversible zinc anode. Furthermore, the BaSO of example 1 4 Symmetric cells @ Zn even at 5mA cm -2 A longer lifetime (900 h) was also obtained, whereas the bare Zn symmetrical battery of comparative example 1 was short-circuited after 62 hours. The polarization voltage was reduced from 139.5mV to 61.7mV. This is mainly due to the inhibition of dendrite growth and the reduction of side reactions by the barium sulfate coating.
The zinc utilization rate is critical to the reversibility of the zinc anode. Thus, the first and second substrates are bonded together, two half batteries (bare zinc and bare copper and BaSO) 4 @Zn||BaSO 4 @ Cu) to evaluate BaSO 4 Effect of the layer on the electrochemical behaviour of the electroplated/stripped Zn. FIG. 2 is a graph showing that the asymmetric cell of example 3, comparative example 2Cu Zn was at 2mA cm -2 And 1mAh cm -2 Coulombic efficiency curve under conditions. At 2mA cm -2 Is measured at current density of half cell, and Zn is added 2+ Plated on bare Cu or BaSO 4 Cu (fixed Capacity: 1mAh cm) -2 ) Then peeled to 0.6V. FIG. 2 shows example 3BaSO 4 @Zn||BaSO 4 The @ Cu cell maintained stable coulombic efficiency for 600 cycles after the initial activation cycle. However, the coulombic efficiency of the comparative example 2 bare zn||bare Cu battery fluctuates after 120 cycles due to side reactions.
FIG. 3 shows that the full battery of example 4 and comparative example 3Zn KVO was 5A g -1 Long cycle performance curve under conditions. From FIG. 3, it can be verified that bare Zn KV is as followsThe cell capacity of the O cell decays faster and does not maintain stable coulombic efficiency after 308 cycles, short-circuits after several cycles, and BaSO 4 The @ Zn KVO provides a relatively stable battery capacity (83.70% capacity retention) and cycle life exceeding 3000 times.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.
Claims (10)
1. A negative electrode of a water-based zinc ion battery, which is characterized by at least comprising a zinc-based current collector and a coating on the surface of the zinc-based current collector;
the coating at least comprises a high dielectric constant material and a binder, wherein the cation of the high dielectric constant material is at least one of barium, calcium and strontium, and the anion is one of sulfate radical and titanate radical.
2. The aqueous zinc-ion battery anode of claim 1, wherein the coating has a loading of 0.6-1.8mg.cm -2 The thickness average value of the coating is 10-18 mu m;
the high dielectric constant material in the coating is at least one selected from barium titanate, barium sulfate, calcium titanate, calcium sulfate, strontium titanate and strontium sulfate;
the binder in the coating is PVDF.
3. The negative electrode of the water-based zinc-ion battery according to claim 2, wherein the mass ratio of the high dielectric constant material to the binder is (6-12): 1, a step of;
preferably, the mass ratio of the high dielectric constant material to the binder is (7.5-9.5): 1, a step of;
preferably, the porosity of the coating is 10% -50%;
preferably, the porosity of the coating is 20% -35%;
preferably, the average pore diameter of the coating is 100-1000nm.
4. A method for preparing the negative electrode of the aqueous zinc-ion battery according to any one of claims 1 to 3, comprising: covering the surface of a zinc-based current collector with slurry comprising a high dielectric constant material, a solvent and a binder, and drying to prepare a water-based zinc ion battery anode;
the negative electrode of the water-based zinc ion battery at least comprises a zinc-based current collector and a coating on the surface of the zinc-based current collector;
the coating comprises at least a high dielectric constant material and a binder;
the cation of the high dielectric constant material is selected from at least one of barium, calcium and strontium, and the anion is selected from one of sulfate radical and titanate radical.
5. The method for preparing a negative electrode of an aqueous zinc-ion battery according to claim 4, wherein the drying temperature is 60-120 ℃ and the drying time is 1-24 hours;
the coating is coated by at least one of coating, spraying, knife coating, printing and roller coating.
6. The method for producing a negative electrode of an aqueous zinc-ion battery according to claim 4, wherein the binder is PVDF;
the solvent is N-methyl pyrrolidone;
the mass ratio of the high dielectric constant material to the binder is (6-12): 1, a step of;
preferably, the mass ratio of the high dielectric constant material to the binder is (7.5-9.5): 1.
7. the method for preparing a negative electrode of an aqueous zinc-ion battery according to claim 4, wherein the coating has a loading of 0.6-1.8mg cm -2 The thickness average value of the coating is 10-18 mu m;
preferably, the porosity of the coating is 10% to 50%;
preferably, the porosity of the coating is 20% to 35%.
8. An aqueous zinc-ion battery comprising the negative electrode of the aqueous zinc-ion battery of any one of claims 1 to 3;
the positive electrode of the water-based zinc ion battery is selected from Zn containing coating, cu containing coating and KV 3 O 8 At least one of them.
9. The aqueous zinc-ion battery according to claim 8, wherein,
KV 3 O 8 the electrode is prepared by mixing KV 3 O 8 Mixing acetylene black and PVDF in N-methyl pyrrolidone solvent, coating on graphite paper, vacuum drying at 60-120deg.C for 8-16 hr to obtain KV 3 O 8 An electrode;
preferably, the KV 3 O 8 KV in electrode 3 O 8 The loading is 1-5mg cm -2 。
10. The aqueous zinc-ion battery according to claim 9, wherein,
the KV 3 O 8 The synthesis method of (2) is as follows: will contain V 2 O 5 、CH 3 Mixing COOK water solution, washing, centrifuging to obtain precipitate, and drying to obtain KV 3 O 8 ；
Preferably, the temperature of mixing is 15-35 ℃, and the mixing time is 4-7 days;
preferably, the solvent is a mixed solution of deionized water and ethanol in the mass ratio of 20:1-1:1 during washing;
preferably, the V 2 O 5 、CH 3 The molar mass ratio of COOK is 1: (3-8);
preferably, the precipitate is dried at a temperature of 60 ℃ to 120 ℃ for a time of 2h to 48h.
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