CN116470162A - Bipolar zinc ion battery and preparation method thereof - Google Patents
Bipolar zinc ion battery and preparation method thereof Download PDFInfo
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- CN116470162A CN116470162A CN202310558959.6A CN202310558959A CN116470162A CN 116470162 A CN116470162 A CN 116470162A CN 202310558959 A CN202310558959 A CN 202310558959A CN 116470162 A CN116470162 A CN 116470162A
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- Prior art keywords
- bipolar
- pole piece
- ion battery
- zinc ion
- electrolyte
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003792 electrolyte Substances 0.000 claims abstract description 66
- 239000000017 hydrogel Substances 0.000 claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 33
- 239000002985 plastic film Substances 0.000 claims abstract description 23
- 229920006255 plastic film Polymers 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000005855 radiation Effects 0.000 claims abstract description 12
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 10
- 239000010959 steel Substances 0.000 claims abstract description 10
- 238000004806 packaging method and process Methods 0.000 claims abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 20
- 239000011267 electrode slurry Substances 0.000 claims description 18
- 238000011068 loading method Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 8
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 8
- 239000011149 active material Substances 0.000 claims description 7
- 239000006258 conductive agent Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- 239000011888 foil Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 6
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 claims description 5
- 239000006256 anode slurry Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 claims description 4
- 239000002174 Styrene-butadiene Substances 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims description 2
- 239000003273 ketjen black Substances 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229960003351 prussian blue Drugs 0.000 claims description 2
- 239000013225 prussian blue Substances 0.000 claims description 2
- 239000002109 single walled nanotube Substances 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims 2
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims 1
- 229920006184 cellulose methylcellulose Polymers 0.000 claims 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims 1
- 229910001935 vanadium oxide Inorganic materials 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 15
- 238000011065 in-situ storage Methods 0.000 abstract description 9
- 239000000243 solution Substances 0.000 description 36
- 210000004027 cell Anatomy 0.000 description 15
- 238000012360 testing method Methods 0.000 description 9
- 239000011701 zinc Substances 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 239000011295 pitch Substances 0.000 description 6
- 238000012216 screening Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000011066 ex-situ storage Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000005405 multipole Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- 229910000368 zinc sulfate Inorganic materials 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
- 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
-
- 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
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/102—Primary casings, jackets or wrappings of a single cell or a single battery characterised by their shape or physical structure
- H01M50/105—Pouches or flexible bags
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a bipolar zinc ion battery and a preparation method thereof, wherein the preparation method comprises the following steps: preparing a positive pole piece, a bipolar pole piece and a negative pole piece, and assembling the positive pole piece, the electrolyte precursor solution, the bipolar pole piece, the electrolyte precursor solution and the negative pole piece into a die in sequence; placing the assembled mould under 10kGy radiation to polymerize the electrolyte for 10 hours; and (3) after the die is disassembled, packaging the battery by using an aluminum plastic film and a steel plastic film to obtain the bipolar zinc ion battery. The hydrogel electrolyte bipolar zinc ion battery is assembled by adopting an in-situ polymerization hydrogel electrolyte mode, can achieve higher mass density in a limited space, increases the working voltage multiple level of the battery, solves the problem of uneven and tight hydrogel contact pole pieces in the prior art, and improves the conductivity of the hydrogel electrolyte.
Description
Technical Field
The invention relates to the field of batteries, in particular to a bipolar zinc ion battery and a preparation method thereof.
Background
The use of traditional fossil energy sources is accompanied by increasingly serious problems such as environmental pollution, and the demand for renewable energy sources is becoming more and more urgent. Most energy sources such as solar energy, tidal energy, and wind energy are limited by many limitations due to the intermittence and instability, and therefore, large-scale chemical energy storage technology is a reliable technology for more efficient storage and transmission of such energy. Lithium ion batteries are dominant in mobile electronic devices and electric vehicles and have been gradually expanded to the energy storage field in recent years. However, the scarcity of lithium resources and the safety issues associated with the use of toxic and flammable organic electrolytes in lithium ion batteries have largely limited the further use of lithium ion batteries.
Rechargeable aqueous zinc ion batteries have received much attention due to their low cost, high safety and environmentally friendly characteristics compared to lithium ion batteries. The zinc metal has the unique advantages of high theoretical capacity, low reduction potential, high abundance and insensitivity to oxygen and humid air, so that the water-based zinc ion battery has good application prospect.
Conventional zinc ion cells are in MnO 2 The anode and the zinc metal are assembled as the cathode and the aqueous electrolyte, however, the assembly mode can not realize multi-pole internal series connection, and can not meet the current market demands of high voltage and high volume density. The prior art solution to this disadvantage is generally to use a hydrogel electrolyte.
However, the zinc ion battery in the prior art has the problem of low voltage (about 1.5V) of the zinc ion battery, which greatly limits the application prospect of the zinc ion battery. Although the series connection of a plurality of batteries can solve the problem of lower voltage of the zinc ion battery, compared with the lithium ion battery, the application of the zinc ion battery in power batteries and energy storage is restricted due to the defect of lower mass density caused by the series connection. Meanwhile, the current hydrogel electrolyte is assembled into a battery in a mode of laminating the anode and the cathode after being synthesized in a die, so that the situation that the lamination of the hydrogel and the anode is not tight exists, the interface impedance is increased, and the zinc ion battery obtained by assembly has high theoretical capacity, but the electrochemical performance practice of the current developed zinc ion battery cannot meet the market demands.
Disclosure of Invention
In order to solve the problems, the invention provides a bipolar zinc ion battery and a preparation method thereof.
The bipolar zinc ion battery comprises an anode plate, a bipolar plate, a cathode plate, a hydrogel electrolyte, an aluminum plastic film or a steel plastic film outer package; the bipolar pole piece consists of a current collector, and positive electrode slurry and negative electrode slurry coated on two sides of the current collector; the bipolar pole piece is a plurality of pieces; the distance between the bipolar pole pieces is 0.2mm; the spacing between the positive pole piece or the negative pole piece and the corresponding bipolar pole piece is 0.2mm; the hydrogel electrolyte is positioned among the positive pole piece, the bipolar pole piece and the negative pole piece; the bipolar battery is coated with an aluminum plastic film or a steel plastic film.
The invention also provides a preparation method of the bipolar zinc ion battery, which comprises the following steps:
1) Mixing an active material, a conductive agent and a binder according to the mass ratio of 7:2:1 to form positive electrode slurry, coating the positive electrode slurry on the positive electrode side of a current collector, and finally enabling the loading amount of the active material to be 1.0mg cm -2 Drying for later use; zinc powder and a binder are mixed into negative electrode slurry according to the mass ratio of 9:1, the negative electrode slurry is coated on the negative electrode side of the current collector, and the final zinc powder loading capacity is 1.2mg cm -2 Drying to obtain a bipolar pole piece;
2) Uniformly coating the anode slurry on one side of the other current collector, and drying to obtain an anode plate;
3) Uniformly coating the negative electrode slurry on one side of the other current collector, and drying to obtain a negative electrode plate;
4) Assembling the positive electrode plate, the electrolyte precursor solution, the bipolar plate, the electrolyte precursor solution and the negative electrode plate into a die in sequence; the electrolyte precursor solution, the bipolar pole pieces and the electrolyte precursor solution are repeated, and the distance between the bipolar pole pieces is 0.2mm; the spacing between the positive pole piece or the negative pole piece and the corresponding bipolar pole piece is 0.2mm;
5) Placing the assembled mould under 10kGy radiation to polymerize the electrolyte for 10 hours;
6) And (3) after the die is disassembled, packaging the battery by using an aluminum plastic film and a steel plastic film to obtain the bipolar zinc ion battery.
Further, the binder is obtained by mixing CMC and SBR according to the mass ratio of 1:1.
Further, the active material comprises one or more of vanadium sodium phosphate compounds, manganese oxide compounds, vanadium oxide compounds and Prussian blue.
Further, the conductive agent comprises one or more of graphite, acetylene black, ketjen black, carbon black conductive agent (super P), carbon nanotubes, single-walled carbon nanotubes.
Further, the binder comprises one or more of polyvinylidene fluoride (PVDF), sodium carboxymethylcellulose (CMC), styrene Butadiene Rubber (SBR), polytetrafluoroethylene (PTFE) and sodium alginate.
Further, the current collector is a titanium foil or a stainless steel foil; the thickness of the current collector is 0.01mm-0.05mm.
Further, the preparation method of the electrolyte precursor solution comprises the steps of dissolving 2-acrylamide-2-methylpropanesulfonic acid in deionized water, adding excessive basic zinc carbonate, filtering after the reaction is completed to obtain an AMPSZn solution, enabling the final concentration of the solution to be 2.0M, adding methylene bisacrylamide with the final concentration of 0.1M, and stirring until the solution is clarified to obtain the electrolyte precursor solution.
The beneficial effects of the invention are as follows:
1. the hydrogel electrolyte bipolar zinc ion battery has the advantages that the operating voltage multiple level of the battery is increased under the condition that the battery structure is not changed, as shown in fig. 12, the left diagram is the bipolar zinc ion battery, the operating voltage reaches 3.520V, and the operating voltage is 1.696V.
2. The invention solves the problem of uneven and compact hydrogel contact pole pieces in the prior art by assembling the hydrogel electrolyte by radiation in-situ polymerization, and improves the conductivity of the hydrogel electrolyte (as in the example 6); and the present invention determined that the radiation dose for in situ polymerization was 10kGy.
3. The invention can limit the flow of electrolyte without additional battery structure, thereby reducing the weight of the zinc ion battery. The bipolar zinc ion battery of the invention forms a positive electrode/electrolyte/negative electrode/positive electrode/electrolyte … negative electrode in the battery
(wherein … represents the repeated structure of 'negative electrode/positive electrode/electrolyte') so as to achieve the purpose of internal series connection, not only can meet the requirement of single battery high voltage in practical application, but also can achieve higher energy density under the same voltage requirement. As shown in fig. 11, the zinc ion battery assembled in the prior art is on the left side, and the bipolar zinc ion battery of the invention is on the right side, and only half of the mass is needed to achieve the same voltage as the prior zinc ion battery.
4. The hydrogel electrolyte used in the zinc ion battery is formed by in-situ polymerization, and can effectively inhibit zinc dendrite growth, reduce interface impedance, improve conductivity and lighten the weight of the zinc ion battery under the condition of keeping various advantages of the hydrogel electrolyte, thereby having market prospect.
Drawings
FIG. 1 is a schematic illustration of an in situ polymerization assembly of bipolar zinc ion cells;
FIG. 2 is a schematic diagram of a bipolar zinc ion cell stack;
FIG. 3 is a schematic illustration of a bipolar zinc ion battery wrapped with an aluminum plastic film and a steel plastic film;
FIG. 4 is a schematic structural view of one of the cores of a bipolar zinc ion battery;
FIG. 5 is a cycle comparison graph of bipolar zinc ion battery with different negative electrode loadings;
FIG. 6 is a tensile strength test of different gel components;
FIG. 7 shows ionic conductivity measurements of gel electrolytes of different thicknesses;
FIG. 8 is a screening test of irradiation intensity (unit: kGy);
FIG. 9 is a schematic diagram of a prior art assembled bipolar battery with free flow battery shorting problem;
FIG. 10 is a schematic diagram showing the complete separation required to assemble zinc ion batteries of the same voltage in the prior art;
FIG. 11 is a comparison of the quality of a prior art battery and the battery of the present patent technology at the same volume and voltage;
fig. 12 is an open circuit voltage of a bipolar zinc ion pouch cell (right panel) and an open circuit voltage of a prior art zinc ion pouch cell (left panel);
FIG. 13 is a comparison of the conductivity of an ex situ polymerized hydrogel of the present invention;
FIG. 14 is a cycle-capacity and coulombic efficiency plot of a bipolar zinc ion battery;
FIG. 15 is a capacity-voltage curve of a bipolar zinc ion battery;
fig. 16 is a comparison of voltage-capacity curves for bipolar zinc ion cells versus prior art zinc ion cells when cycled.
Reference numerals in the drawings:
1. a mold; 2. an electrolyte precursor solution; 3. a hydrogel electrolyte; 4. an aluminum plastic film or a steel plastic film; 5. a bipolar pole piece; 6. a positive electrode sheet; 7. conducting slurry; 8. a negative electrode slurry; 9. a negative electrode plate; 10. an aqueous electrolyte; 11. bipolar zinc ion batteries; 12. zinc ion batteries of the prior art.
Detailed Description
The invention is further illustrated by the following examples.
Example 1 preparation of bipolar zinc-ion batteries
Referring to fig. 1-4, a bipolar zinc ion battery is prepared as follows:
1) Mixing and stirring sodium vanadium phosphate, super P (carbon black conductive agent) and PVDF (polyvinylidene fluoride) uniformly according to the proportion of 7:2:1 to prepare anode slurry; uniformly coating the anode slurry on one side of a stainless steel foil with the thickness of 0.05mm, and drying to ensure that the loading amount of the sodium vanadium phosphate is 1.0mg & lt/cm -2 Drying for later use; zinc powder, CMC (sodium carboxymethylcellulose),
SBR (styrene butadiene rubber) is mixed and stirred uniformly according to the proportion of 18:1:1 to prepare negative electrode slurry; uniformly coating the negative electrode slurry on the other side of the stainless steel foil, and drying to make the zinc powder loading quantity be about 1.2mg cm -2 Preparing a bipolar pole piece; the negative electrode can be in the charge and discharge processThe active material load of the anode is increased to make the mass of the anode be more than that of the cathode, so that the losses can be compensated, and the anode load is higher than the cathode load;
2) Uniformly coating the anode slurry on one side of another stainless steel foil with the thickness of 0.05mm, and drying to ensure that the loading amount of the sodium vanadium phosphate is 1.0mg cm -2 Preparing a positive electrode plate;
3) Uniformly coating the negative electrode slurry on one side of another stainless steel foil with the thickness of 0.05mm, and drying to ensure that the zinc powder loading capacity is about 1.2mg & cm -2 Preparing a negative electrode plate;
4) Assembling the positive electrode plate, the electrolyte precursor solution, the bipolar plate, the electrolyte precursor solution and the positive electrode plate into a die in sequence; the electrolyte precursor solution, the bipolar pole pieces and the electrolyte precursor solution are repeated, and the distance between the bipolar pole pieces is 0.2mm; the spacing between the positive pole piece or the negative pole piece and the corresponding bipolar pole piece is 0.2mm; the preparation method of the electrolyte precursor solution comprises the steps of dissolving 2-acrylamide-2-methylpropanesulfonic acid in deionized water, adding excessive basic zinc carbonate, and filtering after the reaction is completed to obtain an AMPSZn solution, wherein the final concentration of the solution is 2.0
And M, adding methylene bisacrylamide with the final concentration of 0.1M, and stirring until the solution is clear to obtain the electrolyte precursor solution.
5) Placing the assembled mould under 10kGy radiation to perform in-situ polymerization of the electrolyte, wherein the polymerization time is 10 hours;
6) And (3) after the die is disassembled, packaging the battery by using an aluminum plastic film and a steel plastic film to obtain the bipolar zinc ion battery.
Example 2 screening experiment for negative Zinc powder Loading
1) The zinc powder loading amounts of the negative electrode plate and the negative electrode side of the bipolar plate are fixed to be 0.8, 1.0 and 1.2mg & cm respectively in 3 experimental groups -2 Other steps are the same as in example 1;
2) Performing a cyclic test on the bipolar zinc ion batteries assembled by the 3 experimental groups;
3) As shown in FIG. 5, 1.2 mg.cm -2 The coulomb efficiency of the experimental group with zinc powder loading is almost 100% after 500 circles of circulation, and the capacity retention rate is 92.3%; and 0.8 mg/cm -2 And 1.0 mg/cm -2 The coulomb efficiency is obviously reduced after the zinc powder loading capacity is circulated for 500 circles, and the capacity retention rate is only 72.8% and 47.6%, which indicates that the zinc powder loading capacity of the bipolar zinc ion battery prepared by adopting the technical scheme of the invention is 1.2mg cm for the negative electrode and the bipolar pole piece of the bipolar zinc ion battery -2 And has relatively good coulombic efficiency and capacity retention.
Example 3 screening experiments of electrolyte precursor solutions
1) Dissolving AMPS (2-acrylamide-2-methylpropanesulfonic acid) in deionized water, adding excessive basic zinc carbonate, filtering after the reaction is completed to obtain an AMPSZn solution, and dividing the solution into two experimental groups so that the final concentration of the solution is 1.0M and 2.0M;
2) Respectively adding Methylene Bisacrylamide (MBAA) with the final concentration of 0.1M into the solutions with the two concentrations, and stirring until the solutions are clarified to obtain a hydrogel electrolyte precursor solution; the control group was 2.0M AMPSZn solution without MBAA;
3) The hydrogel electrolyte precursor liquid is respectively poured into a tensile test shaping mould, is put into 10kGy radiation, is taken out after being solidified into hydrogel, is put into a tensile machine for testing, and the result is shown in figure 6, under the same stretching condition, the length of the hydrogel electrolyte solidified into 2.0M AMPSZn+0.1MMBAA, which is stretched, is found to be longest, and the final stretching force is the largest, which indicates that the synthesized hydrogel has the best tensile strength under the proportion.
Example 4 Pole piece spacing screening experiment
1) Assembling the positive electrode plate, the electrolyte precursor solution, the bipolar plate, the electrolyte precursor solution and the negative electrode plate into a die in sequence; the method comprises the steps of dividing the pole pieces into 3 experimental groups, controlling the spacing between the pole pieces to be 0.1, 0.2 and 0.5mm, and performing screening test, wherein other steps are the same as those of the embodiment 1;
2) The electrolyte precursor solution was the precursor solution of 2.0M AMPSZn+0.1M MBAA prepared in example 3; electrolyte precursor solution is filled between the pores of the pole piece to ensure complete filling;
3) The die is put into 10kGy radiation for irradiation for 10 hours, and after the precursor liquid is completely solidified into gel, the gel is taken out, and an aluminum plastic film is packaged to obtain the battery;
4) The conductivity test was performed using Solartron (strong force transmission) to cells of different plate pitches, as shown in fig. 7, and it was found that cells of 0.2mm pitch exhibited the lowest resistance in the high frequency region, whereas cells of 0.1mm pitch exhibited the highest resistance in the high frequency region, and cells of 0.5mm pitch exhibited the highest resistance in the high frequency region, so that cells of 0.2mm pitch had the highest conductivity, and the plate pitch was selected for cell assembly.
EXAMPLE 5 radiation intensity screening experiment
1) An electrolyte precursor was prepared in the same manner as in example 3, and the electrolyte precursor prepared with 2.0M AMPSZn+0.1M MBAA was placed in a PP bottle;
2) The PP bottle filled with the electrolyte precursor liquid is respectively placed under the radiation of 10, 30 and 50kGy doses for 10 hours for polymerization, and the control group is 0kGy, so that the hydrogel shown in figure 8 is obtained;
3) The comparison shows that the gels of the rest experimental groups are polymerized except that the control group of 0kGy is not polymerized; however, at radiation doses of 30 and 50kGy, the hydrogel prepared from the electrolyte precursor solution provided by the invention is decomposed, a large number of bubbles are generated, and the bubbles can cause conditions of battery swelling, poor contact performance with a pole piece and the like, so that the electrolyte precursor solution provided by the invention can only adopt 10kGy radiation doses for hydrogel polymerization.
Example 6 comparative experiments of a bipolar zinc-ion battery of the invention and an existing zinc-ion battery
1. In the existing zinc ion battery, aqueous solution or organic solvent is mostly adopted as electrolyte, the flowable solution is adopted as electrolyte, and when the battery is assembled into a bipolar battery by using commercial glass fiber or other battery diaphragms according to the battery assembly mode of the patent, the electrolyte flows between the bipolar electrodes, so that internal short circuit occurs in an intermediate bipolar layer (as can be seen from fig. 9, the internal short circuit is caused by the flowing of the aqueous solution electrolyte between the bipolar electrodes), and the battery fails;
2. the conventional zinc ion battery realizes high voltage by serially assembling a plurality of soft package batteries, as shown in fig. 10, the structure needs a large amount of aluminum plastic film packages or molds, and the light-weight space of the battery is limited. The zinc ion battery assembly technology in the prior art comprises a positive pole piece, glass fiber and a negative pole piece, zinc sulfate electrolyte is injected between the pole pieces, and an aluminum plastic film is used as an outer package of the battery. If the same voltage as the bipolar zinc ion battery of the invention is needed, the zinc ion battery assembled in the prior art needs two complete batteries, and the bipolar battery of the patent only needs one complete battery. The bipolar zinc ion battery assembled by the method is obviously smaller than the zinc ion battery in the prior art (shown in the left chart of FIG. 11) under the same voltage (shown in the right chart of FIG. 11), so that the bipolar zinc ion battery assembled by the method can reach higher mass density in a limited space;
3. the existing zinc ion battery also has hydrogel electrolyte, but the existing zinc ion battery uses the hydrogel electrolyte to solidify in most of the way of ex-situ polymerization (the hydrogel electrolyte is polymerized in other molds and then assembled with the pole piece into the battery), and the way of ex-situ polymerization has the problems that the contact of the pole piece is not tight as in the background technology, the internal resistance of the battery is increased, and the like; the invention can effectively solve the problems by using an in-situ polymerization hydrogel electrolyte assembly mode:
as shown in fig. 12, the open circuit voltage of the zinc ion battery of the present invention was tested with the current assembly mode zinc ion battery using a multimeter, and the open circuit voltage of the battery of the present invention was 2 times that of the current assembly mode zinc ion battery;
the electrical conductivity test is carried out on the zinc ion battery in the prior assembly mode and the battery assembled by the invention by using Solartron respectively, as shown in figure 13, the high-frequency area resistance value of the battery assembled by adopting in-situ polymerization is far smaller than that of the prior zinc ion battery assembled by adopting an ex-situ polymerization method, and the battery with internal resistance smaller than that of the battery assembled by adopting the ex-situ polymerization hydrogel is obtained through fitting calculation, wherein the ionic conductivity is as high as 7.60 x 10 < -2 > S cm -1 The ionic conductivity of the cell assembled from the hydrogel, rather than polymerized in situ, was only 3.67 x 10-2S cm -1 The method comprises the steps of carrying out a first treatment on the surface of the High ionic electricityThe conductivity is favorable for rapid diffusion of ions and reduction of concentration polarization on the surface of the electrode;
4. the zinc ion battery assembled in example 1 was used for battery performance testing, and a new wire cell tester (CT-4008Q-5V 100 mA-124) was used for cycle testing, which was capable of normal charge and discharge cycles. As shown in FIG. 14, the coulomb efficiency was kept stable in 100 cycles, and the initial capacity was about 63mAh g -1 The capacity retention rate is as high as 91.3%; the cycling charge-discharge capacity-voltage curve is shown in fig. 15, in which the charge voltage is about 4.0V and the discharge plateau of the battery can be constantly maintained at 3.44V. As shown in the prior art zinc ion battery 12 in fig. 16, the charging voltage of the assembled zinc ion battery in the prior art is only 2.0V, and the discharging platform of the battery is only 1.1V; the bipolar zinc ion battery of the invention indicated by 11 in fig. 16 has significantly better performance than the zinc ion battery assembled in the prior art, and the bipolar zinc ion battery of the invention can be seen to have significantly lighter mass than the zinc ion battery of the prior art under the same voltage in combination with the above embodiments, so that the bipolar zinc ion battery has better market popularization and application prospects.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (8)
1. The bipolar zinc ion battery is characterized by comprising a positive pole piece, a bipolar pole piece, a negative pole piece, hydrogel electrolyte, an aluminum plastic film or a steel plastic film outer package; the bipolar pole piece consists of a current collector, and positive electrode slurry and negative electrode slurry coated on two sides of the current collector; the bipolar pole piece is a plurality of pieces; the distance between the bipolar pole pieces is 0.2mm; the spacing between the positive pole piece or the negative pole piece and the corresponding bipolar pole piece is 0.2mm; the hydrogel electrolyte is positioned among the positive pole piece, the bipolar pole piece and the negative pole piece; the bipolar battery is coated with an aluminum plastic film or a steel plastic film.
2. The preparation method of the bipolar zinc ion battery is characterized by comprising the following steps of:
1) Mixing an active material, a conductive agent and a binder according to the mass ratio of 7:2:1 to form positive electrode slurry, coating the positive electrode slurry on the positive electrode side of a current collector, and finally enabling the loading amount of the active material to be 1.0mg cm -2 Drying for later use; zinc powder and a binder are mixed into negative electrode slurry according to the mass ratio of 9:1, the negative electrode slurry is coated on the negative electrode side of the current collector, and the final zinc powder loading capacity is 1.2mg cm -2 Drying to obtain a bipolar pole piece;
2) Uniformly coating the anode slurry on one side of the other current collector, and drying to obtain an anode plate;
3) Uniformly coating the negative electrode slurry on one side of the other current collector, and drying to obtain a negative electrode plate;
4) Assembling the negative electrode plate, the electrolyte precursor solution, the bipolar electrode plate, the electrolyte precursor solution and the positive electrode plate into a die in sequence; the bipolar pole pieces are repeated, and the distance between the bipolar pole pieces is 0.2mm; the spacing between the positive pole piece or the negative pole piece and the corresponding bipolar pole piece is 0.2mm;
5) Placing the assembled mould under 10kGy radiation to polymerize the electrolyte for 10 hours;
6) And (3) after the die is disassembled, packaging the battery by using an aluminum plastic film and a steel plastic film to obtain the bipolar zinc ion battery.
3. The bipolar zinc ion battery according to claim 2, wherein the binder is obtained by mixing CMC and SBR according to a mass ratio of 1:1.
4. The bipolar zinc-ion battery of claim 2 wherein the active material comprises one or more of vanadium sodium phosphate, manganese oxide, vanadium oxide, prussian blue.
5. The bipolar zinc-ion battery of claim 2, wherein the conductive agent comprises one or more of graphite, acetylene black, ketjen black, carbon black conductive agent, carbon nanotubes, single-walled carbon nanotubes.
6. The bipolar zinc-ion battery of claim 2 wherein the binder comprises one or more of polyvinylidene fluoride, sodium carboxymethyl cellulose, styrene-butadiene rubber, polytetrafluoroethylene, sodium alginate.
7. The bipolar zinc-ion battery of claim 2 wherein the current collector is a titanium foil or a stainless steel foil; the thickness of the current collector is 0.01mm-0.05mm.
8. The bipolar zinc ion battery according to claim 2, wherein the electrolyte precursor solution is prepared by dissolving 2-acrylamido-2-methylpropanesulfonic acid in deionized water, adding excessive basic zinc carbonate, filtering after the reaction is completed to obtain an AMPSZn solution, enabling the final concentration of the solution to be 2.0M, adding 0.1M methylene bisacrylamide, and stirring until the solution is clarified to obtain the electrolyte precursor solution.
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