CN117219887A - Aqueous zinc ion battery electrolyte containing polyacrylate additive and aqueous zinc ion battery - Google Patents
Aqueous zinc ion battery electrolyte containing polyacrylate additive and aqueous zinc ion battery Download PDFInfo
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- CN117219887A CN117219887A CN202311421563.3A CN202311421563A CN117219887A CN 117219887 A CN117219887 A CN 117219887A CN 202311421563 A CN202311421563 A CN 202311421563A CN 117219887 A CN117219887 A CN 117219887A
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- zinc
- ion battery
- polyacrylate
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 84
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 29
- 239000000654 additive Substances 0.000 title claims abstract description 28
- 230000000996 additive effect Effects 0.000 title claims abstract description 22
- 239000011701 zinc Substances 0.000 claims abstract description 110
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229920005614 potassium polyacrylate Polymers 0.000 claims abstract description 19
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 8
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims abstract description 8
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 150000003751 zinc Chemical class 0.000 claims description 10
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 6
- 229960001763 zinc sulfate Drugs 0.000 claims description 6
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims description 3
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [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
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 239000007774 positive electrode material Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002000 Electrolyte additive Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 238000009472 formulation Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 27
- 238000012360 testing method Methods 0.000 description 18
- 238000005260 corrosion Methods 0.000 description 12
- 230000007797 corrosion Effects 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 150000001450 anions Chemical class 0.000 description 10
- 150000001768 cations Chemical class 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 10
- 238000000151 deposition Methods 0.000 description 10
- 230000008021 deposition Effects 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 description 7
- 238000007086 side reaction Methods 0.000 description 7
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 7
- 210000001787 dendrite Anatomy 0.000 description 6
- 238000002161 passivation Methods 0.000 description 6
- 239000010949 copper Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000006259 organic additive Substances 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 229920002125 Sokalan® Polymers 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000005595 deprotonation Effects 0.000 description 2
- 238000010537 deprotonation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012430 stability testing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- -1 PAALi) Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a water-based zinc ion battery electrolyte containing polyacrylate additives and a water-based zinc ion battery, and belongs to the technical field of weak acid chargeable water-based zinc ion battery electrolytes. The electrolyte additive is one or more of lithium polyacrylate, sodium polyacrylate and potassium polyacrylate, and the dosage of the additive is 0.01-0.5g/L. The organic compound has a zinc-philic characteristic, is used as an electrolyte additive to be applied to a rechargeable zinc ion battery, and is favorable for being adsorbed on the surface of metal zinc to regulate and control interface reaction between electrolyte and a zinc cathode. The electrolyte additive has the advantages of low cost, small dosage, obvious effect, environmental protection, and the like, has simple formula and preparation process, strong operability, and has good application prospect in the field of water-based zinc ion batteries.
Description
Technical Field
The invention relates to the technical field of weak acid chargeable aqueous zinc ion battery electrolyte, in particular to aqueous zinc ion battery electrolyte containing polyacrylate additives and an aqueous zinc ion battery.
Background
The water system zinc ion battery has the advantages of high safety, low cost, high theoretical specific capacity, rich reserves, environmental friendliness and the like, and is a novel green large-scale energy storage system with great development prospect. However, zinc dendrite growth, side reactions (such as hydrogen evolution, corrosion and passivation) and other zinc cathode problems can not only lead to the reduction of the cycle life and performance attenuation of the battery, but also bring potential safety hazards, thus greatly impeding the large-scale practical application of the rechargeable zinc ion battery.
The exploration and development of a high-efficiency stable zinc negative electrode regulation strategy is imperative, and the current optimization strategy mainly comprises surface modification of a zinc negative electrode, composite nanostructure design of the zinc negative electrode, electrolyte modification, quasi-solid electrolyte and the like. The electrolyte is in direct contact with the metallic zinc cathode, is an important medium for zinc ion migration and substance transmission, and the electrolyte additive can regulate and control the electrochemical reaction process of a zinc cathode/electrolyte interface in situ, so that a simple, convenient and effective method is provided for optimizing the performance of the water-based zinc ion battery. The electrolyte organic additive with interface adsorption property not only can regulate zinc ion flow to be uniformly distributed at the anode/electrolyte interface and inhibit uncontrollable growth of zinc dendrite, but also can form an interface molecule adsorption layer in situ to block corrosion of electrolyte solution to metal zinc and inhibit deprotonation process of solvated water molecules, thereby reducing occurrence of irreversible interface side reaction. The polyacrylate compound dissociates into a polyacrylic acid anion and a metal cation in an aqueous solution. Wherein, anions can form a molecular interface adsorption layer on the surface of the zinc negative electrode, and cations can be adsorbed on the tip end part of the zinc negative electrode to inhibit dendrite growth. Therefore, the additive can effectively enhance the reversibility of the zinc cathode through the anion and cation double-ion adsorption effect, and improve the cycle life and coulombic efficiency of the water-based zinc ion battery.
Disclosure of Invention
The invention aims to provide a water-based zinc ion battery electrolyte containing polyacrylate additives and a water-based zinc ion battery, and solves the problems of zinc dendrite growth, hydrogen evolution, corrosion, passivation and the like commonly existing in a weak acid water-filled zinc battery through an anion-cation double-ion adsorption effect.
The technical scheme of the invention is as follows:
the aqueous zinc ion battery electrolyte containing polyacrylate additive comprises polyacrylate additive, water-soluble zinc salt and deionized water; the polyacrylate additive is an organic compound lithium polyacrylate (Lithium polyacrylate, PAALi), sodium polyacrylate (Sodium Polyacrylate, PAANa) and potassium polyacrylate (Potassium polyacrylate, PAAK), and has the following general formula:
wherein R in formula (1) + The represented ion is Li + 、Na + And K + . Such organic molecules dissociate in aqueous solutions into polyacrylic acid anions and metal cations. Wherein, the anions can form a molecular adsorption layer on the surface of the zinc cathode to inhibit side reactions such as hydrogen evolution, corrosion, passivation and the like; cations can be adsorbed at the tip end of the zinc cathode, and the uniform distribution of the electric field and the zinc ion concentration field is regulated. Therefore, the additive can effectively enhance the reversibility of the zinc cathode through the anion and cation double-ion adsorption effect, and improve the cycle life and coulombic efficiency of the water-based zinc ion battery.
Further, the concentration of the polyacrylate additive is 0.01-0.5g/L.
Further, the water-soluble zinc salt is one or more of zinc sulfate, zinc chloride, zinc acetate, zinc nitrate and zinc trifluoromethane sulfonate.
Further, the concentration of the water-soluble zinc salt is 1-3mol/L.
The invention also provides a water-based zinc ion battery, which is assembled by matching the electrolyte with the anode, the cathode and the diaphragm.
Further, the positive electrode active material of the water-based zinc ion battery is manganese, cobalt, vanadium-based compound and Prussian blue analogue or organic compound.
Further, the negative electrode material of the water-based zinc ion battery is one or more of zinc foil, zinc paste, zinc powder, electrodeposited metallic zinc, three-dimensional foam zinc or zinc alloy.
Further, the separator of the water-based zinc ion battery is a glass fiber, cellulose filter paper or a water-based polyolefin separator.
The invention has the advantages and beneficial effects that:
1. according to the invention, one or more of organic compounds such as lithium polyacrylate, sodium polyacrylate, potassium polyacrylate and the like are added into the water-based electrolyte, and the organic compounds are dissociated into polyacrylic acid anions and metal cations in the water solution, wherein the polyacrylic acid anions can form a molecular adsorption layer on the surface of a zinc negative electrode in situ, so that corrosion of water molecules in the electrolyte to metal zinc is blocked, the deprotonation process of solvated water molecules is inhibited, and interface side reactions such as hydrogen evolution, corrosion and passivation are inhibited. Meanwhile, dissociated cations can be adsorbed at the tip end part of the surface of the zinc cathode, and the uniform distribution of the electric field and the zinc ion concentration field is regulated and controlled, so that zinc uniform deposition is promoted.
2. According to the invention, one or more of organic compounds such as lithium polyacrylate, sodium polyacrylate, potassium polyacrylate and the like are added into the aqueous electrolyte, so that the optimized and modified electrolyte has the multifunctional characteristics of regulating and controlling uniform deposition of zinc, inhibiting irreversible side reactions such as hydrogen evolution, corrosion, passivation and the like, and can obviously enhance the reversibility of a zinc cathode through the anion and cation double-ion adsorption effect, thereby prolonging the cycle life and increasing the coulomb efficiency of the aqueous zinc ion battery.
3. The polyacrylate organic additive provided by the invention has the advantages of low cost, small dosage, obvious effect, environmental protection, and the like, and the obtained series of electrolyte has good compatibility with the positive electrode and the negative electrode of the water-based zinc battery, has stable physicochemical properties in the use process, and is favorable for developing the water-based zinc ion battery with excellent performance, green and safety.
Drawings
FIG. 1 is a linear sweep voltammogram of the electrolytes formulated in comparative example 1 and examples 1-4;
FIG. 2 is a surface XRD spectrum of a metallic zinc electrode after 24 hours of immersion in the electrolyte prepared in comparative example 1 and examples 1 to 4;
FIG. 3 is a SEM image of the surface of a metallic zinc electrode before and after soaking in the electrolyte prepared in comparative example 1 and example 2, where a is the non-soaked zinc electrode and b is ZnSO at 1mol/L 4 Zinc electrode soaked in electrolyte, c is ZnSO 1mol/L 4 +0.05g/L zinc electrode after soaking in PAAK electrolyte;
FIG. 4 is a Tafel plot of a metallic zinc electrode in the electrolyte formulated in comparative example 1 and example 2;
FIG. 5 is a SEM image of the surface morphology of a metallic zinc anode in constant current electrodeposition in the electrolyte prepared in comparative example 1 and example 2;
FIG. 6 is a time-voltage plot of a Zn/Zn symmetric cell assembled using the electrolytes formulated in comparative example 1 and examples 2 and 8;
FIG. 7 is a graph of time-voltage for a Zn/Zn symmetric cell assembled using the electrolytes formulated in examples 1-4;
FIG. 8 is the coulombic efficiency of a Zn/Cu asymmetric cell assembled using the electrolytes formulated in comparative example 1 and example 2;
FIG. 9 is a Zn/VO assembled using the electrolytes prepared in comparative example 1 and example 2 2 Long cycle performance of the battery.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the examples of the present invention, but the embodiments of the present invention are not limited thereto. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Aqueous zinc ion battery electrolyte containing polyacrylate additive, wherein the electrolyte comprises potassium Polyacrylate (PAAK) organic additive and zinc sulfate (ZnSO) 4 ) And deionized water. The specific preparation method comprises the following steps: in an air environment (25 ℃), deionized water is used as a solvent, and zinc sulfate electrolyte (1 mol/LZnSO) is prepared according to the volume mole concentration of 1mol/L 4 ) Then adding potassium polyacrylate powder according to the mass concentration of 0.02g/L, and performing ultrasonic dissolution for 10min to uniformly disperse the potassium polyacrylate powder to obtain electrolyte (1 mol/L ZnSO) prepared in example 1 4 +0.02g/L PAAK)。
Examples 2 to 18 and comparative examples 1 to 2
In examples 2 to 18 and comparative examples 1 to 2, the experimental procedure was the same as in example 1 except that the concentrations of the respective constituent components of the electrolytic solutions were formulated as shown in tables 1 and 2. Wherein, lithium polyacrylate: PAALi; sodium polyacrylate: PAANa; potassium polyacrylate: PAAK; zinc trifluoromethane sulfonate: zn (CF) 3 SO 3 ) 2 。
Table 1, examples 1-18 show the concentrations of the respective components of the electrolytes
| Example of the other | Zinc salt species | Concentration of zinc salt | Additive species | Additive concentration |
| Example 1 | ZnSO 4 | 1mol/L | PAAK | 0.02g/L |
| Example 2 | ZnSO 4 | 1mol/L | PAAK | 0.05g/L |
| Example 3 | ZnSO 4 | 1mol/L | PAAK | 0.07g/L |
| Example 4 | ZnSO 4 | 1mol/L | PAAK | 0.1g/L |
| Example 5 | ZnSO 4 | 1mol/L | PAAK | 0.2g/L |
| Example 6 | ZnSO 4 | 1mol/L | PAALi | 0.05g/L |
| Example 7 | ZnSO 4 | 1mol/L | PAALi | 0.1g/L |
| Example 8 | ZnSO 4 | 1mol/L | PAANa | 0.05g/L |
| Example 9 | ZnSO 4 | 1mol/L | PAANa | 0.1g/L |
| Example 10 | ZnSO 4 | 2mol/L | PAAK | 0.02g/L |
| Example 11 | ZnSO 4 | 2mol/L | PAAK | 0.05g/L |
| Example 12 | ZnSO 4 | 2mol/L | PAAK | 0.1g/L |
| Example 13 | Zn(CF 3 SO 3 ) 2 | 1mol/L | PAAK | 0.2g/L |
| Example 14 | Zn(CF 3 SO 3 ) 2 | 1mol/L | PAAK | 0.5g/L |
| Example 15 | Zn(CF 3 SO 3 ) 2 | 2mol/L | PAAK | 0.2g/L |
| Example 16 | Zn(CF 3 SO 3 ) 2 | 2mol/L | PAAK | 0.5g/L |
| Example 17 | Zn(CF 3 SO 3 ) 2 | 3mol/L | PAAK | 0.2g/L |
| Example 18 | Zn(CF 3 SO 3 ) 2 | 3mol/L | PAAK | 0.5g/L |
Table 2 comparative examples 1 to 2 each component composition ratio of the electrolyte
| Example of the other | Zinc salt species | Concentration of zinc salt |
| Comparative example 1 | ZnSO 4 | 1mol/L |
| Comparative example 2 | ZnSO 4 | 2mol/L |
Test example 1
Hydrogen evolution behavior of zinc cathodes in the electrolytes formulated in comparative example 1 and examples 1-4 was tested.
First, commercial zinc foil (30 μm thick) and titanium foil (60 μm thick) were cut into electrode pieces having a diameter of 12mm, and the surfaces of the electrode pieces were ultrasonically cleaned with deionized water and absolute ethyl alcohol in this order. Then, the electrolytes prepared in comparative example 1 and examples 1 to 4 were used to assemble a Zn/Ti asymmetric cell in which Ti foil was the working electrode and Zn foil was the counter electrode and the reference electrode. Finally, the hydrogen evolution behavior during zinc deposition was characterized by linear sweep voltammetry with the aid of an electrochemical workstation at a sweep rate of 1mV/s, the results of which are shown in FIG. 1.
As can be seen from the analysis of FIG. 1, with the increase of the concentration of the potassium polyacrylate, the hydrogen evolution behavior shows a remarkable polarization phenomenon, which indicates that the potassium polyacrylate can obviously inhibit the hydrogen evolution side reaction when being used as an electrolyte additive.
Test example 2
Test of chemical resistance of metallic zinc in electrolytes formulated in comparative example 1 and examples 1 to 4.
First, commercial zinc foil (30 μm thick) was cut into a negative electrode sheet having a diameter of 12mm, and the surface of the zinc negative electrode was ultrasonically cleaned with deionized water and absolute ethyl alcohol in order. Then, metallic zinc anodes were immersed in the electrolytes (10 mL) prepared in comparative example 1 and examples 1 to 4, respectively, and the solution was sealed and allowed to stand at room temperature for 24 hours. Finally, the components of the by-products on the surface of the soaked zinc electrode are characterized by an X-ray diffractometer (XRD), the 2 theta scanning angle is 5-60 degrees, the scanning speed is 12 degrees/min, and the result is shown in figure 2.
As can be seen from the analysis of FIG. 2, the zinc metal cathode has a concentration of 1mol/L ZnSO 4 The XRD spectrum after soaking in the electrolyte shows obvious diffraction characteristic peak at 9.5 DEG position, which corresponds to the by-product basic zinc sulfate (Zn) 4 SO 4 (OH) 6 ·3H 2 O), while in the electrolyte containing the potassium polyacrylate additive, the generation of basic zinc sulfate is obviously inhibited, and the effect of inhibiting corrosion is more obvious along with the increase of the concentration of the potassium polyacrylate.
Further, the surface morphology of metallic zinc before and after immersing in the electrolyte prepared in comparative examples 1 and 2 was compared and observed by a Scanning Electron Microscope (SEM), and the acceleration voltage was 15kV, and the result is shown in fig. 3.
As can be seen from the analysis of FIG. 3, the metal zinc with a smooth surface is 1mol/L ZnSO 4 After 24 hours of soaking in the electrolyte, obvious irregular flaky byproducts appear on the surface of the electrode. ObviouslyZinc cathode in 1mol/L ZnSO 4 After being soaked in the PAAK electrolyte with the concentration of +0.05g/L, the surface of the metallic zinc has no obvious corrosion by-product, and the original shape of the metallic zinc is maintained.
Test example 3
Electrochemical corrosion resistance test of zinc electrode in electrolyte prepared in comparative example 1 and example 2.
First, commercial zinc foil (30 μm thick) was cut into electrode pieces having a diameter of 12mm, and the surfaces of the electrode pieces were ultrasonically cleaned with deionized water and absolute ethyl alcohol in this order. The electrolyte prepared in comparative example 1 and example 2 was then used to assemble a Zn/Zn symmetric cell, and the corrosion current density of the zinc electrode in the electrolyte was measured at room temperature using an electrochemical workstation at a sweep rate of 10mV/s, and the results are shown in FIG. 4.
As can be seen from the analysis of FIG. 4, the catalyst is used in combination with 1mol/L ZnSO 4 The addition of potassium polyacrylate significantly reduces the corrosion current density compared to the electrolyte.
Test example 4
The zinc negative electrode was observed for the growth of dendrites on the surface of constant current electrodeposition in the electrolytes prepared in comparative example 1 and example 2.
First, commercial zinc foil (30 μm thick) was cut into electrode pieces having a diameter of 12mm, and the surfaces of the electrode pieces were ultrasonically cleaned with deionized water and absolute ethyl alcohol in this order. Then, the electrolytes prepared in comparative example 1 and example 2 were used to assemble Zn/Zn symmetric batteries, and constant-current deposition was performed for 1 hour at room temperature using a battery tester with current densities set to 5, 10, 20mA/cm, respectively 2 The surface morphology of zinc cathodes deposited in the electrolytes prepared in comparative examples 1 and 2 at different current densities was compared and observed by means of a Scanning Electron Microscope (SEM), the acceleration voltage was 15kV, and the result is shown in fig. 5.
As can be seen from the analysis of FIG. 5, 1mol/L ZnSO was used for 1h of deposition under different current densities 4 The zinc negative surface of the electrolyte presents a significant number of block dendrites and gradually pulverizes with increasing current density. Obviously, in 1mol/L ZnSO 4 The surface of the zinc anode deposited in the PAAK electrolyte with the concentration of +0.05g/L is smoother and more compact.
Test example 5
The electrolyte prepared in comparative example 1 and examples 2 and 8 was used to assemble Zn/Zn symmetry batteries for cycle stability testing.
First, commercial zinc foil (30 μm thick) was cut into electrode pieces having a diameter of 12mm, and the surfaces of the electrode pieces were ultrasonically cleaned with deionized water and absolute ethyl alcohol in this order. Then, in an air environment, a zinc sheet was used as a positive electrode and a negative electrode, 2 layers of qualitative filter paper was used as a diaphragm (diameter: 16 mm), 30. Mu.L of the above electrolyte was taken, and a LIR2032 type button Zn/Zn symmetric battery was assembled, wherein the electrolyte prepared in comparative example 1 was (1 mol/L ZnSO 4 ) The experimental groups were the electrolytes (1 mol/LZnSO) prepared in examples 2 and 8 4 +0.05g/L PAAK，1mol/L ZnSO 4 +0.05g/L PAANa). Finally, a constant-current charge-discharge cycle test is carried out by using a battery tester at the constant temperature of 25 ℃, and the current density is 1mA/cm 2 The deposition/stripping surface capacity was 1mAh/cm 2 The cycling stability of the zinc anode in the above electrolyte is shown in fig. 6.
As can be seen from the analysis of FIG. 6, 1mol/L ZnSO was used 4 Electrolyte assembled Zn/Zn symmetrical battery at 1mA/cm 2 ，1mAh/cm 2 Short circuit phenomenon appears after 128 hours of circulation under the test condition, and the Zn/Zn symmetrical battery assembled by the electrolyte containing PAAK and PAANa organic additives can be respectively circulated for 600 hours and 200 hours, which shows that the electrolyte additives can obviously improve the circulation stability of the zinc cathode.
Test example 6
The electrolyte prepared in examples 1-4 was used to assemble Zn/Zn symmetrical cells for cycle stability testing.
First, commercial zinc foil (30 μm thick) was cut into electrode pieces having a diameter of 12mm, and the surfaces of the electrode pieces were ultrasonically cleaned with deionized water and absolute ethyl alcohol in this order. Then, in an air environment, a zinc sheet is used as a positive electrode and a negative electrode, 2 layers of qualitative filter paper are used as diaphragms (diameter: 16 mm), 30 mu L of the electrolyte is taken, and the LIR2032 button type Zn/Zn symmetrical battery is assembled, wherein the electrolytes prepared in examples 1-4 are respectively 1mol/L ZnSO 4 +0.02g/L PAAK，1mol/L ZnSO 4 +0.05g/L PAAK，1mol/LZnSO 4 +0.07g/L PAAK，1mol/L ZnSO 4 +0.1g/L PAAK. Finally, benefitConstant-current charge-discharge cyclic test is carried out by a battery tester at the constant temperature of 25 ℃, and the current density is 1mA/cm 2 The deposition/stripping surface capacity was 1mAh/cm 2 The cycling stability of the zinc anode in the above electrolyte is shown in fig. 7.
As can be seen from the analysis of FIG. 7, the Zn/Zn symmetry cell assembled with the electrolyte containing 0.02g/L, 0.05g/L, 0.07g/L, 0.1g/L PAAK organic additive can stably circulate 174h, 600h, 265h, 204h, and 1mol/L ZnSO, respectively 4 (128h) Compared with the PAAK electrolyte additive, the PAAK electrolyte additive can enhance the cycle stability of the zinc anode, wherein the improvement effect is most remarkable when the PAAK additive amount is 0.05 g/L.
Test example 7
Coulombic efficiency tests were performed using the electrolytes prepared in comparative example 1 and example 2 to assemble Zn/Cu asymmetric cells.
First, commercial zinc foil (30 μm thick) and copper foil (10 μm thick) were cut into electrode pieces having a diameter of 12mm, and the surfaces of the electrode pieces were ultrasonically cleaned with deionized water and absolute ethyl alcohol in this order. Then, 30. Mu.L of the above electrolyte was taken out in a room temperature environment using a zinc sheet as a negative electrode and a copper foil as a positive electrode and 2 layers of qualitative filter paper as a separator (diameter: 16 mm), to thereby prepare a LIR2032 button type Zn/Cu asymmetric battery, the experimental group was the electrolyte (1 mol/L ZnSO) prepared in example 2 4 +0.05g/L potassium polyacrylate), the control group is the electrolyte (1 mol/L ZnSO) prepared in comparative example 1 4 ). Finally, a constant-current charge-discharge cycle test is carried out by using a battery tester at the constant temperature of 25 ℃, and the current density is 1mA/cm 2 The deposition surface capacity was 1mAh/cm 2 The peeling cut-off voltage was 0.5V vs. Zn 2+ The result of Zn was shown in FIG. 8.
As can be seen from the analysis of FIG. 8, 1mol/L ZnSO was used 4 Zn/Cu asymmetric battery assembled by electrolyte at 1mA/cm 2 ，1mAh/cm 2 After 60 cycles of cycle under the test conditions of (2) the coulombic efficiency showed a significant fluctuation, whereas 1mol/L ZnSO was used 4 In the case of +0.05g/LPAAK electrolyte, the average coulombic efficiency of Zn/Cu asymmetric cell can reach 99%, and can stably circulate for 300 circles, which shows that the reversibility of zinc deposition/stripping is obviously improved after adding the potassium polyacrylate additive.
Test example 8
Zn/VO Assembly Using electrolyte prepared in example 2 2 The cells were subjected to a cycle stability test.
First, commercial zinc foil (30 μm thick) and titanium foil (60 μm thick) were cut into a negative electrode sheet having a diameter of 12mm, and the surfaces of the electrode sheets were ultrasonically cleaned with deionized water and absolute ethyl alcohol in this order. The preparation process of the positive plate is as follows: weighing active substance vanadium dioxide (VO) according to the mass ratio of 7:2:1 2 ) Conductive carbon Super P, binder polyvinylidene fluoride (PVDF), N-methyl pyrrolidone (NMP) as solvent in an agate mortar was sufficiently ground until a uniform viscous slurry was obtained, which was then uniformly coated on the surface of a titanium foil current collector with a doctor blade (controlling the loading of active material: 1-2mg/cm 2 ) And (5) putting the coated electrode slice into a vacuum oven, and drying at 80 ℃ for 12 hours. Then, VO is performed in the air environment 2 The electrode sheet was positive electrode, zinc foil was negative electrode, 3 layers of filter paper was separator (diameter: 16 mm), and the electrolyte prepared in example 2 (1 mol/L ZnSO 4 +0.05g/L PAAK) 80. Mu.L, assembled into LIR2032 type button Zn/VO 2 And a battery. Finally, a constant-current charge-discharge cycle test is carried out by using a battery tester under the constant temperature of 25 ℃, and the current density is 1A g -1 The voltage interval is 0.3-1.5V vs. Zn 2+ The result of Zn was shown in FIG. 9.
As can be seen from the analysis of FIG. 9, at 1A g -1 Under the test condition, 1mol/L ZnSO is adopted 4 +0.05g/L PAAK electrolyte assembled Zn/VO 2 After 200 charge and discharge cycles, the specific discharge capacity is still kept at 214mAh/g, and the coulomb efficiency is 99.95%, which indicates that the aqueous zinc ion battery has higher cycle stability and reversibility by taking the potassium polyacrylate as the electrolyte additive.
Conclusion: according to the invention, one or more of polyacrylate additives such as lithium polyacrylate, sodium polyacrylate additives, potassium polyacrylate and other organic compounds are introduced into the electrolyte, and the organic compounds have a zinc-philic characteristic, so that the interface reaction between the electrolyte and a zinc negative electrode is regulated and controlled by being adsorbed on the surface of metal zinc. The electrolyte modified by the polyacrylate additive has the multifunctional characteristics of regulating and controlling uniform deposition of zinc, inhibiting irreversible side reactions such as hydrogen evolution, corrosion, passivation and the like, and can obviously enhance the reversibility of a zinc cathode through anion and cation double-ion adsorption effect, thereby prolonging the cycle life and improving the coulombic efficiency of the water-based zinc ion battery. Meanwhile, the electrolyte additive provided by the invention has the advantages of low cost, small dosage, obvious effect, environmental protection, friendly property and the like, and the electrolyte additive has simple formula and preparation process and strong operability, and has good application prospect in the field of water-based zinc ion batteries.
In view of the foregoing, the above embodiments are merely illustrative of the principles and embodiments, and are intended to enable those skilled in the art to understand the present invention and to implement the same without limiting the invention thereto. Any modification, equivalent replacement, improvement, etc. of the present invention without departing from the principle of the present invention should be covered in the protection scope of the present invention.
Claims (8)
1. The water-based zinc ion battery electrolyte containing the polyacrylate additive is characterized by comprising the polyacrylate additive, water-soluble zinc salt and deionized water; the polyacrylate additive is organic compounds of lithium polyacrylate, sodium polyacrylate and potassium polyacrylate, and has the following general formula:
wherein R in formula (1) + The represented ion is Li + 、Na + And K + 。
2. The aqueous zinc ion battery electrolyte containing polyacrylate additive according to claim 1, wherein the concentration of polyacrylate additive is 0.01-0.5g/L.
3. The aqueous zinc ion battery electrolyte containing polyacrylate additives of claim 1, wherein the water-soluble zinc salt is one or more of zinc sulfate, zinc chloride, zinc acetate, zinc nitrate, zinc triflate.
4. The aqueous zinc-ion battery electrolyte containing polyacrylate additive according to claim 1, wherein the concentration of the water-soluble zinc salt is 1-3mol/L.
5. An aqueous zinc ion battery comprising a positive electrode, a negative electrode, a separator, and the electrolyte according to any one of claims 2 to 4.
6. The aqueous zinc-ion battery according to claim 5, wherein the positive electrode active material of the aqueous zinc-ion battery is manganese, cobalt, vanadium-based compound, prussian blue analogue or organic compound.
7. The aqueous zinc-ion battery of claim 5, wherein the negative electrode material of the aqueous zinc-ion battery is one or more of zinc foil, zinc paste, zinc powder, electrodeposited metallic zinc, three-dimensional foam zinc, or zinc alloy.
8. The aqueous zinc-ion battery according to claim 5, wherein the separator of the aqueous zinc-ion battery is a glass fiber, a cellulose filter paper, or an aqueous polyolefin separator.
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