CN117458001A - Application of 1-ethyl-3-methylimidazole trifluoromethane sulfonate as electrolyte cosolvent in water-based zinc ion battery - Google Patents
Application of 1-ethyl-3-methylimidazole trifluoromethane sulfonate as electrolyte cosolvent in water-based zinc ion battery Download PDFInfo
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- CN117458001A CN117458001A CN202311190885.1A CN202311190885A CN117458001A CN 117458001 A CN117458001 A CN 117458001A CN 202311190885 A CN202311190885 A CN 202311190885A CN 117458001 A CN117458001 A CN 117458001A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 49
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- AFSJUFFXOPXIOH-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;trifluoromethanesulfonate Chemical compound CC[NH+]1CN(C)C=C1.[O-]S(=O)(=O)C(F)(F)F AFSJUFFXOPXIOH-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000006184 cosolvent Substances 0.000 title claims abstract description 19
- 239000011701 zinc Substances 0.000 claims description 85
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- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000007614 solvation Methods 0.000 abstract description 4
- JMNFVQWMBCLWAS-UHFFFAOYSA-N C(F)(F)F.C(C)N1CN(C=C1)C Chemical compound C(F)(F)F.C(C)N1CN(C=C1)C JMNFVQWMBCLWAS-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001450 anions Chemical class 0.000 abstract description 2
- 238000004807 desolvation Methods 0.000 abstract description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 60
- 229910052725 zinc Inorganic materials 0.000 description 59
- 230000000052 comparative effect Effects 0.000 description 42
- 210000004027 cell Anatomy 0.000 description 31
- 210000001787 dendrite Anatomy 0.000 description 14
- 238000012360 testing method Methods 0.000 description 12
- 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 8
- 230000001351 cycling effect Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000008021 deposition Effects 0.000 description 7
- 238000004806 packaging method and process Methods 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000002000 Electrolyte additive Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000022131 cell cycle Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
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- 239000006227 byproduct Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
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- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
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- 239000007774 positive electrode material Substances 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
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- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 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
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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
- 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
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides an application of 1-ethyl-3-methylimidazole trifluoromethane sulfonate as an electrolyte cosolvent in a water-based zinc ion battery, and belongs to the technical field of water-based zinc ion battery electrolytes. The molecular formula of the 1-ethyl-3-methylimidazole trifluoromethane sulfonate is shown as a formula I. The invention introduces 1-ethyl-3-methylimidazole trifluoro methane sulfonate as a cosolvent into the electrolyte and passes through OTf ‑ The anion regulates and controls the solvation structure of the zinc ion, reduces the number of active water molecules in a solvation shell layer of the zinc ion, and realizes desolvation, thereby effectively reducing the reaction of side reaction.
Description
Technical Field
The invention belongs to the technical field of aqueous zinc ion battery electrolyte, and particularly relates to application of 1-ethyl-3-methylimidazole trifluoromethane sulfonate as an electrolyte cosolvent in an aqueous zinc ion battery.
Background
With the continuous development of society, exhaustion of fossil energy and environmental deterioration are two major problems facing human beings at present, and the demand of energy is increasing. A series of renewable clean energy sources such as wind energy, solar energy, water energy and tidal energy are widely developed and applied, and because the energy sources have the characteristics of intermittence, uncontrollability and the like, the renewable clean energy sources are difficult to directly apply. To efficiently convert and store these energy sources, energy storage systems have been developedProviding a stable energy supply for both home and industry. Aqueous batteries are considered to be a very promising energy storage device due to their inherent high safety and low cost characteristics, and can be effectively used as an effective complement to existing lithium ion batteries in large-scale grid energy storage applications. Wherein the aqueous zinc ion battery has high specific capacity (volume specific capacity 5855mA h/cm due to reversible and stable electroplating/stripping reaction 3 The mass ratio of 820mA h/g), the battery is intrinsically safe and low in cost, and can be directly assembled in an air atmosphere due to insensitivity to oxygen and humid environment, and the battery can not generate unique advantages of extra cost and the like due to strict anhydrous and anaerobic environments, so that special attention of people is drawn in recent years, and the battery also meets the huge demand of low-cost devices in power grid energy storage.
The development of aqueous zinc ion batteries is largely dependent on the stability of the zinc metal negative electrode. However, further commercial applications of aqueous zinc ion batteries are limited due to problems of dendrite growth, corrosion, and Hydrogen Evolution Reactions (HER) of zinc metal anodes during continuous galvanization and dezincification. In neutral and weak acid electrolyte, zinc metal will be mixed with trace H + The ions react to form hydrogen gas, increasing the internal pressure of the sealed cell, resulting in a cell with lower coulombic efficiency. In addition, during the cycle, a large amount of Zn exists near the surface of the zinc anode 2+ Ions and SO 4 2- Ion, hydrogen evolution results in OH near the surface - The concentration is increased, and a layer of insulating alkaline zinc sulfate is generated on the surface of the zinc cathode, so that the internal impedance of the battery is increased. Meanwhile, the non-uniform distribution of active sites on the surface of the zinc cathode leads to Zn 2+ Uneven nucleation, which aggravates the electric field distribution and the uneven distribution of ion flux, increases localized Zn 2+ The concentration of ions and the current density cause a tip effect, uneven deposition of zinc ions is aggravated to form dendrites, and the grown dendrites can puncture a diaphragm to cause short circuit of the battery, thereby seriously affecting the cycle life of the aqueous zinc ion battery. Various methods have been proposed to address the key challenges of zinc cathodes, including zinc cathode surface coating modification, current collector structural design, electrolyte additives and the like,the method can reduce dendrite growth and side reaction of the zinc cathode, thereby effectively improving coulomb efficiency and cycle stability of the zinc metal cathode. Among them, the electrolyte additive is considered as a simple and effective method of solving dendrites and suppressing side reactions. The electrolyte additives may be selected basically by cationic additives, surfactants, inorganic salts, organic matters, and the like. The cationic additive can form an effective electrostatic shielding layer on the surface of the zinc cathode at the protrusion position to counteract Zn 2+ Is used to promote uniform deposition. The surfactant can inhibit Zn 2+ The growth of irregular and non-planar dendrites in the electroplating process improves the reversibility of the zinc cathode. The inorganic salt can generate compact, stable and high Zn on the surface of the zinc cathode in situ 2+ SEI layer with conductivity, inhibiting dendrite growth, and promoting Zn 2+ Transfer deposition kinetics. In contrast, organic additives may provide more functional options. Some organic compounds can modulate Zn 2+ To reduce the number of active water molecules or to create a water-depleted electric double layer on the surface of the zinc anode to reduce the erosion of the water electrolyte. In addition, other organic compounds are similar to inorganic salts, and can generate SEI layer on the surface of the zinc negative electrode in situ to guide Zn 2+ And (5) orderly diffusing. However, single regulation of the electrolyte is not effective in simultaneously alleviating the two challenges of zinc dendrites and side reactions, resulting in an optimized zinc anode to cathode material coupling full cell cycle life of rarely exceeding 10,000 times, especially at high area capacity. Therefore, based on the above analysis, it is highly desirable to design a multifunctional electrolyte capable of simultaneously inhibiting dendrite growth and side reactions of a zinc anode, and improving long-term cycle stability of the zinc anode and a full cell.
Disclosure of Invention
Aiming at the problems of dendrite and side reaction of a zinc cathode in the existing water-based zinc ion battery, the invention provides application of 1-ethyl-3-methylimidazole trifluoromethane sulfonate as an electrolyte cosolvent in the water-based zinc ion battery.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides an application of 1-ethyl-3-methylimidazole trifluoromethane sulfonate as an electrolyte cosolvent in a water system zinc ion battery, wherein the molecular formula of the 1-ethyl-3-methylimidazole trifluoromethane sulfonate is shown as a formula I:
preferably, the electrolyte co-solvent further comprises water.
Preferably, the volume ratio of the 1-ethyl-3-methylimidazole trifluoro methane sulfonate in the electrolyte is 10-70%.
Preferably, the volume ratio of the 1-ethyl-3-methylimidazole trifluoro methane sulfonate in the electrolyte is 30%.
Preferably, the electrolyte further comprises Zn (OTf) 2 。
Preferably, the concentration is 3M.
The beneficial effects of the invention are that
The invention provides an application of 1-ethyl-3-methylimidazole trifluoromethane sulfonate as an electrolyte cosolvent in a water system zinc ion battery, which is characterized in that 1-ethyl-3-methylimidazole trifluoromethane sulfonate ([ EMIm) is simply and conveniently used]OTf) is introduced as a co-solvent into the electrolyte by OTf - The anion regulates and controls the solvation structure of the zinc ion, reduces the number of active water molecules in a solvation shell layer of the zinc ion, and realizes desolvation, thereby effectively reducing the reaction of side reaction. At the same time, EMIm + Electrostatic shielding effect of cations and EMIm + Cations and OH in the electrolyte - 、OTf - The interaction generates a layer of organic/inorganic hybridization solid electrolyte membrane (SEI) on the surface of the zinc cathode, which is beneficial to the uniform deposition of zinc ions and avoids the generation of dendrites. At 1mA/cm 2 And at 1mA h/cm 2 The cycle life of the zinc cathode is improved from 280 hours to 3400 hours; the combined action of the two realizes the highly stable and reversible zinc metal cathode at 3400 hours, the cycle life of the whole battery 25000 times and 4.5mA h/cm 2 High initial surface capacity and excellent wide-temperature-range adaptability.
The invention has the advantages of low raw material price, environmental protection, simple preparation process, no special equipment requirement, easy operation and good reproducibility, can be used for basic research in laboratories, is suitable for industrial mass production, and can be used as an electrolyte solvent by only mixing pure water according to a certain volume ratio.
Drawings
In order to more clearly illustrate the technical scheme of the invention and the performance of the electrolyte prepared by the technical scheme, the following related diagrams are given.
Fig. 1 is the electrochemical performance of comparative example 1 and examples 1-4 in Zn symmetric cells.
Fig. 2 is an electrochemical impedance spectrum of the assembled symmetrical cell of comparative example 1 and examples 1-4.
FIG. 3 shows the viscosities of the electrolytes prepared in comparative example 1 and examples 1 to 4.
Fig. 4 is an XRD pattern of the zinc anode immersed in comparative example 1 and example 2.
FIG. 5 is an SEM image of the surface of a zinc anode after 100 cycles of constant current, with a test current density of 1mA/cm 2 The surface capacity is 1mA h/cm 2 . (a) is comparative example 1 and (b) is example 2.
FIG. 6 is a Zn symmetric battery assembled in example 2 at 1mA/cm 2 Current density and 1mA h/cm 2 Cycle life plot at face capacity.
FIG. 7 is a Zn symmetry battery assembled in example 2 at 0.5mA/cm 2 Current density and 0.5mA h/cm 2 Area capacity, 1mA/cm 2 Current density and 1mA h/cm 2 Area capacity, 2mA/cm 2 Current density and 2mA h/cm 2 Area capacity, 5mA/cm 2 Current density and 5mA h/cm 2 Area capacity, 10mA/cm 2 Current density and 10mA h/cm 2 Rate performance under different conditions of surface capacity.
FIG. 8 is a zinc negative electrode matching V in example 2 2 O 5 Cycling performance graph of positive assembled full cell at 5A/g current density.
FIG. 9 is a zinc negative electrode matching V in example 2 2 O 5 The positive electrode assembled full cell is respectively 0.5A/g, 1A/g, 2A/g and 5A +.g. Discharge test rate performance plots at different current densities of 10A/g and 15A/g.
FIG. 10 is a zinc negative electrode matching V in example 2 2 O 5 Positive assembled full cell cycle performance at 0 ℃, -20 ℃, -40 ℃ at 1A/g current density, respectively.
FIG. 11 is a zinc negative electrode matching V in example 2 2 O 5 Positive electrode assembled high area capacity full cell cycling performance graph at 0.5A/g current density.
FIG. 12 is a Zn symmetric battery assembled in comparative example 1 at 1mA/cm 2 Current density and 1mA h/cm 2 Cycle life plot at face capacity.
FIG. 13 is a Zn symmetry battery assembled in comparative example 1 at 0.5mA/cm 2 Current density and 0.5mA h/cm 2 Area capacity, 1mA/cm 2 Current density and 1mA h/cm 2 Area capacity, 2mA/cm 2 Current density and 2mA h/cm 2 Area capacity, 5mA/cm 2 Current density and 5mA h/cm 2 Area capacity, 10mA/cm 2 Current density and 10mA h/cm 2 Rate performance under different conditions of surface capacity.
FIG. 14 is a zinc negative electrode match V in comparative example 1 2 O 5 Cycling performance graph of positive assembled full cell at 5A/g current density.
FIG. 15 is a zinc negative electrode match V in comparative example 1 2 O 5 Discharge test rate performance graphs of positive assembled full cells at different current densities of 0.5A/g, 1A/g, 2A/g, 5A/g, 10A/g and 15A/g, respectively.
Detailed Description
The invention provides an application of 1-ethyl-3-methylimidazole trifluoromethane sulfonate as an electrolyte cosolvent in a water-based zinc ion battery, wherein the molecular formula of the 1-ethyl-3-methylimidazole trifluoromethane sulfonate ([ EMim ] OTf) is shown as a formula I:
according to the invention, the electrolyte co-solvent also comprises water. The volume ratio of the 1-ethyl-3-methylimidazole trifluoromethane sulfonate in the electrolyte is preferably 10-70%, more preferably 30%.
According to the invention, the electrolyte further comprises Zn (OTf) 2 The concentration is preferably 3M.
According to the invention, the steps for assembling a battery using the above electrolyte are as follows:
step one: preparation of V according to the prior art 2 O 5 A positive electrode material;
step two: preparing a zinc negative electrode plate according to the prior art;
step three: preparing electrolyte by 3M Zn (OTf) 2 As a solute, pure water and 1-ethyl-3-methylimidazole trifluoromethane sulfonate mixed in different volume ratios are used as solvents, and are stirred to prepare electrolyte;
step four: and assembling the negative electrode shell, the spring piece, the gasket, the zinc negative electrode piece, the diaphragm, the electrolyte, the positive electrode piece and the positive electrode shell in sequence, packaging the battery by a battery packaging machine, and carrying out subsequent tests.
The invention will be described in further detail with reference to the following specific examples, in which the raw materials involved are all commercially available.
Comparative example 1
(1) Preparing a positive electrode plate: first, 0.72. 0.72g V 2 O 5 The powder was uniformly dispersed in 70mL deionized water and H 2 O 2 (volume ratio of 1:6) and performing ultrasonic treatment to obtain a clear solution. The mixture was then maintained in a 100ml Teflon reactor at 190℃for 15 hours to yield V 2 O 5 Gel, and freeze-dried to remove excess moisture. Subsequently, 500mg of the prepared V described above was added 2 O 5 Uniformly dispersed in 50mL deionized water containing 10. Mu.L hydrazine hydrate, and continuously stirred for 1 hour. Finally, the processed suspension is freeze-dried to obtain the final V 2 O 5 And a positive electrode material. V to be prepared 2 O 5 The anode material and Super P are uniformly dispersed in ethanol according to the mass ratio of 8:2. After vacuum filtration, the resulting film was pressed against a titanium mesh with a jack and cut into an area of 0.785cm 2 The wafer of (C) was used as the positive electrode, and the surface loading was 2.5mg/cm 2 。
(2) Preparing a negative electrode plate: a piece of zinc foil of 50X 0.1mm was first sanded to remove the passivation layer and carefully cleaned with absolute ethanol and pressed to an area of 0.785cm 2 Is a circular pole piece.
(3) Preparing electrolyte: with 3M Zn (OTf) 2 Based on dissolution in deionized water.
(4) And assembling the symmetrical batteries according to the sequence of the negative electrode shell, the spring piece, the gasket, the zinc negative electrode piece, the diaphragm, the electrolyte, the zinc negative electrode piece and the positive electrode shell, packaging the batteries by a battery packaging machine, and carrying out subsequent tests.
(5) And assembling the full battery according to the sequence of the negative electrode shell, the spring piece, the gasket, the zinc negative electrode piece, the diaphragm, the electrolyte, the positive electrode piece and the positive electrode shell, packaging the battery by a battery packaging machine, and carrying out subsequent tests.
The XRD pattern of the immersed zinc anode in comparative example 1 is shown in curve 1 of fig. 4, indicating severe corrosion of the zinc anode in comparative example 1. SEM images of the zinc anode after cycling in comparative example 1 are shown in fig. 5a, and the surface morphology of the zinc anode is rough, indicating uneven deposition of zinc ions in comparative example 1.
FIG. 12 is a Zn symmetric battery assembled in comparative example 1 at 1mA/cm 2 Current density and 1mA h/cm 2 Cycle life plot at face capacity. As can be seen from the figure, the symmetrical battery assembled in comparative example 1 exhibited a cycle life of only about 280 hours, indicating that the zinc anode suffered serious dendrite growth and side reactions in comparative example 1, resulting in short-circuit failure of the battery.
FIG. 13 is a Zn symmetry battery assembled in comparative example 1 at 0.5mA/cm 2 Current density and 0.5mA h/cm 2 Area capacity, 1mA/cm 2 Current density and 1mA h/cm 2 Area capacity, 2mA/cm 2 Current density and 2mA h/cm 2 Area capacity, 5mA/cm 2 Current density and 5mA h/cm 2 Area capacity, 10mA/cm 2 Current density and 10mA h/cm 2 Rate performance under different conditions of surface capacity. As can be seen from the figure, at 10mA/cm 2 Current density and 10mA h/cm 2 The current density of the surface capacity and the surface capacity caused the short circuit phenomenon of the symmetrical battery assembled in comparative example 1, which indicates that the zinc cathode in comparative example 1 is easy to cause short circuit failure of the zinc ion battery under the condition of larger current density and surface capacity.
FIG. 14 is a zinc negative electrode match V in comparative example 1 2 O 5 Cycling performance graph of positive assembled full cell at 5A/g current density. There are 2 curves in the graph, curve 1 representing coulombic efficiency and curve 2 representing specific discharge capacity. As can be seen from the graph, the short-circuit failure phenomenon of the full cell in comparative example 1 occurs after about 1000 cycles, which indicates that the passivation layer on the surface of the zinc negative electrode is continuously accumulated due to the growth of dendrite and the occurrence of side reaction in comparative example 1, and the stability and reversibility of the zinc negative electrode are damaged.
FIG. 15 is a zinc negative electrode match V in comparative example 1 2 O 5 Discharge test rate performance graphs of positive assembled full cells at different current densities of 0.5A/g, 1A/g, 2A/g, 5A/g, 10A/g and 15A/g, respectively. As can be seen from the graph, the full cell of comparative example 1 has a low specific discharge capacity and poor rate performance under the respective current density tests.
Example 1:
in the case of the electrolyte formulation of example 1, the difference between that of comparative example 1 is that the solvent is a mixed solvent of deionized water and 1-ethyl-3-methylimidazole trifluoromethane sulfonate (volume ratio: 9:1). The cycle life of the assembled symmetrical cell of example 1 was somewhat extended, but short circuit failure occurred at 450 hours of cycling.
Example 2:
example 2 differs from comparative example 1 in that the electrolyte was formulated using a solvent selected from the group consisting of deionized water and a mixed solvent of 1-ethyl-3-methylimidazole trifluoromethane sulfonate (volume ratio: 7:3).
Fig. 4 is an XRD pattern of the zinc anode immersed in comparative example 1 and example 2. There are two curves in the figure, curve 1 representing immersion in comparative example 1 and curve 2 representing immersion in example 2. As can be seen from the figure, the zinc anode immersed in comparative example 1 showed a stronger diffraction peak belonging to the by-product, whereas the zinc anode immersed in example 2 showed only a lower diffraction peak of the by-product, indicating that the occurrence of the side reaction of the zinc anode can be effectively suppressed in example 2.
FIG. 5 is an SEM image of the surface of a zinc anode after 100 cycles of constant current, with a test current density of 1mA/cm 2 The surface capacity is 1mA h/cm 2 . (a) is comparative example 1 and (b) is example 2. As can be seen from the figure, the surface structure of the recycled zinc anode in comparative example 1 is loose and disordered, and has irregular protrusions, which indicates serious side effects, zn 2+ The deposition is disordered. And example 2. The immersed zinc cathode presents a smooth and compact surface, has no obvious protrusion, and shows that the side reaction is effectively inhibited, zn 2+ Uniform deposition is achieved.
FIG. 6 is a Zn symmetric battery assembled in example 2 at 1mA/cm 2 Current density and 1mA h/cm 2 Cycle life plot at face capacity. As can be seen from the figure, the assembled symmetric battery of example 2 exhibited a cycle life as long as 3400 hours, indicating that the zinc anode has good cycle stability in example 2 and can effectively suppress the generation of dendrites and the occurrence of side reactions.
FIG. 7 is a Zn symmetry battery assembled in example 2 at 0.5mA/cm 2 Current density and 0.5mA h/cm 2 Area capacity, 1mA/cm 2 Current density and 1mA h/cm 2 Area capacity, 2mA/cm 2 Current density and 2mA h/cm 2 Area capacity, 5mA/cm 2 Current density and 5mA h/cm 2 Area capacity, 10mA/cm 2 Current density and 10mA h/cm 2 Rate performance under different conditions of surface capacity. As can be seen from the figure, the zinc anode of example 2 has good rate stability at different current densities and surface capacities.
FIG. 8 is a zinc negative electrode matching V in example 2 2 O 5 Cycling performance graph of positive assembled full cell at 5A/g current density. There are 2 curves in the graph, curve 1 representing coulombic efficiency and curve 2 representing specific discharge capacity. As can be seen from the graph, the full cell in example 2 realizes 25000 stable cycles, the specific discharge capacity can still reach 103mA h/g, and the coulomb efficiency is close to 100%, indicating that the full cell in example 2 has the advantages of stable cycleHas good cycle stability.
FIG. 9 is a zinc negative electrode matching V in example 2 2 O 5 Discharge test rate performance graphs of positive assembled full cells at different current densities of 0.5A/g, 1A/g, 2A/g, 5A/g, 10A/g and 15A/g, respectively. As can be seen from the graph, the full cell in example 2 was stable in cycle under each current density test, and had superior rate performance.
FIG. 10 is a zinc negative electrode matching V in example 2 2 O 5 Positive assembled full cell cycle performance at 0 ℃, -20 ℃, -40 ℃ at 1A/g current density, respectively. In the graph, there are 3 curves, curve 1 is the cycle performance at 0 ℃, curve 2 is the cycle performance at-20 ℃, and curve 3 is the cycle performance at-40 ℃. As can be seen from the figure, the full cell in example 2 has a good wide temperature range adaptation capability.
FIG. 11 is a zinc negative electrode matching V in example 2 2 O 5 Positive electrode assembled high area capacity full cell cycling performance graph at 0.5A/g current density. In the figure, there are two curves, curve 1 represents coulombic efficiency, and curve 2 represents specific discharge capacity. As can be seen from the figure, the full cell in example 2 achieves up to 4.5mA h/cm 2 And successfully cycled through 1500 cycles. As can be seen from the graph, the full cell in example 2 has excellent high capacity cycle performance.
Example 3:
example 3 differs from comparative example 1 in that the electrolyte was formulated using a mixed solvent of deionized water and 1-ethyl-3-methylimidazole trifluoromethane sulfonate (volume ratio 5:5). The cycle life of the assembled symmetrical cell of example 3 was somewhat extended, but the overpotential was greater than that of example 2, indicating the slow kinetics of the zinc ions in example 3.
Example 4:
example 4 differs from comparative example 1 in that the electrolyte was formulated using a mixed solvent of deionized water and 1-ethyl-3-methylimidazole trifluoromethane sulfonate (volume ratio 3:7). The cycle life of the assembled symmetrical cell of example 4 was somewhat extended, but the overpotential was greater than that of example 3, indicating a more retarded reaction kinetics of the zinc ions in example 4.
Fig. 1 is the electrochemical performance of comparative example 1 and examples 1-4 in Zn symmetric cells. (a) is the cyclic performance of comparative example 1; (b) is the cyclic performance of example 1; (c) is the cyclic performance of example 2; (d) is the cyclic performance of example 3; (e) For the cyclic performance of example 4, the above test conditions all had a current density of 1mA/cm 2 The dough kneading capacity is 1mA h/cm 2 . As can be seen from the figures, examples 2 to 4 are all capable of effectively extending the cycle life of Zn symmetric cells, but the symmetric cells of examples 3 to 4 show higher overpotential of example 2.
Fig. 2 is an electrochemical impedance spectrum of the assembled symmetrical cell of comparative example 1 and examples 1-4. There are 5 curves in the figure, curve 1 representing comparative example 1, curve 2 representing example 1, curve 3 representing example 2, curve 4 representing example 3, and curve 5 representing example 4. As can be seen from the figures, the impedance of Zn symmetry cells assembled in comparative example 1 and examples 1 to 4 gradually increases.
FIG. 3 shows the viscosities of the electrolytes prepared in comparative example 1 and examples 1 to 4. There are 5 curves in the figure, curve 1 representing comparative example 1, curve 2 representing example 1, curve 3 representing example 2, curve 4 representing example 3, and curve 5 representing example 4. As can be seen from the graph, the viscosities of comparative example 1 and examples 1 to 4 gradually increase.
Claims (6)
- The application of 1-ethyl-3-methylimidazole trifluoromethane sulfonate as an electrolyte cosolvent in a water-based zinc ion battery is disclosed, wherein the molecular formula of the 1-ethyl-3-methylimidazole trifluoromethane sulfonate is shown in a formula I:
- 2. the use of 1-ethyl-3-methylimidazole trifluoromethane sulfonate as defined in claim 1 as an electrolyte co-solvent in aqueous zinc ion batteries, wherein said electrolyte co-solvent further comprises water.
- 3. The use of 1-ethyl-3-methylimidazole trifluoromethane sulfonate as a cosolvent for an electrolyte in an aqueous zinc ion battery according to claim 1, wherein the volume ratio of 1-ethyl-3-methylimidazole trifluoromethane sulfonate in the electrolyte is 10-70%.
- 4. The use of 1-ethyl-3-methylimidazole trifluoromethane sulfonate as a cosolvent for an electrolyte in an aqueous zinc ion battery according to claim 3, wherein the volume ratio of 1-ethyl-3-methylimidazole trifluoromethane sulfonate in the electrolyte is 30%.
- 5. Use of 1-ethyl-3-methylimidazole trifluoromethane sulfonate as defined in claim 1 as an electrolyte co-solvent in aqueous zinc ion batteries, wherein the electrolyte further comprises Zn (OTf) 2 。
- 6. The use of 1-ethyl-3-methylimidazole trifluoromethane sulfonate as an electrolyte co-solvent in aqueous zinc ion batteries according to claim 1, wherein said concentration is 3M.
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