CN115275399B - Electrolyte and aqueous zinc ion battery using same - Google Patents
Electrolyte and aqueous zinc ion battery using same Download PDFInfo
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- CN115275399B CN115275399B CN202211049238.4A CN202211049238A CN115275399B CN 115275399 B CN115275399 B CN 115275399B CN 202211049238 A CN202211049238 A CN 202211049238A CN 115275399 B CN115275399 B CN 115275399B
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000003792 electrolyte Substances 0.000 title claims abstract description 42
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 8
- 150000003751 zinc Chemical class 0.000 claims abstract description 7
- KVUAALJSMIVURS-ZEDZUCNESA-L calcium folinate Chemical compound [Ca+2].C1NC=2NC(N)=NC(=O)C=2N(C=O)C1CNC1=CC=C(C(=O)N[C@@H](CCC([O-])=O)C([O-])=O)C=C1 KVUAALJSMIVURS-ZEDZUCNESA-L 0.000 claims description 14
- 235000008207 calcium folinate Nutrition 0.000 claims description 14
- 239000011687 calcium folinate Substances 0.000 claims description 14
- 229960001763 zinc sulfate Drugs 0.000 claims description 9
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 9
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 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 7
- FAPWYRCQGJNNSJ-UBKPKTQASA-L calcium D-pantothenic acid Chemical compound [Ca+2].OCC(C)(C)[C@@H](O)C(=O)NCCC([O-])=O.OCC(C)(C)[C@@H](O)C(=O)NCCC([O-])=O FAPWYRCQGJNNSJ-UBKPKTQASA-L 0.000 claims description 6
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000011592 zinc chloride Substances 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
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 30
- 239000011701 zinc Substances 0.000 abstract description 22
- 229910052725 zinc Inorganic materials 0.000 abstract description 21
- 210000001787 dendrite Anatomy 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 16
- 239000000654 additive Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 230000014759 maintenance of location Effects 0.000 description 10
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 8
- 238000000151 deposition Methods 0.000 description 8
- 230000008021 deposition Effects 0.000 description 8
- 238000000840 electrochemical analysis Methods 0.000 description 8
- 239000003365 glass fiber Substances 0.000 description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 description 4
- 125000000539 amino acid group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229960002079 calcium pantothenate Drugs 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- 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
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
-
- 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
- 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)
- Hybrid Cells (AREA)
Abstract
Electrolyte and aqueous zinc ion battery using the same. The electrolyte comprises water-soluble organic calcium salt and zinc salt. The invention can effectively relieve the problems of zinc dendrite, zinc corrosion and hydrogen evolution and gas production by improving the composition of the electrolyte of the water-based zinc ion battery, thereby obviously improving the multiplying power performance and the cycle performance of the battery.
Description
Technical Field
The invention relates to an aqueous zinc ion battery, in particular to an electrolyte thereof.
Background
The water-based Zinc Ion Battery (ZIBs) has wider application prospect in the aspects of comprehensive energy density, adaptation degree with water-based electrolyte, abundance of resources, safety and the like. This is because metallic zinc has a high theoretical capacity (820 mAhg -1) and a relatively low redox potential (-0.76 v vs. she), and is considered to be the most potential aqueous battery system because it can be better matched with aqueous electrolytes and is inexpensive. Although aqueous zinc ion batteries have many advantages, challenges are presented. First, zinc ions tend to deposit in dendritic form during electrodeposition to form zinc dendrites, which grow to a certain extent to exfoliate to form dead zinc, resulting in loss of active species, lower coulomb efficiency, and even puncture of the separator to cause internal shorting.
Disclosure of Invention
The invention aims to provide an electrolyte for an aqueous zinc ion battery, which can at least effectively inhibit zinc dendrite generation.
According to a first aspect of the present invention, there is provided an aqueous zinc-ion battery electrolyte comprising:
A water-soluble organic calcium salt selected from at least one of calcium folinate and calcium D-pantothenate, and having a concentration of 0.2-10g/L in the electrolyte;
Zinc salt, at least one selected from the group consisting of zinc sulfate, zinc chloride, zinc nitrate and zinc triflate, and the concentration thereof in the electrolyte is 0.5-8mol/L.
The aqueous zinc ion battery electrolyte according to the invention, the zinc salt is preferably zinc sulfate and/or zinc chloride.
The concentration of the water-soluble organic calcium salt in the aqueous zinc-ion battery electrolyte according to the invention is preferably 0.5-5g/L.
The concentration of the zinc salt of the aqueous zinc-ion battery electrolyte according to the invention is preferably 1-3mol/L.
According to another aspect of the present invention, there is also provided an aqueous zinc ion battery comprising the above electrolyte.
The invention can effectively relieve the problems of zinc dendrite, zinc corrosion and hydrogen evolution and gas production by improving the composition of the electrolyte of the water-based zinc ion battery, thereby obviously improving the multiplying power performance and the cycle performance of the battery. The excellent performance of the electrolyte can be explained by that the water-soluble organic calcium salt contains a large number of functional groups such as hydroxyl groups, amino groups and the like, and the functional groups have certain specific complexing capacity on zinc ions in the electrolyte, so that the uniform distribution of ion concentration and electric field near a zinc negative electrode can be induced, thereby effectively regulating and controlling the uniform deposition and stripping of the zinc ions on the surface of the zinc negative electrode and inhibiting the formation and growth of zinc dendrites. In addition, the water-soluble organic calcium salt is rich in nitrogen-containing and oxygen-containing functional groups, can form hydrogen bonds with water molecules to reduce the activity of free water in the electrolyte, and reduce electrochemical side reactions on the surface of the zinc cathode, so that the problems of zinc corrosion, passivation of the zinc cathode and the like are effectively solved.
The electrolyte provided by the invention is low in cost, green and efficient, can obviously improve the electrochemical performance and stability of the water-based zinc ion battery, and has great commercial application potential.
Drawings
FIG. 1 is a graph showing comparison of time-voltage curves of the symmetrical cells of example 2 and comparative example 1 according to the present invention at a current density of 1mAcm -2 and a discharge capacity of 1 mAh.
Fig. 2 (a) and fig. 2 (b) are morphology comparison diagrams of zinc deposition after 20 cycles of electrode cycle at a current density of 1mAcm -2 and a discharge capacity of 1mAh for the symmetrical cells of example 2 and comparative example 1, respectively: wherein FIG. 2 (a) is a graph of the deposition profile after cycling of a zinc foil without additives; FIG. 2 (b) is a graph of the deposition profile after zinc foil cycling with the addition of 2.5g/L calcium folinate additive.
FIG. 3 is a graph showing comparison of time-voltage curves of the symmetrical cells of example 2 and comparative example 1 according to the present invention at a current density of 5mAcm -2 and a discharge capacity of 2 mAh.
Detailed Description
The invention is described in further detail below in conjunction with the drawings, comparative examples and examples, but it should be understood by those skilled in the art that they are intended to illustrate and not limit the invention.
Comparative example 1
0.2Mol of zinc sulfate heptahydrate is dissolved in deionized water to prepare 100ml of electrolyte containing 2mol/L of zinc sulfate for standby. Adopting high-purity zinc foil as positive and negative electrodes respectively, and adopting glass fiber as a diaphragm to assemble 2025 type button water-based zinc ion symmetrical battery; and taking the hydrophilic carbon paper coated with manganese dioxide as an anode, taking zinc foil as a cathode, and taking glass fiber as a diaphragm to assemble the water-based zinc ion full battery. Test conditions for symmetrical battery performance: the current density is 1mAcm -2, the discharge capacity is 1mAhcm -2, the current density is 5mAcm -2, the discharge capacity is 2mAhcm -2, and the charge and discharge cycle is completed, and the magnitude of polarization voltage and the time of battery cycle are recorded; full cell performance test conditions: the current density was 1C (1c=308 mA/g), the number of cycles was 100, and the electrochemical test results thereof are shown in table 1. The cycle life of the water-based zinc ion symmetrical battery is 45 hours under the condition of 1mAcm -2, and the cycle life is 72 hours under the condition of 5mA cm -2; the capacity of the full cell at a current density of 1C was only 142mAhg -1 after 100 cycles and the capacity retention after 100 cycles was only 67%.
Example 1
Dissolving 0.05g of calcium folinate and 0.2mol of zinc sulfate heptahydrate in deionized water to prepare 100ml of electrolyte containing 2mol/L zinc sulfate and 0.5g/L calcium folinate for later use; the 2025 type button water-based zinc ion symmetrical battery is assembled by taking high-purity zinc foil as an anode and a cathode respectively and glass fiber as a diaphragm. And taking the hydrophilic carbon paper coated with manganese dioxide as an anode, taking zinc foil as a cathode, and taking glass fiber as a diaphragm to assemble the water-based zinc ion full battery. Test conditions for symmetrical battery performance: the current density is 1mA cm -2, the discharge capacity is 1mAh cm -2, the current density is 5mA cm -2, the discharge capacity is 2mAh cm -2, the charge and discharge cycle is completed, and the polarization voltage and the battery cycle time are recorded; full cell performance test conditions: the current density is 1C, the cycle number is 100, the electrochemical test result is shown in Table 1, the cycle life of the water-based zinc ion symmetrical battery is 722h at 1mA cm -2, and the cycle life is 290h at 5mA cm -2; the full cell still can provide 210mAhg -1 capacity after 100 circles of circulation at 1C, the coulombic efficiency is 97.5%, and the capacity retention rate after 100 circles of circulation reaches 72%.
Example 2
According to the method of example 1, except that the calcium folinate was made to have a mass of 0.25g during the formulation of the electrolyte, the final formulated solution was an electrolyte containing 2mol/L zinc sulfate and containing 2.5g/L calcium folinate additive. The electrochemical test results are shown in Table 1, the cycle life of the water-based zinc ion symmetrical battery is 940h at 1mA cm -2, and the cycle life is 360h at 5mA cm -2; the capacity of the full battery can still provide 284mAh/g after 100 circles of circulation at 1C, the coulombic efficiency is 99.2%, and the capacity retention rate after 100 circles of circulation reaches 92%.
Example 3
According to the method of example 1, except that the calcium folinate was made to have a mass of 0.5g during the formulation of the electrolyte, the final formulated solution was an electrolyte containing 2mol/L zinc sulfate and containing 5g/L calcium folinate additive. The electrochemical test results are shown in Table 1, the cycle life of the water-based zinc ion symmetrical battery is 850h at 1mA cm -2, and 320h at 5mA cm -2; the capacity of the full battery can still provide 282mAhg -1 after 100 circles of circulation at 1C, the coulombic efficiency is 98.3%, and the capacity retention rate after 100 circles of circulation reaches 72%.
Example 4
According to the method of example 2, except that 0.25g of calcium folinate was replaced by 0.25g of calcium D-pantothenate during the preparation of the electrolyte, the final prepared solution was an electrolyte containing 2mol/L zinc sulfate and containing 2.5g/L D g of calcium pantothenate additive. The electrochemical test results are shown in Table 1, the cycle life of the water-based zinc ion symmetrical battery is 850h at 1mA cm -2, and the cycle life is 660h at 5mA cm -2; the capacity of the full battery can still provide 282mAhg -1 after 100 circles of circulation at 1C, the coulombic efficiency is 99.1%, and the capacity retention rate after 100 circles of circulation reaches 91%.
Comparative example 2
0.2Mol of zinc trifluoromethane sulfonate is dissolved in deionized water to prepare 100ml of electrolyte containing 2mol/L of zinc trifluoromethane sulfonate for standby. Adopting high-purity zinc foil as positive and negative electrodes respectively, and adopting glass fiber as a diaphragm to assemble 2025 type button water-based zinc ion symmetrical battery; and taking the hydrophilic carbon paper coated with manganese dioxide as an anode, taking zinc foil as a cathode, and taking glass fiber as a diaphragm to assemble the water-based zinc ion full battery. Test conditions for symmetrical battery performance: the current density is 1mA cm -2, the discharge capacity is 1mAh cm -2, the current density is 5mA cm -2, and the discharge capacity is 2mAhcm -2, and the charge and discharge cycle is completed, and the magnitude of polarization voltage and the time of battery cycle are recorded; full cell performance test conditions: the current density was 1C (1c=308 mA/g), the number of cycles was 100, and the electrochemical test results thereof are shown in table 1. The cycle life of the water-based zinc ion symmetrical battery is 140h under the condition of 5mA cm -2, and the polarization voltage is 55mV; the full cell had a coulombic efficiency of 96.1% and a capacity retention of only 67% after 100 cycles at a current density of 1C.
Example 5
0.25G of calcium folinate and 0.2mol of zinc trifluoromethane sulfonate are dissolved in deionized water to prepare 100ml of electrolyte containing 2mol/L zinc trifluoromethane sulfonate and 2.5g/L calcium folinate for later use; the 2025 type button water-based zinc ion symmetrical battery is assembled by taking high-purity zinc foil as an anode and a cathode respectively and glass fiber as a diaphragm. And taking the hydrophilic carbon paper coated with manganese dioxide as an anode, taking zinc foil as a cathode, and taking glass fiber as a diaphragm to assemble the water-based zinc ion full battery. Test conditions for symmetrical battery performance: the current density is 5mAcm -2, the discharge capacity is 2mAhcm -2, the charge and discharge cycle is completed, and the magnitude of the polarization voltage and the time of the battery cycle are recorded; full cell performance test conditions: the current density was 1C and the number of cycles was 100. The electrochemical test results are shown in Table 1, and the cycle life of the water-based zinc ion symmetrical battery is 430 hours at 5 mA.cm -2; the capacity of the full battery can still provide capacity of 279mAhg -1 after 100 circles of circulation at 1C, the coulombic efficiency is 98.1 percent, and the capacity retention rate after 100 circles of circulation reaches 89 percent.
Example 6
According to the method of example 2, except that 0.25g of calcium folinate was replaced by 0.25g of calcium D-pantothenate during the preparation of the electrolyte, the final prepared solution was an electrolyte containing 2mol/L zinc triflate and containing 2.5g/L D of calcium pantothenate additive. The electrochemical test results are shown in Table 1, and the cycle life of the water-based zinc ion symmetrical battery is 520 hours at 5 mA.cm -2; the full cell still can provide 280mAhg -1 capacity after 100 circles of circulation at 1C, the coulombic efficiency is 98.7 percent, and the capacity retention rate after 100 circles of circulation reaches 89 percent.
Table 1 shows electrochemical performance parameters of the aqueous zinc ion symmetric cells and the full cells of comparative example 1, comparative example 2, and examples 1 to 6.
TABLE 1
* And (3) injection: the capacity retention refers to the retention after 100 cycles relative to the first cycle
FIG. 1 is a graph showing comparison of time-voltage curves of the symmetrical cells of example 2 and comparative example 1 according to the present invention at a current density of 1mAcm -2 and a discharge capacity of 1 mAh. Fig. 2 (a) and fig. 2 (b) are morphology comparison diagrams of zinc deposition after 20 cycles of electrode cycle at a current density of 1mAcm -2 and a discharge capacity of 1mAh for the symmetrical cells of example 2 and comparative example 1, respectively: wherein FIG. 2 (a) is a graph of the deposition profile after cycling of a zinc foil without additives; FIG. 2 (b) is a graph of the deposition profile after zinc foil cycling with the addition of 2.5g/L calcium folinate additive. FIG. 3 is a graph showing comparison of time-voltage curves of the symmetrical cells of example 2 and comparative example 1 according to the present invention at a current density of 5mAcm -2 and a discharge capacity of 2 mAh. As can be seen from table 1 and fig. 1-3: the additive can effectively improve the cycling stability of Zn symmetric batteries, induce zinc ions to be deposited uniformly, inhibit zinc dendrite formation, and finally improve the electrochemical performance of the water-based zinc ion batteries.
The organic calcium salt added in the electrolyte is rich in functional groups such as basic amino acid residues, carbonyl groups and carboxyl groups, the amino acid residues in the weakly acidic electrolyte can be in a positively charged state, and the amino acid residues can be preferentially adsorbed on the surface of zinc in the zinc deposition process, so that nucleation sites are formed, uniform deposition of zinc ions on the surface of a zinc negative electrode is promoted, and dendrite-free growth is realized; and oxygen-containing functional groups such as carbonyl and carboxyl with strong electronegativity can form hydrogen bonds with water molecules, adjust coordination environment around zinc ions, inhibit activity of the water molecules, thereby inhibiting hydrogen and oxygen evolution processes in the battery cycle process and reducing gas generation. The additive of the invention has the advantages of inorganic ions and organic functional group micromolecular additives, so that the zinc cathode can realize no dendrite growth and corrosion inhibition, thereby prolonging the cycle life of the battery.
Claims (5)
1. An aqueous zinc ion battery electrolyte comprising:
A water-soluble organic calcium salt selected from at least one of calcium folinate and calcium D-pantothenate, and having a concentration of 0.2-10g/L in the electrolyte;
Zinc salt, at least one selected from the group consisting of zinc sulfate, zinc chloride, zinc nitrate and zinc triflate, and the concentration thereof in the electrolyte is 0.5-8mol/L.
2. The aqueous zinc-ion battery electrolyte of claim 1, wherein the zinc salt is zinc sulfate and/or zinc chloride.
3. The aqueous zinc-ion battery electrolyte of claim 1, wherein the concentration of the water-soluble organic calcium salt is 0.5-5g/L.
4. The aqueous zinc-ion battery electrolyte of claim 1, wherein the concentration of the zinc salt is 1-3mol/L.
5. An aqueous zinc-ion battery comprising the electrolyte according to any one of claims 1 to 4.
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