CN117728047A - Double-salt-double-solvent electrolyte for high-reversibility water-based zinc ion battery and preparation method thereof - Google Patents
Double-salt-double-solvent electrolyte for high-reversibility water-based zinc ion battery and preparation method thereof Download PDFInfo
- Publication number
- CN117728047A CN117728047A CN202311729547.0A CN202311729547A CN117728047A CN 117728047 A CN117728047 A CN 117728047A CN 202311729547 A CN202311729547 A CN 202311729547A CN 117728047 A CN117728047 A CN 117728047A
- Authority
- CN
- China
- Prior art keywords
- double
- zinc
- salt
- electrolyte
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 126
- 239000002904 solvent Substances 0.000 title claims abstract description 107
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 230000002441 reversible effect Effects 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- 150000003751 zinc Chemical class 0.000 claims abstract description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- -1 zinc tetrafluoroborate Chemical compound 0.000 claims description 18
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 16
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 10
- 229960000314 zinc acetate Drugs 0.000 claims description 10
- 239000004246 zinc acetate Substances 0.000 claims description 10
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [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 9
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims description 7
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- 229920000767 polyaniline Polymers 0.000 claims description 6
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical group [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical group COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 claims description 2
- 229940057499 anhydrous zinc acetate Drugs 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- 239000007774 positive electrode material Substances 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 2
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 57
- 239000011701 zinc Substances 0.000 abstract description 56
- 229910052725 zinc Inorganic materials 0.000 abstract description 54
- 229910052751 metal Inorganic materials 0.000 abstract description 25
- 239000002184 metal Substances 0.000 abstract description 25
- 238000005260 corrosion Methods 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 10
- 230000008021 deposition Effects 0.000 abstract description 2
- 238000013461 design Methods 0.000 abstract description 2
- ARZRWOQKELGYTN-UHFFFAOYSA-N [V].[Mn] Chemical compound [V].[Mn] ARZRWOQKELGYTN-UHFFFAOYSA-N 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 24
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 24
- 230000001351 cycling effect Effects 0.000 description 20
- 238000012360 testing method Methods 0.000 description 13
- 238000010586 diagram Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- HZONRRHNQILCNO-UHFFFAOYSA-N 1-methyl-2h-pyridine Chemical compound CN1CC=CC=C1 HZONRRHNQILCNO-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 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
- Primary Cells (AREA)
Abstract
The invention discloses a double-salt-double-solvent electrolyte for a high reversible water system zinc ion battery and a preparation method thereof. Double salt-double solvent electrolyte based battery with 60% deep zinc negative electrode discharge (DOD) Zn ) The lower has a high zinc negative average Coulombic Efficiency (CE) of 99.8%. The design of the double-salt-double-solvent electrolyte solves the problem of zinc corrosion and slow zinc deposition kinetics in the traditional water system single-component zinc salt electrolyte, and can realize the high reversibility of the 'stripping-deposition' process of the zinc metal cathode. The application of the double-salt-double-solvent electrolyte can effectively improve the comprehensive electrochemical performance of the water-based zinc ion battery based on vanadium-manganese-based oxide or organic positive electrode.
Description
Technical Field
The invention relates to a water-based zinc metal battery electrolyte and a preparation method thereof, in particular to a double-salt-double-solvent electrolyte for a high-reversibility water-based zinc ion battery and a preparation method thereof.
Background
Safe, efficient, green and sustainable energy storage system and technology are research hotspots in the current energy field, especially large-scale power grid storage requiring higher safetyCan be used for equipment. Among the many energy storage batteries currently, lithium ion batteries occupy a major portion of the market due to their high energy density and operating voltage. However, lithium ion batteries are increasingly costly due to shortage of lithium sources, and their commonly used organic electrode solutions are very prone to cause serious accidents under the condition of thermal runaway, and cause losses to the environment and personal and property safety. To solve this problem, researchers have replaced current organic electrolytes with safer aqueous electrolytes to develop new generation energy storage systems and technologies. In many aqueous ion battery systems, zinc metal has high abundance, low cost, and high theoretical capacity (820 mAh g -1 ) The advantages of lower oxidation-reduction potential (-0.762 vs. SHE) and the like make the field of the water-based zinc ion battery gradually become a focus of attention in scientific research and industry.
However, a significant challenge in limiting the advent of commercial aqueous zinc metal or zinc ion batteries is that the availability of zinc metal anodes and their reversibility of the electrochemical "strip-deposit" process are too low, mainly due to the inability of zinc ion batteries to undergo deep charge-discharge cycles and short-circuit failure due to factors such as zinc anode corrosion and zinc dendrite growth in aqueous electrolyte environments. In recent years, various researches show that the use of an electrolyte to regulate the interface between zinc and the electrolyte to reduce corrosion of a zinc cathode and inhibit zinc dendrites is a very effective strategy, because changing the environment of the interface electrolyte affects the reactivity of water and the mass transfer mode of zinc ions. Studies have shown that water molecule activity can be limited to inhibit corrosion by adding a non-aqueous solvent to the electrolyte. However, such non-aqueous solvents form multi-solvent systems in combination with water that reduce the electrolyte conductivity and slow the charge transfer kinetics. Considering that the anionic solvation process of different electrolyte salts can affect interfacial electrolyte composition and charge transfer kinetics, charge transport in an electrolyte can be facilitated by electrolyte salt multiplexing in a multiplexed solvent. The strategy can solve the problem of zinc cathode corrosion caused by the traditional water-based electrolyte and the problem of slow charge transfer dynamics of the multi-element solvent.
Disclosure of Invention
The invention aims to: the invention aims to provide a double-salt-double-solvent electrolyte for a water-based zinc ion battery, which is used for improving the reversibility of an electrochemical stripping-depositing process of a zinc cathode; another object of the present invention is to provide a method for preparing the double salt-double solvent electrolyte.
The technical scheme is as follows: the double salt-double solvent electrolyte for the high reversible water system zinc ion battery is prepared from water and ether mixed solvent, wherein the electrolyte is zinc acetate plus zinc tetrafluoroborate or zinc trifluoromethane sulfonate.
Preferably, the molar concentration of the zinc tetrafluoroborate or zinc trifluoromethane sulfonate is 0.5-2 mol/kg, the molar concentration range of zinc acetate is 0.1-0.5 mol/kg, and the molar ratio of water to ether is 1-120: 1.
preferably, the ether solvent is ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether or tetraethylene glycol dimethyl ether.
The invention relates to a preparation and design method of a double-salt-double-solvent electrolyte capable of realizing a high reversible zinc cathode, which comprises the following steps:
(1) Dissolving zinc tetrafluoroborate or zinc trifluoromethane sulfonate into a mixed solvent of water and ether to form a single-salt-double-solvent electrolyte;
(2) Zinc acetate salt is dissolved in a single salt-double solvent electrolyte to form a double salt-double solvent electrolyte.
Preferably, the zinc tetrafluoroborate salt in the step (1) is zinc tetrafluoroborate hydrate, and the purity is more than or equal to 99%; the zinc salt of the trifluoromethyl sulfonate is anhydrous zinc triflate, and the purity is more than or equal to 98%; the water is deionized water; the purity of the ether solvent is more than or equal to 99 percent.
Preferably, the optimal ratio of the solvent and the optimal concentration configuration of the electrolyte are obtained through zinc metal corrosion resistance and zinc cathode reversibility tests, wherein the zinc metal corrosion resistance is an electrolyte-immersed zinc metal experiment; the reversibility test of the zinc cathode is a zinc-copper battery cycle test under high discharge depth, zinc and copper are high-purity metal foils, and the purity is more than or equal to 99.99%.
Preferably, the zinc acetate salt is anhydrous zinc acetate or zinc acetate hydrate, and the purity is more than or equal to 99%; the molar concentration of the zinc acetate is less than the molar concentration of zinc tetrafluoroborate or zinc trifluoromethane sulfonate.
The prepared double-salt-double-solvent electrolyte not only can improve the reversibility of a zinc cathode, but also can be suitable for anodes of various water-based zinc ion batteries.
The beneficial effects are that: compared with the existing electrolyte type, the invention has the following remarkable advantages: (1) The double salt-double solvent electrolyte inhibits the corrosiveness of the zinc salt electrolyte of a single water solvent under low concentration, and simultaneously solves the slow zinc deposition kinetics problem of a single zinc salt; (2) The double salt-double solvent electrolyte has a depth of discharge (DOD) of 60% of a high zinc negative electrode Zn ) Zinc negative electrode average Coulombic Efficiency (CE) maintained up to 99.8%; (3) The prepared double-salt-double-solvent electrolyte can be applied to various organic polymers and inorganic vanadium-based and manganese-based oxide anode materials of a water-based zinc ion battery.
Drawings
FIG. 1 is a diagram of zinc metal after immersion in a single salt-single solvent electrolyte as a control obtained in example 1;
FIG. 2 is a graphical representation of zinc foil after immersion in the single salt-double solvent electrolyte from example 1;
FIG. 3 is a graphical representation of zinc foil after immersion in the double salt-double solvent electrolyte from example 1;
FIG. 4 is a graph showing the cycling performance of the zinc-copper cell of the control single salt-single solvent electrolyte obtained in example 1 at 20% depth of discharge;
FIG. 5 is a graph showing the cycling performance of the single salt-bi-solvent electrolyte zinc-copper cell obtained in example 1 at 20% depth of discharge;
FIG. 6 is a graph showing the cycling performance of the zinc-copper cell of the double salt-double solvent electrolyte obtained in example 1 at 20% depth of discharge;
FIG. 7 is a graph showing the cycling performance of the single salt-bi-solvent electrolyte zinc-copper cell obtained in example 1 at 60% depth of discharge;
FIG. 8 is a graph showing the cycling performance of the zinc-copper cell of the double salt-double solvent electrolyte obtained in example 1 at 60% depth of discharge;
fig. 9 is the performance of Zn-PANI cells for different electrolytes in example 1;
FIG. 10 shows Zn-VO of different electrolytes in example 1 2 Performance of the battery;
FIG. 11 shows the Zn-MnO of the different electrolytes in example 1 2 Performance of the battery.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
Example 1
(1) Preparing zinc tetrafluoroborate electrolyte with the molar concentration of 1mol/kg by taking water/tetraethyleneglycol dimethyl ether mixed solution as a solvent, wherein the molar ratio of water to tetraethyleneglycol dimethyl ether is 40:1 to obtain single-salt-double-solvent electrolyte, and preparing zinc tetrafluoroborate electrolyte with the molar concentration of 1mol/kg by taking pure water as a solvent for experimental comparison to obtain single-salt-single-solvent electrolyte.
(2) Zinc acetate with the molar concentration of 0.2mol/kg is added into the single-salt-double-solvent electrolyte in the step (1) to be dissolved so as to obtain the double-salt-double-solvent electrolyte.
(3) The single salt-double solvent electrolyte obtained in the step (1), the control single salt-single solvent electrolyte, and the double salt-double solvent electrolyte obtained in the step (2) were subjected to corrosion resistance of zinc metal and reversibility test of zinc anode, the thickness of the foil of zinc and copper metal was 30 μm, and the cycle performance of the zinc-copper battery of the above electrolyte was tested at 20% and 60% anode depth of discharge.
(4) A graphical representation of a zinc metal immersed in a control single salt-single solvent electrolyte for 48 hours is shown in fig. 1; a physical diagram of the zinc metal immersed in the single-salt-double-solvent electrolyte for 48 hours is shown in fig. 2; a physical diagram of the double salt-double solvent electrolyte immersed in zinc metal for 48 hours is shown in fig. 3.
(5) The cycling performance of the control single salt-single solvent electrolyte zinc-copper cell was shown in fig. 4 with an average CE of about 95.174% for 7 cycles under the 20% zinc negative electrode depth of discharge test; the cycling performance of the zinc-copper cell of the single salt-bi-solvent electrolyte is shown in fig. 5, with an average CE of about 99.596% for 250 cycles; the cycling performance of the zinc-copper cell with the double salt-double solvent electrolyte is shown in fig. 6, with an average CE of about 99.838% for 250 cycles; the cycling performance of the zinc-copper cell of the single salt-bi-solvent electrolyte under the 60% zinc negative electrode depth of discharge test is shown in fig. 7, with an average CE of about 99.09% for 20 cycles; the cycling performance of the zinc-copper cell of the double salt-double solvent electrolyte is shown in fig. 8, with an average CE of about 99.80% over 150 cycles.
Example 2
(1) Preparing zinc tetrafluoroborate electrolyte with the molar concentration of 1mol/kg by taking water/tetraethyleneglycol dimethyl ether mixed solution as a solvent, wherein the molar ratio of water to tetraethyleneglycol dimethyl ether is 80:1 to obtain single-salt-double-solvent electrolyte, and preparing zinc tetrafluoroborate electrolyte with the molar concentration of 1mol/kg by taking pure water as a solvent for experimental comparison to obtain single-salt-single-solvent electrolyte.
(2) Zinc acetate with the molar concentration of 0.3mol/kg is added into the single-salt-double-solvent electrolyte in the step (1) to be dissolved so as to obtain the double-salt-double-solvent electrolyte.
(3) The single salt-double solvent electrolyte obtained in the step (1), the control single salt-single solvent electrolyte, and the double salt-double solvent electrolyte obtained in the step (2) were subjected to corrosion resistance of zinc metal and reversibility test of zinc anode, the thickness of the foil of zinc and copper metal was 30 μm, and the cycle performance of the zinc-copper battery of the above electrolyte was tested at 20% and 60% anode depth of discharge.
(4) A physical diagram of zinc metal immersed in a control single salt-single solvent electrolyte for 48 hours is similar to fig. 1; a physical diagram of zinc metal immersed in a single salt-double solvent electrolyte for 48 hours is similar to fig. 2; the physical diagram of the double salt-double solvent electrolyte immersed in zinc metal for 48 hours is similar to that of fig. 3.
(5) The cycling performance of the control single salt-single solvent electrolyte zinc-copper cell was shown in fig. 4 with an average CE of about 95.174% for 7 cycles under the 20% zinc negative electrode depth of discharge test; the cycling performance of the zinc-copper cell of the single salt-bi-solvent electrolyte was similar to that of fig. 5, with an average CE of about 99.597% for 250 cycles; the cycling performance of the zinc-copper cell of the double salt-double solvent electrolyte was similar to that of fig. 6, with an average CE of about 99.812% for 250 cycles; the cycling performance of the single salt-bi-solvent electrolyte zinc-copper cell was similar to that of fig. 7 with an average CE of about 98.737% for 18 cycles under the 60% zinc negative electrode depth of discharge test; the cycling performance of the zinc-copper cell of the double salt-double solvent electrolyte was similar to that of fig. 8, with an average CE of about 99.788% for 100 cycles.
Example 3
(1) Preparing zinc tetrafluoroborate electrolyte with a molar concentration of 1.5mol/kg by taking water/tetraethyleneglycol dimethyl ether mixed solution as a solvent, wherein the molar ratio of water to tetraethyleneglycol dimethyl ether is 40:1 to obtain single-salt-double-solvent electrolyte, and preparing zinc tetrafluoroborate electrolyte with a molar concentration of 1.5mol/kg by taking pure water as a solvent for experimental comparison to obtain single-salt-single-solvent electrolyte.
(2) Zinc acetate with the molar concentration of 0.2mol/kg is added into the single-salt-double-solvent electrolyte in the step (1) to be dissolved so as to obtain the double-salt-double-solvent electrolyte.
(3) The single salt-double solvent electrolyte obtained in the step (1), the control single salt-single solvent electrolyte, and the double salt-double solvent electrolyte obtained in the step (2) were subjected to corrosion resistance of zinc metal and reversibility test of zinc anode, the thickness of the foil of zinc and copper metal was 30 μm, and the cycle performance of the zinc-copper battery of the above electrolyte was tested at 20% and 60% anode depth of discharge.
(4) A photograph of zinc metal immersed in a control single salt-single solvent electrolyte for 48 hours is similar to fig. 1; a photograph of zinc metal immersed in a single salt-double solvent electrolyte for 48 hours is similar to fig. 2; a photograph of a double salt-double solvent electrolyte immersed in zinc metal for 48 hours is similar to fig. 3.
(5) The cycling performance of the control single salt-single solvent electrolyte zinc-copper cell was similar to that of fig. 4 with an average CE of about 94.764% for the 4 cycles under the 20% zinc negative depth of discharge test; the cycling performance of the zinc-copper cell of the single salt-bi-solvent electrolyte was similar to that of fig. 5, with an average CE of about 99.582% for 200 cycles; the cycling performance of the zinc-copper cell of the double salt-double solvent electrolyte was similar to that of fig. 6, with an average CE of about 99.796% for 200 cycles; the cycling performance of the single salt-bi-solvent electrolyte zinc-copper cell was similar to that of fig. 7 with an average CE of about 98.74% for 25 cycles under the 60% zinc negative depth of discharge test; the cycling performance of the zinc-copper cell of the double salt-double solvent electrolyte was similar to that of fig. 8, with an average CE of about 99.793% for 100 cycles.
Battery application examples
An aqueous zinc ion battery was assembled, and the electrolyte prepared in example 1 was used as the electrolyte; the positive electrode material adopts three materials respectively: polyaniline (PANI), vanadium dioxide (VO 2 ) Manganese dioxide (MnO) 2 ). When preparing the positive electrode, mixing an active substance, a conductive agent ketjen black and a binder Polytetrafluoroethylene (PTFE) according to a mass ratio of 7:2:1, adding N-methyl pyridine Luo Wantong (NMP) for grinding to obtain uniform slurry, scraping the slurry onto a stainless steel net and drying in a drying box at 60 ℃ to obtain the positive electrode with a load mass of about 7-10 mg cm -2 . The negative electrode had a thickness of 10 μm and a density of 13mg cm -2 The zinc foil and the diaphragm are made of glass fiber, and Zn-PANI and Zn-VO of different electrolytes are assembled respectively 2 、Zn-MnO 2 The CR2032 button battery of the formula (I) is subjected to constant current charge and discharge test.
Zn-PANI battery with double salt-double solvent as electrolyte has current density of 0.5. 0.5A g -1 The performance of 400 cycles below is shown in figure 9. The triangular pattern is the cell performance of a single salt-single solvent electrolyte, the circular pattern is the cell performance of a single salt-double solvent electrolyte, and the solid square pattern is the cell performance of a double salt-double solvent electrolyte. In addition, zn-VO using double salt-double solvent as electrolyte 2 The current density of the battery is 0.5A g -1 The performance of 100 cycles is shown in FIG. 10, in which Zn-MnO was treated with a double salt-double solvent as an electrolyte 2 The current density of the battery is 0.1A g -1 The performance of the next 60 cycles is shown in figure 11. From the comparison of the cycle performance results, the battery using the double salt-double solvent as the electrolyte has higher capacity and better stability, which benefits from the high-efficiency improvement of the stability of the double salt-double solvent electrolyte to the zinc negative electrode and the 'stripping-deposition' dynamics of the zinc negative electrode.
Claims (10)
1. A double salt-double solvent electrolyte for a high reversible water system zinc ion battery is characterized in that the solvent in the electrolyte is a mixed solvent of water and ether, and the electrolyte is zinc acetate plus zinc tetrafluoroborate or zinc trifluoromethane sulfonate.
2. The double-salt-double-solvent electrolyte for a highly reversible aqueous zinc ion battery according to claim 1, wherein the molar concentration of the zinc tetrafluoroborate or zinc trifluoromethane sulfonate is 0.5 to 2mol/kg.
3. The double salt-double solvent electrolyte for a highly reversible aqueous zinc ion battery according to claim 1, wherein the molar concentration of zinc acetate is in the range of 0.1 to 0.5mol/kg.
4. The double salt-double solvent electrolyte for a highly reversible aqueous zinc-ion battery according to claim 1, wherein the molar ratio of water to ether is 1 to 120:1.
5. the double-salt-double-solvent electrolyte for a highly reversible aqueous zinc-ion battery according to claim 1, wherein the ether solvent is ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether or tetraethylene glycol dimethyl ether.
6. The double-salt-double-solvent electrolyte for a high-reversibility-ratio aqueous zinc ion battery according to claim 1, wherein the zinc tetrafluoroborate salt is zinc tetrafluoroborate hydrate with purity not less than 99%; the zinc salt of the trifluoromethyl sulfonate is anhydrous zinc triflate, and the purity is more than or equal to 98%; the zinc acetate is anhydrous zinc acetate or zinc acetate hydrate, and the purity is more than or equal to 99%.
7. The double-salt-double-solvent electrolyte for a high-reversible aqueous zinc-ion battery according to claim 1, wherein the water is deionized water, and the ether solvent purity is not less than 99%.
8. A method for preparing a double salt-double solvent electrolyte for a high reversible aqueous zinc ion battery according to any one of claims 1 to 7, comprising the steps of:
(1) Dissolving zinc tetrafluoroborate or zinc trifluoromethane sulfonate into a mixed solvent of water and ether to form a single-salt-double-solvent electrolyte;
(2) Zinc acetate is dissolved in a single salt-double solvent electrolyte to form a double salt-double solvent electrolyte.
9. An aqueous zinc ion battery comprising a double salt-double solvent electrolyte according to any one of claims 1 to 7.
10. The aqueous zinc-ion battery of claim 9, wherein the positive electrode material is polyaniline, vanadium dioxide, or manganese dioxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311729547.0A CN117728047A (en) | 2023-12-15 | 2023-12-15 | Double-salt-double-solvent electrolyte for high-reversibility water-based zinc ion battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311729547.0A CN117728047A (en) | 2023-12-15 | 2023-12-15 | Double-salt-double-solvent electrolyte for high-reversibility water-based zinc ion battery and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117728047A true CN117728047A (en) | 2024-03-19 |
Family
ID=90208281
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311729547.0A Pending CN117728047A (en) | 2023-12-15 | 2023-12-15 | Double-salt-double-solvent electrolyte for high-reversibility water-based zinc ion battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117728047A (en) |
-
2023
- 2023-12-15 CN CN202311729547.0A patent/CN117728047A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ma et al. | Progress and perspective of aqueous zinc-ion battery | |
| CN113937341A (en) | Metal zinc secondary battery | |
| CN113422048B (en) | Preparation method and application of anode material of water-based zinc ion battery | |
| CN114551854B (en) | High-energy density and long-cycle-life aqueous zinc-based secondary battery | |
| CN112635698B (en) | Negative pole piece of zinc secondary battery and preparation method and application thereof | |
| CN104064824A (en) | Water system rechargeable battery | |
| CN114204119A (en) | Lithium-sulfur battery electrolyte containing mixed lithium salt of low-polarity ethers | |
| CN102315481A (en) | High specific energy lithium-rich multi-element lithium ion battery and preparation method thereof | |
| CN114530632A (en) | Lithium ion battery electrolyte and lithium ion battery | |
| WO2023185944A1 (en) | Electrolyte system free of free solvent molecules, preparation method therefor, and application thereof | |
| CN112952212A (en) | Aqueous manganese dioxide-metal secondary battery | |
| CN116826193A (en) | Electrolyte additive for aqueous zinc ion secondary battery and battery thereof | |
| CN116111208A (en) | Aqueous zinc ion battery electrolyte and aqueous zinc ion battery containing same | |
| CN116799300B (en) | High-voltage electrolyte suitable for quick-charging lithium battery and lithium battery | |
| CN115084497A (en) | Preparation method and application of transition metal embedded layered vanadium oxide interlayer material | |
| CN117728047A (en) | Double-salt-double-solvent electrolyte for high-reversibility water-based zinc ion battery and preparation method thereof | |
| CN115536066B (en) | Preparation method and application of ammonium vanadate nanomaterial with ammonium ion part removed in advance | |
| CN115663105B (en) | Film-protected three-dimensional porous zinc anode and preparation method and application thereof | |
| CN115911592B (en) | Zinc ion battery electrolyte containing carbon dots and preparation method and application thereof | |
| CN118156612A (en) | Electrolyte for improving electrochemical performance of oxide layered anode and application of electrolyte in sodium ion battery | |
| CN115911594A (en) | High-energy-density aqueous zinc-based double-halogen battery | |
| CN115966772A (en) | Novel amide electrolyte for lithium battery and preparation method thereof | |
| CN116936957A (en) | Low-temperature-resistant water-based metal ion electrolyte and metal ion battery | |
| CN118782882A (en) | Tin metal battery based on organic system | |
| CN117594788A (en) | Zinc-iodine battery using bromide ion as exciting agent and Ni-Fe-I LDH nanoflower as electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |