CN116565346A - Electrolyte for water-based zinc-based battery and preparation and application thereof - Google Patents
Electrolyte for water-based zinc-based battery and preparation and application thereof Download PDFInfo
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- CN116565346A CN116565346A CN202310627478.6A CN202310627478A CN116565346A CN 116565346 A CN116565346 A CN 116565346A CN 202310627478 A CN202310627478 A CN 202310627478A CN 116565346 A CN116565346 A CN 116565346A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 97
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000011701 zinc Substances 0.000 title claims abstract description 47
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 150000001413 amino acids Chemical class 0.000 claims abstract description 38
- 150000003751 zinc Chemical class 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 15
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 37
- 235000001014 amino acid Nutrition 0.000 claims description 37
- RHGKLRLOHDJJDR-BYPYZUCNSA-N L-citrulline Chemical compound NC(=O)NCCC[C@H]([NH3+])C([O-])=O RHGKLRLOHDJJDR-BYPYZUCNSA-N 0.000 claims description 32
- RHGKLRLOHDJJDR-UHFFFAOYSA-N Ndelta-carbamoyl-DL-ornithine Natural products OC(=O)C(N)CCCNC(N)=O RHGKLRLOHDJJDR-UHFFFAOYSA-N 0.000 claims description 32
- 229960002173 citrulline Drugs 0.000 claims description 32
- 235000013477 citrulline Nutrition 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 18
- 229960001763 zinc sulfate Drugs 0.000 claims description 18
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 18
- 239000003365 glass fiber Substances 0.000 claims description 15
- 229920000767 polyaniline Polymers 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 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 8
- 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
- 238000000034 method Methods 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- -1 zinc tetrafluoroborate Chemical compound 0.000 claims description 3
- LDCYZAJDBXYCGN-VIFPVBQESA-N 5-hydroxy-L-tryptophan Chemical compound C1=C(O)C=C2C(C[C@H](N)C(O)=O)=CNC2=C1 LDCYZAJDBXYCGN-VIFPVBQESA-N 0.000 claims description 2
- 229940000681 5-hydroxytryptophan Drugs 0.000 claims description 2
- LCWXJXMHJVIJFK-UHFFFAOYSA-N Hydroxylysine Natural products NCC(O)CC(N)CC(O)=O LCWXJXMHJVIJFK-UHFFFAOYSA-N 0.000 claims description 2
- PMMYEEVYMWASQN-DMTCNVIQSA-N Hydroxyproline Chemical compound O[C@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-DMTCNVIQSA-N 0.000 claims description 2
- AHLPHDHHMVZTML-BYPYZUCNSA-N L-Ornithine Chemical compound NCCC[C@H](N)C(O)=O AHLPHDHHMVZTML-BYPYZUCNSA-N 0.000 claims description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 2
- FFFHZYDWPBMWHY-VKHMYHEASA-N L-homocysteine Chemical compound OC(=O)[C@@H](N)CCS FFFHZYDWPBMWHY-VKHMYHEASA-N 0.000 claims description 2
- AHLPHDHHMVZTML-UHFFFAOYSA-N Orn-delta-NH2 Natural products NCCCC(N)C(O)=O AHLPHDHHMVZTML-UHFFFAOYSA-N 0.000 claims description 2
- UTJLXEIPEHZYQJ-UHFFFAOYSA-N Ornithine Natural products OC(=O)C(C)CCCN UTJLXEIPEHZYQJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000004279 alanine Nutrition 0.000 claims description 2
- YSMODUONRAFBET-UHFFFAOYSA-N delta-DL-hydroxylysine Natural products NCC(O)CCC(N)C(O)=O YSMODUONRAFBET-UHFFFAOYSA-N 0.000 claims description 2
- PMMYEEVYMWASQN-UHFFFAOYSA-N dl-hydroxyproline Natural products OC1C[NH2+]C(C([O-])=O)C1 PMMYEEVYMWASQN-UHFFFAOYSA-N 0.000 claims description 2
- YSMODUONRAFBET-UHNVWZDZSA-N erythro-5-hydroxy-L-lysine Chemical compound NC[C@H](O)CC[C@H](N)C(O)=O YSMODUONRAFBET-UHNVWZDZSA-N 0.000 claims description 2
- QJHBJHUKURJDLG-UHFFFAOYSA-N hydroxy-L-lysine Natural products NCCCCC(NO)C(O)=O QJHBJHUKURJDLG-UHFFFAOYSA-N 0.000 claims description 2
- 229960002591 hydroxyproline Drugs 0.000 claims description 2
- 229960003104 ornithine Drugs 0.000 claims description 2
- LDCYZAJDBXYCGN-UHFFFAOYSA-N oxitriptan Natural products C1=C(O)C=C2C(CC(N)C(O)=O)=CNC2=C1 LDCYZAJDBXYCGN-UHFFFAOYSA-N 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- FGMPLJWBKKVCDB-UHFFFAOYSA-N trans-L-hydroxy-proline Natural products ON1CCCC1C(O)=O FGMPLJWBKKVCDB-UHFFFAOYSA-N 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims 1
- 210000004027 cell Anatomy 0.000 description 46
- 238000012360 testing method Methods 0.000 description 25
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical group O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 24
- 239000000654 additive Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 16
- 230000000996 additive effect Effects 0.000 description 15
- 238000004090 dissolution Methods 0.000 description 9
- 210000001787 dendrite Anatomy 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000008021 deposition Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000007614 solvation Methods 0.000 description 3
- 208000032953 Device battery issue Diseases 0.000 description 2
- 230000022131 cell cycle Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 241000662429 Fenerbahce Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000036963 noncompetitive effect Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- 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
Abstract
The invention discloses an electrolyte for a water-based zinc-based battery and preparation and application thereof, wherein the electrolyte comprises non-coding amino acid, zinc salt and solvent, and can be used for the water-based zinc-based battery to improve the cycle performance of the zinc-based battery.
Description
Technical Field
The invention belongs to the technical field of water-based zinc ion batteries, and particularly relates to a novel high-performance electrolyte for a water-based zinc-based battery, a preparation method and application thereof, and the water-based zinc ion battery.
Background
The growing demand for energy and the increasingly depleted demand for fossil fuel resources seek sustainable energy alternatives, such as renewable energy and sustainable energy conversion/storage technologies. Although renewable energy sources including hydropower, wind energy, solar energy and tides have been widely developed as important clean energy sources in the past few decades, their discontinuous, unstable and uncontrollable power generation characteristics make them difficult to directly utilize. Among the currently available battery systems, lithium Ion Batteries (LIBs) have long been the most attractive and widely used electrical energy storage systems due to their long cycle life and desirable gravimetric energy density. Although the commercialization of LIB brings great convenience to us, the availability and price of lithium and cobalt resources and the safety risks posed by the flammability of organic electrolytes make it non-competitive in large-scale applications.
In recent years, aqueous Zinc Ion Batteries (AZIBs) have come into the line of sight of researchers due to their inherent advantages. Since zinc is abundant in reserves and zinc has a high theoretical capacity (820 mAh.g -1 ) And lower redox potential (-0.763 v vs. she), and nonflammable and high ionic conductivity (1S cm) of aqueous electrolytes -1 ) AZIBs have been considered as promising candidates for large-scale energy storage applications following LIB. Despite these advantages, AZIBs still face various adverse bottlenecks such as dendrite growth, corrosion, hydrogen Evolution Reaction (HER) and byproducts. Zinc anodes are less reversible due to dendrite growth, and on the other hand, hydrogen evolution reactions and accompanying byproducts (e.g., zn 4 SO 4 (OH) 6 ·xH 2 O) will deteriorate the cycle stability, resulting in poor cycle stability and low plating/stripping Coulombic Efficiency (CE), which prevent large-scale implementation of AZIBs. Thus, tuning the deposition orientation and solvation structure of zinc is essential to achieve stable and safe energy storage.
To date, a number of strategies have been proposed to alleviate or inhibit zinc dendrites and side reactions, such as introducing protective layers on the surface of zinc anodes, controlling the crystal orientation of zinc deposition, modifying current collectors, optimizing the internal structure of zinc anodes, membrane optimization, alloying zinc anodes with other chemically inert metals, utilizing zinc-free metal anode "rocking chair" cells and optimizing electrolytes, and the like. Among these strategies, electrolyte engineering has been of great interest due to its ease of preparation and cost effectiveness, mainly involving changing electrolyte composition, mixing some additives, and developing solid electrolytes. Among them, the use of additives is considered one of the most promising methods for its convenience, efficiency and cost effectiveness. There remains a need to develop a high performance electrolyte additive that has the ability to inhibit interfacial side reactions and to inhibit dendrite growth.
Disclosure of Invention
The invention provides a novel high-performance electrolyte for a water-based zinc-based battery and a preparation method thereof, aiming at the problems existing in the prior art. The invention aims to inhibit side reactions such as dendrite growth, corrosion and the like, improve the electrochemical performance of the battery and prolong the service life of the battery.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
in a first aspect, the invention provides a novel high-performance electrolyte, which comprises non-coded amino acid, zinc salt and solvent, can be used for a water-based zinc ion battery, and improves the cycle performance of the zinc ion battery.
Preferably, the non-coding amino acid is citrulline, which has good water solubility and excellent practical effect.
In other embodiments, the non-coding amino acid may be one or more selected from hydroxyproline, hydroxylysine, ornithine, homocysteine, alanine sulfonate, and 5-hydroxytryptophan.
Preferably, the zinc salt is zinc sulfate or zinc trifluoromethane sulfonate.
In other embodiments, the zinc salt may be one or more selected from zinc chloride, zinc tetrafluoroborate and zinc perchlorate, and the solvent is deionized water.
Preferably, the concentration of the non-coding amino acid is 0.1-100 g.L -1 。
Preferably, the concentration of the water-based zinc salt electrolyte is 1-3mol.L -1 。
In a second aspect, the invention provides a preparation method of a novel high-performance electrolyte, wherein zinc salt is dissolved in deionized water, and the water-based zinc salt electrolyte is obtained by stirring to completely dissolve the zinc salt; and adding non-coding amino acid into the water-based zinc salt electrolyte, and stirring and dissolving to obtain the novel high-performance electrolyte.
Preferably, the concentration of the water-based zinc salt electrolyte is 1 to 3mol·L -1 Stirring time is 0.5-12 h, and stirring temperature is 20-80 ℃.
Preferably, the concentration of non-coded amino acid in the novel high-performance electrolyte is 0.1-100 g.L -1 Stirring time is 1-24 h, and stirring temperature is 20-80 ℃.
In a third aspect, there is provided an aqueous zinc-ion battery comprising an electrolyte according to any one of claims 1-5; when the water-based zinc ion battery is formed into a Zn symmetric battery, the current density is 0.1-40 mA.cm -2 The discharge capacity is 0.1-10 mAh cm -2 Can be circulated for 200 to 5000 hours.
Also provided is an aqueous zinc-ion battery comprising the electrolyte according to any one of claims 1-5; when the water-based zinc ion battery is formed into a Zn-PANI full battery, the current density is 0.1-5 A.g -1 Can be cycled for 100 to 4000 cycles.
In a fourth aspect, the invention also provides a Zn symmetric battery, which is assembled by using zinc metal as an anode and a cathode, glass fiber as a diaphragm and the novel high-performance electrolyte as in any one of claims 1-5 as electrolyte, and is used for improving the cycle performance of the symmetric battery.
The invention also provides a Zn PANI full battery which is assembled by adopting zinc metal as a negative electrode, polyaniline as a positive electrode, glass fiber as a diaphragm and the novel high-performance electrolyte as electrolyte according to any one of claims 1-5, and is used for improving the cycle performance of the symmetrical battery.
The invention has the following beneficial effects:
1. the non-coding amino acid additive provided by the invention contains amino, has good coordination effect on zinc, and can regulate and control Zn 2+ And the solvation structure of the electrode/electrolyte interface is remolded, so that the electric charge distribution of the electrode/electrolyte interface is remodeled, the electroplating stripping behavior in the charge and discharge process of the water-based zinc ion battery is regulated, the uniform deposition of zinc ions is induced, the generation of zinc dendrites is avoided, and the cycle stability of the battery and the service life of a battery device are improved.
2. The citrulline has amino, hydroxyl and carboxyl, can coordinate with zinc ions, reduce the action of the zinc ions and water, regulate and control solvation when applied to the electrolyte, and experiments prove that the actual effect of the citrulline is superior to that of other amino acids. In addition, the citrulline has good water solubility, and can be directly applied to a water-based zinc-based battery without considering solubility optimization.
3. The additive provided by the invention is non-coding amino acid commonly used for living, has the advantages of low addition amount, easily available materials, low cost, greenness, no toxicity, safety and the like, and particularly has obvious advantages compared with alcohols and polymers in the aspect of raw material toxicity.
4. The additive provided by the invention is applied to a water-based zinc ion battery, and the time of the symmetrical battery in the recyclable charge and discharge is prolonged to more than 3000 hours.
Drawings
FIG. 1 shows the current density of the symmetrical cells of example 1 and comparative example 1 at 10mA cm -2 Discharge capacity was 10mAh cm -2 The lower time voltage curve, left plot is example 1, right plot is comparative example 1; wherein: the abscissa is Time (h)), and the ordinate is Voltage (V)).
FIG. 2 is a graph showing the current density of 10mA cm for the symmetrical cell of example 1 -2 Discharge capacity was 10mAh cm -2 Negative scanning electron microscope pictures after 200 circles of lower circulation, wherein the scale is 50 μm.
FIG. 3 shows the current density of the symmetrical cell of comparative example 1 at 10mA cm -2 Discharge capacity was 10mAh cm -2 Negative scanning electron microscope pictures after 200 circles of lower circulation, wherein the scale is 50 μm.
FIG. 4 is a graph showing the current density of 5mA cm for the symmetrical cell of example 2 -2 Discharge capacity of 5mAh cm -2 A time voltage curve below, wherein: the abscissa is Time (h)), and the ordinate is Voltage (V)).
FIG. 5 is a graph showing the current density of 0.2mA cm for the symmetrical cell of example 3 -2 Discharge capacity was 0.2mAh cm -2 A time voltage curve below, wherein: the abscissa is Time (h)), and the ordinate isVoltage (V)).
Fig. 6 is a graph of the rate performance of example 4 and comparative example 2, the upper graph of example 4 and the lower graph of comparative example 2; wherein: the abscissa is Time (h)), and the ordinate is Voltage (V)).
FIG. 7 shows the current density of the full cells of example 5 and comparative example 3 at 0.5 A.g -1 Is a long cycle comparison graph of (1), wherein: the abscissa indicates the number of cycles (Cycle number), and the ordinate indicates the Capacity (mAh. G) -1 ))。
FIG. 8 shows the current density of the full cell of example 6 at 1 A.g -1 A cyclic graph under the condition of (1), wherein: the abscissa indicates the number of cycles (Cycle number), and the ordinate indicates the Capacity (mAh. G) -1 ))。
Detailed Description
The invention is further illustrated by the following examples, it being understood that the following examples are given by way of illustration only and are not intended to be limiting.
Unless otherwise indicated, all starting materials in the examples herein were purchased commercially. In the following experiments, the raw materials were respectively: znSO (ZnSO) 4 ·7H 2 O is purchased from the national drug group, and the purity is more than or equal to 99.0 wt%. Non-coding amino acids such as citrulline are purchased from Adamas with purity not less than 98wt.%. The water solvents used in this experiment were deionized water.
Example 1
Preparing water-based zinc salt electrolyte containing non-coding amino acid, wherein zinc sulfate is used as electrolyte, deionized water is used as solvent, and citrulline is used as additive. The electrolyte/battery of this example had a citrulline addition concentration of 50 g.L -1 。
2.8756g of zinc sulfate heptahydrate is weighed and added into deionized water, and stirred for 1h at 40 ℃, and after complete dissolution, the volume is fixed to 5mL, thus obtaining 2 mol.L -1 Zinc sulfate solution.
Weighing 250mg of citrulline, adding into the solution, stirring at 25deg.C for 2 hr, and dissolving completely to obtain electrolyte containing non-coded amino acid, wherein the concentration of citrulline is 50g.L -1 。
The zinc foil (with the thickness of 50 μm) is used as the anode and the cathode, glass fiber is used as the diaphragm, and the electrolyte is added to assemble the button type symmetric zinc ion battery, namely the Zn symmetric battery.
The button cell is tested by adopting a Wuhan blue electric test system (BT 2000), and the Zn symmetry cell of the embodiment has the current density of 10mA cm -2 The discharge capacity was 10mAh cm -2 The performance test under the condition of (2) is shown in fig. 1.
After 670h of cycling, the cell was disassembled and the morphology of the negative zinc foil was observed with SEM, the observations are shown in fig. 2.
Example 2
Preparing water-based zinc salt electrolyte containing non-coding amino acid, wherein zinc sulfate is used as electrolyte, deionized water is used as solvent, and citrulline is used as additive. The electrolyte/cell of this example had a citrulline addition concentration of 10g.L -1 。
2.8756g of zinc sulfate heptahydrate is weighed and added into deionized water, and stirred for 1h at 40 ℃, and after complete dissolution, the volume is fixed to 5mL, thus obtaining 2 mol.L -1 Zinc sulfate solution.
Weighing 50mg of citrulline, adding into the solution, stirring at 25deg.C for 3 hr, and dissolving completely to obtain electrolyte containing non-coded amino acid, wherein the concentration of citrulline is 10g.L -1 。
The zinc foil (with the thickness of 50 μm) is used as the anode and the cathode, glass fiber is used as the diaphragm, and the electrolyte is added to assemble the button type symmetric zinc ion battery, namely the Zn symmetric battery.
The button cell was tested by the Wohan blue electric test system (BT 2000), and the symmetrical cell of this example was tested at a current density of 5mA cm -2 Discharge capacity of 5mAh cm -2 The test was carried out under the condition of 1100h cycle time, and the test results are shown in fig. 4.
Example 3
Preparing water-based zinc salt electrolyte containing non-coding amino acid, wherein zinc sulfate is used as electrolyte, deionized water is used as solvent, and citrulline is used as additive. The electrolyte/cell of this example had a citrulline addition concentration of 5 g.L -1 。
2.8756g of zinc sulfate heptahydrate is weighed and added into deionized water, and stirred at 40 DEG CStirring for 1h, and after complete dissolution, fixing the volume to 10mL to obtain 2mol.L -1 Zinc sulfate solution.
Weighing 25mg of citrulline, adding into the above solution, stirring at 25deg.C for 5 hr, and dissolving completely to obtain electrolyte containing non-coded amino acid, wherein the concentration of citrulline additive is 5g.L -1 。
The zinc foil (with the thickness of 50 μm) is used as the anode and the cathode, glass fiber is used as the diaphragm, and the electrolyte is added to assemble the button type symmetric zinc ion battery, namely the Zn symmetric battery.
The button cell was tested by the Wohan blue electric test system (BT 2000), and the symmetrical cell of this example was tested at a current density of 0.2mA cm -2 Discharge capacity of 0.2mAh cm -2 The test was performed with a cycle time of 3600h, and the test results are shown in FIG. 5.
Example 4
Preparing water-based zinc salt electrolyte containing non-coding amino acid, wherein zinc trifluoromethane sulfonate is used as electrolyte, deionized water is used as solvent, and citrulline is used as additive. The electrolyte/cell of this example had a citrulline addition concentration of 50 g.L -1 。
7.2706g of zinc trifluoromethane sulfonate is weighed and added into deionized water, and stirred for 1h at 40 ℃, and after complete dissolution, the volume is fixed to 10mL, thus obtaining 2 mol.L -1 Zinc trifluoromethane sulfonate solution.
Weighing 250mg of citrulline, adding into the solution, stirring at 25deg.C for 2 hr, and dissolving completely to obtain electrolyte containing non-coded amino acid, wherein the concentration of citrulline is 50g.L -1 。
The zinc foil (with the thickness of 50 μm) is used as the anode and the cathode, glass fiber is used as the diaphragm, and the electrolyte is added to assemble the button type symmetric zinc ion battery, namely the Zn symmetric battery.
The button cell is tested by adopting a Wuhan blue electric test system (BT 2000), and the symmetrical cell of the embodiment has the current density of 1-40 mA cm -2 Discharge capacity of 5mAh cm -2 The test was performed under the conditions of (2) and the test results are shown in FIG. 6. The battery of this example was found to have excellent rate performance as a result of the test.
Example 5
Preparing water-based zinc salt electrolyte containing non-coding amino acid, wherein zinc sulfate is used as electrolyte, deionized water is used as solvent, and citrulline is used as additive. The electrolyte/cell of this example had a citrulline addition concentration of 50 g.L -1 。
2.8756g of zinc sulfate heptahydrate is weighed and added into deionized water, and stirred for 1h at 40 ℃, and after complete dissolution, the volume is fixed to 5mL, thus obtaining 2 mol.L -1 Zinc sulfate solution.
Weighing 250mg of citrulline, adding into the solution, stirring at 25deg.C for 2 hr, and dissolving completely to obtain electrolyte containing non-coded amino acid, wherein the concentration of citrulline is 50g.L -1 。
A button type Zn PANI full battery is assembled by adopting zinc foil (the thickness is 50 μm) as a negative electrode, polyaniline as a positive electrode and glass fiber as a diaphragm and adding the electrolyte.
The button cell was tested by the Wohan blue electric test system (BT 2000), and the full cell of this example was tested at a current density of 0.5 A.g -1 The test is carried out under the following conditions, the test result of the full battery is shown in figure 7, and the specific capacity can reach 70 mAh.g -1 。
Example 6
Preparing water-based zinc salt electrolyte containing non-coding amino acid, wherein zinc sulfate is used as electrolyte, deionized water is used as solvent, and citrulline is used as additive. The electrolyte/cell of this example had a citrulline addition concentration of 50 g.L -1 。
2.8756g of zinc sulfate heptahydrate is weighed and added into deionized water, and stirred for 1h at 40 ℃, and after complete dissolution, the volume is fixed to 5mL, thus obtaining 2 mol.L -1 Zinc sulfate solution.
Weighing 250mg of citrulline, adding into the solution, stirring at 25deg.C for 2 hr, and dissolving completely to obtain electrolyte containing non-coded amino acid, wherein the concentration of citrulline is 50g.L -1 。
Zinc foil (thickness of 50 μm) is used as a negative electrode, polyaniline is used as a positive electrode and glass fiber is used as a diaphragm, and the electrolyte is added to form the button Zn PANI full battery.
The button cell was tested by the Wohan blue electric test system (BT 2000), and the full cell of this example was tested at a current density of 1 A.g -1 The cycle number of the full cell was found to be more than 3000 by practical testing as shown in fig. 8.
Comparative example 1
Preparing water-based zinc salt electrolyte, wherein zinc sulfate is used as electrolyte, and deionized water is used as solvent. The electrolyte/cell of this example does not contain citrulline.
2.8756g of zinc sulfate heptahydrate is weighed and added into deionized water, and stirred for 1h at 40 ℃, and after complete dissolution, the volume is fixed to 5mL, thus obtaining 2 mol.L -1 Zinc sulfate solution.
Zinc foil (thickness is 50 μm) is used as the anode and the cathode, glass fiber is used as the diaphragm, and the electrolyte is added to assemble the button type symmetric zinc ion battery.
The button cell was tested by the Wohan blue electric test system (BT 2000), and the current density of the symmetrical cell of this comparative example was 10mA.cm -2 The discharge capacity was 10mAh cm -2 The cycle test was performed under the conditions of (1) and the results of the performance test are shown in FIG. 1. The test gave a cycle time of 34h.
After 34h of cycling, the cell was disassembled and the morphology of the negative zinc foil was observed with SEM, the observations are shown in figure 3.
Comparative example 2
Preparing water-based zinc salt electrolyte without non-coding amino acid, wherein zinc triflate is used as electrolyte, and deionized water is used as solvent.
7.2706g of zinc trifluoromethane sulfonate is weighed and added into deionized water, and stirred for 1h at 40 ℃, and after complete dissolution, the volume is fixed to 10mL, thus obtaining 2 mol.L -1 Zinc trifluoromethane sulfonate solution.
Zinc foil (thickness is 50 μm) is used as the anode and the cathode, glass fiber is used as the diaphragm, and the electrolyte is added to assemble the button type symmetric zinc ion battery.
The button cell is tested by adopting a Wuhan blue electric test system (BT 2000), and the symmetrical cell of the embodiment has the current density of 1-40 mA cm -2 Discharge capacity of 5mAh cm -2 Is carried out under the condition ofThe test was performed and the test results are shown in fig. 6. When the current density is from 1mA cm -2 Increase to 5mA cm -2 The battery is short-circuited.
Comparative example 3
Preparing water-based zinc salt electrolyte, wherein zinc sulfate is used as electrolyte, and deionized water is used as solvent. The electrolyte/cell of this example does not contain citrulline.
2.8756g of zinc sulfate heptahydrate is weighed and added into deionized water, and stirred for 1h at 40 ℃, and after complete dissolution, the volume is fixed to 5mL, thus obtaining 2 mol.L -1 Zinc sulfate solution.
Zinc foil (thickness is 50 μm) is used as the anode and the cathode, glass fiber is used as the diaphragm, and the electrolyte is added to assemble the button type symmetric zinc ion battery.
The button cell was tested using the marvelin blue electric test system (BT 2000), and the current density was 0.5a·g for the symmetrical cell of this comparative example -1 The test results of the cycle test under the conditions of (2) are shown in FIG. 7. The specific capacity is only 50 mAh.g -1 。
The above experimental procedures for examples 1 to 5 and comparative examples 1 to 3 of the present invention can be obtained by the above examples and accompanying drawings 1 to 8:
FIG. 1 shows the current density of the symmetrical cells of example 1 and comparative example 1 at 1mA cm -2 Discharge capacity of 1mAh cm -2 Time voltage curve below. It can be seen from the figure that the cycle time of a symmetrical cell with the addition of an appropriate amount of non-coded amino acid is significantly increased relative to the cycle life of a symmetrical cell with a zinc sulfate solution without additives, and the performance is far superior to a symmetrical cell without additives.
FIGS. 2 and 3 show the current density of the symmetrical cells of example 1 and comparative example 1, respectively, at 10mA cm -2 The discharge capacity was 10mAh cm -2 Negative scanning electron microscope pictures after 200 circles of lower circulation. It can be seen from fig. 2 and 3 that the zinc sheet surface was flat and smooth after 200 cycles using the electrolyte containing the non-coded amino acid additive. And by using electrolyte without additives, a large amount of dendrites grow on the surface of the zinc sheet after 200 circles of circulation, and hexagonal sheet byproducts are accumulated on the surface. Description of the use of the inventionThe additive of (2) can induce zinc ions to be uniformly deposited, and inhibit hydrogen evolution reaction and the generation of byproducts.
Fig. 4 and 5 are long cycle diagrams of example 2 and example 3, respectively. As can be seen from the figure, the symmetrical battery cycle time with the addition of a proper amount of non-coded amino acid has a stable lifetime of over 1000 turns, and no short circuit phenomenon occurs to cause battery failure.
Fig. 6 is a graph of the rate performance of example 4 and comparative example 2. From the results, the symmetrical battery added with a proper amount of non-coding amino acid has good stability under a larger current density, and no fluctuation occurs between different current density changes, thus proving the stability of the electrolyte.
Fig. 7 is a full cell cycle chart of example 5 and comparative example 3. As can be seen from the figure, the specific capacity of the full cell added with the proper amount of non-coding amino acid is higher than that of the full cell composed of the zinc sulfate solution without the additive, and the full cell added with the proper amount of non-coding amino acid has excellent effect in practical application.
Fig. 8 is a full cell cycle chart of example 6. As can be seen from the figure, the full cell added with the proper amount of non-coding amino acid can be cycled for more than 3000 circles, and no battery failure occurs, thus proving that the full cell added with the proper amount of non-coding amino acid has excellent cycle life.
In conclusion, the novel high-performance electrolyte provided by the invention can be applied to a water-based zinc ion battery to inhibit dendrite growth and corrosion reaction, prolong the service life of the water-based zinc ion battery and improve the cycle stability of the battery. This is of great significance for the scale of the aqueous zinc ion battery.
In addition, the invention also provides a preparation method of the electrolyte based on the electrolyte.
The invention also provides a novel Zn symmetric battery, which is assembled by adopting zinc metal as an anode and a cathode, glass fiber as a diaphragm and the novel high-performance electrolyte as electrolyte in any one of claims 1-5, and is used for improving the cycle performance of the symmetric battery.
The novel Zn PANI full battery is assembled by adopting zinc metal as a negative electrode, polyaniline as a positive electrode, glass fiber as a diaphragm and the novel high-performance electrolyte as electrolyte according to any one of claims 1-5, and is used for improving the cycle performance of the symmetrical battery.
The non-coding amino acid additive provided by the invention can be chemically adsorbed on the surface of a zinc negative electrode in electrolyte, so that the interface environment between the zinc negative electrode and the electrolyte is improved, the electric field distribution near the zinc negative electrode is regulated, and zinc ions are induced to be uniformly deposited, so that the dendrite-free zinc negative electrode is realized, hydrogen evolution reaction and corrosion reaction are inhibited, and the cycle and rate capability of the water-based zinc ion battery are improved. In addition, the additive provided by the invention has the advantages of small addition amount, low cost, no toxicity and environmental protection.
The embodiments described above are preferred embodiments of the present invention, so that those skilled in the art can better understand the present invention to make the scope of the present invention more clearly defined, but the embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. An electrolyte for a water-based zinc ion battery, which is characterized by comprising non-coded amino acid, zinc salt and solvent, and can be used for the water-based zinc ion battery to improve the cycle performance of the zinc ion battery.
2. The electrolyte of claim 1, wherein the non-encoded amino acid comprises one or more of citrulline, hydroxyproline, hydroxylysine, ornithine, homocysteine, alanine sulfonate, and 5-hydroxytryptophan.
3. The electrolyte of claim 1 wherein the zinc salt comprises one or more of zinc sulfate, zinc trifluoromethane sulfonate, zinc chloride, zinc tetrafluoroborate and zinc perchlorate and the solvent is deionized water.
4. The electrolyte according to claim 1, wherein the concentration of the non-encoded amino acid is 0.1 to 100 g.L -1 。
5. The electrolyte according to claim 1, wherein the concentration of the water-based zinc salt electrolyte is 1-3 mol.L -1 。
6. A method for preparing an electrolyte according to any one of claims 1 to 5, wherein the water-based zinc salt electrolyte is obtained by dissolving zinc salt in deionized water and completely dissolving zinc salt by stirring; adding non-coding amino acid into the water-based zinc salt electrolyte, and stirring and dissolving to obtain the electrolyte.
7. The preparation method according to claim 6, wherein the concentration of the water-based zinc salt electrolyte is 1-3 mol.L -1 The stirring time is 0.5-12 h, and the stirring temperature is 20-90 ℃.
8. The method according to claim 6, wherein the concentration of the non-coded amino acid in the electrolyte is 0.1 to 100 g.L -1 Stirring time is 1-24 h, and stirring temperature is 20-90 ℃.
9. An aqueous zinc-ion battery, characterized in that it comprises the electrolyte according to any one of claims 1-5; the water-based zinc ion battery is assembled by adopting zinc metal as an anode and a cathode, glass fiber as a diaphragm and the electrolyte as the electrolyte according to any one of claims 1-5 to form a Zn symmetric battery, and the water-based zinc ion battery is used for improving the cycle performance of the symmetric battery; or, the water-based zinc ion battery is assembled into a Zn PANI full battery by adopting zinc metal as a negative electrode, polyaniline as a positive electrode, glass fiber as a diaphragm and the electrolyte as the electrolyte according to any one of claims 1-5, so as to improve the cycle performance of the full battery.
10. The aqueous zinc-ion battery according to claim 9, wherein the aqueous zinc-ion battery has a current density of 0.1 to 40mA cm when formed as a Zn symmetric battery -2 The discharge capacity is 0.1-10 mAh cm -2 Can be circulated for 200 to 5000 hours under the condition of (2); or, when the aqueous zinc ion battery is formed into a Zn-PANI full battery, the current density is 0.1-5 A.g -1 Can be cycled for 100 to 4000 cycles.
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