CN114665166A - Battery electrolyte containing aluminum ions and battery - Google Patents
Battery electrolyte containing aluminum ions and battery Download PDFInfo
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- CN114665166A CN114665166A CN202011546413.1A CN202011546413A CN114665166A CN 114665166 A CN114665166 A CN 114665166A CN 202011546413 A CN202011546413 A CN 202011546413A CN 114665166 A CN114665166 A CN 114665166A
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- aluminum
- battery
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- zinc
- sulfamate
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 74
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 34
- -1 aluminum ions Chemical class 0.000 title claims abstract description 29
- NLXYLZCLIHHPMA-UHFFFAOYSA-K aluminum;trisulfamate Chemical compound [Al+3].NS([O-])(=O)=O.NS([O-])(=O)=O.NS([O-])(=O)=O NLXYLZCLIHHPMA-UHFFFAOYSA-K 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 44
- 239000011701 zinc Substances 0.000 abstract description 43
- 229910052725 zinc Inorganic materials 0.000 abstract description 42
- 238000005260 corrosion Methods 0.000 abstract description 25
- 230000007797 corrosion Effects 0.000 abstract description 25
- 229910000611 Zinc aluminium Inorganic materials 0.000 abstract description 19
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 abstract description 19
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 229910001148 Al-Li alloy Inorganic materials 0.000 abstract description 7
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 7
- DNEHKUCSURWDGO-UHFFFAOYSA-N aluminum sodium Chemical compound [Na].[Al] DNEHKUCSURWDGO-UHFFFAOYSA-N 0.000 abstract description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011737 fluorine Substances 0.000 abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 abstract description 6
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 abstract description 2
- 230000005518 electrochemistry Effects 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 28
- 229910052739 hydrogen Inorganic materials 0.000 description 28
- 239000001257 hydrogen Substances 0.000 description 28
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 16
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 11
- CMWINYFJZCARON-UHFFFAOYSA-N 6-chloro-2-(4-iodophenyl)imidazo[1,2-b]pyridazine Chemical compound C=1N2N=C(Cl)C=CC2=NC=1C1=CC=C(I)C=C1 CMWINYFJZCARON-UHFFFAOYSA-N 0.000 description 11
- JJKVMNNUINFIRK-UHFFFAOYSA-N 4-amino-n-(4-methoxyphenyl)benzamide Chemical compound C1=CC(OC)=CC=C1NC(=O)C1=CC=C(N)C=C1 JJKVMNNUINFIRK-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- KEXSCPNGYFGPFU-UHFFFAOYSA-L manganese(2+);disulfamate Chemical compound [Mn+2].NS([O-])(=O)=O.NS([O-])(=O)=O KEXSCPNGYFGPFU-UHFFFAOYSA-L 0.000 description 6
- QFIGQGUHYKRFAI-UHFFFAOYSA-K aluminum;trichlorate Chemical compound [Al+3].[O-]Cl(=O)=O.[O-]Cl(=O)=O.[O-]Cl(=O)=O QFIGQGUHYKRFAI-UHFFFAOYSA-K 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- MKGYHFFYERNDHK-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Ti+4].[Li+] Chemical compound P(=O)([O-])([O-])[O-].[Ti+4].[Li+] MKGYHFFYERNDHK-UHFFFAOYSA-K 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- SAPIQCCFEBULSH-UHFFFAOYSA-M lithium;sulfamate Chemical compound [Li+].NS([O-])(=O)=O SAPIQCCFEBULSH-UHFFFAOYSA-M 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- QDWYPRSFEZRKDK-UHFFFAOYSA-M sodium;sulfamate Chemical compound [Na+].NS([O-])(=O)=O QDWYPRSFEZRKDK-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- HEYNLDRKZOOEDN-UHFFFAOYSA-L manganese(2+);trifluoromethanesulfonate Chemical compound [Mn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F HEYNLDRKZOOEDN-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- MJEPCYMIBBLUCJ-UHFFFAOYSA-K sodium titanium(4+) phosphate Chemical compound P(=O)([O-])([O-])[O-].[Ti+4].[Na+] MJEPCYMIBBLUCJ-UHFFFAOYSA-K 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229960001296 zinc oxide Drugs 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 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
- H01M2300/0005—Acid electrolytes
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
- Secondary Cells (AREA)
Abstract
A battery electrolyte containing aluminum ions and a battery belong to the technical field of electrochemistry and relate to a battery electrolyte containing aluminum ions and a battery. The invention uses the sulfamic acid aluminum as the battery electrolyte and the battery containing aluminum ions, can avoid increasing the corrosion self-discharge of a zinc cathode when being used as the zinc-aluminum bi-ion battery electrolyte, simultaneously has lower price of fluoride-free sulfamic acid than fluorine-containing trifluoromethanesulfonic acid and is safer, and the aluminum sulfamate synthesized by sulfamic acid and metal aluminum as the battery electrolyte and the battery containing aluminum ions can reduce the cost of the battery and improve the safety of the battery. The electrolyte can be used for other batteries containing aluminum ions, such as aluminum ion batteries, aluminum lithium double-ion batteries and aluminum sodium double-ion batteries, and can also reduce the cost of the batteries and improve the safety.
Description
Technical Field
Relates to a battery electrolyte containing aluminum ions and a battery.
Background
Since petrochemical energy is a non-renewable resource and serious pollution, most countries are currently developing new energy batteries to replace petrochemical energy, and lithium ion batteries have been developed for a long time in the aspects of electric vehicles and energy storage, whereas commercial lithium ion batteries adopt flammable organic electrolyte, and the assembly and production conditions are harsh, and in addition, the lithium resources are scarce, so that the cost of the lithium ion batteries is high. The metal zinc (Zn) has the theoretical capacity as high as 820 mAhg < -1 >, the secondary battery formed by the zinc cathode and the manganese dioxide anode has very high capacity, but the working voltage is lower, most of the working voltage is lower than 1.4V, the overall energy density of the battery is low, aluminum salt is added into the electrolyte of the acidic zinc-manganese secondary battery to form the zinc-aluminum double-ion battery, the working voltage of the battery can be remarkably improved, and the average working voltage can reach 1.5V to 1.7V. The development of the zinc-aluminum double-ion battery containing aluminum ions has important significance for effectively utilizing renewable energy sources.
At present, various aqueous battery electrolytes containing aluminum ions mainly adopt aluminum trifluoromethanesulfonate as a solute, and zinc-aluminum dual-ion batteries have good charge and discharge performance in high-concentration trifluoromethanesulfonate aqueous solution electrolytes, but the aluminum trifluoromethanesulfonate is expensive, so that the battery cost can be seriously increased by adopting the fluorine-containing salt electrolyte, and the corrosion and self-discharge of a zinc cathode are serious at low concentration. The aluminum sulfate has too low solubility and is not suitable for being used as an electrolyte, the aluminum nitrate has high solubility, but the zinc cathode of the acidic zinc-manganese secondary battery added with the aluminum nitrate is seriously corroded and subjected to hydrogen evolution, the aluminum nitrate has oxidability, the zinc-manganese secondary battery can be combusted due to friction or impact with organic matters, the stability is poor, certain potential safety hazards exist when the aluminum nitrate is used, the aluminum chlorate has poorer stability, the aluminum chlorate can be decomposed and exploded when being heated, and the aluminum chlorate has larger potential safety hazards. Other aqueous batteries containing aluminum ions, such as aqueous aluminum ion batteries, aluminum lithium double ion batteries and aluminum sodium double ion batteries, also commonly adopt fluorine-containing aluminum salt electrolyte such as expensive aluminum trifluoromethanesulfonate, and the like, so that the problem of high cost is difficult to solve. Therefore, the development of the battery electrolyte containing aluminum ions, which is low in price, stable and not easy to corrode a zinc cathode, and the battery have important scientific research and application values.
Disclosure of Invention
Because the price of the aluminum trifluoromethanesulfonate is high, the aluminum trifluoromethanesulfonate is not beneficial to reducing the cost of the battery when used as a battery electrolyte, and the corrosion to the zinc of the negative electrode is serious under the condition of low concentration in the zinc-aluminum dual-ion battery; the aluminum sulfate solubility is too low to be used as electrolyte, the aluminum nitrate solubility is high, but the corrosion of the zinc cathode of the zinc-aluminum dual-ion battery added with the aluminum nitrate to hydrogen evolution is serious, the stability of the aluminum nitrate is poor, certain potential safety hazards also exist when the aluminum nitrate is used, the stability of aluminum chlorate salt is worse, and larger potential safety hazards exist when the aluminum chlorate is used. Other aqueous batteries containing aluminum ions also use expensive fluorine-containing aluminum salt electrolytes such as aluminum trifluoromethanesulfonate, which is difficult to solve. The research of the inventor finds that the sulfamic acid aluminum salt can be synthesized by the reaction of sulfamic acid and metal aluminum, and the sulfamic acid aluminum salt has high solubility, stability and relatively low cost. Aiming at the technical problems, the invention provides the battery electrolyte containing aluminum ions, which has relatively low price, is stable and is not easy to corrode a zinc cathode, and the battery by using the aluminum sulfamate as a solute.
The technical scheme of the invention is as follows:
a battery electrolyte containing aluminum ions comprises a solute and water, wherein the solute comprises aluminum sulfamate, and the molar concentration of the aluminum sulfamate is 0.1-1.5 mol/L.
Further, in the above aluminum ion-containing battery electrolyte, the solute contains aluminum sulfamate, and the molar concentration thereof is preferably 0.5 to 1mol/L.
The battery containing aluminum ions comprises a positive electrode, a negative electrode and electrolyte, wherein the electrolyte of the battery is the electrolyte.
The aluminum sulfamate used in the invention can be synthesized by heating sulfamic acid and metallic aluminum in an aqueous solution, wherein the synthesis temperature is 60-200 ℃.
The electrolyte may contain other electrolytes such as zinc salt, lithium salt, sodium salt and the like, and other electrolytes may be prepared according to different anodes and cathodes of the battery.
The zinc-aluminum double-ion battery is a battery with electrolyte containing zinc sulfamate and aluminum sulfamate at the same time, the aluminum-ion battery is a battery with electrolyte containing aluminum sulfamate aqueous solution, the aluminum-lithium double-ion battery is a battery with electrolyte containing aluminum sulfamate and lithium sulfamate at the same time, and the aluminum-sodium double-ion battery is a battery with electrolyte containing aluminum sulfamate and sodium sulfamate at the same time.
In the present invention, the positive electrode and the negative electrode of the aluminum ion-containing battery are not limited, and may be other conventional choices in the field other than zinc and manganese dioxide, for example, the negative electrode may be at least one of titanium lithium phosphate, lithium titanate, titanium dioxide, titanium disulfide, sodium titanate, molybdenum disulfide, vanadium dioxide, and lithium vanadate materials, and the positive electrode may be at least one of manganese dioxide, vanadium pentoxide, carbon, or graphite materials.
The aluminum sulfamate is adopted as the solute of the battery electrolyte containing aluminum ions, firstly, sulfamic acid, also called solid sulfuric acid, is strong acid and high in stability, the synthesized aluminum sulfamate also has high stability, and secondly, the aluminum sulfamate has higher solubility than aluminum sulfate and is more suitable for being used as the electrolyte. The inventor researches and discovers that the acidic zinc-manganese secondary battery electrolyte added with aluminum sulfamate has very low corrosion to a zinc cathode and is very beneficial to improving the performance of the battery and reducing the cost. The price of the sulfamic acid is much lower than that of the trifluoromethanesulfonic acid, so that the cost of the aluminum sulfamate is much lower than that of the fluorine-containing aluminum trifluoromethanesulfonate, and meanwhile, the fluorine-free aluminum sulfamate is safer and more environment-friendly than the fluorine-containing aluminum trifluoromethanesulfonate. The aluminum sulfamate has the characteristics of higher stability, high solubility and lower cost, and the aluminum sulfamate serving as the solute of the electrolyte can also reduce the cost of other water-system aluminum ion batteries, aluminum-lithium double-ion batteries and aluminum-sodium double-ion batteries and improve the safety and the environmental protection.
In conclusion, the beneficial effects of the invention are as follows:
the aluminum ion-containing battery electrolyte and the battery provided by the invention can avoid increasing the corrosion self-discharge of a zinc cathode when being used as a zinc-aluminum dual-ion battery electrolyte, can reduce the battery cost and improve the battery safety, and can also reduce the battery cost and improve the battery safety when being used for other aluminum ion batteries, aluminum-lithium dual-ion batteries and aluminum-sodium dual-ion batteries.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The present invention will be described in detail below by way of examples.
The preparation method of the aluminum sulfamate comprises the steps of weighing sulfamic acid and metal aluminum according to the mol ratio of 3:1.1, adding the sulfamic acid and the metal aluminum into water, heating the mixture of the water and the sulfamic acid and the metal aluminum to 60-200 ℃ in a closed container with a pressure exhaust valve for reaction, cooling and filtering to remove undissolved substances after the reaction is finished, obtaining a solution, namely an aluminum sulfamate aqueous solution, and blending to the required concentration to be used as an electrolyte.
The positive electrode of the zinc-aluminum double-ion battery can be manganese dioxide, the negative electrode is metal zinc, and the electrolyte is a mixed aqueous solution of zinc sulfamate and aluminum sulfamate; the anode of the aluminum ion battery can be any one of manganese dioxide, vanadium pentoxide and molybdenum disulfide, the cathode is titanium dioxide, and the electrolyte is aluminum sulfamate; the anode of the aluminum-lithium double-ion battery is manganese dioxide, the cathode of the aluminum-lithium double-ion battery is any one of lithium titanate and lithium titanium phosphate, and the electrolyte is a mixed aqueous solution of aluminum sulfamate and lithium sulfamate; the anode of the aluminum-sodium double-ion battery is manganese dioxide, the cathode of the aluminum-sodium double-ion battery is any one of lithium titanium phosphate and sodium titanium phosphate, and the electrolyte is a mixed aqueous solution of aluminum sulfamate and sodium sulfamate.
The zinc-aluminum dual-ion battery described in the following example uses a metal zinc foil as the negative electrode, uses alpha-type manganese dioxide as the positive electrode, and uses a transparent PE plastic film to replace an aluminum plastic film for packaging to form a soft-package battery, so as to facilitate observation of the corrosion condition of the zinc negative electrode.
Example 1
Preparing electrolyte with 1mol/L of aluminum sulfamate, 1mol/L of zinc sulfamate and 0.1mol/L of manganese sulfamate, adding the electrolyte into a zinc-aluminum double-ion battery without the electrolyte for 10 hours to check the corrosion and hydrogen evolution conditions of a zinc cathode, standing and storing the battery for 60 days, and checking the corrosion and hydrogen evolution conditions of the zinc cathode of the battery.
Example 2
Preparing electrolyte with the concentration of 0.5mol/L of aluminum sulfamate, 1mol/L of zinc sulfamate and 0.1mol/L of manganese sulfamate, adding the electrolyte into a zinc-aluminum double-ion battery without the electrolyte for 10 hours to check the corrosion and hydrogen evolution conditions of a zinc cathode, standing and storing the battery for 60 days, and checking the corrosion and hydrogen evolution conditions of the zinc cathode of the battery.
Example 3
Preparing electrolyte with 1.5mol/L of aluminum sulfamate, 0.5mol/L of zinc sulfamate and 0.1mol/L of manganese sulfamate, adding the electrolyte into a zinc-aluminum double-ion battery without the electrolyte, checking the corrosion and hydrogen evolution conditions of a zinc cathode after 10 hours, standing and storing the battery for 60 days, and checking the corrosion and hydrogen evolution conditions of the zinc cathode of the battery.
Example 4
Preparing electrolyte with 0.1mol/L of aluminum sulfamate, 1.5mol/L of zinc sulfamate and 0.1mol/L of manganese sulfamate, adding the electrolyte into a zinc-aluminum double-ion battery without the electrolyte, checking the corrosion and hydrogen evolution conditions of a zinc cathode after 10 hours, standing and storing the battery for 60 days, and checking the corrosion and hydrogen evolution conditions of the zinc cathode of the battery.
Comparative example 1
Preparing electrolyte with the concentration of aluminum trifluoromethanesulfonate of 1mol/L, the concentration of zinc trifluoromethanesulfonate of 1mol/L and the concentration of manganese trifluoromethanesulfonate of 0.1mol/L, then adding the electrolyte into a zinc-aluminum dual-ion battery without the electrolyte for checking the corrosion and hydrogen evolution conditions of a zinc cathode after 10 hours, standing and storing the battery for 60 days, and then checking the corrosion and hydrogen evolution conditions of the zinc cathode of the battery.
Comparative example 2
Preparing electrolyte with the concentration of aluminum trifluoromethanesulfonate of 1mol/L, the concentration of zinc sulfamate of 1mol/L and the concentration of manganese sulfamate of 0.1mol/L, then adding the electrolyte into a zinc-aluminum double-ion battery without the electrolyte for 10 hours to check the corrosion and hydrogen evolution conditions of a zinc cathode, standing and storing the battery for 60 days, and then checking the corrosion and hydrogen evolution conditions of the zinc cathode of the battery.
Comparative example 3
Preparing electrolyte with 1mol/L of aluminum nitrate, 1mol/L of zinc sulfamate and 0.1mol/L of manganese sulfamate, adding the electrolyte into a zinc-aluminum double-ion battery without the electrolyte for 10 hours to check the corrosion and hydrogen evolution conditions of a zinc cathode, standing and storing the battery for 60 days, and checking the corrosion and hydrogen evolution conditions of the zinc cathode of the battery.
| Examples | Cell condition after 10 hours | Battery condition after 60 days |
| Example 1 | The zinc cathode keeps the original metallic color without hydrogen evolution | The zinc cathode keeps the original metallic color without hydrogen evolution |
| Example 2 | The zinc cathode keeps the original metallic color without hydrogen evolution | The zinc cathode keeps the original metallic color without hydrogen evolution |
| Example 3 | The zinc cathode keeps the original metallic color without hydrogen evolution | The zinc cathode keeps the original metallic color without hydrogen evolution |
| Example 4 | The zinc cathode keeps the original metallic color without hydrogen evolution | The zinc cathode keeps the original metallic color without hydrogen evolution |
| Comparative example 1 | The zinc cathode keeps the original metallic color without hydrogen evolution | Black and white corrosion spots appear on the zinc cathode |
| Comparative example 2 | The zinc cathode keeps the original metallic color without hydrogen evolution | Black, white and holes appear on the zinc cathode |
| Comparative example 3 | Zinc cathode large-amount hydrogen evolution battery bulge | Electrolyte drying device for serious gas expansion and deformation of battery |
In the above tests, the batteries prepared from the electrolytes of examples 1 to 4 containing aluminum sulfamate did not undergo significant corrosion of the zinc negative electrode and hydrogen evolution after standing and storing for 10 hours and 60 days, which indicates that the electrolytes containing aluminum sulfamate have very little corrosion to the zinc negative electrode. Comparative examples 1 to 3 the zinc cathodes of the zinc-aluminum dual-ion batteries prepared by the electrolyte containing the aluminum trifluoromethanesulfonate and the aluminum nitrate all have corrosion in different degrees, and particularly after the zinc-aluminum dual-ion battery containing the aluminum nitrate is stored for 60 days, the battery is seriously inflated and deformed, and the electrolyte is completely dried and completely discarded.
The embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (3)
1. The battery electrolyte containing aluminum ions comprises a solute and water, and is characterized in that the solute comprises aluminum sulfamate, and the molar concentration of the aluminum sulfamate is 0.1-1.5 mol/L.
2. The aluminum ion-containing battery electrolyte as claimed in claim 1, wherein the solute comprises aluminum sulfamate, and the molar concentration is preferably 0.5 to 1mol/L.
3. An aluminum ion-containing battery, which comprises a positive electrode, a negative electrode and an electrolyte, and is characterized in that the electrolyte of the battery is the electrolyte of any one of claims 1-2.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115566284A (en) * | 2022-11-03 | 2023-01-03 | 浙江大学 | Water-based zinc ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115566284A (en) * | 2022-11-03 | 2023-01-03 | 浙江大学 | Water-based zinc ion battery |
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