CN112242570B - Application of mixture of carbon material and ionic bromide and aqueous zinc-bromine double-ion battery - Google Patents
Application of mixture of carbon material and ionic bromide and aqueous zinc-bromine double-ion battery Download PDFInfo
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- CN112242570B CN112242570B CN201910654492.9A CN201910654492A CN112242570B CN 112242570 B CN112242570 B CN 112242570B CN 201910654492 A CN201910654492 A CN 201910654492A CN 112242570 B CN112242570 B CN 112242570B
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- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 title claims abstract description 27
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 24
- ZRXYMHTYEQQBLN-UHFFFAOYSA-N [Br].[Zn] Chemical compound [Br].[Zn] ZRXYMHTYEQQBLN-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000000203 mixture Substances 0.000 title claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 59
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 39
- 239000007864 aqueous solution Substances 0.000 claims abstract description 31
- 239000011592 zinc chloride Substances 0.000 claims abstract description 30
- 239000007774 positive electrode material Substances 0.000 claims abstract description 18
- 239000007773 negative electrode material Substances 0.000 claims abstract description 16
- VNDYJBBGRKZCSX-UHFFFAOYSA-L Zinc bromide Inorganic materials Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- 229910021382 natural graphite Inorganic materials 0.000 claims description 20
- 229910002804 graphite Inorganic materials 0.000 claims description 15
- 239000010439 graphite Substances 0.000 claims description 15
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 claims description 14
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 12
- 125000001246 bromo group Chemical group Br* 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 229910021385 hard carbon Inorganic materials 0.000 claims description 9
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 9
- 239000011686 zinc sulphate Substances 0.000 claims description 9
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 7
- 229910001623 magnesium bromide Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 7
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical group [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 6
- 229910001622 calcium bromide Inorganic materials 0.000 claims description 5
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 239000002931 mesocarbon microbead Substances 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- IUHFWCGCSVTMPG-UHFFFAOYSA-N [C].[C] Chemical class [C].[C] IUHFWCGCSVTMPG-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 230000008021 deposition Effects 0.000 abstract description 13
- 239000002184 metal Substances 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 238000004090 dissolution Methods 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 9
- 230000002441 reversible effect Effects 0.000 abstract description 4
- 239000006182 cathode active material Substances 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- 239000011701 zinc Substances 0.000 description 68
- 210000004027 cell Anatomy 0.000 description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 239000011889 copper foil Substances 0.000 description 12
- 239000003365 glass fiber Substances 0.000 description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000002033 PVDF binder Substances 0.000 description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- -1 cation bromide Chemical class 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229940102001 zinc bromide Drugs 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000034964 establishment of cell polarity Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- CHSMNMOHKSNOKO-UHFFFAOYSA-L zinc;dichloride;hydrate Chemical compound O.[Cl-].[Cl-].[Zn+2] CHSMNMOHKSNOKO-UHFFFAOYSA-L 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/365—Zinc-halogen accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/582—Halogenides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
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- Chemical & Material Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides an application of a mixture of a carbon material and an ionic bromide in a battery positive electrode active material of an aqueous electrolyte. The invention also provides a water system zinc-bromine double-ion battery, which comprises a positive electrode active material, a negative electrode active material and electrolyte; wherein the positive electrode active material comprises a mixture of a carbon material and an ionic bromide; the electrolyte contains saturated ZnCl2An aqueous solution. The battery of the invention has longer cycle life and operation stability. Because of the saturated ZnCl adopted in the invention2The deposition and dissolution processes of the metal Zn cathode active material in the hydrate are very efficient and reversible, and no dendritic crystal growth risk exists, so that the cathode side of the hydrate has good operation stability. The battery of the invention has high safety and is environment-friendly. The battery of the invention has low cost and higher energy density.
Description
Technical Field
The invention belongs to the field of electrochemistry. In particular, the invention relates to the use of a mixture of carbon material and ionic bromide and an aqueous zinc-bromine bi-ion battery.
Background
With the rapid development of economy in China, the efficient utilization of the existing energy output and the development of new renewable energy sources have become important contents for upgrading energy structures. The importance of large-scale power energy storage technology as a key supporting technology in energy structure upgrading is increasingly prominent. Among the battery energy storage technologies, the zinc ion battery with the water system electrolyte is very suitable for large-scale power grid-level energy storage due to the advantages of high safety and low cost. Aqueous zinc ion batteries have been reported which generally use metallic zinc as a negative electrode active material, an aqueous solution containing a zinc salt dissolved therein as an electrolyte, and an oxide of manganeseVanadium oxide, metal ferricyanide or the like is a positive electrode active material. However, when an aqueous zinc ion battery is charged and discharged, the surface of the zinc negative electrode active material generates insoluble ZnO and Zn (OH)2These substances hinder the normal deposition and dissolution of zinc, increase the polarization of the battery, and reduce the charge-discharge coulombic efficiency (generally less than 90%) of the battery, and deteriorate the cycle performance. On the other hand, the positive electrode active material of the zinc ion battery reported at present also has the problems of complex process, higher cost, poor dynamics and poor cycle performance.
Disclosure of Invention
The object of the present invention is to provide the use of a mixture of carbon material and ionic bromide. Meanwhile, the invention provides a novel water-based zinc-bromine bi-ion battery which is low in cost and high in safety and is suitable for large-scale electric power energy storage markets.
In one aspect, the invention provides the use of a mixture of a carbon material and an ionic bromide in a battery positive active material in an aqueous electrolyte.
Preferably, in the application of the present invention, the carbon material is selected from at least one of mesocarbon microbeads graphite, natural graphite, expanded graphite, artificial graphite, glassy carbon, carbon-carbon composite material, carbon fiber, hard carbon, porous carbon, highly oriented graphite, three-dimensional graphite, carbon black, carbon nanotubes and graphene.
Preferably, in the use according to the invention, the ionic bromide is selected from KBr, NaBr, MgBr2、CaBr2And ZnBr2At least one of; more preferably, the ionic bromide is ZnBr2。
Preferably, in the use according to the invention, the molar ratio of bromine atoms in the ionic bromide to carbon atoms in the carbon material is from 0.1 to 1: 7.
In a second aspect, the present invention provides an aqueous zinc-bromine bi-ion battery comprising a positive electrode active material, a negative electrode active material and an electrolyte; wherein,
the positive electrode active material comprises a mixture of a carbon material and an ionic bromide;
the electrolyte bagContaining saturated ZnCl2An aqueous solution.
In the cell of the invention, saturated ZnCl is contained2The electrolyte of the aqueous solution realizes the efficient and reversible deposition and dissolution of metallic Zn in the aqueous electrolyte without the risk of dendritic growth. In the traditional water-based electrolyte, when a zinc electrode is deposited and dissolved, insoluble ZnO and Zn (OH) are generated on the surface of a zinc negative electrode active material2These substances hinder the normal deposition and dissolution of zinc, increase cell polarization, and cause the deposition dissolution efficiency of zinc to decrease (typically less than 90%). The invention is achieved by using a catalyst containing saturated ZnCl2The aqueous solution as an electrolyte completely solves the problems of zinc deposition and dissolution in aqueous electrolytes. In saturated ZnCl2In the hydrate of (2), the Zn metal negative active material can realize stable deposition and dissolution, and the deposition dissolution efficiency is as high as more than 99%, because of the high ZnCl content2In concentration of H2The potential window of the cathode side of O is obviously expanded, ZnO and Zn (OH)2The formation of (2) is suppressed. On the other hand, due to saturated ZnCl2Zn in the hydrate of (1)2+Very high concentration of Zn in2+In the deposition and dissolution processes, the growth of Zn dendrites is obviously inhibited, so that the safety of the Zn electrode is obviously improved.
In addition, in the battery of the invention, saturated ZnCl is contained2The electrolyte of the aqueous solution may also be such that H2The potential window of the O on the positive electrode side is obviously expanded to be beneficial to Br in ionic bromide-Reversibly intercalate and deintercalate the carbon material.
Preferably, in the aqueous zinc-bromine bi-ion battery of the present invention, the carbon material is selected from at least one of mesocarbon microbeads graphite, natural graphite, expanded graphite, artificial graphite, glassy carbon, carbon-carbon composite, carbon fiber, hard carbon, porous carbon, highly oriented graphite, three-dimensional graphite, carbon black, carbon nanotubes, and graphene.
Preferably, in the aqueous zinc-bromine bi-ion battery of the invention, the ionic bromide is selected from KBr, NaBr, MgBr2、CaBr2And ZnBr2In (1)At least one of; more preferably, the ionic bromide is ZnBr2。
In the cell of the invention, the ionic bromide of the invention is preferably MgBr2、CaBr2And ZnBr2At least one of; most preferably, the ionic bromide of the present invention is ZnBr2. This is mainly due to the divalent cation bromide (e.g. MgBr)2And CaBr2) Divalent cation bromides are preferred over monovalent cation bromides in view of higher cell energy density for the same mass of bromide relative to monovalent cation bromides such as NaBr and KBr. In addition, when the ionic bromide of the battery positive electrode active material is ZnBr2When the battery is charged, Br-Intercalated with carbon material, and Zn2+The metal Zn is deposited on the negative electrode side through electrolyte transportation, and the electrolyte of the battery does not participate in the battery reaction, so that the energy density of the battery can be greatly improved by limiting the addition amount of the electrolyte. However for non-ZnBr2Of the ionic bromide of (1), whose cations enter the electrolyte during charging of the battery, and Zn in the electrolyte2+Deposit on the negative electrode side, and therefore Zn in the electrolyte after the end of the battery charge2+Largely replaced by other cations; meanwhile, the electrolyte soaks the positive electrode and the negative electrode in the charging and discharging processes of the battery, and also has component change and participates in electrochemical reaction. To ensure sufficient Zn on the negative electrode side2+The deposition amount and the requirement of adding a large amount of electrolyte during the assembly of the battery limit the further improvement of the energy density of the battery, so that the ionic bromide is ZnBr2The energy density of the battery can be improved to the maximum extent.
Preferably, in the aqueous zinc-bromine bi-ion battery of the present invention, the electrolyte further includes ZnSO4、Zn(CH3COO)2、ZnF2、Zn(ClO4)2And ZnBr2One or more of the above; ZnSO in the electrolyte4、Zn(CH3COO)2、ZnF2、Zn(ClO4)2And ZnBr2One or more ofThe total mass of several kinds of ZnCl is20-10% of mass, ZnSO in the electrolyte4、Zn(CH3COO)2、ZnF2、Zn(ClO4)2And ZnBr2The total mass of one or more of them is not 0.
In the battery of the invention, the electrolyte contains, in addition to ZnCl2The aqueous solution may contain ZnSO4、Zn(CH3COO)2、ZnF2、Zn(ClO4)2And ZnBr2One or more of them. This is mainly because the increase in the concentration of the Zn salt concentration can expand the potential window of the electrolyte, which is advantageous for Zn at the negative electrode side2+And the dissolution process of metallic Zn. Therefore, when preparing the electrolyte, ZnCl is added into pure water2Adding ZnSO after saturation4、Zn(CH3COO)2、ZnF2、Zn(ClO4)2And ZnBr2One or more of them, to make them continuously dissolve in saturated ZnCl2In aqueous solution, optionally saturated ZnCl2Obtaining Zn salt aqueous solution with higher concentration on the basis of the aqueous solution, and further expanding the potential window of the electrolyte to ensure that Zn at the negative electrode side2+The efficiency of the deposition and the dissolving process of the metallic Zn is further improved.
Preferably, in the aqueous zinc-bromine bi-ion battery according to the present invention, the molar ratio of bromine atoms in the ionic bromide to carbon atoms in the carbon material is 0.1 to 1: 7.
Preferably, in the aqueous zinc-bromine bi-ion battery according to the present invention, the negative electrode active material is formed of metallic Zn or a material containing metallic Zn.
The battery of the present invention can be prepared by employing the following method:
negative electrode: ideally, in the fully discharged state, the negative electrode side of the battery is free of the negative electrode active material; metal Zn is gradually deposited on the negative current collector in the charging process; in the fully charged state, the battery negative active material is metallic Zn. In order to ensure the stable deposition of metal Zn on the negative current collector and prevent the over-discharge of the battery, the metal Zn can be directly selected as the battery negative current collector during the design of the battery, or a thin layer of metal Zn (the thickness is 1-100 um) is prepared on the negative current collector in advance, or the metal Zn can be alloyed with the negative current collector to form Zn-containing alloy.
And (3) positive electrode: the positive active material of the battery is prepared by uniformly mixing dry ionic bromide and a carbon material according to a specific ratio (the molar ratio of bromine atoms in the bromide to carbon atoms in the graphite is 0.1:7-1:7) and then adding a binder. The adhesive can be one or more of Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), sodium carboxymethyl cellulose (CMC), styrene-butadiene latex (SBR) and the like. The mass ratio of the adhesive to the positive active material (including the ionic bromide and the graphite material) is 0.02-0.1: 9.
Electrolyte: the water system zinc-bromine double-ion battery provided by the invention adopts saturated ZnCl2The hydrate is used as electrolyte and can be prepared by using ZnCl2Adding into pure water until saturation. Notably, due to ZnCl2The solubility in water varies with the temperature, so that saturated ZnCl is obtained at different room temperatures2ZnCl hydrate of2·xH2ZnCl in O2And H2The molar ratio of O varies slightly: e.g. zinc chloride having a solubility in water of 432g at 25 deg.C, saturated ZnCl2The hydrate of (A) is ZnCl2·1.75H2O; at 10 ℃ the solubility of zinc chloride in water is 353g, saturated ZnCl2The hydrate of (A) is ZnCl2·2.15H2And (O). However, in the range of 0-80 deg.C, saturated ZnCl2The composition change of the hydrate does not cause obvious performance change of the electrolyte, namely, the battery can stably operate within the range of 0-80 ℃. ZnCl for ensuring that electrolyte is always saturated when battery operates at different temperatures2In the state, 1 to 10 percent of ZnCl can be added in more when the electrolyte is prepared2Obtaining 1-10% of supersaturated ZnCl2A hydrate.
The invention has the beneficial effects that:
(1) the battery of the invention has longer cycle life and operation stability. Because of the adoption of saturated ZnCl2Metallic Zn cathode in hydrateThe deposition and dissolution process of the active material is very efficient and reversible (efficiency is more than 99%) and has no dendritic growth risk, so that the negative side of the active material has good operation stability. In addition, the positive electrode reacts to Br-The intercalation and deintercalation processes between carbon material layers are very reversible, the kinetic rate is high, and the positive side also has high cycle stability. Therefore, compared with the traditional water system zinc ion battery, the battery has better cycle stability.
(2) The battery of the invention has high safety and is environment-friendly. First of all, the present invention provides a battery that does not have any risk of fire or explosion even if the battery material is completely exposed to the air, because the battery material itself is very safe. Secondly, a metallic Zn negative active material and saturated ZnCl2Due to the matched use of the hydrate, the battery has no short circuit risk due to a dendrite-free mechanism of the negative electrode, and the charging and discharging operation safety is higher. Furthermore, the battery also has a short-circuit self-repairing mechanism: even if a short circuit loop is formed during the operation of the battery, the cathode metal Zn is directly contacted with the carbon material with Br embedded in the anode, and the Br embedded in the anode carbon material is separated and directly chemically reacted with Zn to generate ZnBr2Thus, a part of the metal Zn contacting the positive electrode active material is directly dissolved, and the short circuit of the battery is cut off. Therefore, the short-circuit self-repairing mechanism of the battery also ensures the safe operation of the battery. On the other hand, all materials for constructing the battery are harmless to the environment and are mature industrial products which are nontoxic and harmless, so that the battery is high in safety and environment-friendly.
(3) The battery of the invention has low cost and high energy density. The active materials of the battery of the invention in the full discharge state only comprise zinc chloride hydrate (electrolyte), ionic bromide and carbon material (anode active material), and the materials are all low in cost and rich in yield. Taking a mixed positive active material of a carbon material and zinc bromide as an example, considering that the maximum capacities of the carbon material and the zinc bromide are 319mAh/g and 238mAh/g respectively, the theoretical energy density of the battery containing only the electrode material can be calculated to be 218Wh/kg, and 4g of ZnCl is corresponding to the capacity of the battery according to 1Ah2Calculating the using amount of the electrolyte of the hydrate,the cost of the battery material containing the electrode material and the electrolyte is only 14$/kWh, which is significantly lower than that of the energy storage battery systems commonly used at present, such as lead-acid batteries and lithium ion batteries.
Drawings
Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 shows Zn | saturated ZnCl in example 1 of the present invention2Aqueous solution of | ZnBr2-constant current charge and discharge voltage curve of natural graphite battery at 25 ℃;
FIG. 2 shows Zn | saturated ZnCl in example 1 of the present invention2Aqueous solution of ZnBr2-data of constant current charge-discharge capacity and coulombic efficiency at 25 ℃ of the natural graphite battery along with charge-discharge cycles;
FIG. 3 shows Zn | saturated ZnCl in example 2 of the present invention2A constant-current charge-discharge voltage curve of the aqueous solution NaBr-natural graphite battery at 60 ℃;
FIG. 4 shows Zn | saturated ZnCl in example 2 of the present invention2And the constant-current charge-discharge capacity and the coulombic efficiency of the water solution NaBr-natural graphite battery at 60 ℃ are along with charge-discharge cycle data.
FIG. 5 shows Zn | saturated ZnCl in example 3 of the present invention2Aqueous solution of | MgBr2-constant current charge-discharge voltage curve of natural graphite battery at 25 ℃;
FIG. 6 shows Zn | saturated ZnCl in example 3 of the present invention2Aqueous solution of | MgBr2-data of constant current charge-discharge capacity and coulombic efficiency at 25 ℃ of the natural graphite battery along with charge-discharge cycles;
FIG. 7 shows Zn | saturated ZnCl in example 4 of the present invention2Aqueous solution of | ZnBr2-constant current charge and discharge voltage curve of hard carbon battery at 25 ℃;
FIG. 8 shows Zn | saturated ZnCl in example 4 of the present invention2Aqueous solution of | ZnBr2-constant current charge-discharge capacity and coulombic efficiency at 25 ℃ of the hard carbon battery along with charge-discharge cycle data;
FIG. 9 shows Zn | saturated ZnCl in example 5 of the present invention2Aqueous solution of ZnBr2-ZnSO4|ZnBr2Constant current charge-discharge voltage curve of natural graphite battery at 25 deg.CA wire;
FIG. 10 shows Zn | saturated ZnCl in example 5 of the present invention2Aqueous solution of ZnBr2-ZnSO4|ZnBr2-data of constant current charge-discharge capacity and coulombic efficiency at 25 ℃ of the natural graphite battery along with charge-discharge cycles;
Detailed Description
The present invention is described in further detail below with reference to specific embodiments, which are given for the purpose of illustration only and are not intended to limit the scope of the invention.
Example 1
This example provides a ZnCl saturated with Zn |2Aqueous solution of | ZnBr2Natural graphite batteries. The battery negative active material is a metallic Zn foil with a thickness of 0.1 mm. Electrolyte was prepared at 25 ℃: 432g of ZnCl was added to 100g of pure water2Obtaining saturated ZnCl2After the aqueous solution, a further 21.5g of ZnCl were added2To obtain supersaturated ZnCl2An aqueous solution. Positive electrode is ZnBr2And the natural graphite powder (the particle size is less than 10um) and the PTFE adhesive are uniformly mixed according to the mass ratio of 1.27:1:0.1 (the molar ratio of bromine atoms to carbon atoms in the graphite is 0.95:7) to prepare the film electrode. When the battery is assembled, a film-shaped positive electrode, a glass fiber diaphragm (trade name: Whatman) and a metal Zn foil are combined into a sandwich structure in sequence in the air, electrolyte (4g/Ah) is dripped into the glass fiber diaphragm to completely soak the positive electrode and the negative electrode, then the battery is sealed, and the electrochemical performance test is started at 25 ℃.
Fig. 1 is a typical charge-discharge voltage curve of the cell at a discharge rate of 0.5C, and the equilibrium voltage of the cell is about 1.65V. Fig. 2 is a graph showing the charge capacity, discharge capacity and coulombic efficiency of the battery as a function of cycle, the battery capacity being about 11Ah, and the battery being stably operated about 1900 times at a coulombic efficiency of about 99.5%, which is sufficient to show the cycle stability of the battery. In addition, the energy density of the battery containing only the positive electrode active material and the electrolyte solution used in the battery of this example was 126.8 Wh/kg.
Example 2
The present embodiment provides a Zn | ZnCl2A saturated aqueous solution | NaBr-natural graphite cell. Battery negativeThe pole active material is galvanized copper foil, the copper foil thickness is 10um, and the galvanizing coat thickness is about 5 um. The electrolyte preparation process was the same as in example 1. The positive electrode is a film electrode prepared by uniformly mixing NaBr, natural graphite powder (the particle size is less than 10um) and PVDF adhesive according to the mass ratio of 1.16:1:0.1 (the molar ratio of bromine atoms to carbon atoms in graphite is 0.95: 7). When the battery is assembled, a film-shaped positive electrode, a glass fiber diaphragm (trade name: Whatman) and a galvanized copper foil are combined into a sandwich structure in sequence in the air, electrolyte (7.1g/Ah) is dripped into the glass fiber diaphragm to completely soak the positive electrode and the negative electrode, then the battery is sealed, and the electrochemical performance test is started at 60 ℃.
Fig. 3 is a typical charge-discharge voltage curve of this cell at a discharge rate of 0.5C, the equilibrium voltage of the cell is about 1.65V, and it can be seen that the charge-discharge voltage polarization of the cell is significantly reduced compared to fig. 1, since the rate performance of the cell becomes better after the operating temperature of the cell increases. Fig. 4 is data of the charge capacity, discharge capacity and coulombic efficiency of the battery according to the cycle, the battery capacity is about 5.1Ah, and the battery is stably operated more than 200 times with coulombic efficiency of about 99.4%. In addition, it is noted that in this example, compared to example 1, NaBr (theoretical capacity of 260.5mAh/g) was used instead of ZnBr2That is, the battery needs to additionally consume 2.5g of zinc chloride in the electrolyte per 1Ah of charge, so that 3.1g of saturated ZnCl is required to be added in the present embodiment corresponding to the capacity of the battery per 1Ah in comparison with the amount of the electrolyte used in the embodiment 12As additional electrolyte. The energy density of the cell containing only the positive active material and the electrolyte used in the cell of this example was 103.0Wh/kg, which is smaller than the energy density of the cell described in example 1, indicating that the additional addition of electrolyte decreased the energy density of the cell.
Example 3
This example provides a ZnCl saturated with Zn |2Aqueous solution of | MgBr2Natural graphite batteries. The battery negative electrode active material is a galvanized copper foil, the thickness of the copper foil is 10um, and the thickness of a galvanized layer is about 5 um. The electrolyte preparation process was the same as in example 1. The positive electrode is MgBr2The natural graphite powder (the particle diameter is less than 10um) and the PVDF adhesive are mixed according to the mass ratio1.04:1:0.1 (molar ratio of bromine atoms to carbon atoms in graphite is 0.95:7) and uniformly mixing to prepare the film electrode. When the battery is assembled, a film-shaped positive electrode, a glass fiber diaphragm (trade name: Whatman) and a galvanized copper foil are combined into a sandwich structure in sequence in the air, electrolyte (7.1g/Ah) is dripped into the glass fiber diaphragm to completely soak the positive electrode and the negative electrode, then the battery is sealed, and the electrochemical performance test is started at 25 ℃.
Fig. 5 is a typical charge-discharge voltage curve of the cell at 0.5C discharge rate, with the cell having an equilibrium voltage of about 1.65V. Fig. 6 is data of the charge capacity, discharge capacity and coulombic efficiency of the battery as the cycle progresses, the battery capacity is about 8.7Ah, and the battery is stably operated 900 times with coulombic efficiency of about 99.5%. In addition, it is noted that in this example, compared to example 2, MgBr was used as a result of the use thereof2The mass fraction of the middle Br element is higher, so that under the same matching proportion of the positive electrode capacity, MgBr2The mass ratio of the MgBr powder to the natural graphite powder is smaller, namely the MgBr powder is used for manufacturing the anode2The mass is small. The energy density of the cell containing only the positive electrode active material and the electrolyte used in the cell of this example was 105.9Wh/kg, which was slightly improved compared to the energy density of the cell described in example 2. In addition, compared with the battery in the embodiment 1, the battery in the embodiment still additionally adds a part of electrolyte, so that the energy density of the battery is lower.
Example 4
This example provides a ZnCl saturated with Zn |2Aqueous solution of | ZnBr2-a hard carbon battery. The battery negative active material is a galvanized copper foil, the thickness of the copper foil is 10um, and the thickness of a galvanized layer is about 5 um. The electrolyte preparation process was the same as in example 1. Positive electrode is ZnBr2And the hard carbon and the PVDF adhesive are uniformly mixed according to the mass ratio of 1.27:1:0.1 (the molar ratio of bromine atoms to carbon atoms in the graphite is 0.95:7) to prepare the film electrode. The hard carbon used for the battery anode is spherical hard carbon particles obtained by processing sucrose at 1400 ℃, and the particle size is less than 30 um. When the battery is assembled, a film-shaped positive electrode, a glass fiber diaphragm (trade name: Whatman) and a galvanized copper foil are sequentially combined into a sandwich structure in the air, and an electrolyte (4g/Ah) is dripped into the glass fiber diaphragm to be completely immersedThe positive and negative electrodes were wetted, after which the cell was sealed and electrochemical performance testing was started at 25 ℃.
Fig. 7 is a typical charge-discharge voltage curve of this cell at 0.5C discharge rate, with the cell's equilibrium voltage of about 1.65V. Fig. 8 is data of the charge capacity, discharge capacity and coulombic efficiency of the battery with cycling, the battery capacity being about 103Ah, and the battery being stably operated 320 times with coulombic efficiency of about 99.4%.
Example 5
This example provides a ZnCl saturated with Zn |2Aqueous solution of ZnBr2-ZnSO4|ZnBr2Natural graphite batteries. The battery negative active material is a galvanized copper foil, the thickness of the copper foil is 10um, and the thickness of a galvanized layer is about 5 um. Electrolyte was prepared at 25 ℃: 432g of ZnCl was added to 100g of pure water2Obtaining saturated ZnCl2After the aqueous solution, ZnBr is additionally added2And ZnSO420g each, and finally 21.5g of ZnCl2To obtain a catalyst containing ZnBr2And ZnSO4Supersaturated ZnCl2An aqueous solution. Positive electrode is ZnBr2And the natural graphite powder (the particle size is less than 10um) and the PVDF adhesive are uniformly mixed according to the mass ratio of 1.27:1:0.1 (the molar ratio of bromine atoms to carbon atoms in the graphite is 0.95:7) to prepare the film electrode. When the battery is assembled, a film-shaped positive electrode, a glass fiber diaphragm (trade name: Whatman) and a galvanized copper foil are combined into a sandwich structure in sequence in the air, electrolyte (4g/Ah) is dripped into the glass fiber diaphragm to completely soak the positive electrode and the negative electrode, then the battery is sealed, and the electrochemical performance test is started at 25 ℃.
Fig. 9 is a typical charge-discharge voltage curve of this cell at 0.5C discharge rate, with the cell's equilibrium voltage being about 1.65V. Fig. 10 is a graph of the charge capacity, discharge capacity and coulombic efficiency of the cell as a function of cycle, the cell capacity being about 33.4Ah, with about 99.9% coulombic efficiency operating stably for about 1500 times. It is worth noting that in this example, saturated ZnCl is adopted2ZnBr is additionally added on the basis of the aqueous solution2And ZnSO4Compared with ZnCl saturated in examples 1-42The battery using the aqueous solution as the electrolyte has higher coulombic efficiency, and is beneficial to improvingCycle stability and capacity retention of the battery.
Claims (4)
1. An aqueous zinc-bromine double-ion battery comprises a positive electrode active material, a negative electrode active material and electrolyte; wherein the positive electrode active material comprises a mixture of a carbon material and an ionic bromide; the electrolyte contains saturated ZnCl2An aqueous solution;
the molar ratio of bromine atoms in the ionic bromide to carbon atoms in the carbon material is 0.1-1: 7;
the negative active material is formed of metallic Zn or a material containing metallic Zn.
2. The aqueous zinc-bromine bi-ion battery of claim 1, wherein the carbon material is selected from at least one of mesocarbon microbeads graphite, natural graphite, expanded graphite, artificial graphite, glassy carbon, carbon-carbon composites, carbon fibers, hard carbon, porous carbon, highly oriented graphite, three-dimensional graphite, carbon black, carbon nanotubes, and graphene.
3. The aqueous zinc-bromine bi-ion cell of claim 1 wherein the ionic bromide is selected from KBr, NaBr, MgBr2、CaBr2And ZnBr2At least one of (a).
4. The aqueous zinc-bromine bi-ion battery according to claim 1, wherein the electrolyte further comprises ZnSO4、Zn(CH3COO)2、ZnF2、Zn(ClO4)2And ZnBr2One or more of the above; ZnSO in the electrolyte4、Zn(CH3COO)2、ZnF2、Zn(ClO4)2And ZnBr2Is the total mass of one or more of ZnCl20-10% of the mass.
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| CN113013496B (en) * | 2021-02-22 | 2023-06-13 | 山东大学 | Non-negative electrode zinc battery with high safety coefficient and low cost and application thereof |
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