CN117013103A - Water-based zinc-iodine battery without ion exchange membrane and preparation method thereof - Google Patents
Water-based zinc-iodine battery without ion exchange membrane and preparation method thereof Download PDFInfo
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- CN117013103A CN117013103A CN202310998071.4A CN202310998071A CN117013103A CN 117013103 A CN117013103 A CN 117013103A CN 202310998071 A CN202310998071 A CN 202310998071A CN 117013103 A CN117013103 A CN 117013103A
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- zinc
- iodine
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- exchange membrane
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- CZLMUMZXIXSCFI-UHFFFAOYSA-N [Zn].[I] Chemical compound [Zn].[I] CZLMUMZXIXSCFI-UHFFFAOYSA-N 0.000 title claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000003014 ion exchange membrane Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011701 zinc Substances 0.000 claims abstract description 97
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 74
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000011669 selenium Substances 0.000 claims abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 55
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims abstract description 19
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 15
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 14
- 239000011630 iodine Substances 0.000 claims abstract description 14
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 13
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 13
- 239000001632 sodium acetate Substances 0.000 claims abstract description 13
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 11
- 229940102001 zinc bromide Drugs 0.000 claims abstract description 10
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 10
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 10
- 239000004744 fabric Substances 0.000 claims abstract description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 3
- 239000000835 fiber Substances 0.000 claims abstract 2
- 229910002804 graphite Inorganic materials 0.000 claims abstract 2
- 239000010439 graphite Substances 0.000 claims abstract 2
- 235000019441 ethanol Nutrition 0.000 claims description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 229940091258 selenium supplement Drugs 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000002120 nanofilm Substances 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical compound O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 claims description 3
- 229960001471 sodium selenite Drugs 0.000 claims description 3
- 235000015921 sodium selenite Nutrition 0.000 claims description 3
- 239000011781 sodium selenite Substances 0.000 claims description 3
- 238000000224 chemical solution deposition Methods 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims 2
- 239000004917 carbon fiber Substances 0.000 claims 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims 1
- 150000003751 zinc Chemical class 0.000 abstract description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 8
- 239000002064 nanoplatelet Substances 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 230000002401 inhibitory effect Effects 0.000 description 5
- 239000002135 nanosheet Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- -1 iodide ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 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
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229960002358 iodine Drugs 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 235000013271 sodium hydrogen selenite Nutrition 0.000 description 1
- 239000011792 sodium hydrogen selenite Substances 0.000 description 1
- OHYAUPVXSYITQV-UHFFFAOYSA-M sodium;hydrogen selenite Chemical compound [Na+].O[Se]([O-])=O OHYAUPVXSYITQV-UHFFFAOYSA-M 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 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
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
An aqueous zinc-iodine battery without ion exchange membrane and a preparation method thereof belong to the technical field of aqueous zinc batteries. In particular to a method for modifying the surface of a zinc sheet negative electrode, which can improve the cycle life of a water-based zinc-iodine battery. The method utilizes simple aqueous solution reaction to deposit an amorphous selenium film on the surface of a zinc sheet, and the obtained surface modified zinc cathode is marked as Zn@Se. The reaction liquid contains selenium source, sodium acetate and organic alcohol. Immersing the cleaned zinc sheet in a reaction solution for a certain time to react to obtain Zn@Se; an active carbon coating attached to graphite fiber felt or conductive carbon cloth (paper) or used as an anode adopts an aqueous solution dissolved with zinc sulfate, zinc iodide, zinc bromide and iodine simple substance as electrolyte, and combines with Zn@Se to construct the zinc-iodine rechargeable battery. The preparation process is simple, the cost is low, and the large-size Zn@Se anode is easy to amplify. The prepared zinc-iodine battery discards the ion exchange membrane and has longer cycle life.
Description
Technical Field
The invention relates to the technical field of electrochemical energy storage devices, in particular to a water system zinc-iodine battery without an ion exchange membrane and a preparation method thereof.
Background
With the increasing demand for fossil fuels and the increasing environmental pollution problems, the development of high-performance, clean energy storage devices is an urgent task. Lithium ion batteries are currently availableThe dominant secondary batteries in the market have limited lithium resource reserves, high battery manufacturing cost, and the organic electrolyte used brings fire and explosion risks. Therefore, the development of a novel secondary battery system with low cost, safety and high efficiency has practical significance, and is especially aimed at a large-scale energy storage system. Zinc has a potential of-0.76V relative to standard hydrogen electrodes and has a larger theoretical specific capacity of 820 mAh/g. Flow batteries (CN 201410776231) can be constructed with zinc cathodes and iodine containing electrolytes, but this type of battery requires an ion exchange membrane to separate the two different electrolytes, and an additional circulating water pump. If there is no ion exchange membrane, due to iodine trianion (I 3 - ) Which reacts in contact with the metallic zinc anode, resulting in easy corrosion of the zinc anode, gradual decrease in the capacity of the battery, and decrease in the coulombic efficiency.
To inhibit the shuttle effect of iodine, the existing improvement methods are: will I 2 Anchored on porous support and examined for I 2 Effect of load on cell performance (Journal of Materials Chemistry A2020, 8 (7), 3785-3794); also researchers use Nafion membranes to suppress shuttle effects in zinc-iodine cells (Energy&Environmental Science 2017, 10 (3), 735-741); constructing Zn-BTC MOF layer on surface of zinc cathode to selectively shield I 3 - Ions, thereby suppressing the shuttle effect (Advanced Materials 2020, 32 (38), 2004240). However, the preparation steps of the material coatings are complicated, the front side and the back side of zinc are not easy to process simultaneously, the cost of raw materials is high, and the cost advantage of the zinc-iodine battery can be obviously reduced.
Disclosure of Invention
The invention aims to provide a water-based zinc-iodine battery without an ion exchange membrane and a preparation method thereof, and aims to solve the problem of high cost of the existing preparation method of the battery.
In order to achieve the above object, in a first aspect, the present invention provides a surface-modified zinc anode for an aqueous zinc-iodine battery, the preparation method comprising the steps of:
weighing a selenium source, sodium acetate and organic alcohol according to a certain molar ratio, adding deionized water, stirring and dissolving to obtain a reaction solution;
soaking the cleaned zinc sheet in the reaction solution for standing reaction, sequentially cleaning the zinc sheet after the reaction by deionized water and absolute ethyl alcohol, and vacuum drying to obtain a zinc negative electrode with the surface covered with an amorphous Se nano film, wherein the zinc negative electrode is marked as Zn@Se;
and taking Zn@Se as a negative electrode, taking an active carbon coating or a self-supporting film as a positive electrode, and taking an aqueous solution in which zinc sulfate, zinc iodide, zinc bromide and iodine simple substances are dissolved as an electrolyte to construct the zinc-iodine rechargeable battery.
Wherein the selenium source is one or more of selenium dioxide, selenic acid, sodium selenite and sodium hydrogen selenite, and sodium acetate is added to adjust the pH value to be 4.5-5.5;
the organic alcohol is one or more of ethanol, ethylene glycol, isopropanol and glycerol.
Wherein the concentration of selenium element in the selenium source is 0.1-0.5M;
the concentration of the sodium acetate is 0.02-0.05M;
the volume fraction of the organic alcohol is 5% -30%.
Wherein, the soaking is carried out at room temperature and normal pressure, and the soaking time is 1-12 hours;
the cleaning treatment comprises the steps of ultrasonically cleaning the zinc sheet by using an organic solvent, then flushing the zinc sheet by using deionized water, and then drying;
the standing reaction time is 0.5-2 hours.
Wherein the organic solvent is a mixed solution of acetone and ethanol.
The preparation method of the activated carbon coating comprises the following steps:
placing conductive carbon cloth or carbon paper into dilute nitric acid with the concentration of 1M, ultrasonically cleaning for 3 hours, and then repeatedly cleaning with deionized water to be neutral; drying in a 60 ℃ oven for 6 hours to obtain hydrophilic carbon cloth or hydrophilic carbon paper;
dispersing porous activated carbon powder, polyvinylidene fluoride and acetylene black in N-methyl pyrrolidone according to a mass ratio of 8:1:1, and then magnetically stirring for 12 hours to obtain carbon powder slurry with a concentration of about 20 mg/mL;
and uniformly coating the carbon powder slurry on the hydrophilic carbon cloth or the hydrophilic carbon paper, and then drying in an oven at 100 ℃ for 12 hours to obtain the activated carbon coating.
In a second aspect, the present invention provides an aqueous zinc-iodine battery free of ion exchange membrane, comprising a negative electrode, a positive electrode and an electrolyte;
the negative electrode is Zn@Se;
the positive electrode is an active carbon coating or a self-supporting film;
the electrolyte is an aqueous solution in which zinc sulfate, zinc iodide, zinc bromide and iodine simple substances are dissolved.
The invention relates to a preparation method of a water system zinc-iodine battery without an ion exchange membrane, which comprises the steps of weighing a selenium source, sodium acetate and organic alcohol according to a certain molar ratio, adding deionized water, stirring and dissolving to obtain a reaction solution; soaking the cleaned zinc sheet in the reaction solution for standing reaction, sequentially cleaning the zinc sheet after the reaction by deionized water and absolute ethyl alcohol, and vacuum drying to obtain a zinc negative electrode with the surface covered with an amorphous Se nano film, wherein the zinc negative electrode is marked as Zn@Se; and taking Zn@Se as a negative electrode, taking an active carbon coating or a self-supporting film as a positive electrode, and taking an aqueous solution in which zinc sulfate, zinc iodide, zinc bromide and iodine simple substances are dissolved as an electrolyte to construct the zinc-iodine rechargeable battery. The invention provides a method for forming a layer of amorphous Se film on the surface of a zinc sheet by utilizing a solution reaction method. The ratio of selenium to zinc element in the film decreases with increasing film thickness, and the Se to Zn molar ratio decreases from about 1:6 to about 1:12 as the film thickness increases from 1 micron to 10 microns. The amorphous Se film can allow zinc ions to pass through, and in the charge-discharge cycle process, a layer of amorphous Zn (OH) 2 and ZnO mixed nano-sheet network structure is induced and grown through parasitic reaction, so that the effects of inhibiting hydrogen evolution, inhibiting the shuttle effect of iodide ions and prolonging the cycle life of the battery are achieved. The production process is extremely simple, and commercial metal Zn sheets are reacted in the reaction liquid for a certain time. The invention has wide sources of raw materials, low price and low production cost, and is suitable for large-scale production. The battery adopting the modified zinc cathode has excellent performance, can stably run within 30000 circles and has no short circuit. Solves the problem of the shuttle effect of multi-iodine anions of the existing water-based zinc-iodine battery.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a diagram of (a) a physical optical photograph and (b) a scanning electron microscope morphology after brown amorphous Se nano film is formed on the surface of a zinc sheet.
FIG. 2 is XPS full spectrum after forming Se film on the surface of zinc sheet negative electrode; (b) XRD spectrum comparison of zinc sheet with Se film on surface with pure zinc sheet; (c) obtaining the optical forbidden bandwidth of the Se film by a Tauc Plot method; (d) Raman spectra of Se films.
Fig. 3 is a constant current charge-discharge curve comparison of a zinc-iodine button cell constructed by combining a pure zinc sheet and a zinc sheet covered with Se on the surface as a negative electrode with an active carbon positive electrode, respectively.
Fig. 4 is a graph of the microscopic topography of the surface of the zinc anode after 50 full cell cycles. (a) a zinc sheet having a Se film on the surface thereof; (b) pure zinc sheet without surface treatment.
Fig. 5 is a dark field TEM (inset) and EDS elemental analysis of a nano-sheet network structure formed on the surface of a zinc anode with Se film on the surface in a cycle. (b, c) low and high magnification TEM images of the nanoplatelet structures.
Fig. 6 is a comparison of the cycle performance of a full cell constructed with a zinc sheet negative electrode having a Se film on the surface and a pure zinc sheet negative electrode, respectively. The electrolyte is an aqueous solution containing zinc iodide, zinc bromide, zinc sulfate and iodine simple substance. (b) Comparison of the cycling performance of zinc-iodine full cells constructed with these two zinc cathodes.
Fig. 7 is a series-driven small electric fan of two zinc-iodine batteries.
Fig. 8 is a flowchart of a method for preparing an aqueous zinc-iodine battery without an ion exchange membrane.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
Referring to fig. 1 to 8, the present invention provides a method for preparing an aqueous zinc-iodine battery without an ion exchange membrane, comprising the following steps:
s1, weighing a selenium source, sodium acetate and organic alcohol according to a certain molar ratio, adding deionized water, stirring and dissolving to obtain a reaction solution;
specifically, the selenium source is one or more of selenium dioxide, selenic acid, sodium selenite and sodium hydrosulfite, and sodium acetate is added to adjust the pH value to be 4.5-5.5; the concentration of selenium element in the selenium source is 0.1-0.5M; the organic alcohol is one or more of ethanol, glycol, isopropanol and glycerol, and the volume fraction of the organic alcohol is 5-30%. The concentration of the sodium acetate is 0.02-0.05M.
S2, soaking the cleaned zinc sheet in the reaction solution for standing reaction, sequentially cleaning the zinc sheet after the reaction by deionized water and absolute ethyl alcohol, and vacuum drying to obtain a zinc negative electrode with the surface covered with the selenium-rich amorphous Se nano film, wherein the zinc negative electrode is marked as Zn@Se;
specifically, the soaking is carried out at room temperature and normal pressure, and the soaking time is 1-12 hours; the cleaning treatment comprises the steps of ultrasonically cleaning the zinc sheet by using an organic solvent, then flushing the zinc sheet by using deionized water, and then drying; the organic solvent is a mixed solution of acetone and ethanol. The standing reaction time is 0.5-2 hours.
And S3, taking the Zn@Se as a negative electrode, taking an active carbon coating or a self-supporting film as a positive electrode, and adopting an aqueous solution in which zinc sulfate, zinc iodide, zinc bromide and iodine simple substances are dissolved as an electrolyte to construct the zinc-iodine rechargeable battery.
Specifically, in the process of depositing/stripping circulation of the zinc sheet covered with amorphous Se in electrolyte containing zinc iodide, a layer of amorphous zinc hydroxide/zinc oxide nano sheet network structure can be induced to grow in situ, and the method plays an important role in inhibiting shuttle effect of hydrogen evolution and iodide ions.
The preparation method of the activated carbon coating comprises the following steps:
s31, placing conductive carbon cloth or carbon paper into dilute nitric acid with the concentration of 1M, ultrasonically cleaning for 3 hours, and then repeatedly cleaning with deionized water to be neutral; drying in a 60 ℃ oven for 6 hours to obtain hydrophilic carbon cloth or hydrophilic carbon paper;
s32 porous activated carbon powder, polyvinylidene fluoride and acetylene black are dispersed in N-methyl pyrrolidone (NMP) according to a mass ratio of 8:1:1, and then magnetic stirring is carried out for 12 hours to obtain carbon powder slurry with a concentration of about 20 mg/mL;
and S33, uniformly coating the carbon powder slurry on the hydrophilic carbon cloth or the hydrophilic carbon paper, and then drying in an oven at 100 ℃ for 12 hours to obtain the activated carbon coating.
Specifically, the mass loading of the activated carbon coating can be controlled between 2 and 10 mg/cm < 2 >.
The beneficial effects are that:
(1) The zinc sheet can be modified by adopting simple chemical bath deposition.
(2) The surface-modified Zn cathode exhibits excellent effects in improving coulombic efficiency, resisting corrosion, suppressing hydrogen evolution, and prolonging charge-discharge cycle life.
(3) The method is suitable for normal temperature and normal pressure conditions, does not need expensive equipment, is easy to expand preparation, and can simultaneously treat a plurality of large-size zinc sheets.
(4) After the zinc sheet is subjected to surface modification by the method disclosed by the invention, the zinc sheet can be applied to a water-based zinc-iodine battery, and can also be applied to a rechargeable zinc ion battery system which takes MnO2, V2O5, prussian blue analogues and an aromatic polymer as a positive electrode material.
Example 1
(1) A water-system zinc-iodine battery without ion exchange film is prepared from commercial zinc sheet/foil as raw material through cutting it into rectangular shape, ultrasonic washing in the mixture of acetone and absolute alcohol for 10-30 min, and washing with deionized water.
(2) Preparing a reaction solution: 0.8 g selenium dioxide and 0.5 g sodium acetate are weighed and dissolved in a mixed solution of 100 mL deionized water and 20 mL glycerol.
(3) The cleaned zinc sheet is soaked in the reaction solution and reacts for 2 hours at room temperature, so that the zinc sheet with the brown film covered on the surface is obtained, and the macroscopic and microscopic morphologies are shown in fig. 1 (a) and (b), respectively. X-ray photoelectron spectroscopy (XPS) analysis determined the presence of Se elements as shown in fig. 2 (a). But the element content of Se and Zn is far more than 1 and about 12, so the film has the main component of Se simple substance. The diffraction peaks of the zinc sheet having the Se film on the surface thereof were identical to those of the pure zinc sheet by X-ray diffraction spectrum (XRD) analysis, which revealed that the Se film formed had an amorphous structure, as shown in FIG. 2 (b). By using the Tauc Plot method, the forbidden band width of the Se film obtained according to the ultraviolet-visible absorption spectrum (UV-Vis spectrum) is 1.86eV, which is relatively close to the forbidden band width of the crystal Se (1.85 eV), as shown in fig. 2 (c). Raman scattering (Raman spectra) results showed that the film exhibited the same characteristic peaks as Se, as shown in fig. 2 (d). It is therefore presumed that the Se film is mainly composed of an amorphous Se simple substance.
(4) Two identical round plates are punched on the zinc sheet with Se on the surface in the step (3) and the pure zinc sheet respectively, a glass fiber diaphragm is adopted, an aqueous solution electrolyte containing 1M zinc sulfate, 0.5M zinc iodide and 0.1M zinc bromide and a conductive carbon cloth positive electrode with Active Carbon (AC) coated on the surface are assembled into a CR2032 button battery respectively, and constant current charge and discharge test analysis is carried out on the CR2032 button battery, and the result is shown in figure 3. It can be seen that the median voltage of the discharge platform is 1.2V, and the capacity of the full battery prepared by the zinc cathode modified by the surface Se is obviously higher than that of the battery adopting the pure zinc sheet.
After 50 circles of constant current charge and discharge, the button cell shell is disassembled, and the negative electrode is taken out for observation by a scanning electron microscope. It was found that Se-coated zinc sheets, the surface Se induced amorphous nanoplatelet network structure, as shown in fig. 4 (a). Whereas pure zinc sheet cathodes produce crystalline particle byproducts of ZnO as shown in fig. 4 (b). For the network structure of the nanoplatelets, it was observed by Transmission Electron Microscopy (TEM) for individual nanoplatelets that the nanoplatelets were rough in surface and thin in thickness, as shown in fig. 5 (a). The nanoplatelets were analyzed according to the high resolution transmission photograph without obvious crystal face streaks, indicating that they were amorphous structures, as shown in fig. 5 (b). According to the analysis of an energy spectrometer (EDS), no Se element was found in the nanoplatelets, and the Zn to O ratio was close to 1:2, as shown in fig. 5 (c), so that it was presumed that the nanoplatelets were an amorphous Zn (OH) 2 and ZnO mixed two-dimensional nanostructure.
(5) The Se-covered zinc sheet and the pure zinc sheet are used for constructing a symmetrical battery, and the electrolyte in the step (4) is adopted for cycle test, and the result is shown in fig. 6 (a). The button cell prepared in step (4) was subjected to a long cycle test, and the result is shown in fig. 6 (b). It can be seen that the device of the zinc sheet negative electrode covered by Se is obviously longer in cycle life than the device of the pure zinc sheet negative electrode, whether the device is a symmetrical battery or a full battery, and is attributed to the ion conduction characteristic of Se and the amorphous Zn (OH) 2 and ZnO composite nano-sheet network structure which is induced and generated by the Se, and has the functions of inhibiting hydrogen evolution and dendrites, inhibiting the shuttle effect of iodine ions and the like. In particular, the capacity retention of the battery of the Se-covered zinc sheet anode was 89% after 30000 cycles, whereas the full battery using pure zinc sheet failed after only about 10000 cycles, and the final capacity retention was 74%.
(6) In addition to the button cell as described in step (3), the zinc sheet negative electrode covered with the amorphous Se film in the present invention may be combined with an active carbon positive electrode, a separator, and the iodine-containing electrolyte as described in step (3) to the most synthesized zinc-iodine cartridge battery. As shown in fig. 7, two zinc-iodine batteries based on plastic boxes drive a small electric fan in series. Therefore, the surface Se modified zinc cathode and the electrolyte can be used for small button type and large box type zinc-iodine batteries, and the ion exchange membrane used by the conventional zinc-iodine flow battery is abandoned.
The comparative examples 1 to 8 are shown in Table 1. Examples 1-8 were identical to example 1 except that the solution composition for preparing Se was different.
Table 1, solution ratios of Se film grown on zinc sheet surface in different examples.
| Example of the other | Se source additive and concentration | Sodium acetate concentration | Organic alcohol species and volume fraction | Zinc sheet soaking time (h) |
| 1 | SeO 2 , 0.2 mol/L | 0.01 mol/L | Ethanol, 10% | 1 |
| 2 | SeO 2 , 0.05 mol/L | 0.02 mol/L | Ethanol, 25% | 2 |
| 3 | Na 2 SeO 3 , 0.1 mol/L | 0.01 mol/L | Ethylene glycol, 15% | 3 |
| 4 | Na 2 SeO 3 , 0.2 mol/L | 0.05 mol/L | Glycerol, 20% | 4 |
| 5 | H 2 SeO 3 , 0.1 mol/L | 0.03 mol/L | Isopropanol, 15% | 3 |
| 6 | H 2 SeO 3 , 0.05 mol/L | 0.02 mol/L | Ethylene glycol, 25% | 2 |
| 7 | NaHSeO 3 , 0.1 mol/L | 0.02 mol/L | Ethanol, 25% | 3 |
| 8 | NaHSeO 3 , 0.05 mol/L | 0.05 mol/L | Isopropanol, 20% | 1 |
In a second aspect, the present invention provides an aqueous zinc-iodine battery free of ion exchange membrane, comprising a negative electrode, a positive electrode and an electrolyte;
the negative electrode is Zn@Se;
the positive electrode is an active carbon coating or a self-supporting film;
the electrolyte is an aqueous solution in which zinc sulfate, zinc iodide, zinc bromide and iodine simple substances are dissolved.
Conclusion: the above implementation of the invention can generate an amorphous Se nanometer coating layer on the surface of a zinc sheet, and the obtained surface modified zinc cathode can be used for a water-based zinc-iodine rechargeable battery, and the specific flow is summarized in fig. 8. The amorphous Se coating can induce amorphous Zn (OH) 2/ZnO mixed nano-sheet network structure in the circulation process of the zinc cathode, so that corrosion of the zinc cathode and zinc dendrite generation and hydrogen evolution in the circulation process are inhibited, and the cycle life of the water-based zinc-iodine rechargeable battery is greatly prolonged.
The above disclosure is only a preferred embodiment of a method for preparing an aqueous zinc-iodine battery without an ion exchange membrane, but it is not limited thereto, and those skilled in the art will understand that all or part of the procedures for implementing the above embodiments are equivalent and still fall within the scope of the invention.
Claims (5)
1. A method for preparing an aqueous zinc-iodine battery without an ion exchange membrane, comprising the steps of:
(1) Weighing a selenium source, sodium acetate and organic alcohol according to a certain molar ratio, adding deionized water, stirring and dissolving to obtain a reaction solution; the selenium source in the reaction liquid is one of selenium dioxide, selenic acid, sodium selenite and sodium hydrosulfite, and sodium acetate is added to adjust the pH value to be 4.5-5.5; the organic alcohol is one or more of ethanol, ethylene glycol, isopropanol and glycerol;
(2) Immersing the cleaned zinc sheet in the reaction solution for chemical bath deposition reaction, sequentially cleaning the zinc sheet after the reaction by deionized water and absolute ethyl alcohol, and vacuum drying to obtain a zinc negative electrode with the surface covered with an amorphous Se nano film, which is marked as Zn@Se;
(3) And taking Zn@Se as a negative electrode, taking an active carbon coating as a positive electrode, and taking an aqueous solution in which zinc sulfate, zinc iodide, zinc bromide and iodine simple substances are dissolved as an electrolyte to construct the zinc-iodine rechargeable battery.
2. The method for producing an aqueous zinc-iodine battery not containing an ion exchange membrane according to claim 1, wherein,
the concentration of selenium element in the selenium source is 0.1-0.5M;
the concentration of the sodium acetate is 0.02-0.05M;
the volume fraction of the organic alcohol is 5% -30%.
3. The method for producing an aqueous zinc-iodine battery not containing an ion exchange membrane according to claim 1, wherein,
the soaking is carried out at room temperature and normal pressure, and the soaking time is 1-12 hours;
the standing reaction time is 0.5-2 hours.
4. The method for producing an aqueous zinc-iodine battery not containing an ion exchange membrane according to claim 1, wherein,
the preparation method of the activated carbon coating comprises the following steps:
conducting carbon fiber cloth, carbon fiber paper, graphite fiber felt or the like is used as a current collector, and is put into dilute nitric acid with the concentration of 1M for ultrasonic cleaning for 3 hours, and then deionized water is used for repeatedly cleaning to be neutral; drying in a 60 ℃ oven for 6 hours to obtain a hydrophilic carbon-based current collector;
dispersing porous activated carbon powder, polyvinylidene fluoride and acetylene black in N-methyl pyrrolidone according to a mass ratio of 8:1:1, and then magnetically stirring for 12 hours to obtain carbon powder slurry with a concentration of about 20 mg/mL;
and uniformly coating the carbon powder slurry on the carbon-based current collector, and then drying the carbon powder slurry in an oven at 100 ℃ for 12 hours to obtain the active carbon coated anode.
5. An ion exchange membrane-free aqueous zinc-iodine battery according to claim 1, comprising a negative electrode, a positive electrode and an electrolyte;
the negative electrode is Zn@Se;
the positive electrode is an active carbon coating;
the electrolyte is an aqueous solution in which zinc sulfate, zinc iodide, zinc bromide and iodine simple substances are dissolved.
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