CN113036145A - High-stability zinc-iodine battery and preparation method and application of electrode material - Google Patents
High-stability zinc-iodine battery and preparation method and application of electrode material Download PDFInfo
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- CN113036145A CN113036145A CN202110261577.8A CN202110261577A CN113036145A CN 113036145 A CN113036145 A CN 113036145A CN 202110261577 A CN202110261577 A CN 202110261577A CN 113036145 A CN113036145 A CN 113036145A
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- iodine
- organic framework
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- CZLMUMZXIXSCFI-UHFFFAOYSA-N [Zn].[I] Chemical compound [Zn].[I] CZLMUMZXIXSCFI-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000007772 electrode material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 59
- 239000011630 iodine Substances 0.000 claims abstract description 59
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000013310 covalent-organic framework Substances 0.000 claims abstract description 47
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 12
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 15
- WDYQXCVMKOXLAE-UHFFFAOYSA-N C1=CC(=CC=C1N)N.C1=C(C=C(C=C1C=O)C=O)C=O Chemical compound C1=CC(=CC=C1N)N.C1=C(C=C(C=C1C=O)C=O)C=O WDYQXCVMKOXLAE-UHFFFAOYSA-N 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- 239000004642 Polyimide Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 229920001721 polyimide Polymers 0.000 claims description 7
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 7
- 229960001763 zinc sulfate Drugs 0.000 claims description 7
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 7
- 239000006258 conductive agent Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002262 Schiff base Substances 0.000 claims description 2
- 150000004753 Schiff bases Chemical class 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 238000006056 electrooxidation reaction Methods 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 2
- 229940006461 iodide ion Drugs 0.000 claims description 2
- 239000003273 ketjen black Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 150000003918 triazines Chemical class 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims description 2
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims description 2
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims 1
- QEORIOGPVTWFMH-UHFFFAOYSA-N zinc;bis(trifluoromethylsulfonyl)azanide Chemical compound [Zn+2].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QEORIOGPVTWFMH-UHFFFAOYSA-N 0.000 claims 1
- 230000001351 cycling effect Effects 0.000 abstract description 5
- 230000014759 maintenance of location Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 description 16
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000013543 active substance Substances 0.000 description 8
- 238000000840 electrochemical analysis Methods 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
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- 238000011161 development Methods 0.000 description 4
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- 239000004570 mortar (masonry) Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 238000007306 functionalization reaction Methods 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
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- UXPAASVRXBULRG-UHFFFAOYSA-N (3-boronophenyl)boronic acid Chemical compound OB(O)C1=CC=CC(B(O)O)=C1 UXPAASVRXBULRG-UHFFFAOYSA-N 0.000 description 1
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- QAQOLRCTTDVBAK-UHFFFAOYSA-N 5-bromobenzene-1,3-dicarbaldehyde Chemical compound BrC1=CC(C=O)=CC(C=O)=C1 QAQOLRCTTDVBAK-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
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- GNWXVOQHLPBSSR-UHFFFAOYSA-N oxolane;toluene Chemical compound C1CCOC1.CC1=CC=CC=C1 GNWXVOQHLPBSSR-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
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Images
Classifications
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/388—Halogens
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/028—Positive 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明涉及一种高稳定的锌碘电池及电极材料的制备方法和应用。电极材料包括共价有机框架化合物和活性碘，活性碘负载在共价有机框架化合物形成的孔隙结构中。制备方法为：将共价有机框架化合物与活性碘混合后，在管式炉中，进行加热处理，得到复合材料。有效的稳定了碘正极，改善了锌碘电池的电化学性能。具有较好的电化学性能，循环过程中，具有较好的容量和库伦效率保持的特性。
The invention relates to a preparation method and application of a highly stable zinc-iodine battery and an electrode material. The electrode material includes a covalent organic framework compound and active iodine, and the active iodine is supported in the pore structure formed by the covalent organic framework compound. The preparation method is as follows: after mixing the covalent organic framework compound and active iodine, heating treatment is performed in a tube furnace to obtain a composite material. The iodine cathode is effectively stabilized and the electrochemical performance of the zinc-iodine battery is improved. It has good electrochemical performance, and has the characteristics of good capacity and Coulombic efficiency retention during cycling.
Description
Technical Field
The invention belongs to the technical field of battery anode material iodine, and particularly relates to a high-stability zinc-iodine battery and a preparation method and application of an electrode material.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
With the rapid development of microelectronic information technology, the demands for digital electronic products, electric tools, electric vehicles, large-scale energy storage and the like are increasing day by day, and the development of secondary energy storage chargeable and dischargeable batteries with high performance and large capacity is urgent based on the urgent demands for green, efficient and practical energy storage materials at present. The electrode material is used as a key part determining the energy storage of the battery in the battery composition, and the development of the electrode material with high stability, long service life and high capacity is very important.
The water system rechargeable zinc-iodine battery is considered to be one of powerful competitors of the next generation energy storage system due to the advantages of low cost, high safety and the like, and has scientific research and practical application values. However, the redox reaction and shuttle effect of I3-/I-ions of the positive electrode in the current zinc-iodine battery generally cause the gradual reduction of the capacity and the coulombic efficiency in the circulating process, and further development and application of the battery are seriously hindered.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a high-stability zinc-iodine battery and a preparation method and application of an electrode material.
In order to solve the technical problems, the technical scheme of the invention is as follows:
in a first aspect, an electrode material includes a covalent organic framework compound and active iodine supported in a pore structure formed by the covalent organic framework compound.
After the covalent organic framework compound and the active iodine are treated at a proper temperature, one or more acting forces such as chemical bonds, hydrogen bonds, van der waals force and the like are formed between the iodine active substance and the COFs of the covalent organic framework compound, so that the iodine anode is effectively stabilized, and the electrochemical performance of the zinc-iodine battery is improved.
COFs are carbonized at high temperature to form N/P/B doped porous carbon, the N/P/B doped porous carbon and iodine are fused together after being heated to a certain temperature, the iodine is adsorbed and loaded on a skeleton of the porous carbon at high temperature, and a strong interaction force is formed under the action of high temperature, so that iodine diffusion is effectively inhibited, and an iodine anode is stabilized.
The covalent organic framework compounds COFs have incomparable advantages of other traditional porous materials such as molecular sieves, porous polymers, metal organic framework materials and the like, and have the characteristics of low density, high specific surface area, easiness in modification and functionalization and the like, and a large number of pores can be provided, so that active iodine is well loaded.
The COFs has the excellent characteristics of low density, high specific surface area, high porosity and easiness in modification and functionalization, and the iodine active substance is stably confined in the COFs, so that the characteristic of easy volatilization of the iodine simple substance is improved, the iodine active substance is effectively bound, and the solubility of the iodine active substance is reduced.
In some embodiments of the present invention, the particle size of the electrode material is about 100 to 300 nm.
In some embodiments of the invention, the covalent organic framework compound is one or more of boronic anhydrides and boronic esters, triazines, schiff bases, and polyimide-based covalent organic framework compounds; preferably polyimide covalent organic framework compound COF-LZU1 or boric acid covalent organic framework compound TP-COF-DAB.
In some embodiments of the present invention, the active iodine is one or more of elemental iodine, zinc iodide, polyiodide anion, iodide ion, or other substances capable of generating elemental iodine through electrochemical oxidation/reduction; preferably iodine and zinc iodide.
In some embodiments of the present invention, the active iodine content in the electrode material is 30-80% by mass, preferably 40-60% by mass.
In a second aspect, the preparation method of the electrode material comprises the following specific steps: and (3) mixing the covalent organic framework compound with active iodine, and then heating in a tubular furnace to obtain the composite material.
In some embodiments of the invention, the temperature of the heat treatment is 70-90 ℃ for 10-14 h; preferably 80 ℃ for 12 h. The active iodine enters the skeleton structure by a heating treatment method, so that the active iodine and COFs are integrated to obtain the composite material, the solubility of the active iodine is improved, and the I can be effectively reduced3-/I-Redox reactions of ions and shuttle effects.
In some embodiments of the present invention, the heating rate of the heating treatment is 1 to 10 ℃/min, preferably 2 ℃/min.
In a third aspect, a zinc-iodine battery positive electrode comprises the electrode material.
In some embodiments of the invention, the zinc-iodine battery positive electrode further comprises a conductive agent and a binder.
In some embodiments of the invention, the mass ratio of the composite material to the conductive agent to the binder is 1-8:1-2: 1-2; preferably 1:1:1, 7:2:1, 6:2:2, 8:1: 1.
In some embodiments of the invention, the conductive agent is one or more of MXene, ketjen black, acetylene black, carbon fiber, graphene, carbon nanotubes; MXene is preferred.
In some embodiments of the present invention, the binder is one or more of polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), Styrene Butadiene Rubber (SBR), and the like.
In a fourth aspect, a zinc-iodine battery comprises the positive electrode and the negative electrode of the zinc-iodine battery, electrolyte and a diaphragm.
Compared with the existing zinc-iodine battery, the zinc-iodine battery can better maintain the capacity and improve the coulomb efficiency in the circulating process.
In some embodiments of the invention, the negative electrode is a metallic zinc foil or electrodeposited zinc or other metallic negative electrode containing zinc.
In some embodiments of the invention, the membrane is a glass fiber membrane.
In some embodiments of the invention, the electrolyte comprises a zinc salt and an additive.
Optionally, the zinc salt is one or more of zinc sulfate, zinc trifluoromethanesulfonate, zinc chloride, zinc perchlorate, zinc nitrate, zinc acetate, bis (trifluoromethanesulfonyl) imide zinc, and the like.
Optionally, the additive is one or more of potassium chloride, iodine chloride, zinc iodide and the like.
In a fifth aspect, the zinc-iodine battery is applied to the fields of digital electronic products, electric tools, electric vehicles and the like.
One or more technical schemes of the invention have the following beneficial effects:
according to the invention, covalent organic framework compound COFs and an iodine active substance are compounded to form a stable iodine positive electrode material, the covalent organic framework compound COFs is taken as a template, the COFs has excellent characteristics of low density, high specific surface area, high porosity and easiness in modification and functionalization, the iodine active substance is stably trapped in a COFs framework, the characteristic of easy volatilization of iodine simple substances is improved, the iodine active substance is effectively restrained, and the solubility of the iodine active substance is reduced. In a zinc-iodine cell, the characteristic can trap polyiodide anions in a positive electrode area, and effectively slow down the shuttle effect. Based on the advantages, the covalent organic framework compound-iodine composite material is used as the positive electrode material of the zinc-iodine battery, so that a series of defects of poor cycle performance, low coulombic efficiency, easy volatilization, poor conductivity and the like of the iodine positive electrode can be overcome. In addition, the preparation method has the technical advantages of simplicity, convenience, high efficiency, high yield, high product purity and the like.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the invention and not to limit the invention.
FIG. 1 is a scanning electron micrograph of the COF-LZU1 used in example 1;
FIG. 2 is a scanning electron microscope image of the COF-LZU1 composite iodine simple substance anode in example 1;
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise. The invention will be further illustrated by the following examples
Example 1
A high-stability zinc-iodine battery and a preparation method and application thereof comprise the following steps:
(1) preparation of covalent organic framework compounds: the covalent organic framework compound in the composite material is a polyimide covalent organic framework compound COF-LZU 1.
0.30mmol of 1,3, 5-trimethylacylbenzene and 0.45mmol of 1, 4-diaminobenzene are dissolved in 3mL of 1, 4-dioxane, then 0.6mL of 3mol L-1 dilute acetic acid is added to the mixture, the mixture is stirred on a magnetic stirrer for 5 days, then the obtained product is respectively centrifugally washed by dimethylformamide and tetrahydrofuran in a centrifuge at 2000r/min for 3 times, and then the powder is kept at 80 ℃ in a vacuum oven for 12 hours and is dried, thus obtaining the COF-LZU1 powder.
The active material, conductive carbon black and PVDF binder are mixed and stirred for 12 hours according to the ratio of 6:2:2, then the mixture is coated on carbon paper, and the carbon paper is kept warm for 24 hours at 40 ℃ in a vacuum oven and dried to obtain the positive pole piece.
(2) After the iodine elementary substance is ground by a mortar, 0.1g of iodine elementary substance powder is weighed and uniformly ground with 0.1g of COF-LZU1 powder, then the mixture is put into a tube furnace, the temperature is raised to 80 ℃ at a constant temperature raising rate preferably 2 ℃/min, and the temperature is kept for 12 hours under the protection of argon, so that the COF-LZU1 zinc-iodine battery anode loaded with the iodine elementary substance is obtained.
(3) The iodine anode prepared by the steps is used as a zinc battery anode, 2 mol per liter of zinc sulfate and 0.1 mol per liter of iodine additive are used as electrolyte, a metal zinc foil is used as a cathode, a zinc-iodine battery is assembled, an electrochemical test is carried out at room temperature, and the electrochemical test is carried out at 100mAg-1At a current density of (3), the capacity retention rate was 80.3% after 50 weeks of cycling.
As can be seen from FIG. 1 and FIG. 2, the particle size before and after loading COF-LZU1 with iodine simple substance does not change greatly, and the particle size ranges from 100nm to 300 nm.
Example 2
A high-stability zinc-iodine battery and a preparation method and application thereof comprise the following steps:
(1) preparation of covalent organic framework compounds: the covalent organic framework compound in the composite material is a polyimide covalent organic framework compound COF-LZU1, and the steps are shown in the general example 1.
(2) After the iodine elementary substance is ground by a mortar, 0.1g of iodine elementary substance powder is weighed and uniformly ground with 0.1g of COF-LZU1 powder, then the mixture is put into a tube furnace, the temperature is raised to 80 ℃ at a constant heating rate of 2 ℃/min, and the temperature is kept for 12 hours under the protection of argon, so that the COF-LZU1 zinc-iodine battery anode loaded with the iodine elementary substance is obtained.
The active material and MXene colloidal solution are uniformly mixed in a ratio of 1:1, the mixture is subjected to suction filtration, the mixture is kept at 40 ℃ in a vacuum oven for 24 hours, and the positive pole piece is obtained by drying, wherein the MXene serves as a conductive current collector, the use of inactive conductive additives and binders is avoided, an integrated flexible self-supporting positive pole can be obtained, the structural integrity of the electrode is effectively kept, the conductivity of the whole electrode is improved, and the cost is saved.
(3) The iodine anode prepared by the steps is used as a zinc battery anode, 2 mol per liter of zinc sulfate and 0.1 mol per liter of iodine additive are used as electrolyte, a metal zinc foil is used as a cathode, a zinc-iodine battery is assembled, an electrochemical test is carried out at room temperature, and the electrochemical test is carried out at 100mAg-1At a current density of (3), the capacity retention rate was 81.2% after 50 weeks of cycling.
Example 3
A high-stability zinc-iodine battery and a preparation method and application thereof comprise the following steps:
(1) preparation of covalent organic framework compounds: the covalent organic framework compound in the composite material is a polyimide covalent organic framework compound COF-LZU1, and the steps are shown in the general example 1.
(2) After the iodine simple substance is ground by a mortar, 0.1g of zinc iodide powder is weighed and uniformly ground with 0.1g of COF-LZU1 powder, then the mixture is put into a tube furnace, the temperature is raised to 80 ℃ at a constant heating rate of 2 ℃/min, and the temperature is kept for 12 hours under the protection of argon, so that the COF-LZU1 zinc iodide-loaded zinc-iodine battery positive electrode active material is obtained.
(3) The active material and MXene colloidal solution are uniformly mixed in a ratio of 1:1, the mixture is subjected to suction filtration, the mixture is kept at 40 ℃ in a vacuum oven for 24 hours, and the positive pole piece is obtained by drying, wherein the MXene serves as a conductive current collector, the use of inactive conductive additives and binders is avoided, an integrated flexible self-supporting positive pole can be obtained, the structural integrity of the electrode is effectively kept, the conductivity of the whole electrode is improved, and the cost is saved.
(4) The iodine anode prepared by the steps is used as a zinc battery anode, 2 mol per liter of zinc sulfate and 0.1 mol per liter of iodine additive are used as electrolyte, a metal zinc foil is used as a cathode, a zinc-iodine battery is assembled, an electrochemical test is carried out at room temperature, and the electrochemical test is carried out at 100mAg-1At a current density of (3), the capacity retention rate was 81.8% after 50 weeks of cycling.
Example 4
A high-stability zinc-iodine battery and a preparation method and application thereof comprise the following steps:
(1) preparation of the boronic acid covalent organic framework Compound 200 mg of 1, 3-benzenediboronic acid, 644 mg of 5-bromoisophthalaldehyde, 70 mg of Pd (PPh3)4 and 14 ml of toluene-tetrahydrofuran (volume ratio 1: 1) were mixed and dissolved, followed by addition of 2 ml of 0.6 mol/l Na2CO3The aqueous solution was then subjected to repeated procedures of freezing, vacuum-pumping and thawing 3 times to remove water, and then heated under reflux for 48 hours. And (5) naturally cooling. And (3) removing the solvent by rotary evaporation at room temperature by using a rotary vacuum pump, then washing with dichloromethane, deionized water and saturated NaCl aqueous solution for several times to obtain a large amount of white floccules, and recrystallizing with dichloromethane to obtain a white solid boric acid COF product (TP-COF-DAB for short).
(2) After the iodine elementary substance is ground by a mortar, 0.1g of iodine elementary substance powder is weighed and uniformly ground with 0.1gTP-COF-DAB powder, then the powder is placed into a tube furnace, the temperature is raised to 80 ℃ at a constant heating rate of 2 ℃/min, and the temperature is kept for 12 hours under the protection of argon, so that the TP-COF-DAB iodine elementary substance-loaded zinc-iodine battery anode is obtained.
(3) The iodine positive electrode prepared by the steps is used as a zinc battery positive electrode, and 2 mol of zinc sulfate per liter and 0.1 mol of zinc sulfate per liter are usedEvery liter of iodine additive is used as electrolyte, metal zinc foil is used as negative electrode, zinc-iodine battery is assembled, electrochemical test is carried out at room temperature, and the electrochemical test is carried out at 100mAg-1At a current density of (3), the capacity retention rate after 50 weeks of cycling was 78.9%.
To summarize: when the anode material formed by compounding the covalent organic framework compound COFs and the active iodine is used for the zinc-iodine battery, the COFs can well restrict polyiodide anions formed by the active iodine in circulation, inhibit the diffusion of the polyiodide anions and inhibit the shuttle effect of the active iodine, so that the iodine anode is more stable, and great challenges are effectively solved.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
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