CN116364838A - Multifunctional ferroelectric polymer protective coating, metal zinc electrode and zinc ion battery - Google Patents
Multifunctional ferroelectric polymer protective coating, metal zinc electrode and zinc ion battery Download PDFInfo
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- CN116364838A CN116364838A CN202310367142.0A CN202310367142A CN116364838A CN 116364838 A CN116364838 A CN 116364838A CN 202310367142 A CN202310367142 A CN 202310367142A CN 116364838 A CN116364838 A CN 116364838A
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- ferroelectric polymer
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- 239000011701 zinc Substances 0.000 title claims abstract description 151
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 149
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 149
- 229920000642 polymer Polymers 0.000 title claims abstract description 79
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 71
- 239000002184 metal Substances 0.000 title claims abstract description 71
- 239000011253 protective coating Substances 0.000 title claims abstract description 45
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 150000003751 zinc Chemical class 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims description 24
- 239000002033 PVDF binder Substances 0.000 claims description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 7
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims description 6
- 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 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- 238000004528 spin coating Methods 0.000 claims description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 238000010345 tape casting Methods 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 239000002519 antifouling agent Substances 0.000 claims description 2
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 claims description 2
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 239000003792 electrolyte Substances 0.000 abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 12
- 239000001257 hydrogen Substances 0.000 abstract description 12
- 210000001787 dendrite Anatomy 0.000 abstract description 10
- 238000007086 side reaction Methods 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 6
- 239000007772 electrode material Substances 0.000 abstract description 6
- 238000002161 passivation Methods 0.000 abstract description 6
- 239000010405 anode material Substances 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000005621 ferroelectricity Effects 0.000 abstract description 3
- 239000012466 permeate Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 239000007773 negative electrode material Substances 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000012459 cleaning agent Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000005684 electric field Effects 0.000 description 5
- 239000011241 protective layer Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- MESZHBWNPGMZGK-UHFFFAOYSA-N fluoroform;zinc Chemical compound [Zn].FC(F)F MESZHBWNPGMZGK-UHFFFAOYSA-N 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- XLOFNXVVMRAGLZ-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2-trifluoroethene Chemical group FC(F)=C.FC=C(F)F XLOFNXVVMRAGLZ-UHFFFAOYSA-N 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000006056 electrooxidation reaction Methods 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920000131 polyvinylidene Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000005246 galvanizing Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IDEAEPXBQLUDAI-UHFFFAOYSA-N dibutylcarbamodithioic acid;zinc Chemical compound [Zn].CCCCN(C(S)=S)CCCC IDEAEPXBQLUDAI-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M4/04—Processes of manufacture in general
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The application discloses a multifunctional ferroelectric polymer protective coating, a metal zinc electrode and a zinc ion battery, wherein the multifunctional ferroelectric polymer protective coating comprises the following components: zinc salts, ferroelectric polymers and organic solvents. The multifunctional ferroelectric polymer protective coating can have a stable solid-liquid interface with metallic zinc, can block the entry of water molecules, simultaneously provides a transmission path for zinc ions, and can inhibit side reactions such as hydrogen evolution, corrosion, passivation and the like; the ferroelectric polymer has inherent ferroelectricity, can induce zinc ions to be uniformly deposited, effectively inhibit zinc dendrite growth, and further improve the cycle stability and coulomb efficiency of the zinc anode material; the coating has excellent hydrophilicity, the contact angle is only 28 degrees, and the coating can be beneficial to the electrolyte to permeate into the zinc electrode material after being coated on the surface of the zinc electrode material, so that the reaction kinetic parameters are improved.
Description
Technical Field
The application belongs to the technical field of zinc ion batteries, and particularly relates to a multifunctional ferroelectric polymer protective coating, a metal zinc electrode and a zinc ion battery.
Background
Because lithium ion batteries frequently have fire or even explosion accidents, people pay more attention to the safety problem of the batteries, and the development of high-safety, environment-friendly and low-cost metal ion batteries has become an important and urgent target for wide scientific researchers. Among them, the aqueous zinc ion battery is regarded as the energy storage device with the prospect of the next generation due to the advantages of environmental protection, low cost, high safety, high theoretical capacity, surface hydrogen evolution overpotential and the like.
Currently, in zinc ion batteries, the following problems still exist in metallic zinc cathodes: (1) Uneven distribution of the electric field on the surface of zinc causes unbalanced electroplating of zinc, thereby leading to zinc dendrite formation and dead zinc formation; (2) Although the surface of the electrode has higher hydrogen evolution overpotential, the thermodynamics of metallic zinc in water environment is still unstable, hydrogen is inevitably generated in the galvanizing process, and the pH value of electrolyte is increased and the battery bulges; (3) Zinc in dissolved O 2 Or electrochemical corrosion reaction easily occurs in water; (4) The increase of local pH in the electrolyte can lead to the generation of zinc acid salt, zinc hydroxide and other inactive byproducts on the surface of zinc, and the side reaction leads to lower galvanization/stripping coulomb efficiency, so that the utilization rate of a zinc electrode is low, the cycle performance of the battery is greatly reduced, and the practical application of the zinc ion battery is limited.
Disclosure of Invention
The purpose of the application is to provide a multifunctional ferroelectric polymer protective coating, a metal zinc electrode and a zinc ion battery, so as to solve the problems that in the prior art, uneven electric field distribution on the surface of a metal zinc negative electrode causes unbalanced electroplating of zinc, zinc dendrite and dead zinc are formed, the thermodynamics of the metal zinc in a water environment is unstable, hydrogen is generated in the zinc plating process to cause the pH value of electrolyte to rise and the battery to swell, and zinc is dissolved in O 2 Or electrochemical corrosion reaction easily occurs in water, and the increase of local pH in electrolyte can generate inactive byproducts, so that the zinc plating/stripping coulomb efficiency is lower, the utilization rate of zinc electrodes is reduced, and the battery cycle performance is greatly reduced.
In order to achieve the above purpose, a technical scheme adopted in the application is as follows:
a multifunctional ferroelectric polymer protective coating is provided, which comprises the following components: zinc salts, ferroelectric polymers and organic solvents.
In one or more embodiments, the molar concentration of the zinc salt in the multifunctional ferroelectric polymer protective coating is 20 to 500mg/mL, and the molar concentration of the ferroelectric polymer is 20 to 500mg/mL.
In one or more embodiments, the zinc salt is one or more combinations of zinc trifluoromethane sulfonate, zinc bistrifluorosulfonimide, zinc dibutyldithiocarbamate, zinc sulfate, zinc nitrate, zinc chloride.
In one or more embodiments, the organic solvent is one or more of N-methylpyrrolidone, N-methylformamide, formic acid, phenol, or a combination thereof.
In one or more embodiments, the ferroelectric polymer is one or more combinations of polyvinylidene fluoride, polyvinylidene fluoride copolymer, polyamide, polyurethane, ferroelectric liquid crystal polymer.
In order to achieve the above object, another technical solution adopted in the present application is:
the preparation method of the multifunctional ferroelectric polymer protective coating according to any one of the above embodiments is provided, and comprises the following steps:
and dissolving the zinc salt and the ferroelectric polymer in the organic solvent, and uniformly stirring to obtain the multifunctional ferroelectric polymer protective coating.
In order to achieve the above object, another technical solution adopted in the present application is:
provided is a metallic zinc electrode comprising:
a metal zinc sheet;
the multifunctional ferroelectric polymer protective paint according to any one of the above embodiments is applied and cured on the surface of the metallic zinc sheet.
In order to achieve the above object, another technical solution adopted in the present application is:
the preparation method of the metal zinc electrode according to any one of the above embodiments comprises the following steps:
and (3) removing impurities from the metal zinc sheet, drying, coating the multifunctional ferroelectric polymer protective coating according to any one of the embodiments on the surface of the metal zinc sheet, and drying to obtain the metal zinc electrode.
In one or more embodiments, the coating is one or more combinations of spin coating, knife coating, spray coating; in the step of drying to obtain the metal zinc electrode, the drying is specifically performed at 60-150 ℃.
In order to achieve the above object, another technical solution adopted in the present application is:
provided is a zinc ion battery, wherein the negative electrode of the zinc ion battery adopts the metal zinc electrode according to any one of the embodiments.
The beneficial effect of this application is, in contrast to prior art:
after the multifunctional ferroelectric polymer protective coating is coated on the surface of the metal zinc, a stable solid-liquid interface can be formed between the multifunctional ferroelectric polymer protective coating and the metal zinc, so that entry of water molecules is blocked, a transmission path can be provided for zinc ions, and side reactions such as hydrogen evolution, corrosion, passivation and the like are further inhibited;
the multifunctional ferroelectric polymer protective coating has inherent ferroelectricity of a ferroelectric polymer, can induce uniform deposition of zinc ions after being coated on the surface of metal zinc, effectively inhibits growth of zinc dendrites, and further improves the cycle stability and coulomb efficiency of a zinc anode material;
the multifunctional ferroelectric polymer protective coating has excellent hydrophilicity, the contact angle is only 28 degrees, and electrolyte can be facilitated to permeate into a zinc electrode material after being coated on the surface of the zinc electrode material, so that the reaction kinetic parameters are improved;
when the metal zinc electrode is used as a battery cathode material, side reactions such as hydrogen evolution, corrosion, passivation and the like can be effectively avoided, zinc ions are induced to be uniformly deposited, zinc dendrite growth is avoided, and therefore the cycle stability and coulomb efficiency of the battery are remarkably improved.
Drawings
FIG. 1 is a cross-sectional scanning electron microscope of a metallic zinc electrode prepared in example 1 of the present application;
FIG. 2 is a surface scanning electron microscope image of a metallic zinc electrode prepared in example 1 of the present application;
fig. 3 is a graph showing the contact angle measurement of effect example 2 of the present application;
fig. 4 is an ac impedance diagram of effect example 3 of the present application;
FIG. 5 is a graph showing comparison of the cycle stability of effect example 3 of the present application.
Detailed Description
The present application will be described in detail with reference to the embodiments shown in the drawings. The embodiments are not intended to be limiting and structural, methodological, or functional changes made by those of ordinary skill in the art in light of the embodiments are intended to be included within the scope of the present application.
As in the background art, the uneven electric field distribution on the zinc surface results in unbalanced electroplating of zinc, eventually leading to the formation of zinc dendrites and dead zinc. Although the surface of the zinc electrode has higher hydrogen evolution overpotential, the thermodynamics of metallic zinc in water environment is still unstable, hydrogen is inevitably generated in the galvanizing process, the pH value of electrolyte is increased and a battery bulges, the increase of local pH in the electrolyte can lead to the generation of zinc salts, zinc hydroxides and other inactive byproducts on the surface of the zinc, and the cycle performance of the battery is greatly reduced. In addition, zinc is also susceptible to electrochemical corrosion reactions. The above problems severely limit the practical application of zinc ion batteries.
In order to solve the problems, and to help research of the next generation of environment-friendly, low-cost and high-safety metal ion batteries, the applicant developed a multifunctional ferroelectric polymer protective coating for protecting zinc electrodes, which can improve electrochemical reaction kinetic parameters of zinc cathodes in zinc ion batteries, can shield electric field intensity of zinc surfaces, inhibit uneven distribution of electric fields caused by 'tip effect', further inhibit zinc dendrites and side reactions, and improve cycle stability, coulomb efficiency and utilization rate of zinc electrodes.
Specifically, the multifunctional ferroelectric polymer protective coating comprises the following components: zinc salts, ferroelectric polymers and organic solvents.
In one application scenario, the concentration of zinc salt in the coating may be 20-500 mg/mL and the molar concentration of ferroelectric polymer may be 20-500 mg/mL.
The zinc salt is one or more of zinc trifluoromethane sulfonate, zinc bistrifluoro-sulfonyl imide, zinc dibutyl dithio-carbamic acid, zinc sulfate, zinc nitrate and zinc chloride.
The organic solvent is one or more of N-methyl pyrrolidone, N-methyl formamide, formic acid and phenol.
The ferroelectric polymer is one or more of polyvinylidene fluoride, polyvinylidene fluoride copolymer, polyamide, polyurethane and ferroelectric liquid crystal polymer.
The application also provides a preparation method of the multifunctional ferroelectric polymer protective coating, which comprises the following steps: and (3) dissolving zinc salt and ferroelectric polymer in an organic solvent, and uniformly stirring to obtain the multifunctional ferroelectric polymer protective coating.
After the multifunctional ferroelectric polymer protective coating is coated on the surface of the metal zinc, a stable solid-liquid interface can be formed between the multifunctional ferroelectric polymer protective coating and the metal zinc, water molecules are prevented from entering, a transmission path can be provided for zinc ions, and side reactions such as hydrogen evolution, corrosion, passivation and the like are further inhibited.
In addition, the multifunctional ferroelectric polymer protective coating has inherent ferroelectricity of ferroelectric polymers, can induce uniform deposition of zinc ions, effectively inhibits growth of zinc dendrites, and further improves cycle stability and coulomb efficiency of zinc cathode materials.
Meanwhile, the preparation method of the multifunctional ferroelectric polymer protective coating is simple, has low cost, can be produced in a large scale, and has good industrialization prospect.
The application also provides a metal zinc electrode, which comprises a metal chip and the multifunctional ferroelectric polymer protective coating of any embodiment mode, wherein the multifunctional ferroelectric polymer protective coating is coated and cured on the surface of the metal zinc.
The metal zinc electrode can effectively inhibit side reactions such as hydrogen evolution, corrosion, passivation and the like due to the protective effect of the multifunctional ferroelectric polymer protective coating, induces uniform deposition of zinc ions, effectively inhibits growth of zinc dendrites, and further improves the cycle stability and coulomb efficiency of the zinc anode material.
The application also provides a preparation method of the metal zinc electrode in any embodiment, which specifically comprises the following steps: removing impurities from a metal zinc sheet, drying, coating the multifunctional ferroelectric polymer protective coating in any embodiment on the surface of the metal zinc sheet, and drying to obtain the metal zinc electrode.
In one application scenario, the metal zinc sheet can be subjected to impurity removal by soaking in a cleaning solution, the cleaning solution can comprise one or more of water, alcohols and ketones, and the temperature of drying after impurity removal can be 60-150 ℃. In other application scenarios, other impurity removal means may be adopted, and the drying temperature after impurity removal may be set based on the actual scenario, so that the effects of the embodiment can be achieved.
In one application scene, the coating can be one or more means of spin coating, knife coating and spray coating, and the coating can be uniformly coated on the surface of the metal zinc sheet.
In one application scenario, the step of drying to obtain the zinc metal electrode may be specifically drying at 60-150 ℃. In other application scenes, the drying temperature can be set based on the actual scene, and the coating can be solidified on the surface of the metal zinc sheet.
The application also provides a zinc ion battery, and the negative electrode of the zinc ion battery adopts the metal zinc electrode of any one of the embodiments.
The application also provides a preparation method of the zinc ion battery, which specifically comprises the following steps:
s1, cutting conductive carbon cloth into a round shape by using a slicer with the diameter of a die of 1.5cm to serve as a current collector of a zinc ion battery anode material;
s2, synthesizing manganese dioxide serving as a positive electrode material of the zinc ion battery on the conductive carbon cloth by an electrochemical deposition method;
s3, cutting the fiber diaphragm into a round shape with the diameter of 1.5cm by using a slicer to serve as a diaphragm of the zinc ion battery;
s4, preparing a mixed solution of 1M zinc sulfate and 0.2M manganese sulfate as an electrolyte of the water-based zinc ion battery;
s5, using a metal zinc sheet modified by the multifunctional ferroelectric polymer protective coating as a negative electrode material of the zinc ion battery;
s6, sequentially placing the manganese dioxide positive plate, the electrolyte, the diaphragm, the electrolyte, the modified zinc negative plate, the 0.8mm gasket and the elastic sheet into a positive battery bottom shell of model 2032;
s7, covering the negative electrode battery shell, and pressurizing the battery by using a battery sealing machine to seal the battery under 1.5 Mpa.
The technical scheme and effect of the present application are further elaborated below in conjunction with specific embodiments.
Example 1:
a metal zinc electrode is prepared by the following method:
s1, sequentially and respectively soaking a metal zinc sheet into acetone, alcohol and deionized water to remove impurities, and then drying a cleaning agent in an oven at the temperature of 60 ℃ to obtain a pure metal zinc sheet;
s2, dissolving 0.35g of zinc trifluoromethane sulfonate and 0.35g of polyvinylidene fluoride with molecular weight of 100 ten thousand in 10ml of N-methylpyrrolidone, and uniformly stirring to obtain a zinc trifluoromethane sulfonate-polyvinylidene fluoride multifunctional ferroelectric polymer solution;
s3, spin-coating the multifunctional ferroelectric polymer solution in the step S2 on the surface of the pure metal zinc sheet in the step S1;
and S4, drying in an oven at the temperature of 65 ℃ to obtain the zinc triflate-polyvinylidene fluoride multifunctional ferroelectric polymer protective layer modified metal zinc electrode.
Example 2:
a metal zinc electrode is prepared by the following method:
s1, sequentially and respectively soaking a metal zinc sheet into acetone, alcohol and deionized water to remove impurities, and then drying a cleaning agent in an oven at the temperature of 60 ℃ to obtain a pure metal zinc sheet;
s2, dissolving 5g of zinc trifluoromethane sulfonate and 0.6g of polyamide-66 with a molecular weight of 3 ten thousand in 10ml of anhydrous formic acid, and uniformly stirring to obtain a zinc trifluoromethane sulfonate-polyamide-66 multifunctional ferroelectric polymer solution;
s3, scraping the multifunctional ferroelectric polymer solution in the step S2 onto the surface of the pure metal zinc sheet in the step S1;
and S4, drying in an oven at the temperature of 95 ℃ to obtain the zinc triflate-polyamide-66 multifunctional ferroelectric polymer protective layer modified metal zinc electrode.
Example 3:
a metal zinc electrode is prepared by the following method:
s1, respectively soaking a metal zinc sheet into acetone, alcohol and deionized water to remove impurities, and then drying a cleaning agent in an oven at the temperature of 60 ℃ to obtain a pure metal zinc sheet;
s2, dissolving 0.35g of zinc trifluoromethane sulfonate and 5g of poly (vinylidene fluoride-trifluoroethylene) with molecular weight of 5 ten thousand in 10ml of anhydrous formic acid, and uniformly stirring to obtain a zinc trifluoromethane sulfonate-poly (vinylidene fluoride-trifluoroethylene) multifunctional ferroelectric polymer solution;
s3, scraping the multifunctional ferroelectric polymer solution in the step S2 onto the surface of the pure metal zinc sheet in the step S1;
and S4, drying in an oven at 145 ℃ to obtain the zinc triflate-poly (vinylidene fluoride-trifluoroethylene) multifunctional metal zinc electrode modified by the ferroelectric polymer protective layer.
Comparative example 1:
the pure zinc metal sheet is taken as a comparative example 1, and the specific preparation method is as follows:
and (3) sequentially and respectively soaking the metal zinc sheets into acetone, alcohol and deionized water to remove impurities, and then drying the cleaning agent in an oven at the temperature of 60 ℃ to obtain the pure metal zinc sheets.
Comparative example 2:
a metal zinc electrode is prepared by the following method:
s1, sequentially and respectively soaking a metal zinc sheet into acetone, alcohol and deionized water to remove impurities, and then drying a cleaning agent in an oven at the temperature of 60 ℃ to obtain a pure metal zinc sheet;
s2, dissolving 0.35g of polyvinylidene fluoride with the molecular weight of 100 ten thousand in 10ml of N-methyl pyrrolidone, and uniformly stirring to obtain ferroelectric polymer solution;
s3, spin-coating the ferroelectric polymer solution in the step S2 on the surface of the pure metal zinc sheet in the step S1;
and S4, drying in an oven at the temperature of 65 ℃ to obtain the metal zinc electrode.
Effect example 1:
characterization analysis was performed on the metallic zinc electrode prepared in example 1, specifically, the section of the metallic zinc electrode prepared in example 1 and the side coated with the multifunctional ferroelectric polymer solution were subjected to scanning electron microscopy analysis, respectively, to obtain fig. 1 and 2.
Referring to fig. 1, fig. 1 is a cross-sectional scanning electron microscope of a metal zinc electrode prepared in example 1 of the present application. As shown, the zinc triflate-polyvinylidene fluoride multifunctional ferroelectric polymer protective layer with a thickness of about 45 μm is tightly adhered to the surface of the metallic zinc, providing it with long-term protection and maintaining long-lasting wettability.
Referring to fig. 2, fig. 2 is a surface scanning electron microscope of a metal zinc electrode prepared in example 1 of the present application. As shown in the figure, the zinc trifluoromethane sulfonate-polyvinylidene fluoride multifunctional ferroelectric polymer interface layer presents a three-dimensional porous microstructure formed by mutually connected crystal balls, wherein the crystal balls are formed by Zn (TFO) 2 Salt crystals formed, which are Zn 2+ The rapid migration of ions provides a pathway and increases the solid-liquid contact area.
The experiment shows that after the multifunctional ferroelectric polymer protective coating is coated on the surface of the metal zinc, the multifunctional ferroelectric polymer protective coating can have a stable solid-liquid interface with the metal zinc, can block the entry of water molecules, can provide a transmission path for zinc ions, and further can inhibit side reactions such as hydrogen evolution, corrosion, passivation and the like.
Effect example 2:
contact angle measurements were performed on the coated surface of the metallic zinc electrode prepared in example 1, while contact angles of the metallic zinc sheet of comparative example 1 and the metallic zinc electrode of comparative example 2 were measured, resulting in fig. 3.
Referring to fig. 3, fig. 3 is a graph showing the contact angle measurement of effect example 2 of the present application. As shown in the figure, the multifunctional ferroelectric polymer protective coating of the metallic zinc electrode prepared in example 1 has a smaller contact angle of only 28 ° and is far smaller than the contact angle of the metallic zinc sheet and the polyvinylidene fluoride coating.
From the above experiments, it is known that the multifunctional ferroelectric polymer protective coating of the metal zinc electrode prepared in example 1 has better excellent hydrophilicity compared with the metal zinc sheet and polyvinylidene fluoride coating, which is beneficial to the electrolyte to penetrate into the zinc electrode material and improves the reaction kinetic parameters.
Effect example 3:
the zinc// zinc symmetrical battery was prepared by using the metallic zinc electrode prepared in example 1 as positive and negative electrode materials, and the specific preparation method was as follows:
s1, cutting a fiber diaphragm into a circular diaphragm with the diameter of 1.5cm by using a slicer to serve as a diaphragm of a symmetrical battery;
s2, preparing a zinc sulfate solution with the concentration of 2M as electrolyte of the symmetrical battery;
s3, sequentially placing the anode material, the electrolyte, the diaphragm, the electrolyte, the cathode material, the 0.8mm gasket and the elastic sheet into a positive battery bottom shell of model 2032;
s5, covering the negative electrode battery shell, and pressurizing the battery by using a battery sealing machine to seal the battery under 1.5 Mpa.
Meanwhile, a zinc// zinc symmetrical battery was prepared by using the same preparation method with the metal zinc sheet of comparative example 1 as the positive and negative electrode materials; a zinc// zinc symmetric battery was prepared in the same manner as the preparation method using the metallic zinc electrode of comparative example 2 as the positive and negative electrode materials.
Electrochemical impedance analysis was performed on the symmetric batteries composed of the materials prepared in example 1, comparative example 1, and comparative example 2 as positive and negative electrode materials, to obtain fig. 4.
Referring to fig. 4, fig. 4 is an ac impedance chart of effect example 3 of the present application. As shown, the metallic zinc electrode of example 1 exhibited lower diffusion resistance than comparative examples 1 and 2, which further confirmed that the multifunctional ferroelectric polymer was able to improve electrochemical reaction kinetics.
Meanwhile, for example 1,The material prepared in comparative example 1 was used as a symmetric battery composed of a positive electrode material and a negative electrode material at 0.5mA/cm 2 Current density and 0.5mAh/cm 2 The volume density was analyzed for cycle stability to give fig. 5.
Referring to fig. 5, fig. 5 is a comparison graph of the cycle stability of effect example 3 of the present application, and as shown in the graph, the pure zinc of comparative example 1 has a larger voltage jump after more than 100 hours of cycle, and shows poor cycle stability, mainly due to zinc dendrites and other side reactions.
The metal zinc modified by the multifunctional ferroelectric polymer protective coating can be recycled to about 750 hours due to the excellent characteristics of the multifunctional ferroelectric polymer protective layer, and the multifunctional ferroelectric polymer protective coating has excellent recycling stability.
From the experiment, the multifunctional ferroelectric polymer protective coating can obviously improve the cycle stability and coulombic efficiency of the zinc electrode material.
The previous description of the disclosure is provided to enable any person skilled in the art to make or use the disclosure. Various modifications to the disclosure will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other variations without departing from the scope of the disclosure. Thus, the disclosure is not limited to the examples and designs described herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A multifunctional ferroelectric polymer protective coating, which is characterized by comprising the following components: zinc salts, ferroelectric polymers and organic solvents.
2. The multifunctional ferroelectric polymer protective coating according to claim 1, wherein the concentration of the zinc salt in the multifunctional ferroelectric polymer protective coating is 20 to 500mg/mL, and the molar concentration of the ferroelectric polymer is 20 to 500mg/mL.
3. The multifunctional ferroelectric polymer protective coating according to claim 1, wherein the zinc salt is one or more of zinc trifluoromethane sulfonate, zinc bistrifluoro sulfonimide, zinc dibutyldithiocarbamate, zinc sulfate, zinc nitrate, zinc chloride.
4. The multifunctional ferroelectric polymer protective coating according to claim 1, wherein the organic solvent is one or a combination of more of N-methylpyrrolidone, N-methylformamide, formic acid, and phenol.
5. The multifunctional ferroelectric polymer protective coating according to claim 1, wherein the ferroelectric polymer is one or a combination of more of polyvinylidene fluoride, polyvinylidene fluoride copolymer, polyamide, polyurethane, ferroelectric liquid crystal polymer.
6. A method of preparing the multifunctional ferroelectric polymer protective paint according to any one of claims 1 to 5, comprising:
and dissolving the zinc salt and the ferroelectric polymer in the organic solvent, and uniformly stirring to obtain the multifunctional ferroelectric polymer protective coating.
7. A metallic zinc electrode, comprising:
a metal zinc sheet;
the multifunctional ferroelectric polymer protective coating according to any one of claims 1 to 5, applied and cured on the surface of the metallic zinc sheet.
8. A method of making a metallic zinc electrode according to claim 7, comprising:
removing impurities from a metal zinc sheet, drying, coating the multifunctional ferroelectric polymer protective coating according to any one of claims 1 to 5 on the surface of the metal zinc sheet, and drying to obtain the metal zinc electrode.
9. The method of claim 8, wherein the coating is one or more of spin coating, knife coating, spray coating; in the step of drying to obtain the metal zinc electrode, the drying is specifically performed at 60-150 ℃.
10. A zinc ion battery, characterized in that the negative electrode of the zinc ion battery adopts the metal zinc electrode of claim 7.
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