CN116666638B - Water system zinc ion secondary battery - Google Patents
Water system zinc ion secondary battery Download PDFInfo
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- CN116666638B CN116666638B CN202310904025.3A CN202310904025A CN116666638B CN 116666638 B CN116666638 B CN 116666638B CN 202310904025 A CN202310904025 A CN 202310904025A CN 116666638 B CN116666638 B CN 116666638B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 37
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 164
- 229920001661 Chitosan Polymers 0.000 claims abstract description 97
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000000661 sodium alginate Substances 0.000 claims abstract description 96
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 96
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 96
- 239000011701 zinc Substances 0.000 claims abstract description 81
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 81
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
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- 238000002360 preparation method Methods 0.000 claims description 21
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
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- 239000004626 polylactic acid Substances 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
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- 229920002717 polyvinylpyridine Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 108010020346 Polyglutamic Acid Proteins 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical group 0.000 description 1
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002643 polyglutamic acid Polymers 0.000 description 1
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- 150000004032 porphyrins Chemical class 0.000 description 1
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- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- -1 thio compound Chemical class 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 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
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
- H01M10/0422—Cells or battery with cylindrical casing
- H01M10/0427—Button cells
-
- 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
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
-
- 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 invention provides an artificial solid/liquid interface protective layer, which is a film formed on the surface of metal by different molecules through intermolecular interaction by a layer-by-layer self-assembly technology. The invention provides a multilayer self-assembly protective film formed by alternately adsorbing polyelectrolyte on the metal surface by utilizing the interaction between polyelectrolytes, wherein natural organic polyelectrolyte chitosan and sodium alginate with opposite charges are adsorbed and self-assembled layer by layer on the surface of a zinc electrode by electrostatic adsorption to form an artificial solid/liquid interface protective layer for stabilizing a zinc anode. Both polyelectrolytes contain rich hydroxyl functional groups, so that the solvation structure of zinc ions can be changed, the content of active water molecules is reduced, the water decomposition reaction is reduced, and the stability window of the electrolyte is widened; meanwhile, the gel film has excellent mechanical strength, can even the electric field strength of the electrode surface, adapts to the volume change caused by zinc deposition stripping, and prolongs the service life of the battery.
Description
Technical Field
The invention belongs to the technical field of water-based zinc ion secondary batteries, and particularly relates to an artificial solid/liquid interface protective layer, a metal electrode, a battery and a preparation method and application thereof based on a layer-by-layer self-assembly technology.
Background
The problem of shortage of metal lithium resources, high cost, high toxicity and the like seriously prevent the further application of the lithium battery because the energy demand of the modern society is continuously increased. For replacement, researchers have found a rich deposit of multivalent metallic zinc (Zn). Because metallic zinc has high conductivity, low oxidation-reduction potential (-0.762 VvsSHE), high theoretical specific capacity (820 mAh/g,5851 mAh/cm) 3 ) Low ionic radius (0.075 nm), low cost and abundant supply, and thus can be used as anode material. The water-based zinc ion battery is greatly concerned due to the simple manufacturing technology, high energy density and good safety, and is expected to replace a lithium battery to become a large-scale energy storage device.
However, the metallic zinc anode of current aqueous zinc ion batteries is faced with severe dendrite and water splitting challenges, and direct contact of the zinc anode and the aqueous electrolyte results in uncontrolled side reactions such as hydrogen evolution reactions and zinc corrosion, constantly consuming metallic zinc and causing the battery to expand and collapse. In addition, the uneven electric field distribution near the electrolyte/electrode interface results in severe dendrite growth, which severely threatens the cycle life of the cell.
To overcome these technical problems, a great deal of research is devoted to exploring zinc host structure, electrolyte modification, and electrode/electrolyte interface engineering. Electrodes of high conductivity three-dimensional structure materials such as copper foam exhibit lower nucleation overpotential and smaller zinc core size to reduce dendrite growth. However, an increase in the number of contact points exacerbates hydrogen evolution reactions and corrosion reactions. It has been found that certain amounts of additives such as thiourea, diethyl ether and organic compounds with polar groups such as carbonyl or amino groups promote uniform deposition of zinc. However, unstable electrolytes often limit the widespread use of these materials. High concentration electrolytes, while capable of uniformly distributing zinc ions to the deposit, are limited in their practical application by high cost. The construction of a compact protective layer on the surface of the zinc anode can improve the unstable electrolyte/anode interface on the surface of the electrode material and solve the serious side reaction. CaCO which has been found 3 、TiO 2 、ZrO 2 ZnS, ZIF-8, MCM41, etc., can be used to form a dense protective layer on the surface of the metal anode, thereby inhibiting dendrite growth. However, these delicate coatings are vulnerable to volume changes associated with zinc deposition. Polymeric materials such as polyamide coatings may also be used as protective coatings for zinc anodes to improve interfacial properties, but preparing a stable polymeric layer in an aqueous electrolyte may be a challenge.
The biggest challenge faced by aqueous zinc ion batteries on the application road is the difficult to eradicate side reactions, wherein the primary solution targets are hydrogen evolution reactions and dendrite growth. The electrochemical stability window of water is fixed at 1.23V under objective theory, and too narrow stability window makes the battery of aqueous electrolyte unable to obtain larger electromotive force. With the change of the potential, the water molecules undergo decomposition reaction to generate hydrogen so as to lead the expansion and collapse of the battery, and meanwhile, the local pH value becomes larger so as to lead the irreversible growth of byproducts. The ravines and pits which cannot be observed by naked eyes on the surface of the zinc foil are amplified in the battery cycle, uneven electrode surfaces lead to uneven electric field distribution between the cathode and the anode, and zinc ions are unevenly deposited to generate dendrites under the action of tip effect.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
Disclosure of Invention
In order to solve the technical bottleneck, the invention provides a method for constructing an artificial multilayer protective film on the surface of an electrode by utilizing an interlayer self-assembly technology, remodelling the electrode/electrolyte interface on the surface of metal zinc and optimizing the cycle performance of a water-based zinc ion battery.
The film forming pushing force of the layer-by-layer self-assembled film is mainly the electrostatic acting force of polyelectrolyte molecules or charged substances on a solid/liquid interface, and short-range secondary acting force (such as hydrophilicity/hydrophobicity, charge transfer, pi-pi overlap, hydrogen bond and Van der Waals force) plays an important role in forming a stable layer-by-layer self-assembled film. Self-assembled multilayer films formed by electrostatic force pushing have many advantages, mainly including: (1) Naturally occurring or synthetic polyelectrolytes that may be selected are counted; (2) Self-assembled films generally have better mechanical/chemical stability; (3) The structure of the self-assembled film is easy to control through the assembly mode and process; (4) By selecting and modifying the assembled polyelectrolyte molecules, polymer self-assembled films with different functions can be obtained. The polyelectrolyte with sulfonic acid group, carboxyl group, phosphate group and hydroxyl group, charged polymer, dendrimer, small organic molecule, nanometer particle and biological macromolecule, such as polypyrrole, polythiophene, polyaniline, DNA and the like, can form a multilayer self-assembled film through electrostatic adsorption, and the thickness of the film can be accurately regulated and controlled in a nanometer level monolayer film.
In order to achieve the above-mentioned purpose, the present invention provides an artificial solid/liquid interface protective layer, which is a thin film formed on the metal surface by different molecules through intermolecular interaction by a layer-by-layer self-assembly technique; wherein, the different molecules self-assemble into a single-layer film or a multi-layer film, the thickness of the single-layer film is 30 nm-40 nm, and the thickness of the multi-layer film is 200 nm-400 nm; the driving force of the single-layer film or the multilayer film is electrostatic acting force and short-range secondary acting force, and the different molecules comprise one or more of polyelectrolyte, dendrimer, organic micromolecule, nano particle and biological macromolecule with opposite charges or different polarity functions.
In one or more embodiments, the monolayer film has a thickness of 35nm to 38nm and the multilayer film has a thickness of 280nm to 305nm.
In one or more embodiments, the electrostatic forces and short range secondary forces described above are hydrophilic/hydrophobic, charge transfer, pi-pi overlap, hydrogen bonding, or van der Waals forces.
In one or more embodiments, water, an inorganic solvent, or an organic solvent is selected as the dispersant for the different molecules described above; preferably, the dispersant is water.
In one or more embodiments, the concentration of the above molecules in the dispersant is 2 to 10g/L; preferably, the concentration of the above molecules in the dispersant is 2.5 to 7g/L; most preferably, the concentration of the above molecules in the dispersant is 2.5 to 3.5g/L.
In one or more specific embodiments, the polyelectrolyte is any one or more of polyamide, polyaniline, polypyrrole, polyvinylpyridine, polyacrylamide, polyvinyl alcohol, polylactic acid, glucose, polyglutamic acid, chitosan and sodium alginate; preferably, the polyelectrolyte is any one or more of chitosan, sodium alginate, polyvinyl pyridine, polyacrylamide, polyvinyl alcohol, polylactic acid and glucose; most preferably, the polyelectrolyte is chitosan or sodium alginate.
In one or more embodiments, the dendrimer is any one or more of a polyether dendrimer, a polyester dendrimer, and an amphiphilic dendrimer.
In one or more specific embodiments, the small organic molecule is any one or more of a thio compound, pyridine, furan, biquaternary ammonium salt, phthalocyanine, and porphyrin.
In one or more embodiments, the nanoparticles are any one or more of metal nanoparticles, metal oxide nanoparticles, inorganic nanoparticles, and non-spherical nanoparticles.
In one or more embodiments, the above-described biomacromolecule is any one or more of an enzyme, a protein, DNA, a bacterium.
In one or more specific embodiments, the artificial solid/liquid interface protective layer is constructed on the surface of the metal electrode by chitosan and sodium alginate based on a layer-by-layer self-assembly technology.
Based on the inherent technical problems of the water system zinc ion battery, the invention selects two natural organic degradable polymers sodium alginate (SA for short) and Chitosan (CS for short), and utilizes the layer-by-layer self-assembly technology to obtain a flexible and soft polymer film, which can effectively separate a metal electrode from the water system electrolyte and weaken the decomposition phenomenon of water molecules; through screening, the two polymer structures contain rich polar functional groups, namely hydroxyl groups, so that water molecules in the zinc ion solvation layer can be stripped by utilizing the hydrogen bond effect when zinc ions pass through the film, and the water molecules reaching the surface of the zinc electrode are reduced, so that the hydrogen evolution reaction is radically weakened; in addition, the film formed by self-assembling the chitosan and the sodium alginate selected in the invention is flexible and soft like gel, the surface of the zinc anode can be reconstructed, the surface of the electrode is smoother, zinc ions can be uniformly deposited by uniform electric field strength when the battery works, and the film can adapt to volume change caused by zinc deposition/stripping. In addition, chitosan and sodium alginate are natural degradable polymers, and the self-assembled film formed by the enzymatic degradation experiment is proved to be degradable, nontoxic and harmless.
The present invention also provides a metal electrode comprising: a metal electrode sheet and the above-mentioned artificial solid/liquid interface protective layer; wherein the artificial solid/liquid interface protective layer is a film formed by different molecules on the surface of the metal electrode plate through intermolecular interaction.
In one or more embodiments, the metal electrode sheet is selected from any one of a zinc electrode, an aluminum electrode, a copper electrode, a zinc alloy electrode, an aluminum alloy electrode, and a copper alloy electrode; preferably, the metal electrode sheet is a zinc electrode or a copper electrode; most preferably, the metal electrode sheet is a zinc electrode.
In one or more embodiments, the metal electrode is a zinc foil or copper foil modified by a layer-by-layer self-assembled artificial solid/liquid interface protective layer.
In order to solve the technical problems, the invention also provides a preparation method of the metal electrode, which comprises the following steps: an artificial solid/liquid interface protective layer is formed on the surface of the metal electrode by one or more of a spin coating method, a dripping method, a smearing method and a soaking adsorption method.
When the preparation method is spin coating, the preparation method of the metal electrode comprises the following steps:
(1) Cutting a metal electrode slice, soaking the metal electrode slice in deionized water and ethanol for ultrasonic cleaning, and then drying in vacuum for standby;
(2) Preparing the molecules into a solution with the concentration of 2-10 g/L;
(3) Adsorbing the solution obtained in the step (2) on the metal electrode sheet layer by spin coating; and (5) vacuum drying the metal electrode plate subjected to spin coating, and cutting into metal electrodes with different sizes and shapes for standby.
When the molecules are chitosan and sodium alginate, the metal electrode sheet is zinc foil and copper foil, the chitosan and the sodium alginate are adsorbed on the zinc foil and the copper foil through spin coating, and the preparation method comprises the following steps:
(1) Cutting zinc foil and copper foil; polishing and removing oxide on the surface of the zinc foil by using sand paper, soaking the zinc foil in deionized water and ethanol, performing ultrasonic cleaning, and performing vacuum drying for standby, and soaking the copper foil in deionized water and ethanol, performing ultrasonic cleaning, and performing vacuum drying for standby;
(2) Preparing 2-10 g/L of chitosan solution and sodium alginate solution; preferably, when dissolving chitosan, glacial acetic acid is required to be added dropwise until the chitosan is completely dissolved, and when dissolving sodium alginate, proper heating is required until the chitosan is completely dissolved;
(3) Adsorbing sodium alginate and chitosan on the surfaces of zinc foil and copper foil layer by spin coating by using a spin coater, vacuum drying the spin-coated zinc foil and copper foil, and cutting into electrode plates with different sizes and shapes for later use; wherein, when spin coating adsorption is carried out by using a spin coater, the spin coating is carried out for 7 to 15 seconds at a low rotation speed of 500 to 1000 revolutions per minute and at a high rotation speed of 1200 to 2000 revolutions per minute for 20 to 50 seconds; preferably, when spin-coating adsorption is performed by using a spin coater, the spin coating is performed at a low rotation speed of 700 rpm for 30 seconds and at a high rotation speed of 1500 rpm for 10 seconds.
The invention also provides an application of the artificial solid/liquid interface protection layer in protecting the metal electrode, wherein the artificial solid/liquid interface protection layer is constructed on the surface of the metal electrode to improve the stability of the metal electrode.
In order to solve the technical problems, the invention also provides a secondary metal ion battery which comprises the metal electrode or the metal electrode manufactured by the manufacturing method.
In one or more embodiments, the secondary metal ion battery is a zinc-zinc symmetrical button battery assembled by using the zinc foil as a positive plate and a negative plate, or is a zinc-copper button battery assembled by using the copper foil as a positive plate.
In one or more specific embodiments, an artificial solid/liquid interface protective layer for improving the stability of a metal anode on the surface of a metal electrode based on a layer-by-layer self-assembly technology is constructed. The chitosan solution with positive charges and the sodium alginate solution with negative charges are selected by utilizing electrostatic adsorption, and the layer-by-layer self-assembled film is obtained by alternately adsorbing the chitosan solution with positive charges and the sodium alginate solution with negative charges on the surface of the zinc foil for a plurality of times by a simple spin coating means; the zinc foil substrate needs to be sufficiently polished and cleaned before being coated with the self-assembled film; the concentration of the sodium alginate and the chitosan solution is 3g/L.
In one or more embodiments, the preparation method of the metal electrode specifically includes the following steps:
(1) Cutting zinc foil with proper size (5X 5cm in the scheme), polishing with sand paper to remove surface oxide, placing the zinc foil in deionized water and ethanol, ultrasonically cleaning for 2 min, and vacuum drying for 30 min; the copper foil is only required to be cleaned by ultrasonic before use;
(2) Preparing 3g/L chitosan aqueous solution and 3g/L sodium alginate aqueous solution;
(3) Regulating the low rotation speed of 700 rpm to rotate for 30 seconds and the high rotation speed of 1500 rpm to rotate for 10 seconds by using a spin coater, and alternately spin-coating chitosan solution and sodium alginate solution on the surfaces of the cleaned zinc foil and copper foil to obtain self-assembled films with different layers; and (3) vacuum drying the self-assembled film decorated zinc foil at 50 ℃ for later use.
In one or more specific embodiments, in the step (2), when the chitosan solution and the sodium alginate solution are prepared, a proper amount of glacial acetic acid is required to be added dropwise when the chitosan is dissolved until the chitosan is just completely dissolved; proper heating is needed to dissolve sodium alginate until all the sodium alginate is dissolved.
In one or more embodiments, a button cell is assembled using a copper foil decorated with a self-assembled film as the positive electrode and a zinc foil as the negative electrode for electrochemical testing and cycling testing, and a symmetrical button cell is assembled using a zinc foil for long cycling testing. The assembled button battery is divided into four parts, namely a positive plate, a negative plate and a battery diaphragm, and electrolyte. The button cell comprises the following components in sequence: positive electrode shell-positive electrode plate (the symmetric battery is zinc foil, the zinc-copper battery is copper foil), glass fiber diaphragm-proper electrolyte (160 microliters of 2M zinc sulfate solution in the invention), negative electrode plate (zinc foil), gasket-elastic sheet-negative electrode shell.
The invention has the following technical effects:
the layer-by-layer self-assembled film can remodel an electrode/electrolyte interface, protect a metal electrode from being damaged when a battery circulates, and enhance zinc ion transfer/deposition dynamics, battery electrode reaction reversibility and battery cycle life; the invention provides a strategy which is low in price, simple and environment-friendly for protecting the metal electrode, and is expected to promote the large-scale application of the water-based metal ion battery, especially the water-based zinc ion battery.
Drawings
FIG. 1 is a schematic illustration of layer-by-layer self-assembly film formation; fig. 1a is a schematic diagram of a layer-by-layer self-assembly of oppositely charged polymer chitosan and sodium alginate to form a protective layer; FIG. 1b is a schematic illustration of side reactions of an untreated zinc anode in a cell cycle; FIG. 1c is a schematic diagram of a layer-by-layer self-assembled protective layer formed on the surface of a zinc anode by chitosan and sodium alginate;
FIG. 2 shows the Zeta potential of a 3g/L chitosan solution and sodium alginate solution;
FIG. 3 is a linear sweep voltammetric test of different zinc anodes in aqueous electrolyte; wherein, FIG. 3a is hydrogen evolution potential; FIG. 3b is an oxygen evolution potential;
FIG. 4 is a potentiodynamic scan test of a zinc anode with/without layer-by-layer self-assembled film modification in an aqueous electrolyte;
FIG. 5 is a potentiostatic program test of a zinc anode with/without layer-by-layer self-assembled film modification in an aqueous electrolyte;
FIG. 6 is a long-cycle test of zinc-zinc symmetrical cells assembled with a zinc electrode modified by a layer-by-layer self-assembled film as positive and negative electrode, respectively, with a current density of 1mA/cm 2 The capacity is 1mAh/cm 2 ；
FIG. 7 is a long-cycle test of zinc-zinc symmetrical cells assembled with zinc electrodes modified by self-assembled films of different thicknesses as positive and negative electrodes, respectively, wherein the current density was 1mA/cm 2 The capacity is 1mAh/cm 2 ；
FIG. 8 is a test of a zinc-copper half cell assembled with a zinc electrode modified with self-assembled films of different thickness as the negative electrode and a copper electrode modified with self-assembled films of different thickness as the positive electrode; wherein FIG. 8a is a long cycle test in which the current density is 1mA/cm 2 The capacity is 1mAh/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the FIG. 8b is a charge-discharge curve of a layer-by-layer self-assembled thin film modified zinc-copper cell; FIG. 8c is a charge-discharge curve of a bare zinc-copper cell;
FIG. 9 is a scanning electron microscope image of the zinc anode before and after cycling; wherein, fig. 9a is a freshly prepared layer-by-layer self-assembled protective film zinc anode; FIG. 9b is a cross-sectional view of a freshly prepared layer-by-layer assembled protective film zinc anode; FIG. 9c is a scanning electron microscope result after cycling of bare zinc electrodes; FIG. 9d is a scanning electron microscope image of the layer-by-layer self-assembled protective film after zinc anode cycling; wherein the current density of FIGS. 9c and 9d is 1mA/cm 2 The capacity is 1mAh/cm 2 Cycling for 500 hours;
FIG. 10 is ion migration number of a symmetric cell assembled with zinc electrodes modified with self-assembled thin films of different thickness;
fig. 11 is the reactive activation energy of a symmetric cell assembled with zinc electrodes modified with self-assembled thin films of different thicknesses.
Detailed Description
The following detailed description of embodiments of the invention is, therefore, to be taken in conjunction with the accompanying drawings, and it is to be understood that the scope of the invention is not limited to the specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations thereof such as "comprises" or "comprising", etc. will be understood to include the stated element or component without excluding other elements or components.
Example 1
Preparation of chitosan solution and sodium alginate solution: preparing a 3g/L chitosan aqueous solution and a sodium alginate aqueous solution at normal temperature and normal pressure; respectively weighing 0.6g of sodium alginate and chitosan, and dissolving in 200mL of deionized water; when the chitosan is dissolved, glacial acetic acid is required to be added dropwise until the chitosan is completely dissolved; when the sodium alginate is dissolved, the sodium alginate needs to be properly heated, stirred until the sodium alginate is completely dissolved and cooled to room temperature.
Fig. 2 shows Zeta potential of 3g/L chitosan solution and sodium alginate solution measured by particle size analyzer, and it is proved in theory that chitosan and sodium alginate polyelectrolyte with opposite charges can be self-assembled into a multilayer film by electrostatic action.
Example 2
The preparation of the zinc electrode and the copper electrode of the layer-by-layer self-assembled protective layer comprises the following steps:
preparation of spin coating solution: preparing a 3g/L chitosan aqueous solution and a sodium alginate aqueous solution at normal temperature and normal pressure; respectively weighing 0.6g of sodium alginate and chitosan, and dissolving in 200mL of deionized water; when the chitosan is dissolved, glacial acetic acid is required to be added dropwise until the chitosan is completely dissolved; when the sodium alginate is dissolved, the sodium alginate is properly heated and stirred until the sodium alginate is completely dissolved and cooled to room temperature;
zinc electrode and copper electrode preparation: cutting zinc foil and copper foil with proper sizes (5X 5cm in the scheme), polishing the surface of the zinc foil by sand paper to remove surface oxides, then placing the zinc foil in deionized water and ethanol for ultrasonic cleaning for 2 minutes, and vacuum drying for 30 minutes for later use; the copper foil is only required to be cleaned by ultrasonic and dried in vacuum for 30 minutes before use;
spin coating: regulating the low rotation speed of 700 rpm to rotate for 30 seconds and the high rotation speed of 1500 rpm to rotate for 10 seconds by using a spin coater; alternately spin-coating a chitosan solution and a sodium alginate solution on the surfaces of the cleaned zinc foil and copper foil to obtain self-assembled films with different layers, wherein one layer of self-assembled film is spin-coated with one-time chitosan solution and one-time sodium alginate solution, and the self-assembled film is marked as: (Chitosan/sodium alginate) 1 The scheme selects 2,4 and 6 layers of self-assembled films for comparison experiments, and the experiment shows that the 4 layers of self-assembled films are the optimal thickness and are recorded as follows: (Chitosan/sodium alginate) 4 The method comprises the steps of carrying out a first treatment on the surface of the Cutting zinc foil and copper foil into round electrode plates with radius of 6mm for standby after vacuum drying for 30 minutes;
and (3) battery assembly: respectively combining bare copper foil and (chitosan/sodium alginate) 4 -copper foil as positive electrode, bare zinc foil and (chitosan/sodium alginate) 4 And (3) the zinc foil is used as a negative electrode to be assembled into a zinc-copper half cell, linear sweep voltammetry is carried out, and different voltages are applied to obtain corresponding potentials when the surface of the electrode is subjected to water decomposition to generate hydrogen and oxygen, namely hydrogen evolution potential and oxygen evolution potential.
Fig. 3 shows the results of the linear sweep voltammetric test. Because of the existence of the layer-by-layer assembled protective film, the electrode is separated from the electrolyte, and the water molecules reaching the surface of the electrode are reduced, so that the water-based electrolyte is more stable, and the hydrogen and oxygen evolution becomes more difficult.
Example 3
Zinc electrode preparation: cutting zinc foil with proper size (5X 5cm in the scheme), polishing the surface of the zinc foil by sand paper to remove surface oxides, then placing the zinc foil in deionized water and ethanol for ultrasonic cleaning for 2 minutes, and vacuum drying for 30 minutes for later use;
spin coating: and (3) regulating the lower rotation speed of 800 rpm to rotate for 25 seconds and the higher rotation speed of 1300 rpm to rotate for 15 seconds by using a spin coater. Alternately spin-coating chitosan and sodium alginate solution on the surface of the cleaned zinc foil to obtain 4 layers of self-assembled film zinc electrode, (chitosan/seaweed)Sodium acid) 4 -zinc foil; vacuum drying for 30 min, and cutting into 1 x 2cm electrode slices for later use;
and (3) battery assembly: a three-electrode system is adopted, zinc foil modified by a self-assembled film or not is used as a working electrode, a platinum sheet electrode is used as a counter electrode, a silver/silver chloride electrode is used as a reference electrode, and 2mol/L zinc sulfate solution is used as electrolyte for electrokinetic potential scanning.
Test results tafel curves are shown in fig. 4. Compared with a bare zinc electrode, (chitosan/sodium alginate) 4 The corrosion potential of the zinc electrode becomes more positive, the corrosion current density becomes smaller, and the stability of the zinc anode is higher and the corrosion rate is smaller under the protection of the multilayer self-assembled film.
Example 4
Zinc electrode preparation: cutting zinc foil with proper size (5X 5cm in the scheme), polishing the surface of the zinc foil by sand paper to remove surface oxides, then placing the zinc foil in deionized water and ethanol for ultrasonic cleaning for 2 minutes, and drying in vacuum for 30 minutes for later use;
spin coating: adjusting the lower rotation speed of 600 rpm to rotate for 40 seconds and the higher rotation speed of 1800 rpm to rotate for 7 seconds by using a spin coater; alternately spin-coating chitosan solution and sodium alginate solution on the surface of the cleaned zinc foil to obtain 4 layers of self-assembled film zinc electrode and copper electrode, (chitosan/sodium alginate) 4 -zinc foil. Vacuum drying for 30 min, and cutting into round electrode plates with radius of 6mm for standby;
and (3) battery assembly: and (3) taking zinc foil modified by the self-assembled film or not as a positive electrode and a negative electrode to assemble the zinc foil into a button cell, and carrying out constant potential polarization test.
Fig. 5 shows that the polarization current density of the bare zinc cell continues to increase with the increase of the polarization time, indicating that dendrites continue to grow on the surface of the zinc electrode; (Chitosan/sodium alginate) 4 The polarization current density of the zinc cell was stable after 200s and no longer changed, indicating that zinc ions were uniformly reduced and deposited without significant dendrite growth.
Example 5
Zinc electrode preparation: cutting zinc foil with proper size (5X 5cm in the scheme), polishing the surface of the zinc foil by sand paper to remove surface oxides, then placing the zinc foil in deionized water and ethanol for ultrasonic cleaning for 2 minutes, and drying in vacuum for 30 minutes for later use;
spin coating: adjusting the lower rotating speed of 1000 rpm to rotate for 15 seconds by using a spin coater, and adjusting the higher rotating speed of 1800 rpm to rotate for 7 seconds; alternately spin-coating chitosan solution and sodium alginate solution on the surface of the cleaned zinc foil to obtain 4 layers of self-assembled film zinc electrode, (chitosan/sodium alginate) 4 The zinc foil is dried in vacuum for 30 minutes and then cut into round electrode plates with the radius of 6mm for standby;
and (3) battery assembly: bare zinc foil and (chitosan/sodium alginate) 4 Zinc foil used as positive and negative electrode of battery to be assembled into zinc-zinc symmetrical battery for long-time charge and discharge test, wherein current density is 1mA/cm 2 The capacity is 1mAh/cm 2 。
Fig. 6 shows the long-cycle test results of charge and discharge of zinc-zinc symmetrical cells. The bare zinc electrode symmetrical battery is short-circuited due to side reactions such as dendrites after 400 hours of circulation, so that the battery collapses. Under the protection of the layer-by-layer self-assembled film, the zinc-zinc symmetrical battery can circulate for more than 5000 hours, and the excellent protection effect of the film formed by self-assembling sodium alginate and chitosan on the zinc electrode is proved.
Example 6
Zinc electrode preparation: cutting zinc foil with proper size (5X 5cm in the scheme), polishing the surface of the zinc foil by sand paper to remove surface oxides, then placing the zinc foil in deionized water and ethanol for ultrasonic cleaning for 2 minutes, and drying in vacuum for 30 minutes for later use;
spin coating: adjusting the lower rotation speed of 600 rpm to rotate for 35 seconds and the higher rotation speed of 1400 rpm to rotate for 13 seconds by using a spin coater; alternately spin-coating chitosan solution and sodium alginate solution on the surface of the cleaned zinc foil to obtain 2,4 and 6 layers of self-assembled film zinc electrodes, (chitosan/sodium alginate) 2，4，6 -zinc foil, which is cut into circular electrode pieces with a radius of 6mm for later use after vacuum drying for 30 minutes;
and (3) battery assembly: will (Chitosan/sodium alginate) 2，4，6 Zinc foil used as positive and negative electrode of battery to be assembled into zinc-zinc symmetrical battery for long-time charge and discharge test, wherein current density is 1mA/cm 2 The capacity is 1mAh/cm 2 。
Fig. 7 shows the long-cycle test results of charge and discharge of zinc-zinc symmetrical cells. (Chitosan/sodium alginate) 2 The symmetrical cell can be cycled for more than 1200 hours, (chitosan/sodium alginate) 6 The symmetrical cell can be cycled for more than 2000 hours, (chitosan/sodium alginate) 4 The symmetric battery can circulate for more than 5000 hours, and the excellent protection effect of the chitosan/sodium alginate self-assembled film on the zinc electrode is proved, and the battery performance is improved, wherein the 4-layer self-assembled film has the best effect.
Example 7
Zinc electrode and copper electrode preparation: zinc electrode and copper electrode preparation: cutting zinc foil and copper foil with proper sizes (5X 5cm in the scheme), polishing the surface of the zinc foil by sand paper to remove surface oxides, then placing the zinc foil in deionized water and ethanol for ultrasonic cleaning for 2 minutes, and drying in vacuum for 30 minutes for later use. The copper foil is only required to be cleaned by ultrasonic and dried in vacuum for 30 minutes before use;
spin coating: regulating the low rotation speed of 700 rpm to rotate for 30 seconds and the high rotation speed of 1500 rpm to rotate for 10 seconds by using a spin coater; alternately spin-coating chitosan solution and sodium alginate solution on the surfaces of the cleaned zinc foil and copper foil to obtain 2,4,6 layers of self-assembled film zinc electrodes, (chitosan/sodium alginate) 2，4，6 -zinc foil and copper foil, vacuum dried for 30 minutes and then cut into circular electrode plates with a radius of 6mm for later use;
and (3) battery assembly: bare copper foil and (chitosan/sodium alginate) )2,4,6 Copper foil is used as the positive electrode of the battery, bare zinc foil and (chitosan/sodium alginate) respectively 2，4，6 Zinc foil used as negative electrode of cell, assembled into zinc-copper half cell, and subjected to long-time charge-discharge test, wherein the current density is 1mA/cm 2 The capacity is 1mAh/cm 2 。
Fig. 8a shows the long cycle test results of zinc-copper half cells. Control group zinc-copper half cell without self-assembled film fails after 300 hours of circulation, (chitosan/sodium alginate) 2 Zinc-copper half cell sum (chitosan/sodium alginate) 6 After 700 hours of cycle, the zinc-copper half cell has large fluctuation of coulomb efficiency, and the cell cycle is unstableAnd (5) setting. In comparison (Chitosan/sodium alginate) 4 The zinc-copper half cell can stably circulate for more than 2300 hours, and the coulomb efficiency is stabilized at more than 99.6%, which indicates that the cell has stable circulation and high reversibility of electrode reaction. The layer-by-layer self-assembled film can improve the side reaction degree of the battery and improve the cycle performance of the battery.
The charge and discharge curves of zinc-copper cells can be seen in FIGS. 8b and 8c, wherein (chitosan/sodium alginate) 4 The nucleation overpotential and polarization potential of the zinc-copper half cell are lower than those of the bare zinc-copper half cell, and the zinc ions are proved to have lower energy required for nucleation, easier nucleation and more uniform deposition.
Example 8
Zinc electrode preparation: cutting zinc foil with proper size (5X 5cm in the scheme), polishing the surface of the zinc foil by sand paper to remove surface oxides, then placing the zinc foil in deionized water and ethanol for ultrasonic cleaning for 2 minutes, and drying in vacuum for 30 minutes for later use;
spin coating: regulating the low rotation speed of 700 rpm to rotate for 30 seconds and the high rotation speed of 1500 rpm to rotate for 10 seconds by using a spin coater; alternately spin-coating chitosan solution and sodium alginate solution on the surface of the cleaned zinc foil to obtain 4 layers of self-assembled film zinc electrode, (chitosan/sodium alginate) 4 -zinc foil;
and (3) battery assembly: bare zinc foil and (chitosan/sodium alginate) 4 Zinc foil used as positive and negative electrode of battery to be assembled into zinc-zinc symmetrical battery for long-time charge and discharge test, wherein current density is 1mA/cm 2 The capacity is 1mAh/cm 2 ；
Scanning electron microscope test sample preparation: the newly prepared layer-by-layer self-assembled protective layer (chitosan/sodium alginate) 4 And quenching the zinc electrode by liquid nitrogen to obtain a section scanning electron microscope test sample. Bare zinc foil and (chitosan/sodium alginate) 4 The zinc foil is used as a zinc-zinc symmetrical battery assembled by the anode and the cathode of the battery, and after the zinc foil is circulated for 100 hours, the zinc anode is cleaned and dried in vacuum to obtain a scanning electron microscope test sample.
Fig. 9 shows the scanning electron microscope test results. The newly prepared layer-by-layer self-assembled film was observed to be uniformly transparent in FIG. 9a, and that in FIG. 9b, a cross-sectional electron microscope was observedThe test chart shows that the self-assembled film layer by layer is uniformly adhered to the surface of the zinc electrode and can be filled with fine gaps on the surface of zinc foil, and the thickness is about 300nm. After 100 hours of circulation, a large amount of sharp blocky dendrites exist on the surface of the bare zinc anode, and the dendrites gradually become larger along with the increase of circulation time and finally penetrate through the diaphragm to damage the battery. FIG. 9d demonstrates, (chitosan/sodium alginate) 4 The film can effectively protect the zinc anode and even the electric field, so that zinc ions are uniformly distributed and reduced, the diameter of the bulk package is not found, and the improvement effect of the film on the battery performance is obvious.
Example 9
Zinc electrode preparation: cutting zinc foil with proper size (5X 5cm in the invention), polishing the surface of the zinc foil by sand paper to remove surface oxide, then placing the zinc foil in deionized water and ethanol for ultrasonic cleaning for 2 minutes, and drying in vacuum for 30 minutes for later use.
Spin coating: regulating the low rotation speed of 700 rpm to rotate for 30 seconds and the high rotation speed of 1500 rpm to rotate for 10 seconds by using a spin coater; alternately spin-coating chitosan solution and sodium alginate solution on the surface of the cleaned zinc foil to obtain 2,4,6 layers of self-assembled film zinc electrodes, (chitosan/sodium alginate) 2，4，6 -zinc foil, which is cut into circular electrode pieces with a radius of 6mm for later use after vacuum drying for 30 minutes;
and (3) battery assembly: bare zinc foil and (chitosan/sodium alginate) 2，4，6 -zinc foil is used as the positive and negative electrode of the cell to assemble a zinc-zinc symmetrical cell; and (3) carrying out timing current test on the symmetrical batteries, and calculating the ion migration numbers of different batteries according to the public indication by combining the impedance values before and after the test.
FIG. 10 shows that the number of ion transport measured for the different layers of self-assembled film modified zinc electrode is higher than for the bare zinc electrode (0.3223), wherein (chitosan/sodium alginate) 4 The maximum ion migration number of the zinc electrode (0.7572) proves that the zinc ion transmission kinetics are the fastest, and the uniform deposition of zinc ions is facilitated.
Example 10
Zinc electrode preparation: cutting zinc foil with proper size (5X 5cm in the scheme), polishing the surface of the zinc foil by sand paper to remove surface oxides, then placing the zinc foil in deionized water and ethanol for ultrasonic cleaning for 2 minutes, and drying in vacuum for 30 minutes for later use;
spin coating: regulating the low rotation speed of 700 rpm to rotate for 30 seconds and the high rotation speed of 1500 rpm to rotate for 10 seconds by using a spin coater; alternately spin-coating chitosan solution and sodium alginate solution on the surface of the cleaned zinc foil to obtain 2,4 and 6 layers of self-assembled film zinc electrodes, (chitosan/sodium alginate) 2，4，6 -zinc foil, which is cut into circular electrode pieces with a radius of 6mm for later use after vacuum drying for 30 minutes;
and (3) battery assembly: bare zinc foil and (chitosan/sodium alginate) 2，4，6 The zinc foil is used as the positive and negative electrode of the battery to be assembled into a zinc-zinc symmetrical battery.
The reaction activation energy of the cell modified by the self-assembled thin films of different thickness calculated from the resistance values of the cell at different temperatures is shown in fig. 11. Wherein the reaction activation energy measured by the zinc electrode modified by the self-assembled film with different layers is higher than that of a bare zinc battery (69.62 kJ/mol), wherein (chitosan/sodium alginate) 4 The maximum ion migration number (40.76 kJ/mol) of the zinc electrode proves that the electrode reaction requires less energy, and the reduction and uniform deposition of zinc ions are facilitated.
Table 1 electrochemical and battery performance test result data for the layer-by-layer self-assembled protective layers of examples 2, 3, 5, 6, 7, 9, 10
The electrochemical and battery performance test result data of examples 2, 3, 5, 6, 7, 9 and 10 related to the layer-by-layer self-assembled protective layer are summarized in table 1, so that it can be proved that the self-assembled protective layer can effectively stabilize a metallic zinc anode, slow down the corrosion speed of the anode, induce zinc ions to be uniformly distributed and deposited, and reduce dendrite growth. The transport kinetics of zinc ions are enhanced and the electrode reaction activation energy is reduced so that zinc ions can be transported to the electrode surface faster and deposited more easily.
FIG. 1 is a schematic diagram of layer-by-layer self-assembled film formation. Wherein FIG. 1a is chitosan and seaAnd (3) self-assembling sodium alginate layer by layer on the surface of zinc to form a schematic diagram of the protective film. The chitosan structure contains abundant hydroxyl and amino, a positively charged film can be firmly adsorbed on the surface of the zinc foil, and then negatively charged sodium alginate is spin-coated on the surface, and the sodium alginate contains abundant carboxyl and can be combined with the amino in the chitosan to form the film through electrostatic adsorption; repeating the chitosan/sodium alginate alternate adsorption to finally form a layer-by-layer self-assembled film (chitosan/sodium alginate) 4 A film.
FIG. 1b shows a layer-by-layer self-assembled film (Chitosan/sodium alginate) 4 Schematic diagram of the protection function of the zinc electrode. Both chitosan and sodium alginate contain abundant polar functional groups-hydroxyl. When the hydrated zinc ions pass through the self-assembled film under the action of an electric field, the hydroxyl groups strip water molecules in the solvation structure of the zinc ions through the action of hydrogen bonds, so that the content of water molecules around the zinc ions is reduced, the occurrence of hydrogen evolution reaction is further reduced, and meanwhile, the desolvation energy of the zinc ions is reduced due to the change of the volumetrization structure of the zinc ions, so that the zinc ions are easier to reduce and uniformly deposit.
Fig. 1c is a schematic diagram of a bare zinc electrode undergoing a battery cycle test without any treatment for side reactions. Because of the decomposition of water molecules, hydrogen is generated on the surface of the zinc electrode to expand and break the battery, and meanwhile, the hydrogen evolution reaction can lead to the increase of local pH value, the generation of insoluble byproducts and the passivation and inactivation of zinc are gradually caused; in addition, uneven electric field distribution can lead to uneven zinc deposition layer, and finally sharp dendrites are formed.
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and to implement the same, but are not intended to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
The foregoing descriptions of specific exemplary embodiments of the present invention are presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (5)
1. An aqueous zinc ion secondary battery, characterized in that the aqueous zinc ion secondary battery comprises a metal electrode; the metal electrode includes: a metal electrode sheet and an artificial solid/liquid interface protective layer; the artificial solid/liquid interface protective layer is a film constructed by chitosan and sodium alginate on the surface of the metal electrode plate based on a layer-by-layer self-assembly technology; the chitosan and the sodium alginate have opposite charges, the chitosan and the sodium alginate are self-assembled into a multilayer film, and the thickness of the multilayer film is 300nm; the driving force of the multilayer film is electrostatic acting force and short-range secondary acting force, and the metal electrode sheet is a zinc electrode; the short-range secondary force is hydrogen bond;
the preparation method of the metal electrode comprises the following steps:
(1) Cutting zinc foil; polishing and removing oxide on the surface of the zinc foil by sand paper, soaking in deionized water and ethanol, ultrasonically cleaning, and vacuum drying for later use;
(2) Preparing a chitosan solution and a sodium alginate solution with the concentration of 3 g/L;
(3) Alternately spin-coating and adsorbing sodium alginate solution and chitosan solution on the surface of zinc foil by using a spin-coater, vacuum-drying the spin-coated zinc foil, and cutting into electrode plates with different sizes and shapes for standby, thereby obtaining 4 layers of self-assembled films, wherein the 4 layers of self-assembled films are films obtained by spin-coating the sodium alginate solution and the chitosan solution for 4 times; wherein, when spin coating adsorption is carried out by using a spin coater, the spin coating is carried out for 7-15 seconds at a low rotation speed of 500-1000 rpm for 20-50 seconds and at a high rotation speed of 1200-2000 rpm.
2. The aqueous zinc ion secondary battery according to claim 1, wherein an inorganic solvent or an organic solvent is selected as the dispersing agent for the chitosan and sodium alginate.
3. The aqueous zinc-ion secondary battery according to claim 2, wherein the inorganic solvent is water.
4. The aqueous zinc ion secondary battery according to claim 1, wherein in the step (2), glacial acetic acid is added dropwise until the chitosan is completely dissolved, and heating is appropriately performed until the sodium alginate is completely dissolved.
5. The aqueous zinc-ion secondary battery according to claim 1, wherein in the step (3), when spin-coating adsorption is performed by a spin coater, the spin coating is performed at a low rotation speed of 700 rpm for 30 seconds, at a high rotation speed of 1500 rpm for 10 seconds.
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