An anode material for zinc-ion batteries, its preparation method and application

Abstract

The present invention discloses a negative electrode material for a zinc-ion battery, a preparation method thereof, and an application thereof. The negative electrode material includes a zinc sheet and an SEI protective layer provided on the surface of the zinc sheet; the SEI protective layer includes a polymer and zinc ions; the polymer includes a nitrogen-containing five-membered ring and a nitrogen-containing six-membered ring; in-situ forming an SEI protective layer on the zinc negative electrode, which shows good electrochemical performance as a negative electrode material for a zinc-ion battery, and solves problems such as disordered growth of dendrites, low reversibility caused by the formation of by-products, and short cycle life in the negative electrode material of the zinc-ion battery.

Description

Technical Field

[0001] The present invention belongs to the technical field of new energy materials, and particularly relates to a negative electrode material for a zinc-ion battery, a preparation method thereof, and an application thereof. Background Art

[0002] With the gradual application of lithium-ion batteries in fields such as smart phones and electric vehicles, the demand for lithium has been increasing rapidly year by year. However, its global reserves are very limited, unevenly distributed, and costly, which seriously restricts the rapid development of low-cost and high-performance energy storage devices.

[0003] As a safer electrochemical energy storage technology based on a non-flammable and highly ion-conductive aqueous electrolyte, aqueous rechargeable batteries are receiving increasing attention. Among various aqueous electrochemical reaction systems, zinc-ion batteries have attracted attention due to the advantages of zinc metal such as high volumetric specific capacity, low reduction potential, low cost, and high abundance.

[0004] Common aqueous zinc-ion batteries use zinc metal as the negative electrode and materials such as manganese-based oxides, vanadium-based oxides, and Prussian blue compounds as the positive electrode materials. However, at present, the zinc metal negative electrode of aqueous zinc-ion batteries still has problems such as serious corrosion reactions, hydrogen evolution, and zinc dendrite growth, resulting in low Coulomb efficiency (CE), poor cycle life, and even internal short-circuit problems of zinc-ion batteries.

[0005] Therefore, it is urgent to solve the problems of disordered growth of dendrites and low reversibility and short cycle life caused by the formation of by-products in the negative electrode materials of current zinc-ion batteries. Summary of the Invention

[0006] The present invention aims to solve at least one of the technical problems existing in the prior art. For this purpose, the present invention provides a negative electrode material for a zinc-ion battery, which in-situ forms an artificial SEI protective layer on the zinc negative electrode. As the negative electrode material of the zinc-ion battery, it exhibits good electrochemical performance, and solves the problems of disordered growth of dendrites and low reversibility and short cycle life caused by the formation of by-products in the negative electrode materials of zinc-ion batteries.

[0007] The second aspect of the present invention provides a preparation method of the above-mentioned negative electrode material for a zinc-ion battery.

[0008] The third aspect of the present invention provides a zinc-ion battery, and the zinc-ion battery includes the above-mentioned negative electrode material.

[0009] The fourth aspect of the present invention provides an application of the above-mentioned zinc-ion battery in the field of energy storage.

[0010] A negative electrode material for a zinc-ion battery according to an embodiment of the first aspect of the present invention, the negative electrode material comprising a zinc sheet and an SEI protective layer provided on the surface of the zinc sheet;

[0011] The SEI protective layer includes a polymer and zinc ions;

[0012] The polymer includes a nitrogen-containing five-membered ring and a nitrogen-containing six-membered ring.

[0013] A negative electrode material for a zinc-ion battery according to an embodiment of the present invention has at least the following beneficial effects:

[0014] (1) The SEI protective layer of the present invention contains a nitrogen-containing five-membered ring and a six-membered ring structure, which can form chemical bonds with the water molecules around the hydrated zinc ions, facilitating the desolvation process of the hydrated zinc ions. That is to say, the presence of the nitrogen-containing five-membered ring and the nitrogen-containing six-membered ring improves the ionic conductivity of the SEI protective layer, ultimately improving the rate performance of the resulting battery.

[0015] (2) The uneven deposition of zinc ions will form sharp zinc dendrites, piercing the separator and causing short circuits in the zinc-ion battery, affecting its lifespan; the deposited zinc dendrites are not electrochemically active, consuming zinc ions, that is, affecting its cycling performance; the negative electrode material of the present invention can induce uniform deposition of Zn 2+ Therefore, the generation of zinc dendrites is minimized as much as possible. Therefore, when used as a negative electrode for a zinc-ion battery, this negative electrode material has the characteristics of excellent electrochemical performance, high cycle stability, and long cycle life. At a current density of 1 mA·cm ～2 The assembled zinc-zinc symmetric battery can operate stably for more than 2000 h, and the cycle life is significantly improved.

[0016] (3) The SEI protective layer is a film-like structure, which forms a physical protective layer between the electrolyte and the zinc sheet, avoiding direct erosion of the zinc sheet by the electrolyte and improving the comprehensive electrochemical performance.

[0017] (4) When assembled with a positive electrode activated carbon into a zinc-ion battery, it can stably cycle 24,000 times at a current density of 5 Ag ～1 , far higher than the unmodified battery (only cycling 8000 times). After the batteries after cycling are disassembled respectively, the negative electrodes are taken out, cleaned and naturally dried at room temperature, and then observed by SEM (scanning electron microscope). The surface of the negative electrode material of the present invention remains smooth and flat after cycling 24,000 times, while a large number of dendrites and pulverized particles appear on the surface of the unmodified zinc negative electrode after cycling 8000 times.

[0018] According to some embodiments of the present invention, the thickness of the negative electrode is 1 μm to 1000 μm.

[0019] According to some embodiments of the present invention, the thickness of the SEI protective layer is 5 nm to 5 μm.

[0020] According to some embodiments of the present invention, the raw materials for preparing the SEI protective layer include small molecule additives and zinc salts;

[0021] The small molecule additives include at least one of small molecule amino acids and small molecule peptides;

[0022] The small molecule amino acids include at least one of α-amino acids and non-protein amino acids;

[0023] According to some embodiments of the present invention, the small molecule peptides include at least one of small molecule oligopeptide compounds and small molecule polypeptide compounds.

[0024] According to some embodiments of the present invention, the α-amino acids include at least one of glycine, alanine, valine, leucine, isoleucine, methionine, proline, tryptophan, serine, tyrosine, cysteine, phenylalanine, asparagine, glutamine, threonine, aspartic acid, glutamic acid, lysine, arginine, histidine, selenocysteine, and pyrrolysine.

[0025] According to some embodiments of the present invention, the non-protein amino acids include at least one of 3-aminoglutaric acid, fucine, laminine, palytoxin, 3-hydroxy-D-sulfocysteine, 3-aminopropanesulfonic acid, 3-amino-2-hydroxypropanesulfonic acid, carrageenine, glycoporphyric acid, L-ornithine, L-citrulline, cystathionine, lanthionine, sargine, methionine sulfoxide, N-methylmethionine sulfoxide, S-hydroxymethylhomocysteine, 1-methyl-L-histidine, β-alanine, γ-aminobutyric acid, 2-piperidinecarboxylic acid, 1-aminocyclopropane-1-carboxylic acid (ACC), L-azetidine-2-carboxylic acid, 5-hydroxy-2-piperidinecarboxylic acid, betonicine, 3-iodo-L-tyrosine, domoic acid, 2,5-dicarboxypyrrolidine, γ-guanidinobutyric acid, methyltaurine, kainic acid, taurine, N,N-dimethyltaurine, D-glycerotaurine, petalonic acid, domoic acid, furcellaranine, kainic acid, chondracanthine, and lingulic acid.

[0026] According to some embodiments of the present invention, the small molecule peptides include at least one of dipeptides, tripeptides, and tetrapeptides composed of dehydration condensation of the small molecule amino acids.

[0027] According to some preferred embodiments of the present invention, the molecular weight range of the small molecule peptides is 2 to 50.

[0028] According to some embodiments of the present invention, the molecular weight range of the dipeptides, tripeptides, and tetrapeptides is 2 to 10.

[0029] According to some embodiments of the present invention, the small molecule peptide includes a small molecule polypeptide compound composed of dehydration condensation of the small molecule amino acids.

[0030] According to some embodiments of the present invention, the molecular weight range of the small molecule polypeptide compound composed of dehydration condensation of the small molecule amino acids is 10-50.

[0031] According to some preferred embodiments of the present invention, the small molecule peptide includes glutathione.

[0032] According to some embodiments of the present invention, the small molecule oligopeptide compound includes at least one of alanyl-glutamine, alanyl-glutathione dipeptide, carnosine, thymopentin, and octreotide.

[0033] According to some embodiments of the present invention, in the negative electrode material, the zinc salt includes at least one of zinc fluoride, zinc sulfate, zinc nitrate, zinc bromide, zinc trifluoromethanesulfonate, zinc hexafluorophosphate, zinc bis(trifluoromethanesulfonyl)imide, zinc molybdate, zinc acetate, zinc sulfide, zinc carbonate, zinc phosphate, zinc borate, and zinc stearate.

[0034] According to some preferred embodiments of the present invention, in the negative electrode material, the zinc salt includes zinc trifluoromethanesulfonate.

[0035] According to some preferred embodiments of the present invention, in the negative electrode material, the concentration of the zinc salt is 0.1-5 mol / L.

[0036] According to some preferred embodiments of the present invention, in the negative electrode material, the concentration of the zinc salt is 0.5-1.5 mol / L.

[0037] According to some preferred embodiments of the present invention, in the negative electrode material, the concentration of the zinc salt is 1 mol / L.

[0038] According to some embodiments of the present invention, in the negative electrode material, the concentration of the small molecule additive is 1-2000 mmol / L.

[0039] According to some preferred embodiments of the present invention, in the negative electrode material, the concentration of the small molecule additive is 10-200 mmol / L.

[0040] According to some preferred embodiments of the present invention, in the negative electrode material, the concentration of the small molecule additive is 39-41 mmol / L.

[0041] According to some preferred embodiments of the present invention, in the negative electrode material, the concentration of the small molecule additive is 40 mmol / L.

[0042] According to some embodiments of the present invention, the molecular weight range of the small molecule oligopeptide compound is 2 to 10.

[0043] According to some embodiments of the present invention, the molecular weight range of the small molecule polypeptide compound is 10 to 50.

[0044] According to a preparation method of the negative electrode material for a zinc ion battery according to the second aspect embodiment of the present invention, it includes: using the dispersion liquid of the preparation raw materials of the SEI protective layer as the electrolyte, and performing electrochemical deposition on the surface of the zinc sheet.

[0045] According to some embodiments of the present invention, the preparation method of the negative electrode material for a zinc ion battery includes:

[0046] S1: Sand the zinc sheet, then perform ultrasonic treatment in alcohol, and finally wash it with deionized water to obtain the treated zinc sheet;

[0047] S2: Add zinc salt and a small molecule additive to deionized water according to a certain mass ratio, and stir until completely dissolved to obtain an electrochemical deposition precursor solution;

[0048] S3: Using the zinc sheet treated in step S1 as the negative electrode and a platinum electrode as the positive electrode, place them in the electrochemical deposition precursor solution obtained in step S2, and perform electrochemical deposition using a two-electrode method to in-situ construct a SEI protective layer on the surface of the zinc sheet.

[0049] According to some preferred embodiments of the present invention, in step S2, the concentration of the zinc salt is 0.1 to 5 mol / L.

[0050] According to some preferred embodiments of the present invention, in step S2, the concentration of the zinc salt is 0.5 to 1.5 mol / L.

[0051] According to some preferred embodiments of the present invention, in step S2, the concentration of the zinc salt is 1 mol / L.

[0052] According to some embodiments of the present invention, in step S2, the concentration of the small molecule additive is 1 to 2000 mmol / L.

[0053] According to some preferred embodiments of the present invention, in step S2, the concentration of the small molecule additive is 10 - 200 mmol / L.

[0054] According to some preferred embodiments of the present invention, in step S2, the concentration of the small molecule additive is 39 - 41 mmol / L.

[0055] According to some preferred embodiments of the present invention, in step S2, the concentration of the small molecule additive is 40 mmol / L.

[0056] According to some embodiments of the present invention, the electrochemical deposition includes constant voltage electrochemical deposition.

[0057] According to some embodiments of the present invention, the deposition voltage of the electrochemical deposition is 0.5 - 15 V, and the deposition time of the electrochemical deposition is 90 - 3600 s.

[0058] According to some preferred embodiments of the present invention, the deposition voltage of the electrochemical deposition is 1 - 2 V.

[0059] According to some preferred embodiments of the present invention, the deposition voltage of the electrochemical deposition is 1.5 V.

[0060] According to some preferred embodiments of the present invention, the deposition time of the electrochemical deposition is 350 - 370 s.

[0061] According to some preferred embodiments of the present invention, the deposition time of the electrochemical deposition is 360 s.

[0062] The present invention in-situ constructs a SEI protective layer on the surface of the zinc negative electrode by the method of constant voltage electrodeposition. This film layer fits tightly with the zinc substrate. The SEI protective layer contains five-membered and six-membered ring structures containing nitrogen, and this structure can form chemical bonds with the water molecules around the hydrated zinc ions, which is beneficial to the desolvation process of the hydrated zinc ions. This artificial negative electrode used in zinc-ion batteries has the characteristics of excellent electrochemical performance, high cycle stability, and long cycle life, and can solve problems such as dendrite growth of the negative electrode material of zinc-ion batteries, low reversibility and short cycle life caused by the formation of by-products.

[0063] The third aspect of the present invention provides a zinc-ion battery, which includes the negative electrode material as described above, as well as a positive electrode, a separator, and an electrolyte.

[0064] According to some embodiments of the present invention, the zinc-ion battery further includes: a housing or outer packaging for encapsulation.

[0065] In the present invention, any outer packaging can be appropriately selected without limitation, as long as it is stable to the electrolyte and has sufficient sealing performance.

[0066] The form of the aqueous zinc-ion battery involved in the present invention is not limited to the button type, and can also be designed into forms such as flat type, cylindrical type, or laminated type according to the core components.

[0067] The working principle of the zinc-ion battery of the present invention is as follows: During the charging process, anions in the electrolyte migrate to the positive electrode activated carbon and adsorb on its surface, while zinc ions deposit on the negative electrode zinc metal; during the discharging process, the anions desorb from the positive electrode material and return to the electrolyte, and the zinc ions are stripped from the zinc negative electrode and return to the electrolyte, thereby realizing the entire charge-discharge process.

[0068] The zinc-ion battery of the present invention uses zinc ions as the energy storage medium. This zinc-ion battery replaces lithium salts with zinc salts, so that its application is not restricted by lithium resources and is expected to develop rapidly. In addition, since the price of zinc salts is much lower than that of lithium salts, the production cost of this zinc-ion battery is significantly reduced. The positive and negative electrode materials of the aqueous zinc-ion battery of the present invention are simple, easy to obtain, environmentally friendly, safe, have a simple production process and low cost, and also have a high specific capacity and excellent cycle stability; its negative electrode is a zinc foil metal that can reversibly deposit and strip and contains an SEI protective film. 2+ This layer of SEI protective film can induce Zn 2+ to preferentially deposit on the (002) crystal plane, reduce the disordered growth of zinc dendrites, and improve the cycle stability of the zinc negative electrode. In the electrolyte of this aqueous zinc-ion battery, traditional lithium ions are replaced by zinc ions, alleviating the problem of limited lithium resource reserves, so that its application is no longer restricted by lithium resources. At the same time, the cost of the aqueous battery is significantly reduced compared with the organic system, and the safety performance is improved.

[0069] According to some embodiments of the present invention, the positive electrode includes a positive electrode current collector and a positive electrode material.

[0070] According to some embodiments of the present invention, the positive electrode current collector includes at least one of carbon cloth, carbon-coated aluminum foil, and aluminum foil.

[0071] According to some preferred embodiments of the present invention, the positive electrode current collector includes carbon cloth.

[0072] According to some embodiments of the present invention, the positive electrode material includes a positive electrode material active substance.

[0073] According to some embodiments of the present invention, the positive electrode material active substance of the positive electrode includes at least one of activated carbon, carbon nanotubes, activated carbon fibers, graphene, mesoporous carbon, carbon molecular sieves, and carbon foam.

[0074] According to some preferred embodiments of the present invention, the positive electrode material active substance includes activated carbon.

[0075] The positive electrode material active substance of the present invention is a porous carbon material that can reversibly adsorb and desorb anions in the electrolyte.

[0076] According to some embodiments of the present invention, by weight, the positive electrode material includes: 10-99 parts of positive electrode material active substance, 1-90 parts of conductive agent, and 1-90 parts of binder.

[0077] According to some embodiments of the present invention, the conductive agent includes at least one of conductive carbon black, super P, conductive carbon spheres, conductive graphite, carbon nanotubes, carbon fibers, and graphene.

[0078] According to some embodiments of the present invention, the binder includes at least one of vinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, SBR rubber, and polyolefin.

[0079] According to some embodiments of the present invention, the polyolefin includes at least one of polybutadiene, polyvinyl chloride, and polyisoprene.

[0080] According to some embodiments of the present invention, the electrolyte includes an aqueous solvent containing a zinc salt.

[0081] In the aqueous solvent of the zinc salt, according to some embodiments of the present invention, the zinc salt includes at least one of zinc chloride, zinc fluoride, zinc sulfate, zinc nitrate, zinc bromide, zinc trifluoromethanesulfonate, zinc hexafluorophosphate, zinc bis(trifluoromethanesulfonyl)imide, zinc molybdate, zinc acetate, zinc sulfide, zinc carbonate, zinc phosphate, zinc borate, and zinc stearate.

[0082] In the aqueous solvent of the zinc salt, according to some preferred embodiments of the present invention, the zinc salt includes zinc trifluoromethanesulfonate.

[0083] In the aqueous solvent containing a zinc salt, according to some embodiments of the present invention, the concentration range of the zinc salt is 0.01 - 30 mol / L.

[0084] In the aqueous solvent containing a zinc salt, according to some preferred embodiments of the present invention, the concentration of the zinc salt is 0.1 - 20 mol / L.

[0085] In the aqueous solvent containing a zinc salt, according to some more preferred embodiments of the present invention, the concentration of the zinc salt is 1 mol / L.

[0086] In some more preferred embodiments of the present invention, the concentration of the zinc salt is 0.5 mol / L.

[0087] In some more preferred embodiments of the present invention, the concentration of the zinc salt is 2 mol / L.

[0088] In some more preferred embodiments of the present invention, the concentration of the zinc salt is 3 mol / L.

[0089] In some more preferred embodiments of the present invention, the concentration of the zinc salt is 4 mol / L.

[0090] In some more preferred embodiments of the present invention, the concentration of the zinc salt is 5 mol / L.

[0091] In some more preferred embodiments of the present invention, the concentration of the zinc salt is 10 mol / L.

[0092] The ion concentration affects the ion transport performance of the electrolyte. If the zinc salt concentration in the electrolyte is too low, Zn2+ and too few anions result in poor ion transport performance, low conductivity, and too high a concentration of zinc salt in the electrolyte, where Zn 2+ and too many anions, the viscosity of the electrolyte and the degree of ion association will also increase with the increase of zinc salt concentration, which will in turn reduce the conductivity.

[0093] The present invention uses zinc salt, which is rich in reserves and low in price, as the electrolyte of the zinc ion battery. It can not only reduce the cost of the battery, but also prevent dendrites from piercing the diaphragm during the reaction process, thus having good safety performance.

[0094] According to some embodiments of the present invention, the electrolyte further includes an additive.

[0095] According to some embodiments of the present invention, the additive includes at least one of small molecule α-amino acids, small molecule non-protein amino acids, small molecule oligopeptide compounds, and small molecule polypeptide compounds.

[0096] According to some embodiments of the present invention, in the electrolyte, the concentration of the additive is 1-2000 mmol / L.

[0097] According to some embodiments of the present invention, the diaphragm includes at least one of a porous polymer film, an inorganic porous film, an organic composite film, and an inorganic composite film.

[0098] According to some embodiments of the present invention, the porous polymer film includes at least one of a porous polypropylene film, a porous polyethylene film, and a porous composite polymer film.

[0099] According to some embodiments of the present invention, the inorganic composite film includes at least one of non-woven fabric, glass fiber paper, and a porous ceramic diaphragm.

[0100] The zinc ion battery of the present invention uses zinc ions as the energy storage medium. This zinc ion battery uses zinc salt to replace lithium salt, so that its application is not restricted by lithium resources, and the battery can develop rapidly. In addition, since the price of zinc salt is much lower than that of lithium salt, the production cost of this zinc ion battery is significantly reduced.

[0101] The positive electrode material of the zinc ion battery of the present invention uses a carbon material such as activated carbon material that can adsorb and desorb anions. Activated carbon has the advantages of a large specific surface area, light weight, and high chemical stability. The material source is wide and the price is low. Moreover, no redox reaction occurs during operation, and the physical adsorption and desorption reaction rate is fast. Therefore, it has a higher specific capacity and a longer cycle life.

[0102] The negative electrode material of the zinc ion battery of the present invention uses the negative electrode material modified by an artificial interface, which can supply Zn 2+Reversibly deposit and strip, the negative electrode material is prepared by the method of constant voltage electrochemical in-situ deposition, and the production process is environmentally friendly, safe and low-cost.

[0103] During the reaction of the interface-modified negative electrode of the zinc-ion battery of the present invention, dendrites will not be generated to pierce the diaphragm, and it has good safety performance.

[0104] The zinc-ion battery of the present invention uses an artificial interface-modified zinc foil that can deposit and strip zinc ions as the negative electrode, a porous carbon material that can adsorb and desorb anions as the active material of the positive electrode, and a zinc-ion solution as the electrolyte. Energy storage is achieved through the deposition and stripping of zinc ions on the negative electrode material and the adsorption and desorption of anions on the positive electrode material. The positive and negative electrode materials of this zinc-ion battery are simple, easy to obtain, environmentally friendly, safe, the production process is simple and the cost is low. The zinc-ion battery has excellent electrochemical performance, high capacity and stable cycling performance, and good safety performance at the same time.

[0105] The fourth aspect of the present invention provides an application of the zinc-ion battery described above in the field of energy storage.

[0106] Other features and advantages of the present invention will be described in the subsequent specification, and part of them will be obvious from the specification or understood by implementing the present invention. Description of the Drawings

[0107] The above and / or additional aspects and advantages of the present invention will become obvious and easy to understand from the description of the embodiments in conjunction with the following drawings, wherein:

[0108] Figure 1 is the long-cycle capacity curve of the zinc-ion batteries of Example 1 and Comparative Example 1 of the present invention;

[0109] Figure 2 is the SEM image of the surface of the zinc negative electrode after long cycling of the zinc-ion battery corresponding to Comparative Example 1 of the present invention;

[0110] Figure 3 is the SEM image of the surface of the zinc negative electrode after long cycling of the zinc-ion battery corresponding to Example 1 of the present invention;

[0111] Figure 4 is the EDS energy spectrum of zinc element on the surface of the zinc negative electrode after long cycling of the zinc-ion battery corresponding to Comparative Example 1 of the present invention;

[0112] Figure 5 is the EDS energy spectrum of zinc element on the surface of the zinc negative electrode after long cycling of the zinc-ion battery corresponding to Example 1 of the present invention. Detailed Embodiments

[0113] Embodiments of the present invention will be described in detail below. Examples of the embodiments are shown in the accompanying drawings, where like or similar reference numerals denote like or similar elements or elements having the same or similar functions throughout. The embodiments described below by referring to the drawings are exemplary and are only used to explain the present invention and should not be construed as a limitation of the present invention.

[0114] Example 1

[0115] This example discloses a preparation method of an aqueous zinc-ion battery. The specific steps are as follows:

[0116] A1: Prepare the negative electrode: Polish the zinc sheet with sandpaper, then ultrasonically treat it in deionized water. Put the ultrasonically treated zinc sheet into a precursor solution of 1 mol / L zinc trifluoromethanesulfonate and 40 mmol / L glutathione (precursor solution additive) as the negative electrode. The positive electrode is a platinum sheet. A SEI protective layer is constructed on the surface of the zinc negative electrode by constant voltage electrochemical deposition method. The deposition voltage is set to 1.5 V and the deposition time is 360 s. Wash and dry the surface-modified zinc negative electrode in deionized water, and cut the dried electrode sheet into circular pieces with a diameter of 12 mm.

[0117] B1: Prepare the separator: Cut the glass fiber separator into circular pieces with a diameter of 16 mm, and dry it for later use as the separator.

[0118] Prepare the electrolyte: Weigh 3.63 g of zinc trifluoromethanesulfonate and add it to 10 mL of deionized water. Stir until the zinc trifluoromethanesulfonate is completely dissolved, and stir well to obtain the electrolyte for later use (the electrolyte concentration is 1 M).

[0119] C1: Prepare the positive electrode: Add 0.16 g of activated carbon, 0.02 g of Super P, and 0.02 g of polyvinylidene fluoride to a certain amount of N-methylpyrrolidone solution, and grind thoroughly to obtain a uniform slurry; then uniformly coat the slurry on the surface of the carbon cloth and dry it in vacuum. Cut the dried electrode sheet into circular pieces with a diameter of 10 mm, and compact it for later use as the positive electrode.

[0120] D1: Assembly: Stack the prepared positive electrode, separator, and negative electrode tightly in sequence, drop the electrolyte to completely wet the separator, and then encapsulate the stacked part into a button-type housing to complete the assembly of the aqueous zinc-ion battery.

[0121] The long-cycle capacity curve of the zinc-ion battery in Example 1 Figure 1 is shown as;

[0122] The SEM image of the surface of the zinc negative electrode after the zinc-ion battery in Example 1 has been cycled 24,000 times is as shown in Figure 3 shown, at 5 Ag -1At a current density of, it can cycle stably for 24,000 cycles. After the cycles, the batteries were disassembled respectively. The negative electrodes were taken out, cleaned and naturally dried at room temperature, and then observed by SEM (scanning electron microscope). After 24,000 cycles, the surface of the zinc negative electrode modified by the artificial interface still remained smooth and flat;

[0123] The EDS spectrum of zinc element on the surface of the zinc negative electrode of the zinc-ion battery in Example 1 after 24,000 long cycles is as Figure 5 shown. The EDS spectrum analysis of zinc element further proves that the zinc negative electrode modified by the artificial interface can induce Zn 2+ to deposit uniformly.

[0124] The SEM image of the surface of the zinc negative electrode of the battery in Example 1 after long cycles is as Figure 3 shown.

[0125] Example 2

[0126] A zinc-ion battery, wherein the small molecule additive is glutamic acid, and the others are the same as in Example 1.

[0127] Example 3

[0128] A zinc-ion battery, wherein the small molecule additive is cysteine, and the others are the same as in Example 1.

[0129] Example 4

[0130] A zinc-ion battery, wherein the small molecule additive is glycine, and the others are the same as in Example 1.

[0131] Example 5

[0132] A zinc-ion battery, wherein the small molecule additive is alanine, and the others are the same as in Example 1.

[0133] Example 6

[0134] A zinc-ion battery, wherein the small molecule additive is valine, and the others are the same as in Example 1.

[0135] Example 7

[0136] A zinc-ion battery, wherein the small molecule additive is leucine, and the others are the same as in Example 1.

[0137] Example 8

[0138] A zinc-ion battery, wherein the small molecule additive is isoleucine, and the others are the same as in Example 1.

[0139] Example 9

[0140] A zinc-ion battery, wherein the small molecule additive is methionine, and the others are the same as in Example 1.

[0141] Example 10

[0142] A zinc-ion battery, wherein the small molecule additive is proline, and the others are the same as in Example 1.

[0143] Example 11

[0144] A zinc-ion battery, wherein the small molecule additive is tryptophan, and the others are the same as in Example 1.

[0145] Example 12

[0146] A zinc-ion battery, wherein the small molecule additive is serine, and the others are the same as in Example 1.

[0147] Example 13

[0148] A zinc-ion battery, wherein the small molecule additive is tyrosine, and the others are the same as in Example 1.

[0149] Example 14

[0150] A zinc-ion battery, wherein the small molecule additive is phenylalanine, and the others are the same as in Example 1.

[0151] Example 15

[0152] A zinc-ion battery, wherein the small molecule additive is asparagine, and the others are the same as in Example 1.

[0153] Example 16

[0154] A zinc-ion battery, wherein the small molecule additive is glutamine, and the others are the same as in Example 1.

[0155] Example 17

[0156] A zinc-ion battery, wherein the small molecule additive is threonine, and the others are the same as in Example 1.

[0157] Example 18

[0158] A zinc-ion battery, wherein the small molecule additive is aspartic acid, and the others are the same as in Example 1.

[0159] Example 19

[0160] A zinc-ion battery, wherein the small molecule additive is lysine, and the others are the same as in Example 1.

[0161] Example 20

[0162] A zinc-ion battery, wherein the small molecule additive is arginine, and the others are the same as in Example 1.

[0163] Example 21

[0164] A zinc ion battery, wherein the small molecule additive is histidine, and the others are the same as in Example 1.

[0165] Example 22

[0166] A zinc ion battery, wherein the small molecule additive is selenocysteine, and the others are the same as in Example 1.

[0167] Example 23

[0168] A zinc ion battery, wherein the small molecule additive is pyrrolysine, and the others are the same as in Example 1.

[0169] Example 24

[0170] A zinc ion battery, wherein the small molecule additive is 3-aminoglutaric acid, and the others are the same as in Example 1.

[0171] Example 25

[0172] A zinc ion battery, wherein the small molecule additive is gracillamine, and the others are the same as in Example 1.

[0173] Example 26

[0174] A zinc ion battery, wherein the small molecule additive is laminine, and the others are the same as in Example 1.

[0175] Example 27

[0176] A zinc ion battery, wherein the small molecule additive is palytoxin, and the others are the same as in Example 1.

[0177] Example 28

[0178] A zinc ion battery, wherein the small molecule additive is 3-hydroxy-D-cysteinesulfonic acid, and the others are the same as in Example 1.

[0179] Example 29

[0180] A zinc ion battery, wherein the small molecule additive is 3-aminopropanesulfonic acid, and the others are the same as in Example 1.

[0181] Example 30

[0182] A zinc ion battery, wherein the small molecule additive is chondrine, and the others are the same as in Example 1.

[0183] Example 31

[0184] A zinc ion battery, wherein the small molecule additive is carrageenamine, and the others are the same as in Example 1.

[0185] Example 32

[0186] A zinc ion battery, wherein the small molecule additive is porphyran acid, and the others are the same as in Example 1.

[0187] Example 33

[0188] A zinc ion battery, wherein the small molecule additive is L-ornithine, and the others are the same as in Example 1.

[0189] Example 34

[0190] A zinc ion battery, wherein the small molecule additive is L-citrulline, and the others are the same as in Example 1.

[0191] Example 35

[0192] A zinc ion battery, wherein the small molecule additive is cystathionine, and the others are the same as in Example 1.

[0193] Example 36

[0194] A zinc ion battery, wherein the small molecule additive is lanthionine, and the others are the same as in Example 1.

[0195] Example 37

[0196] A zinc ion battery, wherein the small molecule additive is chordaene, and the others are the same as in Example 1.

[0197] Example 38

[0198] A zinc ion battery, wherein the small molecule additive is methionine sulfoxide, and the others are the same as in Example 1.

[0199] Example 39

[0200] A zinc ion battery, wherein the small molecule additive is N-methylmethionine sulfoxide, and the others are the same as in Example 1.

[0201] Example 40

[0202] A zinc ion battery, wherein the small molecule additive is S-hydroxymethylhomocysteine, and the others are the same as in Example 1.

[0203] Example 41

[0204] A zinc ion battery, wherein the small molecule additive is 1-methyl-L-histidine, and the others are the same as in Example 1.

[0205] Example 42

[0206] A zinc ion battery, wherein the small molecule additive is β-alanine, and the others are the same as in Example 1.

[0207] Example 43

[0208] A zinc ion battery, wherein the small molecule additive is γ-aminobutyric acid, and the others are the same as in Example 1.

[0209] Example 44

[0210] A zinc ion battery, wherein the small molecule additive is 2-piperidinecarboxylic acid, and the others are the same as in Example 1.

[0211] Example 45

[0212] A zinc ion battery, wherein the small molecule additive is 1-aminocyclopropane-1-carboxylic acid (ACC), and the others are the same as in Example 1.

[0213] Example 46

[0214] A zinc ion battery, wherein the small molecule additive is L-azetidine-2-carboxylic acid, and the others are the same as in Example 1.

[0215] Example 47

[0216] A zinc ion battery, wherein the small molecule additive is 5-hydroxy-2-piperidinecarboxylic acid, and the others are the same as in Example 1.

[0217] Example 48

[0218] A zinc ion battery, wherein the small molecule additive is canavanine, and the others are the same as in Example 1.

[0219] Example 49

[0220] A zinc ion battery, wherein the small molecule additive is 3-iodo-L-tyrosine, and the others are the same as in Example 1.

[0221] Example 50

[0222] A zinc ion battery, wherein the small molecule additive is domoic acid, and the others are the same as in Example 1.

[0223] Example 51

[0224] A zinc ion battery, wherein the small molecule additive is 2,5-dicarboxypyrrolidine, and the others are the same as in Example 1.

[0225] Example 52

[0226] A zinc ion battery, wherein the small molecule additive is γ-guanidinobutyric acid, and the others are the same as in Example 1.

[0227] Example 53

[0228] A zinc-ion battery, where the small molecule additive is methyltaurine, and the others are the same as in Example 1.

[0229] Example 54

[0230] A zinc-ion battery, where the small molecule additive is kainic acid, and the others are the same as in Example 1.

[0231] Example 55

[0232] A zinc-ion battery, where the small molecule additive is taurine, and the others are the same as in Example 1.

[0233] Example 56

[0234] A zinc-ion battery, where the small molecule additive is N,N-dimethyltaurine, and the others are the same as in Example 1.

[0235] Example 57

[0236] A zinc-ion battery, where the small molecule additive is D-glycerotaurine, and the others are the same as in Example 1.

[0237] Example 58

[0238] A zinc-ion battery, where the small molecule additive is foliaceous alga amino acid, and the others are the same as in Example 1.

[0239] Example 59

[0240] A zinc-ion battery, where the small molecule additive is chondramine, and the others are the same as in Example 1.

[0241] Example 60

[0242] A zinc-ion battery, where the small molecule additive is gracilaria amino acid, and the others are the same as in Example 1.

[0243] Example 61

[0244] A zinc-ion battery, where the small molecule additive is kainic acid, and the others are the same as in Example 1.

[0245] Example 62

[0246] A zinc-ion battery, where the small molecule additive is sargassum amino acid, and the others are the same as in Example 1.

[0247] Example 63

[0248] A zinc-ion battery, where the small molecule additive is ligulate sargassum amino acid, and the others are the same as in Example 1.

[0249] Example 64

[0250] A zinc-ion battery, in which the small molecule additive is alanyl-glutamine, and the others are the same as in Example 1.

[0251] Example 65

[0252] A zinc-ion battery, in which the small molecule additive is alanyl-glutamic acid dipeptide, and the others are the same as in Example 1.

[0253] Example 66

[0254] A zinc-ion battery, in which the small molecule additive is carnosine, and the others are the same as in Example 1.

[0255] Example 67

[0256] A zinc-ion battery, in which the small molecule additive is thymopentin, and the others are the same as in Example 1.

[0257] Example 68

[0258] A zinc-ion battery, in which the small molecule additive is octreotide, and the others are the same as in Example 1.

[0259] Example 69

[0260] A zinc-ion battery, in which the small molecule additive is glutathione, and its concentration is 10 mmol / L, and the others are the same as in Example 1.

[0261] Example 70

[0262] A zinc-ion battery, in which the small molecule additive is glutathione, and its concentration is 20 mmol / L, and the others are the same as in Example 1.

[0263] Example 71

[0264] A zinc-ion battery, in which the small molecule additive is glutathione, and its concentration is 30 mmol / L, and the others are the same as in Example 1.

[0265] Example 72

[0266] A zinc-ion battery, in which the small molecule additive is glutathione, and its concentration is 50 mmol / L, and the others are the same as in Example 1.

[0267] Example 73

[0268] A zinc-ion battery, in which the small molecule additive is glutathione, and its concentration is 60 mmol / L, and the others are the same as in Example 1.

[0269] Example 74

[0270] A zinc-ion battery, in which the small molecule additive is glutathione, and its concentration is 70 mmol / L, and the others are the same as in Example 1.

[0271] Example 75

[0272] A zinc-ion battery, in which the small molecule additive is glutathione, and its concentration is 80 mmol / L, and the others are the same as in Example 1.

[0273] Example 76

[0274] A zinc-ion battery, in which the small molecule additive is glutathione, and its concentration is 90 mmol / L, and the others are the same as in Example 1.

[0275] Example 77

[0276] A zinc-ion battery, in which the small molecule additive is glutathione, and its concentration is 100 mmol / L, and the others are the same as in Example 1.

[0277] Example 78

[0278] A zinc-ion battery, in which the small molecule additive is glutathione, and its concentration is 200 mmol / L, and the others are the same as in Example 1.

[0279] Example 79

[0280] A zinc-ion battery, in which the small molecule additive is glutathione, and its concentration is 300 mmol / L, and the others are the same as in Example 1.

[0281] Example 80

[0282] A zinc-ion battery, in which the small molecule additive is glutathione, and its concentration is 400 mmol / L, and the others are the same as in Example 1.

[0283] Example 81

[0284] A zinc-ion battery, in which the small molecule additive is glutathione, and its concentration is 500 mmol / L, and the others are the same as in Example 1.

[0285] Example 82

[0286] A zinc-ion battery, in which the small molecule additive is glutathione, and its concentration is 600 mmol / L, and the others are the same as in Example 1.

[0287] Example 83

[0288] A zinc-ion battery, in which the small molecule additive is glutathione, and its concentration is 700 mmol / L, and the others are the same as in Example 1.

[0289] Example 84

[0290] A zinc-ion battery, in which the small molecule additive is glutathione, and its concentration is 800 mmol / L, and the others are the same as in Example 1.

[0291] Example 85

[0292] A zinc-ion battery, in which the small molecule additive is glutathione, and its concentration is 900 mmol / L, and the others are the same as in Example 1.

[0293] Example 86

[0294] A zinc-ion battery, in which the small molecule additive is glutathione, and its concentration is 1000 mmol / L, and the others are the same as in Example 1.

[0295] Example 87

[0296] A zinc-ion battery, in which the small molecule additive is glutathione, and its concentration is 2000 mmol / L, and the others are the same as in Example 1.

[0297] Example 88

[0298] A zinc-ion battery, in which the electrochemical deposition voltage is 0.5 V, and the others are the same as in Example 1.

[0299] Example 89

[0300] A zinc-ion battery, in which the electrochemical deposition voltage is 1 V, and the others are the same as in Example 1.

[0301] Example 90

[0302] A zinc-ion battery, in which the electrochemical deposition voltage is 2 V, and the others are the same as in Example 1.

[0303] Example 91

[0304] A zinc-ion battery, in which the electrochemical deposition voltage is 2.5 V, and the others are the same as in Example 1.

[0305] Example 92

[0306] A zinc-ion battery, in which the electrochemical deposition voltage is 3 V, and the others are the same as in Example 1.

[0307] Example 93

[0308] A zinc-ion battery, in which the electrochemical deposition voltage is 3.5 V, and the others are the same as in Example 1.

[0309] Example 94

[0310] A zinc-ion battery, in which the electrochemical deposition voltage is 4 V, and the others are the same as in Example 1.

[0311] Example 95

[0312] A zinc ion battery, in which the electrochemical deposition voltage is 4.5 V, and the others are the same as in Example 1.

[0313] Example 96

[0314] A zinc ion battery, in which the electrochemical deposition voltage is 5 V, and the others are the same as in Example 1.

[0315] Example 97

[0316] A zinc ion battery, in which the electrochemical deposition voltage is 6 V, and the others are the same as in Example 1.

[0317] Example 98

[0318] A zinc ion battery, in which the electrochemical deposition voltage is 7 V, and the others are the same as in Example 1.

[0319] Example 99

[0320] A zinc ion battery, in which the electrochemical deposition voltage is 8 V, and the others are the same as in Example 1.

[0321] Example 100

[0322] A zinc ion battery, in which the electrochemical deposition voltage is 9 V, and the others are the same as in Example 1.

[0323] Example 101

[0324] A zinc ion battery, in which the electrochemical deposition voltage is 10 V, and the others are the same as in Example 1.

[0325] Example 102

[0326] A zinc ion battery, in which the electrochemical deposition voltage is 11 V, and the others are the same as in Example 1.

[0327] Example 103

[0328] A zinc ion battery, in which the electrochemical deposition voltage is 12 V, and the others are the same as in Example 1.

[0329] Example 104

[0330] A zinc ion battery, in which the electrochemical deposition voltage is 13 V, and the others are the same as in Example 1.

[0331] Example 105

[0332] A zinc ion battery, in which the electrochemical deposition voltage is 14 V, and the others are the same as in Example 1.

[0333] Example 106

[0334] A zinc-ion battery, in which the electrochemical deposition voltage is 15 V, and the others are the same as in Example 1.

[0335] Example 107

[0336] A zinc-ion battery, in which the electrochemical deposition time is 90 s, and the others are the same as in Example 1.

[0337] Example 108

[0338] A zinc-ion battery, in which the electrochemical deposition time is 180 s, and the others are the same as in Example 1.

[0339] Example 109

[0340] A zinc-ion battery, in which the electrochemical deposition time is 270 s, and the others are the same as in Example 1.

[0341] Example 110

[0342] A zinc-ion battery, in which the electrochemical deposition time is 480 s, and the others are the same as in Example 1.

[0343] Example 111

[0344] A zinc-ion battery, in which the electrochemical deposition time is 570 s, and the others are the same as in Example 1.

[0345] Example 112

[0346] A zinc-ion battery, in which the electrochemical deposition time is 660 s, and the others are the same as in Example 1.

[0347] Example 113

[0348] A zinc-ion battery, in which the electrochemical deposition time is 750 s, and the others are the same as in Example 1.

[0349] Example 114

[0350] A zinc-ion battery, in which the electrochemical deposition time is 840 s, and the others are the same as in Example 1.

[0351] Example 115

[0352] A zinc-ion battery, in which the electrochemical deposition time is 930 s, and the others are the same as in Example 1.

[0353] Example 116

[0354] A zinc-ion battery, in which the electrochemical deposition time is 1020 s, and the others are the same as in Example 1.

[0355] Example 117

[0356] A zinc-ion battery, in which the electrochemical deposition time is 1200 s, and the others are the same as in Example 1.

[0357] Example 118

[0358] A zinc-ion battery, in which the electrochemical deposition time is 1380 s, and the others are the same as in Example 1.

[0359] Example 119

[0360] A zinc-ion battery, in which the electrochemical deposition time is 1560 s, and the others are the same as in Example 1.

[0361] Example 120

[0362] A zinc-ion battery, in which the electrochemical deposition time is 1740 s, and the others are the same as in Example 1.

[0363] Example 121

[0364] A zinc-ion battery, in which the electrochemical deposition time is 1920 s, and the others are the same as in Example 1.

[0365] Example 122

[0366] A zinc-ion battery, in which the electrochemical deposition time is 2100 s, and the others are the same as in Example 1.

[0367] Example 123

[0368] A zinc-ion battery, in which the electrochemical deposition time is 2280 s, and the others are the same as in Example 1.

[0369] Example 124

[0370] A zinc-ion battery, in which the electrochemical deposition time is 2460 s, and the others are the same as in Example 1.

[0371] Example 125

[0372] A zinc-ion battery, in which the electrochemical deposition time is 2640 s, and the others are the same as in Example 1.

[0373] Example 126

[0374] A zinc-ion battery, in which the electrochemical deposition time is 2820 s, and the others are the same as in Example 1.

[0375] Example 127

[0376] A zinc-ion battery, in which the electrochemical deposition time is 3000 s, and the others are the same as in Example 1.

[0377] Example 128

[0378] A zinc-ion battery, in which the electrochemical deposition time is 3600 s, and the others are the same as in Example 1.

[0379] Example 129

[0380] A zinc-ion battery, in which the active material of the positive electrode is activated carbon fiber, and the others are the same as in Example 1.

[0381] Example 130

[0382] A zinc-ion battery, in which the active material of the positive electrode is carbon nanotubes, and the others are the same as in Example 1.

[0383] Example 131

[0384] A zinc-ion battery, in which the active material of the positive electrode is graphene, and the others are the same as in Example 1.

[0385] Example 132

[0386] A zinc-ion battery, in which the active material of the positive electrode is mesoporous carbon, and the others are the same as in Example 1.

[0387] Example 133

[0388] A zinc-ion battery, in which the active material of the positive electrode is carbon molecular sieve, and the others are the same as in Example 1.

[0389] Example 134

[0390] A zinc-ion battery, in which the active material of the positive electrode is carbon foam, and the others are the same as in Example 1.

[0391] Example 135

[0392] A zinc-ion battery, in which the zinc salt used in the electrolyte is zinc chloride, and the others are the same as in Example 1.

[0393] Example 136

[0394] A zinc-ion battery, in which the zinc salt used in the electrolyte is zinc fluoride, and the others are the same as in Example 1.

[0395] Example 137

[0396] A zinc-ion battery, in which the zinc salt used in the electrolyte is zinc sulfate, and the others are the same as in Example 1.

[0397] Example 138

[0398] A zinc-ion battery, in which the zinc salt used in the electrolyte is zinc nitrate, and the others are the same as in Example 1.

[0399] Example 139

[0400] A zinc-ion battery, in which the zinc salt used in the electrolyte is zinc bromide, and the others are the same as in Example 1.

[0401] Example 140

[0402] A zinc-ion battery, in which the zinc salt used in the electrolyte is zinc hexafluorophosphate, and the others are the same as in Example 1.

[0403] Example 141

[0404] A zinc-ion battery, in which the zinc salt used in the electrolyte is zinc bis(trifluoromethanesulfonyl)imide, and the others are the same as in Example 1.

[0405] Example 142

[0406] A zinc-ion battery, in which the zinc salt used in the electrolyte is zinc molybdate, and the others are the same as in Example 1.

[0407] Example 143

[0408] A zinc-ion battery, in which the zinc salt used in the electrolyte is zinc acetate, and the others are the same as in Example 1.

[0409] Example 144

[0410] A zinc-ion battery, in which the zinc salt used in the electrolyte is zinc sulfide, and the others are the same as in Example 1.

[0411] Example 145

[0412] A zinc-ion battery, in which the zinc salt used in the electrolyte is zinc carbonate, and the others are the same as in Example 1.

[0413] Example 146

[0414] A zinc-ion battery, in which the zinc salt used in the electrolyte is zinc phosphate, and the others are the same as in Example 1.

[0415] Example 147

[0416] A zinc-ion battery, in which the zinc salt used in the electrolyte is zinc borate, and the others are the same as in Example 1.

[0417] Example 148

[0418] A zinc-ion battery, in which the zinc salt used in the electrolyte is zinc stearate, and the others are the same as in Example 1.

[0419] Example 149

[0420] A zinc-ion battery, the electrolyte concentration is 0.1 M, and the others are the same as in Example 1.

[0421] Example 150

[0422] A zinc-ion battery with an electrolyte concentration of 0.5 M, and the others are the same as in Example 1.

[0423] Example 151

[0424] A zinc-ion battery with an electrolyte concentration of 1.5 M, and the others are the same as in Example 1.

[0425] Example 152

[0426] A zinc-ion battery with an electrolyte concentration of 2 M, and the others are the same as in Example 1.

[0427] Example 153

[0428] A zinc-ion battery with an electrolyte concentration of 2.5 M, and the others are the same as in Example 1.

[0429] Example 154

[0430] A zinc-ion battery with an electrolyte concentration of 3 M, and the others are the same as in Example 1.

[0431] Example 155

[0432] A zinc-ion battery with an electrolyte concentration of 4 M, and the others are the same as in Example 1.

[0433] Example 156

[0434] A zinc-ion battery with an electrolyte concentration of 5 M, and the others are the same as in Example 1.

[0435] Comparative Example 1

[0436] A zinc-ion battery in which the zinc negative electrode is not subjected to any modification treatment, and the others are the same as in Example 1.

[0437] The SEM image of the surface of the zinc negative electrode of the zinc-ion battery in Comparative Example 1 after 8000 long cycles is as Figure 2 shown. At a current density of 5 Ag -1 only 8000 cycles are carried out. After the batteries after cycling are disassembled respectively, the negative electrodes are taken out, cleaned and naturally dried at room temperature, and then SEM (scanning electron microscope) observation is carried out. A large number of dendrites and pulverized particles appear on the surface of the unmodified zinc negative electrode after 8000 cycles;

[0438] The EDS energy spectrum of zinc element on the surface of the zinc negative electrode of the zinc-ion battery in Comparative Example 1 after 8000 long cycles is as Figure 4 shown. Zn 2+ is unevenly deposited on the unmodified zinc negative electrode, and large shadow areas appear in the energy spectrum.

[0439] Test Example 1

[0440] Test Example 1 is that for Comparative Example 1 and Examples 1 to 23, zinc foils treated with different additives are respectively assembled into zinc-ion batteries, and charge-discharge tests are carried out at a current density of 5 A / g. The test results are shown in Table 1:

[0441] Table 1 Charge-discharge Performance Test

[0442]

[0443] The zinc foil negative electrode of Comparative Example 1 was not modified at all. The difference between Examples 2 to 23 and Example 1 lies only in the different precursor solution additives. As can be seen from Table 1, α-amino acid as an additive for the electrochemical deposition precursor solution can in-situ polymerize into a film on the zinc surface, improving the specific capacity and long-cycle stability performance of the zinc-ion battery. Compared with Example 1, in Comparative Example 1, the negative electrode was not modified at the interface. During the cycling process, serious dendrite growth and side reactions occurred on the zinc negative electrode, generating insoluble by-products, which affected the reversible cycling performance of the battery. The battery corresponding to Comparative Example 1 could only cycle 8,000 times at a current density of 5 A / g, far lower than 24,000 times after modification. ～1 The current density of is far lower than 24,000 cycles after modification.

[0444] Test Example 2

[0445] Test Example 2 is that for Example 1 and Examples 24 to 63, zinc foils treated with different additives are respectively assembled into zinc-ion batteries, and charge-discharge tests are carried out at a current density of 5 A / g. The test results are shown in Table 2:

[0446] Table 2 Charge-discharge Performance Test

[0447]

[0448]

[0449]

[0450] As can be seen from Table 2, non-protein amino acids can also be used as additives for the electrochemical deposition precursor solution, inducing in-situ polymerization on the surface of the zinc negative electrode to form a SEI protective layer, improving the specific capacity and cycling stability performance of the zinc-ion battery, but the improvement effect is not as good as that of α-amino acids.

[0451] Test Example 3

[0452] Test Example 3 is that for Example 1 and Examples 64 to 68, zinc foils treated with different additives are respectively assembled into zinc-ion batteries, and charge-discharge tests are carried out at a current density of 5 A / g. The test results are shown in Table 3:

[0453] Table 3 Charge-discharge Performance Test

[0454]

[0455] As can be seen from Table 3, small molecule peptides can also be used as additives for the electrochemical deposition precursor solution, inducing in-situ polymerization on the surface of the zinc negative electrode to form a SEI protective layer, improving the specific capacity and cycle stability of the zinc-ion battery, and the performance improvement effect is better than that of amino acid additives.

[0456] Test Example 4

[0457] Test Example 4 is that zinc-ion batteries assembled with zinc foils treated with different additives in Examples 1 and 69 - 87 are subjected to charge and discharge tests at a current density of 5 A / g, and the test results are shown in Table 4:

[0458] Table 4 Charge and Discharge Performance Test

[0459]

[0460]

[0461] As can be seen from Table 4: Compared with Example 1, for Examples 69 - 87, the addition concentration of the glutathione as the additive for the electrochemical deposition precursor solution is different. Too high or too low concentration will have an adverse effect on the formation of the SEI protective layer, and the optimal additive concentration is 40 mmol / L.

[0462] Test Example 5

[0463] Test Example 5 is that zinc-ion batteries assembled with zinc foils treated with different additives in Examples 1 and 88 - 106 are subjected to charge and discharge tests at a current density of 5 A / g, and the test results are shown in Table 5:

[0464] Table 5 Charge and Discharge Performance Test

[0465]

[0466]

[0467] Compared with Example 1, for Examples 88 - 106, during the constant voltage electrochemical deposition process, the voltage parameters are different, and the growth conditions of the SEI protective layer on the surface of the zinc negative electrode are different at different voltages, with differences in uniformity. Too low or too high deposition voltage will have an adverse effect on the growth of the film, affecting the long-cycle stability of the battery, and the optimal deposition voltage is 1.5 V.

[0468] Test Example 6

[0469] Test Example 6: Zinc foils treated with different additives in Example 1 and Examples 107 to 128 were respectively assembled into zinc-ion batteries, and charge-discharge tests were carried out at a current density of 5 A / g. The test results are shown in Table 6 as follows:

[0470] Table 6 Charge-discharge Performance Test

[0471]

[0472]

[0473] Compared with Example 1, in Examples 107 to 128, the time parameters were different during the constant-voltage electrochemical deposition process. If the deposition time was too short, the growth of the SEI protective layer was insufficient and could not completely cover the surface of the zinc negative electrode; if the deposition time was too long, the thickness of the SEI protective layer would increase, and the surface unevenness would be aggravated, affecting the electrochemical performance of the battery. The optimal deposition time was 360 s. Under this condition, the thickness and uniformity of the SEI protective layer were in the best state.

[0474] Test Example 7

[0475] Test Example 7: Zinc foils treated with different additives in Example 1 and Examples 129 to 134 were respectively assembled into zinc-ion batteries, and charge-discharge tests were carried out at a current density of 5 A / g. The test results are shown in Table 7 as follows:

[0476] Table 7 Charge-discharge Performance Test

[0477]

[0478]

[0479] Compared with Example 1, in Examples 129 to 134, the active material materials used for the positive electrode were different, and the electrochemical performances of the obtained zinc-ion super batteries were different. Among them, the specific capacity of the zinc-ion battery obtained by using activated carbon as the positive electrode active material was higher than that of the zinc-ion batteries obtained by using other carbon materials as the positive electrode active material, and it had better long-cycle performance.

[0480] Test Example 8

[0481] Test Example 8: Zinc foils treated with different additives in Example 1 and Examples 135 to 148 were respectively assembled into zinc-ion batteries, and charge-discharge tests were carried out at a current density of 5 A / g. The test results are shown in Table 8 as follows:

[0482] Table 8 Charge-discharge Performance Test

[0483]

[0484]

[0485] Examples 135 to 148 are different from Example 1 in the zinc salt used in the electrolyte, and the differences in the electrochemical performance of the obtained zinc-ion batteries are shown in the table, indicating that zinc trifluoromethanesulfonate can improve the cycling performance and is a preferred embodiment of the present invention.

[0486] Test Example 9

[0487] Test Example 9: Zinc-ion batteries assembled with zinc foils treated with different additives in Example 1 and Examples 149 to 156 were subjected to charge-discharge tests at a current density of 5 A / g, and the test results are shown in Table 9:

[0488] Table 9 Charge-discharge performance test

[0489]

[0490] Examples 149 to 156 are different from Example 1 in the electrolyte concentration. As the concentration increases, the specific capacity of the battery will gradually increase slightly. When the electrolyte is 1 M, the long-term cycling performance of the zinc-ion battery is the best.

[0491] The zinc-ion battery of the present invention realizes energy storage through the deposition and stripping of zinc ions on the negative electrode material and the adsorption and desorption of anions on the positive electrode material. It not only alleviates the problems of limited lithium-ion resources and high cost, but also has simple and inexpensive positive and negative electrode materials that are environmentally friendly and safe. The production process is simple and the cost is low. It is an aqueous zinc-ion battery with high specific capacity, high cycling performance and high safety.

[0492] The above has described the embodiments of the present invention in detail with reference to the drawings, but the present invention is not limited to the above embodiments. Various changes can be made without departing from the spirit of the present invention within the knowledge of those of ordinary skill in the art.

Claims

1. A negative electrode material for a zinc-ion battery, characterized in that, The negative electrode material includes a zinc sheet and an SEI protective layer provided on the surface of the zinc sheet; The SEI protective layer includes a polymer and zinc ions; The polymer includes a nitrogen-containing five-membered ring and a nitrogen-containing six-membered ring; The preparation raw materials of the SEI protective layer include a small molecule additive and a zinc salt; The small molecule additive is at least one of amino acids and small molecule peptides; The small molecule amino acids include at least one of α-amino acids and non-protein amino acids; The zinc salt includes at least one of zinc fluoride, zinc sulfate, zinc nitrate, zinc bromide, zinc trifluoromethanesulfonate, zinc hexafluorophosphate, zinc bis(trifluoromethylsulfonyl)imide, zinc molybdate, zinc acetate, zinc sulfide, zinc carbonate, zinc phosphate, zinc borate, and zinc stearate; The preparation method of the negative electrode material for the zinc ion battery is: using the dispersion of the preparation raw materials of the SEI protective layer as the electrolyte, and performing electrochemical deposition on the surface of the zinc sheet.

2. The negative electrode material according to claim 1, wherein The molecular weight range of the small molecule peptides is 2 - 50.

3. The negative electrode material according to claim 1, wherein The thickness of the SEI protective layer is 5 nm - 5 μm.

4. The negative electrode material according to claim 1, wherein The electrochemical deposition includes constant voltage electrochemical deposition.

5. The negative electrode material according to claim 4, characterized in that, The deposition voltage of the electrochemical deposition is 0.5 - 15 V.

6. The negative electrode material according to claim 1, wherein The deposition time of the electrochemical deposition is 90 - 3600 s.

7. A zinc-ion battery, characterized in that, It includes the negative electrode material according to any one of claims 1 - 3, as well as a positive electrode, a separator, and an electrolyte.

8. The zinc ion battery according to claim 7, characterized in that The active material of the positive electrode of the positive electrode includes at least one of activated carbon, carbon nanotubes, activated carbon fibers, graphene, mesoporous carbon, carbon molecular sieves, and carbon foams.

9. An application of the zinc ion battery according to claim 7 or 8 in the power field.

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