CN106887581B - Zinc electrode material and preparation and application thereof - Google Patents
Zinc electrode material and preparation and application thereof Download PDFInfo
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- CN106887581B CN106887581B CN201510941019.0A CN201510941019A CN106887581B CN 106887581 B CN106887581 B CN 106887581B CN 201510941019 A CN201510941019 A CN 201510941019A CN 106887581 B CN106887581 B CN 106887581B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/42—Alloys based on zinc
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/04—Cells with aqueous electrolyte
- H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
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Abstract
The invention relates to a zinc electrode material, which microscopically comprises micro-nano particles with a core-shell structure, wherein the micro-nano particles with the core-shell structure take zinc as a core and a second metal as a shell; the second metal shell wraps the outside of the zinc core, and a gap is formed between the zinc core and the second metal shell. The electrode material is obtained by the replacement reaction of zinc powder in a soluble acid solution of a second metal salt, the replaced metal grows into a layer of second metal shell in situ on the surface of zinc particles, when the metal shell completely covers the surface of the zinc particles, the replacement reaction is stopped, and the thickness of the metal layer cannot be further increased. The metal shell with the appropriate thickness effectively reduces the dissolution of zinc oxide in electrolyte and inhibits the growth of dendrite on one hand, and reduces the influence of the metal shell on the electrode performance on the other hand. The acid in the reaction solution further corrodes the zinc, forming voids in the zinc electrode material, which can accommodate the deformation of the electrode material. Therefore, the cycling stability of the zinc electrode material can be greatly improved relative to zinc powder.
Description
The technical field is as follows:
the invention relates to a zinc electrode material, a preparation method and application thereof.
Background art:
because of abundant resources and low price of metal zinc, many battery systems use zinc as an electrode, such as zinc/air batteries, zinc/nickel batteries, zinc/silver batteries, and the like. While the cycle life of zinc electrodes greatly limits the commercial application of zinc-based batteries.
The poor cycle life of zinc electrodes arises from the solubility of the zinc electrode product zinc oxide in alkaline electrolyte, dendrite formation and volume changes. The zinc oxide has certain solubility in the alkaline electrolyte, even under the condition of saturation, the zinc oxide generated by the electrode can be partially dissolved in the electrolyte to form a supersaturated solution, and the zinc oxide can not be precipitated in situ, so that the movement of an active substance is generated, the electrode is deformed, and the cycle life of the zinc electrode is influenced. On the other hand, because the active substances are not uniformly distributed, the current is not uniformly distributed in the charging process, and the zinc electrode is easy to generate dendrite, thereby generating short circuit threat and reducing the cycle life of the zinc electrode.
The density of zinc oxide, which is an oxidation product of zinc, is relatively low compared with that of zinc, so that the volume of the charge-discharge product is changed in the charge-discharge process, the electrode deformation and the structural damage are caused, and the cycle stability of the zinc electrode is influenced.
Disclosure of Invention
Aiming at the solubility, dendrite formation and volume change of zinc oxide in alkaline electrolyte, the invention provides a zinc electrode material protected by a metal layer, and the dissolution, dendrite formation and volume change processes of the zinc oxide can be limited within the metal layer under the protection of the metal layer, so that the cycle stability of the zinc electrode is improved.
The invention solves the problems through the following technical scheme, which comprises the following steps:
a zinc electrode material is microscopically provided with core-shell structured micro-nano particles, wherein the core-shell structured micro-nano particles take zinc as a core and a second metal as a shell; the second metal shell wraps the outside of the zinc core, and a gap is formed between the zinc core and the second metal shell. The gap can provide a place for the contact of zinc and electrolyte, so that the zinc can participate in electrode reaction, the increase of the volume of the zinc discharge process is accommodated, and the damage of an electrode structure is avoided.
The second metal is one or more than two alloy of iron, tin, lead, copper, silver, platinum, gold, indium, bismuth, thallium, gallium and cadmium.
The thickness of the second metal shell is 50nm-1 μm; the diameter range of the zinc core is 20nm-50 μm; the diameter range of the zinc electrode material with the core-shell structure is 100nm-52 mu m.
The preparation method of the zinc electrode material comprises the following steps: adding zinc powder into the soluble acid solution of the second metal salt to perform a displacement reaction. The zinc reacts with the second metal ions to gradually form a protective layer, and at the moment, the zinc also reacts with acid in the solution to generate a gap between the core and the shell.
The second metal in the soluble acid solution of the second metal salt is one or more than two of iron, tin, lead, copper, silver, platinum, gold, indium, bismuth, thallium, gallium and cadmium.
The concentration of the second metal ions in the soluble acid solution of the second metal salt is 0.001-1 mol/L; h+Has a concentration of 10-5-1 mol/L; the ratio of the amount of soluble metal salt species (in terms of divalent metal) to the amount of zinc dust species added is 0.05-0.8; h+The ratio of the amount of the substance(s) to the amount of the zinc dust substance(s) is 0.5 to 1.5.
In the above reaction conditions H+The ratio of the amount of the zinc to the amount of the zinc material determines that the zinc powder is not completely reacted during the reaction and the size of the voids is proper. If the gap between the zinc core and the second metal shell is too small, the electrode structure can still be damaged by the increase of the volume of zinc during discharge, and if the gap between the zinc core and the second metal shell is too large, the strength of the second metal shell is low, collapse is easy to occur, and the specific capacity of the electrode material is low.
The ratio of the amount of the second metal ion to the amount of zinc species depends on the particle diameter of the zinc powder and the thickness of the second metal shell. If the second metal shell is too thin, the second metal shell cannot play a role in protecting the structural change of the electrode material and limiting the migration and diffusion of active substances, and if the second metal shell is too thick, the mass transfer resistance of electrolyte ions through the diffusion of the metal shell is large, so that the performance of the zinc electrode is influenced.
Because the thickness of the second metal layer prepared by the displacement method is limited to a certain extent and is generally less than 1 μm, if the diameter of the zinc particles is too large, the second metal layer is not enough to support the core-shell structure after pores are generated, the second metal shell collapses, and if the diameter of the zinc particles is too small, the surface area is large, and the hydrogen evolution side reaction is more serious.
The solvent in the soluble acid solution of the second metal salt is one or a mixture of more than two of water, ethanol, glycol, acetone and glycerol, wherein the anion of the acid solution is one or a mixture of more than two of chloride ion, sulfate ion, nitrate ion and phosphate ion. The solvent plays a role in dissolving the second metal ions and H + and dispersing the zinc particles, and different solvents can be selected to uniformly disperse the zinc particles according to the diameter and the surface hydrophilicity and hydrophobicity of the zinc particles.
The zinc electrode can be used as a zinc electrode material in zinc/air batteries, zinc/nickel batteries and zinc/silver batteries.
The zinc electrode material and the preparation method thereof are characterized in that the electrode material is obtained by replacing zinc powder in a soluble acid solution of a second metal salt, the replaced metal grows into a layer of second metal shell in situ on the surface of zinc particles, when the metal shell completely covers the surface of the zinc particles, the replacement reaction is stopped, and the thickness of the metal layer cannot be further increased. The metal shell with the appropriate thickness effectively reduces the dissolution of zinc oxide in electrolyte and inhibits the growth of dendrite on one hand, and reduces the influence of the metal shell on the electrode performance on the other hand. The acid in the reaction solution further corrodes the zinc, forming voids in the zinc electrode material, which can accommodate the deformation of the electrode material. Therefore, the cycling stability of the zinc electrode material can be greatly improved relative to zinc powder.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the embodiments are briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
Fig. 1 is a schematic representation of a zinc electrode material.
Fig. 2 is an SEM photograph of the zinc particles used in the examples.
FIG. 3 is an XRF spectrum of the filtrate after the reaction of example 3.
FIG. 4 is an XRF spectrum of the filtrate after the reaction of example 4.
Detailed Description
The following is a clear and complete description of the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without inventive step, are within the scope of the present invention.
Example 1: preparing an aqueous solution containing 0.01mol/L CuSO4 and 0.05mol/L H2SO4, adding 50mL of the reaction solution into a beaker, adding 0.5g of zinc powder (with the average diameter of 5 mu m) under vigorous stirring, reacting for 5 minutes, filtering, washing and drying to obtain the zinc electrode material, wherein the thickness of a copper metal shell of the zinc electrode material is 1.35 mu m, the diameter of a zinc core is about 600nm, and the diameter of the whole core-shell structure zinc electrode material is 4.7 mu m.
Example 2: preparing an aqueous solution containing 0.01mol/L AgNO3 and 0.1mol/L HNO3, adding 50mL of the reaction solution into a beaker, adding 0.5g of zinc powder (average diameter is 5 mu m) under vigorous stirring, reacting for 5 minutes, filtering, washing and drying to obtain the zinc electrode material, wherein the thickness of a silver metal shell of the zinc electrode material is 1.25 mu m, the diameter of a zinc core is about 600nm, and the diameter of the whole core-shell structure zinc electrode material is 4.5 mu m.
Example 3: preparing an ethanol solution containing 0.01mol/L SnCl2 and 0.1mol/L HCl, adding 50mL of the reaction solution into a beaker, adding 0.5g of zinc powder (average diameter is 5 mu m) under vigorous stirring, reacting for 5 minutes, filtering, washing and drying to obtain the zinc electrode material, wherein the thickness of a tin metal shell is 1.5 mu m, the diameter of a zinc core is about 600nm, and the diameter of the whole core-shell structure zinc electrode material is 5 mu m. Fig. 3 is an XRF spectrum of the filtrate after the reaction.
Example 4: preparing an ethanol solution containing 0.01mol/L SnCl2 and 0.1mol/L HCl, adding 100mL of the reaction solution into a beaker, adding 0.5g of zinc powder (average diameter is 5 mu m) under vigorous stirring, reacting for 5 minutes, filtering, washing and drying to obtain the zinc electrode material, wherein the thickness of a tin metal shell is 1.25 mu m, the diameter of a zinc core is about 250nm, and the diameter of the whole core-shell structure zinc electrode material is 5 mu m. Fig. 4 is an XRF spectrum of the filtrate after the reaction.
Claims (5)
1. A preparation method of a zinc electrode material is characterized by comprising the following steps: adding zinc powder into a soluble acid solution of a second metal salt to perform a displacement reaction to obtain a product; the zinc reacts with the second metal ions to gradually form a protective layer on the outer surface of the zinc, and the zinc reacts with acid in the solution at the same time to generate a gap between the core and the shell;
microscopically, the micro-nano particles with the core-shell structure take zinc as a core and second metal as a shell; the second metal shell wraps the outside of the zinc core, and a gap is formed between the zinc core and the second metal shell; the thickness of the second metal shell is 50nm-1 μm; the diameter range of the zinc core is 20nm-50 μm; the diameter range of the zinc electrode material with the core-shell structure is 100nm-52 mu m;
the concentration of the second metal ion in the soluble acid solution of the second metal salt is 0.001-1mol/L；H+Has a concentration of 10-5-1 mol/L; the ratio of the amount of soluble metal salt species to the amount of zinc dust species added is 0.05-0.8; h+The ratio of the amount of the substance(s) to the amount of the zinc dust substance(s) is 0.5 to 1.5.
2. The method for preparing a zinc electrode material according to claim 1, wherein: the second metal is one or more than two alloy of iron, tin, lead, copper, silver, platinum, gold, indium, bismuth, thallium, gallium and cadmium.
3. The method for preparing a zinc electrode material according to claim 1, wherein: the second metal in the soluble acid solution of the second metal salt is one or more than two of iron, tin, lead, copper, silver, platinum, gold, indium, bismuth, thallium, gallium and cadmium.
4. A method for preparing a zinc electrode material according to claim 3, wherein: the solvent in the soluble acid solution of the second metal salt is one or a mixture of more than two of water, ethanol, glycol, acetone and glycerol, wherein the anion of the acid solution is one or a mixture of more than two of chloride ion, sulfate ion, nitrate ion and phosphate ion.
5. The zinc electrode produced by the method for producing a zinc electrode material according to claim 1, wherein: is the zinc electrode material in zinc/air batteries, zinc/nickel batteries and zinc/silver batteries.
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| CN108777293B (en) * | 2018-05-24 | 2021-02-12 | 中南大学 | Nano composite material and preparation method and application thereof |
| CN108808053B (en) * | 2018-06-22 | 2021-10-15 | 浙江裕源储能科技有限公司 | Zinc-nickel liquid flow energy storage battery |
| CN112331933A (en) * | 2020-10-27 | 2021-02-05 | 华中科技大学 | Long-cycle-life cathode of aqueous zinc secondary battery and preparation and application thereof |
| CN113005435A (en) * | 2021-02-09 | 2021-06-22 | 浙江工业大学 | Zinc metal protective layer material and preparation method and application thereof |
| CN117969742A (en) * | 2024-03-29 | 2024-05-03 | 宁德时代新能源科技股份有限公司 | Method and apparatus for comparing coating integrity of positive electrode active materials |
| CN118268562B (en) * | 2024-05-28 | 2024-08-20 | 港华能源创科(深圳)有限公司 | Modified zinc powder and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101252182A (en) * | 2008-04-07 | 2008-08-27 | 深圳市富易达电子科技有限公司 | Preparation method of alkaline battery cathode bar |
| CN101271973A (en) * | 2008-05-09 | 2008-09-24 | 华南师范大学 | Non-mercury alkaline zinc-manganese and zinc-silver button cell cathode and manufacturing method thereof |
| CN102388486A (en) * | 2009-04-01 | 2012-03-21 | 那米克斯公司 | Electrode material, method for producing same, and lithium ion secondary battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101252182A (en) * | 2008-04-07 | 2008-08-27 | 深圳市富易达电子科技有限公司 | Preparation method of alkaline battery cathode bar |
| CN101271973A (en) * | 2008-05-09 | 2008-09-24 | 华南师范大学 | Non-mercury alkaline zinc-manganese and zinc-silver button cell cathode and manufacturing method thereof |
| CN102388486A (en) * | 2009-04-01 | 2012-03-21 | 那米克斯公司 | Electrode material, method for producing same, and lithium ion secondary battery |
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