CN112768700A - Preparation method of corrosion-resistant current collector applied to aluminum ion battery - Google Patents
Preparation method of corrosion-resistant current collector applied to aluminum ion battery Download PDFInfo
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- CN112768700A CN112768700A CN202110054850.XA CN202110054850A CN112768700A CN 112768700 A CN112768700 A CN 112768700A CN 202110054850 A CN202110054850 A CN 202110054850A CN 112768700 A CN112768700 A CN 112768700A
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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Abstract
The invention belongs to the field of electrochemical materials, and particularly relates to a corrosion-resistant current collector applied to an aluminum ion battery and a preparation method thereof. The current collector comprises a metal foil and an amorphous nickel sulfide layer plated on the surface of the metal foil; the amorphous nickel sulfide layer wraps the metal foil; the amorphous nickel sulfide layer has a thickness of 1-1.5 microns. The preparation method of the current collector comprises the steps of electroplating the metal foil for 15-20 minutes in an environment with the current density of 1-2 milliampere per square centimeter; the electroplating solution comprises boric acid, thiourea, nickel sulfate hexahydrate and a solvent medium. The preparation method only needs common and cheap electroplating medicines and electroplating equipment, and has the advantages of low price, easily obtained raw materials and easy preparation. The prepared current collector has high conductivity, and an aluminum ion battery system containing the current collector has stable electrochemical performance, and the oxidation initial potential in electrolyte can reach 2.7V.
Description
Technical Field
The invention belongs to the field of electrochemical materials, and particularly relates to an electrolyte corrosion resistant current collector applied to an aluminum ion battery and a preparation method thereof.
Background
The electrochemical energy storage device is used as an efficient energy storage and conversion device, and greatly promotes the development of the human society. Among them, the aluminum ion battery has many advantages such as safety and stability, and abundant and cheap aluminum resources, and is gradually becoming a research hotspot in the field of electrochemical energy storage. However, the electrolyte in the aluminum ion battery has high-strength lewis acidity, and a metal current collector such as stainless steel, copper, iron, nickel and the like commonly used in the field of electrochemical energy storage can be severely corroded and dissolved when used as the current collector of the aluminum ion battery. The light one can increase the leakage current of the battery, resulting in the self-discharge of the battery, and the heavy one can cause the corrosion perforation of the positive pole piece, and the whole failure of the battery. The problem of the current collector seriously restricts the commercial popularization and application of the aluminum ion battery, so that the current collector material with low price and corrosion resistance is imperatively searched.
With respect to the problems of the current collector, preliminary studies have been conducted by overseas and overseas scholars: when the aluminum ion battery is reviewed and explained by H.Yu et al (Y.ZHANG S.Liu, Y.Ji, J.Ma, H.Yu, adv.Mater.2018, 1706310), the problem of the positive current collector is one of the bottleneck problems of the current aluminum ion battery. S.wang et al (s.wang, k.v.kravcthyk, adv.sci.2018,1700712.) sputter a TiN protective layer on a stainless steel structure by a physical sputtering process to obtain a stable current collector structure.
Current collector materials that have proven applicable today can be grouped into three broad categories, the first being rare precious metals: molybdenum, tungsten and tantalum, which are expensive and have rare yield, are difficult to be commercially popularized. The second type is a carbon current collector, which has a complex process, is only suitable for small-scale experimental production in a laboratory, is not suitable for large-scale popularization, and has low carbon material strength and low conductivity, so that the carbon current collector has more problems as a current collector material. The third kind is semiconductor material, such as titanium nitride, chromium nitride, indium tin oxide, etc., which needs expensive equipment such as inert atmosphere tube furnace, magnetron sputtering, etc., and the prepared material is expensive, has low conductivity, all below 10^5S/m, and is not ideal as current collector material.
Patent CN 109659566 a describes a conductive metal oxide current collector coating for aluminum ion batteries, which produces a metal oxide with high electrochemical stability; however, the coating is indium tin oxide, fluorine-doped tin oxide or LaNiO3, and the coating is covered by a sputtering method, so that expensive equipment is required, the conductivity is low, and the industrial production is not facilitated.
Patent CN 109546154 a describes an aluminum ion battery current collector with a protective layer, which is prepared by using indium tin oxide as a current collector, which can be kept stable under high voltage. However, the protective layer is a titanium-carbon compound, a titanium-nitrogen compound, a boron-titanium compound, a carbon-tungsten compound, a silicon-carbon compound, or a titanium-carbon-oxygen compound, and the production process requires relatively expensive equipment and has low conductivity.
In contrast, in the prior art, a current collector material which is low in price, easy to prepare, high in conductivity and suitable for large-scale commercial popularization and is applied to an aluminum ion battery is lacked.
Disclosure of Invention
In view of the above, the present invention is directed to a current collector for an aluminum battery. The current collector uses a conductive metal compound as a protective layer of a metal substrate, the metal substrate and the conductive metal compound are unified to form the current collector, and the current collector is corrosion-resistant in electrolyte, stable in electrochemical performance and high in conductivity.
It should be noted that the numerical values related to the present invention are equivalent to the numerical values to be protected by the present invention within the range of operation errors and instrumental errors.
The current collector comprises a metal foil and an amorphous nickel sulfide layer; the amorphous nickel sulfide layer wraps the metal foil; the amorphous nickel sulfide layer has a thickness of 1-1.5 microns.
Furthermore, the metal foil material is an alloy composed of one or more of nickel, copper, iron, tin and zinc.
Further, the thickness of the metal foil is 10-1000 microns.
The invention also aims to provide a preparation method of any one of the current collectors. The preparation method has simple process, and the required raw materials and equipment are conventional, cheap and easily available.
The preparation method comprises the following steps: electroplating the metal foil for 15-20 minutes in an environment with the current density of 1-2 milliampere per square centimeter; the electroplating solution comprises boric acid, thiourea, nickel sulfate hexahydrate and a solvent medium.
Preferably, the solvent medium is deionized water.
Preferably, the current density is 2 milliamps per square centimeter and the plating is for 15 minutes.
Preferably, the current density is 1 milliamp per square centimeter and the plating is for 20 minutes.
Preferably, the current density is 1.5 milliamps per square centimeter and the plating is for 17 minutes.
Further, the electroplating solution comprises, by mass, 2 plus or minus 0.1 parts of boric acid, 5 plus or minus 0.1 parts of thiourea, 7 plus or minus 0.1 parts of nickel sulfate hexahydrate and 100 plus or minus 0.1 parts of deionized water as a solvent medium; the pH is 4-4.5. The prepared electroplating solution is green and clear.
Further, the boric acid, the thiourea and the nickel sulfate hexahydrate are all analytically pure.
Further, the current during electroplating is a constant current. The electroplating instrument is a constant current electroplating instrument.
Furthermore, the distance between the positive electrode plate and the negative electrode plate is 2 +/-0.1 cm during electroplating.
Furthermore, the positive pole piece is preferably foamed nickel during electroplating.
Further, the metal foil is pretreated: and removing the surface dirt and the surface oxidation layer.
In some embodiments of the invention, the pre-treatment is specifically: firstly, soaking the metal foil in acetone to remove surface engine oil, then soaking the metal foil in 0.1 mol/L dilute sulfuric acid solution to remove a surface oxidation layer, finally, thoroughly cleaning the surface with deionized water, and drying for later use.
In some embodiments of the present invention, the electroplating is specifically: cutting the metal foil into a proper size, clamping the metal foil on a constant-current electroplating instrument, adjusting the current density to 1-2 milliampere per square centimeter, setting the electroplating time to 15-20 minutes, electroplating, taking down the foil after the electroplating is finished, cleaning the surface of the foil with deionized water, and drying to obtain a final finished product.
The invention also aims to provide an aluminum battery comprising the current collector. The current collector aluminum ion battery system has stable electrochemical performance, and the oxidation initial potential in the electrolyte can reach 2.7V.
The invention has the beneficial effects that:
the current collector provided by the invention has high conductivity which can reach 106S/m is more than or equal to the conductivity of pure metal.
The current collector aluminum ion battery system provided by the invention has stable electrochemical performance, and the oxidation initial potential in the electrolyte can reach 2.7V.
The current collector provided by the invention has certain flexibility and can be used for flexible batteries.
The preparation method of the current collector only needs common and cheap electroplating medicines and electroplating equipment, has low price, easily obtained raw materials and easy preparation, only needs one-step electroplating process, and has short process flow, simple and convenient process control and good product stability.
Drawings
FIG. 1 is a schematic diagram of a plating apparatus.
Fig. 2 is a comparison graph of voltammetry curve tests of the current collector prepared by the present invention and other materials.
Fig. 3 voltammogram test charts of the current collectors prepared in example 2 to example 5.
Fig. 4 is a flexible real image of the prepared current collector.
Detailed Description
The examples are given for the purpose of better illustration of the invention, but the invention is not limited to the examples. Therefore, those skilled in the art should make insubstantial modifications and adaptations to the embodiments of the present invention in light of the above teachings and remain within the scope of the invention.
Example 1 current collector
The invention provides a current collector applied to an aluminum battery, which comprises a metal foil and an amorphous nickel sulfide layer;
wherein an amorphous nickel sulfide layer surrounds the metal foil;
wherein the thickness of the amorphous nickel sulfide layer is 1-1.5 microns.
Wherein the metal foil material is an alloy composed of one or more of nickel, copper, iron, tin and zinc.
Wherein the thickness of the metal foil is 10-1000 microns.
Example 2
(1) Preparation of electroplating solution
Weighing 2 g of boric acid, 5 g of thiourea and 7 g of nickel sulfate hexahydrate, mixing and dissolving the above medicines in 100 ml of deionized water, and adjusting the pH value to 4 by using sulfuric acid and a sodium hydroxide solution to obtain a green clear electroplating solution.
(2) Pretreatment of metal foil
Firstly, soaking a nickel foil in acetone to remove surface engine oil, then soaking in a sulfuric acid solution to remove a surface oxidation layer, finally, thoroughly cleaning the surface with deionized water, and drying for later use.
(3) Step of electroplating
Referring to fig. 1, the positive electrode is foamed nickel, the processed nickel foil is cut to a proper size and then clamped on a constant current electroplating instrument, the current density is adjusted to 2 milliamperes per square centimeter, the electroplating time is set to 15 minutes, electroplating is carried out, after the electroplating is finished, the foil is taken down, the surface is cleaned by deionized water, and the final finished product is obtained by drying.
Example 3
The pH of the plating solution in the step (1) of example 2 was adjusted to 4.5, and the other conditions were the same as in example 2.
Example 4
The nickel foil in step (3) of example 2 was replaced with an iron foil, and the rest of the conditions were the same as in example 2.
Example 5
The current density in step (3) of example 2 was adjusted to 1 milliamp per square centimeter, and the plating time was set to 20 minutes, and the other conditions were the same as in example 2.
EXAMPLE 6 detection and inspection of products
(1) Conductivity test
The current collectors prepared in example 2 to example 5 were selected for conductivity tests, and the test results are shown in table 1 below.
Table 1 conductivity of current collectors prepared in examples 2 to 5
| Example 2 | Example 3 | Example 4 | Example 5 | |
| Thickness um | 1 | 1.2 | 1 | 1.5 |
| Conductivity S/m | 2.34×106 | 2.65×106 | 2.55×106 | 2.78×106 |
(2) Voltammetric curve testing
The materials prepared in examples 2 to 5 were subjected to performance tests by hermetically sealing an electrolytic cell made of polytetrafluoroethylene in a total nitrogen glove box. The test material is clamped by a platinum electrode clamp to be used as a working electrode, a 0.5 cm-thick pure aluminum plate is used as a reference electrode and a counter electrode, aluminum chloride/imidazole chloride ionic liquid electrolyte is added, a battery device is simulated, and a Chenghua electrochemical workstation is used for carrying out volt-ampere curve test.
The test results are shown in fig. 2 and fig. 3, in fig. 2, Ni-S/S is the current collector prepared in example 2, and the initial oxidation potential is 2.7V, which is higher than that of stainless steel by 0.28V, metallic nickel by 0.37V, and metallic molybdenum by 2.5V, which indicates that the electrochemical stability of the current collector material is obviously better than that of the conventional current collector material.
In fig. 3, which is a voltammogram of the current collectors prepared in examples 2 to 5, the voltammograms of the current collectors prepared in examples 2 to 5 have no significant difference, and the initial oxidation potentials thereof are all around 2.7V.
(3) Tortuosity test
The current collector prepared in example 2 was bent, and as can be seen from fig. 4, it was good in flexibility and could be bent at a large angle.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (10)
1. A current collector applied to an aluminum battery is characterized by comprising a metal foil, an amorphous nickel sulfide layer; the amorphous nickel sulfide layer wraps the metal foil; the amorphous nickel sulfide layer has a thickness of 1-1.5 microns.
2. The current collector of claim 1, wherein the metal foil material is an alloy of one or more of nickel, copper, iron, tin, and zinc.
3. The current collector of claim 1, wherein the metal foil has a thickness of 10-1000 microns.
4. A method for preparing a current collector as claimed in any one of claims 1 to 3, characterized in that it comprises the following steps:
electroplating the metal foil for 15-20 minutes in an environment with the current density of 1-2 milliampere per square centimeter; the electroplating solution comprises boric acid, thiourea, nickel sulfate hexahydrate and a solvent medium.
5. The method of claim 4, wherein the current density is 2 milliamps per square centimeter and the plating time is 15 minutes.
6. The preparation method according to claim 4, characterized in that the boric acid is 2 ± 0.1 parts, the thiourea is 5 ± 0.1 parts, the nickel sulfate hexahydrate is 7 ± 0.1 parts, and the solvent medium is 100 ± 0.1 parts of deionized water; the pH is 4-4.5.
7. The preparation method according to claim 4, wherein the positive electrode sheet is foamed nickel during electroplating.
8. The method according to claim 4, wherein the distance between the positive and negative electrode plates is 2 ± 0.1 cm during electroplating.
9. The method for manufacturing according to any one of claims 4 to 8, wherein the metal foil is subjected to a pretreatment: and removing the surface dirt and the surface oxidation layer.
10. An aluminum battery comprising the current collector of any of claims 1-3.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116826065A (en) * | 2023-06-16 | 2023-09-29 | 太仓中科赛诺新能源科技有限公司 | Current collector for water system battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108493454A (en) * | 2018-01-29 | 2018-09-04 | 东莞市航盛新能源材料有限公司 | A kind of copper current collector and preparation method thereof of transient metal sulfide modification |
| CN113422064A (en) * | 2021-06-22 | 2021-09-21 | 广东工业大学 | Lithium metal negative current collector and preparation method and application thereof |
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- 2021-01-15 CN CN202110054850.XA patent/CN112768700B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108493454A (en) * | 2018-01-29 | 2018-09-04 | 东莞市航盛新能源材料有限公司 | A kind of copper current collector and preparation method thereof of transient metal sulfide modification |
| CN113422064A (en) * | 2021-06-22 | 2021-09-21 | 广东工业大学 | Lithium metal negative current collector and preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116826065A (en) * | 2023-06-16 | 2023-09-29 | 太仓中科赛诺新能源科技有限公司 | Current collector for water system battery |
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