CN110676430B - Preparation method and application of porous metal electrode with bionic structure - Google Patents

Preparation method and application of porous metal electrode with bionic structure Download PDF

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CN110676430B
CN110676430B CN201910832000.0A CN201910832000A CN110676430B CN 110676430 B CN110676430 B CN 110676430B CN 201910832000 A CN201910832000 A CN 201910832000A CN 110676430 B CN110676430 B CN 110676430B
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porous
preparation
porous metal
metal salt
metal electrode
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CN110676430A (en
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朱春宇
饶中浩
朱瑞杰
盛楠
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China University of Mining and Technology CUMT
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China University of Mining and Technology CUMT
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a preparation method and application of a porous metal electrode with a bionic structure, wherein the preparation process comprises the following steps: dissolving transition metal salt in an ammonia water solution to prepare a metal salt ammonia water solution with a certain concentration; soaking biomass fibers into the metal salt ammonia water solution, taking out after full soaking, and then placing in air or oxygen atmosphere for precalcination at 800 ℃ at 300 ℃ to obtain an oxide porous structure; and (3) placing the oxide porous structure body in a reducing atmosphere at 300-1000 ℃ for reduction heat treatment to obtain the porous metal electrode with the bionic structure. The invention uses the biomass fiber with bionic structure as the template, after soaking and adsorbing the metal salt raw material, the three-dimensional porous metal or alloy with similar structure to the biomass raw material can be directly prepared by calcining and removing the template and reduction treatment, the preparation method is simple and convenient, the process cost is low, and the invention can be applied to the current collector of lithium metal and the catalytic electrode of water electrolysis.

Description

Preparation method and application of porous metal electrode with bionic structure
Technical Field
The invention belongs to the field of electrochemistry and bionics materials, relates to a porous metal electrode, and particularly relates to a preparation method and application of a porous metal electrode with a bionic structure.
Background
Along with increasingly serious worldwide problems of environmental pollution, energy shortage and the like, new energy and efficient energy storage utilization technology are urgently needed to be developed. The development of electrochemical energy conversion, electrochemical energy storage and utilization technology provides possibility for realizing efficient conversion, utilization and storage of new energy. Preparation and structural design of an electrode material which can not separate electrochemical energy conversion and energy storage. Porous metal electrodes, such as nickel, copper and alloys, have wide application as electrode current collectors of lithium batteries, catalytic electrodes for hydrogen production by water electrolysis and the like.
Three-dimensional porous electrodes such as copper foam and nickel foam are often used as current collectors of lithium metal and are also often used for manufacturing catalytic electrodes for electrolyzing water, and the catalytic performance is improved by improving surface catalytic active sites. Such porous metals have the disadvantages of limited specific surface area, excessively large pore size, and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a porous metal electrode with a bionic structure, and the porous metal electrode with a special porous structure and a high specific surface area is developed.
The invention also aims to provide the application of the porous metal electrode with the bionic structure prepared by the method.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of a porous metal electrode with a bionic structure comprises the following steps:
(1) dissolving transition metal salt in an ammonia water solution to prepare a metal salt ammonia water solution with a certain concentration;
(2) soaking biomass fibers into the metal salt ammonia water solution, taking out after full soaking, and then placing in air or oxygen atmosphere for precalcination at 800 ℃ for 1-180min at 300 ℃ to obtain an oxide porous structure;
(3) and (3) placing the oxide porous structure body in a reducing atmosphere, heating to 300-1000 ℃ for reduction heat treatment for 1-180min to obtain the porous metal electrode with the bionic structure.
Preferably, the transition metal salt is one or more of nickel, copper, cobalt acetate, nitrate, oxalate and sulfate.
Preferably, the concentration of the metal salt ammonia water solution is 0.5-5 mol/L.
Preferably, the biomass fibers are cotton fabrics or wood. More preferably, the cotton textile fabric is a cotton textile fabric subjected to degreasing treatment, and the wood is wood subjected to lignin removal treatment.
The invention also provides application of the porous metal electrode with the bionic structure prepared by the method.
The porous metal electrode has a special bionic porous structure and a high specific surface area, can provide a limited space for lithium metal, inhibits volume expansion during deposition of a lithium cathode, controls the growth of the lithium metal in a three-dimensional porous structure, inhibits the growth of lithium dendrites, and can be used for preparing a high-performance lithium metal current collector.
The porous metal electrode also shows better electrocatalytic hydrogen and oxygen evolution activity, and can be used for preparing an electrolytic water catalytic electrode.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention uses the biomass fiber with bionic structure as the template, after soaking and adsorbing the metal salt raw material, the three-dimensional porous metal or alloy with similar structure to the biomass raw material can be directly prepared by calcining and removing the template and reduction treatment, and the bionic structures have the characteristics of various and controllable structures, larger specific surface area, multi-level pore structure and the like.
2. The preparation method is simple and convenient, and the process cost is low. The obtained porous metal electrode with the bionic structure shows excellent performance when being applied to a current collector of lithium metal and a catalytic electrode for water electrolysis.
3. The invention takes cellulose biomass as raw material, and has the advantages of easily obtained raw material, controllable structure, low cost, large amount, small environmental pollution and the like.
Drawings
FIG. 1 is a flow chart of the present invention example 1, which is a process for synthesizing porous copper metal having a woven structure using cotton cloth as a template.
FIG. 2 is an X-ray diffraction pattern (XRD) of metallic copper after reduction of calcined copper oxide with hydrogen in air according to example 1 of the present invention.
FIG. 3 is a scanning electron micrograph of a cotton cloth material and porous copper synthesized using cotton cloth as a template in example 1 of the present invention.
FIG. 4 shows Ni, Co, Ni-Co and Ni-Cu alloys with textile structures synthesized by using cotton cloth as templates in examples 2-5 of the present invention.
FIG. 5 is the SEM image of pine wood and porous copper with wood bionic structure synthesized by using pine wood as the template in example 6 of the present invention.
Fig. 6 is an electron microscope image of lithium metal deposited in a porous metal current collector having a cotton biomimetic structure of example 2 of the present invention and its lithium dendrites deposited on a copper plate as a comparison.
FIG. 7 shows the electrocatalytic hydrogen evolution and oxygen evolution performance of porous cobalt with cotton cloth bionic structure in example 3 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
The aqueous ammonia solution used in the following examples was industrial aqueous ammonia having a concentration of 20 to 28 wt%.
Example 1
As shown in figure 1, copper acetate hydrate is dissolved in an ammonia solution to prepare a solution containing 2mol/L of copper ions.
Then, a piece of cotton cloth subjected to degreasing treatment is put into the solution, the cotton cloth is taken out after full immersion, and the cotton cloth is pre-calcined by heating to 300 ℃ for 180min in an air atmosphere.
And heating the pre-calcined sample to 300 ℃ in a hydrogen atmosphere, keeping the temperature for 180min, and carrying out reduction treatment to obtain the porous metal copper.
As shown in fig. 2, the copper metal salt is calcined in air and then decomposed to generate copper oxide, the template is removed, and the copper oxide is reduced in hydrogen to obtain the copper metal.
As shown in fig. 3, the metallic copper product prepared by the cotton template method maintained the morphology of the woven structure similar to that of the cotton material.
Example 2
Dissolving nickel acetate hydrate in an ammonia water solution to prepare a solution containing 2.5mol/L of nickel ions.
Then, a piece of cotton cloth subjected to degreasing treatment is put into the solution, the cotton cloth is taken out after full immersion, and the cotton cloth is pre-calcined by heating to 800 ℃ for 60min in an air atmosphere.
And heating the pre-calcined sample to 1000 ℃ in a hydrogen atmosphere, keeping the temperature for 60min, and carrying out reduction treatment to obtain the porous metallic nickel.
Example 3
Dissolving cobalt acetate hydrate in an ammonia solution to prepare a solution containing 5mol/L cobalt ions.
Then, a piece of cotton cloth subjected to degreasing treatment was put into the solution, and after the solution was sufficiently impregnated, the cotton cloth was taken out, and the cotton cloth was pre-calcined by heating to 600 ℃ for 60min in an air atmosphere.
And heating the pre-calcined sample to 600 ℃ in a hydrogen atmosphere, keeping the temperature for 60min, and carrying out reduction treatment to obtain the porous metal cobalt.
Example 4
Mixing cobalt acetate hydrate and nickel acetate hydrate according to a molar ratio of 1:1 is dissolved in ammonia water solution to prepare solution containing 0.5mol/L of metal ions.
Then, a piece of cotton cloth subjected to degreasing treatment is put into the solution, the cotton cloth is taken out after full immersion, and the cotton cloth is pre-calcined by heating to 600 ℃ for 120min in an air atmosphere.
And heating the pre-calcined sample to 600 ℃ in a hydrogen atmosphere, keeping the temperature for 120min, and carrying out reduction treatment to obtain the porous metal nickel-cobalt alloy.
Example 5
Mixing copper acetate hydrate and nickel acetate hydrate according to a molar ratio of 1:1 is dissolved in ammonia water solution to prepare solution containing 2.5mol/L of metal ions.
Then, a piece of cotton cloth subjected to degreasing treatment is put into the solution, the cotton cloth is taken out after full immersion, and the cotton cloth is pre-calcined by heating to 600 ℃ for 120min in an air atmosphere.
And heating the pre-calcined sample to 600 ℃ in a hydrogen atmosphere, keeping the temperature for 120min, and carrying out reduction treatment to obtain the porous metal nickel-copper alloy.
As shown in FIG. 4, the metallic nickel, metallic cobalt, nickel-cobalt alloy and nickel-copper alloy products prepared by the cotton cloth template method can maintain the similar appearance of the woven structure of the cotton cloth raw material.
Example 6
Dissolving copper acetate in an ammonia water solution to prepare a solution containing 2.5mol/L of copper ions.
And then putting a piece of pine wood subjected to lignin removal treatment into the solution, taking out the wood after full impregnation, heating the wood to 600 ℃ in an oxygen atmosphere, and keeping the temperature for 30min for precalcination.
And heating the pre-calcined sample to 600 ℃ in a hydrogen atmosphere, keeping the temperature for 30min, and carrying out reduction treatment to obtain the porous metal copper.
As shown in fig. 5, the metallic copper product prepared by the wood template method can maintain the porous morphology similar to that of the wood raw material.
In order to further illustrate the application prospect of the porous metal electrode prepared by the invention, the electrochemical test is carried out by taking porous metal nickel and porous metal cobalt as examples.
Fig. 6 corresponds to the porous metallic nickel with a cotton biomimetic structure prepared in example 2. The product is used for a current collector of lithium metal. The specific test process is as follows: lithium metal sheets are taken as a counter electrode and a reference electrode, glass fibers are taken as a diaphragm, the metal current collector is taken as a working electrode, and the lithium metal sheets are dissolved in a mixed solvent of 1, 3-dioxolane and ethylene glycol dimethyl ether (DOX/DME,1:1v/v) and added with 1 wt% of LiNO31mol L of-1Lithium bistrifluoromethanesulfonimide (LiTFSI) is used as an electrolyte to assemble a battery to perform an electrodeposition experiment of lithium metal in a porous current collector. A conventional metal copper foil was used as a comparative experiment. FIG. 6 is at 1mA cm-2And the deposition amount of lithium metal is controlled to be 1mAh cm at the current density of (1)-2A topographical map of lithium metal deposited on the metal current collector. As can be seen from fig. 6, the morphology of the lithium metal deposited in the porous metal current collector with the cotton cloth biomimetic structure is uniform, and no lithium dendrite is generated; while lithium metal deposited on the copper foil exhibits a morphology of a large number of dendrites.
Fig. 7 corresponds to the porous metallic cobalt having a cotton biomimetic structure prepared in example 3. The porous metal cobalt electrode is used for catalyzing hydrogen evolution and oxygen evolution electrodes for water electrolysis. FIG. 7 shows the average molecular weight at 1mol L-1In KOH solution of (2) at a scanning speed of 10mV s-1A performance diagram of electrocatalytic hydrogen evolution and oxygen evolution; as can be seen from fig. 7, the porous metal electrode shows better electrocatalytic hydrogen and oxygen evolution activities.

Claims (5)

1. A preparation method of a porous metal electrode with a bionic structure is characterized by comprising the following steps:
(1) dissolving transition metal salt in an ammonia water solution to prepare a metal salt ammonia water solution with a certain concentration; the transition metal salt is one or a mixture of more of acetate, nitrate, oxalate and sulfate of nickel, copper and cobalt;
(2) soaking biomass fibers into the metal salt ammonia water solution, taking out after full soaking, and then placing in air or oxygen atmosphere for precalcination at 800 ℃ for 1-180min at 300 ℃ to obtain an oxide porous structure; the biomass fiber is cotton fabric or wood;
(3) and (3) placing the oxide porous structure body in a reducing atmosphere, heating to 300-1000 ℃ for reduction heat treatment for 1-180min to obtain the porous metal electrode with the bionic structure.
2. The method for preparing the porous metal electrode with the bionic structure according to claim 1, wherein the concentration of the metal salt ammonia water solution is 0.5-5 mol/L.
3. The method for preparing a porous metal electrode with a biomimetic structure according to claim 1, wherein the cotton textile is a cotton textile subjected to degreasing treatment, and the wood is a wood subjected to lignin removal treatment.
4. Use of the porous metal electrode with biomimetic structure prepared by the preparation method of any one of claims 1 to 3 in preparation of a current collector of lithium metal.
5. Use of the porous metal electrode with biomimetic structure prepared by the preparation method of any one of claims 1 to 3 in preparation of an electrolytic water catalytic electrode.
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Publication number Priority date Publication date Assignee Title
CN102115147A (en) * 2011-03-28 2011-07-06 许昌学院 Chemical method for preparing copper oxide crystals with biological micro-nano structures by thermal decomposition
CN104716330A (en) * 2015-03-25 2015-06-17 中国科学院化学研究所 Three-dimensional porous current collector as well as preparation method and use thereof

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CN1259245C (en) * 2004-10-21 2006-06-14 上海交通大学 Process of preparing porous nickel oxide with plant structure
WO2014186207A2 (en) * 2013-05-13 2014-11-20 University Of Connecticut Mesoporous materials and processes for preparation thereof
CN105932295A (en) * 2016-04-22 2016-09-07 清华大学深圳研究生院 Metal lithium secondary battery and negative electrode and porous copper current collector thereof
CN108428901B (en) * 2018-04-13 2019-10-18 华南理工大学 A kind of composite microstructure collector and preparation method thereof for lithium ion battery

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102115147A (en) * 2011-03-28 2011-07-06 许昌学院 Chemical method for preparing copper oxide crystals with biological micro-nano structures by thermal decomposition
CN104716330A (en) * 2015-03-25 2015-06-17 中国科学院化学研究所 Three-dimensional porous current collector as well as preparation method and use thereof

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