CN114525537A - Rapid micro-nano reconstruction processing method for copper metal and application thereof - Google Patents
Rapid micro-nano reconstruction processing method for copper metal and application thereof Download PDFInfo
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Abstract
The invention discloses a rapid micro-nano reconstruction processing method of copper metal and application thereof, and aims to solve the problems of small specific surface area and low roughness of commercial copper metal. The reconstruction processing method comprises the following steps: putting a metal material precursor into a mixed oxidation solution for oxidation treatment, cleaning to obtain a metal oxide precursor with a micro-nano porous fiber structure, putting the metal oxide precursor into a mixed reduction solution for reduction treatment, wherein the mixed reduction solution contains (NH)4)2S2O8And NaOH to obtain the metal material with the micro-nano porous fiber structure.The application is that copper metal with a micro-nano porous fiber structure is used as a current collector or a self-supporting electrode for hydrogen production by water electrolysis. The invention utilizes a two-step solution method to carry out chemical oxidation and reduction treatment, and the micro-nano fiber structure is spontaneously formed on the surface of the copper metal atoms through micro-nano spontaneous reconstruction within a time range of seconds, thereby realizing the purpose of improving the roughness and the specific surface area of the copper metal atoms.
Description
Technical Field
The invention relates to a method for rapidly reconstructing a micro-nano fiber structure on the surface of copper metal through two-step solution treatment, and an efficient water electrolysis hydrogen production electrode applying the treated copper metal to self-support.
Background
Copper is a non-ferrous metal which is very closely related to human beings, has excellent properties such as electrical conductivity, thermal conductivity, ductility, corrosion resistance, wear resistance and the like, can be used as various structural/functional materials, is widely applied to the fields of electric power, electronics, petrifaction, machinery, metallurgy, traffic, light industry, emerging industry and the like, and is second to aluminum in the consumption of non-ferrous metal materials in China.
In recent years, copper has also found very important applications as a current collector in the field of new energy. For example, copper foil is currently a commercial lithium ion battery current collector; the foam copper is used as a current collector of the nickel-zinc battery, is tried by multiple nickel-zinc battery manufacturers and is put into batch use; in addition, copper can also be used as a catalyst current collector of an electrode for producing hydrogen by electrolyzing water. However, studies have shown that when commercialized copper as an electrode/catalyst current collector, the specific surface area is small, the surface is smooth, and adhesion of active materials is not favorable, which is a problem that seriously affects the performance and cycle stability of the electrode. Therefore, how to increase the roughness of the copper metal surface, improve the bonding strength between the current collector and the active material, and reduce the contact resistance between the active material and the current collector becomes a problem to be solved.
In order to increase the specific surface area and roughness of the copper metal surface, various strategies and methods have been proposed in succession, including surface electroplating modification, preparation of micro-nano porous copper metal by a dealloying method, and chemical corrosion with strong acid and strong base to increase the surface roughness. However, these methods of preparation have some disadvantages. For example, electroplating modification is mainly realized by optimizing current density, copper ion concentration, solution temperature and additives, so that the surface electroplating particles are regulated. Besides the complexity of the method, copper ions in the solution are required to be reduced into metal copper particles, the copper ion solution is consumed, and the economy is poor. The dealloying method for preparing the micro-nano porous copper metal needs to introduce a two-phase material, depends heavily on the quality of an alloy precursor, needs a plurality of processes such as alloying and dealloying, and is complex in process and high in cost. And strong acid and strong base are chemically corroded, so that the uniformity of roughening is difficult to ensure, the process controllability is poor, micro-nano surface morphology is difficult to form, and meanwhile, the application of strong acid and strong base can cause environmental pollution to a certain degree. Therefore, the method for treating the surface of the copper metal, which is effective, simple, easy to operate, low in cost and widely applicable in large-scale production, has important significance. In addition, iron, cobalt and nickel have long been considered as potential non-noble metal high-efficiency catalytic electrodes in the hydrogen production by water electrolysis. Copper metal, although similar in chemical properties to these three metals on the periodic table of the elements, has not been considered as an alternative electrode for hydrogen production from electrolysis of water due to its catalytic inertness in electrolysis of water.
Disclosure of Invention
The invention aims to solve the problems of small specific surface area and low roughness of commercial copper metal, and provides a rapid micro-nano reconstruction processing method of copper metal and application thereof in hydrogen production by water electrolysis.
The quick copper metal micro-nano reconstruction processing method is realized according to the following steps:
firstly, taking copper or copper-based alloy metal material as a precursor;
secondly, water is used as a solvent, and the solute comprises the concentration of0.5～5mol L-1(NH)4)2S2O8And 5 to 10mol L-1Preparing NaOH to obtain a mixed oxidation solution;
thirdly, putting the metal material precursor in the step one into a mixed oxidation solution for oxidation treatment, and cleaning and drying to obtain a metal oxide precursor with a micro-nano porous fiber structure;
fourthly, water is used as a solvent, and solutes comprise 50 to 100g L-1Dimethylamine borane (DMAB) and 10 to 50g L-1Preparing NaOH to obtain a mixed reduction solution;
and fifthly, placing the metal oxide precursor in the third step into a mixed reduction solution for reduction treatment to obtain a metal material with a micro-nano porous fiber structure, and finishing the rapid micro-nano reconstruction treatment method of the copper metal.
The invention discloses an application of a metal material with a micro-nano porous fiber structure, which is obtained by a copper metal rapid micro-nano reconstruction processing method, and the metal material is a self-supporting electrode which takes copper metal with the micro-nano porous fiber structure as a current collector or electrolyzes water to produce hydrogen.
The copper metal with the micro-nano porous fiber structure obtained by the rapid micro-nano copper metal reconstruction processing method can be used as a high-efficiency current collector or directly used as a self-supporting electrode for hydrogen production by water electrolysis, and has good electrochemical performance.
The invention utilizes a two-step solution method to carry out chemical oxidation and reduction treatment, and the micro-nano fiber structure is spontaneously formed on the surface of the copper metal atoms through micro-nano spontaneous reconstruction within a time range of seconds, thereby realizing the purpose of improving the roughness and the specific surface area of the copper metal atoms.
The method for realizing micro-nano rapid reconstruction on the surface of copper metal by using the two-step solution method has the following beneficial effects:
1. the method mainly utilizes the solution method to treat the copper metal directly, and forms a porous fiber structure on the metal surface, thereby greatly increasing the specific surface area and the roughness of the metal, and having the advantages of simple process, convenient preparation and no pollution;
2. the invention can realize the formation of the copper metal micro-nano fiber structure within several seconds, meets the industrial production process requirement of the electrolytic copper foil, can realize the matching with the industrial preparation process of the existing electrolytic copper foil and carry out large-scale preparation;
3. the process for preparing the porous metal by the two-step solution treatment method does not relate to a special technical process, has low requirements on equipment and is low in cost;
4. the method is not influenced by the appearance of the copper-based metal sample to be treated, and can realize surface treatment on the copper-based complex metal device;
5. the metal sample to be treated in the present invention may be not only copper metal but also various copper-based alloy samples such as brass, bronze, phosphor copper or cupronickel, etc.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a copper foam precursor of one embodiment;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the micro-nano porous fiber structure treated by the copper foam two-step solution prepared in the first embodiment;
FIG. 3 is a Cyclic Voltammetry (CV) graph of copper foam after two-step solution treatment and untreated copper foam, wherein 1 represents untreated copper foam, and 2 represents micro-nano porous fiber structured copper foam;
FIG. 4 is a Scanning Electron Microscope (SEM) image of an untreated copper foil according to a second embodiment;
FIG. 5 is a Scanning Electron Microscope (SEM) image of the micro-nano porous fiber structure after the copper foil prepared in example two-step solution treatment;
FIG. 6 is a Scanning Electron Microscope (SEM) image of untreated phosphocopper in example three;
FIG. 7 is a Scanning Electron Microscope (SEM) image of the micro-nano porous fiber structure treated by the phosphor-copper two-step solution prepared in the third embodiment;
FIG. 8 shows micro-nano fiber copper foam electrodeposition Co (OH) after treatment2Post Scanning Electron Microscopy (SEM) images;
FIG. 9 shows untreated foamy copper and micro-nano fiber copper as current collectors, electrodeposited Co (OH)2Prepared afterLinear scan of composite electrode, where 1 represents untreated foamy copper-Co (OH)2The electrode is applied to Oxygen Evolution (OER), 2 represents foam copper-Co (OH) with a micro-nano porous fiber structure2The electrode is applied to oxygen evolution;
FIG. 10 is a linear scan graph of a two-step solution-treated copper foam and an untreated copper foam under an oxygen evolution test (OER), wherein 1 represents the application of an untreated copper foam electrode to Oxygen Evolution (OER) and 2 represents the application of a copper foam electrode having a micro-nano porous fiber structure to oxygen evolution;
fig. 11 is a linear scanning graph of a two-step solution-treated copper foam and an untreated copper foam under a hydrogen evolution test (HER), wherein 1 represents that an untreated copper foam electrode is applied to hydrogen evolution, and 2 represents that a copper foam electrode with a micro-nano porous fiber structure is applied to hydrogen evolution.
Detailed Description
The first embodiment is as follows: the rapid micro-nano reconstruction processing method for the copper metal is implemented according to the following steps:
firstly, taking copper or copper-based alloy metal material as a precursor;
secondly, water is used as a solvent, and the solute comprises 0.5-5 mol L-1(NH)4)2S2O8And 5 to 10mol L-1Preparing NaOH to obtain a mixed oxidation solution;
thirdly, putting the metal material precursor in the step one into a mixed oxidation solution for oxidation treatment, and cleaning and drying to obtain a metal oxide precursor with a micro-nano porous fiber structure;
fourthly, water is used as a solvent, and solutes comprise 50 to 100g L-1Dimethylamine borane (DMAB) and 10 to 50g L-1Preparing NaOH to obtain a mixed reduction solution;
and fifthly, placing the metal oxide precursor in the third step into a mixed reduction solution for reduction treatment to obtain a metal material with a micro-nano porous fiber structure, and finishing the rapid micro-nano reconstruction treatment method of the copper metal.
The method has the advantages that the used equipment is simple, the metal material is placed at the normal temperature, and a large number of micro-nano porous fiber structures can be directly and effectively formed on the surface of the metal in situ in the solution.
The embodiment can be used for porous preparation of the foam copper metal material, and the commercial foam copper metal has a porous skeleton structure, has large specific surface area and high catalytic performance, and is used for manufacturing devices such as purification, filtration, catalytic supports, electrodes and the like in petrochemical industry, aerospace and environmental protection. Under the condition of normal temperature, the oxidation and reduction solution is used for carrying out oxidation and reduction treatment on the foam copper metal, a series of micro-nano pore fiber structures can be formed on the surface of the porous framework of the foam copper metal, and the application value and the range of the foam copper metal are further enhanced.
The second embodiment is as follows: the present embodiment is different from the first embodiment in that the copper-based alloy is brass, bronze, cupronickel, or phosphor-copper.
The third concrete implementation mode: the present embodiment is different from the first or second embodiment in that the metal material in the first step is in the form of powder, a metal wire, a metal sheet, or a metal film.
The metal material can also be a prepared copper metal device, and the preparation of the micro-nano fiber structure on the surface of the complex copper device is realized by utilizing a two-step solution treatment method.
The fourth concrete implementation mode: the difference between the present embodiment and one of the first to third embodiments is that the solute in the second step includes 1-3 mol L-1(NH)4)2S2O8And 4 to 6mol L-1NaOH (2).
The fifth concrete implementation mode: the difference between this embodiment and the first to the fourth embodiment is that the temperature of the mixed oxidation solution in the third step is 25 to 55 ℃.
The sixth specific implementation mode: this embodiment is different from one of the first to fifth embodiments in that the time of the oxidation treatment in the third step is 2 seconds to 2 hours.
The seventh concrete implementation mode: this embodiment is different from one of the first to sixth embodiments in that the cleaning in the third step is performed by sequentially using absolute ethyl alcohol and deionized water.
The specific implementation mode is eight: the present embodiment is different from the first to seventh embodiments in that the oxidation degree of the metal oxide precursor in the third step is complete oxidation or surface partial oxidation.
The reduction method of the present embodiment is applicable to oxidized metal precursors of different oxidation degrees.
The specific implementation method nine: the difference between the present embodiment and the first to eighth embodiments is that the solute in the fourth step comprises 80-100 g L-1DMAB and 10-30 g L-1NaOH (2).
The detailed implementation mode is ten: the difference between this embodiment and one of the first to ninth embodiments is that the temperature of the mixed reducing solution in the fifth step is 25 to 55 ℃.
The concrete implementation mode eleven: the present embodiment is different from the first to tenth embodiments in that the time of the reduction treatment in the fifth step is 2 seconds to 2 hours.
The specific implementation mode twelve: the application of the copper metal with the micro-nano porous fiber structure in the embodiment is to use the copper metal with the micro-nano porous fiber structure as a current collector or a self-supporting electrode for hydrogen production by water electrolysis.
The first embodiment is as follows: the quick copper metal micro-nano reconstruction processing method is implemented according to the following steps:
firstly, commercially available copper foam is cut into pieces with a surface area of 4cm2Obtaining a foam copper precursor;
secondly, water is used as a solvent, and a solute (only containing) comprises 1.0mol L-1(NH)4)2S2O8And 5.0mol L-1Preparing NaOH to obtain a mixed oxidation solution;
thirdly, putting the precursor in the first step into a mixed oxidation solution at the temperature of 25 ℃ for oxidation treatment for 5 seconds, sequentially using absolute ethyl alcohol and deionized water for cleaning, and drying to obtain a metal oxide precursor with a micro-nano porous fiber structure;
fourthly, water is used as solvent, and solute (only containing) comprises 100.0g L-1DMAB and 10.0g L-1Preparing NaOH to obtain a mixed reduction solution;
fifthly, placing the metal oxide precursor in the third step into a mixed reduction solution at the temperature of 25 ℃ for reduction treatment for 5 seconds, inducing the micro-nano porous fiber structure, sequentially using absolute ethyl alcohol and deionized water to clean, and airing to obtain the foamy copper with the micro-nano porous fiber structure.
As can be seen from the comparison between FIG. 1 and FIG. 2, after the mixed oxidation and reduction solution treatment, a large number of micro-nanofibers with a length of 10-30 μm (average diameter of 270nm) have been formed on the surface of the copper foam.
The change of the specific surface of the copper foam after the first and second solution treatments in the example was visually compared by Cyclic Voltammetry (CV), and as can be seen from fig. 3, the specific surface of the copper foam after the two solution treatments was 6 times that of the copper foam after the non-treatment.
Example two: the quick copper metal micro-nano reconstruction processing method is implemented according to the following steps:
first, commercially available copper foil having a thickness of 35 μm was cut into pieces having a surface area of 2cm2Obtaining a copper foil precursor;
secondly, water is used as a solvent, and the solute comprises 1.0mol L-1(NH)4)2S2O8And 5.0mol L-1Preparing a mixed oxidation solution by using NaOH;
thirdly, putting the metal material precursor in the step one into a mixed oxidation solution at the temperature of 25 ℃ for oxidation treatment for 5 minutes, sequentially using absolute ethyl alcohol and deionized water to clean, and drying to obtain a metal oxide precursor with a micro-nano porous fiber structure;
fourthly, water is used as solvent, and the solute comprises 100.0g L-1DMAB and 10.0g L-1Preparing NaOH to obtain a mixed reduction solution;
fifthly, placing the metal oxide precursor in the third step into a mixed reduction solution at the temperature of 25 ℃ for reduction treatment for 5 minutes, inducing the micro-nano porous fiber structure, sequentially using absolute ethyl alcohol and deionized water to clean, and airing to obtain the copper metal with the micro-nano porous fiber structure.
As can be seen from comparison between fig. 4 and 5, after the two-step solution mixing treatment, a large number of micro-nanofibers with a diameter of 1-3 μm (average particle diameter of-200 nm) have been formed on the surface of the copper foil.
Example three: the quick copper metal micro-nano reconstruction processing method is implemented according to the following steps:
firstly, commercially available phosphor copper foil with a thickness of 20 μm is cut into pieces with a surface area of 4cm2Obtaining a phosphor-copper precursor;
secondly, water is used as a solvent, and the solute comprises 1.0mol L-1(NH)4)2S2O8And 5.0mol L-1Preparing a mixed oxidation solution by using NaOH;
thirdly, placing the metal material precursor in the first step into a mixed oxidation solution at the temperature of 25 ℃ for oxidation treatment for 2 minutes, sequentially cleaning the metal material precursor with absolute ethyl alcohol and deionized water, and drying the metal material precursor to obtain a metal oxide precursor with a micro-nano porous fiber structure;
fourthly, water is used as solvent, and the solute comprises 100.0g L-1DMAB and 10.0g L-1Preparing NaOH to obtain a mixed reduction solution;
fifthly, placing the metal oxide precursor in the third step into a mixed reduction solution at the temperature of 25 ℃ for reduction treatment for 2 minutes, inducing the micro-nano porous fiber structure, sequentially using absolute ethyl alcohol and deionized water to clean, and airing to obtain the phosphorus-copper metal with the micro-nano porous fiber structure.
As can be seen from comparison between fig. 6 and fig. 7, after the mixed oxidation and reduction solution treatment, a large number of micro-nanofibers with a diameter of 1-8 μm (average particle diameter of 300nm) have been formed on the surface of the phosphor-copper, and the micro-nanofibers exhibit a unique porous structure formed by stacking nanoparticles.
The first application embodiment: and testing the oxygen evolution performance of the electrolyzed water with the micro-nano porous copper foam obtained in the first test example. In the first application example, the raw material and the two-step solution are treatedPerforming electrodeposition Co (OH) on the foam copper after liquid treatment by a potentiostatic method2And forming a composite electrode and testing the oxygen evolution performance of the composite electrolyzed water. Electrochemical deposition of Co (OH)2Adopts a three-electrode system, and the electrolyte is 0.1mol/L of Co (NO)3)2The deposition potential was-1V relative to the Hg/HgO reference electrode.
From FIG. 8, micro-nano fiber structure copper foam electrodeposition Co (OH) can be seen2The latter morphology, as can be seen in the figure, deposited Co (OH)2The nano thin sheets are tightly combined to form a cluster structure.
FIG. 9 is a graph comparing the oxygen evolution performance of the current collector composite electrode made of untreated foamy copper and micro-nanofiber foamy copper, and can be seen from the linear scanning curve, at 10mA/cm2Under the current density, the overpotential taking the micro-nano fiber foamy copper as the current collector electrode is 175mV, which is reduced by 284mV compared with the overpotential 459mV taking untreated foamy copper as the current collector electrode. The micro-nano porous fiber prepared by the method greatly improves the copper current collector and Co (OH)2The contact area of the active material reduces the polarization impedance of the electrode, thereby reducing the overpotential of the electrode.
Application example two: and (3) testing the performance of oxygen evolution and hydrogen evolution of the micro-nano porous copper foam obtained in the first test example as a self-supporting electrode in water electrolysis. In the first application example, the electrochemical test is performed on the foamy copper after the two-step treatment, the instrument used for the test is the Chenghua electrochemical workstation 660E, the electrocatalytic oxygen evolution test and the hydrogen evolution test are respectively performed on the foamy copper, and compared with untreated foamy copper, the foamy copper with a fiber structure shows good electrochemical performance. This is mainly due to the fact that on one hand, the fiber structure formed by the two-step solution treatment increases the specific surface area of the copper foam and increases the active sites of the electrode. On the other hand, the fiber structure has high curvature tip, which can enhance local electric field, thereby inducing higher concentration of hydroxyl ion (OH-) at active sites and optimizing mass transfer process of reactant on the active sites. The combined action of the two improves the electrochemical performance of the electrode.
FIG. 10 shows the electrochemistry of a two-step solution treated copper foam with an untreated copper foamThe linear scanning curve under the condition of the oxygen evolution test can be seen, and the treated foamy copper is 10mA/cm higher than that of the untreated foamy copper2The overpotential at the current density decreased by 140 mV.
Fig. 11 is an overpotential (LSV) curve of the copper foam after the two-step solution treatment and the untreated copper foam under the hydrogen evolution test condition, and it can be seen through observation that the overpotential of the treated copper foam is reduced by 341mV compared with the untreated copper foam, and the two-step treatment of the copper foam not only can significantly improve the oxygen evolution electrochemical performance, but also can improve the hydrogen evolution electrochemical performance, and has universality in practical application.
Claims (10)
1. The quick copper metal micro-nano reconstruction processing method is characterized by being realized according to the following steps:
firstly, taking copper or copper-based alloy metal material as a precursor;
secondly, water is used as a solvent, and the solute comprises 0.5-5 mol L-1(NH)4)2S2O8And 5 to 10mol L-1Preparing NaOH to obtain a mixed oxidation solution;
thirdly, putting the metal material precursor in the step one into a mixed oxidation solution for oxidation treatment, and cleaning and drying to obtain a metal oxide precursor with a micro-nano porous fiber structure;
fourthly, water is used as a solvent, and solutes comprise 50 to 100g L-1Dimethylamine borane and 10 to 50g L-1Preparing NaOH to obtain a mixed reduction solution;
and fifthly, placing the metal oxide precursor in the third step into a mixed reduction solution for reduction treatment to obtain a metal material with a micro-nano porous fiber structure, and finishing the rapid micro-nano reconstruction treatment method for the copper metal.
2. The rapid micro-nano reconstruction processing method of copper metal according to claim 1, characterized in that the copper-based alloy is brass, bronze, cupronickel or phosphor-copper.
3. The rapid micro-nano reconstruction processing method of copper metal according to claim 1, characterized in that the form of the copper or copper-based alloy metal material in the step one is powder, metal wire, metal sheet or metal film.
4. The rapid micro-nano reconstruction processing method of copper metal according to claim 1, wherein the solute in the second step comprises 1-3 mol L of solute-1(NH)4)2S2O8And 4 to 6mol L-1NaOH (2).
5. The rapid copper metal micro-nano reconstitution processing method according to claim 1, wherein the temperature of the mixed oxidation solution in the third step is 25-55 ℃.
6. The rapid micro-nano reconstruction processing method of copper metal according to claim 1, characterized in that the time of the oxidation processing in the third step is 2 seconds to 2 hours.
7. The rapid micro-nano reconstruction processing method of copper metal according to claim 1, wherein the solute in the fourth step comprises 80-100 g L%-1DMAB and 10-30 g L-1NaOH (2).
8. The rapid copper metal micro-nano reconstitution processing method according to claim 1, wherein the temperature of the mixed reducing solution in the fifth step is 25-55 ℃.
9. The rapid copper metal micro-nano reconstruction processing method according to claim 1, characterized in that the time of the reduction processing in the fifth step is 2 seconds to 2 hours.
10. The application of the metal material with the micro-nano porous fiber structure obtained by the treatment method of claim 1 is characterized in that copper metal with the micro-nano porous fiber structure is used as a current collector or a self-supporting electrode for hydrogen production by water electrolysis.
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| WO2021006439A1 (en) * | 2019-07-08 | 2021-01-14 | 전북대학교산학협력단 | Electrochemical water decomposition catalyst and method for producing same |
| CN110548509A (en) * | 2019-08-02 | 2019-12-10 | 深圳大学 | copper-based carbon dioxide electrocatalytic material and preparation method thereof |
| CN111604069A (en) * | 2020-04-17 | 2020-09-01 | 深圳大学 | Copper-based carbon dioxide electrocatalytic material and preparation method thereof |
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