CN111009644A - Preparation method of nano-porous copper surface modified MnO/graphene composite electrode - Google Patents
Preparation method of nano-porous copper surface modified MnO/graphene composite electrode Download PDFInfo
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Abstract
A preparation method of a nano-porous copper surface modified MnO/graphene composite electrode comprises the following steps: (1) preparing an alloy: preparing a CuMn alloy, wherein the atomic content of Cu in the CuMn alloy is 30-50%, and the rest is the atomic content of Mn; (2) preparing the CuMn alloy sheet prepared in the step (1) into toughness gradient nano-porous copper with the aperture of two sides being 50-70nm and the aperture of the middle being 20-30nm by adopting a chemical dealloying method; (3) carrying out heat treatment on the nano-porous copper prepared in the step (2); (4) and (4) carrying out chemical vapor deposition treatment on the nano porous copper prepared in the step (3). Compared with the prior art, the method is simple and low in cost, and the oxide and the graphene are directly formed on the nano-porous copper matrix, so that the oxide and the graphene are combined with the matrix more tightly.
Description
Technical Field
The invention relates to the technical field of electrodes and preparation thereof, in particular to a preparation method of a nano porous copper surface modified MnO/graphene composite electrode.
Background
The lithium ion battery is widely applied to daily life and production as a high-efficiency rechargeable energy storage device. The lithium ion battery mainly comprises four parts, namely a positive electrode material, a negative electrode material, a diaphragm and electrolyte, wherein the performance of the positive electrode material and the performance of the negative electrode material are seriously influenced. Transition metal oxides are considered to be one of the most potential electrode materials for lithium ion batteries, wherein MnO is considered to be one of the most promising negative electrode materials for lithium ion batteries due to its advantages of low cost, high specific capacity (756mAh/g), and environmental friendliness. However, the transition metal oxide has poor conductivity and is easily expanded and pulverized during charge and discharge, and the problems of poor cycle stability and rate capability are caused, so that the application of the transition metal oxide is limited. To improve the conductivity of transition metal oxides and to improve cycle life, many studies have been made to solve these defects by introducing conductive substances or constructing low-dimensional nanostructures.
The graphene has excellent optical, electrical and mechanical properties, has important application prospects in the aspects of materials science, micro-nano processing, energy, biomedicine, drug delivery and the like, and is considered to be a revolutionary material in the future. Common methods for producing graphene are mechanical lift-off, redox, SiC epitaxial growth, Chemical Vapor Deposition (CVD). Graphene can be classified into single-layer graphene, double-layer graphene, few-layer graphene and multi-layer graphene according to the difference of the number of graphene layers.
In order to solve the problem of poor conductivity of the existing transition metal oxides, graphene with good conductivity is introduced, and meanwhile, a low-dimensional nano structure is constructed on the transition metal oxides, so that the self-supporting electrode material of the oxide and the graphene with self-growing surfaces is successfully prepared, and the active substance and the conductive porous metal matrix have a lattice matching relationship, so that the oxide and the graphene can grow together tightly and are difficult to fall off. The advantages are that: 1. the nano porous metal is used as a conductive matrix, and the interface binding force and the conductive capacity can be effectively improved by an autoxidation method, so that the transmission of electrons and ions is facilitated; 2. the graphene grows on the porous metal matrix and MnO by a chemical vapor deposition method, so that the problem of volume expansion of the electrode material can be solved; 3. the construction of the low-dimensional nano structure of the oxide provides a high specific surface area and can load more active substances, thereby improving the specific capacity; 4. the transition metal oxide has rich mineral resources, and the method for preparing the electrode by adopting metal is simple and has lower cost.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
In view of the above, the present invention is directed to a method for preparing a nano-porous copper surface modified MnO/graphene composite electrode, so as to overcome the disadvantages of the prior art.
The technical scheme of the invention is realized as follows:
a preparation method of a nano-porous copper surface modified MnO/graphene composite electrode comprises the following steps:
(1) preparing an alloy: preparing a CuMn alloy, wherein the atomic content of Cu in the CuMn alloy is 30-50%, and the rest is the atomic content of Mn; the CuMn alloy is processed into CuMn alloy sheets with the thickness of 50-100 um;
(2) preparing the CuMn alloy sheet prepared in the step (1) into toughness gradient nano-porous copper with the aperture of two sides being 50-70nm and the aperture of the middle being 20-30nm by adopting a chemical dealloying method;
(3) carrying out heat treatment on the nano-porous copper prepared in the step (2), wherein the heat treatment process comprises the following steps: hydrogen and argon are used as reducing and protective atmosphere, the heat treatment temperature is 600-800 ℃, the heat treatment time is 30-120min, and the gradient nano porous copper is obtained after the heat treatment;
(4) and (3) carrying out chemical vapor deposition treatment on the nano-porous copper prepared in the step (3), wherein the chemical vapor deposition treatment process comprises the following steps: and (3) taking argon, hydrogen and methane as growth atmosphere, depositing at the deposition temperature of 800-1000 ℃, and performing deposition growth for 5-10min to obtain the nano porous copper surface modified MnO/graphene composite electrode.
Further, the alloy in the step (1) is prepared by preparing a single-phase solid solution CuMn alloy ingot by a smelting casting method, and then rolling to obtain a CuMn alloy sheet with the thickness of 50-100 um.
Further, the chemical dealloying method in the step (2) comprises the following specific steps: and (2) corroding the CuMn alloy sheet at the temperature of 20-50 ℃ by using dilute hydrochloric acid as a corrosive solution for 10-30 minutes.
Further, the heat treatment in the step (3) includes the steps of: the gradient nano-porous copper is placed in an atmosphere furnace, 100sccm hydrogen and 100sccm argon are introduced, the temperature is raised to 600-800 ℃ at the heating rate of 10 ℃/min, and the temperature is preserved for 30-120 minutes and then the temperature is naturally reduced.
Further, the chemical vapor deposition treatment in the step (4) comprises the following steps: and (3) placing the gradient nano porous copper subjected to heat treatment in a rapid heating and cooling furnace, introducing 200sccm hydrogen and 100sccm argon, heating to 800-.
Further, the shape of the nano porous copper surface modified MnO/graphene composite electrode prepared in the step (4) is a sharp needle with the length of 5um and the width of about 1 um.
The nano-porous copper surface modified MnO/graphene composite electrode is prepared according to the preparation method.
Compared with the prior art, the preparation method of the nano-porous copper surface modified MnO/graphene composite electrode has the following advantages:
1. according to the invention, the CuMn alloy matrix is directly prepared, and then dealloying treatment is directly carried out on the CuMn alloy matrix, so that gradient nano-porous copper is directly obtained; 2. heat treatment in protective atmosphere, and control of heat treatment process, thereby controlling pore diameter and pore diameter distribution of micropores on the nano-porous copper; 3. on the basis, the lithium battery negative electrode material which takes the gradient nano porous copper as the matrix and is uniformly distributed with the oxide and the graphene on the matrix is directly obtained through a final chemical vapor deposition method. Compared with the prior art, the method is simple and low in cost, and the oxide and the graphene are directly formed on the nano-porous copper matrix, so that the oxide and the graphene are combined with the matrix more tightly.
Drawings
FIG. 1 is a macroscopic view of the CuMn alloy in example 1 after 20min of dealloying in 0.05mol/L hydrochloric acid solution;
FIG. 2 is a sectional SEM photograph of the CuMn alloy in example 1 after 20min of dealloying in 0.05mol/L hydrochloric acid solution;
FIG. 3 is an SEM image of a nano-porous copper surface modified MnO/graphene composite electrode of example 1;
FIG. 4 is a Raman spectrum of the nano-porous copper surface modified MnO/graphene composite electrode of example 1;
FIG. 5 is an XRD (X-ray diffraction) spectrum of the nano-porous copper surface modified MnO/graphene composite electrode in example 1;
FIG. 6 is a charge-discharge curve of the nanoporous copper surface modified MnO/graphene composite electrode of example 1;
fig. 7 is a rate curve of the nano-porous copper surface modified MnO/graphene composite electrode in example 1.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
In the invention, the alloy and various solvents and solutions are purchased from common chemical shops. The electrochemical treatment may be performed using various models and brands of electrochemical stations, and the choice of electrochemical station itself has no essential effect on the present invention. The heat treatment furnace and the rapid temperature raising and lowering furnace are any kind of heat treatment furnace known in the art. The battery test was performed using a battery tester well known in the art.
The present invention will be described in detail with reference to the following examples and accompanying drawings.
A preparation method of a nano-porous copper surface modified MnO/graphene composite electrode comprises the following steps:
(1) preparing an alloy: preparing a CuMn alloy by using a smelting and casting method, wherein in the CuMn alloy, the atomic content of Cu is 30-50%, and the rest is the atomic content of Mn; the CuMn alloy is processed into CuMn alloy sheets with the thickness of 50-100 um;
(2) preparing the CuMn alloy sheet prepared in the step (1) into toughness gradient nano-porous copper with the aperture of two sides being 50-70nm and the aperture of the middle being 20-30nm by adopting a chemical dealloying method; the chemical dealloying method comprises the following specific steps: using dilute hydrochloric acid as a corrosive liquid, and corroding the CuMn alloy sheet at the temperature of 20-50 ℃ for 10-30 minutes;
(3) carrying out heat treatment on the nano-porous copper prepared in the step (2), wherein the heat treatment process comprises the following steps: hydrogen and argon are used as reducing and protective atmosphere, the heat treatment temperature is 600-800 ℃, the heat treatment time is 30-120min, and the gradient nano porous copper is obtained after the heat treatment; the heat treatment comprises the following steps: placing the gradient nano-porous copper in an atmosphere furnace, introducing 100sccm hydrogen and 100sccm argon, raising the temperature to 600-800 ℃ at a heating rate of 10 ℃/min, preserving the temperature for 30-120 minutes, and then naturally cooling;
(4) and (3) carrying out chemical vapor deposition treatment on the nano-porous copper prepared in the step (3), wherein the chemical vapor deposition treatment process comprises the following steps: taking argon, hydrogen and methane as growth atmosphere, depositing at the temperature of 800-; the chemical vapor deposition treatment comprises the following steps: and (3) placing the gradient nano porous copper subjected to heat treatment in a rapid heating and cooling furnace, introducing 200sccm hydrogen and 100sccm argon, heating to 800-.
Example 1
A preparation method of a nano-porous copper surface modified MnO/graphene composite electrode comprises the following steps:
(1) preparing an alloy: the atomic content ratio of CuMn is 40: 60, CuMn metal particles are melted to form a CuMn alloy ingot, and then the CuMn alloy ingot is rolled to form an alloy sheet with the thickness of 100 um;
(2) dealloying to prepare the nano porous metal: polishing the alloy sheet obtained in the step (1) by using sand paper, then performing suction filtration, and performing suction filtration and corrosion for 20min at room temperature by using 0.05mol/L hydrochloric acid;
(3) and (3) heat treatment: fully washing the gradient nano-porous metal thin strip prepared in the step (2) with deionized water for 3 times, then washing with copper absolute ethyl alcohol for 1 time, drying the material in a vacuum drying oven at 50 ℃ for 4-6H after ensuring that no hydrochloric acid remains, and placing the dried metal thin strip in a high-temperature sintering furnace in Ar: H2Heating to 600 deg.C at a rate of 10 deg.C/min under the atmosphere of 100: 100, and maintaining for 90 min;
(4) chemical vapor deposition treatment: placing the gradient nano-porous metal film after the heat treatment prepared in the step (3) in a rapid heating and cooling furnace in Ar: H ratio2Heating to 1000 ℃ at the speed of 10 ℃/min under the atmosphere of 200: 100, introducing 20sccm methane, moving the sample to a hearth heat preservation area, and depositing for 10 min;
(5) assembling the battery: placing the obtained electrode material in an anaerobic glove box to assemble a button cell;
(6) testing the electrochemical performance: and (3) respectively testing the rate capability and the cycling stability of the assembled blue battery testing system for the battery.
FIGS. 1 and 2 are a photomicrograph and a cross-sectional SEM image of a CuMn alloy sheet in example 1 after being dealloyed in 0.05mol/L hydrochloric acid solution for 20min, wherein the photomicrograph shows that the material has certain toughness after being dealloyed, and the cross-sectional SEM image shows that the material is toughness gradient nano-porous copper with the pore diameters of two sides being 50-70nm and the pore diameter of the middle being 20-30 nm;
fig. 3, fig. 4 and fig. 5 are a SEM image, a raman spectrum and an XRD spectrum of the nano-porous copper surface modified MnO/graphene composite electrode in example 1, respectively, where the SEM image shows that the material surface is in a sharp needle-like shape after chemical vapor deposition, the XRD spectrum can determine that the sharp needle-like material is MnO, and the raman spectrum can show that graphene and MnO are generated;
fig. 6 and 7 are a charge-discharge curve and a rate curve of the nano-porous copper surface modified MnO/graphene composite electrode in example 1, and it can be known from the charge-discharge curve that a charge-discharge platform of the material is stable; the current density of the material is 500mA/cm according to the multiplying power curve2Recovered to 100mA/cm2In time, the specific capacity is basically kept unchanged, and the rate capability is better.
Example 2
(1) Preparing an alloy: the atomic content ratio of Cu to Mn is 30: 70, Cu and Mn metal particles are melted to form a CuMn alloy ingot, and then the CuMn alloy ingot is rolled to form an alloy sheet with the thickness of 100 um;
(2) dealloying to prepare the nano porous metal: polishing the alloy sheet obtained in the step (1) by using sand paper, placing the polished alloy sheet in a suction filtration, and performing suction filtration and corrosion for 30min at room temperature by using 0.05mol/L hydrochloric acid;
(3) and (3) heat treatment: fully washing the gradient nano-porous metal sheet prepared in the step (2) with deionized water for 3 times, then washing with copper absolute ethyl alcohol for 1 time, placing the material in a vacuum drying oven for drying at 50 ℃ for 4-6H after ensuring that no hydrochloric acid remains, placing the dried metal thin strip in a high-temperature sintering furnace in Ar: H2Heating to 6 deg.C at a rate of 10 deg.C/min under 100: 100 atmosphereKeeping the temperature at 00 ℃ for 90 min;
(4) chemical vapor deposition treatment: placing the gradient nano-porous metal subjected to heat treatment and prepared in the step (3) in a rapid heating and cooling furnace in Ar: H ratio2Heating to 1000 ℃ at a speed of 10 ℃/min under the atmosphere of 200: 100, introducing 40sccm methane, moving the sample to a hearth heat preservation area, and depositing for 5 min;
(5) assembling the battery: placing the obtained electrode material in an anaerobic glove box to assemble a button cell;
(6) testing the electrochemical performance: and (3) respectively testing the rate capability and the cycling stability of the assembled blue battery testing system for the battery. The material obtained by the test has the current density of 500mA/cm2Recovered to 100mA/cm2During the process, the specific capacity can be kept above 90%, the rate capability is good, and the specific capacity retention rate is above 90% after 70 cycles of circulation.
According to the invention, the CuMn alloy matrix is directly prepared, and then dealloying treatment is directly carried out on the CuMn alloy matrix, so that gradient nano-porous copper is directly obtained; heat treatment in protective atmosphere, and control of heat treatment process, thereby controlling pore diameter and pore diameter distribution of micropores on the nano-porous copper; on the basis, the lithium battery negative electrode material which takes the gradient nano porous copper as the matrix and is uniformly distributed with the oxide and the graphene on the matrix is directly obtained through a final chemical vapor deposition method. Compared with the prior art, the method is simple and low in cost, and the oxide and the graphene are directly formed on the nano-porous copper matrix, so that the oxide and the graphene are combined with the matrix more tightly.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. A preparation method of a nano-porous copper surface modified MnO/graphene composite electrode is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing an alloy: preparing a CuMn alloy, wherein the atomic content of Cu in the CuMn alloy is 30-50%, and the rest is the atomic content of Mn; the CuMn alloy is processed into CuMn alloy sheets with the thickness of 50-100 um;
(2) preparing the CuMn alloy sheet prepared in the step (1) into toughness gradient nano-porous copper with the aperture of two sides being 50-70nm and the aperture of the middle being 20-30nm by adopting a chemical dealloying method;
(3) carrying out heat treatment on the nano-porous copper prepared in the step (2), wherein the heat treatment process comprises the following steps: hydrogen and argon are used as reducing and protective atmosphere, the heat treatment temperature is 600-800 ℃, the heat treatment time is 30-120min, and the gradient nano porous copper is obtained after the heat treatment;
(4) and (3) carrying out chemical vapor deposition treatment on the nano-porous copper prepared in the step (3), wherein the chemical vapor deposition treatment process comprises the following steps: and (3) taking argon, hydrogen and methane as growth atmosphere, depositing at the deposition temperature of 800-1000 ℃, and performing deposition growth for 5-10min to obtain the nano porous copper surface modified MnO/graphene composite electrode.
2. The preparation method of the nano-porous copper surface modified MnO/graphene composite electrode of claim 1, wherein the preparation method comprises the following steps: the alloy preparation method in the step (1) is to prepare a single-phase solid solution CuMn alloy ingot by a smelting and casting method, and then roll the single-phase solid solution CuMn alloy ingot to obtain a CuMn alloy sheet with the thickness of 50-100 um.
3. The preparation method of the nano-porous copper surface modified MnO/graphene composite electrode of claim 1, wherein the preparation method comprises the following steps: the chemical dealloying method in the step (2) comprises the following specific steps: and (2) corroding the CuMn alloy sheet at the temperature of 20-50 ℃ by using dilute hydrochloric acid as a corrosive solution for 10-30 minutes.
4. The preparation method of the nano-porous copper surface modified MnO/graphene composite electrode of claim 1, wherein the preparation method comprises the following steps: the heat treatment in the step (3) includes the steps of: the gradient nano-porous copper is placed in an atmosphere furnace, 100sccm hydrogen and 100sccm argon are introduced, the temperature is raised to 600-800 ℃ at the heating rate of 10 ℃/min, and the temperature is preserved for 30-120 minutes and then the temperature is naturally reduced.
5. The preparation method of the nano-porous copper surface modified MnO/graphene composite electrode of claim 1, wherein the preparation method comprises the following steps: the chemical vapor deposition treatment in the step (4) comprises the following steps: and (3) placing the gradient nano porous copper subjected to heat treatment in a rapid heating and cooling furnace, introducing 200sccm hydrogen and 100sccm argon, heating to 800-.
6. The preparation method of the nano-porous copper surface modified MnO/graphene composite electrode of claim 1, wherein the preparation method comprises the following steps: the shapes of the nano-porous copper surface modified MnO prepared in the step (4) and the graphene electrode material are needle-shaped MnO/graphene composite materials.
7. The nano-porous copper surface modified MnO/graphene composite electrode prepared by the preparation method of any one of claims 1-6.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113871576A (en) * | 2021-08-31 | 2021-12-31 | 天津大学 | Element-doped nano porous bimetal sulfide integrated electrode and preparation method thereof |
| CN114023928A (en) * | 2021-08-31 | 2022-02-08 | 天津大学 | Preparation method for in-situ construction of bimetallic oxide integrated electrode by hierarchical porous copper |
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