CN111009644B - 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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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
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Abstract
The preparation method of the nano-porous copper surface modified MnO/graphene composite electrode comprises the following steps: (1) alloy preparation: preparing a CuMn alloy, wherein the atom content of Cu in the CuMn alloy is 30-50%, and the balance is Mn atom content; (2) Preparing the toughness gradient nano porous copper with the pore diameter of both sides of 50-70nm and the pore diameter of the middle of 20-30nm by adopting a chemical dealloying method for the CuMn alloy sheet prepared in the step (1); (3) Carrying out heat treatment on the nano-porous copper prepared in the step (2); (4) And (3) carrying out chemical vapor deposition treatment on the nano-porous copper prepared in the step (3). Compared with the preparation method existing in the prior art, the preparation method provided by the invention is simple and lower in cost, and the oxide and the graphene are directly formed on the nano-porous copper matrix, so that the combination of the oxide and the graphene with the matrix is tighter.
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 production as a high-efficiency rechargeable energy storage device. The lithium ion battery mainly comprises four parts of anode and cathode materials, a diaphragm and electrolyte, wherein the performance of the anode and cathode materials is seriously influenced by the performance of the anode and cathode materials. Transition metal oxides are considered to be one of the most potential electrode materials for lithium ion batteries, with MnO being considered to be one of the most promising negative electrode materials for lithium ion batteries due to its low cost, high specific capacity (756 mAh/g), and environmental friendliness. However, the transition metal oxide has poor conductivity, and is susceptible to swelling and pulverization during charge and discharge, which results in poor cycle stability and rate performance, so that the application thereof is limited. To increase the conductivity of transition metal oxides and increase cycle life, much research has been devoted to introducing conductive materials or constructing low-dimensional nanostructures to address these drawbacks.
The graphene has excellent optical, electrical and mechanical properties, has important application prospects in the aspects of material science, micro-nano processing, energy sources, biomedicine, drug delivery and the like, and is considered as a revolutionary material in the future. Common methods for graphene production are mechanical exfoliation, redox, siC epitaxial growth, chemical Vapor Deposition (CVD). The graphene can be divided into single-layer graphene, double-layer graphene, few-layer graphene and multi-layer graphene according to the number of graphene layers.
In order to solve the problem of poor conductivity of the transition metal oxide existing at present, graphene with good conductivity is introduced, and meanwhile, a low-dimensional nano structure is constructed on the transition metal oxide, so that the self-supporting electrode material of the oxide with self-grown surface and the graphene is successfully prepared, and active substances of the self-supporting electrode material and the conductive porous metal matrix have a lattice matching relationship, so that the self-supporting electrode material and the conductive porous metal matrix can closely grow together 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 conductivity can be effectively improved by an autoxidation method, so that the transmission of electrons and ions is facilitated; 2. graphene grows on the porous metal matrix and MnO through a chemical vapor deposition method, so that the problem of volume expansion of an electrode material can be restrained; 3. the construction of the oxide low-dimensional nano structure provides high specific surface area and can load more active substances, so that the specific capacity is improved; 4. the transition group metal oxide has abundant 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 of ordinary skill in the art.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing a nano-porous copper surface modified MnO/graphene composite electrode, thereby overcoming the disadvantages of the prior art.
The technical scheme of the invention is realized as follows:
the preparation method of the nano-porous copper surface modified MnO/graphene composite electrode comprises the following steps:
(1) Alloy preparation: preparing a CuMn alloy, wherein the atom content of Cu in the CuMn alloy is 30-50%, and the balance is Mn atom content; the CuMn alloy is processed into a CuMn alloy sheet with the thickness of 50-100 um;
(2) Preparing the toughness gradient nano porous copper with the pore diameter of both sides of 50-70nm and the pore diameter of the middle of 20-30nm by adopting a chemical dealloying method for the CuMn alloy sheet prepared in the step (1);
(3) Carrying out heat treatment on the nano-porous copper prepared in the step (2), wherein the heat treatment process comprises the following steps: taking hydrogen and argon as reducing and protecting atmospheres, and performing heat treatment at 600-800 ℃ for 30-120min to obtain gradient nano porous copper;
(4) Carrying out chemical vapor deposition treatment on the nano-porous copper prepared in the step (3), wherein the chemical vapor deposition treatment comprises the following steps: and taking argon, hydrogen and methane as growth atmosphere, and performing deposition growth for 5-10min at the deposition temperature of 800-1000 ℃ to obtain the nano-porous copper surface modified MnO/graphene composite electrode.
Further, the alloy preparation method in the step (1) is to prepare a single-phase solid solution CuMn alloy ingot by smelting and casting, and then roll the single-phase solid solution CuMn alloy ingot to obtain a CuMn alloy sheet with the thickness of 50-100 um.
Further, the chemical dealloying method in the step (2) specifically comprises the following steps: and (3) using dilute hydrochloric acid as a corrosive liquid, and corroding the CuMn alloy sheet at the temperature of 20-50 ℃ for 10-30 minutes.
Further, the heat treatment in the step (3) includes the steps of: placing the gradient nano porous copper in an atmosphere furnace, introducing 100sccm of hydrogen and 100sccm of argon, raising the temperature to 600-800 ℃ at a heating rate of 10 ℃/min, preserving the temperature for 30-120 minutes, and naturally cooling.
Further, the chemical vapor deposition process in the step (4) includes the following steps: placing the heat-treated gradient nano porous copper in a rapid temperature-raising furnace, introducing 200sccm of hydrogen and 100sccm of argon, raising the temperature to 800-1000 ℃ at a heating rate of 10 ℃/min, introducing 2-40sccm of methane, growing for 5-10min, and rapidly removing and cooling the furnace tube.
Furthermore, the morphology of the nano-porous copper surface modified MnO/graphene composite electrode prepared in the step (4) is a sharp needle with a length of 5um and a width of 1 um.
According to the preparation method, the nano-porous copper surface modified MnO/graphene composite electrode is prepared.
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 are combined, so that the pore diameter and pore diameter distribution of micropores on the nano porous copper are controlled; 3. on the basis, the lithium battery anode material taking the gradient nano porous copper as a matrix and uniformly distributing oxides and graphene on the matrix is directly obtained by a final chemical vapor deposition method. Compared with the preparation method existing in the prior art, the preparation method provided by the invention is simple and lower in cost, and the oxide and the graphene are directly formed on the nano-porous copper matrix, so that the combination of the oxide and the graphene with the matrix is tighter.
Drawings
FIG. 1 is a macroscopic view of the CuMn alloy of example 1 after dealloying in 0.05mol/L hydrochloric acid solution for 20min;
FIG. 2 is a cross-sectional SEM image of the CuMn alloy of example 1 after dealloying in 0.05mol/L hydrochloric acid solution for 20min;
FIG. 3 is an SEM image of a nanoporous copper surface modified MnO/graphene composite electrode of example 1;
FIG. 4 is a Raman spectrum of a nano-porous copper surface-modified MnO/graphene composite electrode of example 1;
FIG. 5 is an XRD pattern of a nanoporous copper surface modified MnO/graphene composite electrode of example 1;
FIG. 6 is a charge-discharge curve of a nano-porous copper surface modified MnO/graphene composite electrode of example 1;
fig. 7 is a graph showing the magnification of the nano-porous copper surface-modified MnO/graphene composite electrode of example 1.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains. 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 present invention, the alloy, various solvents and solutions are purchased from common chemical stores. The electrochemical treatment may use various types, brands of electrochemical workstations, the choice of which has no substantial impact on the invention. The heat treatment furnace and the rapid thermal rise and fall furnace are any kind of heat treatment furnace known in the art. Battery testing is performed using a battery tester as known in the art.
The present invention will be described in detail with reference to the following examples and drawings.
The preparation method of the nano-porous copper surface modified MnO/graphene composite electrode comprises the following steps:
(1) Alloy preparation: preparing CuMn alloy by using a smelting casting method, wherein the atomic content of Cu in the CuMn alloy is 30-50%, and the balance is Mn; the CuMn alloy is processed into a CuMn alloy sheet with the thickness of 50-100 um;
(2) Preparing the toughness gradient nano porous copper with the pore diameter of both sides of 50-70nm and the pore diameter of the middle of 20-30nm by adopting a chemical dealloying method for the CuMn alloy sheet prepared in the step (1); the chemical dealloying method comprises the following specific steps: corroding the CuMn alloy sheet by using dilute hydrochloric acid as a corrosive liquid 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: taking hydrogen and argon as reducing and protecting atmospheres, and performing heat treatment at 600-800 ℃ for 30-120min to obtain gradient nano porous copper; the heat treatment comprises the following steps: placing the gradient nano porous copper in an atmosphere furnace, introducing 100sccm of hydrogen and 100sccm of argon, raising the temperature to 600-800 ℃ at a heating rate of 10 ℃/min, preserving heat for 30-120 minutes, and naturally cooling;
(4) Carrying out chemical vapor deposition treatment on the nano-porous copper prepared in the step (3), wherein the chemical vapor deposition treatment comprises the following steps: taking argon, hydrogen and methane as growth atmosphere, and performing deposition growth for 5-10min at the deposition temperature of 800-1000 ℃ to obtain a nano-porous copper surface modified MnO/graphene composite electrode, wherein the appearance of the prepared nano-porous copper surface modified MnO/graphene composite electrode is a sharp needle with the length of 5um and the width of about 1 um; the chemical vapor deposition process comprises the following steps: placing the heat-treated gradient nano porous copper in a rapid temperature-raising furnace, introducing 200sccm of hydrogen and 100sccm of argon, raising the temperature to 800-1000 ℃ at a heating rate of 10 ℃/min, introducing 2-40sccm of methane, growing for 5-10min, and rapidly removing and cooling the furnace tube.
Example 1
The preparation method of the nano-porous copper surface modified MnO/graphene composite electrode comprises the following steps:
(1) Preparation of the alloy: the atomic content ratio of CuMn is 40:60, the CuMn metal particles are formed into CuMn alloy ingots by a melting mode, and then the CuMn alloy ingots are rolled into alloy sheets with the thickness of 100um by a rolling mode;
(2) Dealloying to prepare a nanoporous metal: polishing the alloy sheet in the step (1) by sand paper, 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 ribbon prepared in the step (2) with deionized water for 3 times, washing copper with absolute ethyl alcohol for 1 time, drying the material in a vacuum drying oven at 50 ℃ for 4-6H after ensuring no hydrochloric acid residue, and placing the dried metal ribbon in a high-temperature sintering furnace at Ar:H 2 Heating to 600 ℃ at a speed of 10 ℃/min under the atmosphere of 100:100, and preserving heat for 90min;
(4) Chemical vapor deposition process: placing the heat-treated gradient nano porous metal thin prepared in the step (3) in a rapid temperature rise and fall furnace in Ar: H 2 Heating to 1000 ℃ at a speed of 10 ℃/min in an atmosphere of 200:100, introducing 20sccm of methane, then moving the sample to a hearth heat preservation area, and depositing for 10min;
(5) Assembling a battery: putting the obtained electrode material into an anaerobic glove box to be assembled into a button cell;
(6) Testing electrochemical performance: the assembled battery is tested by the blue-electricity battery testing system for multiplying power performance and cycling stability respectively.
FIGS. 1 and 2 are a macroscopic photograph and a cross-sectional SEM (scanning electron microscope) diagram of a CuMn alloy sheet in example 1 after dealloying in 0.05mol/L hydrochloric acid solution for 20min, wherein the dealloying of the material is known to have certain toughness through the macroscopic photograph, and the material is known to be toughness gradient nano-porous copper with the pore diameters of both sides of 50-70nm and the pore diameter of the middle of 20-30nm through the cross-sectional SEM diagram;
fig. 3, fig. 4 and fig. 5 are respectively an SEM image, a raman spectrum and an XRD spectrum of the nano-porous copper surface modified MnO/graphene composite electrode in example 1, wherein after chemical vapor deposition is performed on the material according to the SEM image, the surface of the material is in a sharp needle shape, the sharp needle-shaped substance can be determined to be MnO according to the XRD spectrum, and the graphene and MnO can be generated according to the raman spectrum;
fig. 6 and 7 are charge-discharge curves and rate curves of the nano-porous copper surface-modified MnO/graphene composite electrode in example 1, and the charge-discharge plateau of the material can be known to be stable through the charge-discharge curves; the current density of the material is 500mA/cm according to the multiplying power curve 2 Recovery to 100mA/cm 2 When the specific capacity is basically unchanged, the rate capability is better.
Example 2
(1) Preparation of the alloy: the atomic content ratio of Cu to Mn is 30:70, cu and Mn metal particles are formed into CuMn alloy ingots in a melting mode, and then the CuMn alloy ingots are rolled into alloy sheets with the thickness of 100 mu m in a rolling mode;
(2) Dealloying to prepare a nanoporous metal: polishing the alloy sheet in the step (1) by sand paper, placing the polished alloy sheet in 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, washing copper with absolute ethyl alcohol for 1 time, drying the material in a vacuum drying oven at 50 ℃ for 4-6H after ensuring no hydrochloric acid residue, and placing the dried metal sheet in a high-temperature sintering furnace at Ar:H 2 Heating to 600 ℃ at a speed of 10 ℃/min under the atmosphere of 100:100, and preserving heat for 90min;
(4) Chemical vapor deposition process: placing the heat-treated gradient nano porous metal prepared in the step (3) in a rapid temperature rise and fall furnace in Ar: H 2 Heating to 1000 ℃ at a speed of 10 ℃/min in an atmosphere of 200:100, introducing 40sccm of methane, then moving the sample to a hearth heat preservation area, and depositing for 5min;
(5) Assembling a battery: putting the obtained electrode material into an anaerobic glove box to be assembled into a button cell;
(6) Testing electrochemical performance: the assembled battery is tested by the blue-electricity battery testing system for multiplying power performance and cycling stability respectively. The material obtained by testing has a current density of 500mA/cm 2 Recovery to 100mA/cm 2 When the specific capacity is kept above 90%, the multiplying power performance is better, and the specific capacity retention rate is kept above 90% after the cycle of 70 circles.
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 are combined, so that the pore diameter and pore diameter distribution of micropores on the nano porous copper are controlled; on the basis, the lithium battery anode material taking the gradient nano porous copper as a matrix and uniformly distributing oxides and graphene on the matrix is directly obtained by a final chemical vapor deposition method. Compared with the preparation method existing in the prior art, the preparation method provided by the invention is simple and lower in cost, and the oxide and the graphene are directly formed on the nano-porous copper matrix, so that the combination of the oxide and the graphene with the matrix is tighter.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (6)
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) Alloy preparation: preparing a CuMn alloy, wherein the atom content of Cu in the CuMn alloy is 30-50%, and the balance is Mn; the CuMn alloy is processed into a CuMn alloy flake with the thickness of 50-100 mu m;
(2) Preparing the toughness gradient nano porous copper with the pore diameter of both sides of 50-70nm and the pore diameter of the middle of 20-30nm by adopting a chemical dealloying method for the CuMn alloy sheet prepared in the step (1); the chemical dealloying method comprises the following specific steps: corroding the CuMn alloy sheet by using dilute hydrochloric acid as a corrosive liquid 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: taking hydrogen and argon as reducing and protecting atmospheres, and performing heat treatment at 600-800 ℃ for 30-120min to obtain gradient nano porous copper;
(4) Carrying out chemical vapor deposition treatment on the nano-porous copper prepared in the step (3), wherein the chemical vapor deposition treatment comprises the following steps: and taking argon, hydrogen and methane as growth atmosphere, and performing deposition growth for 5-10min at the deposition temperature of 800-1000 ℃ to obtain the nano-porous copper surface modified MnO/graphene composite electrode.
2. The method for preparing the nano-porous copper surface modified MnO/graphene composite electrode according to claim 1, wherein the method is characterized in that: the alloy preparation method in the step (1) is to prepare a single-phase solid solution CuMn alloy ingot by smelting and casting, and then rolling to obtain a CuMn alloy sheet with the thickness of 50-100 mu m.
3. The method for preparing the nano-porous copper surface modified MnO/graphene composite electrode according to claim 1, wherein the method is characterized in that: the heat treatment in the step (3) includes the steps of: placing the gradient nano porous copper in an atmosphere furnace, introducing 100sccm of hydrogen and 100sccm of argon, raising the temperature to 600-800 ℃ at a heating rate of 10 ℃/min, preserving the temperature for 30-120 minutes, and naturally cooling.
4. The method for preparing the nano-porous copper surface modified MnO/graphene composite electrode according to claim 1, wherein the method is characterized in that: the chemical vapor deposition process in the step (4) comprises the following steps: placing the heat-treated gradient nano porous copper in a rapid temperature-raising furnace, introducing 200sccm of hydrogen and 100sccm of argon, raising the temperature to 800-1000 ℃ at a heating rate of 10 ℃/min, introducing 2-40sccm of methane, growing for 5-10min, and rapidly removing and cooling the furnace tube.
5. The method for preparing the nano-porous copper surface modified MnO/graphene composite electrode according to claim 1, wherein the method is characterized in that: and (3) the surface morphology of the nano-porous copper surface modified MnO/graphene composite electrode prepared in the step (4) is sharp needle-shaped.
6. The nano-porous copper surface-modified MnO/graphene composite electrode produced by the production method according to any one of claims 1 to 5.
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| CN107958992A (en) * | 2017-11-09 | 2018-04-24 | 天津工业大学 | Porous binary NiMn oxide lithium cell negative pole materials and preparation method thereof |
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