CN114023928A - Preparation method for in-situ construction of bimetallic oxide integrated electrode by hierarchical porous copper - Google Patents
Preparation method for in-situ construction of bimetallic oxide integrated electrode by hierarchical porous copper Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 137
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 87
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000010276 construction Methods 0.000 title claims abstract description 21
- 239000000956 alloy Substances 0.000 claims abstract description 69
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 69
- 238000010438 heat treatment Methods 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000002485 combustion reaction Methods 0.000 claims abstract description 23
- 230000002269 spontaneous effect Effects 0.000 claims abstract description 22
- 230000009467 reduction Effects 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011258 core-shell material Substances 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- 238000011946 reduction process Methods 0.000 claims abstract description 3
- 239000011148 porous material Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 238000009826 distribution Methods 0.000 claims description 11
- 238000000137 annealing Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 8
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 238000009792 diffusion process Methods 0.000 claims description 6
- 210000003041 ligament Anatomy 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 239000006104 solid solution Substances 0.000 claims description 3
- 238000003723 Smelting Methods 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000011159 matrix material Substances 0.000 description 17
- 229910001416 lithium ion Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 238000010952 in-situ formation Methods 0.000 description 10
- 239000011572 manganese Substances 0.000 description 10
- 229910001415 sodium ion Inorganic materials 0.000 description 10
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 230000009977 dual effect Effects 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910000314 transition metal oxide Inorganic materials 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 244000137852 Petrea volubilis Species 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 229910016411 CuxO Inorganic materials 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
- H01M4/662—Alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
-
- 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 relates to a hierarchical porous copper in-situ construction bimetallic oxide CuxThe preparation method of the O/MnO integrated electrode structure comprises the following steps: preparing a CuMn alloy sheet; preparing graded porous copper with residual Mn content of 10-50% by adopting a dealloying method for the CuMn alloy sheet; spontaneous combustion; carrying out heat treatment to obtain a metal @ oxide core-shell structure with controllable oxide content; carrying out low-temperature reduction treatment, wherein the low-temperature reduction process comprises the following steps: hydrogen is taken as protective atmosphere, the reduction temperature is 200-300 ℃, the reduction time is 10-30min, and the graded porous copper in-situ construction bimetallic oxide Cu is obtainedxAn O/MnO unitary electrode structure wherein x is 1, 2.
Description
Technical Field
The invention relates to a current collector andthe technical field of electrodes and preparation thereof, in particular to a graded porous copper in-situ construction bimetallic oxide CuxA preparation method of an O/MnO (x ═ 1,2) integrated electrode.
Background
Today's society, the economic scale continues to expand, which makes the demand for energy ever-increasing. The traditional fossil energy faces the problem of resource exhaustion, and the combustion products thereof can cause air pollution and aggravate the greenhouse effect. In recent years, electrochemical energy storage devices represented by lithium/sodium ion batteries have been developed, and are becoming the next-generation clean energy with a promise of replacing fossil energy. Sodium and lithium belong to alkali metal elements, have similar physical and chemical properties, and the working principle of sodium ion batteries is almost the same as that of lithium ion batteries. The lithium/sodium ion battery is widely applied to daily life and production as a high-efficiency rechargeable energy storage device. The negative electrode material plays an important role in the performance of the lithium/sodium ion battery. At present, transition metal oxides are the most promising negative electrode materials in lithium/sodium ion batteries, such as CuO, Cu2O, MnO, etc. are widely used in negative electrode materials due to their advantages of low cost, environmental friendliness, high specific capacity, etc. However, during the circulation process, the transition metal oxide undergoes a conversion reaction with lithium/sodium ions, and the volume of the transition metal oxide expands after the circulation process, so that the electrode is pulverized and falls off, and the capacity is reduced. At the same time, the conductivity of this class of materials is also in need of improvement.
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 dual metal oxide CuxO/MnO (x ═ 1,2) integrated electrode in-situ constructed by graded porous copper, so as to overcome the disadvantages of the prior art. The technical scheme of the invention is realized as follows:
hierarchical porous copper in-situ construction bimetallic oxide CuxPreparation method of O/MnO integrated electrode, and method for preparing O/MnO integrated electrodeIs characterized in that: 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 20-50%, and the balance is Mn, and the CuMn alloy is processed into CuMn alloy sheets with the thickness of 50-400 um;
(2) preparing the CuMn alloy sheet prepared in the step (1) into graded porous copper with residual Mn content of 10-50% by adopting a dealloying method;
(3) placing the graded porous copper prepared in the step (2) in an air atmosphere for spontaneous combustion, and preliminarily forming a bimetallic oxide on the surface of the ligament;
(4) carrying out heat treatment on the spontaneous combustion grading porous copper prepared in the step (3), wherein the heat treatment process comprises the following steps: under the air atmosphere, the heat treatment temperature is 200-800 ℃, and the heat treatment time is 30-180min, so that the metal @ oxide core-shell structure with controllable oxide content is obtained;
(5) carrying out low-temperature reduction treatment on the graded porous copper subjected to the heat treatment in the step (4), wherein the low-temperature reduction process comprises the following steps: hydrogen is taken as protective atmosphere, the reduction temperature is 200-300 ℃, the reduction time is 10-30min, and the graded porous copper in-situ construction bimetallic oxide Cu is obtainedxAn O/MnO integral electrode wherein x is 1, 2.
Further: 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 50-400 um.
Further: in the method for preparing the alloy in the step (1), after the CuMn alloy sheet is prepared, the CuMn alloy sheet is subjected to diffusion annealing at the temperature of 500 ℃ and 800 ℃ for 0.5 to 6 hours.
Further: the diffusion annealing method comprises the following steps: the alloy sheet is placed in a high temperature furnace, argon gas with the flow rate of 100 plus 200sccm and hydrogen gas with the flow rate of 150 plus 300sccm are introduced, the temperature is raised to 800 plus 500 ℃ at the heating rate of 10 ℃/min, the temperature is kept for 0.5 to 6 hours, and then the alloy sheet is rapidly removed for cooling.
Further: the dealloying method in the step (2) comprises the following specific steps: weak acid or ammonium salt including ammonium sulfate is used as corrosive liquid, the temperature is controlled within 25-55 ℃, and the corrosion time is controlled within 10-360min or until bubbles completely disappear according to the residual Mn amount requirement.
Further: the heat treatment in the step (4) includes the steps of: placing the spontaneous combustion grading porous copper in an atmosphere furnace, raising the temperature to 200-800 ℃ at the heating rate of 10 ℃/min under the air atmosphere, preserving the temperature for 30-180min, and then naturally cooling.
Further: the low-temperature reduction treatment in the step (4) comprises the following steps: and (3) placing the graded porous copper subjected to heat treatment in an atmosphere furnace, introducing 50-200sccm hydrogen, raising the temperature to 200-300 ℃ at the heating rate of 10 ℃/min, preserving the temperature for 10-30min, and then quickly removing the furnace tube for cooling.
Further: the nano porous copper prepared in the step (5) is used for in-situ construction of CuxThe appearance of the O/MnO bimetal oxide integrated electrode is a nano porous structure with the pore size distribution of about 50-200nm or a bicontinuous hierarchical porous structure with the pore size distribution of 1-10 mu m of large pores and the pore size distribution of 10-200nm of small pores.
The composite electrode slice prepared by the preparation method is a porous flexible self-supporting body, the ligament is of a continuous metal @ oxide core-shell structure, and the oxide layer contains defects such as reduced metal, oxygen vacancy and the like.
Compared with the prior art, the hierarchical porous copper in-situ construction of the bimetallic oxide CuxThe preparation method of the O/MnO (x ═ 1,2) integrated electrode has the following advantages:
1. according to the invention, a CuMn alloy matrix is directly prepared, then the raw material ratio, the annealing temperature and the annealing time of the CuMn alloy matrix are controlled, so that Mn/CuMn dual-phase alloys with different contents are directly obtained, the dealloying temperature and the dealloying time of the CuMn alloy matrix are controlled, and a chemical dealloying method is combined to form the double three-dimensional graded porous copper; 2. the content of copper/manganese oxide in the nano-porous copper is improved by combining a heat treatment process; 3. on the basis, the copper/manganese oxide lithium battery negative electrode material which takes the graded porous copper as the matrix and is uniformly distributed on the matrix is directly obtained through low-temperature reduction treatment. The method used in the invention is simpler and lower in cost than the preparation method existing in the prior art, and because the bimetallic oxide is directly formed on the graded porous copper matrix, the combination of the oxide and the matrix is tighter.
Drawings
FIG. 1 is an EDAX diagram of a graded porous copper section obtained in example 1
FIG. 2 shows the in-situ formation of a dual metal oxide Cu from graded porous copper obtained in example 1xSEM image of O/MnO (x ═ 1,2) integrated electrode
FIG. 3 shows the in-situ formation of a dual metal oxide Cu from graded porous copper obtained in example 1xXRD pattern of O/MnO (x ═ 1,2) integrated electrode
FIG. 4 shows the in-situ formation of a dual metal oxide Cu from the graded porous copper obtained in example 1xCharge-discharge curve of first 5 circles of lithium ion battery assembled by O/MnO (x ═ 1,2) integrated electrode
FIG. 5 is the in-situ construction of bimetallic oxide Cu for graded porous copper in example 1xCharge-discharge curve of first 5 circles of sodium ion battery assembled by O/MnO (x ═ 1,2) integrated electrode
FIG. 6 is the in-situ construction of bimetallic oxide Cu for graded porous copper in example 1xMultiplying power curve of lithium ion battery assembled by O/MnO (x ═ 1,2) integrated electrode
FIG. 7 shows the in-situ formation of bimetallic oxide Cu from graded porous copper obtained in example 2xCharge-discharge curve of first 5 circles of lithium ion battery assembled by O/MnO (x ═ 1,2) integrated electrode
FIG. 8 is the in-situ construction of bimetallic oxide Cu for graded porous copper in example 2xMultiplying power curve of lithium ion battery assembled by O/MnO (x ═ 1,2) integrated electrode
FIG. 9 shows the in-situ formation of a dual metal oxide Cu from graded porous copper obtained in example 3xSEM image of O/MnO (x ═ 1,2) integrated electrode
FIG. 10 shows the in-situ formation of a dual metal oxide Cu for graded porous copper obtained in example 4xSEM image of O/MnO (x ═ 1,2) integrated electrode
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.
In order to solve the problem of poor conductivity of the transition metal oxide, the nano porous metal is introduced, and meanwhile, a three-dimensional porous structure is constructed on the transition metal oxide, so that the electrode material of the bimetal oxide with a self-supporting surface is successfully prepared, and the active substance and the conductive porous metal matrix have a lattice matching relationship, so that the active substance and the conductive porous metal matrix can grow together tightly and are difficult to fall off. The advantages are that: 1. a hierarchical porous structure is constructed to realize uniform current distribution and geometric constraint cooperative coupling, and the micropores can quickly realize surface current density distribution, play a role of uniform macroscopic electric field and have greater advantages in promoting ion/electron transportation; 2. the nano porous metal is used as a conductive matrix, and the interface bonding force and the conductive capacity can be effectively improved by an oxidation-reduction method; 3. the nano porous metal is used as a growth substrate, and the problem of volume expansion of the electrode material can be inhibited through the self-supporting oxide; 4. a porous bimetal oxide is constructed, a high specific surface area is provided, and more active substances can be loaded, so that the specific capacity is improved; 5. 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 invention relates to a graded porous copper in-situ construction method of bimetallic oxide CuxAn O/MnO (x ═ 1,2) integral electrode comprising the steps of:
(1) preparing an alloy: preparing a CuMn alloy, wherein in the CuMn alloy, the atomic content of Cu is 20-50%, and the atomic content of Mn is 50-80%; the CuMn alloy is processed into CuMn alloy sheets with the thickness of 40-500um, the alloy sheets are placed in a high-temperature furnace, 100-plus-200 sccm argon and 150-plus-300 sccm hydrogen are introduced, the temperature is raised to 500-plus-800 ℃ at the heating rate of 10 ℃/min, the temperature is kept for 0.5-6h, and then the alloy sheets are quickly removed for cooling;
(2) preparing the CuMn alloy prepared in the step (1) into graded porous copper with residual Mn content of 10-50% by adopting a dealloying method; wherein the chemical dealloying method comprises the following steps: weak acid or ammonium salt including ammonium sulfate is used as corrosive liquid, the temperature is controlled within 25-55 ℃, and the corrosion time is controlled within 10-360min or until bubbles completely disappear according to the residual Mn amount requirement.
(3) Spontaneous combustion is carried out on the graded porous copper prepared in the step (2) to prepare a bimetal oxide which is preliminarily formed on the surface of the ligament; the method for treating the spontaneous combustion graded porous copper comprises the following steps: and (3) cleaning the dealloyed graded porous copper in water and absolute ethyl alcohol for 1-3 times, and taking out, wherein spontaneous combustion is generated under the air atmosphere due to sudden increase of surface energy.
(4) Preparing a metal @ oxide core-shell structure with controllable oxide content from the spontaneous combustion grading porous copper prepared in the step (3) by adopting a heat treatment method; wherein the heat treatment process comprises the following steps: taking air as atmosphere, raising the temperature to 800 ℃ at the heating rate of 10 ℃/min, and naturally cooling after preserving the temperature for 30-180 min.
(5) Preparing the graded porous copper prepared in the step (4) after heat treatment by adopting a low-temperature reduction treatment method to prepare the graded porous copper in-situ construction bimetallic oxide CuxAn O/MnO (x ═ 1,2) integral electrode; the method for low-temperature reduction treatment comprises the following steps: introducing 50-200sccm hydrogen, raising the temperature to 100-300 ℃ at a heating rate of 10 ℃/min, preserving the temperature for 10-30min, and then quickly removing the furnace tube for cooling to obtain the graded porous copper in-situ constructed CuxO/MnO (x is 1,2) bimetallic oxide integrated electrode, and the prepared hierarchical porous copper in-situ structure bimetallic oxide CuxThe shape of the O/MnO (x ═ 1,2) integrated electrode is a nano porous structure with the pore size distribution of about 50-200nm or a bicontinuous hierarchical porous structure with the pore size distribution of 1-10 mu m and the pore size distribution of 10-200 nm.
Example 1
Hierarchical porous copper in-situ construction bimetallic oxide CuxThe preparation method of the O/MnO (x ═ 1,2) integrated electrode comprises the following steps:
(1) preparing an alloy: the atomic content ratio of CuMn is 30: 70, rolling the CuMn alloy ingot into an alloy sheet with the thickness of 100um in a casting-rolling mode, placing the alloy sheet in a high-temperature furnace, introducing 100sccm of argon and 150sccm of hydrogen, raising the temperature to 600 ℃ at the heating rate of 10 ℃/min, preserving the temperature for 0.5h, and then quickly removing, cooling and cooling;
(2) dealloying to prepare graded porous copper: polishing the alloy sheet in the step (1) by using sand paper, corroding the polished alloy sheet, and freely corroding the polished alloy sheet for 30min at 50 ℃ by using 1mol/L ammonium sulfate;
(3) spontaneous combustion: washing the graded porous copper prepared in the step (2) with deionized water and absolute ethyl alcohol for 1 time, and then placing the copper in the air for spontaneous combustion;
(4) and (3) heat treatment: placing the self-ignited graded porous copper in an atmosphere furnace, heating to 600 ℃ at the speed of 10 ℃/min, and preserving heat for 60 min;
(4) and (3) low-temperature reduction treatment: placing the graded nano-porous copper prepared by the heat treatment in the step (3) in an atmosphere furnace in an H atmosphere2Heating to 200 ℃ at a speed of 10 ℃/min under the atmosphere of 100sccm, preserving heat for 10min, and rapidly removing and cooling the sample to obtain the graded porous copper in-situ constructed bimetallic oxide CuxAnd an O/MnO (x is 1,2) integrated electrode.
(5) Assembling the battery: placing the obtained electrode material in an anaerobic glove box to assemble a button lithium/sodium ion battery;
(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.
FIG. 1 is a cross-sectional EDAX diagram of a CuMn alloy flake in example 1 after 30min of dealloying in 1mol/L ammonium sulfate solution, and it can be seen from the EDAX diagram that graded porous copper with 50.72 wt% of residual Mn element is formed after the material is dealloyed;
FIGS. 2 and 3 are schematic views of in-situ formation of Cu from hierarchical porous Cu in example 1xSEM image and XRD pattern of O/MnO (x ═ 1,2) bimetal oxide integrated electrode,the surface of the material is a porous structure of about 100nm according to SEM pictures, and the porous structure substance can be determined to be Cu through XRD pictures2O/CuO/MnO。
FIGS. 4 and 5 are schematic views of in-situ formation of Cu from hierarchical porous Cu in example 1xThe charge-discharge curve of the lithium/sodium ion battery assembled by the O/MnO (x is 1,2) bimetal oxide integrated electrode can be known, and the charge-discharge platform of the material is stable and has higher specific capacity no matter the material is used for testing the lithium/sodium ion battery through the charge-discharge curve.
FIG. 6 is the in-situ construction of Cu in hierarchical porous copper in example 1xThe multiplying power curve of the lithium ion battery assembled by the O/MnO (x is 1,2) bimetal oxide integrated electrode is that the current density is 0.2mA/cm2The specific capacity is 7.1mAh/cm2When the current density was increased to 1.0mA/cm2The specific capacity is 4.5mAh/cm2The specific capacity can be kept at 63.4%, and the rate capability is good.
Example 2
(1) Preparing an alloy: the same as example 1;
(2) dealloying to prepare the nano porous metal: polishing the alloy sheet in the step (1) by using sand paper, corroding the polished alloy sheet, and freely corroding the polished alloy sheet for 50min at 50 ℃ by using 0.5mol/L ammonium sulfate; (ii) a
(3) Spontaneous combustion: fully washing the graded porous copper prepared in the step (2) with deionized water and absolute ethyl alcohol for 1 time, putting the material in vacuum for spontaneous combustion,
(4) and (3) heat treatment: placing the spontaneous combustion grading porous copper prepared in the step (3) in an atmosphere furnace, heating to 400 ℃ at a speed of 10 ℃/min, and preserving heat for 120 min;
(4) and (3) low-temperature reduction treatment: placing the heat-treated nano-porous metal prepared in the step (3) in an atmosphere furnace in H2Heating to 200 ℃ at a speed of 10 ℃/min under the atmosphere of 50sccm, preserving heat for 10min, and rapidly removing and cooling the sample to obtain the graded porous copper in-situ constructed bimetallic oxide CuxAn O/MnO (x ═ 1,2) integral electrode;
(5) assembling the battery and testing the performance: same as example 1
FIG. 7 shows the in-situ formation of bimetallic oxides from graded porous copper in example 2CuxThe O/MnO (x is 1,2) integrated electrode is assembled into a charge-discharge curve of the lithium ion battery, and the charge-discharge platform of the material is stable and has higher specific capacity through the charge-discharge curve.
FIG. 8 is the in-situ construction of bimetallic oxide Cu for graded porous copper in example 2xMultiplying power curve of lithium ion battery assembled by O/MnO (x is 1,2) integrated electrode, and current density is 0.2mA/cm2The specific capacity is 9.2mAh/cm2When the current density was increased to 1.0mA/cm2The specific capacity is 4.8mAh/cm2The specific capacity can be kept at 52.2%, and the rate capability is good.
Example 3
(1) Preparing an alloy: the alloy sheet obtained in the same example 1 was diffusion annealed at 650 ℃ for 3 hours;
(2) dealloying to prepare the nano porous metal: polishing the alloy sheet in the step (1) by using sand paper, corroding the polished alloy sheet, and freely corroding the polished alloy sheet for 120min at the temperature of 20 ℃ by using 0.5mol/L ammonium sulfate;
(3) spontaneous combustion: fully washing the graded porous copper prepared in the step (2) with deionized water and absolute ethyl alcohol for 1 time, putting the material in vacuum for spontaneous combustion,
(4) and (3) heat treatment: placing the spontaneous combustion grading porous copper prepared in the step (2) in an atmosphere furnace, heating to 800 ℃ at a speed of 10 ℃/min, and preserving heat for 30 min;
(5) and (3) low-temperature reduction treatment: placing the graded porous copper prepared by the heat treatment in the step (3) in an atmosphere furnace in H2Heating to 300 ℃ at a speed of 10 ℃/min under the atmosphere of 50sccm, preserving heat for 20min, and rapidly removing and cooling the sample to obtain the graded porous copper in-situ constructed bimetallic oxide CuxAn O/MnO (x ═ 1,2) integral electrode;
(5) assembling the battery and testing the performance: same as example 1
FIG. 9 shows the in-situ construction of bimetallic oxide Cu by graded porous copper in example 3xAnd (3) SEM images of the O/MnO (x ═ 1,2) integrated electrode, wherein the section of the material is of a hierarchical pore structure with macropores wrapping micropores, and the pore diameter of the micropores is about 50 nm.
Example 4
(1) Preparing an alloy: the alloy sheet obtained in the same example 1 was subjected to diffusion annealing at 700 ℃ for 1 hour;
(2) dealloying to prepare the nano porous metal: polishing the alloy sheet in the step (1) by using sand paper, corroding the polished alloy sheet, and freely corroding the polished alloy sheet for 120min at the temperature of 30 ℃ by using 0.5mol/L ammonium sulfate;
(3) spontaneous combustion: fully washing the graded porous copper prepared in the step (2) with deionized water and absolute ethyl alcohol for 1 time, putting the material in vacuum for spontaneous combustion,
(4) and (3) heat treatment: placing the spontaneous combustion grading porous copper prepared in the step (2) in an atmosphere furnace, heating to 600 ℃ at the speed of 10 ℃/min, and preserving heat for 90 min;
(54) and (3) low-temperature reduction treatment: placing the heat-treated nano-porous metal prepared in the step (3) in an atmosphere furnace in H2Heating to 300 ℃ at a speed of 10 ℃/min under the atmosphere of 50sccm, preserving heat for 10min, and rapidly removing and cooling the sample to obtain the graded porous copper in-situ constructed bimetallic oxide CuxAn O/MnO (x ═ 1,2) integral electrode;
(6) assembling the battery and testing the performance: same as example 1
FIG. 10 shows the in-situ formation of dual metal oxide Cu by graded porous copper in example 4xThe SEM image of the O/MnO (x ═ 1,2) integrated electrode revealed that the surface of the material had a nanoporous structure with pore diameters of about 20nm, and the ligament had a porous structure with pore diameters of about 5 nm.
According to the invention, a CuMn alloy matrix is directly prepared, the raw material ratio, the annealing temperature and the annealing time of the CuMn alloy matrix are controlled, so that Mn/CuMn dual-phase alloys with different contents are directly obtained, and a chemical dealloying method is combined to form the dual three-dimensional graded porous copper; controlling the dealloying temperature and time of the CuMn alloy matrix so as to directly obtain graded porous copper; heat treatment in air atmosphere, and control of heat treatment process are combined, so that the content of copper/manganese oxide in the nano porous copper is increased; on the basis, the lithium/sodium electric negative electrode material which takes the nano-porous copper as the matrix and is uniformly distributed with the copper/manganese bimetallic oxide on the matrix is directly obtained through the final low-temperature reduction treatment. Compared with the preparation method in the prior art, the method provided by the invention is simple and has lower cost, and the oxide is directly formed on the nano-porous copper matrix, so that the oxide and the matrix are combined 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 (9)
1. Hierarchical porous copper in-situ construction bimetallic oxide CuxThe preparation method of the O/MnO integrated 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 20-50%, and the balance is Mn, and the CuMn alloy is processed into CuMn alloy sheets with the thickness of 50-400 um;
(2) preparing the CuMn alloy sheet prepared in the step (1) into graded porous copper with residual Mn content of 10-50% by adopting a dealloying method;
(3) placing the graded porous copper prepared in the step (2) in an air atmosphere for spontaneous combustion, and preliminarily forming a bimetallic oxide on the surface of the ligament;
(4) carrying out heat treatment on the spontaneous combustion grading porous copper prepared in the step (3), wherein the heat treatment process comprises the following steps: under the air atmosphere, the heat treatment temperature is 200-800 ℃, and the heat treatment time is 30-180min, so that the metal @ oxide core-shell structure with controllable oxide content is obtained;
(5) carrying out low-temperature reduction treatment on the graded porous copper subjected to the heat treatment in the step (4), wherein the low-temperature reduction process comprises the following steps: hydrogen is taken as protective atmosphere, the reduction temperature is 200-300 ℃, the reduction time is 10-30min, and the graded porous copper in-situ construction bimetallic oxide Cu is obtainedxAn O/MnO integral electrode wherein x is 1, 2.
2. The graded porous copper in situ built bimetallic oxide Cu as in claim 1xThe preparation method of the O/MnO integrated electrode is characterized by comprising the following steps: the steps of (A), (B), (C), (B), (C), (B), (C), (B), (C)1) The alloy preparation method comprises the steps of preparing a single-phase solid solution CuMn alloy ingot by a smelting and casting method, and then rolling to obtain a CuMn alloy sheet with the thickness of 50-400 mu m.
3. The graded porous copper in situ built bimetallic oxide Cu as in claim 1xThe preparation method of the O/MnO integrated electrode is characterized by comprising the following steps: in the method for preparing the alloy in the step (1), after the CuMn alloy sheet is prepared, the CuMn alloy sheet is subjected to diffusion annealing at the temperature of 500 ℃ and 800 ℃ for 0.5 to 6 hours.
4. The graded porous copper in-situ built bimetallic oxide Cu of claim 3xThe preparation method of the O/MnO integrated electrode is characterized by comprising the following steps: the diffusion annealing method comprises the following steps: placing the alloy sheet in a high temperature furnace, and introducing 100-200sccm
The temperature of argon and hydrogen with the flow rate of 150 plus 300sccm is increased to 800 plus 500 plus at the heating rate of 10 ℃/min, the temperature is maintained for 0.5 to 6 hours, and then the mixture is rapidly removed for cooling.
5. The graded porous copper in situ built bimetallic oxide Cu as in claim 1xThe preparation method of the O/MnO integrated electrode is characterized by comprising the following steps: the dealloying method in the step (2) comprises the following specific steps: weak acid or ammonium salt including ammonium sulfate is used as corrosive liquid, the temperature is controlled within 25-55 ℃, and the corrosion time is controlled within 10-360min or until bubbles completely disappear according to the residual Mn amount requirement.
6. The graded porous copper in situ built bimetallic oxide Cu as in claim 1xThe preparation method of the O/MnO integrated electrode is characterized by comprising the following steps: the heat treatment in the step (4) includes the steps of: placing the spontaneous combustion grading porous copper in an atmosphere furnace, raising the temperature to 200-800 ℃ at the heating rate of 10 ℃/min under the air atmosphere, preserving the temperature for 30-180min, and then naturally cooling.
7. The graded porous copper in situ built bimetallic oxide Cu as in claim 1xO/MnO integrated electrodeThe preparation method is characterized by comprising the following steps: the low-temperature reduction treatment in the step (4) comprises the following steps: and (3) placing the graded porous copper subjected to heat treatment in an atmosphere furnace, introducing 50-200sccm hydrogen, raising the temperature to 200-300 ℃ at the heating rate of 10 ℃/min, preserving the temperature for 10-30min, and then quickly removing the furnace tube for cooling.
8. The graded porous copper in situ built bimetallic oxide Cu as in claim 1xThe preparation method of the O/MnO integrated electrode is characterized by comprising the following steps: the nano porous copper prepared in the step (5) is used for in-situ construction of CuxThe appearance of the O/MnO bimetal oxide integrated electrode is a nano porous structure with the pore size distribution of about 50-200nm or a bicontinuous hierarchical porous structure with the pore size distribution of 1-10 mu m of large pores and the pore size distribution of 10-200nm of small pores.
9. Hierarchical porous copper in-situ structure Cu prepared by the preparation method according to any one of claims 1 to 8xO/MnO bimetal oxide integrated electrode.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024026970A1 (en) * | 2022-08-01 | 2024-02-08 | 宁德时代新能源科技股份有限公司 | Conductive film, preparation method therefor, electrode, current collector, secondary battery and apparatus |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107123811A (en) * | 2017-04-11 | 2017-09-01 | 华南理工大学 | Double yardstick porous copper-aluminum-manganese shape memory alloy composites and preparation method and application |
| 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 |
| CN108188400A (en) * | 2017-12-25 | 2018-06-22 | 西安理工大学 | A kind of micro-nano twin-stage Porous Cu and preparation method thereof |
| CN110635103A (en) * | 2019-08-29 | 2019-12-31 | 天津工业大学 | Flexible nano porous metal oxide cathode for secondary battery and preparation method thereof |
| CN111009644A (en) * | 2019-11-13 | 2020-04-14 | 天津工业大学 | Preparation method of nano-porous copper surface modified MnO/graphene composite electrode |
| CN112349875A (en) * | 2020-10-23 | 2021-02-09 | 四川大学 | Lithium ion battery copper-copper oxide integrated cathode based on hollow tubular three-dimensional nano porous structure and preparation method |
| CN113258050A (en) * | 2020-12-23 | 2021-08-13 | 天津工业大学 | Five-element high-entropy alloy oxide negative electrode material and preparation method and application thereof |
-
2021
- 2021-08-31 CN CN202111023543.1A patent/CN114023928A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107123811A (en) * | 2017-04-11 | 2017-09-01 | 华南理工大学 | Double yardstick porous copper-aluminum-manganese shape memory alloy composites and preparation method and application |
| 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 |
| CN108188400A (en) * | 2017-12-25 | 2018-06-22 | 西安理工大学 | A kind of micro-nano twin-stage Porous Cu and preparation method thereof |
| CN110635103A (en) * | 2019-08-29 | 2019-12-31 | 天津工业大学 | Flexible nano porous metal oxide cathode for secondary battery and preparation method thereof |
| CN111009644A (en) * | 2019-11-13 | 2020-04-14 | 天津工业大学 | Preparation method of nano-porous copper surface modified MnO/graphene composite electrode |
| CN112349875A (en) * | 2020-10-23 | 2021-02-09 | 四川大学 | Lithium ion battery copper-copper oxide integrated cathode based on hollow tubular three-dimensional nano porous structure and preparation method |
| CN113258050A (en) * | 2020-12-23 | 2021-08-13 | 天津工业大学 | Five-element high-entropy alloy oxide negative electrode material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 郭鸿发等: "《冶金工程设计 第1册 设计基础》", 冶金工业出版社, pages: 248 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024026970A1 (en) * | 2022-08-01 | 2024-02-08 | 宁德时代新能源科技股份有限公司 | Conductive film, preparation method therefor, electrode, current collector, secondary battery and apparatus |
| WO2024026620A1 (en) * | 2022-08-01 | 2024-02-08 | 宁德时代新能源科技股份有限公司 | Conducting film and preparation method therefor, electrode, current collector, secondary battery and device |
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