CN114284505A - Porous copper current collector, preparation method thereof and application thereof in zinc/sodium ion battery - Google Patents
Porous copper current collector, preparation method thereof and application thereof in zinc/sodium ion battery Download PDFInfo
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- CN114284505A CN114284505A CN202111591328.1A CN202111591328A CN114284505A CN 114284505 A CN114284505 A CN 114284505A CN 202111591328 A CN202111591328 A CN 202111591328A CN 114284505 A CN114284505 A CN 114284505A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 48
- 239000010949 copper Substances 0.000 title claims abstract description 48
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 32
- 239000011701 zinc Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title abstract description 6
- 229910001415 sodium ion Inorganic materials 0.000 title abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 21
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910000906 Bronze Inorganic materials 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 7
- 239000003929 acidic solution Substances 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 17
- 239000003792 electrolyte Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- -1 polyethylene Polymers 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims description 4
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims description 4
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- XRFJZINEJXCFNW-UHFFFAOYSA-N [Zn+2].[O-][Mn]([O-])(=O)=O Chemical compound [Zn+2].[O-][Mn]([O-])(=O)=O XRFJZINEJXCFNW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- QEORIOGPVTWFMH-UHFFFAOYSA-N zinc;bis(trifluoromethylsulfonyl)azanide Chemical compound [Zn+2].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QEORIOGPVTWFMH-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 14
- 239000002184 metal Substances 0.000 abstract description 14
- 230000008021 deposition Effects 0.000 abstract description 10
- 229910000881 Cu alloy Inorganic materials 0.000 abstract description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007769 metal material Substances 0.000 abstract description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 13
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical class [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 7
- 239000010974 bronze Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 4
- 210000001787 dendrite Anatomy 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
Images
Classifications
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- 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 belongs to the technical field of advanced non-ferrous metal materials, relates to a high-performance copper alloy for electronics, and particularly relates to a porous copper current collector, a preparation method thereof and application thereof in a zinc/sodium ion battery, wherein the preparation method comprises the following steps: the bronze alloy is used as a precursor and is obtained by adopting an electrochemical dealloying method in an acidic solution; the acid solution is one or a mixture of more than two of hydrochloric acid, acetic acid, sulfuric acid, citric acid and oxalic acid; the concentration of the acidic solution is 0.01-5 mol L‑1. The porous copper current collector provided by the invention can induce the uniform deposition of metal zinc and improve the deposition stripping efficiency of zinc. After the zinc-free anode is assembled into a zinc battery without a negative electrode, no metal is usedZinc, so that the energy density of the battery can be greatly improved, the volume and the weight of the battery are reduced, and the application range of the battery is enlarged.
Description
Technical Field
The invention belongs to the technical field of advanced non-ferrous metal materials, relates to a high-performance copper alloy for electrons, and particularly relates to a porous copper current collector, a preparation method thereof and application thereof in a zinc/sodium ion battery.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
According to the research of the inventor, the defects of the target zinc ion battery include: 1. uncontrolled dendrite growth can exacerbate the generation of side reactions, resulting in low coulombic efficiency; 2. during the deposition stripping process, the zinc can generate large volume change, and the performance deterioration can be further aggravated; 3. in the assembly process of the zinc ion battery, the metal zinc cathode is excessively used, so that the energy density of the battery is reduced. In order to solve the problem of dendritic crystal growth, methods which can be adopted include zinc cathode surface modification, three-dimensional zinc cathode, diaphragm modification and electrolyte modification, however, the methods still can not effectively solve the problem of low energy density of the zinc ion battery. Meanwhile, due to the problems 2 and 3, the conventional zinc ion battery is large in size and weight, and is not beneficial to the application of the zinc ion battery.
Disclosure of Invention
In order to solve the problems of uncontrollable growth of zinc dendrite, low coulombic efficiency, excessive use of metal zinc, low energy density and large volume in the prior art, the invention aims to provide a porous copper current collector, a preparation method thereof and application in a zinc/sodium ion battery. After the zinc-free battery is assembled into a zinc battery without a negative electrode, the energy density of the battery can be greatly improved, the volume and the weight of the battery are reduced, and the application range of the battery is enlarged because metal zinc is not used.
In order to achieve the purpose, the technical scheme of the invention is as follows:
on one hand, the preparation method of the porous copper current collector is obtained by taking bronze alloy as a precursor and adopting an electrochemical dealloying method in an acid solution;
the acid solution is one or a mixture of more than two of hydrochloric acid, acetic acid, sulfuric acid, citric acid and oxalic acid;
the concentration of the acidic solution is 0.01-5 mol L-1。
The bronze alloy is used as a raw material, is a copper-tin alloy, has high tin content and unique property, can have good affinity with most metal cathodes, and can be used as a nucleating agent to induce uniform deposition and growth of metals. However, the inventor researches and finds that the bronze alloy is difficult to induce the uniform deposition of the metal zinc directly, so that the preparation method provided by the invention adopts an electrochemical dealloying method under an acidic condition, and can regulate and control the micro-morphology and the tin content in the bronze alloy, thereby inducing the uniform deposition of the metal zinc and improving the deposition stripping efficiency of the zinc. In addition, the metal activity of tin is high, the tin can directly react with hydrogen ions, and in order to improve the control of the tin content in the porous copper current collector, the invention adopts specific acid and concentration to ensure the control of the tin content in the porous copper current collector.
In another aspect, a porous copper current collector obtained by the above-described manufacturing method.
In a third aspect, the porous copper current collector is applied to a negative current collector of a zinc ion battery.
In a fourth aspect, a non-negative electrode zinc ion battery is composed of a positive current collector, a positive electrode, a diaphragm, electrolyte and a negative current collector, wherein the positive electrode is arranged on the positive current collector, and the negative current collector is the porous copper current collector.
In a fifth aspect, the non-negative electrode zinc ion battery is applied to the fields of electric appliances, energy sources or vehicles.
In a sixth aspect, a use of the above porous copper current collector in a secondary battery, the secondary battery is a lithium battery, a sodium battery, a potassium battery, a magnesium battery, a calcium battery or an aluminum battery.
The invention has the beneficial effects that:
1. the porous copper current collector can be prepared by an electrochemical dealloying method. The content of tin in the porous copper current collector of the product can be regulated and controlled by controlling parameters.
2. The bronze alloy adopted by the invention contains tin, and has good affinity with most metal cathodes due to the unique property of tin, and the micro-morphology of the bronze alloy and the content of tin are regulated and controlled by an electrochemical dealloying method to form a porous copper current collector, so that the tin in the porous copper current collector can be used as a nucleating agent to induce the uniform deposition and growth of metal.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
Fig. 1 is an XRD pattern of the porous copper current collector prepared in example 1 of the present invention;
fig. 2 is an SEM image of the porous copper current collector prepared in example 1 of the present invention;
fig. 3 is an SEM image of the porous copper current collector prepared in example 1 of the present invention;
FIG. 4 is a graph of cycle life for zinc cells prepared in example 1 of the present invention;
fig. 5 is a graph of coulombic efficiency for zinc cells prepared in example 1 of the present invention;
fig. 6 is a charge and discharge graph of a zinc battery prepared in example 1 of the present invention.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In order to solve the problems of uncontrollable growth of zinc dendrite, low coulombic efficiency, excessive use of metal zinc, low energy density and large volume in the prior art, the invention provides a porous copper current collector, a preparation method thereof and application thereof in a zinc/sodium ion battery.
The invention provides a typical implementation mode of a preparation method of a porous copper current collector, which is obtained by taking bronze alloy as a precursor and adopting an electrochemical dealloying method in an acid solution;
the acid solution is one or a mixture of more than two of hydrochloric acid, acetic acid, sulfuric acid, citric acid and oxalic acid;
the concentration of the acidic solution is 0.01-5 mol L-1。
The bronze alloy is used as a raw material, is prepared by adopting an electrochemical dealloying method under an acidic condition, and can regulate and control the micro morphology and the tin content in the bronze alloy, so that the uniform deposition of metal zinc can be induced, and the deposition stripping efficiency of zinc is improved. In addition, the invention adopts specific acid and concentration to ensure the control of the tin content in the porous copper current collector.
Wherein, the acid cleaning solution is one or a mixture of more than two of hydrochloric acid, acetic acid, sulfuric acid, citric acid and oxalic acid, wherein, the hydrochloric acid and the sulfuric acid are inorganic acids, the acetic acid, the citric acid and the oxalic acid are organic acids, the release of hydrogen ions of the inorganic acids in water is more complete, and the concentration of the acid solution is 0.01-1 mol L-1However, the hydrogen ions of the organic acid in the water are not completely released, and the concentration of the acidic solution is 1-5 mol L-1。
In some examples of this embodiment, the electrochemical dealloying process is performed in a galvanostatic manner. The electrochemical dealloying method can adopt a constant voltage method and a constant current method.
In one or more embodiments, the current density in the electrochemical dealloying process is 0.1 to 10mA cm-1。
In one or more embodiments, the time of the electrochemical dealloying method is 0.2 to 10 hours.
In another embodiment of the present invention, there is provided a porous copper current collector obtained by the above-mentioned preparation method.
In a third embodiment of the invention, the porous copper current collector is applied to a negative current collector of a zinc ion battery.
In a fourth embodiment of the present invention, a non-negative electrode zinc-ion battery is provided, which is composed of a positive electrode current collector, a positive electrode, a separator, an electrolyte, and a negative electrode current collector, wherein the positive electrode is disposed on the positive electrode current collector, and the negative electrode current collector is the above porous copper current collector.
In some examples of this embodiment, the positive electrode is selected from one or a mixture of two or more of manganese oxide, zinc manganate, and lithium manganate.
In some embodiments of this embodiment, the membrane is selected from a cellulose membrane, a glass fiber membrane, a polyethylene nonwoven fabric, or a microporous filter paper.
In some examples of this embodiment, the electrolyte comprises an aqueous electrolyte or an oil electrolyte.
The water system electrolyte consists of soluble zinc salt and water, and the concentration of the soluble salt is 0.2-10 mol L-1. The soluble salt is selected from one or a mixture of more than two of zinc sulfate, zinc trifluoromethanesulfonate, zinc chloride, bis (trifluoromethanesulfonyl) imide zinc, zinc hexafluorophosphate, lithium sulfate, bis (fluorosulfonyl) imide lithium and zinc perchlorate.
The oil electrolyte consists of soluble zinc salt, an organic solvent and an additive, wherein the concentration of the soluble salt is 0.1-2 mol L-1(ii) a The soluble salt is one or a mixture of more than two of zinc hexafluorophosphate, zinc trifluoromethanesulfonate, zinc perchlorate and bis-trifluoromethanesulfonylimide.
In a fifth embodiment of the invention, an application of the non-negative electrode zinc ion battery in the fields of electric appliances, energy sources or vehicles is provided.
In a sixth embodiment of the present invention, there is provided a use of the above porous copper current collector in a secondary battery, which is a lithium battery, a sodium battery, a potassium battery, a magnesium battery, a calcium battery or an aluminum battery.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1
A preparation method of a porous copper current collector comprises the following steps:
taking 2cm by 2cm bronze sheet, soaking in 0.125moL L-1In hydrochloric acid solution, electrochemical dealloying method is adopted, and current density is 1mA cm-2And the reaction time is 2 hours, and after the reaction is finished, the copper-based porous current collector can be prepared by washing with deionized water and drying.
Assembling the battery: the product is used as a current collector, a zinc foil is used as a negative electrode, 2M zinc sulfate aqueous solution is used as electrolyte, and glass fiber is used as a diaphragm.
The parameters for testing the coulombic efficiency are as follows: the discharge current was 0.5mA, the discharge time was 1h, the charge current was 0.5mA, and the charge voltage was 0.5V.
The parameters for testing cyclicity were: the charge and discharge current was 0.5mA, and the charge and discharge time was 1 h.
Fig. 1 is an XRD pattern of the porous copper current collector prepared in example 1 of the present invention, which is free of impurities, indicating that the product purity is high.
Fig. 2 and 3 are SEM images of the porous copper current collector prepared in example 1 of the present invention, demonstrating that the product exhibits a porous structure.
Fig. 4 is a cycle life diagram of a zinc battery prepared in example 1 of the present invention, in which the voltage is maintained stable during the battery cycle when the copper-based current collector is used, illustrating that the growth of dendrites is inhibited.
Fig. 5 is a coulombic efficiency chart of the zinc cell prepared in example 1 of the present invention, which maintains high and stable efficiency during the operation of the cell, further demonstrating the superiority of the current collector.
Fig. 6 is a charge-discharge curve diagram of the zinc battery prepared in example 1 of the present invention, which demonstrates that the battery can stably cycle for more than 200 hours.
Example 2
A preparation method of a porous copper current collector comprises the following steps:
taking 2cm by 2cm bronze sheet, soaking in 0.05moL L-1In the sulfuric acid solution, an electrochemical dealloying method is adopted, and the current density is 0.5mA cm-2And the reaction time is 4 hours, and after the reaction is finished, the copper-based porous current collector can be prepared by washing with deionized water and drying.
Example 3
A preparation method of a porous copper current collector comprises the following steps:
taking 2cm by 2cm bronze sheet, soaking in 0.5moL L-1In the acetic acid solution, an electrochemical dealloying method is adopted, and the current density is 5mA cm-2And the reaction time is 1h, and after the reaction is finished, the porous copper-based current collector can be prepared by washing with deionized water and drying.
Example 4
A preparation method of a porous copper current collector comprises the following steps:
taking 2cm by 2cm bronze sheet, soaking into 3.0moL L-1In the citric acid solution, an electrochemical dealloying method is adopted, and the current density is 8mA cm-2And the reaction time is 0.6h, and after the reaction is finished, the copper-based porous current collector can be prepared by washing with deionized water and drying.
Example 5
A preparation method of a porous copper current collector comprises the following steps:
taking 2cm by 2cm bronze sheet, soaking in 0.2moL L-1In hydrochloric acid solution, electrochemical dealloying method is adopted, and current density is 0.8mA cm-2And the reaction time is 1.2h, and after the reaction is finished, the copper-based porous current collector can be prepared by washing with deionized water and drying.
Example 6
A preparation method of a porous copper current collector comprises the following steps:
taking 2cm by 2cm bronze sheet, soaking in 4.5moL L-1In the oxalic acid solution, an electrochemical dealloying method is adopted, and the current density is 8mA cm-2And the reaction time is 1.1h, and after the reaction is finished, the copper-based porous current collector can be prepared by washing with deionized water and drying.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a porous copper current collector is characterized in that a bronze alloy is used as a precursor, and is obtained by adopting an electrochemical dealloying method in an acid solution;
the acid solution is one or a mixture of more than two of hydrochloric acid, acetic acid, sulfuric acid, citric acid and oxalic acid;
the concentration of the acidic solution is 0.01-5 mol L-1。
2. The method of preparing a porous copper current collector as claimed in claim 1, wherein the electrochemical dealloying is performed in a constant current manner.
3. The method of claim 2, wherein the current density in the electrochemical dealloying process is 0.1 to 10mA cm-1；
Or the time of the electrochemical dealloying method is 0.2-10 h.
4. A porous copper current collector obtained by the production method according to any one of claims 1 to 3.
5. Use of the porous copper current collector of claim 4 in a negative current collector for a zinc ion battery.
6. A non-negative electrode zinc ion battery, which consists of a positive electrode current collector, a positive electrode, a diaphragm, electrolyte and a negative electrode current collector, wherein the positive electrode is arranged on the positive electrode current collector, and the non-negative electrode zinc ion battery is characterized in that the negative electrode current collector is the porous copper current collector in claim 4.
7. The non-negative electrode zinc ion battery according to claim 6, wherein the positive electrode is selected from one or a mixture of more than two of manganese oxide, zinc manganate and lithium manganate;
or the diaphragm is selected from a cellulose diaphragm, a glass fiber membrane, a polyethylene non-woven fabric or microporous filter paper.
8. The non-negative electrode zinc-ion battery according to claim 6, wherein the electrolyte comprises an aqueous electrolyte or an oil electrolyte;
preferably, the aqueous electrolyte consists of soluble zinc salt and water, and the concentration of the soluble salt is 0.2-10 mol L-1(ii) a Preferably, the soluble salt is selected from one or a mixture of more than two of zinc sulfate, zinc trifluoromethanesulfonate, zinc chloride, zinc bistrifluoromethanesulfonimide, zinc hexafluorophosphate, lithium sulfate, lithium bistrifluorosulfonimide and zinc perchlorate.
Preferably, the oil electrolyte consists of soluble zinc salt, an organic solvent and an additive, and the concentration of the soluble salt is 0.1-2 mol L-1(ii) a Preferably, the soluble salt is selected from one or a mixture of more than two of zinc hexafluorophosphate, zinc trifluoromethanesulfonate, zinc perchlorate and zinc bistrifluoromethanesulfonylimide.
9. The application of the non-negative electrode zinc ion battery of any one of claims 6 to 8 in the fields of electric appliances, energy sources or vehicles.
10. Use of the porous copper current collector of claim 4 in a secondary battery which is a lithium, sodium, potassium, magnesium, calcium or aluminum battery.
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