CN117558892A - Lamellar nanoporous Zn/Cu/Al 2 Cu alloy electrode and preparation method and application thereof - Google Patents
Lamellar nanoporous Zn/Cu/Al 2 Cu alloy electrode and preparation method and application thereof Download PDFInfo
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000011701 zinc Substances 0.000 claims abstract description 122
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 41
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 35
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000006023 eutectic alloy Substances 0.000 claims abstract description 7
- 210000003041 ligament Anatomy 0.000 claims abstract description 6
- 239000011258 core-shell material Substances 0.000 claims abstract description 5
- 239000002344 surface layer Substances 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 113
- 239000000243 solution Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- 238000003723 Smelting Methods 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 239000010410 layer Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 229910052593 corundum Inorganic materials 0.000 claims description 10
- 239000010431 corundum Substances 0.000 claims description 10
- 230000007797 corrosion Effects 0.000 claims description 9
- 238000005260 corrosion Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 6
- 229910001338 liquidmetal Inorganic materials 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000005498 polishing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 229910017767 Cu—Al Inorganic materials 0.000 claims description 2
- 238000006073 displacement reaction Methods 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims description 2
- 230000005496 eutectics Effects 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 abstract description 17
- 239000000956 alloy Substances 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 7
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- 238000009713 electroplating Methods 0.000 abstract description 6
- 230000006911 nucleation Effects 0.000 abstract description 6
- 238000010899 nucleation Methods 0.000 abstract description 6
- 230000002441 reversible effect Effects 0.000 abstract description 3
- 229910016343 Al2Cu Inorganic materials 0.000 abstract 7
- 210000004027 cell Anatomy 0.000 description 26
- 239000000203 mixture Substances 0.000 description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 14
- 239000004744 fabric Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 7
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- WPPDFTBPZNZZRP-UHFFFAOYSA-N aluminum copper Chemical compound [Al].[Cu] WPPDFTBPZNZZRP-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 208000032953 Device battery issue Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000447 polyanionic polymer Chemical class 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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- 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
- H01M4/42—Alloys based on zinc
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- H—ELECTRICITY
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- H01M4/46—Alloys based on magnesium or aluminium
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- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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Abstract
The present disclosure provides a nanoporous Zn/Cu/Al with lamellar structure 2 Cu alloy electrode and its preparation method and application are provided. The core-shell structure of the nano-porous Zn/Cu/Al2Cu alloy electrode with lamellar structure is not formed from insideThe fully corroded Al2Cu core and the fully corroded Cu shell on the surface layer form; the Al phase originally existing in the eutectic alloy alternately with Al2Cu is dealloyed to form a lamellar macroporous channel; the Cu/Al2Cu alloy ligaments of the lamellar macroporous channels and the lamellar macroporous channels are both of a certain thickness, and Zn replaced by the surface layer is used as an initial circulating zinc source. The nano-porous Zn/Cu/Al2Cu alloy electrode with lamellar structure provided by the present disclosure has a couple pair composed of Al2Cu core and Cu shell with different electrode potential, which makes it possible to realize highly reversible zinc stripping/electroplating process while reducing nucleation overpotential and local current density. Compared with a pure zinc metal negative electrode, the symmetrical battery prepared by using the lamellar nano-porous Zn/Cu/Al2Cu alloy electrode and the water-based zinc ion full battery have higher electrochemical activity and structural stability.
Description
Technical Field
The present disclosure relates to the technical field of aqueous zinc ion battery electrode materials, and in particular to a nanoporous Zn/Cu/Al electrode material with lamellar structure 2 The technical field of Cu alloy electrodes.
Background
With the continuous adjustment of energy systems, the storage and conversion of renewable energy sources is attracting attention, and the development of convenient, controllable and sustainable energy storage technologies to compensate for the intermittent and uncontrollable nature of renewable energy sources is urgent. Lithium ion batteries dominate large-scale electrical energy storage systems due to their longer cycle life and higher energy density compared to other energy storage technologies. However, the ever-increasing raw material prices, limited lithium resource reserves, and safety issues caused by organic electrolytes of lithium ion battery assemblies severely limit their further development, forcing the development of new generation energy storage systems with greater potential. Aqueous multivalent metal ion batteries are of great interest because of their inherent high safety, excellent ionic conductivity, good thermal stability, and higher cycling performance. Aqueous zinc ion batteries with moderate redox potential (-0.76V vs SHE), high elemental abundance and excellent theoretical capacity are of great interest compared to other aqueous systems.
The zinc ion battery insensitive to oxygen and moisture can be directly assembled in the air due to the high safety brought by the water-based electrolyte, so that the assembling process of the battery is greatly simplified, and the manufacturing cost of the battery is effectively reduced. In addition, the direct application of metallic zinc in the aqueous electrolyte can not only utilize the high theoretical mass capacity (720 mAh g -1 ) And volumetric capacity (5855 mAh cm) -3 ) And its intrinsic stability in aqueous solutions gives the possibility of long-term stable cycling of aqueous zinc-ion batteries. The working principle of the zinc ion battery is similar to that of a lithium ion battery, and a series of feasible water-based zinc ion battery anode materials including manganese-based oxides, vanadium-based oxides, prussian blue analogues, cobalt-based phosphates, polyanion compounds and organic compounds, which show excellent stability in a water-based electrolyte, are researched by the inspired of a lithium ion battery system. However, the zinc foil is commonly used as a negative electrode of the aqueous zinc ion battery, and adverse side reactions generated in the repeated stripping/electroplating process inevitably lead to the degradation of the battery performance, so that the battery cannot meet the requirements of practical application. Dendrite growth, surface corrosion, passivation and hydrogen evolution problems caused by the high reactivity of zinc with aqueous solutions during cycling are major causes of instability of zinc cathodes and battery failure, so establishing an efficient and stable zinc stripping/electroplating process is critical to improving its performance.
The eutectic alloy of aluminum and copper is chemically dealloyed for a controlled time to obtain an alloy electrode with a layered large-channel porous structure, and the structure can keep good machining performance. The formed three-dimensional porous structure not only can obviously increase the specific surface of the electrodeThereby reducing the local current density of the electrode and nucleation overpotential of ion deposition, and not corroding the complete Al 2 The different electrode potentials between the Cu intermetallic compound phase and the metal Cu phase obtained in the dealloying process form rich local couples in the alloy, and the reversible dendrite-free zinc stripping/electroplating behavior is effectively guided. The synergistic effect of different potential phases and a porous structure provides possibility for batch preparation of zinc ion battery cathodes which can be stably circulated for a long time.
Disclosure of Invention
In order to overcome the deficiencies of the prior art, the present disclosure provides a nanoporous Zn/Cu/Al with lamellar structure 2 Cu alloy electrode and its preparation method and application are provided.
According to a first aspect of the present disclosure, there is provided a nanoporous Zn/Cu/Al having a lamellar structure 2 A Cu alloy electrode, characterized in that,
the nano-porous Zn/Cu/Al with lamellar structure 2 The core-shell structure of the Cu alloy electrode is formed by Al which is not completely corroded in the interior 2 The Cu core and the Cu shell with complete surface corrosion are formed;
original and Al in eutectic alloy 2 The Al phase existing alternately in the Cu phase is dealloyed to form a layered macroporous channel;
Cu/Al of the lamellar macropore channel 2 The Cu alloy ligament and the lamellar macroporous channel are both provided with a certain thickness, and the Zn with the surface layer replaced serves as an initial circulating zinc source.
Preferably, the Cu/Al is 2 The thickness dimension of the Cu alloy ligament is 500nm, and the thickness of the lamellar macroporous channel is 300nm.
According to a second aspect of the present disclosure, there is provided a nanoporous Zn/Cu/Al having a lamellar structure 2 A method for preparing a Cu alloy electrode is characterized in that,
1) Determining the Cu-Al ratio according to the eutectic point, respectively weighing a pure copper ingot and a pure aluminum ingot, and removing a surface oxide layer;
2) Placing the copper ingot in a corundum crucible, placing the corundum crucible in a smelting furnace protected by nitrogen, smelting at a certain smelting temperature, and preserving heat;
3) After the copper ingot is confirmed to be completely melted, adding the aluminum ingot, continuously preserving heat at the temperature, and slightly stirring to ensure that the two metals are completely dissolved and fully mixed into a metal mixed solution;
4) Pouring the high-temperature liquid metal mixed solution into a mould to ensure that the metal mixed solution is solidified into a metal block at a proper cooling speed;
5) Cutting the completely cooled metal block into metal sheets with the thickness of 200-300 mu m on a wire cut electric discharge machine, and polishing to remove an oxide layer on the surface;
6) The metal sheet is placed in HCl solution for chemical dealloying, and Cu/Al with lamellar nano porous structure with thickness of 100 mu m is prepared 2 A Cu alloy electrode;
7) The Cu/Al after dealloying is performed 2 Cu alloy electrode is placed in a solution containing Zn (NO) 3 ) 3 And NaOH to obtain nano porous Zn/Cu/Al with surface substitution zinc as initial circulating zinc source 2 Cu alloy electrode.
Preferably, the smelting temperature in the step 2) is 900-1400 ℃, and the heat preservation time is 1-2 hours;
preferably, the incubation time of step 3) is 0.5-1.5 hours;
preferably, the cooling rate of step 4) is 100K s -1 ；
Preferably, step 6) is performed by subjecting the metal sheet to chemical dealloying in HCl solution, wherein the dealloying HCl solution has a concentration of 1mol L -1 The etching time is 1 hour;
preferably, zn (NO) in the zinc leaching solution of step 7) 3 ) 3 Is 0.15mol L -1 NaOH concentration of 2mol L -1 The displacement time was 3 minutes.
According to a third aspect of the present disclosure, there is provided a nanoporous Zn/Cu/Al having a lamellar structure 2 The application of the Cu alloy electrode is characterized in that,
nano-porous Zn/Cu/Al with lamellar structure 2 Construction of Cu alloy electrode as negative electrode of water-based zinc ion batteryAn aqueous zinc ion battery.
The beneficial effects of the present disclosure are:
the present disclosure provides nanoporous Zn/Cu/Al with lamellar structure 2 The Cu alloy electrode has Al different from electrode potential 2 The galvanic couple of Cu core and Cu shell allows for highly reversible zinc stripping/electroplating processes while reducing nucleation overpotential and local current density. Use of lamellar nanoporous Zn/Cu/Al compared to pure zinc metal anodes 2 The symmetrical battery and the water-based zinc ion full battery prepared by the Cu alloy electrode have higher electrochemical activity and structural stability.
Drawings
The above and other features, advantages and aspects of embodiments of the present disclosure will become more apparent by reference to the following detailed description when taken in conjunction with the accompanying drawings. For a better understanding of the present disclosure, and without limiting the disclosure thereto, the same or similar reference numerals denote the same or similar elements, wherein:
FIG. 1, nanoporous Zn/Cu/Al with lamellar structure 2 A field emission (FESEM) map of the Cu alloy electrode;
FIG. 2, nanoporous Zn/Cu/Al with lamellar structure 2 XRD pattern of Cu alloy electrode;
FIG. 3 nanoporous Zn/Cu/Al with lamellar structure 2 EDS spectrum of Cu alloy electrode;
FIG. 4, nanoporous Zn/Cu/Al with lamellar structure 2 A flow chart of a preparation method of the Cu alloy electrode is shown;
FIG. 5, nanoporous Zn/Cu/Al with lamellar structure 2 Nucleation overpotential curves (time-voltage curves) of Cu alloy electrodes;
FIG. 6 nanoporous Zn/Cu/Al with lamellar structure 2 Symmetrical cell with standard Cu alloy electrode composition at 0.5mA cm -2 Constant current charge-discharge test patterns (voltage-time curves) were run for 4000h at current density;
FIG. 7, nanoporous Zn/Cu/Al with lamellar structure 2 Electrochemical cell with standard symmetric cell composed of Cu alloy electrodeAn impedance diagram (EIS);
FIG. 8, nanoporous Zn/Cu/Al with lamellar structure 2 Cu alloy electrode and carbon cloth loaded Zn 0.12 V 2 O 5 Electrode composition standard aqueous zinc ion full cell is 0.2mV s -1 A Cyclic Voltammetry (CV) test chart below;
FIG. 9, nanoporous Zn/Cu/Al with lamellar structure 2 Cu alloy electrode and carbon cloth loaded Zn 0.12 V 2 O 5 Electrochemical Impedance (EIS) spectrum of the standard aqueous zinc ion full cell with the electrode composition in the frequency range of 100kHz to 10 mHz;
FIG. 10, nanoporous Zn/Cu/Al with lamellar structure 2 Cu alloy electrode and carbon cloth loaded Zn 0.12 V 2 O 5 The standard aqueous zinc ion full cell with the electrode composition is 0.5Ag -1 A cycling stability test chart at current density;
FIG. 11, nanoporous Zn/Cu/Al with lamellar structure 2 Cu alloy electrode and carbon cloth loaded Zn 0.12 V 2 O 5 The electrode composition standard aqueous zinc ion full cell is 10Ag -1 A cycling stability test chart at current density;
FIG. 12, nanoporous Zn/Cu/Al with lamellar structure 2 Cu alloy electrode and carbon cloth loaded Zn 0.12 V 2 O 5 The electrode composition standard aqueous zinc ion full cell is 0.2-10Ag -1 Is a graph of the rate performance test performed at the current density of (c).
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present disclosure more apparent, the technical solutions of the embodiments of the present disclosure will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present disclosure, and it is apparent that the described embodiments are some embodiments of the present disclosure, but not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments in this disclosure without inventive faculty, are intended to be within the scope of this disclosure.
Example 1
Nanoporous Zn/Cu/Al with lamellar structure of the disclosure 2 The preparation method of the Cu alloy electrode comprises the following steps:
A. weighing 760g of pure aluminum ingot (Al, purity 99.99%) and 243g of pure copper ingot (Cu, purity 99.99%), and removing the surface oxide layer;
B. placing the copper ingot in a corundum crucible, and placing the corundum crucible in a smelting furnace protected by nitrogen, heating to 900 ℃ and preserving heat for 1 hour;
C. after the copper ingot is confirmed to be completely melted, adding the aluminum ingot, continuously preserving heat at 900 ℃ for 0.5 hour, and slightly stirring to ensure that the two metals are completely dissolved and fully mixed to form a metal mixed solution;
D. pouring the high-temperature liquid metal mixed solution into a heat-preserving iron mold to ensure that the metal mixed solution is 100K s -1 Solidifying the mixture into a metal block at a cooling rate;
E. cutting the completely cooled metal block into metal sheets with the thickness of 200-300 mu m on a wire cut electric discharge machine, and polishing to remove an oxide layer on the surface;
F. placing the metal sheet in a 1M HCl solution for corrosion for 1 hour;
G. the dealloyed porous Cu/Al 2 The Cu alloy electrode was placed in a solution containing 0.15M Zn (NO) 3 ) 3 And 2M NaOH for 3 min to obtain nano porous Zn/Cu/Al with surface substitution zinc as initial circulating zinc source 2 Cu alloy electrode, this electrode can be used as the negative pole of the aqueous zinc ion battery.
Example 2
Nanoporous Zn/Cu/Al with lamellar structure of the disclosure 2 The preparation process of the Cu alloy electrode is as follows:
A. weighing 760g of pure aluminum ingot (Al, purity 99.99%) and 243g of pure copper ingot (Cu, purity 99.99%), and removing the surface oxide layer;
B. placing the copper ingot in a corundum crucible, and placing the corundum crucible in a smelting furnace protected by nitrogen, heating to 1300 ℃ and preserving heat for 1.5 hours;
C. after the copper ingot is confirmed to be completely melted, adding the aluminum ingot, continuously preserving heat at 1300 ℃ for 1 hour, and slightly stirring to ensure that the two metals are completely dissolved and fully mixed into a metal mixed solution;
D. pouring the high-temperature liquid metal mixed solution into a heat-preserving iron mold to ensure that the metal mixed solution is 100K s -1 Solidifying the mixture into a metal block at a cooling rate;
E. cutting the completely cooled metal block into metal sheets with the thickness of 200-300 mu m on a wire cut electric discharge machine, and polishing to remove an oxide layer on the surface;
F. placing the metal sheet in a 1M HCl solution for corrosion for 2 hours;
G. placing the dealloyed porous Cu electrode in a solution containing 1M ZnSO 4 Electroplating for 3 minutes at-0.05V to obtain the nano-porous Zn/Cu electrode which can be used as the negative electrode of the water-based zinc ion battery.
Example 3
Nanoporous Zn/Cu/Al with lamellar structure of the disclosure 2 The preparation process of the Cu alloy electrode is as follows:
A. weighing 760g of pure aluminum ingot (Al, purity 99.99%) and 243g of pure copper ingot (Cu, purity 99.99%), and removing the surface oxide layer;
B. placing the copper ingot in a corundum crucible, and placing the corundum crucible in a smelting furnace protected by nitrogen, heating to 1400 ℃ and preserving heat for 2 hours;
C. after the copper ingot is confirmed to be completely melted, adding the aluminum ingot, continuously preserving heat at 1400 ℃ for 1.5 hours, and slightly stirring to ensure that the two metals are completely dissolved and fully mixed to form a metal mixed solution;
D. pouring the high-temperature liquid metal mixed solution into a heat-preserving iron mold to ensure that the metal mixed solution is 100K s -1 Solidifying the mixture into a metal block at a cooling rate;
E. cutting the completely cooled metal block into metal sheets with the thickness of 200-300 mu m on a wire cut electric discharge machine, and polishing to remove an oxide layer on the surface;
F. placing the metal sheet in a 1M HCl solution for corrosion for 3 hours;
G. the dealloyed porous Cu/Al 2 The Cu alloy electrode was placed in a solution containing 0.15M Zn (NO) 3 ) 3 And 2M NaOH for 3 minutes to obtain the surfaceNanoporous Zn/Cu/Al with displaced zinc as initial circulating zinc source 2 Cu alloy electrode, this electrode can be used as the negative pole of the aqueous zinc ion battery.
XRD verification proves that the aluminum copper eutectic alloy with the controlled time corrosion for 1 hour forms Cu/Al 2 And (3) a Cu core-shell structure, wherein the aluminum-copper eutectic alloy is corroded for 4 hours under control to form a porous Cu structure.
Taking example 1 as an example, the morphology and structure characterization of the material and the electrochemical performance characterization result of the material are further compared.
(1) Characterization of morphology and structure of the material.
By field emission (FESEM) characterization, zn/Cu/Al after dealloying and substitution of zinc source 2 The Cu alloy electrode shows a lamellar nano porous structure as shown in figure 1, and the inside of the alloy electrode sample is proved to be lamellar porous structure, the ligament size is 500nm, and the lamellar macropore channel size is 300nm. The field emission scanning electron microscope energy spectrum test more intuitively proves that the Zn layer is successfully replaced on the alloy surface obtained by the method, and the existence of Al proves that the intermetallic compound Al 2 Successful retention of Cu.
FIG. 2 is a nano-porous Zn/Cu/Al with lamellar structure 2 XRD spectrum of Cu alloy electrode, in which, besides existence of small quantity of characteristic peaks of Al phase whose interior is not corroded thoroughly, it is proved that Zn phase and Al phase are 2 Coexistence of Cu phase and Cu phase.
FIG. 3 is a nano-porous Zn/Cu/Al having a lamellar structure 2 The EDS spectrum of Cu, whose chemical composition is shown in Table 1,
| element(s) | Wt％ | At％ |
| Zn | 71.0 | 61.0 |
| Cu | 19.8 | 16.5 |
| Al | 6.5 | 13.1 |
| O | 2.7 | 9.4 |
TABLE 1
The results demonstrate that the lamellar nano-porous alloy sample consists of a Cu shell and Al 2 The core-shell structure formed by Cu cores, and the presence of a large amount of Zn confirm the successful replacement of the surface residual Al after controlled time corrosion.
The preparation process of the electrode in the disclosure is shown in fig. 4, and the eutectic alloy ingot obtained by smelting in a high-temperature smelting furnace is 1mol L -1 And (3) controlling time corrosion in a hydrochloric acid solution to obtain a lamellar nano porous alloy electrode so as to facilitate subsequent electrochemical performance test.
(2) The electrochemical performance of the material characterizes the results.
The nanoporous Zn/Cu// Al with lamellar structure prepared in example 1 2 Cutting a Cu alloy sheet into an electrode sheet, and then taking the alloy electrode sheet as a working electrode by 1mol L -1 Zn (OTf) 2 As a solute, the ratio to water was 2:1, using the diethylene glycol dimethyl ether mixture as a solution to form an electrolyte, and forming a standard symmetrical battery for electrochemical test;
the nanoporous Zn/Cu// Al with lamellar structure prepared in example 1 2 Cu alloy electrode at 0.5mA cm -2 Nucleation overpotential testing (time-voltage curve) was performed at current density.
The nanoporous Zn/Cu// Al with lamellar structure prepared in example 1 2 Cu alloy electrode assembled symmetrical cell at 0.5mA cm -2 Current density 4000h constant current charge-discharge test (voltage-time curve) was performed.
The nanoporous Zn/Cu// Al with lamellar structure prepared in example 1 2 Cu alloy electrode assembly symmetric cells were subjected to Electrochemical Impedance Spectroscopy (EIS) at a frequency range of 100kHz to 10 mHz.
The nanoporous Zn/Cu// Al with lamellar structure of example 1 was prepared 2 Cu alloy electrode as battery cathode and carbon cloth loaded Zn 0.12 V 2 O 5 Electrode as positive electrode of battery, 1mol L -1 Zn (OTf) 2 As a solute, the ratio to water was 2:1 as a solution to form an electrolyte, and forming a standard water-based zinc ion full battery for electrochemical test.
The nanoporous Zn/Cu// Al with lamellar structure prepared in example 1 2 Cu alloy electrode and carbon cloth loaded Zn 0.12 V 2 O 5 Standard aqueous zinc ion full cell with electrode composition was placed at 0.2mV s -1 Cyclic Voltammetry (CV) testing was performed at the scan rate of (c).
The nanoporous Zn/Cu// Al with lamellar structure prepared in example 1 2 Cu alloy electrode and carbon cloth loaded Zn 0.12 V 2 O 5 Standard aqueous zinc ion full cells of electrode composition were subjected to Electrochemical Impedance Spectroscopy (EIS) at frequencies ranging from 100kHz to 10 mHz.
The nanoporous Zn/Cu// Al with lamellar structure prepared in example 1 2 Cu alloy electrode and carbon cloth loaded Zn 0.12 V 2 O 5 Standard aqueous zinc ion full cell with electrode composition is placed in 0.5Ag -1 Is subjected to a 200-turn cycle stability test at a current density.
In the time-voltage curve of FIG. 5, nanoporous Zn with lamellar structure/Cu//Al 2 The Cu alloy electrode only has a nucleation overpotential of-2.2 mV, and the excellent zinc-philicity of the alloy electrode in the disclosure is proved to effectively reduce the energy barrier in the electrochemical plating process, thereby effectively improving the electrochemical performance of the alloy electrode. As can be seen from the results of the symmetrical cell test in FIG. 6, nanoporous Zn/Cu// Al having lamellar structure 2 Cu alloy electrode symmetrical battery with 0.5mA cm -2 Can be tested for a current density of over 4000 hours without significant voltage hysteresis. In contrast, pure zinc symmetrical cells exhibit significant voltage hysteresis over a test time of 200 hours. FIG. 7 is a pure zinc symmetric cell and nanoporous Zn/Cu// Al with lamellar structure 2 Impedance contrast of Cu alloy electrode symmetric cell, nanoporous Zn/Cu// Al with lamellar structure 2 The charge transfer resistance of the Cu alloy electrode symmetric cell was about 5 Ω, in contrast to about 635 Ω for the pure zinc symmetric cell, demonstrating nanoporous Zn/Cu// Al with lamellar structure 2 The Cu alloy electrode has a stronger electrochemical activity than pure zinc foil. FIG. 8 is a nanoporous Zn/Cu// Al with lamellar structure 2 Cu alloy electrode and carbon cloth loaded Zn 0.12 V 2 O 5 The aqueous zinc ion battery with the electrode composition is under the voltage range of 0.4-1.4V and the voltage range of 0.2mV s -1 Is a CV test curve obtained by the sweeping speed of the test piece. The reduction peaks of the redox curves of the cells appear at 0.67V and 0.96V, respectively, while the oxidation peaks appear at 0.79V and 1.10V, respectively. FIG. 9 is a graph of nanoporous Zn/Cu// Al with lamellar structure in the frequency range of 100kHz to 10mHz 2 Cu alloy electrode and pure zinc foil respectively with Zn loaded by carbon cloth 0.12 V 2 O 5 Electrochemical Impedance (EIS) comparison of aqueous zinc ion full cells of electrode composition. As can be seen from fig. 9, the charge transfer resistance of the full cell assembled using the alloy electrode was only 5 Ω, in contrast to the charge transfer resistance of the full cell using pure zinc foil as the negative electrode, which is as high as 90 Ω. Together, the small charge transfer resistance and degree of polarization demonstrate that the assembled full cell of alloy electrodes has excellent electrochemical activity. FIG. 10 is a nanoporous Zn/Cu// Al with lamellar structure 2 Cu alloy electrode and pure zinc electrode are respectively loaded with carbon clothZn of (2) 0.12 V 2 O 5 The positive electrode is assembled into a standard water system zinc ion full battery of 0.5A g -1 Is a cycle curve at current density. As can be seen from FIG. 10, when nanoporous Zn/Cu// Al having lamellar structure 2 Zn loaded with carbon cloth on Cu alloy electrode 0.12 V 2 O 5 When the electrode is composed of a water-based zinc ion full battery, the water-based zinc ion full battery is 0.5. 0.5A g -1 Can still keep more than 330mAh g after 400 hours of current density circulation -1 Is a specific capacity of (a). In sharp contrast, the aqueous zinc ion full cell assembled from pure zinc sheet electrodes failed rapidly after only 50h of cycle, leaving only 100mAh g at last -1 Is a specific capacity of (a). This fully demonstrates the unique advantage of the unique structure inside the alloy electrode in terms of cycling stability of the zinc ion battery. As shown in FIG. 11, the alloy electrode exhibits great advantage in terms of high current density, which is 10Ag, thanks to the effect of the porous structure greatly reducing the local current density and regulating the ion flux -1 Has a mAh g of more than 235mAh g after 5000 circles of stable circulation under high current density -1 The specific capacity of (c) demonstrates its excellent rate capability. FIG. 12 is a nanoporous Zn/Cu// Al with lamellar structure 2 Cu alloy electrode and carbon cloth loaded Zn 0.12 V 2 O 5 The electrode composition standard aqueous zinc ion full cell is 0.2-10Ag -1 Is used for testing the multiplying power performance under the current density. At a charge/discharge current density of from 0.2Ag -1 Up to 10A g -1 When the battery was able to retain more than 50% of its capacity, its excellent rate performance was demonstrated. The above performance tests all show that compared with pure zinc metal anode, nano-porous Zn/Cu// Al with lamellar porous structure is used 2 The symmetric battery prepared by the Cu alloy electrode and the water-based zinc ion full battery have higher electrochemical activity and structural stability, and have good application prospects in the field of water-based batteries, and the method can be further expanded to other energy storage battery systems, so that a new method and thinking are provided for improving the electrochemical activity and structural stability of the metal electrode.
Claims (9)
1. With laminar knotsStructured nanoporous Zn/Cu/Al 2 A Cu alloy electrode, characterized in that,
the nano-porous Zn/Cu/Al with lamellar structure 2 The core-shell structure of the Cu alloy electrode is formed by Al which is not completely corroded in the interior 2 The Cu core and the Cu shell with complete surface corrosion are formed;
original and Al in eutectic alloy 2 Forming a lamellar macroporous channel after dealloying Al phases existing alternately in the Cu phase;
Cu/Al of the lamellar macropore channel 2 The Cu alloy ligament and the lamellar macroporous channel are both provided with a certain thickness, and Zn with surface layer replaced is used as an initial circulating zinc source.
2. The nanoporous Zn/Cu/Al having lamellar structures according to claim 1 2 A Cu alloy electrode, characterized in that,
the Cu/Al is 2 The thickness dimension of the Cu alloy ligament is 500nm, and the thickness of the lamellar macroporous channel is 300nm.
3. The nanoporous Zn/Cu/Al having lamellar structure according to claim 1 or 2 2 A method for preparing a Cu alloy electrode is characterized in that,
1) Determining the Cu-Al ratio according to the eutectic point, respectively weighing a pure copper ingot and a pure aluminum ingot, and removing a surface oxide layer;
2) Placing the copper ingot in a corundum crucible, placing the corundum crucible in a smelting furnace protected by nitrogen, smelting at a certain smelting temperature, and preserving heat;
3) After the copper ingot is confirmed to be completely melted, adding the aluminum ingot, continuously preserving heat at the temperature, and slightly stirring to ensure that the two metals are completely dissolved and fully mixed into a metal mixed solution;
4) Pouring the high-temperature liquid metal mixed solution into a mould to ensure that the metal mixed solution is solidified into a metal block at a proper cooling speed;
5) Cutting the completely cooled metal block into metal sheets with the thickness of 200-300 mu m on a wire cut electric discharge machine, and polishing to remove an oxide layer on the surface;
6) The metal sheet is placed in HCl solution for chemical dealloying, and Cu/Al with lamellar nano porous structure with thickness of 100 mu m is prepared 2 A Cu alloy electrode;
7) The Cu/Al after dealloying in the step 6) is performed 2 Cu alloy electrode is placed in a solution containing Zn (NO) 3 ) 3 And NaOH to obtain nano porous Zn/Cu/Al with surface substitution zinc as initial circulating zinc source 2 Cu alloy electrode.
4. The nanoporous Zn/Cu/Al having a lamellar structure according to claim 3 2 The preparation method of the Cu alloy electrode is characterized in that the smelting temperature of the step 2) is 900-1400 ℃.
5. The nanoporous Zn/Cu/Al having a lamellar structure according to claim 3 2 The preparation method of the Cu alloy electrode is characterized in that the continuous temperature in the step 3) is kept for 0.5-1.5 hours.
6. The nanoporous Zn/Cu/Al having a lamellar structure according to claim 3 2 A method for producing a Cu alloy electrode, characterized in that the cooling rate in step 4) is 100 to K s -1 。
7. The nanoporous Zn/Cu/Al having a lamellar structure according to claim 3 2 A method for producing a Cu alloy electrode, characterized in that the HCl solution concentration in step 6) is 1mol L -1 The etching time was 1 hour.
8. The nanoporous Zn/Cu/Al having a lamellar structure according to claim 3 2 A method for producing a Cu alloy electrode, characterized by comprising the step 7) of immersing Zn (NO) in the zinc bath 3 ) 3 Is 0.15mol L -1 NaOH concentration of 2mol L -1 The displacement time was 3 minutes.
9. As claimed in claim 1 or 2Nanoporous Zn/Cu/Al with lamellar structure 2 The application of the Cu alloy electrode is characterized in that:
nano-porous Zn/Cu/Al with lamellar structure 2 The Cu alloy electrode is used as a negative electrode of the water-based zinc ion battery to construct the water-based zinc ion battery.
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