CN114005995B - Preparation method of flexible metal electrode - Google Patents
Preparation method of flexible metal electrode Download PDFInfo
- Publication number
- CN114005995B CN114005995B CN202111281269.8A CN202111281269A CN114005995B CN 114005995 B CN114005995 B CN 114005995B CN 202111281269 A CN202111281269 A CN 202111281269A CN 114005995 B CN114005995 B CN 114005995B
- Authority
- CN
- China
- Prior art keywords
- metal
- gallium
- liquid metal
- simple substance
- alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 79
- 239000002184 metal Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910001338 liquidmetal Inorganic materials 0.000 claims abstract description 97
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 60
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 25
- 239000000956 alloy Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002923 metal particle Substances 0.000 claims abstract description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 8
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 8
- YZZNJYQZJKSEER-UHFFFAOYSA-N gallium tin Chemical compound [Ga].[Sn] YZZNJYQZJKSEER-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 239000004744 fabric Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 13
- -1 cation salt Chemical class 0.000 claims description 11
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 229910052718 tin Inorganic materials 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- 239000007769 metal material Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229910002056 binary alloy Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical group 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910001325 element alloy Inorganic materials 0.000 claims description 3
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical group [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- KVFIZLDWRFTUEM-UHFFFAOYSA-N potassium;bis(trifluoromethylsulfonyl)azanide Chemical compound [K+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F KVFIZLDWRFTUEM-UHFFFAOYSA-N 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 239000007788 liquid Substances 0.000 abstract description 7
- 229910005538 GaSn Inorganic materials 0.000 abstract description 3
- 230000005496 eutectics Effects 0.000 abstract description 3
- 229910052716 thallium Inorganic materials 0.000 abstract description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011149 active material Substances 0.000 abstract 1
- 239000003570 air Substances 0.000 description 46
- 239000007772 electrode material Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical compound [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 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 description 2
- 238000005275 alloying Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Hybrid Cells (AREA)
- Inert Electrodes (AREA)
Abstract
The invention relates to a preparation method of a flexible metal electrode. According to the method, firstly, gallium-based liquid metal alloys such as eutectic gallium-tin (GaSn) and gallium-indium-tin (GaInSn) which are liquid at room temperature are prepared, then, metal particles such as ruthenium, platinum, thallium, palladium and the like with high specific surface energy and high catalytic activity are introduced by a mechanical grinding method, so that the metal particles are ensured to be fully contacted with liquid metal, the surface tension of the metal particles is reduced, the active surface area of a liquid metal electrode can be increased, meanwhile, the metal particles are well contacted with a current collector, the problem of stripping of active materials in the circulation process and in the face of certain mechanical change of the flexible metal electrode is avoided, and the circulation performance and the mechanical performance of the flexible metal-air battery are effectively improved. The method is simple, low in cost, practical and effective.
Description
Technical Field
The invention relates to a preparation method and application of a liquid metal electrode, in particular to a preparation method and application of a flexible metal-air battery liquid metal electrode in a battery, and belongs to the related field of secondary batteries.
Background
In recent years, with the progress of scientific technology and industrial technology, flexible electronic products with light weight, portability and high flexibility are attracting attention, and bring convenience to the life of people. In order to further realize the popularization of the flexible electronic, it is crucial and challenging to develop a corresponding flexible energy storage system, meet the portable and flexible standards of the flexible electronic, and provide uninterrupted power supply for the flexible electronic. All components in a flexible lithium air battery should be flexible to accommodate stresses and strains in deformation while ensuring electrochemical performance. However, the cathode and the current collector are usually made of rigid carbon paper or porous metal, so that the requirements of the flexible lithium air battery are difficult to meet, and the development of the flexibility of the battery is severely restricted. In addition, the cathode should have high catalytic activity to promote oxygen evolution and oxygen reduction reactions of the lithium-air battery. Therefore, there is an urgent need to develop a flexible high-performance cathode material having high mechanical stability and catalytic activity for a flexible lithium air battery. However, the current preparation method of the flexible air electrode is mostly complexThe preparation of a portion of the flexible electrode requires certain conditions to form. CN 107863494a discloses a method for preparing a flexible gas electrode for lithium air battery, which comprises loading metal catalyst on pretreated carbon cloth, growing CNTs on the surface, and finally applying composite electrode material on KMnO 4 And H 2 SO 4 The mixed solution of the above is subjected to reaction, washing and drying, the process is complex, and the energy consumption and the cost are increased; CN 0.9216679a discloses a preparation method of a needled flexible air electrode material, nickel acetate, cobalt acetate and thioacetic acid amide are added into deionized water and stirred to form a uniform mixed solution, then the mixed solution and carbon cloth undergo a hydrothermal reaction, and after the reaction is finished, the product is cooled to room temperature and taken out, so that the needled flexible air electrode is obtained, and the method is complex and complex in process;
gallium-based liquid metal alloys such as eutectic gallium-tin (GaSn) and gallium-indium-tin (GaInSn) are receiving widespread attention for their excellent properties, including high electrical and thermal conductivity, high surface tension, low vapor pressure, low toxicity, etc., as well as good fluidity and chemical stability. In the energy storage field, liquid metals such as Ga, ga/Sn and Ga/In have been used as anodes for LIBs. In the field of metal-air batteries, the research of air anodes is limited due to their high surface tension and relatively low catalytic activity; luo et al (Mater. Today energy.2020.18.10055) firstly prepare gallium tin liquid metal, and the liquid metal composite electrode is prepared by ultrasonic dispersion of liquid metal particles and compositing the liquid metal particles with multi-wall carbon nanotubes according to a certain proportion.
Disclosure of Invention
The invention aims at solving the problems and provides a preparation method and application of a flexible liquid metal electrode. According to the method, firstly, gallium-based liquid metal alloys such as eutectic gallium-tin (GaSn) and gallium-indium-tin (GaInSn) which are liquid at room temperature are prepared, then, metal particles such as ruthenium, platinum, thallium, palladium and the like with high specific surface energy and high catalytic activity are introduced by a mechanical grinding method, so that the metal particles are ensured to be fully contacted with liquid metal, the surface tension of the metal particles is reduced, the active surface area of a liquid metal electrode can be increased, meanwhile, the metal particles are well contacted with a current collector, the flexible metal electrode is prevented from peeling off in the circulation process and facing to certain mechanical changes, and the circulation performance and the mechanical performance of the flexible metal-air battery are effectively improved. The method is simple, low in cost, practical and effective.
The technical scheme of the invention is as follows:
a method for preparing a flexible metal electrode, comprising the steps of:
(1) Weighing a gallium simple substance or a related metal simple substance of a gallium-based liquid metal alloy, then placing the gallium simple substance or the related metal simple substance of the gallium-based liquid metal alloy on a heating table, heating the gallium simple substance or the related metal simple substance of the gallium-based liquid metal alloy to be completely melted, keeping the temperature constant for 2-3 hours, naturally cooling the gallium simple substance or the related metal simple substance of the gallium-based liquid metal alloy to the room temperature, and collecting the gallium simple substance or the related metal simple substance of the gallium-based liquid metal alloy to obtain preset liquid metal;
the gallium-based liquid metal alloy is specifically gallium tin, gallium indium or gallium indium tin;
when the gallium is simple substance, the heating temperature is 30-60 ℃; in the case of gallium-based liquid metal alloy, the heating temperature is 180-220 ℃;
(2) Adding the added metal particles into preset liquid metal, and mechanically grinding for 10-20 minutes at room temperature to obtain a flexible liquid metal material;
wherein, the metal particle material amount is 0.1-0.2 g in each g of preset liquid metal, and the mass percentage of the metal gallium in the room temperature gallium-based liquid metal is preferably 70-99%;
the added metal is one or more of ruthenium, platinum, palladium and molybdenum;
the particle diameter range of the added metal particles is in the micron order (1-5 μm);
the grinding is artificial grinding and mechanical grinding;
the gallium-based liquid metal is one or more of binary alloy and multi-element alloy;
the gallium-based liquid metal binary alloy is Ga/In, ga/Sn, ga/Bi, ga/Cd, ga/Al, ga/Zn, ga/Hg, ga/Ag and the like; the room temperature gallium-based liquid metal multi-component alloy is Ga/In/Sn, ga/In/Sn/Zn, ga/In/Sn/Fe and the like.
(3) Coating the mixed liquid metal material obtained in the previous step on a carbon cloth current collector, and coating 1-5 mg of mixed liquid metal on each square centimeter of carbon cloth to obtain a flexible metal electrode;
the application of the flexible metal electrode is used as a flexible metal air anode in a battery;
assembling the flexible metal electrode, the metal lithium negative electrode and the ether-based electrolyte into a lithium air battery according to a correct sequence;
wherein the solvent of the ether-based electrolyte is an ether solvent; the salt in the ether electrolyte is metal cation salt corresponding to the components contained in the lithium material; the mass percentage concentration of the metal cation salt in the electrolyte is 0.01-40%;
the ether solvent is one or more of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether;
when the metal cation salt is one, the metal cation salt is lithium salt; when the metal cation salt is various, the metal cation salt is lithium salt and other salts, and the other salts are one or two of sodium salt or potassium salt; in particular NaTFSI and NaClO 4 、NaCF 3 SO 3 、KClO 4 、KCF 3 SO 3 Or KTFSI.
The battery is preferably a button battery or a soft package battery.
The beneficial effects of the invention are as follows:
according to the method, the liquid metal electrode of the flexible metal-air battery is prepared by adopting a simple method, gallium-based liquid metal which is liquid at room temperature is prepared, and the flexible metal electrode is prepared by introducing metal particles with high specific surface energy and excellent catalytic activity. The flexible metal electrode prepared by the method does not need conditions such as ultrasonic and hydrothermal reaction, and the flexible metal electrode can be directly ground and manufactured, so that the method is more flexible and the application is wider. In addition, no conductive agent and binder participate in the electrode preparation process, so that side reactions in the battery system circulation process are avoided, and the electrode is applied to corresponding metal-air batteries, so that decomposition of discharge products can be effectively promoted, and the mechanical performance and catalytic performance of the batteries are improved. The flexible metal electrode prepared by the method is applied to a flexible lithium ion battery system, and can inhibit growth of lithium dendrites through liquid metal alloying, so that the safety and long-cycle performance of the battery are improved. In addition, the preparation process does not need operation procedures such as ultrasonic and hydrothermal reaction, and the method is simple and widely applied.
As will be described in detail below with reference to example 1, the liquid metal is difficult to spread on the flexible carbon cloth substrate due to its large surface tension, and has poor interface contact with the carbon cloth, and is easy to fall off.
Cutting and assembling the obtained flexible metal electrode into a lithium air battery, and performing a first-circle full discharge test, wherein the discharge capacity is 2.7mAh/cm 2 Compared with the original liquid metal, the capacity is improved by 5.4 times, meanwhile, the initial cycle of the liquid metal is tested for cycle performance, the initial cycle of the liquid metal shows low overpotential (0.55V), the liquid metal can be overstable and circulated for more than 40 cycles in a real air environment, the liquid metal can be stably circulated for 95 cycles in an oxygen atmosphere, the attenuation of discharge voltage and charging voltage is small (the charging voltage is less than or equal to 4.5V and the discharge voltage is less than or equal to 2.5V), the liquid metal can be kept relatively stable, the long cycle performance is excellent, and the long cycle life is shown; and the battery after circulating in the real air environment is disassembled, the electrode is cleaned and dried, and the battery is reassembled for repeated test, so that excellent circulating performance can be maintained.
Drawings
Fig. 1 is an optical photograph of a flexible metal electrode of a lithium air battery obtained in example 1.
Fig. 2 is an XRD pattern of different metallic ruthenium contents of the flexible metal electrode of the lithium air battery obtained in example 1.
Fig. 3 is a graph showing a comparison of first discharge of the flexible metal electrode of the lithium air battery obtained in example 1.
Fig. 4 is a charge-discharge cycle curve of the lithium air battery of example 1 assembled from flexible metal electrodes in a rechargeable lithium air battery directly in ambient air.
Fig. 5 is a cycle performance curve of a button lithium-oxygen battery of the flexible metal electrode of the lithium-air battery obtained in example 2.
FIG. 6 is an optical photograph of a soft pack lithium air battery of the flexible metal electrode of the lithium air battery obtained in example 2
Detailed Description
The invention is further described below with reference to examples.
Example 1:
1) Preparing gallium indium tin liquid metal alloy according to the mass ratio of 7:2:1, respectively weighing gallium, indium and tin. Collecting the weighed medicines in a metal crucible, placing the metal crucible on a heating table, keeping the heating temperature at 200 ℃ for 2 hours, and naturally cooling to room temperature for collection.
Wherein, because gallium metal melts (melting point 29 ℃), tin metal begins to melt at about 120 ℃, indium melts at about 157 ℃, and after the alloy is heated continuously to ensure that the alloying reaction is sufficient, the alloy is cooled to room temperature, namely, the melting point of gallium indium tin alloy is about 6 ℃, and the alloy exists in a liquid state;
2) Adding metal ruthenium particles (particle size is 3 mu m) into preset liquid metal, wherein the mass ratio of the metal ruthenium particles to the preset liquid metal is 1:10, grinding and mixing the metal ruthenium particles and the liquid metal by using a mortar at the room temperature of about 25 ℃ for about 15 minutes, reducing the surface tension of the liquid metal, and increasing the viscosity of the mixed liquid metal material (figure 1) to obtain a flexible metal electrode material;
3) The flexible metal electrode material with oxygen reduction/oxygen precipitation catalytic activity obtained in the previous step is uniformly coated on a carbon cloth current collector, and the loading capacity is controlled to be 4mg/cm 2 Then cutting out electrodes with proper sizes according to different battery specifications to obtain flexible metal electrodes;
the flexible metal electrode is used as an air battery anode, and a button type lithium air battery (model CR 2032) is assembled with a metal lithium cathode and an ether electrolyte according to the correct sequence to carry out a conventional cycle test; wherein the electrolyte is a tetraethylene glycol dimethyl ether solution containing 0.5M LiTFSI.
The initial discharge performance curve of the cell is shown in FIG. 3, and the lithium air cell with liquid metal electrode having ORR/OER catalytic activity is at 0.1mA/cm 2 Provides a current density of 2.7mAh/cm 2 Is a high discharge capacity.
The cycle performance curve of the battery is shown in FIG. 4, and the specific capacity of the battery is 0.1mAh/cm 2 Constant current charge and discharge test was performed at a current density of 0.1mA/cm, and no significant voltage decay was observed after 40 cycles.
Fig. 1 is an optical photograph of the resulting flexible metal electrode. Unlike the original liquid metal, the liquid metal electrode after the metal ruthenium is compounded with the room temperature liquid metal has low surface tension, and can be easily coated on the carbon cloth current collector.
Fig. 2 is an XRD representation of the obtained liquid metal electrode materials with different metal ruthenium contents, and it can be seen that with increasing ruthenium content, the intensity of the metal ruthenium diffraction peak in the composite liquid metal electrode material is gradually increased, and the broad peak at 29 ° -50 ° still remains, and the special broad peak region represents the liquid metal short-range disordered liquid structure, which indicates that the gallium-based liquid metal in the composite liquid metal electrode material still maintains the original structure.
Fig. 3 is a graph of the first discharge performance of the lithium air battery of the obtained liquid metal electrode, the abscissa represents the discharge capacity, and the ordinate represents the voltage in V. As can be seen, the lithium air battery of the obtained liquid metal electrode was at 0.1mA/cm 2 Has excellent discharge capacity at the current density, and the decay of the discharge voltage is small (the discharge voltage is ∈ 2.5V), and can be kept relatively stable.
Fig. 4 is a cycle performance curve of the resulting lithium air battery of the liquid metal electrode. As can be seen, the lithium-oxygen battery of the obtained liquid metal electrode was at 0.1mA/cm 2 The first turn exhibits a small overpotential of 0.47V during the 40-turn cycleThe discharge voltage and the charge voltage have small attenuation (the charge voltage is less than or equal to 4.5V and the discharge voltage is less than or equal to 2.5V), can be kept relatively stable, and has excellent cycle performance.
Example 2:
1) Preparing gallium-tin liquid metal alloy, and weighing gallium and tin according to a binary alloy phase diagram, wherein the content of gallium is 88% and the mass content of tin is 12%. Collecting the weighed medicines in a metal crucible, placing the metal crucible on a heating table, heating to 180 ℃ and keeping the temperature for 2 hours, naturally cooling to room temperature, and collecting.
Steps 2) -3) are identical to example 1.
The resulting liquid metal electrode was similar to example 1.
The cycle performance curve of the resulting lithium air battery of the liquid metal electrode is similar to example 1.
The cycle performance curve of the obtained lithium-oxygen battery with liquid metal electrode is shown in fig. 5, the abscissa represents cycle time, and the ordinate represents voltage in V. As can be seen, the lithium-oxygen battery of the obtained liquid metal electrode was at 0.1mA/cm 2 The discharge voltage and the charge voltage of the battery are very small in attenuation (the charge voltage is less than or equal to 4.5V, and the discharge voltage is less than or equal to 2.5V) in the course of 90 circles of circulation, so that the battery can be kept relatively stable and has excellent long-circulation performance.
The obtained liquid metal electrode assembled lithium air soft package battery is shown in fig. 6, the soft package battery can normally light a blue LED bulb in different states such as bending, doubling and creasing, and the flexible metal electrode shows excellent mechanical performance and electrochemical performance.
Example 3:
1) Weighing gallium simple substance, placing the gallium simple substance on a heating table, heating the gallium simple substance to 35 ℃ and keeping the temperature for 3 hours, naturally cooling the gallium simple substance to room temperature, and collecting the gallium simple substance to obtain preset liquid gallium;
2) The metal ruthenium, palladium and platinum particles are added into preset liquid metal gallium, the ratio of the metal ruthenium to the palladium to the platinum is 0.1g to 1g, and the metal ruthenium, the palladium and the platinum particles are ground and mixed by a mortar under the air condition at the room temperature of about 26-30 ℃ for about 15-25 minutes, wherein the metal ruthenium, the palladium and the platinum particles can be used in the ground preset liquid metal Ga.
Step 3) is the same as step 3) in example 1.
The resulting liquid metal electrode was similar to example 1.
The cycle performance curve of the resulting lithium air battery of the liquid metal electrode is similar to example 1.
Example 4:
steps 1) -2) are identical to example 1.
3) Uniformly coating the mixed liquid metal material with ORR/OER catalytic activity obtained in the previous step on a carbon cloth current collector to obtain a liquid metal electrode; cutting a flexible metal electrode into square shapes, and assembling a sodium-air battery, in particular a button-type sodium-air battery, with a metal sodium negative electrode and an ether-based electrolyte according to a correct sequence, wherein the electrolyte is a tetraethylene glycol dimethyl ether solution containing 0.5M NaTFSI.
And (3) taking the liquid metal electrode obtained above as an air positive electrode in the battery, and assembling the battery into a sodium-air battery, in particular a button-type sodium-air battery.
The resulting liquid metal electrode was similar to example 1.
The cycling performance curve of the resulting sodium air cell for the liquid metal electrode was similar to example 1.
Comparative example 1:
1) The liquid metal Ga/In/Sn was not subjected to the treatment of step 2 of example 1, to obtain liquid metal droplets having a large surface tension.
2) And coating the liquid metal liquid drops which have larger surface tension and do not contain metal ruthenium on carbon cloth, and performing a flexibility test. Assembled into a lithium air battery, wherein the lithium air battery is a CR2032 button battery. Wherein the electrolyte is a tetraethylene glycol dimethyl ether solution containing 0.5M LiTFSI.
The obtained pure liquid metal coated carbon cloth is easy to fall off, the liquid metal does not have good adhesiveness on a flexible carbon cloth substrate, the discharge voltage and the charging voltage of a lithium air battery of a carbon cloth anode are seriously attenuated (the charging voltage is not less than 4.4V, the discharge voltage is not less than 2.3V), the stability cannot be kept, and the long-cycle performance is poor.
The invention is not a matter of the known technology.
Claims (6)
1. The preparation method of the flexible metal electrode is characterized by comprising the following steps of:
(1) Weighing a gallium simple substance or a related metal simple substance of a gallium-based liquid metal alloy, then placing the gallium simple substance or the related metal simple substance of the gallium-based liquid metal alloy on a heating table, heating the gallium simple substance or the related metal simple substance of the gallium-based liquid metal alloy to be completely melted, keeping the temperature constant for 2-3 hours, naturally cooling the gallium simple substance or the related metal simple substance of the gallium-based liquid metal alloy to the room temperature, and collecting the gallium simple substance or the related metal simple substance of the gallium-based liquid metal alloy to obtain preset liquid metal;
the gallium-based liquid metal alloy is specifically gallium tin, gallium indium or gallium indium tin;
when the gallium is simple substance, the heating temperature is 30-60 ℃; in the case of gallium-based liquid metal alloy, the heating temperature is 180-220 ℃;
(2) Adding the added metal particles into preset liquid metal, and grinding for 10-20 minutes at room temperature to obtain a flexible liquid metal material;
wherein, the amount of the metal particle material added into each gram of preset liquid metal is 0.1-0.2 g,
the added metal is one or more of ruthenium, platinum, palladium and molybdenum;
(3) Coating the mixed liquid metal material obtained in the previous step on a carbon cloth current collector, and coating 1-5 mg of mixed liquid metal on each square centimeter of carbon cloth to obtain a flexible metal electrode;
the gallium-based liquid metal alloy is one or more of binary alloy and multi-element alloy; the binary alloy is Ga/In, ga/Sn, ga/Bi, ga/Cd, ga/Al, ga/Zn, ga/Hg or Ga/Ag; the multi-element alloy is Ga/In/Sn, ga/In/Sn/Zn or Ga/In/Sn/Fe;
the mass percentage of the gallium metal in the gallium-based liquid metal alloy is 70-99 percent;
the particle diameter range of the added metal particles is 1-5 mu m;
the grinding is artificial grinding and mechanical grinding.
2. Use of a flexible metal electrode prepared by the method of claim 1 as a flexible metal air positive electrode in a battery.
3. The use according to claim 2, characterized in that the liquid metal electrode, the lithium metal negative electrode and the ether-based electrolyte are assembled in the correct order into a lithium air battery;
wherein the solvent of the ether-based electrolyte is an ether solvent; the salt in the ether electrolyte is metal cation salt corresponding to the components contained in the lithium material; the mass percentage concentration of the metal cation salt in the electrolyte is 0.01-40%.
4. The use according to claim 3, wherein the ether solvent is one or more of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether;
when the metal cation salt is one, the metal cation salt is lithium salt; when plural, the metal cation salt is a lithium salt and other salts, and the other salts are one or both of sodium salt and potassium salt.
5. The process according to claim 4, wherein the other salt is NaTFSI or NaClO 4 、NaCF 3 SO 3、 KClO 4 、KCF 3 SO 3 Or KTFSI.
6. The use according to claim 2, wherein the battery is a button battery or a pouch battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111281269.8A CN114005995B (en) | 2021-11-01 | 2021-11-01 | Preparation method of flexible metal electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111281269.8A CN114005995B (en) | 2021-11-01 | 2021-11-01 | Preparation method of flexible metal electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114005995A CN114005995A (en) | 2022-02-01 |
| CN114005995B true CN114005995B (en) | 2023-11-10 |
Family
ID=79925985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111281269.8A Active CN114005995B (en) | 2021-11-01 | 2021-11-01 | Preparation method of flexible metal electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114005995B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115029130B (en) * | 2022-06-27 | 2023-03-14 | 云南大学 | Method for preparing perovskite structure luminescent material based on liquid metal |
| CN115613027A (en) * | 2022-10-19 | 2023-01-17 | 四川大学 | Coating containing liquid metal and preparation method and application thereof |
| CN117866484A (en) * | 2024-03-12 | 2024-04-12 | 成都先进金属材料产业技术研究院股份有限公司 | Liquid metal printing ink and preparation method thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1645655A (en) * | 2003-09-27 | 2005-07-27 | 三星Sdi株式会社 | High concentration carbon supported catalyst, method of preparing the same, catalyst electrode utilizing the catalyst, and fuel cell utilizing the same |
| CN105098291A (en) * | 2015-07-21 | 2015-11-25 | 清华大学深圳研究生院 | Liquid metal-gas battery and preparation method thereof |
| CN105609899A (en) * | 2016-02-16 | 2016-05-25 | 云南科威液态金属谷研发有限公司 | Flexible liquid metal air battery and battery pack |
| CN108110261A (en) * | 2017-12-29 | 2018-06-01 | 成都新柯力化工科技有限公司 | A kind of fuel cell metallic-liquid metal catalyst and preparation method |
| CN108448066A (en) * | 2018-03-22 | 2018-08-24 | 中国科学院合肥物质科学研究院 | A kind of preparation method of adhesive-free, nearly room temperature gallium base fluid state metal-silicon composite negative pole without conductive additive |
| CN109070064A (en) * | 2016-04-19 | 2018-12-21 | 日产自动车株式会社 | Electrode catalyst and the membrane-electrode assembly and fuel cell for using the electrode catalyst |
| WO2019039631A1 (en) * | 2017-08-23 | 2019-02-28 | (주)엘켐텍 | Electrode catalyst layer having web structure, membrane electrode assembly for electrochemical cell using same, and production method therefor |
| CN109494431A (en) * | 2018-11-12 | 2019-03-19 | 西安鸿钧睿泽新材料科技有限公司 | Flexible aluminium air battery of flexible |
| KR20200041591A (en) * | 2018-10-12 | 2020-04-22 | 한국과학기술연구원 | Eutectic liquid metal-air batteries comprising liquid metal electrode and method of preparation thereof |
| CN111682182A (en) * | 2020-06-22 | 2020-09-18 | 吉林大学 | Printable's novel flexible paper base aluminium air battery |
| CN112054216A (en) * | 2020-08-14 | 2020-12-08 | 上海文施绿极科技有限公司 | Electrode slurry for fuel cell and method for producing same |
-
2021
- 2021-11-01 CN CN202111281269.8A patent/CN114005995B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1645655A (en) * | 2003-09-27 | 2005-07-27 | 三星Sdi株式会社 | High concentration carbon supported catalyst, method of preparing the same, catalyst electrode utilizing the catalyst, and fuel cell utilizing the same |
| CN105098291A (en) * | 2015-07-21 | 2015-11-25 | 清华大学深圳研究生院 | Liquid metal-gas battery and preparation method thereof |
| CN105609899A (en) * | 2016-02-16 | 2016-05-25 | 云南科威液态金属谷研发有限公司 | Flexible liquid metal air battery and battery pack |
| CN109070064A (en) * | 2016-04-19 | 2018-12-21 | 日产自动车株式会社 | Electrode catalyst and the membrane-electrode assembly and fuel cell for using the electrode catalyst |
| WO2019039631A1 (en) * | 2017-08-23 | 2019-02-28 | (주)엘켐텍 | Electrode catalyst layer having web structure, membrane electrode assembly for electrochemical cell using same, and production method therefor |
| CN108110261A (en) * | 2017-12-29 | 2018-06-01 | 成都新柯力化工科技有限公司 | A kind of fuel cell metallic-liquid metal catalyst and preparation method |
| CN108448066A (en) * | 2018-03-22 | 2018-08-24 | 中国科学院合肥物质科学研究院 | A kind of preparation method of adhesive-free, nearly room temperature gallium base fluid state metal-silicon composite negative pole without conductive additive |
| KR20200041591A (en) * | 2018-10-12 | 2020-04-22 | 한국과학기술연구원 | Eutectic liquid metal-air batteries comprising liquid metal electrode and method of preparation thereof |
| CN109494431A (en) * | 2018-11-12 | 2019-03-19 | 西安鸿钧睿泽新材料科技有限公司 | Flexible aluminium air battery of flexible |
| CN111682182A (en) * | 2020-06-22 | 2020-09-18 | 吉林大学 | Printable's novel flexible paper base aluminium air battery |
| CN112054216A (en) * | 2020-08-14 | 2020-12-08 | 上海文施绿极科技有限公司 | Electrode slurry for fuel cell and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114005995A (en) | 2022-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114005995B (en) | Preparation method of flexible metal electrode | |
| CN110620223B (en) | Lithium ion battery pre-lithiation silicon-carbon multilayer composite negative electrode material and preparation method thereof | |
| CN102479949B (en) | Anode active material of lithium ion battery, preparation method thereof and lithium ion battery | |
| JP4043852B2 (en) | Method for producing electrode material | |
| CN108666553B (en) | Cobalt sulfide/carbon fiber compound and preparation method and application thereof | |
| CN102332572B (en) | Anode material and manufacturing method thereof as well as lithium ion battery and negative plate thereof | |
| CN110600707B (en) | High-capacity electrode material for high-nitrogen-doped carbon-coated metal sodium sulfide secondary battery and application of high-capacity electrode material | |
| CN111653744B (en) | Sodium ion battery positive electrode sodium supplement additive, sodium ion battery positive electrode plate and sodium ion battery | |
| CN101800304B (en) | Different-orientation spherical natural graphite negative electrode material and preparation method thereof | |
| CN101764253A (en) | Secondary aluminum battery and preparation method thereof | |
| CN102208617B (en) | Method for preparing cathode active substance of lithium ion secondary cells | |
| CN108736056B (en) | Lithium metal interface protection structure and preparation and application thereof | |
| CN105047861A (en) | Sulfur-carbon composite material and preparation method thereof | |
| CN109273672B (en) | Na-K liquid alloy electrode coated with in-situ SEI film as well as preparation method and application thereof | |
| CN109509870A (en) | Use Li2The method that S manufactures the electrode of lithium-sulfur cell as active material | |
| CN117219777B (en) | Lithium supplementing agent, preparation method thereof, positive electrode plate and secondary battery | |
| CN110890540A (en) | Fluorine-containing silicon monoxide negative electrode material and preparation method and application thereof | |
| KR101481230B1 (en) | Positive Electrode for Lithium Air Battery, Method of Preparing the Same, and Lithium Air Battery Employing the Same | |
| CN111653724B (en) | Surface-modified lithium nickel manganese oxide positive electrode material and preparation method thereof | |
| CN115881915A (en) | Large-scale preparation method for in-situ construction of zinc cathode metal composite protective layer by ultrafast microwave technology and application thereof | |
| CN112768756B (en) | Solid electrolyte material, and composite solid electrolyte and all-solid-state battery prepared from same | |
| CN115566132B (en) | Silver-bismuth dual-function electrode and preparation method and application thereof | |
| CN115133109B (en) | Water system copper ion battery | |
| CN114210990B (en) | Tin-iron alloy nanoparticle high-performance lithium and sodium storage material and application thereof | |
| CN117199360B (en) | Sodium carbonate/carbon composite positive electrode sodium supplementing additive, preparation method thereof and application thereof in negative electrode-free sodium metal battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |