CN113764674B - Electrode carrier loaded with sodium-potassium alloy and preparation method thereof - Google Patents
Electrode carrier loaded with sodium-potassium alloy and preparation method thereof Download PDFInfo
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- CN113764674B CN113764674B CN202010496659.6A CN202010496659A CN113764674B CN 113764674 B CN113764674 B CN 113764674B CN 202010496659 A CN202010496659 A CN 202010496659A CN 113764674 B CN113764674 B CN 113764674B
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- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 229910000799 K alloy Inorganic materials 0.000 title claims abstract description 157
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002131 composite material Substances 0.000 claims abstract description 32
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 29
- 239000000654 additive Substances 0.000 claims abstract description 22
- 230000000996 additive effect Effects 0.000 claims abstract description 22
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 14
- 239000013310 covalent-organic framework Substances 0.000 claims abstract description 13
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 37
- 229910052700 potassium Inorganic materials 0.000 claims description 36
- 239000011591 potassium Substances 0.000 claims description 36
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 34
- 229910052708 sodium Inorganic materials 0.000 claims description 34
- 239000011734 sodium Substances 0.000 claims description 34
- 239000011259 mixed solution Substances 0.000 claims description 25
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000009736 wetting Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- 229910001887 tin oxide Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000013474 COF-1 Substances 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- -1 zeolite imidazole ester Chemical class 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 238000011068 loading method Methods 0.000 abstract description 5
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 235000012431 wafers Nutrition 0.000 description 20
- 238000005520 cutting process Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- 239000012528 membrane Substances 0.000 description 13
- 238000000967 suction filtration Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229910000574 NaK Inorganic materials 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 108010025899 gelatin film Proteins 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910003251 Na K Inorganic materials 0.000 description 2
- 235000005811 Viola adunca Nutrition 0.000 description 2
- 240000009038 Viola odorata Species 0.000 description 2
- 235000013487 Viola odorata Nutrition 0.000 description 2
- 235000002254 Viola papilionacea Nutrition 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229910001338 liquidmetal Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003746 surface roughness Effects 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/666—Composites in the form of mixed materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/668—Composites of electroconductive material and synthetic resins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides an electrode carrier loaded with sodium-potassium alloy and a preparation method thereof. The electrode carrier for loading the sodium-potassium alloy comprises the following components in parts by weight: 4-8 parts of graphene and 1-8 parts of an additive, wherein the additive comprises at least one of nano oxide, metal-organic framework material and covalent organic framework material. The sodium-potassium alloy-loaded electrode carrier can ensure the high conductivity of the electrode, and the existence of the sodium-potassium alloy composite electrode can not influence the conductivity of the electrode, so that the high energy density of the electrode is ensured; the additive and the functional groups rich in the surface of the graphene can greatly reduce the surface tension of the electrode carrier, increase the wettability between the electrode carrier and the sodium-potassium alloy, accelerate the diffusion of the sodium-potassium alloy on the electrode carrier, further fully infiltrate and uniformly distribute the sodium-potassium alloy, and the electrode carrier has the characteristics of relatively low mass occupation, high surface area and light mass, and relatively high load capacity.
Description
Technical Field
The invention relates to the field of new energy materials, in particular to an electrode carrier for loading sodium-potassium alloy and a preparation method thereof.
Background
In order to meet the requirements of large-scale energy storage of new energy automobiles, large-scale energy storage equipment (such as a power grid) and the like, rechargeable batteries with excellent performance are extremely important. Sodium metal batteries have a sufficiently high voltage, a long cycle life and a fast charge and discharge rate, and sodium is ubiquitous in the ocean, and the reserves are thousands of times that of lithium, with low cost and easy availability, so sodium metal batteries are considered as one of the next generation battery systems to replace lithium batteries, being a powerful competitor for lithium batteries. However, the intrinsic dendrite growth problem of sodium metal makes it very prone to puncture the separator during cycling, resulting in internal shorting of the cell, and poses a serious safety problem.
Sodium and potassium can form liquid sodium-potassium alloy at room temperature, and the sodium-potassium alloy is hopeful to solve the problem of dendrite of sodium metal as a cathode material. The sodium-potassium alloy cathode is generally composed of sodium-potassium alloy and a carrier for loading the sodium-potassium alloy, carbon carriers such as carbon cloth are often selected as the carrier, but the sodium-potassium alloy has high surface tension, so that the wettability is poor, self-agglomeration is easy to occur to form liquid drops, and the carrier surface falls off, so that voltage fluctuation in the battery circulation process is caused, and the performance of the battery is influenced. The wettability of the sodium-potassium alloy on the carrier can be improved in a high-temperature state, but after the room temperature is recovered, the surface tension of the sodium-potassium alloy is recovered, so that the problem that the liquid sodium-potassium alloy falls off from the surface of the carrier cannot be fundamentally solved by adopting high-temperature heating.
In order to increase the structural stability of a sodium-potassium alloy cathode, chinese patent literature (CN 109273672A) discloses a preparation method of an in-situ SEI film coated Na-K liquid alloy electrode, wherein liquid sodium-potassium alloy is heated to 300-800 ℃, then a conductive carrier is contacted with the liquid sodium-potassium alloy, so that the liquid sodium-potassium alloy wets the conductive carrier, and after the liquid sodium-potassium alloy is fully absorbed, the non-cooled conductive carrier loaded with the liquid sodium-potassium alloy is inserted into electrolyte for quenching, so that the in-situ SEI film coated Na-K liquid alloy electrode is obtained. According to the method, the stability of the electrode structure is improved by high wettability of Wen Disheng liquid sodium-potassium alloy on a conductive carrier and quenching to form an in-situ SEI film on the surface. However, this method requires high temperature treatment (300 to 800 ℃) and is cumbersome in steps, difficult to operate and unsuitable for mass production.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defect that the sodium-potassium alloy-loaded electrode carrier in the prior art has poor wettability on the sodium-potassium alloy, so that the sodium-potassium alloy is easy to fall off from the surface of the carrier to influence the performance of a battery, thereby providing the sodium-potassium alloy-loaded electrode carrier and a preparation method thereof.
In a first aspect, the invention provides an electrode carrier for supporting sodium-potassium alloy, comprising the following components in parts by weight:
4-8 parts of graphene and the like,
1-8 parts of an additive,
the additive comprises at least one of a nano-oxide, a metal-organic framework material, and a covalent organic framework material.
Further, the mass ratio of the graphene to the additive is 1-4: 1.
further, the nano oxide comprises at least one of nano tin oxide, nano zinc oxide, nano aluminum oxide and nano titanium oxide, and the particle size of the nano oxide is 10-100 nm;
the metal-organic framework material comprises a zeolite imidazole ester framework material ZIF-67;
the covalent organic framework material comprises a two-dimensional lamellar covalent organic framework material COF-1.
In a second aspect, the invention provides a method for preparing the sodium-potassium alloy-loaded electrode carrier, which comprises the following steps:
uniformly mixing the graphene, the additive and water to obtain a mixed solution;
vacuum filtering the mixed solution to obtain a gel state film;
the gel-state film is subjected to drying,
wherein when the additive is selected from metal-organic framework materials and/or covalent organic framework materials, the method further comprises the following steps: and calcining the dried gel state film.
Further, in the mixed solution, the concentration of the graphene is 1 to 2 mg/mL -1 The concentration of the additive is 0.25-2 mg.mL -1 。
Further, the drying is vacuum drying at 80 ℃ for more than 24 hours, and the calcining is calcining at 500 ℃ in nitrogen atmosphere for 1 hour.
In a third aspect, the invention provides a sodium-potassium alloy composite electrode, which comprises sodium-potassium alloy, and the sodium-potassium alloy-loaded electrode carrier or the sodium-potassium alloy-loaded electrode carrier obtained by the preparation method.
In a fourth aspect, the invention provides a method for preparing the sodium-potassium alloy composite electrode, which comprises the following steps: and wetting the sodium-potassium alloy-loaded electrode carrier with sodium-potassium alloy to obtain the sodium-potassium alloy composite electrode.
Further, the preparation method of the sodium-potassium alloy comprises the following steps: and mixing metal sodium and metal potassium, and melting to obtain the sodium-potassium alloy, wherein the mass ratio of the metal sodium to the metal potassium is 3:7.
In a fifth aspect, the invention provides a sodium-potassium alloy battery, comprising the sodium-potassium alloy composite electrode, or the sodium-potassium alloy composite electrode obtained by the preparation method.
The technical scheme of the invention has the following advantages:
1. the electrode carrier for loading the sodium-potassium alloy comprises graphene and an additive, wherein the additive comprises at least one of nano oxide, metal-organic framework materials (Metal-Organic Frameworks, MOFs) and covalent organic framework materials (Covalent Organic Frameworks, COFs). The high conductivity of the electrode can be ensured, the conductivity of the electrode cannot be influenced when the sodium-potassium alloy composite electrode exists, and the high energy density of the electrode is ensured; the additive and the functional groups rich in the surface of the graphene can greatly reduce the surface tension of the electrode carrier, particularly the additive can increase the surface roughness of the carrier in the electrode carrier, meanwhile, the additive and the potassium-sodium alloy have better wettability and can serve as diffusion sites, the wettability between the electrode carrier and the sodium-potassium alloy is increased, the diffusion of the sodium-potassium alloy on the electrode carrier is accelerated, and the sodium-potassium alloy can be fully infiltrated and uniformly distributed, in addition, the electrode carrier has the characteristics of relatively low mass occupation, high surface area and light mass, and has higher loading capacity, so that the electrode carrier is an ideal electrode carrier material.
2. According to the preparation method of the sodium-potassium alloy-loaded electrode carrier, graphene, an additive and water are uniformly mixed to obtain a mixed solution; vacuum filtering the mixed solution to obtain a gel state film; drying the gel state film, wherein when the additive is selected from metal-organic framework materials and/or covalent organic framework materials, the gel state film further comprises: and calcining the dried gel state film. The prepared electrode carrier has good wettability to the sodium-potassium alloy, can be directly combined at normal temperature to form a stable electrode material, has simple steps in the preparation process of the electrode carrier loaded with the sodium-potassium alloy, is easy to operate, has no special equipment requirement, has high consistency of the obtained product, and is suitable for large-scale processing production.
3. The sodium-potassium alloy composite electrode provided by the invention comprises the sodium-potassium alloy and the electrode carrier loaded with the sodium-potassium alloy, wherein the sodium-potassium alloy is in a liquid state at room temperature, so that the sodium-potassium alloy has the flow characteristic of liquid, the deformation and self-repairing capacity of the sodium-potassium alloy composite electrode are ensured, and the dendrite problem can be fundamentally avoided; compared with the traditional high-temperature liquid metal system, the room-temperature liquid metal does not need extra energy input to maintain the liquid characteristic, and the problems of encapsulation, maintenance, corrosion and the like caused by high temperature are avoided; the negative electrode based on the sodium-potassium alloy also provides higher capacity and energy density for the battery, so that the battery becomes an ideal metal negative electrode; the sodium-potassium alloy can be fully wetted and uniformly distributed on the electrode carrier loaded with the sodium-potassium alloy, and the formed potassium-sodium alloy composite electrode has excellent cycle stability, long service life and high energy density, and the preparation method is simple and can be widely popularized and used as a novel metal electrode.
4. According to the preparation method of the sodium-potassium alloy composite electrode, the sodium-potassium alloy-loaded electrode carrier is obtained by wetting the sodium-potassium alloy-loaded electrode carrier, the prepared sodium-potassium alloy-loaded electrode carrier has good wettability to the sodium-potassium alloy, stable electrode materials can be directly formed by combination at normal temperature, the preparation process of the sodium-potassium alloy and the sodium-potassium alloy-loaded electrode carrier is simple in steps, easy to operate, free of special equipment requirements, high in consistency of the obtained product, free of by-product production, and suitable for large-scale processing production of metal electrodes.
5. The sodium-potassium alloy battery provided by the invention comprises the sodium-potassium alloy composite electrode, and based on the excellent cycle stability, long service life and high energy density of the potassium-sodium alloy composite electrode, the sodium-potassium alloy battery formed by matching the sodium-potassium alloy composite electrode with the flexible solid electrolyte material can realize better flexibility and safety performance of the battery, and the metal battery is promoted to be widely applied.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the effect of adsorbing a sodium-potassium alloy on a sodium-potassium alloy-supported electrode carrier obtained in example 1;
FIG. 2 is a graph showing the effect of the sodium-potassium alloy adsorption on the sodium-potassium alloy-supported electrode carrier obtained in the comparative example;
FIG. 3 is an electrochemical cycle diagram of the assembled sodium-potassium alloy composite electrode pair cell obtained in example 11;
fig. 4 is an electrochemical cycle diagram of an assembled potassium cell.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The sources of reagents, instruments and other experimental materials involved in the examples, comparative examples and test examples of the present invention are shown in table 1.
Table 1 reagents, instrumentation and other sources of laboratory materials
The particle size of the nano tin oxide and the nano tin oxide is 10-100nm.
In the embodiment, the zeolite imidazole ester framework material ZIF-67 is a metal-organic framework Material (MOFs) with a zeolite topological structure, and is obtained by the following preparation method:
mixing 40mL of dimethyl imidazole solution (0.4M) and 40mL of cobalt nitrate solution (0.05M), stirring for 4 hours, standing overnight, centrifuging the solution to obtain a blue-violet precipitate, cleaning the precipitate, transferring the precipitate to a vacuum constant temperature drying oven, and vacuum drying at 60 ℃ overnight to obtain the blue-violet precipitate.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The materials or instruments used are all conventional products commercially available, including but not limited to those used in the examples of the present application.
Example 1
The preparation method of the sodium-potassium alloy-loaded electrode carrier comprises the following operation steps:
(1) Placing 0.01g of nano zinc oxide and 0.04g of graphene in water, stirring for 1h by using a constant-temperature heating magnetic stirrer, and performing ultrasonic treatment for 0.5h to obtain a mixed solution (in the mixed solution, the concentration of nano zinc oxide is 0.25 mg.mL) -1 The concentration of graphene is 1 mg.mL -1 )；
(2) Taking 40mL of the mixed solution for vacuum suction filtration to obtain a gel state membrane;
(3) And vacuum drying the gel membrane obtained by suction filtration in a vacuum constant temperature drying oven at 80 ℃ for more than 24 hours to obtain the electrode carrier with the thickness of 5 mu m and loaded with the sodium-potassium alloy.
Example 2
The preparation method of the sodium-potassium alloy-loaded electrode carrier comprises the following operation steps:
(1) Putting 0.08g of nano zinc oxide and 0.08g of graphene into water, stirring for 1h by using a constant-temperature heating magnetic stirrer, and performing ultrasonic treatment for 0.5h to obtain a mixed solution (in the mixed solution, the concentration of nano zinc oxide is 2 mg.mL) -1 The concentration of graphene is 2 mg.mL -1 )；
(2) Taking 40mL of the mixed solution for vacuum suction filtration to obtain a gel state membrane;
(3) Vacuum drying the gel film obtained by suction filtration in a vacuum constant temperature drying oven at 80 ℃ for more than 24 hours to obtain the electrode carrier with the thickness of 15 mu m and loaded with the sodium-potassium alloy.
Example 3
The preparation method of the sodium-potassium alloy-loaded electrode carrier comprises the following operation steps:
(1) Placing 0.04g of nano zinc oxide and 0.04g of graphene in water, stirring for 1h by using a constant-temperature heating magnetic stirrer, and performing ultrasonic treatment for 0.5h to obtain a mixed solution (in the mixed solution, the concentration of nano zinc oxide is 1 mg.mL) -1 The concentration of graphene is 1 mg.mL -1 )；
(2) Taking 40mL of the mixed solution for vacuum suction filtration to obtain a gel state membrane;
(3) And vacuum drying the gel membrane obtained by suction filtration in a vacuum constant temperature drying oven at 80 ℃ for more than 24 hours to obtain the electrode carrier with the thickness of 8 mu m and loaded with the sodium-potassium alloy.
Example 4
The preparation method of the sodium-potassium alloy-loaded electrode carrier comprises the following operation steps:
(1) Placing 0.03g of nano tin oxide and 0.06g of graphene in water, stirring for 1h by using a constant-temperature heating magnetic stirrer, and performing ultrasonic treatment for 0.5h to obtain a mixed solution (in the mixed solution, the concentration of nano tin oxide is 0.5 mg.mL) -1 The concentration of graphene is 1 mg.mL -1 )；
(2) Vacuum filtering 60mL of the mixed solution to obtain a gel state membrane;
(3) And vacuum drying the gel membrane obtained by suction filtration in a vacuum constant temperature drying oven at 80 ℃ for more than 24 hours to obtain the electrode carrier with the thickness of 8 mu m and loaded with the sodium-potassium alloy.
Example 5
The preparation method of the sodium-potassium alloy-loaded electrode carrier comprises the following operation steps:
(1) Putting 0.01g of ZIF-67 and 0.04g of graphene into water, stirring for 1h by using a constant-temperature heating magnetic stirrer, and performing ultrasonic treatment for 0.5h to obtain a mixed solution (ZIF-in-water)67 concentration was 0.25 mg/mL -1 The concentration of graphene is 1 mg.mL -1 )；
(2) Taking 40mL of the mixed solution for vacuum suction filtration to obtain a gel state membrane;
(3) Vacuum drying the gel membrane obtained by suction filtration in a vacuum constant temperature drying oven at 80 ℃ for more than 24 hours;
(4) The dried gel film was calcined in a tube furnace for 1 hour (nitrogen atmosphere, 500 ℃ C.) to obtain a sodium-potassium alloy-supported electrode carrier having a thickness of 5. Mu.m.
Example 6
The preparation method of the sodium-potassium alloy-loaded electrode carrier comprises the following operation steps:
(1) Placing 0.01g of COF-1 and 0.04g of graphene into deionized water, stirring for 1h by using a constant-temperature heating magnetic stirrer, and performing ultrasonic treatment for 0.5h to obtain a mixed solution (in the mixed solution, the concentration of COF-1 is 0.25 mg.mL) -1 The concentration of graphene is 1 mg.mL -1 )；
(2) Taking 40mL of the mixed solution for vacuum suction filtration to obtain a gel state membrane;
(3) Vacuum drying the gel membrane obtained by suction filtration in a vacuum constant temperature drying oven at 80 ℃ for more than 24 hours;
(4) The dried gel film was calcined in a tube furnace for 1 hour (nitrogen atmosphere, 500 ℃ C.) to obtain a sodium-potassium alloy-supported electrode carrier having a thickness of 5. Mu.m.
Example 7
The preparation method of the sodium-potassium alloy composite electrode comprises the following operation steps:
(1) Respectively taking 30g of metallic sodium and 70g of metallic potassium (the metallic sodium and the metallic potassium remove surface oxides), simultaneously placing the metallic sodium and the metallic potassium in a reaction bottle in a glove box at room temperature, and gradually melting the metallic sodium and the metallic potassium into uniform sodium-potassium alloy after contact;
(2) Cutting the electrode carrier loaded with the sodium-potassium alloy and prepared in the embodiment 1 into a wafer with the diameter of 11mm by using a cutting machine, putting the wafer into a reaction bottle of the sodium-potassium alloy prepared in the step (1), and diffusing and wetting the wafer by the sodium-potassium alloy to form a sodium-potassium alloy electrode.
Example 8
The preparation method of the sodium-potassium alloy composite electrode comprises the following operation steps:
(1) Respectively taking 30g of metallic sodium and 70g of metallic potassium (the metallic sodium and the metallic potassium remove surface oxides), simultaneously placing the metallic sodium and the metallic potassium in a reaction bottle in a glove box at room temperature, and gradually melting the metallic sodium and the metallic potassium into uniform sodium-potassium alloy after contact;
(2) Cutting the electrode carrier loaded with the sodium-potassium alloy and prepared in the embodiment 2 into a wafer with the diameter of 11mm by using a cutting machine, putting the wafer into a reaction bottle of the sodium-potassium alloy prepared in the step (1), and diffusing and wetting the wafer by the sodium-potassium alloy to form a sodium-potassium alloy electrode.
Example 9
The preparation method of the sodium-potassium alloy composite electrode comprises the following operation steps:
(1) Respectively taking 30g of metallic sodium and 70g of metallic potassium (the metallic sodium and the metallic potassium remove surface oxides), simultaneously placing the metallic sodium and the metallic potassium in a reaction bottle in a glove box at room temperature, and gradually melting the metallic sodium and the metallic potassium into uniform sodium-potassium alloy after contact;
(2) Cutting the electrode carrier loaded with the sodium-potassium alloy and prepared in the embodiment 3 into a wafer with the diameter of 11mm by using a cutting machine, putting the wafer into a reaction bottle of the sodium-potassium alloy prepared in the step (1), and diffusing and wetting the wafer by the sodium-potassium alloy to form a sodium-potassium alloy electrode.
Example 10
The preparation method of the sodium-potassium alloy composite electrode comprises the following operation steps:
(1) Respectively taking 30g of metallic sodium and 70g of metallic potassium (the metallic sodium and the metallic potassium remove surface oxides), simultaneously placing the metallic sodium and the metallic potassium in a reaction bottle in a glove box at room temperature, and gradually melting the metallic sodium and the metallic potassium into uniform sodium-potassium alloy after contact;
(2) Cutting the electrode carrier loaded with the sodium-potassium alloy and prepared in the embodiment 4 into a wafer with the diameter of 11mm by using a cutting machine, putting the wafer into a reaction bottle of the sodium-potassium alloy prepared in the step (1), and diffusing and wetting the wafer by the sodium-potassium alloy to form a sodium-potassium alloy electrode.
Example 11
The preparation method of the sodium-potassium alloy composite electrode comprises the following operation steps:
(1) Respectively taking 30g of metallic sodium and 70g of metallic potassium (the metallic sodium and the metallic potassium remove surface oxides), simultaneously placing the metallic sodium and the metallic potassium in a reaction bottle in a glove box at room temperature, and gradually melting the metallic sodium and the metallic potassium into uniform sodium-potassium alloy after contact;
(2) Cutting the electrode carrier loaded with the sodium-potassium alloy and prepared in the embodiment 5 into a wafer with the diameter of 11mm by using a cutting machine, putting the wafer into a reaction bottle of the sodium-potassium alloy prepared in the step (1), and diffusing and wetting the wafer by the sodium-potassium alloy to form a sodium-potassium alloy electrode.
Example 12
The preparation method of the sodium-potassium alloy composite electrode comprises the following operation steps:
(1) Respectively taking 30g of metallic sodium and 70g of metallic potassium (the metallic sodium and the metallic potassium remove surface oxides), simultaneously placing the metallic sodium and the metallic potassium in a reaction bottle in a glove box at room temperature, and gradually melting the metallic sodium and the metallic potassium into uniform sodium-potassium alloy after contact;
(2) Cutting the electrode carrier loaded with the sodium-potassium alloy and prepared in the embodiment 6 into a wafer with the diameter of 11mm by using a cutting machine, putting the wafer into a reaction bottle of the sodium-potassium alloy prepared in the step (1), and diffusing and wetting the wafer by the sodium-potassium alloy to form a sodium-potassium alloy electrode.
Comparative example
The preparation method of the sodium-potassium alloy-loaded electrode carrier comprises the following operation steps:
(1) Placing graphene in water, stirring for 1h, and performing ultrasonic treatment for 0.5h to obtain graphene solution (in which the concentration of graphene is 1 mg/mL) -1 )；
(2) Taking 50mL of graphene solution, and carrying out vacuum suction filtration to obtain a gel state membrane;
(3) And vacuum drying the gel membrane obtained by suction filtration in a vacuum constant temperature drying oven at 80 ℃ for more than 24 hours to obtain the electrode carrier with the thickness of 5 mu m and loaded with the sodium-potassium alloy.
Experimental example 1
1. Purpose of experiment
Wettability between the sodium-potassium alloy-supported electrode carrier prepared in comparative example 1 and comparative example and the sodium-potassium alloy.
2. Experimental method
(1) Respectively taking 30g of metallic sodium and 70g of metallic potassium (the metallic sodium and the metallic potassium remove surface oxides), simultaneously placing the metallic sodium and the metallic potassium in a reaction bottle in a glove box at room temperature, and gradually melting the metallic sodium and the metallic potassium into uniform sodium-potassium alloy after contact;
(2) Cutting the sodium-potassium alloy-loaded electrode carriers prepared in the example 1 and the comparative example into wafers with the diameter of 11mm by using a cutting machine, putting the wafers into the sodium-potassium alloy reaction bottle prepared in the step (1), and observing the wetting condition of the sodium-potassium alloy to the electrode carrier after 1 min.
3. Experimental results
After the sodium-potassium alloy-supported electrode carriers prepared in example 1 and comparative example were contacted with the sodium-potassium alloy for the same time, respectively, the wetting condition of the sodium-potassium alloy to the electrode carrier prepared in example 1 was shown in fig. 1, and the wetting condition of the sodium-potassium alloy to the electrode carrier prepared in comparative example was shown in fig. 2. As can be seen from fig. 1 and fig. 2, the sodium-potassium alloy-loaded electrode carrier prepared in embodiment 1 of the present invention has better wettability to the sodium-potassium alloy than the graphene film, which proves that adding MOFs to graphene during the preparation of the electrode carrier can significantly increase wettability between the electrode carrier and the sodium-potassium alloy, and accelerate diffusion of the sodium-potassium alloy on the electrode carrier, so that the sodium-potassium alloy-loaded electrode carrier can be fully infiltrated with the potassium-sodium alloy and uniformly distributed.
Experiments were performed on the sodium-potassium alloy-supported electrode carriers prepared in examples 2 to 6 under the same conditions, and the wettability with respect to the sodium-potassium alloy was significantly improved as compared with the comparative examples.
Experimental example 2
The sodium-potassium alloy composite electrode, the battery case and the glass fiber diaphragm prepared in the above examples 7-12 are respectively assembled into a CR2032 standard button-type symmetrical battery by using a sealing machine, and the electrolyte adopts KPF of 1M 6 Electrolyte (EC/DEC with solvent volume ratio of 1:1) electrochemical test was performed using a Land battery test system and electrochemical workstation (test conditions: room temperature, current density of 1 mA. Cm -2 Charge-discharge capacity 1mAh cm -2 ). Meanwhile, the same battery case, glass fiber diaphragm and electrolyte are used, potassium metal is used as a working electrode and a counter electrode, a CR2032 standard button-type symmetrical battery is assembled by using a sealing machine, and electrochemical test is carried out under the same test condition.
Examples 7 to 12The assembled sodium-potassium alloy composite electrode of the pair cell has the current density of 1mA cm -2 Charge-discharge capacity 1mAh cm -2 The conditions of (2) were such that the cycle could be stabilized for 170 hours or more and the coulombic efficiency was maintained at 97% or more, wherein example 11 was able to be stabilized for 200 hours and the coulombic efficiency was maintained at 99.4% or more, the charge and discharge curves were as shown in fig. 3 and the charge and discharge curves for the potassium cell were as shown in fig. 4. As can be seen from fig. 3 and 4, the assembled battery of the sodium-potassium alloy composite electrode of the present application exhibits significant electrochemical performance advantages over the potassium battery.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (9)
1. The preparation method of the sodium-potassium alloy composite electrode is characterized by wetting a sodium-potassium alloy-loaded electrode carrier with sodium-potassium alloy to obtain the sodium-potassium alloy composite electrode, wherein the sodium-potassium alloy-loaded electrode carrier comprises the following components in parts by weight:
4-8 parts of graphene and the like,
1-8 parts of an additive,
the additive comprises at least one of a nano-oxide, a metal-organic framework material, and a covalent organic framework material.
2. The preparation method of the sodium-potassium alloy composite electrode according to claim 1, wherein the mass ratio of the graphene to the additive is 1-4: 1.
3. the method for producing a sodium-potassium alloy composite electrode according to claim 1 or 2, wherein,
the nano oxide comprises at least one of nano tin oxide, nano zinc oxide, nano aluminum oxide and nano titanium oxide, and the particle size of the nano oxide is 10-100 nm;
the metal-organic framework material comprises a zeolite imidazole ester framework material ZIF-67;
the covalent organic framework material comprises a two-dimensional lamellar covalent organic framework material COF-1.
4. The method for preparing a sodium-potassium alloy composite electrode according to claim 1, wherein the method for preparing a sodium-potassium alloy comprises: and mixing metal sodium and metal potassium, and melting to obtain the sodium-potassium alloy, wherein the mass ratio of the metal sodium to the metal potassium is 3:7.
5. A method for producing the sodium-potassium alloy-supported electrode carrier according to any one of claims 1 to 4, comprising:
uniformly mixing the graphene, the additive and water to obtain a mixed solution;
vacuum filtering the mixed solution to obtain a gel state film;
the gel-state film is subjected to drying,
wherein when the additive is selected from metal-organic framework materials and/or covalent organic framework materials, the method further comprises the following steps: and calcining the dried gel state film.
6. The method for producing a sodium-potassium alloy-supported electrode carrier according to claim 5, wherein the concentration of the graphene in the mixed solution is 1 to 2 mg/mL -1 The concentration of the additive is 0.25-2 mg.mL -1 。
7. The method for producing a sodium-potassium alloy-supported electrode carrier according to claim 5 or 6, wherein the drying is vacuum-dried at 80 ℃ for 24 hours or more, and the calcination is calcination at 500 ℃ under a nitrogen atmosphere for 1 hour.
8. A sodium-potassium alloy composite electrode, which is characterized by comprising sodium-potassium alloy, a preparation method of the sodium-potassium alloy composite electrode according to any one of claims 1 to 4 or an electrode carrier loaded with the sodium-potassium alloy and obtained by the preparation method according to any one of claims 5 to 7.
9. A sodium-potassium alloy battery comprising the sodium-potassium alloy composite electrode of claim 8 or obtained by the method of any one of claims 1 to 4.
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