CN114361430B - Method for rapidly preparing non-Newtonian fluid state potassium-sodium alloy electrode by micro-short circuit method and application - Google Patents
Method for rapidly preparing non-Newtonian fluid state potassium-sodium alloy electrode by micro-short circuit method and application Download PDFInfo
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- 229910000574 NaK Inorganic materials 0.000 title claims abstract description 90
- 239000012530 fluid Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 33
- 239000003792 electrolyte Substances 0.000 claims abstract description 21
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 239000011268 mixed slurry Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 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 9
- 239000011734 sodium Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 238000003487 electrochemical reaction Methods 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- -1 hexafluorophosphate Chemical compound 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- 150000003385 sodium Chemical class 0.000 claims description 2
- 125000005463 sulfonylimide group Chemical group 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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 1
- 239000007788 liquid Substances 0.000 abstract description 28
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 9
- 150000001340 alkali metals Chemical group 0.000 abstract description 9
- 210000001787 dendrite Anatomy 0.000 abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 abstract description 4
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007774 positive electrode material Substances 0.000 abstract description 3
- 229960003351 prussian blue Drugs 0.000 abstract description 3
- 239000013225 prussian blue Substances 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- 239000002002 slurry Substances 0.000 abstract 1
- 230000008569 process Effects 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000009969 flowable effect Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910002065 alloy metal Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 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 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
-
- 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a non-Newtonian fluid state potassium-sodium alloy electrode prepared by a micro-short circuit method and application thereof as a cathode material of a potassium-sodium alloy secondary alkali metal battery, wherein the method comprises the following steps: mixing and stirring powder materials and electrolyte under the protection of inert gas to form precursor slurry; under the protection of inert gas, adding liquid potassium-sodium alloy into a precursor of the non-Newtonian fluid potassium-sodium alloy composite material, uniformly mixing to form micro short circuit, and then coating the material on a carrier to obtain the non-Newtonian fluid potassium-sodium alloy electrode. The electrode comprises a carrier and a non-Newtonian fluid potassium-sodium alloy composite material coated on the carrier. The powder material has high selectivity, and the electrode has the characteristics of high coulomb efficiency, no dendrite growth, stable structure and the like, can be used as a potassium metal negative electrode and a sodium metal battery negative electrode simultaneously, and can obviously improve the energy density and the cycle stability of a full battery when being matched with sulfur, prussian blue and other positive electrode materials.
Description
Technical Field
The invention relates to the technical field of potassium-sodium alloy secondary alkali metal battery negative electrode materials, in particular to a method for rapidly preparing a non-Newtonian fluid state potassium-sodium alloy electrode by using a micro-short circuit method and application of the non-Newtonian fluid state potassium-sodium alloy electrode as a potassium-sodium alloy secondary battery negative electrode material.
Background
With the development of technology and the popularization of electronic products, conventional lithium ion batteries have failed to meet the demands. Compared with the traditional carbon materials, metal oxides and the like, the alkali metal battery has higher specific capacity and higher energy density, and becomes a new research hot spot, but because dendrite growth exists on the alkali metal electrode, the alkali metal electrode is easy to short-circuit, potential safety hazards are caused, and the development of the alkali metal battery in practical power grids and electronic product application is hindered. The liquid potassium-sodium alloy has the characteristics of low toxicity, wide stability temperature (even at the normal temperature of-12.6 ℃ in liquid form) and the like. In addition, dendrites are not existed in the liquid alloy metal deposition process, so that the growth of dendrites can be completely inhibited, and the method becomes an emerging research direction of dendrite-free cathode materials. However, the liquid potassium-sodium alloy has high surface tension, is difficult to wet on the surface of a current collector, and seriously hinders the commercialization application of the liquid potassium-sodium alloy. The potassium-sodium alloy battery is used as a novel energy storage device, has the characteristics of large reserve, low preparation cost, wide electrochemical window, no dendrite and the like, and has wide application prospect in the fields of mobile electronic products, electric automobiles, large-scale energy storage, power grids and the like. Therefore, research on the liquid metal electrode with stable structure at normal temperature has important significance for the application and development of the potassium-sodium alloy secondary battery.
Research shows that the high-temperature treatment (more than 420 ℃) can improve the wettability of the liquid potassium-sodium alloy on the carbon paper, and the porous material can store more liquid potassium-sodium alloy, so that the problem of fluidity of the potassium-sodium liquid alloy is solved. However, when the composite electrode is applied at room temperature, the liquid potassium-sodium alloy on the surface of the composite electrode is easy to fall off due to the large surface tension of the liquid potassium-sodium alloy, and particularly, the internal alloy can be extruded out under the action of external force to form potassium-sodium alloy particles. Therefore, the problem of interfacial stability cannot be fundamentally solved by simply loading the liquid potassium-sodium alloy with the carbon carrier.
Therefore, changing the fluid property of the liquid potassium-sodium alloy is a key for essentially solving the problem of the structural stability of the liquid potassium-sodium alloy electrode. Only the research team builds a non-Newtonian fluid electrode by mixing the special structure of acetylene black with potassium-sodium alloy, but because the selection requirement on powder materials is high, other materials are selected or do not react or have extremely low reaction speed, the construction of a stable electrode with high selectivity and high reaction speed is a key problem which is continuously solved by large-scale application of liquid potassium-sodium alloy cathodes.
Disclosure of Invention
Aiming at the problems in the background technology, the invention aims to provide a method for rapidly preparing a non-Newtonian fluid state potassium-sodium alloy electrode and an application of the non-Newtonian fluid state potassium-sodium alloy electrode serving as a cathode material of a potassium-sodium alloy secondary battery by utilizing a micro-short circuit method.
A method for preparing a non-Newtonian fluid state potassium-sodium alloy electrode by utilizing micro short circuit, which comprises the following steps:
1) Mixing and stirring a powder precursor material and a proper amount of electrolyte to obtain mixed slurry;
2) And (3) mixing the mixed slurry prepared in the step (1) with a proper amount of potassium-sodium alloy, uniformly stirring, and constructing a micro-short circuit reaction to obtain the non-Newtonian fluid potassium-sodium alloy composite material.
3) And (3) coating the material prepared in the step (2) on a conductive carrier to form a non-Newtonian fluid potassium-sodium alloy coating, thereby obtaining the non-Newtonian fluid potassium-sodium alloy electrode.
In the step 1), the powder material may be carbon powder, metal powder, inorganic nonmetal powder, metal derivative powder or mixed powder.
The carbon powder comprises graphite, carbon nanotubes, acetylene black and the like.
The metal powder comprises copper powder, aluminum powder, silver powder and the like.
The inorganic nonmetallic powder comprises silicon powder, sulfur powder and the like.
The metal derivative powder comprises metal oxide, metal nitride, metal phosphide, metal sulfide and the like.
The mixed powder is obtained by mixing two or more of the above powders according to any proportion.
The powder should be an active material that can react electrochemically with sodium or potassium ions.
In the step 1), the electrolyte is a composition of metal salt and organic solvent.
The electrolyte solute can be one or more of lithium, sodium and potassium salts.
The salt in the electrolyte solute can be one or more of perchlorate, trifluoromethane sulfonate, hexafluorophosphate, bistrifluoromethane sulfonyl imide salt and the like.
The electrolyte liquid solvent is one or a combination of more of propylene carbonate, acetonitrile, propylene carbonate, ethylene glycol dimethyl ether and the like, ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, butyl acrylate and the like.
In the step 1), the volume ratio of the mass of the powder particles to the added electrolyte is 1 g:10-1000 mu L, preferably 1 g:20-200 mu L, and most preferably 1 g:50-100 mu L.
The electrolyte is added in an amount sufficient to wet the powder material.
The mixed slurry in the step 1) is composed of powder materials wetted by electrolyte.
The mixed slurry should have a slurry-like structure, have certain flexibility, and have no layering phenomenon.
In the step 2), the potassium-sodium alloy is a liquid alloy which is composed of potassium metal and sodium metal and exists in a liquid form at room temperature.
The mass ratio of the potassium-sodium alloy sodium to the potassium metal is 1:0.1-20, preferably 1:1-10, and most preferably 1:3-5.
In the step 2), the mass ratio of the mixed slurry to the added potassium-sodium alloy is 1:1-200, preferably 1:10-100, and most preferably 1:20-50.
In the step 2), the micro short circuit reaction is electrochemical reaction of the interface between the potassium-sodium alloy and the wet electrolyte powder material, and potassium or sodium derivatives are formed at the interface between the powder material and the potassium-sodium alloy, so as to change the surface tension of the potassium-sodium alloy on the surface of the powder material.
In the step 2), the non-Newtonian fluid potassium-sodium alloy composite material is paint-like alloy, and can be smeared on a carrier by using tools such as a brush.
In step 3), the conductive carrier may be any conductive solid carrier. The material-based composite material can be classified into a one-dimensional carrier, a two-dimensional carrier and a three-dimensional carrier according to dimensions, and can be classified into a metal carrier, an organic carrier and an inorganic carrier according to materials. Preferably a two-dimensional thin film conductive support of a certain thickness, most preferably a two-dimensional thin film carbon material of a certain thickness and area. The non-Newtonian fluid potassium-sodium alloy itself has good conductivity and therefore does not limit the carrier conductivity characteristics.
The thickness of the conductive carrier is 0.1 to 10mm, more preferably 0.5 to 5mm, and most preferably 1 to 2mm.
The non-Newtonian fluid state potassium-sodium alloy electrode is 0.001-10 gcm according to the electrode area -2 More preferably 0.01 to 5gcm -2 Most preferably 0.05 to 0.2gcm -2 。
The preparation method for rapidly preparing the non-Newtonian fluid state potassium-sodium alloy electrode by using the micro-short circuit method is completed under the protection of inert gas, and the water content is less than 0.1ppm.
The non-Newtonian fluid state potassium-sodium alloy electrode comprises a carrier and a non-Newtonian fluid state potassium-sodium alloy loaded on the carrier. The non-Newtonian fluid state potassium-sodium alloy/nano carbon composite material is paint-shaped, has the characteristic of being capable of being coated, is not limited by the area of a carrier, and can be used for preparing electrodes with larger sizes.
The non-Newtonian fluid state potassium-sodium alloy electrode can be used as a cathode material of a potassium metal battery and a sodium metal battery at the same time.
The non-Newtonian fluid potassium-sodium alloy composite material has strong stretching and bending resistance and the like, and can be used as a flexible battery cathode.
Compared with the prior art, the invention has the following advantages and outstanding effects:
the invention aims at preparing a dendrite-free liquid alloy negative electrode with a stable structure. The invention has the following two characteristics: 1) The conventional liquid state potassium-sodium alloy is difficult to mix with powder materials because of strong surface tension, and the potassium-sodium alloy is embedded into the powder materials by utilizing electrolyte to construct micro short circuit reaction, so that the method can be suitable for various powder materials. 2) In inert gas, the reaction speed of liquid potassium-sodium alloy and powder material is limited, and the method can rapidly change the flowable physical property of the liquid potassium-sodium alloy by utilizing the rapid release of energy in the micro-short circuit process. 3) The potassium-sodium alloy is easy to fall off from the surface of the electrode due to stronger surface tension, so that the electrode structure is unstable. The non-Newtonian fluid state potassium-sodium alloy electrode prepared by utilizing the micro-short circuit has the characteristics of high coulomb efficiency, no dendrite growth, stable structure and the like. The powder material has high selectivity, and the electrode has the characteristics of high coulomb efficiency, no dendrite growth, stable structure and the like, can be used as a potassium metal negative electrode and a sodium metal battery negative electrode simultaneously, and can obviously improve the energy density and the cycle stability of a full battery when being matched with sulfur, prussian blue and other positive electrode materials.
Drawings
FIG. 1 is a scan of a non-Newtonian fluid state potassium-sodium alloy prepared in example 1;
fig. 2 is a scan of the powder material in example 3.
Fig. 3 is a schematic diagram of a micro-shorting process.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
Example 1
1) 100. Mu.L of electrolyte (1M KPF) was added dropwise to 1g of graphite precursor under inert gas 6 EC: dec=1:1), a mixed slurry is obtained;
2) Adding the mixed slurry prepared in the step 1) and 50 times of liquid potassium-sodium alloy (the mass ratio of sodium to potassium is 1:3.5) into a polyvinylidene fluoride beaker, and stirring to obtain micro short circuit in the process and obtain the non-Newtonian fluid potassium-sodium alloy composite material.
3) The material is coated on a copper sheet to form a non-Newtonian fluid state potassium-sodium alloy coating, and the non-Newtonian fluid potassium-sodium alloy electrode is obtained.
The reaction diagram is shown in FIG. 1, and the microstructure SEM diagram is shown in FIG. 2.
Example 2 of the embodiment
1) 50. Mu.L of electrolyte (1M NaPF) was added dropwise to 1g of biomass carbon precursor under inert gas 6 EC: dmc=1:1), a mixed slurry is obtained;
2) Adding the mixed slurry prepared in the step 1) and 30 times of liquid potassium-sodium alloy (the mass ratio of sodium to potassium is 1:4) into a polyvinylidene fluoride beaker, and stirring to obtain micro short circuit in the process and obtain the non-Newtonian fluid potassium-sodium alloy composite material.
3) The material is coated on carbon paper to form a non-Newtonian fluid state potassium-sodium alloy coating, and the non-Newtonian fluid potassium-sodium alloy electrode is obtained.
An SEM image of the microstructure is shown in fig. 3.
Example 3
1) Under the protection of inert gas, 40 mu L of electrolyte (1M LiPF) was added dropwise to 1g of lithium titanate precursor 6 EC: DEC: dmc=1:1:1), obtaining a mixed slurry;
2) Adding the mixed slurry prepared in the step 1) and liquid potassium-sodium alloy (the mass ratio of sodium to potassium is 1:5) with the mass ratio of 25 times into a polyvinylidene fluoride beaker, and stirring to obtain micro short circuit in the process and obtain the non-Newtonian fluid potassium-sodium alloy composite material.
3) The material is coated on an aluminum sheet to form a non-Newtonian fluid state potassium-sodium alloy coating, and the non-Newtonian fluid potassium-sodium alloy electrode is obtained.
The performance test method comprises the following steps:
the electrode is used as a negative electrode and a positive electrode to be assembled into a button cell, the diaphragm is made of glass fiber, and the solute of electrolyte is KPF 6 、KClO 4 、KTFSI、NaPF 6 、NaClO 4 One or more than two of NaTFSI; the solvent is one or more of ethylene carbonate, diethyl carbonate, dimethyl carbonate and propylene carbonate, and the current density is 50mAg -1 The overpotential of the alkali metal negative electrode in the symmetric electrode system was measured in an environment of 25 ℃. The composite materials of the deposited alkali metals prepared in the above examples 1 to 3 were assembled into symmetrical batteries as active materials when the coulomb efficiency was tested, the current density was 1mAh cm-2, and the amount of the electrodeposited alkali metal in the cyclic process was 1mAh cm -2 The dealkalized potential was 1V and the overpotential of the potassium (or sodium) metal negative electrode in the symmetric electrode system was measured in an environment of 25±5 ℃.
Compared with liquid potassium-sodium alloy, the non-Newtonian fluid potassium-sodium alloy has a better stable structure, maintains the dendrite-free characteristic of the liquid state, changes the flowable property of the liquid potassium-sodium alloy, and ensures the stability of the electrode structure. Therefore, the invention not only has the advantages of high powder material selectivity, rapid reaction and the like, but also has the characteristics of high coulombic efficiency, no dendrite growth, stable structure and the like, and can be used as a potassium metal negative electrode and a sodium metal battery negative electrode, and when being matched with positive electrode materials such as sulfur, prussian blue and the like, the invention obviously improves the energy density and the cycle stability of the whole battery, has great significance on the modification of the metal negative electrode of a potassium-sodium alloy secondary battery, and is favorable for the large-scale application of the dendrite-free potassium-sodium alloy negative electrode.
Claims (4)
1. The preparation method for rapidly preparing the non-Newtonian fluid state potassium-sodium alloy electrode by using the micro-short circuit method is characterized by comprising the following steps of:
1) Mixing and stirring a powder precursor material and a proper amount of electrolyte to obtain mixed slurry;
2) Mixing the mixed slurry prepared in the step 1) with a proper amount of potassium-sodium alloy, uniformly stirring, and constructing a micro-short circuit reaction to obtain a non-Newtonian fluid potassium-sodium alloy composite material;
3) Coating the material prepared in the step 2) on a conductive carrier to form a non-Newtonian fluid potassium-sodium alloy coating, and obtaining a non-Newtonian fluid potassium-sodium alloy electrode;
in the step 1), the powder material is graphite, biological carbon or lithium titanate;
in the step 1), the electrolyte is a composition of metal salt and organic solvent, the metal salt is one or more of lithium, sodium and potassium salt, the metal salt is one or more of perchlorate, triflate, hexafluorophosphate or bistrifluoromethane sulfonyl imide salt, the organic solvent is one or more of propylene carbonate, acetonitrile, ethylene glycol dimethyl ether, ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate and butyl acrylate, the volume ratio of the mass of powder particles to the added electrolyte is 1g to 50-100 mu L, and the added electrolyte is sufficient to moisten the powder material;
in the step 2), the potassium-sodium alloy is composed of potassium metal and sodium metal, and the mass ratio of the potassium-sodium alloy sodium to the potassium metal is 1:3-5, and the mass ratio of the mixed slurry to the added potassium-sodium alloy is 1:20-50; the preparation method is completed under the protection of inert gas, and the water content is less than 0.1ppm.
2. The method for rapidly preparing a non-newtonian fluid state potassium-sodium alloy electrode by using a micro-short circuit method according to claim 1, wherein in the step 1), the mixed slurry is composed of powder materials wetted by the electrolyte, and the mixed slurry has a slurry-like structure, has a certain flexibility, and does not have layering phenomenon.
3. The method for rapidly preparing a non-newtonian fluid state potassium-sodium alloy electrode by micro-shorting according to claim 1, wherein in step 2), the micro-shorting reaction is an electrochemical reaction between potassium-sodium alloy and a wet electrolyte powder material, and potassium or sodium derivatives are formed at the interface between the powder material and the potassium-sodium alloy, and the purpose of the method is to change the surface tension of the potassium-sodium alloy on the surface of the powder material.
4. A method for preparing a non-newtonian fluid state potassium-sodium alloy electrode rapidly by micro-shorting according to any one of claims 1-3, wherein the non-newtonian fluid state potassium-sodium alloy electrode comprises a carrier and a non-newtonian fluid state potassium-sodium alloy supported on the carrier.
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| JP2013131373A (en) * | 2011-12-21 | 2013-07-04 | Toyota Motor Corp | Method for manufacturing negative electrode material for metal battery, and metal battery containing negative electrode material for metal battery manufactured by the manufacturing method |
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| CN109244441A (en) * | 2018-08-29 | 2019-01-18 | 浙江大学 | Non-newtonian flow posture Na-K alloy electrode and its preparation method and application |
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| JP2013131373A (en) * | 2011-12-21 | 2013-07-04 | Toyota Motor Corp | Method for manufacturing negative electrode material for metal battery, and metal battery containing negative electrode material for metal battery manufactured by the manufacturing method |
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