CN114975897A - Alkali metal cathode with stable circulation, preparation method thereof and alkali metal battery - Google Patents
Alkali metal cathode with stable circulation, preparation method thereof and alkali metal battery Download PDFInfo
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- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 206
- 150000001340 alkali metals Chemical class 0.000 title claims abstract description 206
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000011259 mixed solution Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 15
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 10
- 239000002798 polar solvent Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 22
- -1 perfluorobutanefluoride Chemical compound 0.000 claims description 16
- 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 13
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 239000011591 potassium Substances 0.000 claims description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000011889 copper foil Substances 0.000 claims description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 6
- 239000012025 fluorinating agent Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- NRKYWOKHZRQRJR-UHFFFAOYSA-N 2,2,2-trifluoroacetamide Chemical compound NC(=O)C(F)(F)F NRKYWOKHZRQRJR-UHFFFAOYSA-N 0.000 claims description 4
- KIPSRYDSZQRPEA-UHFFFAOYSA-N 2,2,2-trifluoroethanamine Chemical compound NCC(F)(F)F KIPSRYDSZQRPEA-UHFFFAOYSA-N 0.000 claims description 4
- IKGLACJFEHSFNN-UHFFFAOYSA-N hydron;triethylazanium;trifluoride Chemical compound F.F.F.CCN(CC)CC IKGLACJFEHSFNN-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- CBEFDCMSEZEGCX-UHFFFAOYSA-N 1,1,2,2,2-pentafluoro-n,n-bis(1,1,2,2,2-pentafluoroethyl)ethanamine Chemical compound FC(F)(F)C(F)(F)N(C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)F CBEFDCMSEZEGCX-UHFFFAOYSA-N 0.000 claims description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 3
- ZQXCQTAELHSNAT-UHFFFAOYSA-N 1-chloro-3-nitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC(C(F)(F)F)=C1 ZQXCQTAELHSNAT-UHFFFAOYSA-N 0.000 claims description 3
- FOBJABJCODOMEO-UHFFFAOYSA-N 2,2,3,3,4,4,4-heptafluorobutanamide Chemical compound NC(=O)C(F)(F)C(F)(F)C(F)(F)F FOBJABJCODOMEO-UHFFFAOYSA-N 0.000 claims description 3
- DGCOGZQDAXUUBY-UHFFFAOYSA-N 2,2-difluoro-1,3-benzodioxole Chemical compound C1=CC=C2OC(F)(F)OC2=C1 DGCOGZQDAXUUBY-UHFFFAOYSA-N 0.000 claims description 3
- BPVYCXMGJPKOTQ-UHFFFAOYSA-N 2-[3-(trifluoromethyl)phenyl]ethanamine Chemical compound NCCC1=CC=CC(C(F)(F)F)=C1 BPVYCXMGJPKOTQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 claims description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- FCFXLXGZHDHJLB-UHFFFAOYSA-N pyridine-2-sulfonyl fluoride Chemical compound FS(=O)(=O)C1=CC=CC=N1 FCFXLXGZHDHJLB-UHFFFAOYSA-N 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- ZLNOPUSWCPWBFC-UHFFFAOYSA-M 2-methylpropan-2-ol;tetrabutylazanium;fluoride Chemical compound [F-].CC(C)(C)O.CC(C)(C)O.CC(C)(C)O.CC(C)(C)O.CCCC[N+](CCCC)(CCCC)CCCC ZLNOPUSWCPWBFC-UHFFFAOYSA-M 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 24
- 239000000126 substance Substances 0.000 abstract description 4
- 230000007935 neutral effect Effects 0.000 abstract description 3
- 238000002161 passivation Methods 0.000 abstract description 3
- 229910001515 alkali metal fluoride Inorganic materials 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 24
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 238000012360 testing method Methods 0.000 description 10
- 230000001351 cycling effect Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 7
- 238000011065 in-situ storage Methods 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000012876 topography Methods 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 description 5
- 238000011066 ex-situ storage Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- 229910001290 LiPF6 Inorganic materials 0.000 description 4
- NCZYUKGXRHBAHE-UHFFFAOYSA-K [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] Chemical compound [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] NCZYUKGXRHBAHE-UHFFFAOYSA-K 0.000 description 4
- ZCPSPTHSPJKCRR-UHFFFAOYSA-K [Na+].[Na+].P(=O)([O-])([O-])[O-].[V+5] Chemical compound [Na+].[Na+].P(=O)([O-])([O-])[O-].[V+5] ZCPSPTHSPJKCRR-UHFFFAOYSA-K 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
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- 230000015572 biosynthetic process Effects 0.000 description 3
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- 238000005516 engineering process Methods 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
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- 230000009257 reactivity Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
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- 230000002238 attenuated effect Effects 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
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- 230000014759 maintenance of location Effects 0.000 description 2
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- 239000012046 mixed solvent Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- JDVIRCVIXCMTPU-UHFFFAOYSA-N ethanamine;trifluoroborane Chemical compound CCN.FB(F)F JDVIRCVIXCMTPU-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 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
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- LUYQYZLEHLTPBH-UHFFFAOYSA-N perfluorobutanesulfonyl fluoride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O LUYQYZLEHLTPBH-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- GRJJQCWNZGRKAU-UHFFFAOYSA-N pyridin-1-ium;fluoride Chemical compound F.C1=CC=NC=C1 GRJJQCWNZGRKAU-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N tert-butyl alcohol Substances CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/26—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a circulation stable alkali metal cathode, a preparation method thereof and an alkali metal battery, wherein the preparation method of the alkali metal fluoride cathode comprises the following steps: adding a fluorination reagent into an aprotic polar solvent to obtain a mixed solution; and adding the alkali metal cathode into the mixed solution for reaction, and drying to obtain the alkali metal cathode with stable circulation. According to the preparation method of the alkali metal cathode with stable circulation, disclosed by the invention, the neutral fluorination reagent with high selectivity is used for carrying out surface passivation treatment on the alkali metal, so that a fluorinated artificial SEI film is prepared on the surface of the alkali metal; the fluorinated artificial SEI film has the characteristics of uniformity, compactness, high film-forming quality, controllable thickness, high mechanical property, close contact with a negative electrode, low electrochemical impedance of the electrode, stability in air and chemical and electrochemical inertness to electrolyte.
Description
Technical Field
The invention relates to the technical field of alkali metal batteries, in particular to an alkali metal cathode with stable circulation, a preparation method thereof and an alkali metal battery.
Background
Alkali metal anodes have received much attention from researchers due to their high energy density. Alkali metal anodes include lithium, sodium, potassium metal anodes that exhibit unique advantages in various respectsAnd (4) potential. The lithium metal negative electrode has extremely high theoretical capacity (3860mAh g) -1 ) And the lowest electrochemical potential (-3.04V vs hydrogen standard potential) is the most ideal negative electrode material for the next generation of energy storage systems. Similar to the working mechanism of lithium metal negative electrodes, sodium and potassium metals achieve ion transport on the negative electrode side through electrochemical deposition and stripping, and also exhibit higher theoretical capacity (sodium is 1165mAh g) -1 687mAh g as potassium -1 ). Sodium and potassium metals are more abundant in the earth than lithium metal and therefore less expensive. However, the use of alkali metal cathodes is faced with the problems of metal dendrite growth, metal cathode pulverization and serious volume effect, which causes the battery capacity to generate 'water jump' attenuation, especially the battery thermal runaway and fire explosion caused by the penetration of metal dendrite in the battery, and seriously hinders the commercial application of the alkali metal cathodes.
Aiming at the high reactivity of the alkali metal cathode, the current main countermeasure strategy is to modify a layer of ion-conductive and electron-insulating surface film, namely an artificial SEI film, on the surface of the cathode. The technical development routes of researchers include: and preparing the artificial SEI film by in-situ and ex-situ means. The non-in-situ preparation of the artificial SEI film is to form a heterogeneous interface layer on the surface of the negative electrode, wherein the interface layer does not react with the negative electrode in the preparation process, and the specific preparation methods mainly comprise a solution pouring method, a gas phase chemical deposition method, an atomic layer deposition technology, a rolling method and the like. The artificial SEI film prepared by the ex-situ method has the advantages of high and compact film forming quality, controllable film forming thickness and adjustable and controllable experimental parameters. However, the artificial SEI film prepared by the ex-situ method is generally poor in interface contact with a negative electrode, so that the battery has large interface impedance; the artificial SEI film prepared in an ex-situ manner is usually a non-lithium ion conductor, and needs to be lithiated in the working process of a negative electrode, and the lithiation process usually causes the modified interface film to form pores and crack, so that the interface film fails. The in-situ method is to modify an artificial SEI film on the interface by using the high reactivity of the cathode to react with the oxidizing material, and comprises the chemical reaction between the cathode and the gas/liquid phase material and the diffusion effect between the cathode and the solid phase. The in-situ formed artificial SEI film can generate a conformal interface with the negative electrode, so that the contact problem between the negative electrode and the interface film is effectively solved; the artificial SEI film is usually a certain salt of alkali metal, and is beneficial to improving the ion transmission of alkali metal ions at an interface to obtain good rate performance.
At present, alkali metal cathodes, especially potassium cathodes, have very high chemical activity, safe disposal of the alkali metal cathodes cannot be realized by in-situ or ex-situ methods in the prior art, and severe reaction with a treated solvent or a treated reactant can still occur in an inert atmosphere glove box in the interface treatment process of potassium metal to cause fire explosion; in the existing disposal method, multi-step experimental operation treatment is required to obtain an artificial SEI film, the film forming quality of the prepared interface film is not high, impurities exist, and the preparation cost is increased for the preparation of an alkali metal cathode; the interface stability of the alkali metal cathode cannot be realized by the prior art means, and particularly, the interface stability of the sodium and potassium metals with high reactivity cannot be realized in the current reports when the metal deposition and stripping are carried out on the alkali metal battery for a long time.
Based on the technical problems of the current alkali metal negative electrodes, there is a need for improvement.
Disclosure of Invention
In view of the above, the present invention provides a cyclically stable alkali metal negative electrode, a preparation method thereof, and an alkali metal battery, which solve or at least partially solve the technical defects in the prior art.
In a first aspect, the present invention provides a method for preparing a cycle stable alkali metal anode, comprising the steps of:
adding a fluorination reagent into an aprotic polar solvent to obtain a mixed solution;
adding the alkali metal cathode into the mixed solution for reaction, and drying to obtain the alkali metal cathode with stable circulation;
wherein the fluorinating agent comprises at least one of pentadecafluorotriethylamine, borontrifluoroethylamine, 2,2, 2-trifluoroethylamine, triethylamine trihydrofluoride, ammonium fluoride, ammonium bifluoride perfluorobutanefluoride, pyridine-2-sulfonyl fluoride, hydropyridine fluoride, fluoroethylene carbonate, trifluoroacetamide, heptafluorobutanamide, trifluoromethane, 1-chloromethyl-4-fluoro-1, 4-diazabicyclo (2.2.2) octane bis (tetrafluoroborate) salt, 2- (3-trifluoromethylphenyl) ethylamine, tetrabutylammonium fluoride tetra-tert-butanol complex, bis (2-methoxyethyl) amidosulfur trifluoride, 2, 2-difluoro-1, 3-benzodioxole;
the aprotic polar solvent comprises at least one of N-methylpyrrolidone, N-dimethylformamide, 1, 3-dimethyl-2-imidazolidinone, dimethylacetamide, tetrahydrofuran, pyridine, ethylene glycol dimethyl ether and ethylene carbonate.
Preferably, the method for preparing the cycle-stable alkali metal negative electrode comprises a current collector and an alkali metal loaded on the current collector.
Preferably, in the preparation method of the alkali metal cathode with stable circulation, if the alkali metal is lithium, the alkali metal cathode is added into the mixed solution to react at 20-150 ℃;
if the alkali metal is sodium, adding an alkali metal cathode into the mixed solution to react at 20-90 ℃;
and if the alkali metal is potassium, adding an alkali metal cathode into the mixed solution to react at 20-60 ℃.
Preferably, in the preparation method of the alkali metal negative electrode with stable circulation, the mass ratio of the fluorination reagent to the aprotic polar solvent is 1 (1-100).
Preferably, in the method for preparing the alkali metal cathode with stable circulation, the alkali metal cathode is added into the mixed solution for reaction, and the reaction is carried out every cm 2 2-200 mL of mixed liquid is added into the alkali metal cathode.
Preferably, in the preparation method of the alkali metal cathode with stable circulation, the alkali metal cathode is added into the mixed solution for reaction, and the reaction time is 10 s-6 h.
Preferably, in the preparation method of the alkali metal negative electrode with stable cycle, the current collector comprises any one of copper foil, nickel foil, titanium foil and stainless steel sheet.
In a second aspect, the invention also provides an alkali metal cathode with stable circulation, and the alkali metal cathode is prepared by the preparation method.
In a third aspect, the invention also provides an alkali metal battery comprising the cycle-stable alkali metal anode.
Compared with the prior art, the alkali metal cathode with stable circulation, the preparation method thereof and the alkali metal battery have the following beneficial effects:
1. according to the preparation method of the alkali metal cathode with stable circulation, disclosed by the invention, the neutral fluorination reagent with high selectivity is used for carrying out surface passivation treatment on the alkali metal, so that a fluorinated artificial SEI film is prepared on the surface of the alkali metal; the strong oxidizing property in the fluorinating reagent is weakened due to the complexation of the protonic fluorinating group and organic micromolecules or inorganic salts, the reaction speed of a reaction reagent and alkali metal is greatly reduced, the preparation of the artificial SEI film is more controllable, the experimental steps are simplified, the operability and safety of the experiment are improved, and the problems that the thickness and the film forming quality of the in-situ prepared artificial SEI film are difficult to control are solved; the fluorinated artificial SEI film has the characteristics of uniformity, compactness, high film-forming quality, controllable thickness, high mechanical property, close contact with a negative electrode, low electrochemical impedance of the electrode, stability in air and chemical and electrochemical inertness to electrolyte;
2. the preparation method of the alkali metal cathode with stable circulation, disclosed by the invention, has the advantages that the technical implementation means is simple and feasible, the reaction from reactants to reaction products can be realized by one step, the reaction products are free of impurities, the reaction reagent after reaction can be recycled after simple purification, the technical path is short and direct, and the large-scale application of the technology in actual production is facilitated;
3. the alkali metal battery comprises the alkali metal cathode which is stable in circulation, the excellent electrochemical performance of the alkali metal full battery is realized, and the long circulation performance of the lithium and sodium full battery is realized under the condition of using less electrolyte. Because the prepared artificial SEI film has good ion transmission property, the interfacial impedance of the electrode is reduced, and the total alkali metal content is reduced compared with the unmodified alkali metal cathodeBattery cell voltage polarization; the invention realizes excellent electrochemical performance in the alkali metal symmetrical battery, and the electrochemical performance is 8mA cm -2 High current density and 8mAh cm -2 The stable cycle time is more than 200h under the high-capacity density, the short circuit of the battery is avoided, and the application of the alkali metal cathode in the alkali metal battery is promoted.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a surface topography and a cross-sectional topography of a cyclically stable alkali metal anode prepared in example 1 of the present invention;
FIG. 2 is an XRD pattern of a cyclically stable alkali metal anode prepared in example 1 of the present invention;
FIG. 3 is a graph showing the results of charge and discharge cycles of a lithium metal symmetric cell assembled with the alkali metal negative electrode having cycling stability according to example 1 of the present invention and a lithium metal symmetric cell assembled with the alkali metal negative electrode according to comparative example 1;
FIG. 4 is a surface topography and a cross-sectional topography of a cyclically stable alkali metal anode prepared in example 2 of the present invention;
FIG. 5 is an XRD pattern of a cyclically stable alkali metal anode prepared in example 2 of the present invention;
FIG. 6 is a graph showing the charge and discharge test results of a lithium-iron phosphate lithium full cell assembled by using alkali metal cathodes prepared in examples 1 to 2 of the present invention and in comparative example 1 by different methods as a lithium metal cell cathode;
FIG. 7 is a surface topography and a cross-sectional topography of a cyclically stable alkali metal anode prepared in example 3 of the present invention;
FIG. 8 is an XRD pattern of a cyclically stable alkali metal anode prepared in example 3 of the present invention;
FIG. 9 is a graph showing the results of charge and discharge cycles of a sodium metal symmetric cell assembled with the alkali metal cathode having cycling stability according to example 3 of the present invention and a sodium metal symmetric cell assembled with the alkali metal cathode according to comparative example 2;
fig. 10 is a charge and discharge test chart at a rate of 0.5C of a sodium-sodium vanadium phosphate full cell assembled by using the alkali metal negative electrode prepared in example 3 and comparative example 2 as a sodium metal cell negative electrode and sodium vanadium phosphate as a positive electrode.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention provides a preparation method of an alkali metal cathode with stable circulation, which comprises the following steps:
s1, adding a fluorination reagent into the aprotic polar solvent to obtain a mixed solution;
s2, adding the alkali metal cathode into the mixed solution for reaction, and drying to obtain the alkali metal cathode with stable circulation;
wherein the fluorinating agent comprises at least one of pentadecafluorotriethylamine, boron trifluoride ethylamine, 2,2, 2-trifluoroethylamine, triethylamine trihydrofluoride salt, ammonium fluoride, ammonium bifluoride perfluorobutylsulfonyl fluoride, pyridine-2-sulfonyl fluoride, hydrogen fluoride pyridine, fluoroethylene carbonate, trifluoroacetamide, heptafluorobutanamide, trifluoromethane, 1-chloromethyl-4-fluoro-1, 4-diazabicyclo (2.2.2) octane bis (tetrafluoroborate) salt, 2- (3-trifluoromethylphenyl) ethylamine, tetrabutylammonium fluoride tetra-tert-butyl alcohol complex, bis (2-methoxyethyl) amidosulfur trifluoride, 2, 2-difluoro-1, 3-benzodioxole;
the aprotic polar solvent comprises at least one of N-methylpyrrolidone, N-dimethylformamide, 1, 3-dimethyl-2-imidazolidinone, dimethylacetamide, tetrahydrofuran, pyridine, ethylene glycol dimethyl ether and ethylene carbonate.
The preparation method of the alkali metal cathode with stable circulation utilizes the neutral fluorination reagent with high selectivity to carry out surface passivation treatment on the alkali metal, wherein the strong oxidizing property in the fluorination reagent is weakened due to the complexation of the protonic fluorination group and organic micromolecules or inorganic salts, the reaction speed of the reaction reagent and the alkali metal is greatly reduced, the preparation of the artificial SEI film is more controllable, the experimental steps are simplified, the operability and the safety of the experiment are improved, and the problems that the thickness and the film forming quality of the artificial SEI film prepared in situ are difficult to control are solved. The preparation method of the alkali metal cathode with stable circulation can promote the rapid transmission of ions at the interface and homogenize the ion flow at the interface, simultaneously ensure the stability of the alkali metal to the electrolyte, reduce the cost of the alkali metal cathode in production and manufacture, and finally promote the industrialization process of the alkali metal battery.
In some embodiments, the alkali metal negative electrode includes a current collector and an alkali metal supported on the current collector.
Specifically, the preparation method of the alkali metal cathode comprises the following steps: cutting the alkali metal (lithium, sodium and potassium) blocks into corresponding sheets, determining the area shape of each sheet by a corresponding current collector, placing the sheets at the position 1mm away from the edge of the current collector in the right center of the current collector, and rolling the cut fresh alkali metal sheets and the current collector to obtain the alkali metal cathode. The thickness of the alkali metal foil is 10-500 μm.
In some embodiments, if the alkali metal is lithium, adding the alkali metal cathode into the mixed solution to react at 20-150 ℃;
if the alkali metal is sodium, adding an alkali metal cathode into the mixed solution to react at 20-90 ℃;
and if the alkali metal is potassium, adding the alkali metal cathode into the mixed solution to react at 20-60 ℃.
Obviously, before the alkali metal cathode is added into the mixed solution for reaction, the method further comprises the steps of preheating the mixed solution to a corresponding temperature, and then adding the alkali metal cathode into the mixed solution for reaction.
In some embodiments, the mass ratio of the fluorinating agent to the aprotic polar solvent is 1 (1-100).
In some embodiments, the alkali metal cathode is added to the step of reacting in the mixed solution every cm 2 2-200 mL of mixed liquid is added into the alkali metal cathode.
In some embodiments, the alkali metal cathode is added into the mixed solution for reaction for 10s to 6 h.
In some embodiments, the current collector comprises any one of a copper foil, a nickel foil, a titanium foil, a stainless steel sheet.
In some embodiments, after the alkali metal cathode is added into the mixed solution for reaction, the alkali metal cathode is taken out, the residual solution is sucked to be dry by using absorbent paper, and the drying is carried out for 12 hours at the temperature of 40-60 ℃ so as to further remove the residual solution on the surface of the alkali metal cathode, and finally the fluorinated alkali metal cathode is prepared.
Based on the same inventive concept, the embodiment of the application also provides the alkali metal cathode with stable circulation, and the alkali metal cathode is prepared by adopting the preparation method.
Based on the same inventive concept, the invention also provides an alkali metal battery, which comprises the alkali metal cathode with stable circulation. Specifically, the alkali metal cathode with stable circulation in the alkali metal battery is used as the cathode of the battery, and the alkali metal battery further comprises an electrolyte, a diaphragm and a positive electrode.
Specifically, the electrolyte comprises 1M LiPF 6 in EC/DEC (i.e. LiPF) 6 Dissolving in mixed solvent of EC and DEC, wherein the volume ratio of EC to DEC is 1:1, LiPF 6 At a concentration of 1M); or, the electrolyte comprises 1M NaPF 6 in EC/DEC (i.e., NaPF) 6 Dissolving in mixed solvent of EC and DEC, wherein the volume ratio of EC to DEC is 1:1, NaPF 6 At a concentration of 1M); the diaphragm is Celgard 2400 polypropylene diaphragm and whatman glass fiber diaphragm; the positive electrode includes lithium iron phosphate, sodium vanadium phosphate, and the like.
The alkali metal cathode with stable circulation, the preparation method thereof and the alkali metal battery have the following advantages:
1. the invention develops a general strategy to realize the preparation of fluorinated artificial SEI films on the surfaces of lithium, sodium and potassium. The fluorinated artificial SEI film has the characteristics of uniformity, compactness, high film-forming quality, controllable thickness, high mechanical property, close contact with a negative electrode, low electrochemical impedance of the electrode, stability in air and chemical and electrochemical inertness to electrolyte;
2. the invention realizes excellent electrochemical performance in the alkali metal symmetrical battery, and the electrochemical performance is 8mA cm -2 High current density and 8mAh cm -2 Under the high-capacity density, the stable cycle time is longer than 200h, no battery short circuit occurs, and the application of the alkali metal cathode in the alkali metal battery is promoted;
3. the invention realizes excellent electrochemical performance in the alkali metal full cell and long cycle performance of the lithium and sodium full cell under the condition of using less electrolyte. Because the prepared artificial SEI film has good ion transmission property, the interfacial impedance of the electrode is reduced, and the voltage polarization of the alkali metal full-cell battery is reduced compared with an unmodified alkali metal cathode;
4. the technical implementation means of the invention is simple and easy, only one step from reactants to reaction products is needed, the reaction products have no impurities, the reaction reagents after reaction can be recycled after simple purification, the technical path is short and direct, and the invention is beneficial to the large-scale application of the technology in the actual production.
The following further describes, with specific examples, a method for producing a cycle-stable alkali metal negative electrode and a method for producing an alkali metal battery according to the present application. This section further illustrates the present invention with reference to specific examples, which should not be construed as limiting the invention. The technical means employed in the examples are conventional means well known to those skilled in the art, unless otherwise specified. Reagents, methods and apparatus employed in the present invention are conventional in the art unless otherwise indicated.
Example 1
The embodiment of the application provides a preparation method of an alkali metal negative electrode with stable circulation, which comprises the following steps:
s1, dissolving 1g of 2,2, 2-trifluoroethylamine in 10g of tetrahydrofuran, and stirring for 4 hours to form a homogeneous solution, namely preparing a mixed solution;
s2, rolling the cut lithium metal sheet onto a copper foil through a roller press to prepare an alkali metal negative electrode; wherein the thickness of the lithium metal sheet is 250 μm, the alkali metal cathode is a circular sheet, and the diameter of the alkali metal cathode is 12 mm;
s3, adding 5.65mL of the mixed solution prepared in the step S1 into a polytetrafluoroethylene tank, preheating the mixed solution at 50 ℃ for 0.5h, and then placing the alkali metal cathode prepared in the step S2 into the polytetrafluoroethylene tank to react at 50 ℃ for 1 h;
and S4, absorbing the excessive solution of the alkali metal cathode reacted in the step S3 by using absorbent paper, and drying at 60 ℃ for 12h to finally obtain the alkali metal cathode with stable circulation.
The cycle stable alkali metal negative electrode prepared in example 1 was assembled into a lithium metal symmetric battery. The positive electrode and the negative electrode of the battery are prepared alkali metal negative electrodes with stable circulation, the used electrolyte is a carbonate electrolyte, specifically 1M LiPF6 in EC/DEC (the volume ratio of EC to DEC is 1:1), and the used diaphragm is a Celgard 2400 polypropylene diaphragm. The assembled lithium metal symmetrical battery is charged at 8mA cm -2 Current density of 8mAh cm -2 The capacity density of (2) is subjected to charge-discharge cycles.
The lithium-iron phosphate full cell is assembled by taking the alkali metal cathode with stable circulation prepared in the embodiment 1 as a lithium metal battery cathode and lithium iron phosphate as a cathode, the used electrolyte is a carbonate electrolyte, specifically 1M LiPF6 in EC/DEC (the volume ratio of the solvent EC to the DEC is 1:1), and the used diaphragm is a Celgard 2400 polypropylene diaphragm. The full cell was subjected to charge and discharge tests at a rate of 0.5C.
Example 2
The embodiment of the application provides a preparation method of an alkali metal negative electrode with stable circulation, which comprises the following steps:
s1, dissolving 1g of trifluoroacetamide in 7g of dimethyl ether, and stirring for 6 hours to form a homogeneous solution, namely preparing a mixed solution;
s2, rolling the cut lithium metal sheet onto a copper foil through a roller press to prepare an alkali metal negative electrode; wherein the thickness of the lithium metal sheet is 250 μm, the alkali metal cathode is a circular sheet, and the diameter of the alkali metal cathode is 12 mm;
s3, adding 11.3mL of the mixed solution prepared in the step S1 into a polytetrafluoroethylene tank, preheating for 0.5h at 100 ℃, and then putting the alkali metal cathode prepared in the step S2 into the polytetrafluoroethylene tank to react for 0.2h at 100 ℃;
and S4, absorbing the excessive solution of the alkali metal cathode reacted in the step S3 by using absorbent paper, and drying at 60 ℃ for 12h to finally obtain the alkali metal cathode with stable circulation.
The lithium-lithium iron phosphate full cell is assembled by taking the alkali metal cathode with stable circulation prepared in the embodiment 2 as a lithium metal battery cathode and lithium iron phosphate as a positive electrode, the used electrolyte is a carbonate electrolyte, specifically 1M LiPF6 in EC/DEC (the volume ratio of the solvent EC to the DEC is 1:1), and the used diaphragm is a Celgard 2400 polypropylene diaphragm. The full cell was subjected to charge and discharge tests at a rate of 0.5C.
Example 3
The embodiment of the application provides a preparation method of an alkali metal negative electrode with stable circulation, which comprises the following steps:
s1, dissolving 1g of triethylamine trihydrofluoride in 5g of dimethyl ether, and stirring for 2 hours to form a homogeneous solution, namely preparing a mixed solution;
s2, rolling the cut sodium metal sheet onto a copper foil through a roller press to prepare an alkali metal cathode; wherein the thickness of the sodium metal sheet is 250 μm, the alkali metal cathode is a circular sheet, and the diameter of the alkali metal cathode is 12 mm;
s3, adding 11.3mL of the mixed solution prepared in the step S1 into a polytetrafluoroethylene tank, preheating the mixed solution for 0.5h at 60 ℃, and then putting the alkali metal cathode prepared in the step S2 into the polytetrafluoroethylene tank to react for 0.1h at 60 ℃;
and S4, absorbing the excessive solution of the alkali metal cathode reacted in the step S3 by using absorbent paper, and drying at 40 ℃ for 12h to finally obtain the alkali metal cathode with stable circulation.
The cycling-stable alkali metal negative electrode prepared in example 3 was assembled into a sodium metal symmetric cell with the prepared cycling-stable alkali on both the positive and negative electrode sidesThe metal cathode uses a carbonate electrolyte, specifically 1M NaPF6 in EC/DEC (the volume ratio of EC to DEC is 1:1), and the used diaphragm is a whatman glass fiber diaphragm. The assembled sodium metal symmetrical battery is charged at 2mA cm -2 Current density of 2mAh cm -2 The capacity density of (2) is subjected to charge-discharge cycles.
The alkali metal cathode with stable circulation prepared in the example 3 is used as a cathode of a sodium metal battery, sodium vanadium phosphate is used as an anode, a sodium-sodium vanadium phosphate full battery is assembled, the used electrolyte is a carbonate electrolyte, specifically 1M NaPF6 in EC/DEC (the volume ratio of the solvent EC to the DEC is 1:1), and the used diaphragm is a whatman glass fiber diaphragm. The full cell was subjected to charge and discharge tests at a rate of 0.5C.
Comparative example 1
The present comparative example provides a method of making an alkali metal anode, comprising the steps of:
s1, rolling the cut lithium metal sheet onto a copper foil through a roller press to prepare an alkali metal negative electrode; wherein the thickness of the lithium metal thin sheet is 250 μm, and the alkali metal cathode is a circular sheet with a diameter of 12 mm.
The alkali metal negative electrode prepared in comparative example 1 was assembled into a lithium metal symmetrical battery, and the assembled lithium metal symmetrical battery was charged at 8mA cm -2 Current density of 8mAh cm -2 The capacity density of (2) is subjected to charge-discharge cycles.
The lithium-lithium iron phosphate full cell is assembled by taking the alkali metal cathode prepared in the comparative example 1 as the cathode of the lithium metal cell and lithium iron phosphate as the anode, the used electrolyte is a carbonate electrolyte, specifically 1M LiPF6 in EC/DEC (the volume ratio of the solvent EC to the DEC is 1:1), and the used diaphragm is a Celgard 2400 polypropylene diaphragm. The full cell was subjected to charge and discharge tests at a rate of 0.5C.
Comparative example 2
The present comparative example provides a method of making an alkali metal anode, comprising the steps of:
s1, rolling the cut sodium metal sheet onto a copper foil through a roller press to prepare an alkali metal cathode; wherein the thickness of the sodium metal sheet is 250 μm, and the alkali metal cathode is a disk with a diameter of 12 mm.
Assembling the alkali metal cathode prepared in the comparative example 2 into a sodium metal symmetrical battery, and arranging the assembled sodium metal symmetrical battery at a power of 2mA cm -2 Current density of 2mAh cm -2 The capacity density of (2) is subjected to charge-discharge cycles.
And (3) assembling the alkali metal cathode prepared in the comparative example 2 as a cathode of the sodium metal battery and the sodium vanadium phosphate as an anode of the sodium-sodium vanadium phosphate full battery, wherein the used electrolyte is a carbonate electrolyte, specifically 1M NaPF6 in EC/DEC (the volume ratio of the solvent EC to the DEC is 1:1), and the used diaphragm is a whatman glass fiber diaphragm. The full cell was subjected to charge and discharge tests at a rate of 0.5C.
Performance testing
The surface morphology and the cross-sectional morphology of the alkali metal anode with stable cycling prepared in example 1 were tested, and the results are shown in fig. 1. In FIG. 1, a is the surface profile and b is the cross-sectional profile.
As can be seen from fig. 1, the fluorinated interface film on the surface of the alkali metal negative electrode with stable cycle obtained in example 1 was dense, had no significant pores and cracks, and had good film formation quality, with an interface film thickness of about 2 μm.
The XRD pattern of the cyclically stable alkali metal anode prepared in example 1 was tested and the results are shown in fig. 2. As can be seen from fig. 2, the fluorinated interface film on the surface of the cycle-stable alkali metal anode had a composition of LiF.
The lithium metal symmetric battery is assembled by the alkali metal cathode with stable circulation in the example 1 and the lithium metal symmetric battery is assembled by the alkali metal cathode in the comparative example 1, and the lithium metal symmetric battery is assembled at the temperature of 8mA cm -2 Current density of 8mAh cm -2 The results of the charge-discharge cycle with the capacity density of (a) are shown in FIG. 3.
As can be seen from fig. 3, the alkali metal cathode with stable cycling in example 1 is assembled into a lithium metal symmetric battery, and the battery operates stably for 200 hours, the average value of the polarization voltage is 35mV, and no battery micro short circuit occurs, which indicates that no lithium dendrite is formed during the operation of the battery, and the interface between the electrode and the electrolyte is stable.
The surface morphology and the cross-sectional morphology of the alkali metal anode with stable cycling prepared in example 2 were tested, and the results are shown in fig. 4. In FIG. 4, a is the surface profile and b is the cross-sectional profile.
As can be seen from fig. 4, the fluorinated interfacial film on the surface of the alkali metal negative electrode prepared in example 2, which is stable in cycling, is dense, has no significant pores and cracks, and has good film formation quality, and the thickness of the interfacial film is about 300 nm.
The XRD pattern of the cyclically stable alkali metal anode prepared in example 2 was tested and the results are shown in fig. 5. As can be seen from fig. 5, the composition of the fluorinated interface film on the cycle-stable alkali metal anode surface was LiF.
The alkali metal negative electrodes prepared in examples 1 to 2 and comparative example 1 by different methods were used as the negative electrode of the lithium metal battery, lithium iron phosphate was used as the positive electrode, a lithium-lithium iron phosphate full battery was assembled, and a charge and discharge test was performed at a rate of 0.5C, and the results are shown in fig. 6.
As can be seen from FIG. 6, with the lithium metal negative electrode of comparative example 1, the first-turn specific capacity was only 141.4mA h g -1 After 30 cycles of circulation, the capacity is attenuated to 2.3mA h g -1 . The full batteries assembled by the lithium metal negative electrodes modified by the fluorinated interfaces of the examples 1 and 2 have higher battery capacity and capacity retention rate.
The surface morphology and the cross-sectional morphology of the alkali metal anode with stable cycling prepared in example 3 were tested, and the results are shown in fig. 7. In FIG. 7, a is the surface profile and b is the cross-sectional profile.
As can be seen from fig. 7, the fluorinated interface film on the surface of the alkali metal negative electrode with stable cycle obtained in example 3 was dense, had no significant pores and cracks, and had good film formation quality, with an interface film thickness of about 1.6 μm.
The XRD pattern of the cyclically stable alkali metal anode prepared in example 3 was tested and the result is shown in fig. 8. As can be seen from fig. 8, the fluorinated interface film on the surface of the alkali metal negative electrode, which is cycle-stable, had NaF as a component.
The alkali metal cathode with stable circulation in the example 3 is assembled into a sodium metal symmetric battery, and the alkali metal cathode in the comparative example 2 is assembled into a sodium metal symmetric batteryAt 2mA cm for sodium metal symmetrical cell -2 Current density of 2mAh cm -2 The results of the charge and discharge cycles with the capacity density of (2) are shown in FIG. 9.
As can be seen from fig. 9, the alkali metal cathode with stable cycling in example 3 is assembled into a sodium metal symmetric battery and operates smoothly for 100h, the average polarization voltage is 20mV, and no battery micro short circuit occurs, which indicates that no lithium dendrite is formed during the operation of the battery, and the interface between the electrode and the electrolyte is stable.
The alkali metal negative electrodes prepared in example 3 and comparative example 2 by different methods were used as the negative electrode of the sodium metal battery, and sodium vanadium phosphate was used as the positive electrode, and a sodium-sodium vanadium phosphate full battery was assembled, and the charge and discharge test was performed at a rate of 0.5C, and the result is shown in fig. 10.
As can be seen from FIG. 10, with the sodium metal negative electrode of comparative example 2, the first-turn specific capacity was only 103.4mA hr g -1 After circulating for 40 circles, the capacity is attenuated to 4mA h g -1 . The full cells assembled by the sodium metal cathode modified by the fluorinated interface of the example 3 have higher cell capacity and capacity retention rate.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A preparation method of a circularly stable alkali metal cathode is characterized by comprising the following steps:
adding a fluorination reagent into an aprotic polar solvent to obtain a mixed solution;
adding the alkali metal cathode into the mixed solution for reaction, and drying to obtain the alkali metal cathode with stable circulation;
wherein the fluorinating agent comprises at least one of pentadecafluorotriethylamine, borontrifluoroethylamine, 2,2, 2-trifluoroethylamine, triethylamine trihydrofluoride, ammonium fluoride, ammonium bifluoride perfluorobutanefluoride, pyridine-2-sulfonyl fluoride, hydropyridine fluoride, fluoroethylene carbonate, trifluoroacetamide, heptafluorobutanamide, trifluoromethane, 1-chloromethyl-4-fluoro-1, 4-diazabicyclo (2.2.2) octane bis (tetrafluoroborate) salt, 2- (3-trifluoromethylphenyl) ethylamine, tetrabutylammonium fluoride tetra-tert-butanol complex, bis (2-methoxyethyl) amidosulfur trifluoride, 2, 2-difluoro-1, 3-benzodioxole;
the aprotic polar solvent comprises at least one of N-methylpyrrolidone, N-dimethylformamide, 1, 3-dimethyl-2-imidazolidinone, dimethylacetamide, tetrahydrofuran, pyridine, ethylene glycol dimethyl ether and ethylene carbonate.
2. The method of making a cycle stable alkali metal anode of claim 1, wherein the alkali metal anode comprises a current collector and an alkali metal supported on the current collector.
3. The method for preparing a cyclically stable alkali metal negative electrode according to claim 2, wherein if the alkali metal is lithium, the alkali metal negative electrode is added into the mixed solution to react at 20 to 150 ℃;
if the alkali metal is sodium, adding an alkali metal cathode into the mixed solution to react at 20-90 ℃;
and if the alkali metal is potassium, adding an alkali metal cathode into the mixed solution to react at 20-60 ℃.
4. The method for producing a cyclically stable alkali metal negative electrode according to claim 1, wherein the mass ratio of the fluorinating agent to the aprotic polar solvent is 1 (1 to 100).
5. The method of claim 1, wherein the alkali metal cathode is added to the mixture for reaction in the step of adding the alkali metal cathode to the mixture per cm 2 2-200 mL of mixed solution is added into the alkali metal cathode.
6. The method of claim 1, wherein the alkali metal cathode is added to the mixture for reaction for 10 s-6 h.
7. The method of making a cycle stable alkali metal anode of claim 2, wherein the current collector comprises any one of a copper foil, a nickel foil, a titanium foil, a stainless steel sheet.
8. A cyclically stable alkali metal cathode, characterized in that it is prepared by the preparation method as claimed in any one of claims 1 to 7.
9. An alkali metal battery comprising the cycle-stable alkali metal anode of claim 8.
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