CN114212803B - Preparation method of fluorine-doped Prussian blue sodium ion battery positive electrode material - Google Patents
Preparation method of fluorine-doped Prussian blue sodium ion battery positive electrode material Download PDFInfo
- Publication number
- CN114212803B CN114212803B CN202111259968.2A CN202111259968A CN114212803B CN 114212803 B CN114212803 B CN 114212803B CN 202111259968 A CN202111259968 A CN 202111259968A CN 114212803 B CN114212803 B CN 114212803B
- Authority
- CN
- China
- Prior art keywords
- sodium
- mixed solution
- solution
- transition metal
- fluorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 32
- 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 title claims abstract description 27
- 229960003351 prussian blue Drugs 0.000 title claims abstract description 27
- 239000013225 prussian blue Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000007774 positive electrode material Substances 0.000 title description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 37
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 30
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 28
- 239000002244 precipitate Substances 0.000 claims abstract description 21
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 235000012247 sodium ferrocyanide Nutrition 0.000 claims abstract description 21
- 239000000264 sodium ferrocyanide Substances 0.000 claims abstract description 21
- 239000010405 anode material Substances 0.000 claims abstract description 20
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 16
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000011780 sodium chloride Substances 0.000 claims abstract description 15
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 14
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 14
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 13
- 239000012266 salt solution Substances 0.000 claims abstract description 11
- 150000003624 transition metals Chemical class 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 230000032683 aging Effects 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 23
- 235000006708 antioxidants Nutrition 0.000 claims description 15
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229940099596 manganese sulfate Drugs 0.000 claims description 6
- 235000007079 manganese sulphate Nutrition 0.000 claims description 6
- 239000011702 manganese sulphate Substances 0.000 claims description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229940032296 ferric chloride Drugs 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229940053662 nickel sulfate Drugs 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 235000010388 propyl gallate Nutrition 0.000 claims description 2
- 239000000473 propyl gallate Substances 0.000 claims description 2
- 229940075579 propyl gallate Drugs 0.000 claims description 2
- 239000004250 tert-Butylhydroquinone Substances 0.000 claims description 2
- 235000019281 tert-butylhydroquinone Nutrition 0.000 claims description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims 2
- 239000011737 fluorine Substances 0.000 abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 abstract description 11
- -1 fluorine ions Chemical class 0.000 abstract description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000000975 co-precipitation Methods 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 4
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- 230000036632 reaction speed Effects 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 159000000000 sodium salts Chemical class 0.000 abstract description 2
- 239000011734 sodium Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008139 complexing agent Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000004255 Butylated hydroxyanisole Substances 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000019282 butylated hydroxyanisole Nutrition 0.000 description 1
- 229940043253 butylated hydroxyanisole Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000002288 cocrystallisation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- PANJMBIFGCKWBY-UHFFFAOYSA-N iron tricyanide Chemical compound N#C[Fe](C#N)C#N PANJMBIFGCKWBY-UHFFFAOYSA-N 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- FZGIHSNZYGFUGM-UHFFFAOYSA-L iron(ii) fluoride Chemical compound [F-].[F-].[Fe+2] FZGIHSNZYGFUGM-UHFFFAOYSA-L 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/08—Simple or complex cyanides of metals
- C01C3/12—Simple or complex iron cyanides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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 discloses a preparation method of a Prussian blue sodium ion battery anode material doped with fluorine, which comprises the steps of preparing a mixed solution of sodium ferrocyanide and sodium fluoride, adding an antioxidant into the mixed solution, adding a transition metal salt solution into the mixed solution at a certain flow rate, adding a sodium chloride solution into the mixed solution after the addition, aging, carrying out solid-liquid separation on the aged material to obtain a precipitate, and washing and drying the precipitate to obtain the Prussian blue sodium ion battery anode material. The mixed solution contains a large amount of fluorine ions, when the transition metal ions are added, the fluorine ions are complexed with the transition metal ions, so that the precipitation reaction speed is inhibited, crystallization is slowly carried out, particles with better crystallinity are obtained, fluorine complexed metal sodium salt can also generate precipitation along with the progress of the reaction, and co-precipitation is carried out with ferrocyanide to form co-crystals, and the fluorine ions play a role of a supporting framework of the material.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a preparation method of a fluorine-doped Prussian blue sodium ion battery anode material.
Background
Lithium ion batteries are widely used in portable electronic devices and electric vehicles due to their long life and high specific energy. However, potential safety hazards and limited lithium resources have prevented the use of lithium ion batteries in large-scale energy storage systems. In this case, the low cost, long life of the sodium ion battery provides a more attractive solution for the energy storage system to replace the lithium ion battery. Therefore, development of sustainable electrode materials for sodium-ion batteries is imperative.
The sodium ion battery has the characteristics of low raw material cost, abundant resources, large electrochemical performance potential and the like, is expected to be applied to the field of large-scale energy storage, and is one of important research directions of the next-generation battery technology. Currently, the positive electrode materials of sodium ion batteries mainly comprise transition metal oxides, phosphates, prussian blue materials and the like. The Prussian blue material has the advantages of higher voltage platform (> 3V), large ion channel, large specific capacity, low price, no toxicity, easy preparation and the like, and becomes a research hotspot of the sodium ion battery anode material. However, the material is found to have poor cycle performance after being applied to a nonaqueous sodium ion battery.
The Prussian blue sodium ion battery anode material can be synthesized by a thermal decomposition method, a hydrothermal method and a coprecipitation method. The thermal decomposition method and the hydrothermal method both adopt the decomposition principle of sodium ferrocyanide as a single iron source, the obtained product has few lattice defects and low water content, but the two methods have low production efficiency and yield, and the toxic NaCN byproducts produced in the synthesis process pollute the environment and are unfavorable for large-scale production. The coprecipitation method is a green and environment-friendly method capable of realizing expanded production, however, the method for preparing the Prussian blue cathode material by the coprecipitation method reported in the current patent literature mainly comprises the following steps: a method for preparing Prussian blue positive electrode material, a sodium ion battery (CN 107364875A), a method for preparing low-defect nano Prussian blue, application thereof (CN 106745068A) and the like. However, the above synthesis method simply mixes the transition metal salt and the sodium ferrocyanide solution, and the reaction speed is difficult to control, so that the crystallinity of the material is poor, the sodium content is not high, the moisture content in the material is still high, the electrochemical performance is poor, and the practical application is further affected.
In order to further control the crystallization performance of the material, various complexing agents are used in the prior art to improve the crystallinity of the material, however, the general complexing agents are expensive, and the residue on the crystal surface caused by the general complexing agents is unavoidable.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides a preparation method of the Prussian blue sodium ion battery anode material doped with fluorine, which can solve the problems of poor crystallinity, poor cycle performance and residual crystal surface of the Prussian blue sodium ion battery anode material.
According to one aspect of the invention, a preparation method of a Prussian blue sodium ion battery anode material doped with fluorine is provided, which comprises the following steps:
s1: preparing a mixed solution of sodium ferrocyanide and sodium fluoride, and adding an antioxidant into the mixed solution;
s2: adding a transition metal salt solution into the mixed solution at a certain flow rate, adding a sodium chloride solution into the mixed solution after the addition, and aging;
s3: and (3) carrying out solid-liquid separation on the aged material in the step (S2) to obtain a precipitate, and washing and drying the precipitate to obtain the Prussian blue sodium ion battery anode material.
In some embodiments of the invention, in step S1, the antioxidant is one or more of butylated hydroxyanisole, dibutylhydroxytoluene, propyl gallate, tert-butylhydroquinone, or ascorbic acid.
In some embodiments of the invention, in step S1, the concentration of sodium ferrocyanide in the mixed solution is 0.01-1mol/L; the concentration of the sodium fluoride is 0.01-1mol/L.
In some embodiments of the invention, in step S1, the concentration of the antioxidant in the mixed solution is 0.001-0.25mol/L.
In some embodiments of the invention, in step S2, the transition metal salt solution is at least one of nickel sulfate, cobalt sulfate, manganese sulfate, iron sulfate, ferrous sulfate, nickel nitrate, cobalt nitrate, manganese nitrate, iron nitrate, ferrous nitrate, nickel chloride, cobalt chloride, manganese chloride, ferric chloride, or ferrous chloride solution.
In some embodiments of the present invention, in step S2, the concentration of the transition metal salt solution is 0.01 to 1mol/L, and the ratio of the added volume of the transition metal salt solution to the volume of the mixed solution is (0.9 to 1.1): 1, a step of; the flow rate of the transition metal salt solution is 25-50mL/h.
In some embodiments of the invention, in step S2, the concentration of the sodium chloride solution is 1 to 4mol/L, and the ratio of the added volume of the sodium chloride solution to the volume of the mixed solution is (0.9 to 1.1): 1.
in some embodiments of the invention, in step S2, the aging time is 2 to 48 hours.
In some embodiments of the invention, in step S3, the washing is washing the precipitate with deionized water and absolute ethanol.
In some embodiments of the invention, in step S3, the drying is performed by vacuum drying the precipitate at 100-120 ℃ for 12-24 hours.
According to a preferred embodiment of the invention, there is at least the following advantageous effect:
1. the ferrous cyanide ions are easily converted into the ferric cyanide ions or dissociated into the ferric ions and the cyanide ions under illumination, and the antioxidant is added to relieve the reaction and further improve the purity of the target product;
2. the mixed solution contains a large amount of fluoride ions, when the transition metal ions are added, oneIn the aspect, complex is carried out with transition metal ions, so that the precipitation reaction speed is restrained, crystallization is carried out slowly, and particles with better crystallinity are obtained; on the other hand, fluorine-complexed metal sodium salts also precipitate as the reaction proceeds and co-precipitate with ferrocyanide to form co-crystals. Fluoride ions are adopted as complexing agents, are different from common complexes, can not cause residues, and are directly used as a part of the anode material, and play a role of a supporting framework of the material in the subsequent charge and discharge process, such as: na (Na) 4 MeF 6 Upon charging, it is converted into Na 2 MeF 6 The material has lower quality, can further improve gram capacity of the material, and is rarely reported to be used as a positive electrode material of a sodium ion battery at present.
3. Adding sodium chloride solution with higher concentration into the mixed solution for long-time aging, so that the metal ion complex is further separated out, the co-crystallization is more stable, and the production efficiency of the product is improved.
Drawings
The invention is further described with reference to the accompanying drawings and examples, in which:
fig. 1 is an SEM image of a fluorine-doped prussian blue type sodium ion battery cathode material prepared in example 1 of the present invention.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
Example 1
The embodiment prepares the fluorine-doped Prussian blue sodium ion battery anode material, which comprises the following specific processes:
(1) Preparing 100mL of mixed solution of sodium ferrocyanide and sodium fluoride, and adding ascorbic acid as an antioxidant, wherein the concentration of sodium ferrocyanide in the mixed solution is 0.1mol/L, the concentration of sodium fluoride is 0.6mol/L, and the concentration of the antioxidant is 0.01mol/L;
(2) Respectively preparing 100mL of manganese sulfate solution with the concentration of 0.1mol/L and 100mL of sodium chloride solution with the concentration of 2 mol/L;
(3) Adding a manganese sulfate solution into a mixed solution of sodium ferrocyanide and sodium fluoride at a fixed flow rate of 25 mL/h;
(4) Adding sodium chloride solution into the mixed solution after the addition is finished, and aging for 12 hours;
(5) Solid-liquid separation to obtain precipitate;
(6) Washing the precipitate with deionized water and absolute ethanol, and vacuum drying at 100-120deg.C for 12-24 hr to obtain Na 6 Mn 2 [Fe(CN) 6 ]F 6 The Prussian blue sodium ion battery anode material doped with fluorine.
Example 2
The embodiment prepares the fluorine-doped Prussian blue sodium ion battery anode material, which comprises the following specific processes:
(1) Preparing 100mL of mixed solution of sodium ferrocyanide and sodium fluoride, and adding ascorbic acid as an antioxidant, wherein the concentration of sodium ferrocyanide in the mixed solution is 0.1mol/L, the concentration of sodium fluoride is 0.6mol/L, and the concentration of the antioxidant is 0.01mol/L;
(2) Preparing 100mL of mixed solution of ferrous chloride with the concentration of 0.25mol/L and ferric chloride with the concentration of 0.05mol/L, and preparing 100mL of sodium chloride solution with the concentration of 2 mol/L;
(3) Adding the ferric salt mixed solution into the mixed solution of sodium ferrocyanide and sodium fluoride at a fixed flow rate of 25 mL/h;
(4) Adding sodium chloride solution into the mixed solution after the addition is finished, and aging for 48 hours;
(5) Solid-liquid separation to obtain precipitate;
(6) Washing the precipitate by deionized water and absolute ethyl alcohol, and then vacuum drying the precipitate at 100-120 ℃ for 12-24 hours to obtain the Prussian blue sodium ion battery anode material doped with fluorine.
In the embodiment, fluoride ions are not complexed with ferrous ions, but are precipitated to form ferrous fluoride, sodium ferrocyanide is complexed with ferrous ions in a ratio of 1:1, fluoride ions are complexed with ferric ions in a ratio of 3:1, and after sodium chloride is added, the mixture is aged and recrystallized for a long time to obtain Na as a chemical formula 7 Fe 6 [Fe(CN) 6 ] 2 F 12 Is a crystalline body of (a).
Example 3
The embodiment prepares the fluorine-doped Prussian blue sodium ion battery anode material, which comprises the following specific processes:
(1) Preparing 100mL of mixed solution of sodium ferrocyanide and sodium fluoride, and adding butyl hydroxy anisole as an antioxidant, wherein the concentration of sodium ferrocyanide in the mixed solution is 0.01mol/L, the concentration of sodium fluoride is 0.06mol/L, and the concentration of the antioxidant is 0.001mol/L;
(2) Respectively preparing 100mL of cobalt sulfate solution with the concentration of 0.01mol/L and 100mL of sodium chloride solution with the concentration of 4 mol/L;
(3) Adding a cobalt sulfate solution into a mixed solution of sodium ferrocyanide and sodium fluoride at a fixed flow rate of 50 mL/h;
(4) Adding sodium chloride solution into the mixed solution after the addition is finished, and aging for 24 hours;
(5) Solid-liquid separation to obtain precipitate;
(6) Washing the precipitate with deionized water and absolute ethanol, and vacuum drying at 100-120deg.C for 12-24 hr to obtain Na 6 Co 2 [Fe(CN) 6 ]F 6 The Prussian blue sodium ion battery anode material doped with fluorine.
Comparative example
The comparative example prepares a Prussian blue sodium ion battery anode material, which comprises the following specific processes:
(1) Preparing 100mL of sodium ferrocyanide solution, and adding ascorbic acid as an antioxidant, wherein the concentration of sodium ferrocyanide in the solution is 0.1mol/L, and the concentration of the antioxidant is 0.01mol/L;
(2) Respectively preparing 100mL of manganese sulfate solution with the concentration of 0.1 mol/L;
(3) Adding a manganese sulfate solution into a sodium ferrocyanide solution at a fixed flow rate of 25 mL/h;
(4) Aging for 12 hours after the addition is finished;
(5) Solid-liquid separation to obtain precipitate;
(6) Washing the precipitate with deionized water and absolute ethanol, and vacuum drying at 100-120deg.C for 12-24 hr to obtain Na 2 Mn[Fe(CN) 6 ]Prussian blue sodium ion battery anode material.
Test examples
The positive electrode materials of the Prussian blue sodium ion batteries prepared in the examples and the comparative examples are assembled into an organic electrolyte system sodium ion half battery, and electrochemical performance tests are carried out, and the test results are shown in table 1.
TABLE 1
| Specific capacity mAh/g of 0.1C initial discharge | Specific discharge capacity mAh/g after 200 cycles | |
| Example 1 | 157.6 | 130.8 |
| Example 2 | 162.7 | 137.6 |
| Example 3 | 152.1 | 123.1 |
| Comparative example | 138.1 | 93.2 |
As can be seen from table 1, the specific capacity and cycle performance of the undoped fluorine comparative example are significantly lower than those of the examples, since the comparative example is a simple mixing of the transition metal salt and sodium ferrocyanide solution, the reaction rate is difficult to control, the crystallinity of the material is poor, the sodium content is not high, and the electrochemical performance is poor.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of one of ordinary skill in the art without departing from the spirit of the present invention. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (9)
1. The preparation method of the fluorine-doped Prussian blue sodium ion battery anode material is characterized by comprising the following steps of:
s1: preparing a mixed solution of sodium ferrocyanide and sodium fluoride, and adding an antioxidant into the mixed solution; the concentration of sodium ferrocyanide in the mixed solution is 0.01-1mol/L; the concentration of the sodium fluoride is 0.01-1mol/L;
s2: adding a transition metal salt solution into the mixed solution at a certain flow rate, adding a sodium chloride solution into the mixed solution after the addition, and aging; the concentration of the transition metal salt solution is 0.01-1mol/L, and the ratio of the added volume of the transition metal salt solution to the volume of the mixed solution is (0.9-1.1): 1, a step of;
s3: and (3) carrying out solid-liquid separation on the aged material in the step (S2) to obtain a precipitate, and washing and drying the precipitate to obtain the Prussian blue sodium ion battery anode material.
2. The preparation method according to claim 1, wherein in the step S1, the antioxidant is one or more of butyl hydroxy anisole, dibutyl hydroxy toluene, propyl gallate, tert-butyl hydroquinone and ascorbic acid.
3. The method according to claim 1, wherein the concentration of the antioxidant in the mixed solution in step S1 is 0.001 to 0.25mol/L.
4. The method according to claim 1, wherein in the step S2, the transition metal salt solution is at least one of nickel sulfate, cobalt sulfate, manganese sulfate, iron sulfate, ferrous sulfate, nickel nitrate, cobalt nitrate, manganese nitrate, ferric nitrate, ferrous nitrate, nickel chloride, cobalt chloride, manganese chloride, ferric chloride, or ferrous chloride solution.
5. The method according to claim 1, wherein in step S2, the transition metal salt solution is added at a flow rate of 25 to 50mL/h.
6. The method according to claim 1, wherein in step S2, the concentration of the sodium chloride solution is 1 to 4mol/L, and the ratio of the added volume of the sodium chloride solution to the volume of the mixed solution is (0.9 to 1.1): 1.
7. the method according to claim 1, wherein in step S2, the aging time is 2 to 48 hours.
8. The method according to claim 1, wherein in step S3, the washing is washing the precipitate with deionized water and absolute ethanol.
9. The method according to claim 1, wherein in step S3, the drying is performed by vacuum drying the precipitate at 100 to 120 ℃ for 12 to 24 hours.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111259968.2A CN114212803B (en) | 2021-10-28 | 2021-10-28 | Preparation method of fluorine-doped Prussian blue sodium ion battery positive electrode material |
| GB2318294.2A GB2621296A (en) | 2021-10-28 | 2022-07-28 | Preparation method for fluorine-doped Prussian-blue-type sodium ion battery positive electrode material |
| PCT/CN2022/108658 WO2023071338A1 (en) | 2021-10-28 | 2022-07-28 | Preparation method for fluorine-doped prussian-blue-type sodium ion battery positive electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111259968.2A CN114212803B (en) | 2021-10-28 | 2021-10-28 | Preparation method of fluorine-doped Prussian blue sodium ion battery positive electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114212803A CN114212803A (en) | 2022-03-22 |
| CN114212803B true CN114212803B (en) | 2023-09-12 |
Family
ID=80696240
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111259968.2A Active CN114212803B (en) | 2021-10-28 | 2021-10-28 | Preparation method of fluorine-doped Prussian blue sodium ion battery positive electrode material |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN114212803B (en) |
| GB (1) | GB2621296A (en) |
| WO (1) | WO2023071338A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114212803B (en) * | 2021-10-28 | 2023-09-12 | 广东邦普循环科技有限公司 | Preparation method of fluorine-doped Prussian blue sodium ion battery positive electrode material |
| CN114873609B (en) * | 2022-04-01 | 2023-10-27 | 深圳先进技术研究院 | carbon/Prussian blue-like composite material, and preparation method and application thereof |
| CN115072741B (en) * | 2022-07-08 | 2023-11-17 | 金驰能源材料有限公司 | Prussian blue positive electrode material, continuous preparation method thereof and sodium ion battery |
| CN115504488B (en) * | 2022-10-13 | 2023-10-17 | 广东邦普循环科技有限公司 | Prussian blue electrode material and preparation method and application thereof |
| CN115611296B (en) * | 2022-12-19 | 2023-05-09 | 中节能万润股份有限公司 | Preparation method and application of Prussian blue sodium ion battery positive electrode material |
| CN117430134B (en) * | 2023-12-21 | 2024-04-05 | 山东海化集团有限公司 | Preparation method of ferromanganese-based Prussian blue sodium electric positive electrode material and positive electrode material prepared by method |
| CN117457902A (en) * | 2023-12-25 | 2024-01-26 | 宁波容百新能源科技股份有限公司 | Prussian blue positive electrode material, preparation method thereof and battery |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105555712A (en) * | 2013-10-30 | 2016-05-04 | 夏普株式会社 | Sodium iron(II)-hexacyanoferrate(II) battery electrode and synthesis method |
| CN107611404A (en) * | 2017-09-14 | 2018-01-19 | 上海汉行科技有限公司 | A kind of white composite in Prussia and its preparation method and application |
| WO2018209653A1 (en) * | 2017-05-18 | 2018-11-22 | 宁德时代新能源科技股份有限公司 | Prussian blue positive electrode material, preparation method therefor, and electrochemical energy storage device |
| CN109761246A (en) * | 2018-12-07 | 2019-05-17 | 上海汉行科技有限公司 | The Prussian blue sill of doping vario-property and preparation method for sodium-ion battery |
| CN109824060A (en) * | 2019-04-01 | 2019-05-31 | 西北工业大学 | A kind of Prussian blue material in richness ammonia concave surface and preparation method |
| CN110078096A (en) * | 2019-05-14 | 2019-08-02 | 上海汉行科技有限公司 | A kind of Prussian blue material and preparation method thereof |
| CN110504447A (en) * | 2019-08-30 | 2019-11-26 | 湖南金富力新能源股份有限公司 | A kind of nickel cobalt manganese presoma of Fluorin doped and the preparation method and application thereof |
| CN110921681A (en) * | 2019-11-28 | 2020-03-27 | 国网浙江省电力有限公司电力科学研究院 | Prussian blue material and preparation method and application thereof |
| CN111600011A (en) * | 2020-04-24 | 2020-08-28 | 国网浙江省电力有限公司电力科学研究院 | Doped prussian blue material and preparation method and application thereof |
| CN112607748A (en) * | 2020-12-24 | 2021-04-06 | 三峡大学 | Multielement Prussian blue sodium ion battery positive electrode material and preparation method thereof |
| CN113479911A (en) * | 2021-06-21 | 2021-10-08 | 华中科技大学 | Iron-based Prussian blue, preparation method and application thereof |
| CN113488646A (en) * | 2021-06-17 | 2021-10-08 | 三峡大学 | Prussian blue type sodium ion battery positive electrode material and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011180469A (en) * | 2010-03-03 | 2011-09-15 | National Institute Of Advanced Industrial Science & Technology | Electrochemical element having prussian blue type metal complex nanoparticle, electrochromic element and secondary battery using the same |
| US9450224B2 (en) * | 2012-03-28 | 2016-09-20 | Sharp Laboratories Of America, Inc. | Sodium iron(II)-hexacyanoferrate(II) battery electrode and synthesis method |
| CN110165167A (en) * | 2019-05-14 | 2019-08-23 | 上海汉行科技有限公司 | Modified ferrocyanogen material in a kind of surface and preparation method thereof |
| CN110451525B (en) * | 2019-08-07 | 2021-05-11 | 清华大学 | Method for rapidly preparing Prussian blue analogue with monoclinic crystal structure |
| CN112968165A (en) * | 2020-12-31 | 2021-06-15 | 天津中电新能源研究院有限公司 | Modified sodium ion positive electrode material, modified sodium ion electrode and preparation method |
| CN114212803B (en) * | 2021-10-28 | 2023-09-12 | 广东邦普循环科技有限公司 | Preparation method of fluorine-doped Prussian blue sodium ion battery positive electrode material |
-
2021
- 2021-10-28 CN CN202111259968.2A patent/CN114212803B/en active Active
-
2022
- 2022-07-28 WO PCT/CN2022/108658 patent/WO2023071338A1/en active Application Filing
- 2022-07-28 GB GB2318294.2A patent/GB2621296A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105555712A (en) * | 2013-10-30 | 2016-05-04 | 夏普株式会社 | Sodium iron(II)-hexacyanoferrate(II) battery electrode and synthesis method |
| WO2018209653A1 (en) * | 2017-05-18 | 2018-11-22 | 宁德时代新能源科技股份有限公司 | Prussian blue positive electrode material, preparation method therefor, and electrochemical energy storage device |
| CN107611404A (en) * | 2017-09-14 | 2018-01-19 | 上海汉行科技有限公司 | A kind of white composite in Prussia and its preparation method and application |
| CN109761246A (en) * | 2018-12-07 | 2019-05-17 | 上海汉行科技有限公司 | The Prussian blue sill of doping vario-property and preparation method for sodium-ion battery |
| CN109824060A (en) * | 2019-04-01 | 2019-05-31 | 西北工业大学 | A kind of Prussian blue material in richness ammonia concave surface and preparation method |
| CN110078096A (en) * | 2019-05-14 | 2019-08-02 | 上海汉行科技有限公司 | A kind of Prussian blue material and preparation method thereof |
| CN110504447A (en) * | 2019-08-30 | 2019-11-26 | 湖南金富力新能源股份有限公司 | A kind of nickel cobalt manganese presoma of Fluorin doped and the preparation method and application thereof |
| CN110921681A (en) * | 2019-11-28 | 2020-03-27 | 国网浙江省电力有限公司电力科学研究院 | Prussian blue material and preparation method and application thereof |
| CN111600011A (en) * | 2020-04-24 | 2020-08-28 | 国网浙江省电力有限公司电力科学研究院 | Doped prussian blue material and preparation method and application thereof |
| CN112607748A (en) * | 2020-12-24 | 2021-04-06 | 三峡大学 | Multielement Prussian blue sodium ion battery positive electrode material and preparation method thereof |
| CN113488646A (en) * | 2021-06-17 | 2021-10-08 | 三峡大学 | Prussian blue type sodium ion battery positive electrode material and preparation method thereof |
| CN113479911A (en) * | 2021-06-21 | 2021-10-08 | 华中科技大学 | Iron-based Prussian blue, preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 普鲁士蓝钠离子电池正极材料高收率合成过程及性能;孙李琪;严小敏;唐婉;何雨石;马紫峰;廖小珍;;过程工程学报(第04期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023071338A1 (en) | 2023-05-04 |
| GB202318294D0 (en) | 2024-01-17 |
| CN114212803A (en) | 2022-03-22 |
| GB2621296A (en) | 2024-02-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114212803B (en) | Preparation method of fluorine-doped Prussian blue sodium ion battery positive electrode material | |
| CN114212802B (en) | Preparation method of Prussian blue type sodium ion battery positive electrode material | |
| KR101198489B1 (en) | A method for preparing iron source used for preparing lithium ferrous phosphate, and a method for preparing lithium ferrous phosphate | |
| CN111082058B (en) | Nasicon structure sodium titanium phosphate surface modified P2 type manganese-based sodium ion battery positive electrode material and preparation method thereof | |
| CN103151505B (en) | A kind of Lithium-titanate composite negative pole and preparation method thereof | |
| EP3611132B1 (en) | Method for preparing cathode active material | |
| CN113479911A (en) | Iron-based Prussian blue, preparation method and application thereof | |
| CN113830792B (en) | Anhydrous Prussian white material, preparation method and application | |
| CN113948697B (en) | Doped sodium iron phosphate positive electrode material, and preparation method and application thereof | |
| CN113839032A (en) | Low-cost Prussian white material, and preparation method and application thereof | |
| EP4310952A1 (en) | Iron-manganese-based positive electrode material, and preparation method therefor and use thereof | |
| CN105428628A (en) | Preparation method of porous spherical high-voltage lithium ion battery positive electrode material | |
| CN108448113B (en) | Preparation method of doped modified lithium iron phosphate positive-grade material | |
| CN115020670A (en) | MOFs modified silicon-based negative electrode material and preparation method thereof | |
| CN115548336A (en) | Prussian blue positive electrode material, preparation method thereof and electrochemical device | |
| CN116504940A (en) | Polyanion type sodium ion battery positive electrode material, preparation method and application thereof | |
| CN116111072A (en) | Positive electrode sodium supplement additive and preparation method and application thereof | |
| CN114388757A (en) | Prussian white material for positive electrode of sodium-ion battery and preparation method thereof | |
| CN114551861A (en) | Nickel-cobalt-manganese ternary cathode material nanorod and application thereof | |
| CN108598443B (en) | Macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material and preparation method thereof | |
| CN114649582A (en) | Electrolyte containing six-membered cyclic nitrogen-based salt structure and preparation method and application thereof | |
| CN114335552B (en) | Positive electrode material, modification process thereof and solid-state battery | |
| CN112811471B (en) | Silver, cobalt and nickel doped lithium manganate positive electrode material of lithium ion battery and preparation method thereof | |
| CN114644644B (en) | Electrolyte containing nitrogen-based salt structure, and preparation method and application thereof | |
| CN117430134B (en) | Preparation method of ferromanganese-based Prussian blue sodium electric positive electrode material and positive electrode material prepared by method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |