CN114212803A - Preparation method of fluorine-doped Prussian blue type sodium ion battery positive electrode material - Google Patents
Preparation method of fluorine-doped Prussian blue type sodium ion battery positive electrode material Download PDFInfo
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- CN114212803A CN114212803A CN202111259968.2A CN202111259968A CN114212803A CN 114212803 A CN114212803 A CN 114212803A CN 202111259968 A CN202111259968 A CN 202111259968A CN 114212803 A CN114212803 A CN 114212803A
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 33
- 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 11
- 239000007774 positive electrode material Substances 0.000 title claims description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 38
- 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 27
- 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
- 239000002244 precipitate 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
- 230000032683 aging Effects 0.000 claims abstract description 11
- 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
- 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 6
- 238000000034 method Methods 0.000 claims description 21
- 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
- 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
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 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
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 239000004255 Butylated hydroxyanisole Substances 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
- 235000019282 butylated hydroxyanisole Nutrition 0.000 claims description 2
- 229940043253 butylated hydroxyanisole Drugs 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
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 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
- 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
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 claims 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims 1
- 229910000358 iron sulfate Inorganic materials 0.000 claims 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims 1
- 229940053662 nickel sulfate Drugs 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 11
- -1 fluorine ions Chemical class 0.000 abstract description 10
- 239000011737 fluorine Substances 0.000 abstract description 7
- 229910052731 fluorine Inorganic materials 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 5
- 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 2
- 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
- 238000010668 complexation reaction Methods 0.000 abstract 1
- 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
- 238000001291 vacuum drying Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 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
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 230000000694 effects Effects 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
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 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 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
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000002288 cocrystallisation Methods 0.000 description 1
- 150000001875 compounds Chemical class 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
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940032296 ferric chloride Drugs 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
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 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
- 230000007774 longterm Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 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
Images
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 fluorine-doped Prussian blue type sodium ion battery anode material, 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 is finished, aging, carrying out solid-liquid separation on the aged material to obtain a precipitate, washing and drying the precipitate to obtain the Prussian blue type sodium ion battery anode material. The mixed solution contains a large amount of fluorine ions, and 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, the crystallization is slowly carried out, particles with better crystallinity are obtained, metal sodium salt subjected to fluorine complexation can also generate precipitation along with the reaction, and is co-precipitated with ferrocyanide to form a co-crystal, and the fluorine ions play a role in supporting a 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 type 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, safety concerns and limited lithium resources have prevented the application of lithium ion batteries to large scale energy storage systems. In this case, low cost, long life sodium ion batteries provide a more attractive alternative to lithium ion batteries for energy storage systems. Therefore, the 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 potential of electrochemical performance and the like, so the sodium ion battery is expected to be applied to the field of large-scale energy storage and is one of important research directions of next-generation battery technology. At present, the positive electrode material of the sodium ion battery mainly comprises transition metal oxide, phosphate, prussian blue material and the like. The Prussian blue material has the advantages of high voltage platform (>3V), large ion channel, large specific capacity, low price, no toxicity, easiness in preparation and the like, and becomes a research hotspot of the sodium-ion battery anode material. But the material is found to have poor cycle performance after being applied to a non-aqueous sodium-ion battery.
The Prussian blue type sodium ion battery positive electrode 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 a single iron source of sodium ferrocyanide, and the obtained product has few lattice defects and low water content, but the two methods have low production efficiency and yield, and toxic NaCN byproducts generated in the synthesis process pollute the environment and are not beneficial to large-scale production. The coprecipitation method is an 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 anode material and a sodium ion battery (CN107364875A), a method for preparing low-defect nano Prussian blue and application thereof (CN106745068A), 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 further the practical application is affected.
In order to further control the crystallization performance of the material, various complexing agents are used to improve the crystallinity of the material in the prior art, however, the general complexing agents are not only expensive, but also cause crystal surface residue which cannot be avoided.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a preparation method of a fluorine-doped Prussian blue type sodium ion battery anode material, which can solve the problems of poor crystallinity, poor cycle performance and crystal surface residue of the Prussian blue type sodium ion battery anode material.
According to one aspect of the invention, the preparation method of the fluorine-doped Prussian blue type sodium ion battery cathode material 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 is finished, and aging;
s3: and (4) carrying out solid-liquid separation on the material aged in the step S2 to obtain a precipitate, and washing and drying the precipitate to obtain the Prussian blue type sodium ion battery positive electrode material.
In some embodiments of the invention, in step S1, the antioxidant is one or more of butylated hydroxyanisole, butylated hydroxytoluene, propyl gallate, tert-butylhydroquinone, or ascorbic acid.
In some embodiments of the present invention, in step S1, the concentration of sodium ferrocyanide in the mixed solution is 0.01-1 mol/L; the concentration of the sodium fluoride is 0.01-1 mol/L.
In some embodiments of the present invention, in step S1, the concentration of the antioxidant in the mixed solution is 0.001 to 0.25 mol/L.
In some embodiments of the invention, in step S2, the transition metal salt solution is at least one of a solution of nickel sulfate, cobalt sulfate, manganese sulfate, ferric sulfate, ferrous sulfate, nickel nitrate, cobalt nitrate, manganese nitrate, ferric nitrate, ferrous nitrate, nickel chloride, cobalt chloride, manganese chloride, ferric chloride, or ferrous chloride.
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 volume of the transition metal salt solution added to the volume of the mixed solution is (0.9 to 1.1): 1; the flow rate of the transition metal salt solution is 25-50 mL/h.
In some embodiments of the present invention, in step S2, the concentration of the sodium chloride solution is 1 to 4mol/L, and the ratio of the volume of the added sodium chloride solution to the volume of the mixed solution is (0.9 to 1.1): 1.
in some embodiments of the invention, the aging time in step S2 is 2 to 48 hours.
In some embodiments of the present invention, in step S3, the washing is performed by washing the precipitate with deionized water and absolute ethanol.
In some embodiments of the present invention, in step S3, the drying step is to vacuum-dry the precipitate at 120 ℃ for 12-24h at 100 ℃.
According to a preferred embodiment of the present invention, at least the following advantages are provided:
1. the ferrous cyanide ions are easily converted into ferric cyanide ions or dissociated into ferric ions and 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, and when the transition metal ions are added, on one hand, the mixed solution can be complexed with the transition metal ions, so that the precipitation reaction speed is inhibited, the crystallization is slowly carried out, and particles with better crystallinity are obtained; on the other hand, the fluorine-complexed metal sodium salt is precipitated along with the reaction and is co-precipitated with ferrocyanide to form a co-crystal. Fluorine ions are adopted as a complexing agent, different from a common complex, the fluorine ions do not cause residue, but directly serve as a part of a positive electrode material, and play a role of a supporting framework of the material in the subsequent charging and discharging processes, such as: na (Na)4MeF6On charging, conversion to Na2MeF6The material has lower mass, can further improve the gram capacity of the material, and reports that the fluoride is adopted as the positive electrode material of the sodium ion battery at present are very rare.
3. And adding a sodium chloride solution with higher concentration into the mixed solution, and aging for a long time to further separate out the metal ion complex, so that the cocrystallization is more stable, and the production efficiency of the product is improved.
Drawings
The invention is further described with reference to the following figures and examples, in which:
fig. 1 is an SEM image of a fluorine-doped prussian blue-based sodium ion battery positive electrode material prepared in example 1 of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The preparation method of the fluorine-doped Prussian blue type sodium ion battery anode material comprises the following specific steps:
(1) preparing 100mL of a mixed solution of sodium ferrocyanide and sodium fluoride, and adding ascorbic acid as an antioxidant, wherein the concentration of the sodium ferrocyanide, the concentration of the sodium fluoride and the concentration of the antioxidant in the mixed solution are respectively 0.1mol/L, 0.6mol/L and 0.01 mol/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) after the addition is finished, adding a sodium chloride solution into the mixed solution, and aging for 12 hours;
(5) carrying out solid-liquid separation to obtain a precipitate;
(6) washing the precipitate with deionized water and anhydrous ethanol, and vacuum drying at 120 deg.C for 12-24 hr to obtain Na6Mn2[Fe(CN)6]F6The fluorine-doped Prussian blue type sodium ion battery positive electrode material.
Example 2
The preparation method of the fluorine-doped Prussian blue type sodium ion battery anode material comprises the following specific steps:
(1) preparing 100mL of a mixed solution of sodium ferrocyanide and sodium fluoride, and adding ascorbic acid as an antioxidant, wherein the concentration of the sodium ferrocyanide, the concentration of the sodium fluoride and the concentration of the antioxidant in the mixed solution are respectively 0.1mol/L, 0.6mol/L and 0.01 mol/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 mixed solution of ferric salt into the mixed solution of sodium ferrocyanide and sodium fluoride at a fixed flow rate of 25 mL/h;
(4) after the addition is finished, adding a sodium chloride solution into the mixed solution, and aging for 48 hours;
(5) carrying out solid-liquid separation to obtain a precipitate;
(6) washing the precipitate by using deionized water and absolute ethyl alcohol, and then placing the precipitate at the temperature of 100-120 ℃ for vacuum drying for 12-24h to obtain the fluorine-doped Prussian blue type sodium ion battery anode material.
In this example, fluoride ions are not complexed with ferrous ions, but ferrous fluoride precipitates are generated, 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, sodium chloride is added, and long-term aging and recrystallization are performed to obtain a compound with a chemical formula of Na7Fe6[Fe(CN)6]2F12The crystals of (2).
Example 3
The preparation method of the fluorine-doped Prussian blue type sodium ion battery anode material comprises the following specific steps:
(1) preparing 100mL of a mixed solution of sodium ferrocyanide and sodium fluoride, and adding butyl hydroxy anisole as an antioxidant, wherein the concentration of the sodium ferrocyanide, the concentration of the sodium fluoride and the concentration of the antioxidant in the mixed solution are respectively 0.01mol/L, 0.06mol/L and 0.001 mol/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) after the addition is finished, adding a sodium chloride solution into the mixed solution, and aging for 24 hours;
(5) carrying out solid-liquid separation to obtain a precipitate;
(6) washing the precipitate with deionized water and anhydrous ethanol, and vacuum drying at 120 deg.C for 12-24 hr to obtain Na6Co2[Fe(CN)6]F6The fluorine-doped Prussian blue type sodium ion battery positive electrode material.
Comparative example
The Prussian blue type sodium ion battery positive electrode material is prepared by the comparative example, and the specific process comprises the following steps:
(1) preparing 100mL of sodium ferrocyanide solution, and adding ascorbic acid as an antioxidant, wherein the concentration of the sodium ferrocyanide in the solution is 0.1mol/L, and the concentration of the antioxidant is 0.01 mol/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) after the feeding is finished, aging for 12 hours;
(5) carrying out solid-liquid separation to obtain a precipitate;
(6) washing the precipitate with deionized water and anhydrous ethanol, and vacuum drying at 120 deg.C for 12-24 hr to obtain Na2Mn[Fe(CN)6]The Prussian blue sodium-ion battery cathode material.
Test examples
The prussian blue sodium-ion battery positive electrode materials 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, wherein the test results are shown in table 1.
TABLE 1
| Specific capacity mAh/g of 0.1C first 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 comparative example not doped with fluorine has significantly lower specific capacity and cycle performance than the examples, because the comparative example simply mixes the transition metal salt and the sodium ferrocyanide solution, the reaction rate is difficult to control, so that the material has poor crystallinity and the sodium content is not high, resulting in poor electrochemical performance.
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 those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A preparation method of a fluorine-doped Prussian blue type sodium ion battery positive electrode material is characterized by comprising 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 is finished, and aging;
s3: and (4) carrying out solid-liquid separation on the material aged in the step S2 to obtain a precipitate, and washing and drying the precipitate to obtain the Prussian blue type sodium ion battery positive electrode material.
2. The method according to claim 1, wherein in step S1, the antioxidant is one or more selected from butylated hydroxyanisole, dibutyl hydroxytoluene, propyl gallate, tert-butyl hydroquinone, and ascorbic acid.
3. The method according to claim 1, wherein in step S1, the concentration of sodium ferrocyanide in the mixed solution is 0.01-1 mol/L; the concentration of the sodium fluoride is 0.01-1 mol/L.
4. The method according to claim 1, wherein in step S1, the antioxidant is present in the mixed solution at a concentration of 0.001 to 0.25 mol/L.
5. The method according to claim 1, wherein in step S2, the transition metal salt solution is at least one of a solution 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, iron chloride, or ferrous chloride.
6. The production method according to claim 1, wherein in step S2, the concentration of the transition metal salt solution is 0.01 to 1mol/L, and the ratio of the volume of the transition metal salt solution added to the volume of the mixed solution is (0.9 to 1.1): 1; the flow rate of the transition metal salt solution is 25-50 mL/h.
7. 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 volume of the sodium chloride solution added to the volume of the mixed solution is (0.9 to 1.1): 1.
8. the method according to claim 1, wherein the aging time in step S2 is 2 to 48 hours.
9. The method according to claim 1, wherein in step S3, the washing is performed by washing the precipitate with deionized water and absolute ethanol.
10. The method as claimed in claim 1, wherein the drying step S3 is carried out by drying the precipitate at 120 ℃ for 12-24h under vacuum.
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| WO2023071338A1 (en) * | 2021-10-28 | 2023-05-04 | 广东邦普循环科技有限公司 | Preparation method for fluorine-doped prussian-blue-type sodium ion battery positive electrode material |
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