WO2023093158A1 - 多孔钠离子电池正极材料磷酸铁钠的制备方法 - Google Patents
多孔钠离子电池正极材料磷酸铁钠的制备方法 Download PDFInfo
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- WO2023093158A1 WO2023093158A1 PCT/CN2022/114920 CN2022114920W WO2023093158A1 WO 2023093158 A1 WO2023093158 A1 WO 2023093158A1 CN 2022114920 W CN2022114920 W CN 2022114920W WO 2023093158 A1 WO2023093158 A1 WO 2023093158A1
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- Prior art keywords
- sodium
- preparation
- carbonate
- silver
- ion battery
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 27
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- AWRQDLAZGAQUNZ-UHFFFAOYSA-K sodium;iron(2+);phosphate Chemical compound [Na+].[Fe+2].[O-]P([O-])([O-])=O AWRQDLAZGAQUNZ-UHFFFAOYSA-K 0.000 title claims abstract description 16
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 39
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims abstract description 39
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 22
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000227 grinding Methods 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 17
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 16
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 235000009518 sodium iodide Nutrition 0.000 claims abstract description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 238000005245 sintering Methods 0.000 claims abstract description 12
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims abstract description 10
- 235000019799 monosodium phosphate Nutrition 0.000 claims abstract description 10
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- 229910052742 iron Inorganic materials 0.000 claims description 15
- 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 10
- 239000007788 liquid Substances 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-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
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical group 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 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 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
- 239000012535 impurity Substances 0.000 abstract description 8
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 abstract description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052709 silver Inorganic materials 0.000 abstract description 7
- 239000004332 silver Substances 0.000 abstract description 7
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 abstract description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004277 Ferrous carbonate Substances 0.000 abstract description 4
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 abstract description 4
- 235000019268 ferrous carbonate Nutrition 0.000 abstract description 4
- 229960004652 ferrous carbonate Drugs 0.000 abstract description 4
- 229910000015 iron(II) carbonate Inorganic materials 0.000 abstract description 4
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 abstract description 4
- 229910001958 silver carbonate Inorganic materials 0.000 abstract description 4
- 229910001923 silver oxide Inorganic materials 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 2
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 239000007790 solid phase Substances 0.000 abstract description 2
- 230000005496 eutectics Effects 0.000 abstract 1
- OVMJVEMNBCGDGM-UHFFFAOYSA-N iron silver Chemical compound [Fe].[Ag] OVMJVEMNBCGDGM-UHFFFAOYSA-N 0.000 abstract 1
- 238000002955 isolation Methods 0.000 abstract 1
- 239000010406 cathode material Substances 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 238000012827 research and development Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- DJENHUUHOGXXCB-UHFFFAOYSA-N 2-butyl-6-methoxyphenol Chemical group CCCCC1=CC=CC(OC)=C1O DJENHUUHOGXXCB-UHFFFAOYSA-N 0.000 description 1
- KCBWAFJCKVKYHO-UHFFFAOYSA-N 6-(4-cyclopropyl-6-methoxypyrimidin-5-yl)-1-[[4-[1-propan-2-yl-4-(trifluoromethyl)imidazol-2-yl]phenyl]methyl]pyrazolo[3,4-d]pyrimidine Chemical compound C1(CC1)C1=NC=NC(=C1C1=NC=C2C(=N1)N(N=C2)CC1=CC=C(C=C1)C=1N(C=C(N=1)C(F)(F)F)C(C)C)OC KCBWAFJCKVKYHO-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- -1 Prussian blue sodium salts Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 230000003446 memory effect Effects 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
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
Definitions
- the invention belongs to the technical field of sodium ion batteries, and in particular relates to a preparation method of sodium iron phosphate, a positive electrode material of a porous sodium ion battery.
- Lithium-ion batteries have gradually attracted scientific research due to their advantages such as no memory effect, high voltage platform, large specific energy, environmental friendliness, small self-discharge, safety and stability, and small specific gravity. The attention of personnel has become the star object in the chemical power supply. With the rapid growth of demand for lithium-ion batteries in various application fields and the rapid improvement of people's expectations for the use of various electrical appliances and equipment, in-depth research and development of lithium-ion battery materials is of great significance to the development of human society and the improvement of people's living standards. Significance.
- Sodium which is in the same main group as lithium, is the second lightest metal element and has a very high abundance in the earth's crust, reaching 2.3%-2.8%.
- the half-cell potential of sodium-ion batteries is only 0.3V higher than that of lithium-ion batteries.
- sodium and lithium have similar electrochemical properties, so sodium ions can be used instead of lithium ions.
- the development of sodium-ion batteries can alleviate the shortage of lithium resources to a certain extent, and it will give us a greater market competitive advantage. Therefore, the research and development of electrode materials for sodium-ion batteries has gradually become a hot topic in energy storage research.
- the currently reported sodium storage cathode materials mainly include polyanionic compounds, Prussian blue sodium salts, and transition metal oxides.
- polyanionic compounds mainly include transition metal (pyro) phosphate, fluorophosphate, etc.
- polyanionic phosphate materials may become the best cathode materials for sodium-ion batteries due to their stable structure and high operating voltage.
- iron-based phosphate materials Due to its good safety and low cost, iron-based phosphate materials have great development prospects as battery cathode materials.
- due to the low electrical conductivity and slow ion diffusion speed of this type of material its industrial application is limited.
- iron-based phosphate sodium ion battery positive electrode materials phosphorus sources, iron sources, sodium sources and carbon sources are often sintered together, and the pyrolysis effect of carbon sources is used.
- iron is reduced to Bivalent, on the other hand, carbonizes to form coke and improves the conductivity of the material, which can be said to kill two birds with one stone, and is the most commonly used technical means in the prior art.
- gases such as carbon monoxide and hydrogen will be produced.
- ferric ions can be reduced to simple iron, and magnetic foreign matter will be generated; in addition, a small amount of FeP and Fe 2 will also be generated.
- the present invention aims to solve at least one of the technical problems in the above-mentioned prior art. For this reason, the present invention proposes a preparation method of sodium iron phosphate, a positive electrode material of a porous sodium ion battery.
- propose a kind of preparation method of porous sodium ion battery cathode material sodium iron phosphate comprise the following steps:
- step S1 in the mixed solution, the concentration of the ferrous nitrate is 0.1-2.0mol/L, and the molar ratio of the ferrous nitrate to the silver nitrate is 100: (0.8-4).
- the reducing agent is one or more of butyl hydroxyanisole, dibutyl hydroxytoluene, propyl gallate, tert-butyl hydroquinone or ascorbic acid species; the concentration of the reducing agent in the mixed solution is 0.001-0.25mol/L.
- described carbonate solution is at least one in the solution of sodium carbonate, potassium carbonate or ammonium carbonate;
- concentration of carbonate ion in described carbonate solution is 0.1 -1.0mol/L.
- step S2 during the dropping process, the concentration of carbonate ions in the reaction solution is controlled to be always ⁇ 0.01 mol/L.
- step S3 the molar ratio of Fe, P, and I elements in the grinding material is (1.01-1.2):1:(0.01-0.2).
- step S3 the grinding time is 1-2 hours.
- step S4 the sintering temperature is 550-800° C., and the heating rate is 2-5° C./min.
- step S4 the sintering time is 8-12h.
- the organic solvent is at least one of anhydrous methanol, anhydrous ethanol or acetone.
- step S4 the soaking time is 0.5-1 h.
- the present invention firstly prepares a mixture of silver carbonate and ferrous carbonate by co-precipitation method to obtain a co-crystal doped with silver and iron at atomic level, and then co-sinters with sodium dihydrogen phosphate and sodium iodide to prepare sodium ferric phosphate.
- sodium dihydrogen phosphate provides phosphorus source and sodium source.
- silver carbonate gradually decomposes into carbon dioxide and silver oxide, and silver oxide decomposes into silver element and oxygen, and silver element has excellent Conductivity can increase the conductivity of the material, and the silver element is an inert metal, which does not cause safety hazards to the battery like other magnetic foreign matter impurities.
- sodium iodide plays the role of reduction, preventing ferrous iron from being oxidized to ferric iron, and the reducibility of sodium iodide is limited, and it will not reduce ferrous iron to simple iron, resulting in the formation of magnetic foreign matter. It will also not capture the oxygen in the phosphate radical and produce phosphide impurities; and the oxidized sodium iodide will generate iodine element, which will be sublimated into iodine vapor and separated from the material during sintering.
- Fig. 1 is the SEM image of the sodium iron phosphate porous sodium ion battery cathode material prepared in Example 1 of the present invention.
- This embodiment has prepared a kind of porous sodium ion battery cathode material sodium iron phosphate, and the specific process is:
- This embodiment has prepared a kind of porous sodium ion battery cathode material sodium iron phosphate, and the specific process is:
- This embodiment has prepared a kind of porous sodium ion battery cathode material sodium iron phosphate, and the specific process is:
- This comparative example prepared a kind of carbon-coated NaFePO Material, the specific process is:
- the discharge gram capacity of the embodiment is significantly higher than that of the comparative example at a rate of 0.2C, and the content of magnetic foreign matter is much lower than that of the comparative example.
- the carbon source of the comparative example will produce carbon monoxide and hydrogen during pyrolysis.
- Such gases can reduce ferric ions to simple iron during calcination, produce magnetic foreign matter, and generate a small amount of impurities.
- the existence of these impurities will reduce the specific capacity of the material, and the porous structure of the embodiment can also improve the performance of the material. .
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Abstract
Description
0.1C放电克容量mAh/g | 0.2C放电克容量mAh/g | 磁性异物含量ppb | |
实施例1 | 151 | 93 | 2 |
实施例2 | 146 | 88 | 3 |
实施例3 | 147 | 86 | 2 |
对比例 | 143 | 80 | 18 |
Claims (10)
- 一种多孔钠离子电池正极材料磷酸铁钠的制备方法,其特征在于,包括以下步骤:S1:将硝酸亚铁、硝酸银和还原剂混合配制成混合溶液;S2:在隔绝氧气的条件下,将所述混合溶液滴加到碳酸盐溶液中进行反应,固液分离得到沉淀物;S3:将所述沉淀物与磷酸二氢钠、碘化钠混合后研磨,得到研磨物料;S4:将所述研磨物料在隔绝空气的条件下进行烧结,得到烧结后物料,将所述烧结后物料置于有机溶剂中浸泡,固液分离,即得所述多孔钠离子电池正极材料磷酸铁钠。
- 根据权利要求1所述的制备方法,其特征在于,步骤S1中,所述混合溶液中,所述硝酸亚铁的浓度为0.1-2.0mol/L,所述硝酸亚铁与所述硝酸银的摩尔比为100:(0.8-4)。
- 根据权利要求1所述的制备方法,其特征在于,步骤S1中,所述还原剂为丁基羟基茴香醚、二丁基羟基甲苯、没食子酸丙酯、特丁基对苯二酚或抗坏血酸中的一种或几种。
- 根据权利要求1所述的制备方法,其特征在于,步骤S2中,所述碳酸盐溶液为碳酸钠、碳酸钾或碳酸铵的溶液中的至少一种。
- 根据权利要求1所述的制备方法,其特征在于,步骤S2中,所述滴加的过程中,控制反应溶液中碳酸根离子的浓度始终≥0.01mol/L。
- 根据权利要求1所述的制备方法,其特征在于,步骤S3中,所述研磨物料中Fe、P、I元素的摩尔比为(1.01-1.2):1:(0.01-0.2)。
- 根据权利要求1所述的制备方法,其特征在于,步骤S3中,所述研磨的时间为1-2h。
- 根据权利要求1所述的制备方法,其特征在于,步骤S4中,所述烧结的温度为550-800℃。
- 根据权利要求1所述的制备方法,其特征在于,步骤S4中,所述有机溶剂为无水甲醇、无水乙醇或丙酮中的至少一种。
- 根据权利要求1所述的制备方法,其特征在于,步骤S4中,所述浸泡的时间为0.5-1h。
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ES202390073A ES2963371A2 (es) | 2021-11-26 | 2022-08-25 | Metodo de preparacion de fosfato de hierro y sodio poroso usado como material de catodo de bateria de iones de sodio |
US18/260,033 US20240067525A1 (en) | 2021-11-26 | 2022-08-25 | Preparation method of porous sodium iron phosphate used as sodium ion battery cathode material |
HU2400063A HUP2400063A1 (en) | 2021-11-26 | 2022-08-25 | Preparation method for porous sodium ion battery positive electrode material sodium iron phosphate |
DE112022000196.8T DE112022000196T5 (de) | 2021-11-26 | 2022-08-25 | Herstellungsverfahren von porösem natriumeisenphosphat als kathodenmaterial für natriumionenbatterien |
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