CN114249311A - 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
- Publication number
- CN114249311A CN114249311A CN202111421179.4A CN202111421179A CN114249311A CN 114249311 A CN114249311 A CN 114249311A CN 202111421179 A CN202111421179 A CN 202111421179A CN 114249311 A CN114249311 A CN 114249311A
- Authority
- CN
- China
- Prior art keywords
- sodium
- carbonate
- ion battery
- porous
- iron phosphate
- 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.)
- Granted
Links
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 28
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 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 18
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 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
- 238000000034 method Methods 0.000 claims abstract description 19
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 18
- 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
- 238000005245 sintering 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
- 238000002791 soaking Methods 0.000 claims abstract description 12
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 11
- 238000002156 mixing 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
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000002955 isolation Methods 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 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
- 239000010405 anode material Substances 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 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
- 239000004250 tert-Butylhydroquinone Substances 0.000 claims description 3
- 235000019281 tert-butylhydroquinone Nutrition 0.000 claims description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 2
- 238000003801 milling Methods 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
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 claims 1
- 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 1
- 230000005496 eutectics Effects 0.000 abstract description 4
- OVMJVEMNBCGDGM-UHFFFAOYSA-N iron silver Chemical compound [Fe].[Ag] OVMJVEMNBCGDGM-UHFFFAOYSA-N 0.000 abstract description 4
- 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 3
- 239000004277 Ferrous carbonate Substances 0.000 abstract description 3
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 abstract description 3
- 235000019268 ferrous carbonate Nutrition 0.000 abstract description 3
- 229960004652 ferrous carbonate Drugs 0.000 abstract description 3
- 229910000015 iron(II) carbonate Inorganic materials 0.000 abstract description 3
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 abstract description 3
- 229910001958 silver carbonate Inorganic materials 0.000 abstract description 3
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 10
- 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 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000010406 cathode material Substances 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
- 230000000694 effects Effects 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- MRBKEAMVRSLQPH-UHFFFAOYSA-N 3-tert-butyl-4-hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1 MRBKEAMVRSLQPH-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000005955 Ferric phosphate Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910021312 NaFePO4 Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 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
- 229940032958 ferric phosphate Drugs 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 229910000399 iron(III) phosphate Inorganic materials 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
- 238000012827 research and development Methods 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 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
- 239000004255 Butylated hydroxyanisole Substances 0.000 description 1
- 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
- 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
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- -1 Prussian blue sodium salts Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 235000019282 butylated hydroxyanisole Nutrition 0.000 description 1
- 229940043253 butylated hydroxyanisole Drugs 0.000 description 1
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000003795 desorption 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
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement 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
- 230000003446 memory effect Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229920000447 polyanionic polymer Polymers 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
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明公开了一种多孔钠离子电池正极材料磷酸铁钠的制备方法,包括将硝酸亚铁、硝酸银和还原剂混合配制成混合溶液,将混合溶液滴加到碳酸盐溶液中进行反应,得到沉淀物,将沉淀物与磷酸二氢钠、碘化钠混合后研磨,将研磨物料在隔绝空气的条件下进行烧结,将烧结后物料置于有机溶剂中浸泡,即得多孔钠离子电池正极材料磷酸铁钠。本发明通过共沉淀法制备碳酸银和碳酸亚铁的混合物,得到银铁原子级掺杂的共晶体,再与磷酸二氢钠、碘化钠共烧结,制备得到磷酸铁钠,磷酸二氢钠与碳酸亚铁进行固相混合烧结时,碳酸银分解为二氧化碳和氧化银,氧化银再分解为银单质和氧气,银单质可增加材料的导电性,且不像其它磁性异物杂质一样给电池造成安全隐患。
Description
技术领域
本发明属于钠离子电池技术领域,具体涉及多孔钠离子电池正极材料磷酸铁钠的制备方法。
背景技术
近年来全球逐渐开始采用电化学能源作为动力能源装置,锂离子电池因其具有无记忆效应、电压平台高、比能量大、环境友好、自放电小、安全稳定和比重小等优点逐渐吸引了科研人员的关注,成为化学电源里的明星对象。随着锂离子电池在各类应用领域需求量的快速增长以及人们对各种电器以及设备使用期望的快速提升,深入研究和开发锂离子电池材料,对于人类社会的发展和人民生活水平的改善具有重要意义。
与锂位于同主族的钠,是重量第二轻的金属元素,在地壳中有相当高的丰度,达到了2.3%-2.8%。此外,钠离子电池的半电池电势仅仅只比锂离子电池高出0.3V,同时钠、锂具有相似的电化学性质,因此完全可以用钠离子代替锂离子,随着锂资源的价格日益飙升,资源的日益匮乏,研发储钠技术以及工业化生产,将具有重大的商业价值。
钠离子电池的开发可在一定程度上缓和锂资源短缺的问题,具体更大的市场竞争优势。因此钠离子电池电极材料的研究和开发逐渐成为储能研究的热点课题。目前报道的储钠正极材料主要有聚阴离子型化合物、普鲁士蓝类钠盐和过渡金属氧化物。
其中,聚阴离子型化合物主要有过渡金属(焦)磷酸盐,氟磷酸盐等,其中,聚阴离子型磷酸盐材料由于其结构稳定和较高的工作电压,可能成为最佳的钠离子电池正极材料。铁基磷酸盐材料由于其安全性好、成本低廉等优点,作为电池正极材料是很有发展前景的。然而,由于该类材料的本身电导率较低及离子扩散速度较慢等问题,限制了其工业化应用。
为解决上述难题,在制备铁基磷酸盐钠离子电池正极材料时,多采用将磷源、铁源、钠源以及碳源共同进行烧结,利用碳源热解效应,一方面,将铁还原为二价,另一方面,碳化生成焦炭,提高材料的导电性,可谓是一举两得,是现有技术中最为常用的技术手段。然而,碳源在热解时,会产生一氧化碳和氢气等气体,在500-700℃下可将三价铁离子还原成铁单质,产生磁性异物;除此,还会生成少量的FeP、Fe2P以及Fe2P2O7等杂质。这些杂质的存在,会降低材料的比容量和能量密度,杂质铁还会在电解液中溶解发生副反应,从而影响电池的使用寿命和安全性能。
发明内容
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此,本发明提出一种多孔钠离子电池正极材料磷酸铁钠的制备方法。
根据本发明的一个方面,提出了一种多孔钠离子电池正极材料磷酸铁钠的制备方法,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。
在本发明的一些实施方式中,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)。
在本发明的一些实施方式中,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;所述混合溶液中还原剂的浓度为0.001-0.25mol/L。
在本发明的一些实施方式中,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;所述碳酸盐溶液中碳酸根离子的浓度为0.1-1.0mol/L。
在本发明的一些实施方式中,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。
在本发明的一些实施方式中,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)。
在本发明的一些实施方式中,步骤S3中,所述研磨的时间为1-2h。
在本发明的一些实施方式中,步骤S4中,所述烧结的温度为550-800℃,升温速率为2-5℃/min。
在本发明的一些实施方式中,步骤S4中,所述烧结的时间为8-12h。
在本发明的一些实施方式中,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。
在本发明的一些实施方式中,步骤S4中,所述浸泡的时间为0.5-1h。
根据本发明的一种优选的实施方式,至少具有以下有益效果:
1、本发明首先通过共沉淀法制备碳酸银和碳酸亚铁的混合物,得到银铁原子级掺杂的共晶体,再与磷酸二氢钠、碘化钠共烧结,制备得到磷酸铁钠。其中,磷酸二氢钠提供磷源和钠源,与碳酸亚铁进行固相混合烧结时,碳酸银逐渐分解为二氧化碳和氧化银,氧化银再分解为银单质和氧气,而银单质具有优异的电导率,可增加材料的导电性,且银单质为惰性金属并不像其它磁性异物杂质一样给电池造成安全隐患。
2、烧结过程中,碘化钠起到还原的作用,避免亚铁被氧化为三价铁,且碘化钠的还原性有限,不会将亚铁还原为铁单质,造成磁性异物的生成,也不会夺取磷酸根中的氧,产生磷化物杂质;且被氧化的碘化钠生成碘单质,在烧结时,升华为碘蒸气脱离物料。同时,烧结反应结束后,通过在有机溶剂中浸泡,利用碘化钠易溶于有机溶剂的特性,除去多余的碘化钠和残留的碘单质,从而得到金属银单质修饰的多孔钠离子电池正极材料磷酸铁钠。
3、该材料在烧结制备时,随着反应的进行,气体溢出,材料变成多孔结构,此结构在作为负极材料使用时,更加利于电解液的浸润,利于钠离子的脱嵌,进而提成倍率性能。
附图说明
下面结合附图和实施例对本发明做进一步的说明,其中:
图1为本发明实施例1制备的多孔钠离子电池正极材料磷酸铁钠的SEM图。
具体实施方式
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述,以充分地理解本发明的目的、特征和效果。显然,所描述的实施例只是本发明的一部分实施例,而不是全部实施例,基于本发明的实施例,本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例,均属于本发明保护的范围。
实施例1
本实施例制备了一种多孔钠离子电池正极材料磷酸铁钠,具体过程为:
(1)配制硝酸亚铁、硝酸银和还原剂的混合溶液,其中,硝酸亚铁的浓度为2.0mol/L,硝酸亚铁与硝酸银的浓度比为100:4,还原剂为抗坏血酸,浓度为0.25mol/L;
(2)配制浓度为0.2mol/L碳酸钠溶液;
(3)在隔绝氧气的条件下,将混合溶液逐滴加入到碳酸钠溶液中进行反应,并保证反应溶液中的碳酸根离子浓度始终≥0.01mol/L;
(4)反应结束后,固液分离,按照Fe、P、I元素摩尔比1.01:1:0.1,将沉淀物与磷酸二氢钠、碘化钠混合均匀后研磨2h,制得研磨物料;
(5)将研磨物料在隔绝空气的条件下以2℃/min的升温速率加热到550℃下保持12小时;
(6)将烧结后的物料,加入到无水乙醇中浸泡0.5h,浸泡结束后,固液分离,干燥固体物料,即得多孔钠离子电池正极材料磷酸铁钠。
实施例2
本实施例制备了一种多孔钠离子电池正极材料磷酸铁钠,具体过程为:
(1)配制硝酸亚铁、硝酸银和还原剂的混合溶液,其中,硝酸亚铁的浓度为1.0mol/L,硝酸亚铁与硝酸银的浓度比为100:2,还原剂为丁基羟基茴香醚,浓度为0.1mol/L;
(2)配制浓度为0.5mol/L碳酸钾溶液;
(3)在隔绝氧气的条件下,将混合溶液逐滴加入到碳酸钾溶液中进行反应,并保证反应溶液中的碳酸根离子浓度始终≥0.01mol/L;
(4)反应结束后,固液分离,按照Fe、P、I元素摩尔比1.1:1:0.15,将沉淀物与磷酸二氢钠、碘化钠混合均匀后研磨1h,制得研磨物料;
(5)将研磨物料在隔绝空气的条件下以3℃/min的升温速率加热到670℃下保持10小时;
(6)将烧结后的物料,加入到丙酮中浸泡1h,浸泡结束后,固液分离,干燥固体物料,即得多孔钠离子电池正极材料磷酸铁钠。
实施例3
本实施例制备了一种多孔钠离子电池正极材料磷酸铁钠,具体过程为:
(1)配制硝酸亚铁、硝酸银和还原剂的混合溶液,其中,硝酸亚铁的浓度为0.1mol/L,硝酸亚铁与硝酸银的浓度比为100:0.8,还原剂为特丁基对苯二酚,浓度为0.001mol/L;
(2)配制浓度为1.0mol/L碳酸铵溶液;
(3)在隔绝氧气的条件下,将混合溶液逐滴加入到碳酸铵溶液中进行反应,并保证反应溶液中的碳酸根离子浓度始终≥0.01mol/L;
(4)反应结束后,固液分离,按照Fe、P、I元素摩尔比1.08:1:0.08,将沉淀物与磷酸二氢钠、碘化钠混合均匀后研磨1.5h,制得研磨物料;
(5)将研磨物料在隔绝空气的条件下以5℃/min的升温速率加热到800℃下保持8小时;
(6)将烧结后的物料,加入到无水甲醇中浸泡0.5h,浸泡结束后,固液分离,干燥固体物料,即得多孔钠离子电池正极材料磷酸铁钠。
对比例
本对比例制备了一种碳包覆的NaFePO4材料,具体过程为:
将0.1mol Fe(NO3)3、0.1mol NaH2PO4、5.0g葡萄糖、12.5g柠檬酸放入烧杯中,加入76mL乙二醇作为分散剂,在70℃的水浴温度下,以200r/min的搅拌速度搅拌8h形成凝胶,然后在90℃的烘箱烘24h,将材料取出后进行研磨,研磨结束后,将材料在600℃氩气中煅烧8h,得到碳包覆的NaFePO4材料。
试验例
本取实施例1-3制得的钠离子电池正极材料和对比例分别制备钠离子电池正极极片,并以金属钠片作为对电极负极,电解液为1mol/L NaPF6电解液,分别装配制成CR2032扣式电池;将装配好的扣式电池在25℃下测试倍率性能,按(1C=155mA/g)设置倍率,结果如表1所示。
表1
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 |
由表1可知,实施例在0.2C的倍率下放电克容量明显高于对比例,且磁性异物含量较对比例低很多,这是由于对比例的碳源在热解时,会产生一氧化碳和氢气等气体,在煅烧时可将三价铁离子还原成铁单质,产生磁性异物,还会生成少量杂质,这些杂质的存在,会降低材料的比容量,同时实施例的多孔结构也可提升材料性能。
上面结合附图对本发明实施例作了详细说明,但是本发明不限于上述实施例,在所属技术领域普通技术人员所具备的知识范围内,还可以在不脱离本发明宗旨的前提下作出各种变化。此外,在不冲突的情况下,本发明的实施例及实施例中的特征可以相互组合。
Claims (10)
1.一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。
2.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)。
3.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。
4.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。
5.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。
6.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)。
7.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。
8.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℃。
9.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。
10.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。
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111421179.4A CN114249311B (zh) | 2021-11-26 | 2021-11-26 | 多孔钠离子电池正极材料磷酸铁钠的制备方法 |
DE112022000196.8T DE112022000196B4 (de) | 2021-11-26 | 2022-08-25 | Herstellungsverfahren von porösem natriumeisenphosphat als kathodenmaterial für natriumionenbatterien |
US18/260,033 US12012331B2 (en) | 2021-11-26 | 2022-08-25 | Preparation method of porous sodium iron phosphate used as sodium ion battery cathode material |
GB2309481.6A GB2616234B8 (en) | 2021-11-26 | 2022-08-25 | Preparation method for porous sodium ion battery positive electrode material sodium iron phosphate |
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 |
HU2400063A HUP2400063A1 (hu) | 2021-11-26 | 2022-08-25 | Porózus nátrium-vas-foszfát nátriumion akkumulátor pozitívelektród-anyag elõállítására szolgáló eljárás |
PCT/CN2022/114920 WO2023093158A1 (zh) | 2021-11-26 | 2022-08-25 | 多孔钠离子电池正极材料磷酸铁钠的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111421179.4A CN114249311B (zh) | 2021-11-26 | 2021-11-26 | 多孔钠离子电池正极材料磷酸铁钠的制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114249311A true CN114249311A (zh) | 2022-03-29 |
CN114249311B CN114249311B (zh) | 2023-03-07 |
Family
ID=80791223
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111421179.4A Active CN114249311B (zh) | 2021-11-26 | 2021-11-26 | 多孔钠离子电池正极材料磷酸铁钠的制备方法 |
Country Status (7)
Country | Link |
---|---|
US (1) | US12012331B2 (zh) |
CN (1) | CN114249311B (zh) |
DE (1) | DE112022000196B4 (zh) |
ES (1) | ES2963371A2 (zh) |
GB (1) | GB2616234B8 (zh) |
HU (1) | HUP2400063A1 (zh) |
WO (1) | WO2023093158A1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023093158A1 (zh) * | 2021-11-26 | 2023-06-01 | 广东邦普循环科技有限公司 | 多孔钠离子电池正极材料磷酸铁钠的制备方法 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN118016818B (zh) * | 2024-04-09 | 2024-08-06 | 宁波容百新能源科技股份有限公司 | 自支撑电极及其制备方法和钠离子电池 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104752717A (zh) * | 2013-12-27 | 2015-07-01 | 比亚迪股份有限公司 | 一种磷酸铁锂及其制备方法和应用 |
JP6101771B1 (ja) * | 2015-11-09 | 2017-03-22 | 太平洋セメント株式会社 | ナトリウムイオン電池用正極活物質及びその製造方法 |
CN106629648A (zh) * | 2016-10-13 | 2017-05-10 | 西南大学 | Na3.64Fe2.18(P2O7)2正极材料及制备方法和应用 |
CN108039491A (zh) * | 2017-11-30 | 2018-05-15 | 华南理工大学 | 一种钠离子电池负极材料三磷酸铁钠及其制备方法 |
CN110957490A (zh) * | 2019-07-30 | 2020-04-03 | 哈尔滨工业大学 | 一种中空结构的碳包覆磷酸铁钠电极材料的制备方法 |
CN111056544A (zh) * | 2019-12-16 | 2020-04-24 | 合肥国轩高科动力能源有限公司 | 一种磷酸铁钠复合材料及其制备方法、应用 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS611771U (ja) * | 1984-06-11 | 1986-01-08 | 日産自動車株式会社 | 歯車機構の潤滑構造 |
CN100390052C (zh) * | 2006-02-28 | 2008-05-28 | 北大先行科技产业有限公司 | 一种合成类球形磷酸金属锂盐的方法 |
CN102674291A (zh) | 2012-05-25 | 2012-09-19 | 广西诺方储能科技有限公司 | 超细纳米磷酸铁锂电极材料的制备方法及应用 |
CN105845974A (zh) | 2016-06-06 | 2016-08-10 | 四川国润新材料有限公司 | 一种钠离子电池正极材料NaFePO4/C的制备方法 |
CN108751158A (zh) | 2018-05-29 | 2018-11-06 | 王子韩 | 一种磷酸铁钠纳米线的制备方法 |
CN113526483B (zh) * | 2021-07-13 | 2022-12-30 | 内蒙古大学 | 一种磷铁钠矿型正极材料及其制备方法和用途 |
CN114249311B (zh) * | 2021-11-26 | 2023-03-07 | 广东邦普循环科技有限公司 | 多孔钠离子电池正极材料磷酸铁钠的制备方法 |
-
2021
- 2021-11-26 CN CN202111421179.4A patent/CN114249311B/zh active Active
-
2022
- 2022-08-25 WO PCT/CN2022/114920 patent/WO2023093158A1/zh active Application Filing
- 2022-08-25 ES ES202390073A patent/ES2963371A2/es active Pending
- 2022-08-25 DE DE112022000196.8T patent/DE112022000196B4/de active Active
- 2022-08-25 GB GB2309481.6A patent/GB2616234B8/en active Active
- 2022-08-25 HU HU2400063A patent/HUP2400063A1/hu unknown
- 2022-08-25 US US18/260,033 patent/US12012331B2/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104752717A (zh) * | 2013-12-27 | 2015-07-01 | 比亚迪股份有限公司 | 一种磷酸铁锂及其制备方法和应用 |
JP6101771B1 (ja) * | 2015-11-09 | 2017-03-22 | 太平洋セメント株式会社 | ナトリウムイオン電池用正極活物質及びその製造方法 |
CN106629648A (zh) * | 2016-10-13 | 2017-05-10 | 西南大学 | Na3.64Fe2.18(P2O7)2正极材料及制备方法和应用 |
CN108039491A (zh) * | 2017-11-30 | 2018-05-15 | 华南理工大学 | 一种钠离子电池负极材料三磷酸铁钠及其制备方法 |
CN110957490A (zh) * | 2019-07-30 | 2020-04-03 | 哈尔滨工业大学 | 一种中空结构的碳包覆磷酸铁钠电极材料的制备方法 |
CN111056544A (zh) * | 2019-12-16 | 2020-04-24 | 合肥国轩高科动力能源有限公司 | 一种磷酸铁钠复合材料及其制备方法、应用 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023093158A1 (zh) * | 2021-11-26 | 2023-06-01 | 广东邦普循环科技有限公司 | 多孔钠离子电池正极材料磷酸铁钠的制备方法 |
GB2616234A (en) * | 2021-11-26 | 2023-08-30 | Guangdong Brunp Recycling Technology Co Ltd | Preparation method for porous sodium ion battery positive electrode material sodium iron phosphate |
US12012331B2 (en) | 2021-11-26 | 2024-06-18 | Guangdong Brunp Recycling Technology Co., Ltd. | Preparation method of porous sodium iron phosphate used as sodium ion battery cathode material |
GB2616234B (en) * | 2021-11-26 | 2024-08-07 | Guangdong Brunp Recycling Technology Co Ltd | Preparation method for porous sodium ion battery positive electrode material sodium iron phosphate |
Also Published As
Publication number | Publication date |
---|---|
US12012331B2 (en) | 2024-06-18 |
GB2616234A (en) | 2023-08-30 |
US20240067525A1 (en) | 2024-02-29 |
CN114249311B (zh) | 2023-03-07 |
WO2023093158A1 (zh) | 2023-06-01 |
ES2963371A2 (es) | 2024-03-26 |
DE112022000196B4 (de) | 2024-11-07 |
GB202309481D0 (en) | 2023-08-09 |
HUP2400063A1 (hu) | 2024-05-28 |
GB2616234B8 (en) | 2024-09-11 |
GB2616234B (en) | 2024-08-07 |
DE112022000196T5 (de) | 2023-09-14 |
GB2616234A8 (en) | 2024-09-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110690437B (zh) | 一种钠离子电池负极补钠添加剂、钠离子电池负极极片和钠离子电池 | |
EP3319152A1 (en) | Doped conductive oxide and improved electrochemical energy storage device polar plate based on same | |
CN114249311B (zh) | 多孔钠离子电池正极材料磷酸铁钠的制备方法 | |
CN102544447A (zh) | 一种锂离子电池正极材料的制备方法 | |
CN110148787A (zh) | 一种提高锂硫电池容量的电解液及锂硫电池 | |
CN115744860A (zh) | 一种碳包覆磷酸锰铁锂材料及其制备方法与电池 | |
CN101150191A (zh) | 锂离子二次电池正极材料镧或锕掺杂型磷酸铁锂及其制备方法 | |
CN115133023A (zh) | 一种掺杂改性焦磷酸铁钠正极材料的制备方法 | |
CN101841039A (zh) | 一种锂离子电池正极材料-掺杂金属离子的磷酸铁及其制备方法 | |
CN103956491A (zh) | 一种锂离子电池正极材料磷酸铁锰锂及其制备方法 | |
CN113078319A (zh) | 一种磷酸锰铁锂/碳复合纳米颗粒正极材料的制备方法 | |
CN100499215C (zh) | 锂离子电池炭负极材料的制备方法 | |
CN109638236B (zh) | 一种室温钠硫电池复合正极材料及其制备方法 | |
CN108110254B (zh) | 磷酸铁及磷酸铁复合材料作为负极在锂离子电池中的应用 | |
CN114361421A (zh) | 一种聚阴离子型高电压钠离子电池正极材料及其制备方法 | |
CN110492099B (zh) | 一种层状聚阴离子正极材料、制备方法、钾离子电池正极、钾离子电池及应用 | |
FR3143209A1 (fr) | Matériau de cathode de phosphate de lithium-manganèse-fer et son procédé de préparation | |
CN102244247A (zh) | 一种碳包覆的锂离子电池正极材料LiFePO4/C的制备方法 | |
CN113611863A (zh) | 一种阳离子掺杂的磷酸铁锂正极材料及其制备方法和应用 | |
CN110459737B (zh) | 一种核壳结构的碳包覆硼酸亚铁的制备方法及其应用 | |
CN111106398A (zh) | 一种低成本水系锌铁二次电池 | |
CN117361484A (zh) | 一种高压实焦磷酸铁纳的制备方法 | |
CN118738316A (zh) | 一种铁基正极材料及其制备方法和应用 | |
CN118231610A (zh) | 一种正极材料及其制备方法和应用 | |
CN115377483A (zh) | 高性能硫化物固态电解质材料及其制备方法和在全固态电池中的应用 |
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 |