CN116750741A - 一种钛掺杂的碳包覆磷酸焦磷酸铁钠材料的制备方法及其应用 - Google Patents
一种钛掺杂的碳包覆磷酸焦磷酸铁钠材料的制备方法及其应用 Download PDFInfo
- Publication number
- CN116750741A CN116750741A CN202310620884.XA CN202310620884A CN116750741A CN 116750741 A CN116750741 A CN 116750741A CN 202310620884 A CN202310620884 A CN 202310620884A CN 116750741 A CN116750741 A CN 116750741A
- Authority
- CN
- China
- Prior art keywords
- sodium
- titanium
- source
- ferric
- coated
- 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.)
- Pending
Links
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XWQGIDJIEPIQBD-UHFFFAOYSA-J sodium;iron(3+);phosphonato phosphate Chemical compound [Na+].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O XWQGIDJIEPIQBD-UHFFFAOYSA-J 0.000 title claims abstract description 13
- 239000011734 sodium Substances 0.000 claims abstract description 55
- 239000010936 titanium Substances 0.000 claims abstract description 38
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 33
- 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 abstract description 28
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 24
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 17
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 17
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 17
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 16
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 5
- 239000011645 ferric sodium diphosphate Substances 0.000 claims abstract description 4
- 235000019851 ferric sodium diphosphate Nutrition 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 65
- 239000002002 slurry Substances 0.000 claims description 19
- 238000001694 spray drying Methods 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims description 17
- 239000011574 phosphorus Substances 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 14
- 239000004576 sand Substances 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 13
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 8
- 229930006000 Sucrose Natural products 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000005720 sucrose Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 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 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- LFKXWKGYHQXRQA-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;iron Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LFKXWKGYHQXRQA-FDGPNNRMSA-N 0.000 claims description 2
- 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 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 238000007605 air drying Methods 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 239000011640 ferrous citrate Substances 0.000 claims description 2
- 235000019850 ferrous citrate Nutrition 0.000 claims description 2
- 229940062993 ferrous oxalate Drugs 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- -1 indene titanium trichloride Chemical compound 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- APVZWAOKZPNDNR-UHFFFAOYSA-L iron(ii) citrate Chemical compound [Fe+2].OC(=O)CC(O)(C([O-])=O)CC([O-])=O APVZWAOKZPNDNR-UHFFFAOYSA-L 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 229940001516 sodium nitrate Drugs 0.000 claims description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 0.000 claims description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 2
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 2
- MNWRORMXBIWXCI-UHFFFAOYSA-N tetrakis(dimethylamido)titanium Chemical compound CN(C)[Ti](N(C)C)(N(C)C)N(C)C MNWRORMXBIWXCI-UHFFFAOYSA-N 0.000 claims description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- BYTVRGSKFNKHHE-UHFFFAOYSA-K sodium;[hydroxy(oxido)phosphoryl] phosphate;iron(2+) Chemical compound [Na+].[Fe+2].OP([O-])(=O)OP([O-])([O-])=O BYTVRGSKFNKHHE-UHFFFAOYSA-K 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 19
- 150000002500 ions Chemical class 0.000 abstract description 10
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000001488 sodium phosphate Substances 0.000 abstract description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 abstract description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 abstract description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 19
- 235000015424 sodium Nutrition 0.000 description 17
- 229910010413 TiO 2 Inorganic materials 0.000 description 14
- 239000007774 positive electrode material Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 5
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 235000019837 monoammonium phosphate Nutrition 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- BRFMYUCUGXFMIO-UHFFFAOYSA-N phosphono dihydrogen phosphate phosphoric acid Chemical compound OP(O)(O)=O.OP(O)(=O)OP(O)(O)=O BRFMYUCUGXFMIO-UHFFFAOYSA-N 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 235000011008 sodium phosphates Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 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 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 230000035515 penetration Effects 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
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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
-
- 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
- C01B25/38—Condensed phosphates
- C01B25/42—Pyrophosphates
-
- 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
- C01B25/38—Condensed phosphates
- C01B25/42—Pyrophosphates
- C01B25/425—Pyrophosphates of alkali metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明公开了一种钛掺杂的碳包覆磷酸焦磷酸铁钠材料的制备方法及其应用,属于钠离子电池技术领域。通过本发明制备方法得到的二氧化钛和非晶碳层包覆钛掺杂的磷酸焦磷酸铁钠的电子电导率和离子扩散率高、倍率性能和循环性能好,振实密度高,该法工艺流程简单,成本低,适用于大规模生产应用;本发明通过精确控制钛源的加入量,使得一部分的二氧化钛包覆在材料的表面,剩下的部分二氧化钛以钛离子的形式掺杂进入磷酸焦磷酸铁钠晶格中,并结合碳包覆法共同改性,提高了磷酸焦磷酸铁钠复合材料的电子电导率和离子扩散率,进而提高了磷酸焦磷酸铁钠复合材料在高倍率下的放电容量。
Description
技术领域
本发明属于钠离子电池技术领域,具体涉及一种钛掺杂的碳包覆磷酸焦磷酸铁钠材料的制备方法及其应用。
背景技术
随着风能、太阳能、潮汐能等清洁能源的快速发展,高效储能设施也得到了快速的发展。在众多储能设备中,钠离子电池由于其关键原材料来源较为丰富,工作原理与商用的锂离子电池相似,在大规模储能领域中备受关注。目前钠离子电池的发展仍面临来自电极材料的严峻挑战。在对钠离子电池的电极材料不断探索的过程中,负极材料取得了长足的进步并逐渐开始商业化,但与之相匹配的正极材料仍需进一步研究和开发。
铁基磷酸焦磷酸盐正极材料从原材料的获得和结构稳定性的角度上来看,是极具商业化应用潜力的一类钠离子电池正极材料。尽管铁基磷酸焦磷酸盐具有许多优异的性能,但也存在着明显的缺点。
通常制备的Na4Fe3(PO4)2(P2O7)一次颗粒之间存在着较大的间隙,导致其振实密度较低,进而导致其体积能量密度较低;此外,大尺寸的PO4 3-基团的固有隔离特性导致铁基混合磷酸盐较低的电子电导率和缓慢的离子扩散,对其电化学性能造成了阻碍。因此解决铁基磷酸焦磷酸盐正极材料的低振实密度、低电子电导率和离子电导率差的问题就显的尤为重要。
公开号为CN113060713A的专利申请公开了一种均相法制备Na4Fe3(PO4)2(P2O7)的方法及应用,采用湿法均相砂磨联合喷雾干燥法制备Na4Fe3(PO4)2(P2O7),其制备方法如下:将碳源、铁源、钠源、磷源按照一定化学计量比混合,加入有机溶剂经砂磨形成均相分散体系;喷雾干燥后得到前驱体并在惰性气氛中烧结,获得Na4Fe3(PO4)2(P2O7)粉体。该发明的方法可显著改善Na4Fe3(PO4)2(P2O7)微纳米粉体的团聚现象,改善粉体形貌和电性能,所使用的有机溶剂可经冷却系统回收二次利用,而有机溶剂汽化潜热远低于水,节省加热功耗。该发明制备的Na4Fe3(PO4)2(P2O7)正极材料相比现有的过渡金属氧化物、普鲁士蓝类和钒基聚阴离子型化合物正极材料,其成本更低廉、循环稳定性更好、绿色无污染,可为商品化钠离子电池提供一种理想正极;电池性能测试结果表明Na4Fe3(PO4)2(P2O7)组装的扣式半电池在0.2C下可逆容量达到112mAh/g,在10C下可逆容量达到75mAh/g;说明该发明的倍率性能略差。
发明内容
本发明的目的在于提供一种高容量、高振实密度的Na4Fe3(PO4)2(P2O7)制备方法及应用,解决现有技术中的Na4Fe3(PO4)2(P2O7)材料振实密度低、电子电导率低和离子扩散率低的问题。
本发明的具体技术方案如下:
一种钛掺杂的碳包覆磷酸焦磷酸铁钠材料的制备方法,所述制备方法包括以下步骤:
(1)将钠源、磷源、碳源加入到去离子水中,混合均匀后形成溶液,再依次加入铁源、钛源,混合均匀后形成浆料,干燥得到前驱体粉末;
所述钠源中的钠元素、铁源中的铁元素、磷源中的磷元素和钛源中的钛元素的摩尔比为4∶3∶4∶0.01~0.05;
(2)将步骤(1)中得到的前驱体粉末在惰性气氛下,于480-550℃下煅烧得到钛掺杂的碳包覆磷酸焦磷酸铁钠材料。
在本发明实施例中优选方案之一,所述钠源中的钠元素、铁源中的铁元素、磷源中的磷元素和钛源中的钛元素的摩尔比为4∶3∶4∶0.03。
所述钛掺杂的碳包覆磷酸焦磷酸铁钠材料中磷酸焦磷酸铁钠与碳的质量比为98∶2~97∶3。
本发明中部分磷酸根在高温时会聚合成焦磷酸根,本发明只使用了一种磷源。
步骤(1)中,
所述钠源为碳酸钠、氯化钠、磷酸氢二钠、磷酸二氢钠、硝酸钠、草酸钠、焦磷酸钠、三聚磷酸、乙醇钠中的至少一种;
所述铁源为磷酸铁、柠檬酸亚铁、草酸亚铁、乙酰丙酮亚铁、硝酸铁、氯化铁,硫酸亚铁中的至少一种;
所述钛源为二氧化钛、四氯化钛、三氯化茚钛、四(二甲氨基)钛中的至少一种;
所述碳源为蔗糖、葡萄糖、柠檬酸、聚乙二醇、草酸、碳酸钠、抗坏血酸中的至少一种。
优选的,步骤(1)中,干燥前使用砂磨机进行研磨;
所述砂磨机的转速为2000r/min,流量为200L/h,研磨时间为40-100min;
研磨后浆料的固含量为45%-50%,砂磨粒径为300-350nm;所述固含量为质量百分比。
优选的,步骤(1)中,所述干燥的方法为喷雾干燥、鼓风干燥或真空干燥。
当所述干燥的方法为喷雾干燥时,喷雾干燥的进料速率为60-90mL/min,雾化盘的频率为450Hz,进料温度为220℃,出料温度为90-100℃。
湿法均相砂磨联合喷雾干燥是一种实现粒径均匀球形粉体批量制备的有效方法,能够实现前驱体盐在纳米尺度上的均匀分散,提高粉体的纯度和电性能。
所述煅烧的条件为:在温度为480-550℃下,煅烧10-13h。
在所述煅烧参数条件下更有利于最终材料的形成,若煅烧温度过高会导致材料过烧存在杂相,若煅烧温度过低会导致烧结不充分,导致材料结晶度低。由于蔗糖在惰性气氛下的高温分解作用,使得部分碳包覆在主体材料表面,碳的包覆有利于增加材料的导电性,提高材料的振实密度。
本发明还提供了所述的制备方法制备的钛掺杂的碳包覆磷酸焦磷酸铁钠材料。
本发明还提供了所述钛掺杂的碳包覆磷酸焦磷酸铁钠材料在制备钠离子电池中的应用。
本发明还提供了一种钠离子电池,包括所述钛掺杂的碳包覆磷酸焦磷酸铁钠材料。
与现有技术相比,本发明的有益效果体现在以下几方面:
(1)通过本发明制备方法得到的二氧化钛和非晶碳层包覆钛掺杂的磷酸焦磷酸铁钠的电子电导率和离子扩散率高、倍率性能和循环性能好,振实密度高,该法工艺流程简单,成本低,适用于大规模生产应用;
(2)本发明通过精确控制钛源的加入量,使得一部分的二氧化钛包覆在材料的表面,剩下的部分二氧化钛以钛离子的形式掺杂进入磷酸焦磷酸铁钠晶格中,并结合碳包覆法共同改性,提高了磷酸焦磷酸铁钠复合材料的电子电导率和离子扩散率,进而提高了磷酸焦磷酸铁钠复合材料在高倍率下的放电容量;
(3)本发明通过在原料中加入复合碳源,使其作为形貌控制剂能够协同喷雾造形技术有效调控材料颗粒的球形化度,进而提高材料的振实密度;
(4)当在磷酸焦磷酸铁钠复合材料中掺杂化合价高于Fe2+的阳离子时,可以形成价态平衡的Na+空位,有利于Na+的扩散。由于Ti4+的离子半径比Fe2+的离子半径小,且TiO6八面体比FeO6八面体更稳定,因此Ti4+的掺杂往往使得晶体结构更加稳定;
(5)本发明的制备方法简单,易于放大。
附图说明
图1为实施例1、对比例1以及TiO2的X射线衍射图(XRD图);
图2为实施例1的透射电子显微镜(TEM图);
图3为实施例1和对比例1的XRD局部放大图;
图4为实施例1的扫描电子显微镜(SEM图);其中,a为全景图,b为局部单个球体,c为单个球体的表面图;
图5为实施例1、实施例2、实施例3、实施例4以及对比例1在0.2C时的充放电曲线。
具体实施方式
实施例1
一种钠离子二次电池正极材料Ti0.03-Na4Fe3(PO4)2(P2O7)@TiO2@C的制备方法,包括如下步骤:
(1)按照化学计量比称取424g无水碳酸钠、230g磷酸二氢铵、由60g蔗糖和90g聚乙二醇组成的复合碳源加入去离子水中,搅拌均匀后形成溶液;后加入905g磷酸铁、4.8g二氧化钛,搅拌均匀后形成浆料;将所述浆料倒往储料罐中,在砂磨机中以2000r/min的转速,200L/h的流量下研磨60min,砂磨之后的粒径控制在300-350nm之间;混合物内的钠元素、铁元素、磷元素与钛元素的摩尔比为4∶3∶4∶0.03;
(2)将步骤(1)所得浆料在进口温度220℃、出口温度95℃下,进行喷雾干燥处理得到前驱体粉料;
(3)将喷雾干燥处理得到前驱体粉料在氮气的惰性气体下中以2℃/min的升温速率加热到300℃,保温2h,在以5℃/min的升温速率加热到500℃煅烧,保温10h;以得到Ti0.03-Na4Fe3(PO4)2(P2O7)@TiO2@C复合正极材料。
实施例2
一种钠离子二次电池正极材料Ti0.01-Na4Fe3(PO4)2(P2O7)@TiO2@C的制备方法,包括如下步骤:
(1)按照化学计量比称取424g无水碳酸钠、230g磷酸二氢铵、由60g蔗糖和90g聚乙二醇组成的复合碳源加入去离子水中,搅拌均匀后形成溶液;后加入905g磷酸铁、1.6g二氧化钛,搅拌均匀后形成浆料;将所述浆料倒往储料罐中,在砂磨机中以2000r/min的转速,200L/h的流量下研磨60min,砂磨之后的粒径控制在300-350nm之间;混合物内的钠元素、铁元素、磷元素与钛元素的摩尔比为4∶3∶4∶0.01;
(2)将步骤(1)所得浆料在进口温度220℃、出口温度95℃下,进行喷雾干燥处理得到前驱体粉料;
(3)将喷雾干燥处理得到前驱体粉料在氮气的惰性气体下中以2℃/min的升温速率加热到300℃,保温2h,在以5℃/min的升温速率加热到500℃煅烧,保温10h;以得到Ti0.01-Na4Fe3(PO4)2(P2O7)@TiO2@C复合正极材料。
实施例3
一种钠离子二次电池正极材料Ti0.05-Na4Fe3(PO4)2(P2O7)@TiO2@C的制备方法,包括如下步骤:
(1)按照化学计量比称取424g无水碳酸钠、230g磷酸二氢铵、由60g蔗糖和90g聚乙二醇组成的复合碳源加入去离子水中,搅拌均匀后形成溶液;后加入905g磷酸铁、8g二氧化钛,搅拌均匀后形成浆料;将所述浆料倒往储料罐中,在砂磨机中以2000r/min的转速,200L/h的流量下研磨60min,砂磨之后的粒径控制在300-350nm之间;混合物内的钠元素、铁元素、磷元素与钛元素的摩尔比为4∶3∶4∶0.05;
(2)将步骤(1)所得浆料在进口温度220℃、出口温度95℃下,进行喷雾干燥处理得到前驱体粉料;
(3)将喷雾干燥处理得到前驱体粉料在氮气的惰性气体下中以2℃/min的升温速率加热到300℃,保温2h,在以5℃/min的升温速率加热到500℃煅烧,保温10h;以得到Ti0.05-Na4Fe3(PO4)2(P2O7)@TiO2@C复合正极材料。
实施例4
一种钠离子二次电池正极材料Ti0.03-Na4Fe3(PO4)2(P2O7)@TiO2@C的制备方法,包括如下步骤:
(1)按照化学计量比称取424g无水碳酸钠、230g磷酸二氢铵、由60g蔗糖和90g聚乙二醇组成的复合碳源加入去离子水中,搅拌均匀后形成溶液;后加入905g磷酸铁、11.4g四氯化钛,搅拌均匀后形成浆料;将所述浆料倒往储料罐中,在砂磨机中以2000r/min的转速,200L/h的流量下研磨60min,砂磨之后的粒径控制在300-350nm之间;混合物内的钠元素、铁元素、磷元素与钛元素的摩尔比为4∶3∶4∶0.03;
(2)将步骤(1)所得浆料在进口温度220℃、出口温度95℃下,进行喷雾干燥处理得到前驱体粉料;
(3)将喷雾干燥处理得到前驱体粉料在氮气的惰性气体下中以2℃/min的升温速率加热到300℃,保温2h,在以5℃/min的升温速率加热到500℃煅烧,保温10h;以得到Ti0.03-Na4Fe3(PO4)2(P2O7)@TiO2@C复合正极材料。
对比例1
一种钠离子二次电池正极材料Na4Fe3(PO4)2(P2O7)@C的制备方法,包括如下步骤:
(1)按照化学计量比称取424g无水碳酸钠、230g磷酸二氢铵、由60g蔗糖和90g聚乙二醇组成的复合碳源加入去离子水中,搅拌均匀后形成溶液;后加入905g磷酸铁,搅拌均匀后形成浆料;将所述浆料倒往储料罐中,在砂磨机中以2000r/min的转速,200L/h的流量下研磨60min,砂磨之后的粒径控制在300-350nm之间;混合物内的钠元素、铁元素与磷元素的摩尔比为4∶3∶4,未加钛元素;
(2)将步骤(1)所得浆料在进口温度220℃、出口温度95℃下,进行喷雾干燥处理得到前驱体粉料;
(3)将喷雾干燥处理得到前驱体粉料在氮气的惰性气体下中以2℃/min的升温速率加热到300℃,保温2h,在以5℃/min的升温速率加热到500℃煅烧,保温10h;以得到Na4Fe3(PO4)2(P2O7)@C复合正极材料。
测试例1
对将实施例1-4和对比例1的制备得到的复合正极材料进行理化性能和扣式电池测试,结果如下表1,其中,理化性能测试包含碳含量测试和振实密度测试。
扣式电池的测试方法为:将活性物质∶Super p∶PVDF按质量比为8∶1∶1的浆料组装成扣式电池并在截止电压为2.0V-4.0V的条件下进行测试;振实密度采用振实密度仪。
表1实施例1-3和对比例1材料测试结果
由上表1中数据可见,实施例1-3和对比例1制备得到的复合正极材料的差别在于钛含量的差别,可以看出混合物最佳比例为:铁元素、钛元素的摩尔比为3∶0.03,过多或太少都会导致材料的倍率性能、循环性能和振实密度有所下降,这是因为过多的钛离子掺入会导致材料晶格畸变更加严重,导致其可逆性下降,循环性能也就随之下降;而过低的钛离子掺入对于材料电子电导率和离子扩散率的提升有限,又不足以提高其倍率性能和循环性能,所以经过上述对比实验测试可知最佳的钛离子掺入量为0.03%。实施例4也表明0.03为最优掺杂量,且不同钛源对其容量的释放影响是非常小的。
(1)将实施例1、对比例1得到的样品材料以及TiO2进行X射线衍射测试,XRD测试结果图1所示,不同钛掺杂含量制备的样品的衍射峰与标准卡片的衍射峰均一一对应,且没有杂峰,说明样品为纯相;此外,掺杂量为0.03的样品中,出现了二氧化钛的衍射峰,说明得到的样品中存在部分的二氧化钛。图中没有看到碳的衍射峰,说明碳呈无定型的状态。
(2)将实施例1得到的样品材料进行投射电子显微镜测试,如图2所示,可以看出Ti0.03-Na4Fe3(PO4)2(P2O7)@TiO2@C样品呈现明显的核壳结构,可以清楚的观察到Na4Fe3(PO4)2(P2O7)的晶格条纹外存在着TiO2晶格条纹,包覆着一层TiO2。
(3)Na4Fe3(PO4)2(P2O7)@C和Ti0.03-Na4Fe3(PO4)2(P2O7)@TiO2@C的XRD局部放大图如图3所示。可以观察到钛掺杂样品的XRD衍射峰相对于未掺杂样品往右偏,这是Ti4+的离子半径小于Fe2+所致。说明存在部分的Ti4+占据了Fe2+的位点,Ti4+成功掺杂进入了Na4Fe3(PO4)2(P2O7)的晶体结构中。
(4)图4展示了Ti0.03-Na4Fe3(PO4)2(P2O7)@TiO2@C的微观结构特征。不同放大倍数下的图像如图4所示。全景图a清楚地显示了钛掺杂样品的微球粒径的均匀性。此外,从图b、c的放大SEM图像可以清楚地看到,钛掺杂样品的球体在一次粒子聚集生长过程中表面粗糙,有利于电解质的渗透和电极-电解质界面的膨胀,从而有利于快速反应动力学。
(5)图5显示不同钛掺杂量以及不同钛源的样品在0.2C时的充放电曲线,可以看出钛掺杂量为0.03时,电化学性能最优。所有钛掺杂样品的电化学性能均优于未掺杂样品。
Claims (10)
1.一种钛掺杂的碳包覆磷酸焦磷酸铁钠材料的制备方法,其特征在于,所述制备方法包括以下步骤:
(1)将钠源、磷源、碳源加入到水中,混合均匀后形成溶液,再依次加入铁源、钛源,混合均匀后形成浆料,干燥得到前驱体粉末;
所述钠源中的钠元素、铁源中的铁元素、磷源中的磷元素和钛源中的钛元素的摩尔比为4∶3∶4∶0.01~0.05;
(2)将步骤(1)中得到的前驱体粉末在惰性气氛下煅烧,得到钛掺杂的碳包覆磷酸焦磷酸铁钠材料。
2.如权利要求1所述的制备方法,其特征在于,所述钠源中的钠元素、铁源中的铁元素、磷源中的磷元素和钛源中的钛元素的摩尔比为4∶3∶4∶0.03;
所述钛掺杂的碳包覆磷酸焦磷酸铁钠材料中磷酸焦磷酸铁钠与碳的质量比为98∶2~97∶3。
3.如权利要求1所述的制备方法,其特征在于,步骤(1)中,
所述钠源为碳酸钠、氯化钠、磷酸氢二钠、磷酸二氢钠、硝酸钠、草酸钠、焦磷酸钠、三聚磷酸、乙醇钠中的至少一种;
所述铁源为磷酸铁、柠檬酸亚铁、草酸亚铁、乙酰丙酮亚铁、硝酸铁、氯化铁、硫酸亚铁中的至少一种;
所述钛源为二氧化钛、四氯化钛、三氯化茚钛、四(二甲氨基)钛中的至少一种;
所述碳源为蔗糖、葡萄糖、柠檬酸、聚乙二醇、草酸、碳酸钠、抗坏血酸中的至少一种。
4.如权利要求1所述的制备方法,其特征在于,步骤(1)中,干燥前使用砂磨机进行研磨;
所述砂磨机的转速为2000r/min,流量为200L/h,研磨时间为40-100min;
研磨后浆料的固含量为45%-50%,砂磨粒径为300-350nm。
5.如权利要求1所述的制备方法,其特征在于,步骤(1)中,所述干燥的方法为喷雾干燥、鼓风干燥或真空干燥。
6.如权利要求5所述的制备方法,其特征在于,当所述干燥的方法为喷雾干燥时,喷雾干燥的进料速率为60-90mL/min,雾化盘的频率为450Hz,进料温度为220℃,出料温度为90-100℃。
7.如权利要求1所述的制备方法,其特征在于,步骤(2)中,所述煅烧的条件为:在温度为480-550℃下,煅烧10-13h。
8.如权利要求1~7任一项所述的制备方法制备的钛掺杂的碳包覆磷酸焦磷酸铁钠材料。
9.如权利要求8所述钛掺杂的碳包覆磷酸焦磷酸铁钠材料在制备钠离子电池中的应用。
10.一种钠离子电池,其特征在于,包括权利要求8所述钛掺杂的碳包覆磷酸焦磷酸铁钠材料。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310620884.XA CN116750741A (zh) | 2023-05-29 | 2023-05-29 | 一种钛掺杂的碳包覆磷酸焦磷酸铁钠材料的制备方法及其应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310620884.XA CN116750741A (zh) | 2023-05-29 | 2023-05-29 | 一种钛掺杂的碳包覆磷酸焦磷酸铁钠材料的制备方法及其应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN116750741A true CN116750741A (zh) | 2023-09-15 |
Family
ID=87956346
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202310620884.XA Pending CN116750741A (zh) | 2023-05-29 | 2023-05-29 | 一种钛掺杂的碳包覆磷酸焦磷酸铁钠材料的制备方法及其应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116750741A (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN118062822A (zh) * | 2024-04-17 | 2024-05-24 | 苏州大学 | 一种磷酸焦磷酸铁钠衍生物及其制备方法和钠离子电池 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105140489A (zh) * | 2015-09-25 | 2015-12-09 | 中南大学 | 一种钛掺杂的碳包覆磷酸铁钠材料及其制备方法 |
CN113060714A (zh) * | 2021-02-25 | 2021-07-02 | 湖北万润新能源科技股份有限公司 | 一种从FePO4液相制备Na4Fe3(PO4)2(P2O7)的方法 |
CN114538403A (zh) * | 2022-01-27 | 2022-05-27 | 上海交通大学 | 钠离子电池正极材料磷酸焦磷酸铁钠的制备方法及其应用 |
CN115974033A (zh) * | 2022-12-21 | 2023-04-18 | 华南理工大学 | 氮掺杂介孔碳包覆磷酸焦磷酸铁钠复合材料及制备方法 |
CN116119642A (zh) * | 2023-02-10 | 2023-05-16 | 西安理工大学 | 富钠型焦磷酸磷酸铁钠正极材料、制法和应用 |
CN116169264A (zh) * | 2023-02-10 | 2023-05-26 | 西安理工大学 | 碳包覆富钠型焦磷酸磷酸铁钠复合正极材料、制法和应用 |
-
2023
- 2023-05-29 CN CN202310620884.XA patent/CN116750741A/zh active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105140489A (zh) * | 2015-09-25 | 2015-12-09 | 中南大学 | 一种钛掺杂的碳包覆磷酸铁钠材料及其制备方法 |
CN113060714A (zh) * | 2021-02-25 | 2021-07-02 | 湖北万润新能源科技股份有限公司 | 一种从FePO4液相制备Na4Fe3(PO4)2(P2O7)的方法 |
CN114538403A (zh) * | 2022-01-27 | 2022-05-27 | 上海交通大学 | 钠离子电池正极材料磷酸焦磷酸铁钠的制备方法及其应用 |
CN115974033A (zh) * | 2022-12-21 | 2023-04-18 | 华南理工大学 | 氮掺杂介孔碳包覆磷酸焦磷酸铁钠复合材料及制备方法 |
CN116119642A (zh) * | 2023-02-10 | 2023-05-16 | 西安理工大学 | 富钠型焦磷酸磷酸铁钠正极材料、制法和应用 |
CN116169264A (zh) * | 2023-02-10 | 2023-05-26 | 西安理工大学 | 碳包覆富钠型焦磷酸磷酸铁钠复合正极材料、制法和应用 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN118062822A (zh) * | 2024-04-17 | 2024-05-24 | 苏州大学 | 一种磷酸焦磷酸铁钠衍生物及其制备方法和钠离子电池 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109336193B (zh) | 多元素原位共掺杂三元材料前驱体及其制备方法和应用 | |
CN113148969B (zh) | 掺杂的磷酸锰铁锂-碳复合材料及其制备方法 | |
CN113889619A (zh) | 一种钠离子电池正极材料及其制备方法和应用 | |
CN106711435B (zh) | 一种层状富锂锰基/石墨烯纳米带正极复合材料的制备方法 | |
Lu et al. | Co-precipitation preparation of LiNi0. 5Mn1. 5O4 hollow hierarchical microspheres with superior electrochemical performance for 5 V Li-ion batteries | |
CN102244244B (zh) | 一种提高锂离子电池复合正极材料xLiFePO4·yLi3V2(PO4)3振实密度的方法 | |
CN114361435A (zh) | 钠离子电池的纳米级前驱体、复合正极材料及制备方法 | |
CN106058249A (zh) | 一种溶剂热制备碳包覆纳米棒状氟磷酸亚铁钠材料的方法 | |
CN102623705A (zh) | 一种锂离子电池正极材料LiFePO4/C及其制备方法和应用 | |
Herrera et al. | LiMnPO 4: Review on synthesis and electrochemical properties | |
CN113725418A (zh) | 一种稀土氧化物包覆改性的锂离子电池用三元正极材料及其制备方法 | |
CN115101738A (zh) | 一种碳包覆的铁钒双金属磷酸焦磷酸钠复合材料及其制备方法和应用 | |
CN114772572A (zh) | 一种纳米金属离子包覆磷酸铁锂正极材料及其制备方法 | |
JP2023548993A (ja) | ハイレートのリン酸鉄リチウム正極材料の製造方法 | |
CN116750741A (zh) | 一种钛掺杂的碳包覆磷酸焦磷酸铁钠材料的制备方法及其应用 | |
Wang et al. | Nano-sized over-lithiated oxide by a mechano-chemical activation-assisted microwave technique as cathode material for lithium ion batteries and its electrochemical performance | |
CN111653782A (zh) | 正极材料及其制备方法和应用 | |
CN116534830A (zh) | 一种钠离子电池正极材料及其制备方法和应用 | |
CN116053446A (zh) | 一种复合掺杂改性的镍基正极材料及其制备方法 | |
CN107069034B (zh) | 一种锂离子电池正极材料及其制备方法和应用 | |
CN112599736B (zh) | 一种掺硼磷酸锂包覆锂离子电池正极材料及其制备方法 | |
CN104332603A (zh) | 一种磷酸锰锂纳米片的制备方法及产品 | |
CN110182780B (zh) | 一种致密化球形磷酸铁锂及其制备方法 | |
CN102263248A (zh) | 一种制备碳包覆的纳米磷酸亚铁锂的方法 | |
CN113745486B (zh) | 一种水系锂离子电池用原位碳掺杂磷酸钛锂及其制备方法和应用 |
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 |