CN116605869A - 一种中空介孔碳球封装的复合磷酸铁钠材料及其制备方法和应用 - Google Patents
一种中空介孔碳球封装的复合磷酸铁钠材料及其制备方法和应用 Download PDFInfo
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- CN116605869A CN116605869A CN202310559525.8A CN202310559525A CN116605869A CN 116605869 A CN116605869 A CN 116605869A CN 202310559525 A CN202310559525 A CN 202310559525A CN 116605869 A CN116605869 A CN 116605869A
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- Prior art keywords
- mesoporous carbon
- hollow mesoporous
- sodium
- iron phosphate
- source
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- 239000002131 composite material Substances 0.000 title claims abstract description 71
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 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 71
- 239000000463 material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- 239000012298 atmosphere Substances 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011734 sodium Substances 0.000 claims abstract description 16
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 16
- 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 14
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000001694 spray drying Methods 0.000 claims abstract description 9
- 239000007774 positive electrode material Substances 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000006184 cosolvent Substances 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 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 12
- 238000005406 washing Methods 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 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 8
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 8
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 8
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 8
- 238000005530 etching Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 6
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 6
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000005955 Ferric phosphate Substances 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 229940032958 ferric phosphate Drugs 0.000 claims description 5
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 5
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229960003638 dopamine Drugs 0.000 claims description 3
- 229940062993 ferrous oxalate Drugs 0.000 claims description 3
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 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
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 9
- 230000008859 change Effects 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 4
- 235000011180 diphosphates Nutrition 0.000 abstract description 3
- 239000007784 solid electrolyte Substances 0.000 abstract description 3
- 239000012798 spherical particle Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000002265 prevention Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 239000010405 anode material Substances 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-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
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229940048084 pyrophosphate Drugs 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- 238000007792 addition Methods 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012466 permeate Substances 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
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004094 surface-active agent Substances 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
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- 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
- C01B25/455—Phosphates containing halogen
-
- 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
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- 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
- H01M4/36—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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- C01P2006/12—Surface area
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- 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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
本发明公开了中空介孔碳球封装的复合磷酸铁钠材料及其制备方法和应用。制备方法:将中空介孔碳球与铁源、钠源、磷源和助溶剂溶解在去离子水中,搅拌均匀后将溶液加热干燥或喷雾干燥,再经烧结获得产品。本发明制备的材料为纳米级球形颗粒,中空介孔碳球能够有效避免体积变化,形成稳定的固体‑电解质界面从而提高材料稳定性。合成过程中碳球与气氛提供了还原性的条件,保证复合磷酸铁钠中焦磷酸根的稳定。此外,中空介孔碳球封装有效规避了紧密碳层包覆阻碍离子和电子传导的缺陷,提高倍率性能。同时,较大的比表面积使电解液与材料充分接触,有利于钠离子扩散,制备的钠离子电池正极材料表现出优异的倍率性能和循环稳定性。
Description
技术领域
本发明涉及钠离子电池技术领域,尤其涉及一种中空介孔碳球封装的复合磷酸铁钠材料及其制备方法和应用。
背景技术
锂离子电池由于其高能量密度被广泛用作电子产品的便携式电源,然而随着需求量的不断攀升,锂离子电池面临的锂资源消耗和未来的短缺问题不断突出。与锂同族的钠化学性质与锂非常接近,其自然界储量非常丰富,地壳中丰度极高,在海洋和盐湖中也有巨大的储量,有望成为锂元素的优良替代品。但是,目前钠离子电池成本比锂离子电池略高,且钠离子质量比锂离子大,比容量和能量密度低,同时,由于钠离子半径(0.102nm)比锂离子半径(0.076nm)大得多,导致钠离子在刚性结构中相对稳定,可逆脱嵌困难,动力学缓慢,容易引起电极材料晶体结构不可逆的相变和体积变化,降低电池的循环性能。通过材料和生产工艺的优化,钠离子电池的性能有着极大的提升空间,且成本可以大大降低,使钠离子电池在资源、成本、安全性和寿命方面与锂离子电池相比优势巨大。
近年来,具有稳定结构的聚阴离子型正极材料成为钠离子电池正极材料的焦点,而复合磷酸盐由于具有能量密度高、功率密度高、稳定性好等优点得到了广泛的研究。目前主要采用掺杂、氟化、碳包覆等方法改善复合磷酸盐正极材料的性能,其中碳包覆是改善材料整体导电性的有效手段之一。专利号为CN 113104828 A的发明专利以柠檬酸为碳源,通过氯化钠和表面活性剂聚乙烯吡咯烷酮引入了多孔结构的包覆碳层,极大地提高了复合磷酸铁钠的容量。但是微米级复合磷酸铁钠正极材料被碳层紧密包裹,离子传输受到限制,而且无法有效避免体积变化,从而导致材料稳定性较差。
发明内容
本发明的目的在于,针对现有技术的上述不足,提出一种中空介孔碳球封装的复合磷酸铁钠材料及其制备方法和应用。
本发明的一种中空介孔碳球封装的复合磷酸铁钠材料,包括中空介孔碳球,和封装在所述中空介孔碳球内的复合磷酸铁钠Na4Fe3(PO4)2(P2O7)。
一种如上述的中空介孔碳球封装的复合磷酸铁钠材料的制备方法,包括如下步骤:
S1、制备中空介孔碳球;
S2、将铁源、钠源、磷源和助溶剂按照一定比例溶解在去离子水中,搅拌一定时间后溶液变为黄绿色透明溶液,在溶液中加入中空介孔碳球并继续搅拌若干时间,再经加热干燥或喷雾干燥获得复合磷酸铁钠前驱体粉末;
S3、将复合磷酸铁钠前驱体粉末在一定气氛下进行煅烧,随炉冷却后获得中空介孔碳球封装的复合磷酸铁钠材料。
进一步的,步骤S1中制备中空介孔碳球的具体操作为将一定比例的乙醇、去离子水、氨水和正硅酸乙酯混合,搅拌一定时间后加入碳源和聚合剂,继续搅拌若干时间后离心洗涤、干燥,得到SiO2@C模板;将SiO2@C模板煅烧并用氢氟酸刻蚀,再经过离心洗涤、干燥得到中空介孔碳球。
进一步的,步骤S1中,乙醇、去离子水、氨水和正硅酸乙酯的体积比为7:1:0.3:0.1~1;正硅酸乙酯与聚合剂、碳源的物质的量之比为3:1~3:0.5~2;将SiO2@C模板置于管式炉中,在N2或Ar气氛下700~900℃温度煅烧1~6h;步骤S1中,所述的聚合剂为甲醛、苯甲醛、聚氨酯中的一种或几种,碳源为邻苯二酚、间苯二酚、多巴胺中的一种或几种。
进一步的,步骤S2中,铁源、钠源、磷源、助溶剂和碳源的物质的量之比为3:1:2:5~10:1~10,溶液的搅拌时间为0.5~5h。
进一步的,步骤S2中,加热干燥温度为60~150℃,时间为1~5h;喷雾干燥进口温度为150-200℃、进料量10-20ml/min,喷雾气氛为氮气或空气。
进一步的,步骤S2中,所述铁源为硝酸铁、硝酸亚铁、草酸铁、草酸亚铁、乙酸铁、磷酸铁中的一种或几种,所述钠源为碳酸钠、磷酸钠、焦磷酸钠、磷酸二氢钠、磷酸氢二钠中的一种或几种,所述磷源为磷酸二氢铵、磷酸氢二铵、磷酸钠、焦磷酸钠、磷酸铁中的一种或几种,所述助溶剂为草酸、硝酸、磷酸中的一种或几种。
进一步的,步骤S3中,前驱体粉末的煅烧气氛为氮气或氢/氩混合气气氛,煅烧过程中先加热到300~400℃保温1~3h,再加热到500~650℃保温8~12h,两段升温速率均为3~8℃/min。
一种如上述的中空介孔碳球封装的复合磷酸铁钠材料在制备钠离子电池正极活性材料中的应用。
进一步的,采用所述中空介孔碳球封装的复合磷酸铁钠材料与BP 2000、PVDF以5~8:1~2:1质量比混合制得正极片。
相比于现有技术,本发明有益效果如下:
(1)本发明制备的中空介孔碳球封装的复合磷酸铁钠材料为纳米级球形颗粒,粒径约为200-500nm。创新性地采用中空结构的介孔碳球封装复合磷酸铁钠,纳米化的复合磷酸铁钠能够提高材料的比容量,在封装后复合磷酸铁钠与中空介孔碳球之间存在空心层,空气层给予复合磷酸铁钠一定的体积变化空间,从而能够有效避免本发明制备的中空介孔碳球封装的复合磷酸铁钠材料体积变化,形成稳定的固体-电解质界面(SEI),从而提高材料的循环稳定性能。
(2)本发明在制备中空介孔碳球封装的复合磷酸铁钠的过程中,通过碳球或还原性气氛提供了还原性的条件,保证复合磷酸铁钠中焦磷酸根的稳定。由于不含焦磷酸根的磷酸铁钠(NaFePO4)具有合成困难或性能较低的问题,因此复合磷酸铁钠材料需要维持焦磷酸根的存在使其在成分和性能上均明显区别于磷酸铁钠材料。
(3)本发明通过引入中空介孔碳球封装层,中空介孔碳球封装有效规避了紧密碳层包覆阻碍离子和电子传导的缺陷,能够提高电子传导速率,较大的比表面积使电解液与材料充分接触,能够使电解液充分渗透,与碳球内部的复合磷酸铁钠材料充分接触,促进钠离子传输,有效规避了其他碳球壳层包覆阻碍离子传输的缺陷,从而提高电池的倍率性能。
(4)本发明原料来源广,价格便宜,制作工艺简单,生产周期短,产量高,制备得到的钠离子电池正极材料倍率性能优异,循环性能好,具有工业化的潜力。
附图说明
图1为本发明实施例1所制备的中空介孔碳球封装的复合磷酸铁钠材料的XRD图。
图2为本发明实施例1所制备的中空介孔碳球封装的复合磷酸铁钠材料的FESEM图(a)和本发明对比例1所制备的复合磷酸铁钠材料的SEM图(b)。
图3为本发明实施例1所制备的中空介孔碳球封装的复合磷酸铁钠正极材料组装成的电池的倍率性能图。
图4为本发明实施例1所制备的中空介孔碳球封装的复合磷酸铁钠正极材料组装成的电池与对比例1所制备的未用中空介孔碳球作碳源的材料组装成的电池在1C倍率下的循环性能对比图。
具体实施方式
以下是本发明的具体实施例并结合附图,对本发明的技术方案作进一步的描述,但本发明并不限于这些实施例。
<实施例1>
(1)将乙醇、去离子水和氨水分别量取70mL、10mL、3mL并于烧杯中混合,再缓慢地将3.46mL正硅酸乙酯滴加到混合溶液中,搅拌15min后再加入0.4g间苯二酚和0.56mL甲醛,继续搅拌24h后离心洗涤、干燥,得到SiO2@C模板。将SiO2@C模板置于管式炉中,在800℃氮气气氛下煅烧2h,随炉冷却至室温后用氢氟酸刻蚀,再经过离心洗涤、干燥得到中空介孔碳球。
(2)将1.2116g硝酸铁、0.2659g焦磷酸钠、0.2301g磷酸二氢铵和0.8103g草酸溶解在20mL去离子水中,搅拌30min后溶液为黄绿色透明溶液,在溶液中加入0.7134g中空介孔碳球并继续搅拌3h,随后在80℃下加热搅拌2h,获得复合磷酸铁钠前驱体粉末。
(3)将前驱体粉末置于管式炉中,在氢/氩混合气氛下以5℃/min的升温速率升温至350℃并保温2h,再以5℃/min的升温速率升温至550℃并保温10h,随炉冷却后获得中空介孔碳球封装的复合磷酸铁钠材料。
<实施例2>
(1)将乙醇、去离子水和氨水分别量取70mL、10mL、3mL并于烧杯中混合,再缓慢地将1mL正硅酸乙酯滴加到混合溶液中,搅拌15min后再加入0.12g间苯二酚和0.16mL甲醛,继续搅拌24h后离心洗涤、干燥,得到SiO2@C模板。将SiO2@C模板置于管式炉中,在900℃氮气气氛下煅烧1h,随炉冷却至室温后用氢氟酸刻蚀,再经过离心洗涤、干燥得到中空介孔碳球。
(2)将1.2116g硝酸铁、0.2659g焦磷酸钠、0.2301g磷酸二氢铵和0.4502g草酸溶解在20mL去离子水中,搅拌30min后溶液为黄绿色透明溶液,在溶液中加入0.1982g中空介孔碳球并继续搅拌5h,随后在60℃下加热搅拌5h,获得复合磷酸铁钠前驱体粉末。
(3)将前驱体粉末置于管式炉中,在氮气气氛下以3℃/min的升温速率升温至300℃并保温2h,再以3℃/min的升温速率升温至500℃并保温12h,随炉冷却后获得中空介孔碳球封装的复合磷酸铁钠材料。
<实施例3>
(1)将乙醇、去离子水和氨水分别量取70mL、10mL、3mL并于烧杯中混合,再缓慢地将10mL正硅酸乙酯滴加到混合溶液中,搅拌15min后再加入2.4g邻苯二酚和3.33mL苯甲醛,继续搅拌24h后离心洗涤、干燥,得到SiO2@C模板。将SiO2@C模板置于管式炉中,在700℃氩气气氛下煅烧6h,随炉冷却至室温后用氢氟酸刻蚀,再经过离心洗涤、干燥得到中空介孔碳球。
(2)将1.2116g硝酸铁、0.2659g焦磷酸钠、0.2301g磷酸二氢铵和0.9003g草酸溶解在20mL去离子水中,搅拌30min后溶液为黄绿色透明溶液,在溶液中加入1.9817g中空介孔碳球并继续搅拌0.5h,随后在150℃下加热搅拌1h,获得复合磷酸铁钠前驱体粉末。
(3)将前驱体粉末置于管式炉中,在氢/氩混合气氛下以8℃/min的升温速率升温至300℃并保温1h,再以8℃/min的升温速率升温至500℃并保温8h,随炉冷却后获得中空介孔碳球封装的复合磷酸铁钠材料。
<实施例4>
(1)将乙醇、去离子水和氨水分别量取70mL、10mL、3mL并于烧杯中混合,再缓慢地将3.46mL正硅酸乙酯滴加到混合溶液中,搅拌15min后再加入1.7g多巴胺和2.31mL聚氨酯,继续搅拌24h后离心洗涤、干燥,得到SiO2@C模板。将SiO2@C模板置于管式炉中,在800℃氮气气氛下煅烧2h,随炉冷却至室温后用氢氟酸刻蚀,再经过离心洗涤、干燥得到中空介孔碳球。
(2)将0.4316g草酸亚铁、0.2102g碳酸钠、0.2641g磷酸氢二铵和0.3151g硝酸溶解在20mL去离子水中,搅拌30min后溶液为黄绿色透明溶液,在溶液中加入0.1982g中空介孔碳球并继续搅拌3h,随后喷雾干燥设备设定参数进口温度150℃,进料量15ml/min,喷雾氛围为氮气,喷雾干燥后获得复合磷酸铁钠前驱体粉末。
(3)将前驱体粉末置于管式炉中,在氮气气氛下以3℃/min的升温速率升温至350℃并保温3h,再以3℃/min的升温速率升温至550℃并保温8h,随炉冷却后获得中空介孔碳球封装的复合磷酸铁钠材料。
<实施例5>
(1)将乙醇、去离子水和氨水分别量取70mL、10mL、3mL并于烧杯中混合,再缓慢地将3.46mL正硅酸乙酯滴加到混合溶液中,搅拌15min后再加入0.8g间苯二酚和1.15mL甲醛,继续搅拌24h后离心洗涤、干燥,得到SiO2@C模板。将SiO2@C模板置于管式炉中,在800℃氮气气氛下煅烧2h,随炉冷却至室温后用氢氟酸刻蚀,再经过离心洗涤、干燥得到中空介孔碳球。
(2)将0.5819g乙酸铁、0.4798g磷酸二氢钠、0.2641g磷酸氢二铵和0.6301g硝酸溶解在20mL去离子水中,搅拌30min后溶液为黄绿色透明溶液,在溶液中加入1.9817g中空介孔碳球并继续搅拌3h,随后随后喷雾干燥设备设定参数进口温度200℃,进料量20ml/min,喷雾氛围为空气,喷雾干燥后获得复合磷酸铁钠前驱体粉末。
(3)将前驱体粉末置于管式炉中,在氢/氩混合气氛下以8℃/min的升温速率升温至400℃并保温3h,再以8℃/min的升温速率升温至650℃并保温12h,随炉冷却后获得中空介孔碳球封装的复合磷酸铁钠材料。
一种钠离子电池,包括正极片、电解液、隔膜和对电极,所述正极片由上述方法制得的中空介孔碳球封装的复合磷酸铁钠正极材料与BP 2000、PVDF以5~8:1~2:1质量比混合制得,所述电解液由1mol/L NaClO4与3%氟代碳酸乙烯酯溶解在碳酸丙烯酯制得,所述隔膜为玻璃纤维,所属对电极为金属钠片或硬碳。
<实施例6>
(1)按照质量之比为8:1:1,分别称取0.2g由实施例1所述方法制备的中空介孔碳球封装的复合磷酸铁钠正极材料、0.025g BP 2000以及0.025gPVDF溶解在1000μL N-甲基吡咯烷酮溶液中,在混料机中混合均匀,得到电极浆料。
(2)将混合好的电极浆料均匀地涂覆于铝箔上,置于真空干燥箱中在100℃温度下干燥12h,切成载量约为3mg的电极圆片后采用CR2032型纽扣电池进行组装。
(3)以中空介孔碳球封装的复合磷酸铁钠正极材料为工作电极,金属钠片为对电极,采用玻璃纤维隔膜和1mol/L NaClO4与3%氟代碳酸乙烯酯溶解在碳酸丙烯酯为电解液组装成电池并进行性能测试。
<实施例7>
(1)按照质量之比为5:2:1,分别称取0.2g由实施例1所述方法制备的中空介孔碳球封装的复合磷酸铁钠正极材料、0.08g BP 2000以及0.04gPVDF溶解在1000μL N-甲基吡咯烷酮溶液中,在混料机中混合均匀,得到电极浆料。
(2)将混合好的电极浆料均匀地涂覆于铝箔上,置于真空干燥箱中在100℃温度下干燥12h,切成载量约为3mg的电极圆片后采用CR2032型纽扣电池进行组装。
(3)以中空介孔碳球封装的复合磷酸铁钠正极材料为工作电极,金属钠片为对电极,采用玻璃纤维隔膜和1mol/L NaClO4与3%氟代碳酸乙烯酯溶解在碳酸丙烯酯为电解液组装成电池并进行性能测试。
<对比例1>
(1)将1.2116g硝酸铁、0.2659g焦磷酸钠、0.2301g磷酸二氢铵和0.8103g草酸溶解在10mL去离子水中,搅拌30min后溶液为黄绿色透明溶液,不加入中空介孔碳球,随后在80℃下加热搅拌2h,获得复合磷酸铁钠前驱体粉末。
(2)将前驱体粉末置于管式炉中,在氢/氩混合气氛下以5℃/min的升温速率升温至350℃并保温2h,再以5℃/min的升温速率升温至550℃并保温10h,随炉冷却后获得复合磷酸铁钠材料。
对比例1与实施例1的区别仅在于没有加入中空介孔碳球作为碳源。
以实施例1产物空介孔碳球封装的复合磷酸铁钠正极材料为例,其颗粒大小约为200-500nm,其XRD图如图1所示。
图2为实施例1所制备的中空介孔碳球封装的复合磷酸铁钠材料的FESEM图(a)和对比例1所制备的复合磷酸铁钠材料的SEM图(b)。图2(a)显示中空介孔碳球封装的复合磷酸铁钠材料为纳米级球形颗粒,复合磷酸铁钠材料与中空介孔碳球之间存在空心层,中空的封装结构能够限制体积变化,形成稳定的固体-电解质界面(SEI),提高材料的循环稳定性能。同时,引入的中空介孔碳球封装层也提高了电子传导速率,并能够使电解液充分渗透,与碳球内部的复合磷酸铁钠材料充分接触,促进钠离子传输,进而提高电池的倍率性能。而图2(b)中对比例1所制备的复合磷酸铁钠材料为微米级无规则块体,在充放电过程中由于体积变化等问题导致其循环稳定性较差,且由于材料导电性较差,因此初始容量也较低。
图3为本发明实施例1所制备的中空介孔碳球封装的复合磷酸铁钠正极材料组装成的电池,电压区间在1.5~4.2V,在0.1C、0.5C、1C、2C、3C、5C和10C倍率下进行恒电流充放电测试所得的倍率性能图。其中,在1C倍率下,首圈比容量高达77mAh g-1,首圈库伦效率为95.9%,此外,在0.1C、0.5C、2C的倍率下分别测试的放电比容量分别为102,84,72mAh g-1,表现出优异的倍率性能。
图4为本发明实施例1所制备的中空介孔碳球封装的复合磷酸铁钠正极材料组装成的电池与对比例1所制备的未用中空介孔碳球作碳源的材料组装成的电池在1C倍率下的循环性能对比图。实施例1中所得材料首圈比容量高达80mAh g-1,首圈库伦效率为97.1%,且在循环350圈后保持有84mAh g-1的放电比容量,容保持率为105%;而对比例1中所得材料首圈比容量为66mAh g-1,首圈库伦效率为95.0%,且在循环350圈后仅有40mAh g-1的放电比容量,容保持率为60.6%。通过对比表明该空心球封装复合磷酸铁钠正极的结构稳定性很好,可以承受高电流密度下的充电和放电,并且展现出优异的循环性能。
综上,本发明所制备的中空介孔碳球封装的复合磷酸铁钠正极材料,原料来源广,价格便宜,制作工艺简单,生产周期短,产量高,倍率性能优异,循环性能好,具有工业化的潜力。
以上未涉及之处,适用于现有技术。
虽然已经通过示例对本发明的一些特定实施例进行了详细说明,但是本领域的技术人员应该理解,以上示例仅是为了进行说明,而不是为了限制本发明的范围,本发明所属技术领域的技术人员可以对所描述的具体实施例来做出各种各样的修改或补充或采用类似的方式替代,但并不会偏离本发明的方向或者超越所附权利要求书所定义的范围。本领域的技术人员应该理解,凡是依据本发明的技术实质对以上实施方式所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围。
Claims (10)
1.一种中空介孔碳球封装的复合磷酸铁钠材料,其特征在于:包括中空介孔碳球,和封装在所述中空介孔碳球内的复合磷酸铁钠Na4Fe3(PO4)2(P2O7)。
2.一种如权利要求1所述的中空介孔碳球封装的复合磷酸铁钠材料的制备方法,其特征在于:包括如下步骤:
S1、制备中空介孔碳球;
S2、将铁源、钠源、磷源和助溶剂按照一定比例溶解在去离子水中,搅拌一定时间后溶液变为黄绿色透明溶液,在溶液中加入中空介孔碳球并继续搅拌若干时间,再经加热干燥或喷雾干燥获得复合磷酸铁钠前驱体粉末;
S3、将复合磷酸铁钠前驱体粉末在一定气氛下进行煅烧,随炉冷却后获得中空介孔碳球封装的复合磷酸铁钠材料。
3.如权利要求2所述的制备方法,其特征在于:步骤S1中制备中空介孔碳球的具体操作为将一定比例的乙醇、去离子水、氨水和正硅酸乙酯混合,搅拌一定时间后加入碳源和聚合剂,继续搅拌若干时间后离心洗涤、干燥,得到SiO2@C模板;将SiO2@C模板煅烧并用氢氟酸刻蚀,再经过离心洗涤、干燥得到中空介孔碳球。
4.如权利要求3所述的制备方法,其特征在于:步骤S1中,乙醇、去离子水、氨水和正硅酸乙酯的体积比为7:1:0.3:0.1~1;正硅酸乙酯与聚合剂、碳源的物质的量之比为3:1~3:0.5~2;将SiO2@C模板置于管式炉中,在N2或Ar气氛下700~900℃温度煅烧1~6h;
步骤S1中,所述的聚合剂为甲醛、苯甲醛、聚氨酯中的一种或几种,碳源为邻苯二酚、间苯二酚、多巴胺中的一种或几种。
5.如权利要求2所述的制备方法,其特征在于:步骤S2中,铁源、钠源、磷源、助溶剂和碳源的物质的量之比为3:1:2:5~10:1~10,溶液的搅拌时间为0.5~5h。
6.如权利要求2所述的制备方法,其特征在于:步骤S2中,加热干燥温度为60~150℃,时间为1~5h;喷雾干燥进口温度为150-200℃、进料量10-20ml/min,喷雾气氛为氮气或空气。
7.如权利要求2所述的制备方法,其特征在于:步骤S2中,所述铁源为硝酸铁、硝酸亚铁、草酸铁、草酸亚铁、乙酸铁、磷酸铁中的一种或几种,所述钠源为碳酸钠、磷酸钠、焦磷酸钠、磷酸二氢钠、磷酸氢二钠中的一种或几种,所述磷源为磷酸二氢铵、磷酸氢二铵、磷酸钠、焦磷酸钠、磷酸铁中的一种或几种,所述助溶剂为草酸、硝酸、磷酸中的一种或几种。
8.如权利要求2所述的制备方法,其特征在于:步骤S3中,前驱体粉末的煅烧气氛为氮气或氢/氩混合气气氛,煅烧过程中先加热到300~400℃保温1~3h,再加热到500~650℃保温8~12h,两段升温速率均为3~8℃/min。
9.一种如权利要求1所述的中空介孔碳球封装的复合磷酸铁钠材料在制备钠离子电池正极活性材料中的应用。
10.如权利要求9所述的应用,其特征在于:采用所述中空介孔碳球封装的复合磷酸铁钠材料与BP 2000、PVDF以5~8:1~2:1质量比混合制得正极片。
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