CN115924980A - Preparation method of iron-based sodium-ion battery layered positive electrode material precursor of composite phosphate - Google Patents
Preparation method of iron-based sodium-ion battery layered positive electrode material precursor of composite phosphate Download PDFInfo
- Publication number
- CN115924980A CN115924980A CN202211675841.3A CN202211675841A CN115924980A CN 115924980 A CN115924980 A CN 115924980A CN 202211675841 A CN202211675841 A CN 202211675841A CN 115924980 A CN115924980 A CN 115924980A
- Authority
- CN
- China
- Prior art keywords
- solution
- iron
- sodium
- precursor
- 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 149
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 74
- 239000002243 precursor Substances 0.000 title claims abstract description 68
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 46
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 44
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 26
- 239000010452 phosphate Substances 0.000 title claims abstract description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 121
- 239000002585 base Substances 0.000 claims abstract description 44
- 239000008139 complexing agent Substances 0.000 claims abstract description 38
- 239000012266 salt solution Substances 0.000 claims abstract description 38
- 239000003513 alkali Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000654 additive Substances 0.000 claims abstract description 26
- 230000000996 additive effect Effects 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000004094 surface-active agent Substances 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 17
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- 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 12
- 239000008103 glucose Substances 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 11
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 11
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 11
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 11
- 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 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 10
- 229910021645 metal ion Inorganic materials 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 9
- 239000011790 ferrous sulphate Substances 0.000 claims description 7
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 7
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- PYIDGJJWBIBVIA-UYTYNIKBSA-N lauryl glucoside Chemical compound CCCCCCCCCCCCO[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O PYIDGJJWBIBVIA-UYTYNIKBSA-N 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 6
- 239000000176 sodium gluconate Substances 0.000 claims description 6
- 235000012207 sodium gluconate Nutrition 0.000 claims description 6
- 229940005574 sodium gluconate Drugs 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000001488 sodium phosphate Substances 0.000 claims description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 5
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 5
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 5
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 4
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 3
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 3
- 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 3
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 14
- 238000001556 precipitation Methods 0.000 abstract description 9
- 238000010668 complexation reaction Methods 0.000 abstract description 4
- 238000005245 sintering Methods 0.000 abstract description 4
- 150000002505 iron Chemical class 0.000 abstract description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 4
- 229920000447 polyanionic polymer Polymers 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 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 3
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- 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
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a preparation method of a layered positive electrode material precursor of an iron-based sodium-ion battery of composite phosphate, which comprises the following steps: preparing a solution containing iron salt; preparing an alkali solution; preparing a complexing agent solution; preparing a base solution; stirring the base solution, heating, and introducing nitrogen; and introducing the iron-containing salt solution, the alkali solution and the complexing agent solution into the base solution for reaction, filtering the reaction solution after the reaction is finished, washing the obtained solid with deionized water, and drying to obtain the precursor of the layered positive electrode material of the iron-based sodium ion battery of the composite phosphate. According to the method, the selected additive has both reducibility and complexation on ferrous ions, so that the ferrous ions can be prevented from being oxidized, and meanwhile, the additive has complexation on the ferrous ions in the reaction, so that the precipitation speed of the ferrous ions can be controlled, and uneven precipitation can be prevented; phosphate is added into the reaction solution, so that the polyanionic material can be compounded in one step, and the mixing-sintering process of the traditional composite material is reduced.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a preparation method of a precursor of a layered positive electrode material of an iron-based sodium-ion battery of composite phosphate.
Background
Sodium ion batteries are more advantageous in cost and safety as potential replacements for lithium ion batteries in the fields of energy storage and low-speed power batteries. The positive electrode material is one of core materials of the sodium ion battery, and determines the electrochemical properties of the sodium ion battery, such as energy density, safety, cycle retention rate and the like. Different from lithium ion batteries, sodium ion batteries have lower energy density and lower cost, and the future application fields mainly focus on energy storage and low-speed power batteries, so that the iron-based layered anode has the cost advantage over the traditional nickel-cobalt-manganese ternary anode, and has a wider application prospect in the field of sodium electricity. Because the iron element is introduced into the system, the nickel-cobalt-manganese coprecipitation method cannot be used for reference in the synthesis of the precursor hydroxide, because the complexing effect of ferrous ions and ammonia in a solution is far inferior to that of nickel-cobalt-manganese, the precipitation speed of the ferrous ions is too high, and the phenomenon of uneven precipitation is finally caused. In addition, the cycling performance of the layered oxide positive electrode is poor generally, and the cycling performance of the polyanion positive electrode is good, so that the cycling performance of the positive electrode material can be improved by mixing, grinding and sintering the prepared layered oxide and a small amount of polyanion material in a laboratory, but the compounding effect is difficult to control by the method, and part of the polyanion material is possibly not combined with the layered oxide positive electrode.
Therefore, it is necessary to develop a phosphate-compounded iron-based sodium-ion battery layered positive electrode material precursor to solve the above problems.
Disclosure of Invention
The invention provides a preparation method of a precursor of a layered positive electrode material of an iron-based sodium-ion battery of composite phosphate, which aims to solve the technical problems.
The invention provides a preparation method of a layered positive electrode material precursor of an iron-based sodium-ion battery of composite phosphate, which comprises the following steps:
(1) Preparing an iron-containing salt solution, wherein the iron-containing salt solution is prepared from soluble metal salt, an additive and water, the soluble metal salt at least comprises three elements of iron, nickel and manganese, the total molar concentration of all metal ions in the iron-containing salt solution is 0.5-2.5mol/L, and the molar ratio of the iron, the nickel and the manganese in the iron-containing salt solution is X 1 ：X 2 ：X 3 And then 0.2 is less than or equal to X 1 ≤0.6、0.2≤X 2 ≤0.6、X 1 +X 2 +X 3 =1, wherein the additive comprises at least one of citric acid, sodium citrate, glucose and sodium gluconate, and when the molar ratio of the additive to ferrous ions is Z, Z is more than or equal to 0.01 and less than or equal to 0.1;
(2) Preparing an alkaline solution, wherein the alkaline solution consists of an alkaline substance and a phosphorus source, the alkaline substance comprises at least one of sodium hydroxide, sodium carbonate and sodium bicarbonate, and the phosphorus source comprises at least one of phosphoric acid, pyrophosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate and sodium pyrophosphate;
(3) Preparing a complexing agent solution, wherein the complexing agent solution contains NH 3 NH of said 3 The molar concentration of the complexing agent in the complexing agent solution is 1-3mol/L;
(4) Preparing a base solution, wherein the base solution contains NH 3 And additives, the NH 3 The molar concentration of the additive in the base solution is 0.1-1mol/L, the additive is at least one of citric acid, sodium citrate, glucose and sodium gluconate, and the molar concentration of the additive in the base solution is 0.001-0.05mol/L;
(5) Stirring the base solution, heating to 40-60 ℃, and introducing nitrogen at the speed of 0.2-0.6L/min;
(6) And after the nitrogen is introduced for 4-10 hours, introducing the iron-containing salt solution, the alkali solution and the complexing agent solution into the base solution for reaction, filtering the reaction solution after the reaction is finished, washing the obtained solid with deionized water, and drying to obtain the iron-based multi-hydroxide, namely the precursor of the layered positive electrode material of the iron-based sodium ion battery of the composite phosphate.
As a preferable scheme of the preparation method of the layered positive electrode material precursor of the iron-based sodium-ion battery of the composite phosphate, the soluble metal salt in the step (1) further comprises one or more of magnesium sulfate, zinc sulfate, calcium nitrate, copper sulfate and titanium sulfate, and when the molar ratio of magnesium, zinc, calcium, copper, aluminum and titanium in the iron-containing salt solution to the total metal content is Y, Y is greater than or equal to 0 and less than or equal to 0.1.
As a preferable scheme of the preparation method of the layered positive electrode material precursor of the iron-based sodium-ion battery of the composite phosphate, the soluble metal salt containing three elements of iron, nickel and manganese in the step (1) is selected from at least three of ferrous sulfate, ferrous chloride, ferrous nitrate, nickel sulfate, nickel chloride, nickel nitrate, manganous sulfate, manganous chloride and manganous nitrate.
As a preferable scheme of the preparation method of the precursor of the layered positive electrode material of the iron-based sodium-ion battery of the composite phosphate, in the step (2), the molar concentration of P in the alkali solution is 0.005-0.05mol/L, and OH is - The molar concentration in the alkali solution is 1-5mol/L.
As a preferable embodiment of the preparation method of the precursor of the layered positive electrode material of the iron-based sodium-ion battery of the composite phosphate, in the step (3), the complexing agent solution further contains a surfactant, and the surfactant is selected from at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, stearic acid, polyethylene glycol, and dodecyl glucoside.
As a preferable scheme of the preparation method of the precursor of the layered positive electrode material of the iron-based sodium-ion battery of the composite phosphate, the molar concentration of the surfactant in the complexing agent solution is 0-1mol/L.
As a preferable embodiment of the preparation method of the precursor of the layered positive electrode material of the iron-based sodium-ion battery of the composite phosphate, in the step (4), the base solution further contains a surfactant, and the surfactant is selected from at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, stearic acid, polyethylene glycol, and dodecyl glucoside.
In a preferable embodiment of the method for preparing the precursor of the layered positive electrode material of the phosphate-compounded iron-based sodium-ion battery, the molar concentration of the surfactant in the base solution is 0-0.05mol/L.
As a preferable scheme of the preparation method of the precursor of the layered positive electrode material of the iron-based sodium-ion battery of the composite phosphate, the stirring rotating speed in the step (5) is 150-300r/min.
As a preferable scheme of the preparation method of the layered positive electrode material precursor of the iron-based sodium-ion battery of the composite phosphate, in the step (6), when the iron-containing salt solution, the alkali solution and the complexing agent solution are introduced into the base solution for reaction, total metal ions in the iron-containing salt solution and OH in the alkali solution introduced in unit time are reacted - The molar ratio of (1).
Compared with the prior art, the preparation method of the precursor of the layered positive electrode material of the iron-based sodium-ion battery of the composite phosphate has the advantages that:
1. the selected additive has both reducibility and complexation on ferrous ions, can prevent the ferrous ions from being oxidized, has complexation on the ferrous ions in the reaction, can control the precipitation speed of the ferrous ions, and can prevent uneven precipitation;
2. phosphate is added into the reaction solution, so that the polyanionic material can be compounded in one step, and the mixing-sintering process of the traditional composite material is reduced.
Drawings
Fig. 1 is an SEM image of a precursor material prepared in example 1 by the method for preparing a phosphate-compounded iron-based sodium-ion battery layered positive electrode material precursor of the present invention, the SEM image being 2 ten thousand times larger;
fig. 2 is an SEM image of a precursor material prepared in example 2 by the method for preparing a phosphate-compounded iron-based sodium-ion battery layered positive electrode material precursor of the present invention, the SEM image being 2 ten thousand times larger;
fig. 3 is an SEM image of a precursor material prepared in example 3 by the method for preparing a phosphate-compounded iron-based sodium-ion battery layered positive electrode material precursor of the present invention, the SEM image being 2 ten thousand times larger;
fig. 4 is an SEM image of a precursor material prepared in the comparative example, magnified 2 ten thousand times.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments in order to make the above objects, features and advantages more apparent and understandable.
First, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The preparation method of the novel phosphate-compounded iron-based sodium-ion battery layered positive electrode material precursor comprises the following specific operation steps:
(1) Preparing a solution containing iron salt: the solution is prepared from soluble metal salt, an additive and water. The soluble metal salt at least comprises soluble metal salts of 3 elements of iron, nickel and manganese, wherein the optional metal salts comprise ferrous sulfate, ferrous chloride, ferrous nitrate, nickel sulfate, nickel chloride, nickel nitrate, manganous sulfate, manganous chloride and manganous nitrate; the soluble metal salt may also contain one or more of magnesium sulfate, zinc sulfate, calcium nitrate, copper sulfate, and titanium sulfate; the total molar concentration of all metal ions in the iron-containing salt solution is 0.5-2.5mol/L, and the molar ratio X of iron, nickel and manganese in the iron-containing salt solution 1 ：X 2 ：X 3 Should satisfy X is more than or equal to 0.2 1 ≤0.6；0.2≤X 2 ≤0.6；X 1 +X 2 +X 3 =1, the molar ratio Y of magnesium, zinc, calcium, copper, aluminum and titanium in the iron-containing salt solution to the total metal content should satisfy that Y is more than or equal to 0 and less than or equal to 0.1, the metal elements are added in the ratio range, the crystal structure stability of the final anode product can be improved, the structural collapse caused by sodium ion intercalation and deintercalation is reduced, and the material is improvedMaterial stability; the additive comprises at least one of citric acid, sodium citrate, glucose and sodium gluconate, the molar ratio Z of the additive to ferrous ions is more than or equal to 0.01 and less than or equal to 0.1, the Z range can play the role of the additive in resisting oxidation and complexing ferric ions on one hand, and on the other hand, the phenomenon that the ferrous precipitation rate is too low due to too high complexing effect, so that the precipitation is asynchronous is avoided.
(2) Preparing an alkali solution: the solution consists of an alkaline substance and a source of phosphorus. The alkaline substance comprises at least one of sodium hydroxide, sodium carbonate and sodium bicarbonate, the phosphorus source comprises at least one of phosphoric acid, pyrophosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate and sodium pyrophosphate, the molar concentration of P in the alkaline solution is between 0.005 and 0.05mol/L, and OH in the alkaline solution is - The molar concentration is in the range of 1-5mol/L. The molar concentration range of P in the alkali solution, on one hand, a phosphate structure is added into the crystal, the structural strength is enhanced, the cycle performance is improved, and on the other hand, the reduction of the effective structure caused by overhigh P concentration is avoided, and the specific capacity is reduced.
(3) Preparing a complexing agent solution: the solution contains NH 3 ，NH 3 Is in the range of 1-3 mol/L. Optionally, the complexing agent solution further comprises a surfactant, the surfactant comprises at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, stearic acid, polyethylene glycol and dodecyl glucoside, and the molar concentration of the surfactant in the complexing agent solution is in the range of 0-1mol/L.
(4) Preparing a base solution: the base liquid contains NH 3 And additive, NH 3 The molar concentration of the additive is between 0.1 and 1mol/L, the additive comprises at least one of citric acid, sodium citrate, glucose and sodium gluconate, and the concentration of the additive is within the range of 0.001 to 0.05mol/L. Optionally, the base solution comprises a surfactant, the surfactant comprises at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, stearic acid, polyethylene glycol and dodecyl glucoside, and the molar concentration of the surfactant in the base solution is in the range of 0-0.05mol/L. NH in the base liquid 3 The concentration range of the additive is combined to ensure that the metals Ni, fe and Mn are close in speedAnd the sediment is avoided being uneven.
(5) Stirring the base solution at 150-300r/min, heating to 40-60 deg.C, and introducing nitrogen at 0.2-0.6L/min.
(6) Introducing the prepared iron-containing salt solution, alkali solution and complexing agent solution into the base solution at a certain flow rate after introducing nitrogen for 4-10h, wherein total metal ions in the iron-containing salt solution and OH in the alkali solution are introduced in unit time - The molar ratio of (1) to (2), the reaction pH value is between 8.5 and 10.5, the reaction time is within the range of 50 to 100 hours, the solution is filtered after the reaction is finished, the obtained solid is washed by deionized water and then dried, and the target product iron-based multi-hydroxide, namely a precursor, is obtained.
For a detailed description and related comparison, see the following examples:
example 1
The invention relates to a preparation method of a novel phosphate-compounded layered positive electrode material precursor of an iron-based sodium-ion battery, which comprises the following steps:
ferrous sulfate, nickel sulfate, manganous sulfate and citric acid are taken, water is added to prepare 2L of salt solution with the total metal ion concentration of 1mol/L, wherein the molar ratio of iron, nickel and manganese is 3. Sodium hydroxide and trisodium phosphate are taken, water is added to prepare 2L of aqueous alkali, so that the concentration of hydroxide radical is 2mol/L, and the concentration of phosphate radical is 0.01mol/L. Adding ammonia water and sodium dodecyl benzene sulfonate into water to prepare 0.5L complexing agent solution, wherein NH is 3 The concentration of (A) is 1.8mol/L, and the molar concentration of the sodium dodecyl benzene sulfonate is 0.2mol/L. Adding ammonia water, sodium dodecyl benzene sulfonate and citric acid into water to prepare 5L base solution, wherein NH 3 The concentration of the sodium dodecyl benzene sulfonate is 0.2mol/L, the molar concentration of the sodium dodecyl benzene sulfonate is 0.02mol/L, and the molar concentration of the citric acid is 0.002mol/L. The bottom liquid is heated to 50 ℃ while stirring at 160r/min, and nitrogen is introduced into the bottom liquid for 6 hours at the flow rate of 0.5L/min. And simultaneously introducing the salt solution, the alkali solution and the complexing agent solution into the base solution, controlling the pH of the base solution to be 9.55, and controlling the flow rates of the salt solution, the alkali solution and the complexing agent solution to be 0.55mL/min, 0.55mL/min and 0.14mL/min respectively when the salt solution, the alkali solution and the complexing agent solution are stable. After 55 hours of reaction, the base solution is taken out and filtered to obtain the precursorWashing the solid of the displacement body by using deionized water until sulfate radical in the filtrate can not be detected, drying and sieving by using a 300-mesh sieve for later use.
Example 2
The invention relates to a preparation method of a novel phosphate-compounded iron-based sodium-ion battery layered positive electrode material precursor, which comprises the following steps:
ferrous sulfate, nickel sulfate, manganous sulfate and glucose are taken, water is added to prepare 2L of salt solution with the total metal ion concentration of 1mol/L, wherein the molar ratio of iron, nickel and manganese is 1. Sodium hydroxide and sodium dihydrogen phosphate are taken and added with water to prepare 2L of aqueous alkali, so that the concentration of hydroxide radical is 2mol/L and the concentration of phosphate radical is 0.01mol/L. Adding ammonia water into water to obtain 0.5L complexing agent solution (NH) 3 The concentration of (2) is 1.8mol/L. Adding ammonia water and glucose into water to obtain 5L base solution, wherein NH 3 The concentration of (2) was 0.2mol/L, and the concentration of glucose was 0.004mol/L. The bottom liquid is heated to 50 ℃ while stirring at 200r/min, and nitrogen is introduced into the bottom liquid for 6 hours at the flow rate of 0.5L/min. And simultaneously introducing the salt solution, the alkali solution and the complexing agent solution into the base solution, controlling the pH of the base solution to be 9.25, and controlling the flow rates of the salt solution, the alkali solution and the complexing agent solution to be 0.55mL/min, 0.55mL/min and 0.14mL/min respectively when the salt solution, the alkali solution and the complexing agent solution are stable. And after 55 hours of reaction, taking out the base solution, filtering, washing the obtained precursor solid with deionized water until sulfate radical in the filtrate can not be detected, drying, and sieving with a 300-mesh sieve for later use.
Example 3
The invention relates to a preparation method of a novel phosphate-compounded iron-based sodium-ion battery layered positive electrode material precursor, which comprises the following steps:
ferrous sulfate, nickel sulfate, manganous sulfate and glucose are taken, water is added to prepare 2L of salt solution with the total metal ion concentration of 1mol/L, wherein the molar ratio of iron, nickel and manganese is 1. Sodium carbonate and trisodium phosphate are taken, water is added to prepare 2L of aqueous alkali, so that the concentration of hydroxide radical is 2mol/L, and the concentration of phosphate radical is 0.01mol/L. Adding ammonia water into water to obtain 0.5L complexing agent solution containing NH 3 The concentration of (2) is 1.8mol/L. Adding ammonia water and glucose into water to obtain 5L base solution,wherein NH 3 The concentration of (2) was 0.2mol/L, and the concentration of glucose was 0.002mol/L. The bottom liquid is heated to 55 ℃ while stirring at 200r/min, and nitrogen is introduced into the bottom liquid for 6 hours at the flow rate of 0.5L/min. And simultaneously introducing the salt solution, the alkali solution and the complexing agent solution into the base solution, controlling the pH of the base solution to be 9.25, and controlling the flow rates of the salt solution, the alkali solution and the complexing agent solution to be 0.55mL/min, 0.55mL/min and 0.14mL/min respectively when the salt solution, the alkali solution and the complexing agent solution are stable. And after 55 hours of reaction, taking out the base solution, filtering, washing the obtained precursor solid with deionized water until sulfate radical in the filtrate can not be detected, drying, and sieving with a 300-mesh sieve for later use.
Comparative example
Ferrous sulfate, nickel sulfate and manganous sulfate are taken, water is added to prepare 2L of salt solution with the total metal ion concentration of 1mol/L, wherein the molar ratio of iron, nickel and manganese is 1. Sodium hydroxide is taken and added with water to prepare 2L of alkali solution, so that the concentration of hydroxide radical is 2mol/L. Adding ammonia water into water to obtain 0.5L complexing agent solution (NH) 3 The concentration of (2) is 1.8mol/L. Adding ammonia water into water to obtain 5L base solution containing NH 3 The concentration of (2) was 0.2mol/L. The bottom liquid is heated to 55 ℃ while stirring at 200r/min, and nitrogen is introduced into the bottom liquid for 6 hours at the flow rate of 0.5L/min. And simultaneously introducing the salt solution, the alkali solution and the complexing agent solution into the base solution, controlling the pH of the base solution to be 9.25, and controlling the flow rates of the salt solution, the alkali solution and the complexing agent solution to be 0.55mL/min, 0.55mL/min and 0.14mL/min respectively when the salt solution, the alkali solution and the complexing agent solution are stable. And after 55 hours of reaction, taking out the base solution, filtering, washing the obtained precursor solid with deionized water until sulfate radical in the filtrate can not be detected, drying, and sieving with a 300-mesh sieve for later use.
The test results of the comparative example and the example are shown in fig. 1 to 4 and table 1 below. 1. SEM test
Referring to fig. 1 to 4, fig. 1 is an SEM image of a precursor material prepared in example 1 by the method for preparing a precursor of a phosphate-compounded iron-based sodium-ion battery layered positive electrode material according to the present invention, the SEM image being 2 ten thousand times larger; fig. 2 is an SEM image of a precursor material prepared in example 2 by the method for preparing a phosphate-compounded iron-based sodium-ion battery layered positive electrode material precursor of the present invention, the SEM image being 2 ten thousand times larger; fig. 3 is an SEM image of a precursor material prepared in example 3 by the method for preparing a phosphate-compounded iron-based sodium-ion battery layered positive electrode material precursor of the present invention, the SEM image being 2 ten thousand times larger; fig. 4 is an SEM image of a precursor material prepared in the comparative example, magnified 2 ten thousand times. As shown in fig. 1 to 4, the precursors of examples 1, 2, and 3 had significant primary particles and good crystallinity; the precursor of the comparative example had a loose structure, poor crystallinity, and no apparent primary particles. The method of the invention can effectively control the coprecipitation reaction, reduce the floccule generated by the rapid precipitation of ferrous ions, slow the overall reaction rate and be beneficial to the growth of primary particle crystals.
2. Sintering of positive electrode material
And uniformly mixing the precursor and anhydrous sodium carbonate, wherein the molar ratio of total metal elements in the precursor to sodium elements in the sodium carbonate is 1.02. The mixed solid is put into a muffle furnace and sintered for 24 hours at 870 ℃. The obtained anode material is sieved by a 300-mesh sieve for later use.
3. Power-off test
The positive electrode material, the conductive agent and the binder are uniformly mixed according to the proportion of 8. And cutting the dried pole piece into a wafer. The button cell is assembled by using the anode wafer, the diaphragm, the sodium metal cathode sheet and the sodium ion battery electrolyte. The cell was charged and discharged at a voltage window of 2.0-4.0V, cycled at 0.1C for 2 cycles, and then cycled at 1C for 50 cycles. (1C = 120mA/g) the test results are shown in Table 1.
TABLE 1
As shown in table 1, the specific discharge capacities of examples 1, 2 and 3 at 0.1C and 1C were all higher than those of the comparative examples, and the cycle retention rate was also significantly better than that of the comparative examples. On one hand, the crystallinity of the precursor is improved after the synthesis method of the precursor is optimized, and on the other hand, a small amount of phosphate in the precursor reacts with a sodium source to generate a stable polyanion cathode material.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A preparation method of a precursor of a layered positive electrode material of an iron-based sodium-ion battery compounded with phosphate is characterized by comprising the following steps:
(1) Preparing a ferrous salt solution, wherein the ferrous salt solution is prepared from soluble metal salt, an additive and water, the soluble metal salt at least comprises three elements of iron, nickel and manganese, the total molar concentration of all metal ions in the ferrous salt solution is 0.5-2.5mol/L, and the molar ratio of the iron, the nickel and the manganese in the ferrous salt solution is X 1 ：X 2 ：X 3 And then 0.2 is less than or equal to X 1 ≤0.6、0.2≤X 2 ≤0.6、X 1 +X 2 +X 3 =1, wherein the additive comprises at least one of citric acid, sodium citrate, glucose and sodium gluconate, and when the molar ratio of the additive to ferrous ions is Z, Z is more than or equal to 0.01 and less than or equal to 0.1;
(2) Preparing an alkaline solution, wherein the alkaline solution consists of alkaline substances and a phosphorus source, the alkaline substances comprise at least one of sodium hydroxide, sodium carbonate and sodium bicarbonate, and the phosphorus source comprises at least one of phosphoric acid, pyrophosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate and sodium pyrophosphate;
(3) Preparing a complexing agent solution, wherein the complexing agent solution contains NH 3 NH of said 3 The molar concentration of the complexing agent in the complexing agent solution is 1-3mol/L;
(4) Preparing a base solution, wherein the base solution contains NH 3 And additives, the NH 3 The molar concentration of the additive in the base solution is 0.1-1mol/L, the additive is at least one of citric acid, sodium citrate, glucose and sodium gluconate, and the additive in the base solutionThe molar concentration is 0.001-0.05mol/L;
(5) Stirring the base solution, heating to 40-60 ℃, and introducing nitrogen at the speed of 0.2-0.6L/min;
(6) And after the nitrogen is introduced for 4-10 hours, introducing the iron-containing salt solution, the alkali solution and the complexing agent solution into the base solution for reaction, filtering the reaction solution after the reaction is finished, washing the obtained solid with deionized water, and drying to obtain the iron-based multi-hydroxide, namely the precursor of the layered positive electrode material of the iron-based sodium ion battery of the composite phosphate.
2. The method for preparing the precursor of the layered positive electrode material of the phosphate-compounded iron-based sodium-ion battery according to claim 1, wherein the precursor comprises the following steps: the soluble metal salt in the step (1) also comprises one or more of magnesium sulfate, zinc sulfate, calcium nitrate, copper sulfate and titanium sulfate, and the molar ratio of magnesium, zinc, calcium, copper, aluminum and titanium in the iron-containing salt solution to the total metal content is Y, so that Y is more than or equal to 0 and less than or equal to 0.1.
3. The method for preparing the precursor of the layered positive electrode material of the phosphate-compounded iron-based sodium-ion battery according to claim 1, wherein the precursor comprises the following steps: the soluble metal salt containing three elements of iron, nickel and manganese in the step (1) is selected from at least three of ferrous sulfate, ferrous chloride, ferrous nitrate, nickel sulfate, nickel chloride, nickel nitrate, manganous sulfate, manganous chloride and manganous nitrate.
4. The method for preparing the precursor of the layered positive electrode material of the phosphate-compounded iron-based sodium-ion battery according to claim 1, wherein the precursor comprises the following steps: the molar concentration of P in the alkali solution in the step (2) is 0.005-0.05mol/L, OH - The molar concentration in the alkali solution is 1-5mol/L.
5. The method for preparing the precursor of the layered positive electrode material of the phosphate-compounded iron-based sodium-ion battery according to claim 1, wherein the precursor comprises the following steps: and (3) the complexing agent solution also comprises a surfactant, wherein the surfactant is selected from at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, stearic acid, polyethylene glycol and dodecyl glucoside.
6. The method for preparing the precursor of the layered positive electrode material of the phosphate-compounded iron-based sodium-ion battery according to claim 5, wherein the precursor comprises the following steps: the molar concentration of the surfactant in the complexing agent solution is 0-1mol/L.
7. The method for preparing the precursor of the layered positive electrode material of the phosphate-compounded iron-based sodium-ion battery according to claim 1, wherein the precursor comprises the following steps: and (4) the base solution also comprises a surfactant, wherein the surfactant is selected from at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, stearic acid, polyethylene glycol and dodecyl glucoside.
8. The method for preparing the precursor of the layered positive electrode material of the phosphate-compounded iron-based sodium-ion battery according to claim 7, wherein the precursor comprises the following steps: the molar concentration of the surfactant in the base solution is 0-0.05mol/L.
9. The method for preparing the precursor of the layered positive electrode material of the iron-based sodium-ion battery of composite phosphate according to claim 1, which is characterized in that: the rotating speed of the stirring in the step (5) is 150-300r/min.
10. The method for preparing the precursor of the layered positive electrode material of the phosphate-compounded iron-based sodium-ion battery according to claim 1, wherein the precursor comprises the following steps: when the iron-containing salt solution, the alkali solution and the complexing agent solution are introduced into the base solution for reaction in the step (6), total metal ions in the iron-containing salt solution and OH in the alkali solution introduced in unit time are reacted - The molar ratio of (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211675841.3A CN115924980B (en) | 2022-12-26 | 2022-12-26 | Preparation method of iron-based sodium ion battery layered cathode material precursor of composite phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211675841.3A CN115924980B (en) | 2022-12-26 | 2022-12-26 | Preparation method of iron-based sodium ion battery layered cathode material precursor of composite phosphate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115924980A true CN115924980A (en) | 2023-04-07 |
| CN115924980B CN115924980B (en) | 2024-06-11 |
Family
ID=86555540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211675841.3A Active CN115924980B (en) | 2022-12-26 | 2022-12-26 | Preparation method of iron-based sodium ion battery layered cathode material precursor of composite phosphate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115924980B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117125743A (en) * | 2023-08-29 | 2023-11-28 | 荆门市格林美新材料有限公司 | Sodium ion battery positive electrode precursor material and preparation method and application thereof |
| CN118387944A (en) * | 2024-06-26 | 2024-07-26 | 浙江帕瓦新能源股份有限公司 | Sodium ion battery positive electrode precursor material and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101728519A (en) * | 2009-12-04 | 2010-06-09 | 哈尔滨工业大学 | Preparation method of high-energy density secondary lithium battery positive pole material LiFePO4/C |
| CN109250698A (en) * | 2018-08-22 | 2019-01-22 | 江苏元景锂粉工业有限公司 | A kind of high-tap density lithium iron manganese phosphate anode material and its preparation method and application |
| CN112794376A (en) * | 2021-01-20 | 2021-05-14 | 湖南德景源科技有限公司 | Preparation method of nickel-cobalt-manganese ternary material precursor |
| CN114057177A (en) * | 2021-11-23 | 2022-02-18 | 湖北融通高科先进材料有限公司 | Ferrous manganese phosphate and preparation method and application thereof |
| CN114512660A (en) * | 2020-11-17 | 2022-05-17 | 松山湖材料实验室 | Positive electrode active material precursor, preparation method thereof and positive electrode active material |
| WO2022105696A1 (en) * | 2020-11-17 | 2022-05-27 | 松山湖材料实验室 | Positive electrode active material precursor and preparation method therefor, positive electrode active material and preparation method therefor, positive electrode of lithium ion secondary battery, and lithium ion secondary battery |
| CN115043387A (en) * | 2022-06-28 | 2022-09-13 | 广东邦普循环科技有限公司 | Preparation method of manganese iron ammonium phosphate, lithium manganese iron phosphate and application thereof |
| WO2022242184A1 (en) * | 2021-05-17 | 2022-11-24 | 广东邦普循环科技有限公司 | Doped iron phosphate, and preparation method therefor and application thereof |
| CN115403079A (en) * | 2022-10-17 | 2022-11-29 | 宁波容百新能源科技股份有限公司 | Positive electrode precursor material and preparation method and application thereof |
| CN115513452A (en) * | 2022-09-19 | 2022-12-23 | 深圳珈钠能源科技有限公司 | Polyanion type sodium ion battery positive electrode material and preparation method thereof |
-
2022
- 2022-12-26 CN CN202211675841.3A patent/CN115924980B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101728519A (en) * | 2009-12-04 | 2010-06-09 | 哈尔滨工业大学 | Preparation method of high-energy density secondary lithium battery positive pole material LiFePO4/C |
| CN109250698A (en) * | 2018-08-22 | 2019-01-22 | 江苏元景锂粉工业有限公司 | A kind of high-tap density lithium iron manganese phosphate anode material and its preparation method and application |
| CN114512660A (en) * | 2020-11-17 | 2022-05-17 | 松山湖材料实验室 | Positive electrode active material precursor, preparation method thereof and positive electrode active material |
| WO2022105696A1 (en) * | 2020-11-17 | 2022-05-27 | 松山湖材料实验室 | Positive electrode active material precursor and preparation method therefor, positive electrode active material and preparation method therefor, positive electrode of lithium ion secondary battery, and lithium ion secondary battery |
| CN112794376A (en) * | 2021-01-20 | 2021-05-14 | 湖南德景源科技有限公司 | Preparation method of nickel-cobalt-manganese ternary material precursor |
| WO2022242184A1 (en) * | 2021-05-17 | 2022-11-24 | 广东邦普循环科技有限公司 | Doped iron phosphate, and preparation method therefor and application thereof |
| CN114057177A (en) * | 2021-11-23 | 2022-02-18 | 湖北融通高科先进材料有限公司 | Ferrous manganese phosphate and preparation method and application thereof |
| CN115043387A (en) * | 2022-06-28 | 2022-09-13 | 广东邦普循环科技有限公司 | Preparation method of manganese iron ammonium phosphate, lithium manganese iron phosphate and application thereof |
| CN115513452A (en) * | 2022-09-19 | 2022-12-23 | 深圳珈钠能源科技有限公司 | Polyanion type sodium ion battery positive electrode material and preparation method thereof |
| CN115403079A (en) * | 2022-10-17 | 2022-11-29 | 宁波容百新能源科技股份有限公司 | Positive electrode precursor material and preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117125743A (en) * | 2023-08-29 | 2023-11-28 | 荆门市格林美新材料有限公司 | Sodium ion battery positive electrode precursor material and preparation method and application thereof |
| CN118387944A (en) * | 2024-06-26 | 2024-07-26 | 浙江帕瓦新能源股份有限公司 | Sodium ion battery positive electrode precursor material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115924980B (en) | 2024-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102689398B1 (en) | Sodium-containing oxide anode material and its manufacturing method and application, anode plate and its application | |
| JP5426654B2 (en) | Method for preparing an iron source for preparing lithium iron phosphate and method for preparing lithium iron phosphate | |
| CN104577093A (en) | Surface coating modified lithium ion battery cathode material and preparation method thereof | |
| CN105161705A (en) | Lithium manganese phosphate-coated nickel-cobalt lithium manganate cathode material and preparation method thereof | |
| CN103715409A (en) | Method for preparing coated lithium ion battery cathode material of lithium nickel manganese oxide | |
| CN115924980B (en) | Preparation method of iron-based sodium ion battery layered cathode material precursor of composite phosphate | |
| EP4266419A1 (en) | Sodium ion battery positive electrode active substance, preparation method therefor, and use thereof | |
| CN114057177A (en) | Ferrous manganese phosphate and preparation method and application thereof | |
| CN104966820A (en) | Lithium-ion battery precursor material, composite positive electrode material and preparation method thereof | |
| CN114940485B (en) | Lithium manganese iron phosphate precursor and preparation method and application thereof | |
| CN109103446B (en) | Silicon oxide coated high-nickel precursor, modified high-nickel material and preparation method thereof | |
| CN106486657B (en) | Surface in-situ coated lithium-rich material and preparation method thereof | |
| CN114512649A (en) | Composite lithium manganese iron phosphate cathode material, preparation method and application thereof | |
| CN112340785A (en) | Doped high-nickel ternary material and preparation method thereof | |
| CN112624207A (en) | Full-concentration gradient-distributed lithium-rich manganese-based lithium cathode material and preparation method and application thereof | |
| CN103956456A (en) | Halogen anion doped lithium-rich positive electrode material as well as preparation method and application of positive electrode material | |
| CN105161715A (en) | Lithium nickel cobalt manganese oxide positive electrode precursor and preparation method thereof as well as lithium nickel cobalt manganese oxide positive electrode material and preparation method thereof | |
| CN116504940A (en) | Polyanion type sodium ion battery positive electrode material, preparation method and application thereof | |
| CN110690443B (en) | Preparation method and application of lithium-rich manganese material with nickel element in gradient distribution | |
| CN114314541B (en) | Ferric phosphate for high-pressure compaction and preparation method thereof | |
| CN117525317A (en) | Manganese-assisted carbon-coated lithium iron manganese phosphate material and preparation method thereof | |
| CN116581270A (en) | Manganese and titanium in-situ doped carbon-containing lithium iron phosphate composite material and preparation method and application thereof | |
| CN101209820B (en) | Iron source material used for preparing lithium iron phosphate and method for preparing iron source material used for preparing lithium iron phosphate | |
| CN114361439A (en) | Preparation method and application of novel water-based zinc ion battery electrode material | |
| CN114655991B (en) | Modified sodium manganate material and preparation method and application thereof |
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 |