CN117577830A - Ferric sodium pyrophosphate material, and preparation method and application thereof - Google Patents
Ferric sodium pyrophosphate material, and preparation method and application thereof Download PDFInfo
- Publication number
- CN117577830A CN117577830A CN202311612894.5A CN202311612894A CN117577830A CN 117577830 A CN117577830 A CN 117577830A CN 202311612894 A CN202311612894 A CN 202311612894A CN 117577830 A CN117577830 A CN 117577830A
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- CN
- China
- Prior art keywords
- sodium
- pyrophosphate
- manganese
- ferromanganese
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 78
- XWQGIDJIEPIQBD-UHFFFAOYSA-J sodium;iron(3+);phosphonato phosphate Chemical compound [Na+].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O XWQGIDJIEPIQBD-UHFFFAOYSA-J 0.000 title claims description 12
- 239000011645 ferric sodium diphosphate Substances 0.000 title claims description 10
- 235000019851 ferric sodium diphosphate Nutrition 0.000 title claims description 10
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 97
- 239000011734 sodium Substances 0.000 claims abstract description 91
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 71
- 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 70
- 229910000616 Ferromanganese Inorganic materials 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000002243 precursor Substances 0.000 claims abstract description 46
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000000975 co-precipitation Methods 0.000 claims abstract description 43
- 235000011180 diphosphates Nutrition 0.000 claims abstract description 41
- 229940048084 pyrophosphate Drugs 0.000 claims abstract description 41
- 239000012266 salt solution Substances 0.000 claims abstract description 37
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 30
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 30
- 239000011574 phosphorus Substances 0.000 claims abstract description 30
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 29
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 29
- 150000002696 manganese Chemical class 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000498 ball milling Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 18
- 239000010452 phosphate Substances 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 230000001681 protective effect Effects 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 239000011247 coating layer Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- OOIOHEBTXPTBBE-UHFFFAOYSA-N [Na].[Fe] Chemical compound [Na].[Fe] OOIOHEBTXPTBBE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229940005657 pyrophosphoric acid Drugs 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 71
- 239000011572 manganese Substances 0.000 claims description 42
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 21
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 20
- 229940099596 manganese sulfate Drugs 0.000 claims description 18
- 239000011702 manganese sulphate Substances 0.000 claims description 18
- 235000007079 manganese sulphate Nutrition 0.000 claims description 18
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 17
- 239000011790 ferrous sulphate Substances 0.000 claims description 17
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 17
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 17
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 17
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- HXANRRBZAUXOMS-UHFFFAOYSA-J sodium iron(2+) manganese(2+) phosphonato phosphate Chemical compound [O-]P([O-])(=O)OP(=O)([O-])[O-].[Na+].[Fe+2].[Mn+2] HXANRRBZAUXOMS-UHFFFAOYSA-J 0.000 claims description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 10
- 239000007774 positive electrode material Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 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
- 229940116007 ferrous phosphate Drugs 0.000 claims description 7
- 150000002505 iron Chemical class 0.000 claims description 7
- 229910000155 iron(II) phosphate Inorganic materials 0.000 claims description 7
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 claims description 7
- 239000010410 layer Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 6
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 6
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 6
- BYTVRGSKFNKHHE-UHFFFAOYSA-K sodium;[hydroxy(oxido)phosphoryl] phosphate;iron(2+) Chemical compound [Na+].[Fe+2].OP([O-])(=O)OP([O-])([O-])=O BYTVRGSKFNKHHE-UHFFFAOYSA-K 0.000 claims description 6
- 239000002344 surface layer Substances 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 229940071125 manganese acetate Drugs 0.000 claims description 5
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- 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 4
- 239000008103 glucose Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920000858 Cyclodextrin Polymers 0.000 claims description 3
- 239000001116 FEMA 4028 Substances 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 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
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 3
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 3
- 229960004853 betadex Drugs 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- 229940062993 ferrous oxalate Drugs 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 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
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 235000011007 phosphoric acid Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 239000005696 Diammonium phosphate Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 19
- 239000010405 anode material Substances 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 5
- PZQNFVCVNORNPG-UHFFFAOYSA-M [Na+].OP(O)([O-])=O.OP(O)(=O)OP(O)(O)=O Chemical compound [Na+].OP(O)([O-])=O.OP(O)(=O)OP(O)(O)=O PZQNFVCVNORNPG-UHFFFAOYSA-M 0.000 abstract 3
- 229910052748 manganese Inorganic materials 0.000 description 27
- 229910052742 iron Inorganic materials 0.000 description 24
- 230000002572 peristaltic effect Effects 0.000 description 22
- 238000009826 distribution Methods 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 230000008901 benefit Effects 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- UMZUVDAJYPZSCI-UHFFFAOYSA-K sodium [hydroxy(oxido)phosphoryl] phosphate manganese(2+) Chemical compound [O-]P([O-])(=O)OP(=O)([O-])O.[Mn+2].[Na+] UMZUVDAJYPZSCI-UHFFFAOYSA-K 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 230000009471 action Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 230000000977 initiatory effect Effects 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 239000006012 monoammonium phosphate Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910001415 sodium ion 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 group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical class [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 2
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000447 polyanionic polymer Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 230000005536 Jahn Teller effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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Abstract
The invention discloses a sodium ferromanganese pyrophosphate material, a preparation method and application thereof, and belongs to the technical field of anode materials. The ferromanganese phosphate sodium pyrophosphate material comprises a ferromanganese phosphate sodium pyrophosphate inner core and a ferromanganese phosphate sodium pyrophosphate coating layer coated on the surface of the inner core. The preparation method of the sodium ferromanganese pyrophosphate material comprises the following steps: co-precipitation reaction is carried out on manganese salt solution, phosphorus source solution and ammonia water solution in a parallel flow adding mode, meanwhile, ferric salt solution is connected into the manganese salt solution in a continuous flow mode to form phosphate precursor cores, and then precursor particles are obtained through aging; mixing the precursor particles, the supplemented sodium source, the phosphorus source and the carbon source, and then ball milling to obtain a mixed material; calcining the mixture at a lower temperature under a protective atmosphere, and then preserving heat at a higher temperature to obtain the pyrophosphoric acid ferromanganese sodium iron material. In the charge-discharge cycle process, the material has higher specific discharge capacity and good cycle stability.
Description
Technical Field
The invention relates to the technical field of anode materials, in particular to a sodium ferromanganese pyrophosphate material, a preparation method and application thereof.
Background
The problems of exhaustion of energy sources and environmental pollution caused by traditional fossil fuels are increasingly serious, and along with the rapid development of renewable energy sources such as solar energy, wind energy and the like, the importance of energy storage technology is increasingly remarkable. Among them, the secondary battery occupies a wide market in the electrochemical energy storage field by virtue of its high energy density and rapid response. Particularly, the sodium ion battery is hopeful to replace the lithium ion battery in the fields of large-scale energy storage and low-speed electric traffic by virtue of rich resources and cost advantages. Heretofore, a variety of sodium ion battery cathode materials have been widely studied, including layered/tunnel transition metal oxides, polyanionic compounds, ferricyanide analogs, and organic materials. Layered/tunnel transition metal oxides are often accompanied by large volume changes and complex phase changes during electrochemical reactions and are highly sensitive to air, impeding their commercial application. Ferricyanide analogues often have problems in practical use such as low utilization, poor efficiency and unstable circulation, which are related to poor thermal stability and rich lattice defects. Organic compounds have a low theoretical capacity due to their large molecular weight and low sodium content, and have poor rate capability, slow kinetics and severe material dissolution phenomena. Compared with the polyanion compound, the polyanion compound has the advantages of low cost, stable structure, small volume change in the circulating process and the like, and meets the actual requirements of an energy storage system. Among them, mixed iron phosphate (NFPP) is considered as a potential sodium ion battery positive electrode material, whose three-dimensional channel favors Na + And (5) transmission. In addition, NFPP has a high theoretical capacity (129 mAh.g -1 ) Low cost and excellent cycle stability. However, since NFPP has a low operating voltage, the space for further increasing the energy density of the battery is extremely limited, and how to further increase the energy density of NFPP has become an important point of research on sodium iron pyrophosphate modification.
Similar to lithium iron manganese phosphate, sodium iron manganese pyrophosphate replaced the site of iron by a portion of manganese element, sodium iron pyrophosphate was discharged to a plateau of 2.9V (vs Na/Na + ) To about 3.7V (corresponding to Fe) 2+ With Fe 3+ 、Mn 2+ With Mn 3+ Redox reaction between them), with the potential advantage of high energy density. And the structure is an ordered olivine structure, and has the characteristics of high safety, stability and the like. However, the ionic conductivity and the electronic conductivity of the material are low, the capacity of the material is difficult to develop, side reactions and other problems can occur with electrolyte, and Mn formed after sodium removal is generated along with the increase of the charge and discharge times of the material 3+ The method is affected by Jahn-Teller effect, the crystal structure is subjected to irreversible phase change, a sodium deintercalation channel is compressed, and part of manganese ions are subjected to disproportionation reaction and dissolved in electrolyte, so that the cycle performance of the material is poor, and the like.
Disclosure of Invention
The invention aims to overcome the technical defects, and provides a sodium ferromanganese pyrophosphate material, a preparation method and application thereof, and solves the technical problem of poor cycle performance of sodium ferromanganese pyrophosphate in the prior art.
In order to achieve the technical aim, the technical scheme of the invention provides a sodium ferromanganese pyrophosphate material, which comprises a sodium ferromanganese pyrophosphate inner core and a sodium ferropyrophosphate coating layer coated on the surface of the inner core; along the direction from the center of the inner core to the surface layer of the inner core, the content of manganese element in the inner core of the sodium ferromanganese pyrophosphate is reduced in a gradient manner, and the content of iron element is increased in a gradient manner.
Further, in some embodiments, the sodium ferromanganese pyrophosphate of the core has the formula Na 4 (Mn x Fe 1-x ) 3 (PO 4 ) 2 PO 4 Wherein 0 < x < 1.
Further, in some embodiments, the coated sodium iron pyrophosphate has the formula Na 4 Fe 3 (PO 4 ) 2 PO 4 。
In addition, the invention also provides a preparation method of the ferric sodium pyrophosphate manganese iron material, which comprises the following steps:
s1, performing coprecipitation reaction on a manganese salt solution, a phosphorus source solution and an ammonia water solution in a parallel flow adding mode, and simultaneously, introducing an iron salt solution into the manganese salt solution in a continuous flow mode to form a phosphate precursor core; after the consumption of the manganese salt solution is finished, the rest ferric salt solution continues to carry out coprecipitation reaction with the phosphorus source solution and the ammonia water solution to form a ferrous phosphate layer outside the phosphate precursor core, and then the precursor particles are obtained by aging;
s2, mixing the precursor particles, the supplemented sodium source, the phosphorus source and the carbon source, and then ball milling to obtain a mixed material;
and S3, calcining the mixed material at a lower temperature under a protective atmosphere, and then preserving heat at a higher temperature to obtain the pyrophosphoric acid ferromanganese sodium iron material.
Further, in certain embodiments, in step S1, the concentrations of the iron salt solution and the manganese salt solution are the same, both being 0.1-2.0mol/L; and/or the concentration of the phosphorus source solution is 0.1-3.0mol/L; and/or the solubility of the ammonia water solution is 2-8mol/L; and/or in the step S1, the pH value of the coprecipitation reaction solution is 4-8, the temperature of the coprecipitation reaction is 40-80 ℃, the rotating speed of the coprecipitation reaction is 80-400 rpm, and the time of the coprecipitation reaction is 4-10 hours; and/or the flow speed of the manganese salt solution and the flow speed of the phosphorus source solution are the same, and the flow speed of the ferric salt solution is slower than the flow speed of the manganese salt.
Further, in some embodiments, in step S1, the aging is at a temperature of 40-80℃for a period of 4-10 hours.
Further, in some embodiments, in step S3, the temperature is raised at a temperature raising rate of 2-8 ℃/min, the calcination is performed at a lower temperature of 400-500 ℃ for 2-3 hours, and then the temperature is raised to a higher temperature of 600-800 ℃ and the heat is preserved for 8-18 hours, so that the sodium ferromanganese pyrophosphate material is obtained.
Further, in some embodiments, in step S2, the molar ratio of total metal ions in the precursor particles to sodium and phosphorus in the supplemental sodium and phosphorus sources, respectively, is 3 (4-5): 4-5; and/or the carbon source comprises one or more of citric acid, glucose, starch, urea, sucrose, beta cyclodextrin, graphene and carbon nanotubes; the sodium source includes one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, sodium dihydrogen phosphate, disodium hydrogen phosphate, and sodium pyrophosphate.
Further, in some embodiments, in step S1, the iron salt comprises one or more of ferrous sulfate, ferrous chloride, ferrous nitrate, and ferrous oxalate; the manganese salt comprises one or more of manganese oxalate, manganese sulfate, manganese nitrate and manganese acetate; the phosphorus source compound comprises one or more of phosphoric acid, diammonium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate and ammonium dihydrogen phosphate.
In addition, the invention also provides an application of the manganese iron sodium pyrophosphate material or the manganese iron sodium pyrophosphate material prepared by the preparation method in a battery as a positive electrode material.
Compared with the prior art, the invention has the beneficial effects that: the invention provides a ferric sodium manganese pyrophosphate material, which comprises a ferric sodium manganese pyrophosphate inner core and a ferric sodium pyrophosphate coating layer coated on the surface of the inner core; along the direction from the center of the inner core to the surface layer of the inner core, the content of manganese element in the inner core of the sodium ferromanganese pyrophosphate is reduced in a gradient manner, and the content of iron element is increased in a gradient manner. The material has the advantages of good stability and high conductivity of sodium ferric pyrophosphate, overcomes the defect of low voltage platform of sodium ferric pyrophosphate, and the problems of poor conductivity and low capacity retention rate of sodium manganese pyrophosphate, fully plays the advantages of a high voltage platform, and relieves the defect problem caused by John-Teller effect. The invention obviously improves the electrochemical sodium intercalation and deintercalation capability of the material and shows excellent electrochemical performance. In the charge-discharge cycle process, the material has higher specific discharge capacity and good cycle stability.
Drawings
FIG. 1 is a schematic diagram showing the concentration gradient distribution of manganese and iron elements in manganese iron phosphate precursor particles prepared in example 1;
FIG. 2 is a graph of the microscopic morphology of the sodium ferromanganese pyrophosphate material prepared in example 1;
FIG. 3 is an X-ray diffraction (XRD) pattern of the sodium ferromanganese pyrophosphate material prepared in example 1;
FIG. 4 is a charge-discharge curve of the sodium ferromanganese pyrophosphate prepared in example 1 and comparative example 1;
fig. 5 is a charge-discharge cycle chart of the sodium ferromanganese pyrophosphate material prepared in example 1 and comparative example 1.
Detailed Description
In the description of the present invention reference is made to "some embodiments," "this embodiment," and examples, etc., which describe a subset of all possible embodiments, but it is to be understood that "some embodiments" may be the same subset or different subsets of all possible embodiments and may be combined with one another without conflict.
The term "and/or" in the present invention is merely an association relation describing an associated object, and indicates that three relations may exist, for example, object a and/or object B may indicate: there are three cases where object a alone exists, object a and object B together, and object B alone exists.
The specific embodiment provides a sodium ferromanganese pyrophosphate material, which comprises a sodium ferromanganese pyrophosphate inner core and a sodium ferropyrophosphate coating layer coated on the surface of the inner core; along the direction from the center of the inner core to the surface layer of the inner core, the content of manganese element in the inner core of the sodium ferromanganese pyrophosphate is reduced in a gradient manner, and the content of iron element is increased in a gradient manner; further, the molecular formula of the sodium ferromanganese pyrophosphate with the inner core is Na 4 (Mn x Fe 1-x ) 3 (PO 4 ) 2 PO 4 Wherein 0 < x < 1; further, the molecular formula of the coated sodium iron pyrophosphate is Na 4 Fe 3 (PO 4 ) 2 PO 4 。
In addition, the specific embodiment also provides a preparation method of the ferric sodium pyrophosphate ferromanganese phosphate material, which comprises the following steps:
s1, performing coprecipitation reaction on a manganese salt solution, a phosphorus source solution and an ammonia water solution in a parallel flow adding mode, and simultaneously, introducing an iron salt solution into the manganese salt solution in a continuous flow mode to form a phosphate precursor core; after the consumption of the manganese salt solution is finished, the rest ferric salt solution continues to carry out coprecipitation reaction with the phosphorus source solution and the ammonia water solution to form a ferrous phosphate layer outside the phosphate precursor core, and then the precursor particles are obtained after aging for 4-10 hours at 40-80 ℃; the concentration of the ferric salt solution is 0.1-2.0mol/L as the concentration of the manganese salt solution is the same; and/or the concentration of the phosphorus source solution is 0.1-3.0mol/L; and/or the solubility of the ammonia water solution is 2-8mol/L; and/or in the step S1, the pH value of the coprecipitation reaction solution is 4-8, the temperature of the coprecipitation reaction is 40-80 ℃, the rotating speed of the coprecipitation reaction is 80-400 rpm, and the time of the coprecipitation reaction is 4-10 hours; the flow speeds of the manganese salt solution and the phosphorus source solution are the same, and the flow speed of the ferric salt solution is slower than that of the manganese salt; the ferric salt comprises one or more of ferrous sulfate, ferrous chloride, ferrous nitrate and ferrous oxalate; the manganese salt comprises one or more of manganese oxalate, manganese sulfate, manganese nitrate and manganese acetate; the phosphorus source compound comprises one or more of phosphoric acid, diammonium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate and ammonium dihydrogen phosphate;
s2, mixing the precursor particles, the supplemented sodium source, the phosphorus source and the carbon source, and then ball milling to obtain a mixed material; the molar ratio of the total metal ions in the precursor particles to the sodium and phosphorus in the supplemented sodium source and phosphorus source is 3 (4-5): 4-5; and/or the carbon source comprises one or more of citric acid, glucose, starch, urea, sucrose, beta cyclodextrin, graphene and carbon nanotubes; the sodium source comprises one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, sodium dihydrogen phosphate, disodium hydrogen phosphate and sodium pyrophosphate;
s3, calcining the mixed material at a lower temperature under a protective atmosphere, and then preserving heat at a higher temperature to obtain the pyrophosphoric acid ferromanganese sodium phosphate material; heating according to the heating rate of 2-8 ℃/min, calcining for 2-3 hours at the lower temperature of 400-500 ℃, and then heating to the higher temperature of 600-800 ℃ and preserving heat for 8-18 hours to obtain the sodium ferromanganese pyrophosphate material.
In addition, the specific embodiment also provides application of the ferric sodium pyrophosphate material or the ferric sodium pyrophosphate material prepared by the preparation method in a battery as a positive electrode material.
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the following examples, the prepared ferromanganese phosphate material comprises a ferromanganese phosphate core and a ferromanganese phosphate coating layer coated on the surface of the core; along the direction from the center of the inner core to the surface layer of the inner core, the manganese element content in the inner core is reduced in a gradient manner and the iron element content is increased in a gradient manner, and the molecular formula of the inner core sodium manganese pyrophosphate is Na 4 (Mn x Fe 1-x ) 3 (PO 4 ) 2 PO 4 Wherein 0 < x < 1. The molecular formula of the coated sodium iron pyrophosphate is Na 4 Fe 3 (PO 4 ) 2 PO 4 。
Example 1
The embodiment provides a sodium ferromanganese pyrophosphate anode material with concentration gradient distribution of iron and manganese elements, which is prepared by the following steps:
s1, respectively taking 1.5mol/L ferrous sulfate solution (FeSO 4 ) 110ml of a 1.5mol/L manganese sulfate solution (MnSO 4 ) 100ml, 1.0mol/L monoammonium phosphate solution (NH) 4 H 2 PO 4) 200ml and 4mol/L ammonia water, and the four solutions are fully and uniformly stirred. The ferrous sulfate solution is connected into the manganese sulfate solution through a peristaltic pump pipe, then the manganese sulfate solution, ammonium dihydrogen phosphate and ammonia water are added into a coprecipitation reaction kettle in parallel under the action of a peristaltic pump to participate in the coprecipitation reaction to form phosphate precursor cores, the peristaltic pump speeds corresponding to the manganese sulfate solution and the ammonium dihydrogen phosphate solution are kept consistent, the flow speeds are all 2ml/min, and the peristaltic pump speed corresponding to the ferrous sulfate solution is 1ml/min. In the reaction process, inert gas is always introduced as shielding gas. By adjusting fluidity of the added ammonia waterThe pH of the reaction solution in the reactor is controlled to be about 5.0+/-0.3. The reaction temperature in the kettle is controlled at 65 ℃, the stirring speed is controlled at 200 revolutions per minute, the consumption of manganese source solution is slightly less than that of other solutions, after the consumption of manganese salt solution is finished, the residual ferric salt solution continues to carry out coprecipitation reaction with phosphorus source solution and ammonia water solution to form a ferrous phosphate layer outside phosphate precursor nucleus, the total coprecipitation reaction time is 6 hours, then the mixture is aged for 8 hours, and precursor particles with iron and manganese elements in concentration gradient distribution are obtained after filtering, washing and drying, and the structural formula of the particles is (Fe x Mn 1-x ) 3 (PO 4 ) 2 The concentration gradient distribution diagram of manganese and iron elements is shown in figure 1, and the content of manganese element in the manganese iron phosphate core is reduced in a gradient manner and the content of iron element is increased in a gradient manner along the direction from the center of the particle to the surface layer of the particle;
s2, 7.13g of precursor particles are taken in a ball milling tank, and 5.68g of disodium hydrogen phosphate (Na 2 HPO 4 ) As phosphoric acid and sodium source, leading Na (Fe+Mn): P=4:3:4 in the mixture, introducing 2.8g glucose as carbon source, adding proper amount of ethanol as ball milling medium, and ball milling for 4h in a ball mill at the rotating speed of 300r/min; drying the obtained slurry in a drying oven at 100 ℃ for 8 hours, and removing balls to obtain a mixed material;
s3, placing the material in an inert atmosphere furnace, heating up at a heating rate of 5 ℃/min under an argon protective atmosphere, presintering for 2h at 400 ℃, heating up to 600 ℃, preserving heat for 8h, and naturally cooling to obtain the manganese iron sodium pyrophosphate anode material with iron and manganese elements distributed in a full-concentration gradient mode.
The preparation of the positive pole piece is as follows:
the prepared ferromanganese pyrophosphate sodium iron material is weighed, acetylene black is added as a conductive agent, PVDF is used as a binder, mixed slurry is obtained after full grinding, and a proper amount of N-methyl pyrrolidone (NMP) is added for mixing to form uniform black pasty slurry (wherein the ferromanganese pyrophosphate sodium material is 80% of the mass of the mixture, the acetylene black is 10% of the mass of the mixture, and the PVDF is 10% of the mass of the mixture). The obtained slurry is coated on an aluminum foil, placed in a vacuum oven at 120 ℃ for drying for 8 hours, cut into round pole pieces with the diameter of 14mm by a cutting machine, and the pole pieces are manufactured into CR2025 button cells in a high-purity argon glove box. And (3) carrying out constant-current charge and discharge test at room temperature (25 ℃) under the limit voltage of 1.7-4.3V. Wherein the electrolyte system is 1MNAPF6/EC: DMC (1:1) +5% FEC.
The concentration gradient distribution schematic diagram of manganese and iron elements in the precursor of the sodium ferromanganese pyrophosphate anode material is shown in figure 1; a microscopic morphology diagram of the precursor of the ferric sodium pyrophosphate anode material is shown in fig. 2; the X-ray diffraction (XRD) pattern of the prepared manganese iron sodium pyrophosphate positive electrode material is shown in figure 3, and figure 3 shows that the manganese iron sodium pyrophosphate material is successfully synthesized; the charge-discharge curve graph and the charge-discharge cycle graph of the present example are shown in FIGS. 4 and 5, the initial effect reaches 92.4% and the specific discharge capacity reaches 110.48 mAh.g at a rate of 0.2C -1 The method comprises the steps of carrying out a first treatment on the surface of the At a rate of 1C, the specific discharge capacity reaches 95.42 mAh.g -1 The method comprises the steps of carrying out a first treatment on the surface of the Meanwhile, the charge and discharge efficiency of 600 times of circulation at the 1C multiplying power is kept at about 92.6%, and the high-stability lithium ion battery has good stability.
Example 2
The embodiment provides a sodium ferromanganese pyrophosphate anode material with concentration gradient distribution of iron and manganese elements, which is prepared by the following steps:
s1, respectively taking 2mol/L ferrous sulfate solution (FeSO) 4 ) 55ml, 2mol/L manganese sulfate solution (MnSO 4 ) 50ml, 1.5mol/L monoammonium phosphate solution (NH) 4 H 2 PO 4 ) 95ml and 6mol/L ammonia water, and the four solutions are fully and uniformly stirred. The ferrous sulfate solution is connected into the manganese sulfate solution through a peristaltic pump pipe, then the manganese sulfate solution, ammonium dihydrogen phosphate and ammonia water are added into a coprecipitation reaction kettle in parallel under the action of a peristaltic pump to participate in the coprecipitation reaction to form phosphate precursor cores, the peristaltic pump speeds corresponding to the manganese sulfate solution and the ammonium dihydrogen phosphate solution are kept consistent, the flow speeds are all 2ml/min, and the peristaltic pump speed corresponding to the ferrous sulfate solution is 1ml/min. In the reaction process, inert gas is always introduced as shielding gas. The pH of the reaction solution in the kettle is controlled to be about 6.5+/-0.3 by adjusting the fluidity of the added ammonia water. Reaction temperature in the kettleControlling the temperature at 80 ℃, controlling the stirring speed at 200 revolutions per minute, controlling the consumption of a manganese source solution to be slightly less than that of other solutions, continuously performing coprecipitation reaction on the rest ferric salt solution, the phosphorus source solution and an ammonia water solution after the consumption of the manganese salt solution is finished, forming a ferrous phosphate layer outside a phosphate precursor core, wherein the total coprecipitation reaction time is 8 hours, aging for 8 hours, filtering, washing and drying to obtain precursor particles with iron and manganese elements distributed in concentration gradient.
S2, 7.13g of precursor particles are taken in a ball milling tank, and 5.68g of disodium hydrogen phosphate (Na 2 HPO 4 ) As phosphoric acid and sodium source, leading Na (Fe+Mn): P=4:3:4 in the mixture, introducing 3.5g of starch as carbon source, adding proper amount of ethanol as ball milling medium, and ball milling for 4 hours at the rotating speed of 300r/min; drying the obtained slurry in a drying oven at 100 ℃ for 8 hours, and removing balls to obtain a mixed material;
s3, placing the material in an inert atmosphere furnace, heating up at a heating rate of 8 ℃/min under an argon protective atmosphere, presintering for 2h at 400 ℃, heating up to 600 ℃, preserving heat for 8h, and naturally cooling to obtain the manganese iron sodium pyrophosphate anode material with iron and manganese elements distributed in a full-concentration gradient mode.
The sodium ferromanganese pyrophosphate material prepared in the embodiment is used as a positive electrode active material to prepare a positive electrode plate, and the positive electrode plate and the sodium plate are assembled into a button cell for electrochemical performance test. Through testing, the button cell assembled by the embodiment has the initial effect of 91.6% and the specific discharge capacity of 99.48 mAh.g under the multiplying power of 0.2C -1 The method comprises the steps of carrying out a first treatment on the surface of the At a rate of 1C, the specific discharge capacity reaches 93.45 mAh.g -1 The method comprises the steps of carrying out a first treatment on the surface of the Meanwhile, the charge and discharge efficiency of 600 cycles at the 1C multiplying power is kept at about 90.2%.
Example 3
The embodiment provides a sodium ferromanganese pyrophosphate anode material with concentration gradient distribution of iron and manganese elements, which is prepared by the following steps:
s1, respectively taking 1.5mol/L ferrous sulfate solution (FeSO 4 ) 105ml of 1.5mol/L manganese sulfate (MnSO 4 ) 100ml, 1.0mol/L monoammonium phosphate (NH) 4 H 2 PO 4 ) 200ml and 4mol/L ammonia water, and the four solutions are fully and uniformly stirred. The ferrous sulfate solution is connected into the manganese sulfate solution through a peristaltic pump pipe, then the manganese sulfate solution, ammonium dihydrogen phosphate and ammonia water are added into a coprecipitation reaction kettle in parallel under the action of a peristaltic pump to participate in the coprecipitation reaction to form phosphate precursor cores, the peristaltic pump speeds corresponding to the manganese sulfate solution and the ammonium dihydrogen phosphate solution are kept consistent, the flow speeds are all 2ml/min, and the peristaltic pump speed corresponding to the ferrous sulfate solution is 1ml/min. In the reaction process, inert gas is always introduced as shielding gas. The pH of the reaction solution in the kettle is controlled to be about 5.0+/-0.3 by adjusting the fluidity of the added ammonia water. After the consumption of the manganese source solution is slightly less than that of other solutions, the residual ferric salt solution continues to carry out coprecipitation reaction with the phosphorus source solution and the ammonia water solution to form a ferrous phosphate layer outside the phosphate precursor core, the total coprecipitation reaction time is 6 hours, the obtained product is aged for 8 hours, filtered, washed and dried, and then precursor particles with iron and manganese elements in concentration gradient distribution are obtained.
S2, 7.13g of precursor particles are taken in a ball milling tank, and 5.68g of disodium hydrogen phosphate (Na 2 HPO 4 ) As phosphoric acid and sodium source, na (Fe+Mn): P=4:3:4 in the mixture, 4.2g of citric acid is introduced as carbon source, and then proper amount of ethanol is added as ball milling medium, so that the material is thoroughly mixed. Finally, placing the mixture in a ball mill for ball milling for 4 hours at the rotating speed of 300r/min; the resulting slurry was dried in an oven at 100 ℃ for 8h and deagglomerated to give a mixture.
And S3, placing the material in an inert atmosphere furnace, heating up at a heating rate of 2 ℃/min under an argon protective atmosphere, presintering for 2h at 350 ℃, heating up to 550 ℃, preserving heat for 10h, and naturally cooling to obtain the manganese iron sodium pyrophosphate anode material with iron and manganese elements distributed in a full-concentration gradient manner.
The sodium ferromanganese pyrophosphate material prepared in the embodiment is used as a positive electrode active material to prepare a positive electrode plate, and the positive electrode plate and the sodium plate are assembled into a button cell for electrochemical performance test. Through testing, the button cell assembled by the embodiment has the initial effect reaching 90.3% and the specific discharge capacity reaching 101.32 mAh.g under the multiplying power of 0.2C -1 The method comprises the steps of carrying out a first treatment on the surface of the Discharge ratio at a magnification of 1CThe capacity reaches 91.12 mAh.g -1 The method comprises the steps of carrying out a first treatment on the surface of the Meanwhile, the charge and discharge efficiency of 600 cycles at the 1C multiplying power is kept at about 89.4%.
Example 4
The embodiment provides a sodium ferromanganese pyrophosphate anode material with concentration gradient distribution of iron and manganese elements, which is prepared by the following steps:
s1, respectively preparing 1.5mol/L ferrous acetate ((CH) 3 COO) 2 Fe) 120ml, 1.5mol/L manganese acetate ((CH) 3 COO) 2 Mn) 100ml, 1.0mol/L phosphoric acid (H) 3 PO 4 ) 210ml and 8mol/L ammonia water, and the four solutions are fully and uniformly stirred. The ferrous sulfate solution is connected into the manganese sulfate solution through a peristaltic pump pipe, then the manganese sulfate solution, ammonium dihydrogen phosphate and ammonia water are added into a coprecipitation reaction kettle in parallel under the action of a peristaltic pump to participate in the coprecipitation reaction to form phosphate precursor cores, peristaltic pump speeds corresponding to the manganese acetate solution and the phosphoric acid solution are kept consistent, the flowing speeds are all 2ml/min, and the peristaltic pump speed corresponding to the ferrous acetate solution is 1ml/min. In the reaction process, inert gas is always introduced as shielding gas. The pH of the reaction solution in the kettle is controlled to be about 6.0+/-0.3 by adjusting the fluidity of the added ammonia water. The reaction temperature in the kettle is controlled at 65 ℃, the stirring speed is controlled at 200 revolutions per minute, the consumption of the manganese source solution is slightly less than that of other solutions, after the consumption of the manganese salt solution is finished, the rest ferric salt solution continues to carry out coprecipitation reaction with the phosphorus source solution and the ammonia water solution to form a ferrous phosphate layer outside the phosphate precursor core, the total coprecipitation reaction time is 6 hours, then the precursor is aged for 8 hours, and the precursor particles with the concentration gradient distribution of the iron and the manganese elements are obtained after filtering, washing and drying.
S2, 7.13g of precursor particles are taken in a ball milling tank, and 5.318g of sodium pyrophosphate (Na 4 P 2 O 7 ) As phosphoric acid and sodium source, na (Fe+Mn): P=4:3:4 in the mixture, introducing 2.03g of carbon nano tube as carbon source, adding proper amount of ethanol as ball milling medium, and passing through the material. Finally, the mixture is placed in a ball mill for ball milling for 4 hours at the rotating speed of 300r/min. Drying the obtained slurry in a drying oven at 100 ℃ for 8 hours, and removing balls to obtain a mixed material;
and S3, placing the material in an inert atmosphere furnace, heating up at a heating rate of 8 ℃/min under an argon protective atmosphere, presintering for 1h at 400 ℃, heating up to 610 ℃, preserving heat for 8h, and naturally cooling to obtain the manganese iron sodium pyrophosphate anode material with iron and manganese elements distributed in a full-concentration gradient manner.
The sodium ferromanganese pyrophosphate material prepared in the embodiment is used as a positive electrode active material to prepare a positive electrode plate, and the positive electrode plate and the sodium plate are assembled into a button cell for electrochemical performance test. Through testing, the button cell assembled by the embodiment has the initial effect reaching 90.7% and the specific discharge capacity reaching 99.35 mAh.g under the multiplying power of 0.2C -1 The method comprises the steps of carrying out a first treatment on the surface of the The specific discharge capacity reaches 92.64 mAh.g under the multiplying power of 1C -1 The method comprises the steps of carrying out a first treatment on the surface of the Meanwhile, the charge and discharge efficiency of 600 cycles at the 1C multiplying power is kept at about 91.6%.
Comparative example 1
The difference between this comparative example and example 1 is mainly that the iron source solution is not connected into the manganese source solution any more, but is combined into the coprecipitation reaction kettle together with the other three sets of solution raw materials, comprising the following steps:
s1, respectively preparing 2mol/L ferrous sulfate (FeSO) 4 ) 55ml, 2mol/L manganese sulfate (MnSO 4 ) 50ml, 1.5mol/L monoammonium phosphate (NH) 4 H 2 PO 4 ) 100ml and 6mol/L ammonia water, the four solutions are fully and uniformly stirred, and are added into a coprecipitation reaction kettle in parallel under the action of a peristaltic pump to participate in the coprecipitation reaction, the peristaltic pump speeds corresponding to the manganese sulfate solution and the ammonium dihydrogen phosphate are kept consistent, the flowing speeds are all 2ml/min, and the peristaltic pump speed corresponding to the ferrous sulfate solution is 1ml/min. In the reaction process, inert gas is always introduced as shielding gas. The pH of the reaction solution in the kettle is controlled to be about 5.5+/-0.3 by adjusting the fluidity of the added ammonia water. The reaction temperature in the kettle is controlled at 60 ℃, the stirring speed is controlled at 200 revolutions per minute, the total reaction time of coprecipitation reaction is 6 hours, then the reaction time is aged for 6 hours, and the precursor particles of the iron and manganese elements without concentration gradient distribution are obtained after filtering, washing and drying.
S2, 7.13g of precursor particles are taken in a ball milling tank, and 5.68g of disodium hydrogen phosphate (Na 2 HPO 4 ) As phosphoric acid and sodium source, leading Na (Fe+Mn): P=4:3:4 in the mixture, introducing 3.5g of starch as carbon source, adding proper amount of ethanol as ball milling medium, and placing the mixture in a ball mill for ball milling for 4 hours at the rotating speed of 300r/min; the resulting slurry was dried in an oven at 100 ℃ for 8h and deagglomerated to give a mixture.
And S3, placing the material in an inert atmosphere furnace, heating up at a heating rate of 5 ℃/min under the protection of argon, presintering for 2h at 400 ℃, heating up to 600 ℃, preserving heat for 8h, and naturally cooling to obtain the ferric sodium manganese pyrophosphate anode material.
The sodium ferromanganese pyrophosphate material prepared in the comparative example is used as a positive electrode active material to prepare a positive electrode plate, and the positive electrode plate and the sodium plate are assembled into a button cell for electrochemical performance test. As shown in FIGS. 4 and 5, the charge-discharge curve graph and the charge-discharge cycle graph of the comparative example show that the initial effect reaches 86.9% and the specific discharge capacity reaches 96.31 mAh.g at a rate of 0.2C -1 The method comprises the steps of carrying out a first treatment on the surface of the At a rate of 1C, the specific discharge capacity reaches 89.52 mAh.g -1 The method comprises the steps of carrying out a first treatment on the surface of the Meanwhile, the charge and discharge efficiency of 600 cycles at the 1C multiplying power is kept at about 68.3%.
Comparative example 2
The difference between this comparative example and example 1 is mainly that the iron source solution is not connected into the manganese source solution any more, but is combined into the coprecipitation reaction kettle together with the other three sets of solution raw materials, comprising the following steps:
s1, respectively preparing 1.5mol/L ferrous sulfate (FeSO) 4 ) 110ml, 1.5mol/L manganese sulfate (MnSO 4 ) 100ml, 1mol/L monoammonium phosphate (NH) 4 H 2 PO 4 ) 200ml and 4mol/L ammonia water, the four solutions are fully and uniformly stirred, and are added into a coprecipitation reaction kettle in parallel under the action of a peristaltic pump to participate in coprecipitation reaction, the peristaltic pump speeds corresponding to the manganese sulfate solution and the ammonium dihydrogen phosphate are kept consistent, the flowing speeds are all 2ml/min, and the peristaltic pump speed corresponding to the ferrous sulfate solution is 1ml/min. In the reaction process, inert gas is always introduced as shielding gas. The pH of the reaction solution in the kettle is controlled to be about 8+/-0.3 by adjusting the fluidity of the added ammonia water. The reaction temperature in the kettle is controlled at 80 ℃, and the stirring speed is controlledAnd (3) at 300 rpm, the total time of the coprecipitation reaction is 6 hours, then the mixture is aged for 8 hours, and the precursor particles with concentration gradient distribution of iron and manganese elements are obtained after filtration, washing and drying.
S2, 7.13g of precursor particles are taken in a ball milling tank, and 5.318g of sodium pyrophosphate (Na 4 P 2 O 7 ) As phosphoric acid and sodium source, na (Fe+Mn): P=4:3:4 in the mixture, 3.1g of citric acid and 0.8g of carbon nano tube are introduced as carbon source, and then proper amount of ethanol is added as ball milling medium, so that the material is thoroughly mixed. Finally, placing the mixture in a ball mill for ball milling for 4 hours at the rotating speed of 300r/min. The resulting slurry was dried in an oven at 100 ℃ for 8h and deagglomerated to give a mixture.
And S3, placing the material in an inert atmosphere furnace, heating up at a heating rate of 5 ℃/min under the protection of argon, presintering for 2h at 400 ℃, heating up to 600 ℃, preserving heat for 8h, and naturally cooling to obtain the ferric sodium manganese pyrophosphate anode material.
The sodium ferromanganese pyrophosphate material prepared in the comparative example is used as a positive electrode active material to prepare a positive electrode plate, and the positive electrode plate and the sodium plate are assembled into a button cell for electrochemical performance test. Through testing, the button cell assembled by the comparative example has the initial effect reaching 79.5 percent and the specific discharge capacity reaching 88.17 mAh.g under the multiplying power of 0.2C -1 The method comprises the steps of carrying out a first treatment on the surface of the At a rate of 1C, the specific discharge capacity reaches 80.42 mAh.g -1 The method comprises the steps of carrying out a first treatment on the surface of the Meanwhile, the charge and discharge efficiency of 600 cycles at the 1C multiplying power is kept at about 58.4%.
The performance data obtained for the materials obtained in examples 1-4 and comparative examples 1-2 are shown in Table 1.
TABLE 1 results of Performance test of the materials prepared in examples 1-4 and comparative examples 1-2
Compared with the prior art, the invention has the following remarkable advantages:
1. the invention relates to a method for controlling the morphology and the particle size of a product sodium ferromanganese pyrophosphate by controlling the morphology and the particle size of a precursor. The obtained product has the characteristic that the iron and manganese elements in the obtained product show full concentration gradient distribution in the sodium ferromanganese pyrophosphate core crystal.
2. The invention focuses on starting from precursor preparation, realizes concentration gradient distribution of manganese and iron elements in the precursor by changing the preparation method of the precursor, and obtains the high-performance ferric sodium manganese pyrophosphate anode material with concentration gradient distribution of manganese and iron elements through solid phase reaction. The invention provides a simple, easy-to-maintain and control technology process, which can realize the controllability of the morphology and the particle size of the product and effectively solve the distribution problem of ferromanganese in the material, thereby obtaining the high-performance ferric sodium manganese pyrophosphate anode material. The new process has the characteristics of low energy consumption and low cost, and is suitable for large-scale industrial production. The invention can produce high-performance ferric sodium ferromanganese pyrophosphate anode material and provides a reliable solution for the field of batteries. The technology not only improves the performance of the material, but also realizes the optimization of resource utilization in the production process, and has good economic benefit.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any other corresponding changes and modifications made in accordance with the technical idea of the present invention shall be included in the scope of the claims of the present invention.
Claims (10)
1. The ferromanganese sodium pyrophosphate material is characterized by comprising a ferromanganese sodium pyrophosphate inner core and a ferromanganese sodium pyrophosphate coating layer coated on the surface of the inner core; along the direction from the center of the inner core to the surface layer of the inner core, the content of manganese element in the inner core of the sodium ferromanganese pyrophosphate is reduced in a gradient manner, and the content of iron element is increased in a gradient manner.
2. The manganese iron sodium pyrophosphate material of claim 1 wherein the core manganese iron sodium pyrophosphate has the formula Na 4 (Mn x Fe 1-x ) 3 (PO 4 ) 2 PO 4 Wherein 0 < x < 1.
3. The sodium ferromanganese pyrophosphate material of claim 2 wherein the coated sodium iron pyrophosphate has a molecular formula of Na 4 Fe 3 (PO 4 ) 2 PO 4 。
4. A method for preparing the ferric sodium pyrophosphate material according to any one of claims 1 to 3, comprising the steps of:
s1, performing coprecipitation reaction on a manganese salt solution, a phosphorus source solution and an ammonia water solution in a parallel flow adding mode, and simultaneously, introducing an iron salt solution into the manganese salt solution in a continuous flow mode to form a phosphate precursor core; after the consumption of the manganese salt solution is finished, the rest ferric salt solution continues to carry out coprecipitation reaction with the phosphorus source solution and the ammonia water solution to form a ferrous phosphate layer outside the phosphate precursor core, and then the precursor particles are obtained by aging;
s2, mixing the precursor particles, the supplemented sodium source, the phosphorus source and the carbon source, and then ball milling to obtain a mixed material;
and S3, calcining the mixed material at a lower temperature under a protective atmosphere, and then preserving heat at a higher temperature to obtain the pyrophosphoric acid ferromanganese sodium iron material.
5. The method for producing a manganese iron sodium pyrophosphate material according to claim 4, characterized in that in step S1, the concentrations of said iron salt solution and said manganese salt solution are the same, both being 0.1 to 2.0mol/L; and/or the concentration of the phosphorus source solution is 0.1-3.0mol/L; and/or the solubility of the ammonia water solution is 2-8mol/L; and/or in the step S1, the pH value of the coprecipitation reaction solution is 4-8, the temperature of the coprecipitation reaction is 40-80 ℃, the rotating speed of the coprecipitation reaction is 80-400 rpm, and the time of the coprecipitation reaction is 4-10 hours; and/or the flow speed of the manganese salt solution and the flow speed of the phosphorus source solution are the same, and the flow speed of the ferric salt solution is slower than the flow speed of the manganese salt.
6. The method for preparing a sodium ferromanganese pyrophosphate material according to claim 4, wherein the aging temperature is 40-80 ℃ and the time is 4-10 hours in the step S1.
7. The method for producing a sodium ferromanganese pyrophosphate material according to claim 4, wherein in step S3, the sodium ferromanganese pyrophosphate material is obtained by heating up at a heating rate of 2 to 8 ℃/min, calcining at a lower temperature of 400 to 500 ℃ for 2 to 3 hours, and then heating up to a higher temperature of 600 to 800 ℃ and preserving heat for 8 to 18 hours.
8. The method for producing a manganese iron sodium pyrophosphate material according to claim 4, characterized in that in step S2, the molar ratio of total metal ions in said precursor particles to sodium and phosphorus in the fed sodium source and phosphorus source, respectively, is 3 (4-5): 4-5; and/or the carbon source comprises one or more of citric acid, glucose, starch, urea, sucrose, beta cyclodextrin, graphene and carbon nanotubes; the sodium source includes one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, sodium dihydrogen phosphate, disodium hydrogen phosphate, and sodium pyrophosphate.
9. The method of preparing a ferric sodium pyrophosphate material according to claim 4, wherein in step S1, the iron salt comprises one or more of ferrous sulfate, ferrous chloride, ferrous nitrate and ferrous oxalate; the manganese salt comprises one or more of manganese oxalate, manganese sulfate, manganese nitrate and manganese acetate; the phosphorus source compound comprises one or more of phosphoric acid, diammonium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate and ammonium dihydrogen phosphate.
10. Use of the sodium ferromanganese pyrophosphate material of any one of claims 1-3 or the sodium ferromanganese pyrophosphate material of any one of claims 4-9 as a positive electrode material in a battery.
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