CN116262609A - Preparation method of polyanion compound and application of polyanion compound in alkali metal ion battery - Google Patents
Preparation method of polyanion compound and application of polyanion compound in alkali metal ion battery Download PDFInfo
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- CN116262609A CN116262609A CN202111539107.XA CN202111539107A CN116262609A CN 116262609 A CN116262609 A CN 116262609A CN 202111539107 A CN202111539107 A CN 202111539107A CN 116262609 A CN116262609 A CN 116262609A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229920000447 polyanionic polymer Polymers 0.000 title claims abstract description 25
- 229910001413 alkali metal ion Inorganic materials 0.000 title claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 191
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 133
- 238000010438 heat treatment Methods 0.000 claims abstract description 97
- 238000000498 ball milling Methods 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 44
- 238000002156 mixing Methods 0.000 claims abstract description 34
- 238000001816 cooling Methods 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 105
- 229910052734 helium Inorganic materials 0.000 claims description 88
- 239000001307 helium Substances 0.000 claims description 88
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 88
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 75
- 229910052698 phosphorus Inorganic materials 0.000 claims description 46
- 229910052720 vanadium Inorganic materials 0.000 claims description 42
- 235000015165 citric acid Nutrition 0.000 claims description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 23
- 239000002105 nanoparticle Substances 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 18
- 229910052742 iron Inorganic materials 0.000 claims description 16
- 229910052748 manganese Inorganic materials 0.000 claims description 13
- 239000007774 positive electrode material Substances 0.000 claims description 11
- 229930091371 Fructose Natural products 0.000 claims description 9
- 239000005715 Fructose Substances 0.000 claims description 9
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 9
- 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 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 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 9
- 229930006000 Sucrose Natural products 0.000 claims description 9
- 239000011668 ascorbic acid Substances 0.000 claims description 9
- 235000010323 ascorbic acid Nutrition 0.000 claims description 9
- 229960005070 ascorbic acid Drugs 0.000 claims description 9
- 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 9
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 239000008103 glucose Substances 0.000 claims description 9
- 235000001727 glucose Nutrition 0.000 claims description 9
- 235000006408 oxalic acid Nutrition 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 239000005720 sucrose Substances 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 3
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 3
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims 1
- 150000001649 bromium compounds Chemical class 0.000 claims 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims 1
- 150000001805 chlorine compounds Chemical class 0.000 claims 1
- 150000002222 fluorine compounds Chemical class 0.000 claims 1
- 150000004679 hydroxides Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 150000003891 oxalate salts Chemical class 0.000 claims 1
- 235000021317 phosphate Nutrition 0.000 claims 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 1
- 150000003568 thioethers Chemical class 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 23
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 80
- 239000000463 material Substances 0.000 description 73
- GLMOMDXKLRBTDY-UHFFFAOYSA-A [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GLMOMDXKLRBTDY-UHFFFAOYSA-A 0.000 description 69
- 239000012002 vanadium phosphate Substances 0.000 description 69
- 239000011734 sodium Substances 0.000 description 65
- 229910002804 graphite Inorganic materials 0.000 description 61
- 239000010439 graphite Substances 0.000 description 61
- 239000011572 manganese Substances 0.000 description 47
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 45
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 45
- 235000019837 monoammonium phosphate Nutrition 0.000 description 45
- 239000002243 precursor Substances 0.000 description 44
- 235000013024 sodium fluoride Nutrition 0.000 description 40
- 239000011775 sodium fluoride Substances 0.000 description 40
- 239000007790 solid phase Substances 0.000 description 38
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 36
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 36
- 239000011574 phosphorus Substances 0.000 description 36
- 239000000203 mixture Substances 0.000 description 34
- 239000006012 monoammonium phosphate Substances 0.000 description 32
- 238000000227 grinding Methods 0.000 description 31
- 229910001415 sodium ion Inorganic materials 0.000 description 31
- 239000011777 magnesium Substances 0.000 description 30
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 28
- 239000011651 chromium Substances 0.000 description 24
- 235000011121 sodium hydroxide Nutrition 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 239000007795 chemical reaction product Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 22
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 22
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 description 21
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 20
- 239000007789 gas Substances 0.000 description 20
- 229910052708 sodium Inorganic materials 0.000 description 20
- 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 19
- -1 amide compounds Chemical class 0.000 description 18
- 239000012535 impurity Substances 0.000 description 17
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 17
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000000843 powder Substances 0.000 description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 14
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 13
- 238000001035 drying Methods 0.000 description 13
- 229910000398 iron phosphate Inorganic materials 0.000 description 13
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 12
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 12
- 239000011737 fluorine Substances 0.000 description 12
- 229910052731 fluorine Inorganic materials 0.000 description 12
- 229910052749 magnesium Inorganic materials 0.000 description 11
- 238000003980 solgel method Methods 0.000 description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 10
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 10
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 10
- 235000019838 diammonium phosphate Nutrition 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 235000011007 phosphoric acid Nutrition 0.000 description 10
- 238000005245 sintering Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 8
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- 235000017550 sodium carbonate Nutrition 0.000 description 7
- 229920002994 synthetic fiber Polymers 0.000 description 7
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 6
- 239000004137 magnesium phosphate Substances 0.000 description 6
- 229960002261 magnesium phosphate Drugs 0.000 description 6
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 6
- 235000010994 magnesium phosphates Nutrition 0.000 description 6
- 229940071125 manganese acetate Drugs 0.000 description 6
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 6
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 5
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 description 5
- 229910001935 vanadium oxide Inorganic materials 0.000 description 5
- 239000005696 Diammonium phosphate Substances 0.000 description 4
- 229910000628 Ferrovanadium Inorganic materials 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 229910001222 NaVPO4F Inorganic materials 0.000 description 4
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 description 4
- 238000000713 high-energy ball milling Methods 0.000 description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 4
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- ZRPYRHACYVTJHG-UHFFFAOYSA-L sodium fluoro-dioxido-oxo-lambda5-phosphane manganese(2+) Chemical compound P(=O)([O-])([O-])F.[Mn+2].[Na+] ZRPYRHACYVTJHG-UHFFFAOYSA-L 0.000 description 4
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 229910017855 NH 4 F Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 3
- 235000011285 magnesium acetate Nutrition 0.000 description 3
- 239000011654 magnesium acetate Substances 0.000 description 3
- 229940069446 magnesium acetate Drugs 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- ZBNAQSDJSAIZSF-UHFFFAOYSA-L P(=O)([O-])([O-])F.[Cr+3].[V+5].[Na+] Chemical compound P(=O)([O-])([O-])F.[Cr+3].[V+5].[Na+] ZBNAQSDJSAIZSF-UHFFFAOYSA-L 0.000 description 2
- CHQMXRZLCYKOFO-UHFFFAOYSA-H P(=O)([O-])([O-])F.[V+5].[Na+].P(=O)([O-])([O-])F.P(=O)([O-])([O-])F Chemical compound P(=O)([O-])([O-])F.[V+5].[Na+].P(=O)([O-])([O-])F.P(=O)([O-])([O-])F CHQMXRZLCYKOFO-UHFFFAOYSA-H 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 description 1
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZCZNSUUONOWGBP-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Mn+2].[V+5].[Na+] Chemical compound P(=O)([O-])([O-])[O-].[Mn+2].[V+5].[Na+] ZCZNSUUONOWGBP-UHFFFAOYSA-K 0.000 description 1
- QAUGYFLWKAIBLZ-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Na+].[V+5].[Fe+2] Chemical compound P(=O)([O-])([O-])[O-].[Na+].[V+5].[Fe+2] QAUGYFLWKAIBLZ-UHFFFAOYSA-K 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 description 1
- ICCUNKAUJJAHGX-UHFFFAOYSA-D [V+5].[V+5].[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O Chemical compound [V+5].[V+5].[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O ICCUNKAUJJAHGX-UHFFFAOYSA-D 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- HEVWJXJIIXJVKU-UHFFFAOYSA-K sodium;manganese(2+);phosphate Chemical compound [Na+].[Mn+2].[O-]P([O-])([O-])=O HEVWJXJIIXJVKU-UHFFFAOYSA-K 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/455—Phosphates containing halogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a polyanion compound, which comprises the following steps: mixing raw materials I containing M source, carbon source and X source, and heat treating in inactive atmosphere I to obtain carbon-coated MXO e The method comprises the steps of carrying out a first treatment on the surface of the The time of the heat treatment I is 1-20 h; the carbon-coated MXO obtained in the step (1) e Ball milling to obtain nano carbon coated MXO e The method comprises the steps of carrying out a first treatment on the surface of the Mixing raw materials III containing N source and X source, and heat treating III in inactive atmosphere III to obtain NXO e The method comprises the steps of carrying out a first treatment on the surface of the Containing said nanoRice grade carbon coated MXO e The NXO e Mixing a raw material II of a source A, a source X and a source D, performing heat treatment II in an atmosphere II, and then cooling in the atmosphere II to obtain the polyanion compound; the time of the heat treatment II is 2-20 h. The invention can realize the synthesis of high-purity polyanion compound and fully exert the capacity and stability of the synthesized electrode material.
Description
Technical Field
The invention relates to an alkali metal ion battery positive electrode material, belongs to the field of alkali metal ion batteries, and in particular relates to a preparation method of a polyanion compound and application of the polyanion compound in an alkali metal ion battery.
Background
The alkali metal cell system has similar structure and operation principle, and the sodium ion cell is taken as an example for the description below. The sodium ion battery realizes the conversion of chemical energy and electric energy by the deintercalation of sodium ions in the anode material and the cathode material. Alkali metal batteries have a broad potential for use in power cells and large-scale energy storage.
Sodium ion battery products that have been reported to date mainly include three categories: oxides, prussian blues and polyanionic compounds. Compared with the former two systems, polyanion compounds such as vanadium sodium phosphate, vanadium sodium fluorophosphate, ferric sodium phosphate, manganese sodium phosphate and various binary or multi-element transition metal compounds such as vanadium manganese sodium phosphate and vanadium iron sodium phosphate become preferable positive electrode materials of sodium ion batteries with high specific energy, high specific power and high stability due to the advantages of stable structure, rapid sodium diffusion, high safety and the like.
The conventional methods for preparing the polyanion compound at present comprise a sol-gel method, a solid phase high temperature sintering method, a water bath solvothermal method and the like. In the existing sol-gel method, the solid phase method is often insufficient or uneven in precursor mixing, so that transition metal oxide with higher melting point (such as MnO melting point of 1650 ℃ and Cr) exists in precursor synthesized by polyanion compound 2 O 3 Melting point is 2266 ℃, fe 2 O 3 Melting point 1565 ℃, V 2 O 3 The melting point is 1970 ℃, and transition metal oxide with higher melting point is in a solid phase in the high-temperature sintering process, so incomplete conversion is very easy to occur, the purity of the final product is lower, the advantages of raw materials cannot be fully exerted, and the prepared polyanion type positive electrode material has the problems of lower capacity, poor stability and the like.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for preparing a polyanionic compound, which can synthesize a polyanionic compound having high purity.
In one aspect, the present invention provides a method of preparing a polyanionic compound having a structure represented by formula I:
A 1+q (M 1-b N b ) y (XO e ) z D d a formula I;
in formula I:
a is at least one of Li, na and K;
m is selected from at least one of Fe, mn, ni, co, V, cr;
n is selected from at least one of Nb, Y, mg, B, ti, cu, zr, al;
x is selected from at least one of P, S, V, si, nb, mo, al, B;
d is at least one selected from F, OH, cl, br;
-0.2≤q≤3；0.9≤y≤2；0≤d≤4；1≤z≤3；1≤e≤4；0≤b≤0.1；
wherein 1+q is multiplied by the valence of A by n 1 Y and M 1-b N b Valence product n of (2) 2 Z and XO 4 Valence product n of (2) 3 Price product n of D and D 4 ；n 1 +n 2 +n 3 +n 4 =0 to keep the material electrically neutral.
The preparation method of the polyanion compound comprises the following steps:
Step (1), mixing raw materials I containing an M source, a carbon source and an X source, and performing heat treatment I in an inactive atmosphere I to obtain carbon-coated MXO e The method comprises the steps of carrying out a first treatment on the surface of the The time of the heat treatment I is 1-20 h;
step (2), the carbon-coated MXO obtained in the step (1) e Ball milling to obtain nano carbon coated MXO e ；
Step (3) obtaining NXO e ；
Step (4) comprising the nanoscale carbon-coated MXO e The NXO e Raw materials II mixing of A source, X source and D sourceHeat treatment II is carried out in atmosphere II, and then cooling is carried out in atmosphere II, so as to obtain the polyanion compound; the time of the heat treatment II is 2-20 h.
The invention adopts the preparation steps, and can avoid the generation of impurities such as manganese oxide and the like.
Optionally, the mass of the carbon source accounts for 10% -30% of the total mass of the M source and the X source.
Optionally, the total amount of the A source, the X source and the D source are (1+q), wherein z is D, and the z is calculated according to the molar amount of A in the A source, the molar amount of X in the X source and the molar amount of D in the D source respectively; the total amount of the X sources is the sum of the amount of the X sources in the step (1), the amount of the X sources in the step (3) and the amount of the X sources in the step (4); wherein the amount of the source A ranges from 1 to 1.1 times of (1+x);
in the step (1), the molar ratio of the M source to the X source is (1-b) X y: M; wherein 0<m is less than or equal to z;
In the step (3), the molar ratio of the N source to the X source is by; wherein n is 0.ltoreq.n < z;
in the step (4), the molar ratio of the D source to the X source is D (z-m-n); wherein n/(m+n) is more than or equal to 0 and less than or equal to 0.1.
Optionally, the temperature of the heat treatment I is 500-1000 ℃, preferably 750 ℃.
Optionally, when X is selected from P and M is selected from Mn, the temperature of the heat treatment II is 660-1200 ℃, and the molar ratio of the M source to the X source is 2:3, based on the molar amount of M in the M source and the molar amount of X in the X source;
optionally, when X is selected from P and M is selected from Fe, the temperature of the heat treatment II is 1000-1400 ℃, and the molar ratio of the M source to the X source is 1:1, based on the molar amount of M in the M source and the molar amount of X in the X source;
optionally, when X is selected from P and M is selected from one or more of Cr, ni and Co, the temperature of the heat treatment II is 500-1200 ℃, and the molar ratio of an M source to an X source is 1:1; based on the molar amount of M in the M source and the molar amount of X in the X source;
optionally, when X is selected from P and M is selected from V, the temperature of the heat treatment II is 700-1200 ℃, and the molar ratio of the M source to the X source is 1:1, based on the molar amount of M in the M source and the molar amount of X in the X source;
optionally, when X is selected from S and M is selected from Mn, the temperature of the heat treatment II is 700-1200 ℃, and the molar ratio of the M source to the X source is 3:2, based on the molar amount of M in the M source and the molar amount of X in the X source;
Optionally, when X is selected from S and M is selected from Fe, co and Cr, the temperature of the heat treatment II is 500-1000 ℃, and the molar ratio of the M source to the X source is 3:2, based on the molar amount of M in the M source and the molar amount of X in the X source;
optionally, when X is selected from S and M is selected from Ni, the temperature of the heat treatment II is 500-840 ℃, and the molar ratio of the M source to the X source is 3:2, based on the molar amount of M in the M source and the molar amount of X in the X source;
optionally, when X is selected from V, si, nb, mo, al and M is selected from Fe, co, cr, ni, the temperature of the heat treatment II is 500-1000 ℃, and the molar ratio of the M source to the X source is 3:2, based on the molar amount of M in the M source and the molar amount of X in the X source;
alternatively, when X is selected from V, si, nb, mo, al and M is selected from Mn, the temperature of the heat treatment II is 700-1200 ℃, and the molar ratio of the M source to the X source is 3:2, based on the molar amount of M in the M source and the molar amount of X in the X source.
Alternatively, when M is selected from at least two elements, step (2) is preferably divided into multiple steps to produce the corresponding MXO respectively e And the temperature of the heat treatment II in the step (4) is selected from lower temperature ranges in the respective corresponding temperature ranges of the two elements, and the lower temperature limit is the lower limit. For example, X is selected from P and B; when M is selected from Mn and V, the temperature of heat treatment II in single Mn is 660-1200 ℃, the temperature of heat treatment II in single V is 700-1200 ℃, and when M is selected from Mn and V in mixed existence, the temperature range of heat treatment II is 660-1200 ℃;
Optionally, in the step (3), an NXO is obtained e The method comprises mixing raw materials III containing N source and X source, and heat treating III in inactive atmosphere III to obtain NXO e 。
Optionally, in step (3), the molar ratio of the N source to the X source has the formula b×y: n;0< n < z, and m+n < z;
when N is selected from at least two elements, the step (2) is divided into multiple steps to respectively prepare the corresponding NXO e The method comprises the steps of carrying out a first treatment on the surface of the Each NXO e The salt is carried out in the following manner;
when X is selected from P, B; when N is selected from Mg, ti, cu, zr, the molar ratio of the N source to the X source is 3:2, and the molar ratio is calculated by the molar amount of N in the N source and the molar amount of X in the X source;
when X is selected from P, B; when N is selected from Al, nb and Y, the molar ratio of the N source to the X source is 1:1, and the molar amount of N in the N source and the molar amount of X in the X source are calculated;
when X is selected from S, si, mn, mo; when N is selected from Mg, ti, cu, zr, the molar ratio of the N source to the X source is 1:1, based on the molar amount of N in the N source and the molar amount of X in the X source;
when X is selected from S, si, mn, mo; when N is selected from Al, nb and Y, the molar ratio of the N source to the X source is 2:3, based on the molar amount of N in the N source and the molar amount of X in the X source;
when X is selected from V, nb and Al; when N is selected from Mg, ti, cu, zr, the molar ratio of the N source to the X source is 1:2, based on the molar amount of N in the N source and the molar amount of X in the X source;
When X is selected from V, nb and Al; when N is selected from Al, nb and Y, the molar ratio of the N source to the X source is 1:3, based on the molar amount of N in the N source and the molar amount of X in the X source.
Optionally, the time of the heat treatment III is 2-5 hours; the temperature of the heat treatment III is 600-1000 ℃. Wherein the molar ratio of the N source and the X source is such that the product of the valence of N and the number of moles of N, i, XO e Valence state of (2) and XO e The sum of the molar products ii, i and ii is zero.
Optionally, in step (1), the carbon source is at least one selected from citric acid, oxalic acid, ascorbic acid, glucose, sucrose, fructose, polyethylene glycol.
Optionally, the mass of the carbon source is 5% -40% of the total mass of the M source and the X source.
Optionally, in the step (2), a high-energy ball mill is adopted for ball milling, the rotating speed is 200-800 r/min, and the ball milling treatment is carried out for 2-6 h;
optionally, in step (2), the nanoparticle has a particle size of 1nm to 100nm, preferably 50nm to 80nm.
Optionally, in the step (4), the cooling time is 10 s-5 min, and the cooling time is 20-30 ℃;
optionally, the inactive atmosphere I, inactive atmosphere III are each independently selected from helium and/or nitrogen; the atmosphere II is selected from helium, nitrogen and H 2 At least one of them.
Optionally, the a, M, N, X, D sources are selected from compounds containing the corresponding elements, i.e. a, M, N, X, D elements, especially oxide and/or carbonate and/or hydroxide and/or oxalate and/or nitrate and/or phosphate and/or metal and/or chloride and/or fluoride and/or bromide and/or sulphide and/or amide compounds; these compounds may preferably be selected from Li 2 O、Li 2 CO 3 、LiOH、LiH 2 PO 4 、Li 3 PO 4 、LiF、Na 2 CO 3 、NaOH、KOH、Fe、Fe 2 O 3 、Fe 3 O 4 、FeO、Co 3 O 4 、CoO、V 2 O 5 、Nb 2 O 5 、Y 2 O 3 、B 2 O 3 、TiO 2 、Cu 2 O、CuO、Cr 2 O 3 、NH 4 H 2 PO 4 、(NH 4 ) 2 HPO 4 、H 3 PO 4 、P 2 O 5 、SiO 2 、Al 2 O 3 、MoO、MnO、Mn 2 O 3 、MnO 2 、Mn 3 O 4 、MgO、MgCO 3 、Mg(CH 3 COO) 2 、NiO、NH 4 F。
Alternatively, the A source is selected from Li 2 O、Li 2 CO 3 、LiOH、LiH 2 PO 4 、Li 3 PO 4 、LiF、Na 2 CO 3 At least one of NaOH and KOH;
optionally, the M source is selected from Fe, fe 2 O 3 、Fe 3 O 4 、FeO、Co 3 O 4 、CoO、V 2 O 5 、Cr 2 O 3 、MnO、Mn 2 O 3 、MnO 2 、Mn 3 O 4 At least one of NiO;
optionally, the N source is selected from Nb 2 O 5 、Y 2 O 3 、B 2 O 3 、TiO 2 、Cu 2 O、CuO、MgO、MgCO 3 、Mg(CH 3 COO) 2 At least one of (a) and (b);
optionally, the X source is selected from Nb 2 O 5 、V 2 O 5 、NH 4 H 2 PO 4 、(NH 4 ) 2 HPO 4 、H 3 PO 4 、P 2 O 5 、SiO 2 、Al 2 O 3 、MoO。
The invention also provides the polyanion compound obtained by any one of the preparation methods, wherein the purity of the compound is more than 99.9 percent, and the purity is calculated according to the percentage of the peak area of impurities and the proportion of all peak areas in an XRD test curve.
The invention also provides application of the polyanion compound as a positive electrode material in an alkali metal ion battery.
Optionally, the alkali metal cell is a sodium ion cell, a potassium ion cell or a lithium ion cell.
The invention also provides a positive electrode material containing any one of the polyanion compounds.
Optionally, the positive electrode material contains 70-96 wt% of polyanion compound, conductive agent and binder.
Taking magnesium sodium manganese phosphate as an example (magnesium as a doping element), the invention proposes to first synthesize carbon-coated manganese phosphate (Mn) with nanoparticle size 3 (PO 4 ) 2 A melting point of 654 ℃ and a magnesium phosphate precursor, wherein the main precursor manganese phosphate has a melting point much lower than that of the corresponding manganese oxide (melting point of 1650 ℃) at a temperature in the temperature range of conventional high-temperature sintering, and then adding a sodium source and the like for mixing, and setting a melting temperature higher than that of the phosphate to sinter at a high temperature to synthesize the final productThe precursors are fully and uniformly mixed and reacted to realize the synthesis of the high-purity polyanion compound, and the capacity and the stability of the synthesized electrode material can be fully exerted.
Drawings
FIG. 1 is a carbon-coated VPO according to example 6 4 An XRD pattern of (b);
FIG. 2 is a carbon-coated VPO according to example 6 4 TG thermogravimetric data of (2);
FIG. 3 is the VPO before ball milling in example 6 4 SEM image of @ C;
FIG. 4 is VPO after ball milling in example 6 4 SEM image of @ C;
FIG. 5 is NaVPO in example 6 4 SEM image of F;
FIG. 6 is an XRD pattern of a precursor prepared by the sol-gel method of comparative example 6;
FIG. 7 is an XRD pattern of non-carbon coated vanadium phosphate of comparative example 6-2;
FIG. 8 is a morphology of non-carbon coated vanadium phosphate after ball milling of comparative example 6-2;
FIG. 9 is a morphology of NVPF as an end product prepared by using non-carbon coated vanadium phosphate of comparative example 6-2 as a precursor.
Detailed Description
As one embodiment, the present invention employs the following steps to prepare polyanionic compound-vanadium manganese sodium fluorophosphate (M source is binary composition of Mn and V, no N source (n=0), na 4 MnV(PO 4 ) 2 F 3 ) The compound can be used for a positive electrode material of a sodium ion battery:
step a-1, uniformly mixing a vanadium source, a carbon source and a phosphorus source, and treating for 1-20 hours at 500-1000 ℃ in an inert atmosphere to obtain carbon-coated vanadium phosphate; the molar ratio of the vanadium source to the phosphorus source is 1:1, and the pure vanadium phosphate can be obtained by the molar ratio; the mass of the carbon source is 5% -40% of the total mass of the vanadium source and the phosphorus source; the inert atmosphere gas is one or two of helium and nitrogen; the vanadium source is at least one of ammonium metavanadate, vanadium pentoxide, ammonium polyvanadate, vanadium trioxide and vanadium dioxide; preferably at least one of ammonium metavanadate, vanadium pentoxide and ammonium polyvanadate; the carbon source is at least one of citric acid, oxalic acid, ascorbic acid, glucose, sucrose, fructose and polyethylene glycol; the phosphorus source is at least one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate and phosphoric acid;
Step a-2, evenly mixing a manganese source, a carbon source and a phosphorus source, and treating for 1-20 hours at 500-1000 ℃ in an inert atmosphere to obtain a carbon-coated manganese phosphate precursor; the molar ratio of the manganese source to the phosphorus source is 3:2; the inert atmosphere gas is one or two of helium and nitrogen; the manganese source is at least one of manganese acetate, manganese nitrate and manganese oxalate, and manganese acetylacetonate; the carbon source is at least one of citric acid, oxalic acid, ascorbic acid, glucose, sucrose, fructose and polyethylene glycol; the phosphorus source is at least one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate and phosphoric acid;
a step a-3 of placing the carbon-coated vanadium phosphate and the carbon-coated manganese phosphate obtained in the step a-1 and the step a-2 into a high-energy ball mill, wherein the rotating speed is 200-800 r/min, and performing high-energy ball milling treatment for 2-6 h to obtain a precursor of the carbon-coated manganese phosphate and the carbon-coated vanadium phosphate with the particle range of 10-100 nm;
a step a-4 of mixing the carbon-coated vanadium phosphate, the carbon-coated manganese phosphate, the sodium source, the phosphorus source and the fluorine source of the nano particles obtained in the step a-3, treating for 2-20 hours at 660-1200 ℃ in an inert atmosphere, and then rapidly cooling to room temperature in the inert atmosphere to obtain the vanadium manganese sodium fluorophosphate (Na 4MnV (PO) 4 )2F 3 ) A compound; the molar ratio of the nano-particle carbon-coated vanadium phosphate to the carbon-coated manganese phosphate to the sodium source to the phosphorus source to the fluorine source is 3:1:12:1:9, and the inert atmosphere gas is one or two of helium and nitrogen; the rapid cooling time is 10 s-5 min; the sodium source is at least one of sodium hydroxide, sodium carbonate, sodium bicarbonate and sodium bicarbonate; the fluorine source is at least one of hydrogen fluoride, sodium fluoride, ammonium fluoride and polytetrafluoroethylene; the phosphorus source is at least one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate and phosphoric acid.
As one embodiment, the invention adopts the following steps to prepare the polyanion compound-sodium vanadium fluorophosphate (M source is binary composition of Fe and V, no N source (n=0), na 4 FeV(PO 4 ) 2 F 3 ) The compound can be used for positive electrode of sodium ion batteryPolar material:
step b-1, uniformly mixing a vanadium source, a carbon source and a phosphorus source, and treating for 1-20 hours at 500-1000 ℃ in an inert atmosphere to obtain carbon-coated vanadium phosphate; the molar ratio of the vanadium source to the phosphorus source is 1:1, and the mass of the carbon source is 5% -40% of the total mass of the vanadium source and the phosphorus source; the inert atmosphere gas is one or two of helium and nitrogen; the vanadium source is at least one of ammonium metavanadate, vanadium pentoxide, ammonium polyvanadate, vanadium trioxide and vanadium dioxide; preferably at least one of ammonium metavanadate, vanadium pentoxide and ammonium polyvanadate; the carbon source is at least one of citric acid, oxalic acid, ascorbic acid, glucose, sucrose, fructose and polyethylene glycol; the phosphorus source is at least one of monoammonium phosphate, diammonium phosphate and phosphoric acid.
Step b-2, uniformly mixing an iron source, a phosphorus source and a carbon source, and treating for 1-20 hours at 500-1000 ℃ in an inert atmosphere to obtain a carbon-coated iron phosphate precursor; the molar ratio of the iron source to the phosphorus source is 1:1, and the mass of the carbon source is 5% -40% of the total mass of the iron source and the phosphorus source; the inert atmosphere gas is helium, nitrogen or one or two of helium, nitrogen and hydrogen mixed gas; the iron source is at least one of ferrous sulfate, ferrous chloride and ferrous nitrate; the carbon source is at least one of citric acid, oxalic acid, ascorbic acid, glucose, sucrose, fructose and polyethylene glycol; the phosphorus source is at least one of monoammonium phosphate, diammonium phosphate and phosphoric acid.
B-3, placing the carbon-coated vanadium phosphate and the iron phosphate obtained in the steps b-1 and b-2 into a high-energy ball mill, wherein the rotating speed is 200-800 r/min, and performing high-energy ball milling treatment for 2-6 h to obtain a carbon-coated vanadium phosphate and iron phosphate mixture of nano particles;
b-4, mixing the carbon-coated vanadium phosphate of the nano-particles obtained in the step b-3 with the carbon-coated iron phosphate, a sodium source, a fluorine source and a carbon source, treating for 2-20 h at 1000-1400 ℃ in an inert atmosphere, and then rapidly cooling to room temperature in the inert atmosphere to obtain the sodium vanadium iron fluorophosphate (Na 4 FeV(PO 4 )2F 3 ) A compound. Nano granular carbon coated vanadium phosphate, carbon coated iron phosphate, sodium source,The molar ratio of the fluorine source to the carbon source is 1:1:4:3:1, and the inert atmosphere gas is one or two of helium and nitrogen; the rapid cooling time is 10 s-5 min; the sodium source is at least one of sodium hydroxide, sodium carbonate, sodium bicarbonate and sodium bicarbonate; the fluorine source is at least one of hydrogen fluoride, sodium fluoride, ammonium fluoride and polytetrafluoroethylene.
As one embodiment, the present invention employs the following steps to prepare a polyanionic compound, namely vanadium chromium sodium fluorophosphate (M source is binary composition of Cr and V, no N source (n=0), na 3 CrV(PO4) 2 F 3 ) The compound can be used for a positive electrode material of a sodium ion battery:
step c-1, uniformly mixing a vanadium source, a carbon source and a phosphorus source, and treating for 1-20 hours at 500-1000 ℃ in an inert atmosphere to obtain carbon-coated vanadium phosphate; the molar ratio of the vanadium source to the phosphorus source is 1:1, and the mass of the carbon source is 5% -40% of the total mass of the vanadium source and the phosphorus source; the inert atmosphere gas is one or two of helium and nitrogen; the vanadium source is at least one of ammonium metavanadate, vanadium pentoxide, ammonium polyvanadate, vanadium trioxide and vanadium dioxide; preferably at least one of ammonium metavanadate, vanadium pentoxide and ammonium polyvanadate; the phosphorus source is at least one of monoammonium phosphate, diammonium phosphate and phosphoric acid; the carbon source is at least one of citric acid, oxalic acid, ascorbic acid, glucose, sucrose, fructose and polyethylene glycol.
Step c-2, uniformly mixing a chromium source, a carbon source and a phosphorus source, and treating for 1-20 hours at 500-1000 ℃ in an inert atmosphere to obtain a carbon-coated chromium phosphate precursor; the molar ratio of the chromium source to the phosphorus source is 1:1, and the mass of the carbon source is 5% -40% of the total mass of the vanadium source and the phosphorus source; the inert atmosphere gas is one or two of helium and nitrogen; the chromium source is Cr (NO) 3 ) 3 ,Cr(ClO 4 ) 3 ,Cr 2 (SO 4 ) 3 ,CrCl 3 At least one of (a) and (b); the carbon source is at least one of citric acid, oxalic acid, ascorbic acid, glucose, sucrose, fructose and polyethylene glycol; the phosphorus source is at least one of monoammonium phosphate, diammonium phosphate and phosphoric acid.
C-3, placing the carbon-coated vanadium phosphate and the carbon-coated chromium phosphate obtained in the steps c-1 and c-2 into a high-energy ball mill, wherein the rotating speed is 200-800 r/min, and performing high-energy ball milling treatment for 20-6 h to obtain a mixture of the carbon-coated vanadium phosphate and the carbon-coated chromium phosphate of the nano particles;
c-4, mixing the carbon-coated vanadium phosphate of the nano-particles obtained in the step c-3 with a carbon-coated chromium phosphate, a sodium source and a fluorine source, treating for 2-20h at 500-1200 ℃ in an inert atmosphere, and then rapidly cooling to room temperature in the inert atmosphere to obtain the vanadium chromium sodium fluorophosphate (Na 3 CrV(PO 4 ) 2 F 3 ) A compound; in the step (4), the molar ratio of the carbon-coated vanadium phosphate to the chromium phosphate to the sodium source to the fluorine source is 1:1:3:3, and the inert atmosphere gas is one or two of helium and nitrogen; the rapid cooling time is 10s-5min; the sodium source is at least one of sodium hydroxide, sodium carbonate, sodium bicarbonate and sodium bicarbonate; the fluorine source is at least one of hydrogen fluoride, sodium fluoride, ammonium fluoride and polytetrafluoroethylene.
As one embodiment, the invention adopts the following steps to prepare the polyanion compound-magnesium doped sodium vanadium fluorophosphate (M source is V, N source is Mg; na) 1.1 V 0.9 Mg 0.1 PO 4 F) The compound can be used for a positive electrode material of a sodium ion battery:
step a-1, uniformly mixing a vanadium source, a carbon source and a phosphorus source, and treating for 1-20 hours at 500-1000 ℃ in an inert atmosphere to obtain carbon-coated vanadium phosphate; the molar ratio of the vanadium source to the phosphorus source is 1:1, and the pure vanadium phosphate can be obtained by the molar ratio; the mass of the carbon source is 5% -40% of the total mass of the vanadium source and the phosphorus source; the inert atmosphere gas is one or two of helium and nitrogen; the vanadium source is at least one of ammonium metavanadate, vanadium pentoxide, ammonium polyvanadate, vanadium trioxide and vanadium dioxide; preferably at least one of ammonium metavanadate, vanadium pentoxide and ammonium polyvanadate; the carbon source is at least one of citric acid, oxalic acid, ascorbic acid, glucose, sucrose, fructose and polyethylene glycol; the phosphorus source is at least one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate and phosphoric acid;
a step a-2 of placing the carbon-coated vanadium phosphate obtained in the step a-1 into a high-energy ball mill, wherein the rotating speed is 200-800 r/min, and performing high-energy ball milling treatment for 2-6 h to obtain a precursor of the carbon-coated vanadium phosphate with the particle range of 10-100 nm;
Step a-3, uniformly mixing a magnesium source and a phosphorus source, and treating for 2-5 hours at 600-1000 ℃ in an inert atmosphere to obtain magnesium phosphate; the molar ratio of the magnesium source to the phosphorus source is 3:2; the inert atmosphere gas is one or two of helium and nitrogen; the magnesium source is MgO, mgCO 3 、Mg(CH 3 COO) 2 At least one of (a) and (b); the phosphorus source is at least one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate and phosphoric acid;
a step a-4 of mixing the carbon-coated vanadium phosphate of the nano particles obtained in the step a-2, the magnesium phosphate, the sodium source, the phosphorus source and the fluorine source obtained in the step a-3, treating for 2-20h at 700-1200 ℃ in an inert atmosphere, and then rapidly cooling to room temperature in the inert atmosphere to obtain Na 1.1 V 0.9 Mg 0.1 PO 4 A compound F; the molar ratio of the nano-particle carbon coated vanadium phosphate to the magnesium phosphate to the sodium source to the phosphorus source to the fluorine source is 0.9 (1/30): 1.1 (1/30): 1, and the inert atmosphere gas is one or two of helium and nitrogen; the rapid cooling time is 10 s-5 min; the sodium source is at least one of sodium hydroxide, sodium carbonate, sodium bicarbonate and sodium bicarbonate; the fluorine source is at least one of hydrogen fluoride, sodium fluoride, ammonium fluoride and polytetrafluoroethylene; the phosphorus source is at least one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate and phosphoric acid.
The pure product of the examples of the present invention was tested by calculation using the percentage of the impurity peak area and the ratio of all peak areas in the XRD test curve.
Example 1 with VPO 4 @C，Mn 3 (PO 4 ) 2 Preparation of Na with @ C as precursor 4 VMn(PO 4 ) 2 F 3
Step (1), 0.05mol of vanadium pentoxide V 2 O 5 0.1mol of monoammonium phosphate NH 4 H 2 PO 4 0.2mol of citric acid C 6 H 8 O 7 By solid phase ball millingAfter being evenly mixed, the mixture is transferred into a graphite crucible and then is placed into a tube furnace, and is preserved for 5 hours under the helium atmosphere at 750 ℃, and the heating rate is 5 ℃/min, thus obtaining the carbon-coated vanadium phosphate VPO 4 @C；
Step (2), 0.1mol of manganese acetate Mn (CH) 3 COO) 2 .4H 2 O, 0.07mol of monoammonium phosphate NH 4 H 2 PO 4 0.2mol of citric acid C 6 H 8 O 7 After being evenly mixed by a solid-phase ball milling mode, the mixture is transferred into a graphite crucible, and then is placed in a tube furnace to be kept at 550 ℃ for 5 hours under helium atmosphere, and the heating rate is 5 ℃/min, thus obtaining the carbon-coated manganese phosphate Mn 3 (PO 4 ) 2 @C；
Step (3), the vanadium phosphate VPO coated with carbon 4 @C and carbon-coated manganese phosphate Mn 3 (PO 4 ) 2 Transferring @ C into a high-energy ball mill for treatment for 4 hours, and setting the rotating speed to 400r/min to obtain nano-granular carbon-coated vanadium phosphate VPO 4 @C and carbon-coated manganese phosphate Mn 3 (PO 4 ) 2 A mixture of @ C, having a particle size of 50-80 nm;
step (4), 0.3mol of sodium fluoride NaF, 0.1mol of sodium hydroxide NaOH and 0.034mol of monoammonium phosphate NH 4 H 2 PO 4 And (3) the nano-granular carbon-coated vanadium phosphate VPO4@C and carbon-coated Mn prepared in the step (3) 3 (PO 4 ) 2 Uniformly mixing @ C by a solid-phase ball milling mode, transferring into a graphite crucible, and then placing into a tube furnace to be subjected to heat preservation for 8 hours at 700 ℃ under helium atmosphere, wherein the heating rate is 5 ℃/min; then the reaction product is placed in helium atmosphere and is rapidly cooled to room temperature for 1min at the cooling temperature of 25 ℃, and the sodium vanadium manganese fluorophosphate Na is obtained after uniform grinding 4 VMn(PO 4 ) 2 F 3 The purity of the material was 99.95%, designated as material # 1.
The prepared electrode material 1# is assembled into a button cell of a sodium ion battery, and the capacities of the button cell at different multiplying powers of 0.2C, 1C, 2C, 5C and 10C are respectively as follows: 131mAh/g,120mAh/g,110mAh/g,105mAh/g and 95mAh/g. Due to the high purity of the material, the specific capacity of the battery at 0.2C is close to the theoretical specific capacity.
Comparative example 1 preparation of Na by sol-gel method 4 VMn(PO 4 ) 2 F 3
0.2mol of citric acid C is added into a beaker 6 H 8 O 7 And 50mL of deionized water, dissolving in a water bath at 85 ℃ at a rotating speed of 150r/min, and slowly adding 0.1mol of ammonium metavanadate NH into the beaker 4 VO 3 When the color of the solution changes from yellow to green to blue and no bubbles are generated, 0.1mol of Mn (CH) acetate is added in sequence 3 COO) 2 .4H 2 O, 0.3mol of sodium fluoride NaF, 0.1mol of sodium hydroxide NaOH, 0.2mol of ammonium dihydrogen phosphate NH 4 H 2 PO 4 Continuously maintaining the temperature at 85 ℃ for water bath heating, placing the reaction solution in a 90 ℃ blast drying oven to remove residual moisture and residual gas after the reaction solution is in a gel state, completely drying the product, crushing and grinding, transferring the uniformly ground powder into a graphite crucible, placing the graphite crucible in a tube furnace, and preserving the heat for 5 hours under the helium atmosphere at the temperature of 350 ℃ and the heating rate of 5 ℃/min; taking out, carrying out secondary grinding, transferring the ground precursor into a graphite crucible again, placing the graphite crucible in a tube furnace, and preserving heat for 8 hours at 750 ℃ in helium atmosphere; then the reaction product is placed in helium atmosphere and is rapidly cooled to room temperature for 1min at the cooling temperature of 25 ℃, and the sodium vanadium manganese fluorophosphate Na is obtained after uniform grinding 4 VMn(PO 4 ) 2 F 3 A material. The precursor contains more vanadium oxide and manganese oxide impurities, and the purity is 89%, which is marked as a material A1.
The prepared electrode material A1 is assembled into a button cell of the sodium ion battery, and the prepared material A1 contains more impurities, so that the capacity of the battery is lower, and the capacities of the battery under different multiplying powers of 0.2C, 1C, 2C, 5C and 10C are respectively as follows: 112mAh/g,102mAh/g,95mAh/g,80mAh/g,70mAh/g.
Comparative examples 1-2 with VPO 4 ，Mn 3 (PO 4 ) 2 Preparation of Na for precursor 4 VMn(PO 4 ) 2 F 3
Step (1), 0.05mol of vanadium pentoxide V 2 O 3 0.1mol of monoammonium phosphate NH 4 H 2 PO 4 Uniformly mixing by a solid-phase ball milling method, transferring into a graphite crucible, placing into a tube furnace, preserving heat for 5 hours at 750 ℃ under helium atmosphere, and obtaining vanadium phosphate VPO at a heating rate of 5 ℃/min 4 ；
Step (2), 0.1mol of manganese acetate Mn (CH) 3 COO) 2 .4H 2 O, 0.07mol of monoammonium phosphate NH 4 H 2 PO 4 After being evenly mixed by a solid-phase ball milling mode, the mixture is transferred into a graphite crucible, and then is placed in a tube furnace to be kept at 550 ℃ for 5 hours under helium atmosphere, and the temperature rising rate is 5 ℃/min, thus obtaining the precursor manganese phosphate Mn 3 (PO 4 ) 2 ；
Step (3), vanadium phosphate VPO 4 And manganese phosphate Mn 3 (PO 4 ) 2 Transferring into a high-energy ball mill for treatment for 4 hours, setting the rotating speed to 400r/min, and obtaining the nano-granular vanadium phosphate VPO 4 And manganese phosphate Mn 3 (PO 4 ) 2 The particle size of the mixture is 50-80 nm;
step (4), 0.3mol of sodium fluoride NaF, 0.1mol of sodium hydroxide NaOH and 0.034mol of monoammonium phosphate NH 4 H 2 PO 4 And (3) the nano-granular vanadium phosphate VPO prepared in the step (3) 4 And manganese phosphate Mn 3 (PO 4 ) 2 Mixture and 0.2mol of citric acid C 6 H 8 O 7 After being evenly mixed by a solid-phase ball milling mode, the mixture is transferred into a graphite crucible and then placed in a tube furnace to be kept at 700 ℃ for 8 hours under helium atmosphere, and the heating rate is 5 ℃/min; then the reaction product is placed in helium atmosphere and is rapidly cooled to room temperature for 1min at the cooling temperature of 25 ℃, and the sodium vanadium manganese fluorophosphate Na is obtained after uniform grinding 4 VMn(PO 4 ) 2 F 3 The purity of the material was 99.97%, designated as material A1-2.
The prepared electrode material A1-2 is assembled into a button cell of a sodium ion battery, and as the prepared material A1-2 is coated with a carbon layer in a high-temperature sintering process, synthetic material particles are larger and are in um level, so that the capacity of the battery is lower than that of an embodiment, and the capacities of the battery under different multiplying powers of 0.2C, 1C, 2C, 5C and 10C are respectively: 120mAh/g,113mAh/g,105mAh/g,95mAh/g, and 80mAh/g.
Example 2 with VPO 4 @C，FePO 4 Preparation of Na with @ C as precursor 4 VFe(PO 4 ) 2 F 3
Step (1), 0.05mol of vanadium pentoxide V 2 O 5 0.1mol of monoammonium phosphate NH 4 H 2 PO 4 0.2mol of citric acid C 6 H 8 O 7 After being evenly mixed by a solid-phase ball milling method, the mixture is transferred into a graphite crucible and then placed in a tube furnace, and the mixture is preserved for 5 hours under the helium atmosphere at 750 ℃ with the temperature rising rate of 5 ℃/min, thus obtaining the carbon-coated vanadium phosphate VPO 4 @C；
Step (2), 0.1mol of ferric nitrate Fe (NO) 3 ).9H 2 O, 0.1mol of monoammonium phosphate NH 4 H 2 PO 4 0.2mol of citric acid C 6 H 8 O 7 After being evenly mixed by a solid-phase ball milling method, the mixture is transferred into a graphite crucible, and then is placed in a tube furnace to be kept at 550 ℃ for 5 hours under helium atmosphere, and the heating rate is 5 ℃/min, thus obtaining carbon-coated iron phosphate FePO 4 @C；
Step (3), followed by the carbon-coated vanadium phosphate VPO 4 @ C and carbon-coated iron phosphate FePO 4 @C; transferring into a high-energy ball mill for treatment for 4 hours, setting the rotating speed to 400r/min, and obtaining the carbon-coated vanadium phosphate VPO of the nano particles 4 Carbon coated iron phosphate FePO of @ C and nanoparticles 4 @C, wherein the particle size is 50-80 nm;
step (4), 0.3mol of sodium fluoride NaF, 0.1mol of sodium hydroxide NaOH and 0.2mol of citric acid C 6 H 8 O 7 And (3) carbon-coated vanadium phosphate VPO of the nanoparticles prepared in step (3) 4 Carbon coated iron phosphate FePO of @ C and nanoparticles 4 Uniformly mixing @ C by a solid-phase ball milling mode, transferring into a graphite crucible, and then placing into a tube furnace to be insulated for 8 hours at 850 ℃ under helium atmosphere, wherein the heating rate is 5 ℃/min; then the reaction product is placed in helium atmosphere and is rapidly cooled to room temperature for 1min at the cooling temperature of 25 ℃, and the sodium ferrovanadium fluorophosphate Na is obtained after uniform grinding 4 VFe(PO 4 ) 2 F 3 PowderThe purity of the material was 99.98%, designated as material # 2.
The prepared electrode material 2# is assembled into a button cell of a sodium ion battery, and the capacities of the button cell at different multiplying powers of 0.2C, 1C, 2C, 5C and 10C are respectively as follows: 128mAh/g,121mAh/g,112mAh/g,103mAh/g,94mAh/g. Due to the high purity of the material, the specific capacity of the battery at 0.2C is close to the theoretical specific capacity.
Comparative example 2 preparation of Na by sol-gel method 4 VFe(PO 4 ) 2 F 3
0.4mol of citric acid C is added into a beaker 6 H 8 O 7 And 50mL of deionized water, dissolving in a water bath at 85 ℃ at a rotating speed of 150r/min, and slowly adding 0.1mol of ammonium metavanadate NH into the beaker 4 VO 3 When the color of the solution changes from yellow to green to blue and NO bubbles are generated, 0.1mol of ferric nitrate Fe (NO) is added in sequence 3 ).9H 2 O, 0.3mol of sodium fluoride NaF, 0.1mol of sodium hydroxide NaOH, 0.2mol of ammonium dihydrogen phosphate NH 4 H 2 PO 4 Continuously maintaining the temperature at 85 ℃ for water bath heating, placing the reaction solution in a 90 ℃ blast drying oven to remove residual moisture and residual gas after the reaction solution is in a gel state, completely drying the product, crushing and grinding, transferring the uniformly ground powder into a graphite crucible, placing the graphite crucible in a tube furnace, and preserving the heat for 5 hours under the helium atmosphere at the temperature of 350 ℃ and the heating rate of 5 ℃/min; taking out, carrying out secondary grinding, transferring the ground precursor into a graphite crucible again, placing the graphite crucible in a tube furnace, and preserving heat for 8 hours at 850 ℃ under helium atmosphere, wherein the heating rate is 5 ℃/min; then the reaction product is placed in helium atmosphere and is rapidly cooled to room temperature for 1min at the cooling temperature of 25 ℃, and the obtained product is taken out and ground uniformly to obtain the sodium ferrovanadium phosphate Na 4 VFe(PO 4 ) 2 F 3 And (3) powder. Since the precursor contains more vanadium oxide and iron oxide impurities, the purity of the material is 85%, and the material is denoted as a material B1.
The prepared electrode material B1 is assembled into a button cell of the sodium ion battery, and the prepared material B1 contains more impurities, so that the capacity of the battery is lower, and the capacities of the battery under different multiplying powers of 0.2C, 1C, 2C, 5C and 10C are respectively as follows: 110mAh/g,100mAh/g,93mAh/g,78mAh/g,75mAh/g.
Comparative example 2-2 with VPO 4 ，FePO 4 Preparation of Na for precursor 4 VFe(PO 4 ) 2 F 3
Step (1), 0.05mol of vanadium pentoxide V 2 O 5 0.1mol of monoammonium phosphate NH 4 H 2 PO 4 Uniformly mixing by a solid-phase ball milling method, transferring into a graphite crucible, placing into a tube furnace, preserving heat for 5 hours at 750 ℃ under helium atmosphere, and obtaining vanadium phosphate VPO at a heating rate of 5 ℃/min 4 ；
Step (2), 0.1mol of ferric nitrate Fe (NO) 3 ).9H 2 O, 0.1mol of monoammonium phosphate NH 4 H 2 PO 4 Uniformly mixing by a solid-phase ball milling method, transferring into a graphite crucible, placing into a tube furnace, preserving heat for 5 hours at 550 ℃ under helium atmosphere, and obtaining a precursor iron phosphate FePO at a heating rate of 5 ℃/min 4 ；
Step (3), followed by the vanadium phosphate VPO prepared in steps (1) and (2) 4 And iron phosphate FePO 4 The method comprises the steps of carrying out a first treatment on the surface of the Transferring into a high-energy ball mill for treatment for 4 hours, setting the rotating speed to 400r/min, and obtaining the vanadium phosphate VPO of the nano particles 4 And nanoparticle iron phosphate FePO 4 The grain diameter is 50-80 nm;
step (4), 0.3mol of sodium fluoride NaF, 0.1mol of sodium hydroxide NaOH and 0.2mol of citric acid C 6 H 8 O 7 And vanadium phosphate VPO of the nano particles prepared in the step (3) 4 And nanoparticle iron phosphate FePO 4 And 0.2mol of citric acid C 6 H 8 O 7 After being evenly mixed by a solid-phase ball milling mode, the mixture is transferred into a graphite crucible and then placed in a tube furnace to be preserved for 8 hours at 850 ℃ under helium atmosphere, and the heating rate is 5 ℃/min; then the reaction product is placed in helium atmosphere and is rapidly cooled to room temperature for 1min at the cooling temperature of 25 ℃, and the sodium ferrovanadium fluorophosphate Na is obtained after uniform grinding 4 VFe(PO 4 ) 2 F 3 The powder had a purity of 99.95% and was designated as material B1-2.
The prepared electrode material B1-2 is assembled into a button cell of the sodium ion battery, and as the prepared material B1-2 is coated with a carbon layer in the high-temperature sintering process, synthetic material particles are larger and are in um level, so that the capacity of the battery is lower than that of the embodiment, and the capacities of the battery under different multiplying powers of 0.2C, 1C, 2C, 5C and 10C are respectively: 118mAh/g,110mAh/g,101mAh/g,90mAh/g,72mAh/g.
Example 3 with VPO 4 @C，CrPO 4 Preparation of Na with @ C as precursor 3 CrV(PO4) 2 F 3
Step (1), 0.05mol of vanadium pentoxide V 2 O 5 0.1mol of monoammonium phosphate NH 4 H 2 PO 4 0.2mol of citric acid C 6 H 8 O 7 After being evenly mixed by a solid-phase ball milling method, the mixture is transferred into a graphite crucible and then placed in a tube furnace, and the mixture is preserved for 5 hours under the helium atmosphere at 750 ℃ with the temperature rising rate of 5 ℃/min, thus obtaining the carbon-coated vanadium phosphate VPO 4 @C；
Step (2), 0.1mol of chromium nitrate Cr (NO 3 ).9H 2 O, 0.1mol of monoammonium phosphate NH 4 H 2 PO 4 0.2mol of citric acid C 6 H 8 O 7 After being evenly mixed by a solid-phase ball milling mode, the mixture is transferred into a graphite crucible, and then is placed in a tubular furnace to be kept at 550 ℃ for 5 hours under helium atmosphere, and the heating rate is 5 ℃/min, thus obtaining the carbon-coated chromium phosphate CrPO 4 @C；
Step (3) obtaining the carbon-coated vanadium phosphate VPO 4 @C and carbon coated chromium phosphate CrPO 4 Transferring @ C into a high-energy ball mill for treatment for 4 hours, and setting the rotating speed to 400r/min to obtain nano-granular carbon-coated vanadium phosphate VPO 4 Carbon coated chromium phosphate CrPO @ C and nanoparticles 4 @C, wherein the particle size is 50-80 nm;
step (4), 0.3mol of sodium fluoride NaF and the nano-particle carbon coated vanadium phosphate VPO prepared in the step (3) are mixed 4 Carbon coated chromium phosphate CrPO @ C and nanoparticles 4 Uniformly mixing @ C by a solid-phase ball milling mode, transferring into a graphite crucible, and then placing into a tube furnace to perform heat preservation for 8 hours at 650 ℃ under helium atmosphere, wherein the heating rate is 5 ℃/min; the reaction product was then placed in a helium atmosphereRapidly cooling to room temperature for 1min at 25deg.C, and grinding to obtain sodium vanadium chromium sodium fluorophosphate Na 3 CrV(PO4) 2 F 3 The purity of the powder was 99.99%, designated as material 3#.
The prepared electrode material 3# is assembled into a button cell of a sodium ion battery, and the capacities of the button cell at different multiplying powers of 0.2C, 1C, 2C, 5C and 10C are respectively as follows: 135mAh/g,122mAh/g,114mAh/g,110mAh/g,101mAh/g. Due to the high purity of the material, the specific capacity of the battery at 0.2C is close to the theoretical specific capacity.
Comparative example 3 preparation of Na by sol-gel method 3 CrV(PO4) 2 F 3
0.4mol of citric acid C is added into a beaker 6 H 8 O 7 And 50mL of deionized water, dissolving in a water bath at 85 ℃ at a rotating speed of 150r/min, and slowly adding 0.1mol of ammonium metavanadate NH into the beaker 4 VO 3 When the color of the solution changes from yellow to green to blue and NO bubbles are generated, 0.1mol of chromium nitrate Cr (NO) is added in sequence 3 ).9H 2 O, 0.3mol of sodium fluoride NaF, 0.2mol of ammonium dihydrogen phosphate NH 4 H 2 PO 4 Continuously maintaining the temperature at 85 ℃ for water bath heating, placing the reaction solution in a 90 ℃ blast drying oven to remove residual moisture and residual gas after the reaction solution is in a gel state, completely drying the product, crushing and grinding, transferring the uniformly ground powder into a graphite crucible, placing the graphite crucible in a tube furnace, and preserving the heat for 5 hours under the helium atmosphere at the temperature of 350 ℃ and the heating rate of 5 ℃/min; taking out, carrying out secondary grinding, transferring into a graphite crucible again, placing into a tube furnace, and preserving heat for 8 hours at 650 ℃ under helium atmosphere, wherein the heating rate is 5 ℃/min; then the reaction product is placed in helium atmosphere and is rapidly cooled to room temperature for 1min at the cooling temperature of 25 ℃, and the obtained product is taken out and ground uniformly to obtain the sodium ferrovanadium phosphate Na 3 CrV(PO4) 2 F 3 And (3) powder. Since the precursor contains more vanadium oxide and chromium oxide impurities, the purity of the material is 88%, which is marked as material C1.
The prepared electrode material C1 is assembled into a button cell of the sodium ion battery, and the prepared material C1 contains more impurities, so that the capacity of the battery is lower, and the capacities of the battery under different multiplying powers of 0.2C, 1C, 2C, 5C and 10C are respectively as follows: 114mAh/g,104mAh/g,97mAh/g,83mAh/g,77mAh/g.
Comparative example 3-2 with VPO 4 ，CrPO 4 Preparation of Na for precursor 3 CrV(PO4) 2 F 3
Step (1), 0.05mol of vanadium pentoxide V 2 O 5 0.1mol of monoammonium phosphate NH 4 H 2 PO 4 Uniformly mixing by a solid-phase ball milling method, transferring into a graphite crucible, placing into a tube furnace, preserving heat for 5 hours at 750 ℃ under helium atmosphere, and obtaining vanadium phosphate VPO at a heating rate of 5 ℃/min 4 ；
Step (2), 0.1mol of chromium nitrate Cr (NO 3 ).9H 2 O, 0.1mol of monoammonium phosphate NH 4 H 2 PO 4 Uniformly mixing by a solid-phase ball milling method, transferring into a graphite crucible, placing into a tubular furnace, preserving heat for 5 hours at 550 ℃ under helium atmosphere, and obtaining the chromium phosphate CrPO at a heating rate of 5 ℃/min 4 ；
Step (3) obtaining vanadium phosphate VPO 4 And chromium phosphate CrPO 4 Transferring into a high-energy ball mill for treatment for 4 hours, setting the rotating speed to 400r/min, and obtaining the nano-granular vanadium phosphate VPO 4 And nanoparticulate chromium phosphate CrPO 4 The grain diameter is 50-80 nm;
step (4), 0.3mol of sodium fluoride NaF and the nano-granular vanadium phosphate VPO prepared in the step (3) are added 4 And nanoparticulate chromium phosphate CrPO 4 0.2mol of citric acid C 6 H 8 O 7 After being evenly mixed by a solid-phase ball milling mode, the mixture is transferred into a graphite crucible and then placed in a tube furnace to be kept at 650 ℃ for 8 hours under helium atmosphere, and the heating rate is 5 ℃/min; then the reaction product is placed in helium atmosphere and is rapidly cooled to room temperature for 1min at the cooling temperature of 25 ℃, and the sodium vanadium chromium sodium fluorophosphate Na is obtained after uniform grinding 3 CrV(PO4) 2 F 3 The powder had a purity of 99.95% and was designated as material C1-2.
The prepared electrode material C1-2 is assembled into a button cell of the sodium ion battery, and as the prepared material C1-2 is coated with a carbon layer in the high-temperature sintering process, synthetic material particles are larger and are in um level, so that the capacity of the battery is lower than that of the embodiment, and the capacities of the battery under different multiplying powers of 0.2C, 1C, 2C, 5C and 10C are respectively: 120mAh/g,115mAh/g,104mAh/g,94mAh/g,81mAh/g.
Example 4 use of Mn 3 (PO 4 ) 2 Preparation of Na with @ C as precursor 5 Mn 2 (PO4) 2 F 3
Step (1), 0.2mol of manganese acetate Mn (CH) 3 COO) 2 .4H 2 O, 0.13mol of monoammonium phosphate NH 4 H 2 PO 4 And 0.2mol of citric acid C 6 H 8 O 7 After being evenly mixed by a solid-phase ball milling method, the mixture is transferred into a graphite crucible, and then is placed in a tube furnace to be kept at 750 ℃ and under helium atmosphere for 2 hours, and the heating rate is 5 ℃/min, thus obtaining carbon-coated manganese phosphate Mn 3 (PO 4 ) 2 @C；
Step (2), obtaining carbon-coated manganese phosphate Mn coated with carbon 3 (PO 4 ) 2 Transferring @ C into a high-energy ball mill, treating for 4 hours, and setting the rotating speed to 400r/min to obtain nano-granular carbon-coated manganese phosphate Mn 3 (PO 4 ) 2 @C, wherein the particle size is 50-80 nm;
step (3), 0.3mol of sodium fluoride NaF, 0.2mol of sodium hydroxide NaOH and 0.067mol of monoammonium phosphate NH 4 H 2 PO 4 0.067mol of carbon-coated manganese phosphate Mn prepared in the step (2) 3 (PO 4 ) 2 Uniformly mixing @ C by a solid-phase ball milling method, transferring into a graphite crucible, placing into a tube furnace, preserving heat for 8 hours at 800 ℃ under helium atmosphere, heating at a rate of 5 ℃/min, placing the reaction product into helium atmosphere, rapidly cooling to room temperature for 1min, cooling at 25 ℃, and grinding uniformly to obtain sodium manganese fluorophosphate Na 5 Mn 2 (PO4) 2 F 3 The purity of the powder was 99.98%, designated as material # 4.
The prepared electrode material 4# is assembled into a button cell of a sodium ion battery, and the capacities of the button cell at different multiplying powers of 0.2C, 1C, 2C, 5C and 10C are respectively as follows: 125mAh/g,118mAh/g,107mAh/g,105mAh/g,100mAh/g. Due to the high purity of the material, the specific capacity of the battery at 0.2C is close to the theoretical specific capacity.
Comparative example 4 Sol gel method Na 5 Mn 2 (PO4) 2 F 3
0.2mol of citric acid C is added into a beaker 6 H 8 O 7 And 50mL deionized water, dissolving in water bath at 85deg.C at 150r/min, and sequentially adding manganese acetate 0.2mol Mn (CH) 3 COO) 2 .4H 2 O, 0.3mol of sodium fluoride NaF, 0.2mol of sodium hydroxide NaOH, 0.2mol of ammonium dihydrogen phosphate NH 4 H 2 PO 4 Continuously maintaining the temperature at 85 ℃ for water bath heating, placing the reaction solution in a 90 ℃ blast drying oven to remove residual moisture and residual gas after the reaction solution is in a gel state, completely drying the product, crushing and grinding, transferring the uniformly ground powder into a graphite crucible, placing the graphite crucible in a tube furnace, and preserving the heat for 5 hours under the helium atmosphere at the temperature of 350 ℃ and the heating rate of 5 ℃/min; taking out, carrying out secondary grinding, transferring into a graphite crucible again, placing into a tube furnace, and preserving heat for 8 hours at 750 ℃ under helium atmosphere, wherein the heating rate is 5 ℃/min; then the reaction product is placed in helium atmosphere and is rapidly cooled to room temperature for 1min at the cooling temperature of 25 ℃, and the obtained sodium manganese fluorophosphate Na is obtained after being taken out and ground uniformly 5 Mn 2 (PO4) 2 F 3 Since the precursor contains a large amount of manganese oxide impurities, the purity of the material is 90%, which is denoted as material D1.
The prepared electrode material D1 is assembled into a button cell of the sodium ion battery, and the prepared material D1 contains more impurities, so that the capacity of the battery is lower, and the capacities of the battery under different multiplying powers of 0.2C, 1C, 2C, 5C and 10C are respectively as follows: 115mAh/g,103mAh/g,98mAh/g,89mAh/g,83mAh/g.
Comparative example 4-2 with Mn 3 (PO 4 ) 2 Preparation of Na for precursor 5 Mn 2 (PO4) 2 F 3
Step (1), 0.2mol of manganese acetate Mn (CH) 3 COO) 2 .4H 2 O, 0.13mol of monoammonium phosphate NH 4 H 2 PO 4 After being evenly mixed by a solid-phase ball milling method, the mixture is transferred into a graphite crucible, and then is placed in a tube furnace to be kept at 750 ℃ and under helium atmosphere for 2 hours, and the heating rate is 5 ℃/min, thus obtaining manganese phosphate Mn 3 (PO 4 ) 2 ；
Step (2), manganese phosphate Mn is obtained 3 (PO 4 ) 2 Transferring into a high-energy ball mill for treatment for 4 hours, setting the rotating speed to 400r/min, and obtaining the nano-granular manganese phosphate Mn 3 (PO 4 ) 2 The grain diameter is 50-80 nm;
step (3), 0.3mol of sodium fluoride NaF, 0.2mol of sodium hydroxide NaOH and 0.067mol of monoammonium phosphate NH 4 H 2 PO 4 Manganese phosphate Mn prepared in step (2) 3 (PO 4 ) 2 And 0.2mol of citric acid C 6 H 8 O 7 After being evenly mixed by a solid-phase ball milling mode, the mixture is transferred into a graphite crucible and then placed in a tube furnace to be kept at 800 ℃ for 8 hours under helium atmosphere, and the heating rate is 5 ℃/min; then the reaction product is placed in helium atmosphere and is rapidly cooled to room temperature for 1min at 25 ℃, and the sodium manganese fluorophosphate Na is obtained after uniform grinding 5 Mn 2 (PO4) 2 F 3 The powder had a purity of 99.98% and was designated as material D1-2.
The prepared electrode material D1-2 is assembled into a button cell of the sodium ion battery, and as the prepared material D1-2 is coated with a carbon layer in the high-temperature sintering process, synthetic material particles are larger and are in um level, so that the capacity of the battery is lower than that of the embodiment, and the capacities of the battery under different multiplying powers of 0.2C, 1C, 2C, 5C and 10C are respectively: 120mAh/g,111mAh/g,102mAh/g,93mAh/g,85mAh/g.
Example 5 CrPO 4 Preparation of Na with @ C as precursor 3 Cr 2 (PO 4 ) 2 F 3
Step (1), 0.2mol of chromium nitrate Cr (NO 3 ) 3 .9H 2 O, 0.2mol of monoammonium phosphate NH 4 H 2 PO 4 And 0.2mol of citric acid C 6 H 8 O 7 Uniformly mixing by a solid-phase ball milling mode, and transferring into a graphite crucibleThen placing the mixture into a tube furnace, and preserving heat for 5 hours at 700 ℃ under helium atmosphere, wherein the temperature rising rate is 5 ℃/min, thus obtaining the carbon-coated chromium phosphate CrPO 4 @C。
Step (2), obtaining the carbon-coated chromium phosphate CrPO 4 Transferring @ C into a high-energy ball mill, treating for 4 hours, and setting the rotating speed to 400r/min to obtain nano-granular carbon-coated chromium phosphate CrPO 4 @C, wherein the particle size is 50-80 nm;
step (3), coating 0.3mol of sodium fluoride NaF and the precursor carbon prepared in the step (2) with chromium phosphate CrPO 4 Uniformly mixing @ C by a solid-phase ball milling mode, transferring into a graphite crucible, and then placing into a tube furnace to perform heat preservation for 8 hours at 600 ℃ under helium atmosphere, wherein the heating rate is 5 ℃/min; then the reaction product is placed in helium atmosphere and is rapidly cooled to room temperature for 1min at 25 ℃, and the sodium chromium fluorophosphate Na is obtained after uniform grinding 3 Cr 2 (PO 4 ) 2 F 3 The purity of the material was 99.99%, designated as material # 5.
And assembling the prepared electrode material 5# into a button cell of the sodium ion battery, wherein the capacities of the button cell at different multiplying powers of 0.2C, 1C, 2C, 5C and 10C are respectively as follows: 129mAh/g,122mAh/g,111mAh/g,106mAh/g,97mAh/g. Due to the high purity of the material, the specific capacity of the battery at 0.2C is close to the theoretical specific capacity.
Comparative example 5 preparation of Na by sol-gel method 3 Cr 2 (PO 4 ) 2 F 3
0.2mol of citric acid C is added into a beaker 6 H 8 O 7 And 50mL deionized water, dissolving in water bath at 85deg.C, setting rotation speed at 150r/min, and sequentially adding 0.2mol chromium nitrate Cr (NO) 3 ) 3 .9H 2 O, 0.3mol of sodium fluoride NaF, 0.2mol of ammonium dihydrogen phosphate NH 4 H 2 PO 4 Continuously heating in water bath at 85deg.C, standing in air drying oven at 90deg.C to remove residual water and residual gas after the reaction solution shows gel state, completely drying the product, pulverizing, grinding, transferring the ground powder into graphite crucible, placing in tubular furnace, maintaining temperature at 350deg.C under helium atmosphere for 5 hr, and heating at 5deg.CA/min; taking out, carrying out secondary grinding, transferring into a graphite crucible again, placing into a tube furnace, and preserving heat for 8 hours at 750 ℃ under helium atmosphere, wherein the heating rate is 5 ℃/min; then the reaction product is placed in helium atmosphere and is rapidly cooled to room temperature for 1min at the cooling temperature of 25 ℃, and the obtained sodium chromium fluorophosphate Na is obtained after being taken out and ground uniformly 3 Cr 2 (PO 4 ) 2 F 3 Since the precursor contains a large amount of chromium oxide impurities, the purity of the material is 87%, which is denoted as material E1.
The prepared electrode material E1 is assembled into a button cell of the sodium ion battery, and the prepared material E1 contains more impurities, so that the capacity of the battery is lower, and the capacities of the battery under different multiplying powers of 0.2C, 1C, 2C, 5C and 10C are respectively as follows: 109mAh/g,101mAh/g,98mAh/g,87mAh/g,76mAh/g.
Comparative example 5-2 CrPO 4 Preparation of Na for precursor 3 Cr 2 (PO 4 ) 2 F 3
Step (1), 0.2mol of chromium nitrate Cr (NO 3 ) 3 .9H 2 O, 0.2mol of monoammonium phosphate NH 4 H 2 PO 4 After being evenly mixed by a solid-phase ball milling method, the mixture is transferred into a graphite crucible, and then is placed in a tube furnace to be kept at 700 ℃ for 5 hours under helium atmosphere, and the heating rate is 5 ℃/min, thus obtaining chromium phosphate CrPO 4 。
Step (2), obtaining chromium phosphate CrPO 4 Transferring into a high-energy ball mill for treatment for 4 hours, setting the rotating speed to 400r/min, and obtaining the nano-granular chromium phosphate CrPO 4 The grain diameter is 50-80 nm;
step (3), 0.3mol of sodium fluoride NaF and the precursor chromium phosphate CrPO prepared in the step (2) 4 And 0.2mol of citric acid C 6 H 8 O 7 After being evenly mixed by a solid-phase ball milling mode, the mixture is transferred into a graphite crucible and then placed in a tube furnace to be kept at 600 ℃ for 8 hours under helium atmosphere, and the heating rate is 5 ℃/min; then the reaction product is placed in helium atmosphere and is rapidly cooled to room temperature for 1min at 25 ℃, and the sodium chromium fluorophosphate Na is obtained after uniform grinding 3 Cr 2 (PO 4 ) 2 F 3 The purity of the material was 99.98%, designated as material E1-2.
The prepared electrode material E1-2 is assembled into a button cell of the sodium ion battery, and as the prepared material E1-2 is coated with a carbon layer in the high-temperature sintering process, synthetic material particles are larger and are in um level, so that the capacity of the battery is lower than that of the embodiment, and the capacities of the battery under different multiplying powers of 0.2C, 1C, 2C, 5C and 10C are respectively: 115mAh/g,106mAh/g,100mAh/g,92mAh/g,80mAh/g.
Example 6 with VPO 4 Preparation of NaVPO with @ C as a precursor 4 F
Step (1), 0.05mol of vanadium pentoxide V 2 O 5 0.1mol of monoammonium phosphate NH 4 H 2 PO 4 0.2mol of citric acid C 6 H 8 O 7 Uniformly mixing by a solid phase ball milling method, transferring into a graphite crucible, placing into a tube furnace, preserving heat for 5 hours at 750 ℃ under helium atmosphere, and obtaining the carbon-coated vanadium phosphate VPO at a heating rate of 5 ℃/min 4 @C; XRD in fig. 1 can see that VPO4 is very pure and the spectra correspond well. FIG. 2 is VPO 4 Carbon content of @ C was measured and as can be seen from the figure, the carbon content was about 3%. VPO in FIG. 3 4 The particle size of @ C is um level, and the size is larger.
Step (2), the vanadium phosphate VPO coated with carbon 4 Transferring @ C into a high-energy ball mill for treatment for 4 hours, and setting the rotating speed to 400r/min to obtain nano-granular carbon-coated vanadium phosphate VPO 4 After ball milling, VPO can be seen in FIG. 4@ C 4 The granularity of @ C is obviously reduced, and the granularity is 50-80 nm.
Step (3), uniformly mixing 0.1mol of sodium fluoride NaF and the nano-granular carbon-coated vanadium phosphate VPO4@C prepared in the step (2) in a solid phase ball milling mode, transferring the mixture into a graphite crucible, and then placing the graphite crucible in a tube furnace for heat preservation at 700 ℃ under helium atmosphere for 8 hours, wherein the heating rate is 5 ℃/min; and then the reaction product is placed in helium atmosphere and is rapidly cooled to room temperature for 1min at 25 ℃, and the NaVPO4F material with the purity of 99.99% and the purity of material No. 6 is obtained after uniform grinding. As can be seen from fig. 5, the final product obtained in the examples is on the nano scale and the particles are distributed very uniformly.
The prepared electrode material 6# is assembled into a button cell of a sodium ion battery, and the capacities of the button cell at different multiplying powers of 0.2C, 1C, 2C, 5C and 10C are respectively as follows: 135mAh/g,128mAh/g,120mAh/g,110mAh/g,103mAh/g. Due to the high purity of the material, the specific capacity of the battery at 0.2C is close to the theoretical specific capacity.
Comparative example 6 Sol gel method NaVPO 4 F
0.2mol of citric acid C is added into a beaker 6 H 8 O 7 And 50mL of deionized water, dissolving in a water bath at 85 ℃ at a rotating speed of 150r/min, and slowly adding 0.1mol of ammonium metavanadate NH into the beaker 4 VO 3 When the color of the solution changes from yellow to green to blue and no bubbles are generated, 0.1mol of sodium fluoride NaF and 0.1mol of ammonium dihydrogen phosphate NH are added in sequence 4 H 2 PO 4 Continuously maintaining the temperature at 85 ℃ for water bath heating, placing the reaction solution in a 90 ℃ blast drying oven to remove residual moisture and residual gas after the reaction solution is in a gel state, completely drying the product, crushing and grinding, transferring the uniformly ground powder into a graphite crucible, placing the graphite crucible in a tube furnace, and preserving the heat for 5 hours under the helium atmosphere at the temperature of 350 ℃ and the heating rate of 5 ℃/min; taking out, performing secondary grinding, transferring the grinded precursor (shown as XRD of the precursor prepared by the sol-gel method in comparative example 6 in FIG. 6, the precursor containing oxide and a large amount of vanadium trioxide) into a graphite crucible again, placing the graphite crucible in a tube furnace, and preserving the temperature for 8 hours under the helium atmosphere at 750 ℃; and then the reaction product is placed in helium atmosphere and is rapidly cooled to room temperature for 1min at the cooling temperature of 25 ℃, and the NaVPO4F material is obtained after uniform grinding. The precursor contains more vanadium oxide impurities, the purity is 90%, and the precursor is marked as a material F1.
The prepared electrode material F1 is assembled into a button cell of the sodium ion battery, and the prepared material FA1 contains more impurities, so that the capacity of the battery is lower, and the capacities of the battery under different multiplying powers of 0.2C, 1C, 2C, 5C and 10C are respectively as follows: 110mAh/g,101mAh/g,93mAh/g,82mAh/g,74mAh/g.
Comparative example 6-2 with VPO 4 Is a precursorPreparation of NaVPO in vivo 4 F
Step (1), 0.05mol of vanadium pentoxide V 2 O 3 0.1mol of monoammonium phosphate NH 4 H 2 PO 4 Uniformly mixing by a solid-phase ball milling method, transferring into a graphite crucible, placing into a tube furnace, preserving heat for 5 hours at 750 ℃ under helium atmosphere, and obtaining vanadium phosphate VPO at a heating rate of 5 ℃/min 4 The method comprises the steps of carrying out a first treatment on the surface of the FIG. 7 shows the synthesized vanadium phosphate VPO 4 Is pure phase.
Step (2), vanadium phosphate VPO 4 Transferring into a high-energy ball mill for treatment for 4 hours, setting the rotating speed to 400r/min, and obtaining the nano-granular vanadium phosphate VPO 4 FIG. 8 is an SEM of comparative example 6-2 after ball milling without carbon-coated vanadium phosphate, and the morphology of the ball milled without carbon-coated vanadium phosphate, as can be seen, the particle size is 50-80 nm;
step (3), 0.1mol of sodium fluoride NaF and the nano-granular vanadium phosphate VPO prepared in the step (2) 4 And 0.2mol of citric acid C 6 H 8 O 7 After being evenly mixed by a solid-phase ball milling mode, the mixture is transferred into a graphite crucible and then placed in a tube furnace to be kept at 700 ℃ for 8 hours under helium atmosphere, and the heating rate is 5 ℃/min; and then the reaction product is placed in helium atmosphere and rapidly cooled to room temperature for 1min at the cooling temperature of 25 ℃, and the NaVPO4F material is obtained after uniform grinding, but the particle size of the NaVPO4F material is obviously larger than that of the example (see figure 9, which is SEM (large particle) of the final product NVPF prepared by taking vanadium phosphate without carbon coating of comparative example 6-2 as a precursor), and the purity is 99.97 percent, which is marked as material F1-2.
The prepared electrode material F1-2 is assembled into a button cell of the sodium ion battery, and as the prepared material F1-2 is coated with a carbon layer in the high-temperature sintering process, synthetic material particles are larger and are in um level, so that the capacity of the battery is lower than that of the embodiment, and the capacities of the battery under different multiplying powers of 0.2C, 1C, 2C, 5C and 10C are respectively: 127mAh/g,117mAh/g,107mAh/g,95mAh/g,82mAh/g.
EXAMPLE 7 VPO 4 Preparation of Mg-doped Na with @ C as precursor 1.1 V 0.9 Mg 0.1 PO 4 F
Step (1), 0.45mol of vanadium pentoxide V 2 O 5 0.9mol of monoammonium phosphate NH 4 H 2 PO 4 2mol of citric acid C 6 H 8 O 7 Uniformly mixing by a solid phase ball milling method, transferring into a graphite crucible, placing into a tube furnace, preserving heat for 5 hours at 750 ℃ under helium atmosphere, and obtaining the carbon-coated vanadium phosphate VPO at a heating rate of 5 ℃/min 4 @C；
Step (2), the vanadium phosphate VPO coated with carbon 4 Transferring @ C into a high-energy ball mill for treatment for 4 hours, and setting the rotating speed to 400r/min to obtain nano-granular carbon-coated vanadium phosphate VPO 4 @C, wherein the particle size is 50-80 nm;
step (3), 1/30mol of magnesium acetate Mg (CH 3 COO) 2 1/20mol of monoammonium phosphate NH 4 H 2 PO 4 After being evenly mixed by a solid-phase ball milling mode, the mixture is transferred into a graphite crucible and then placed into a tube furnace, and the mixture is preserved for 5 hours under the helium atmosphere at the temperature of 750 ℃ and the heating rate of 5 ℃/min, thus obtaining magnesium phosphate Mg 3 (PO 4 ) 2 ；
Step (4), 0.55mol of sodium carbonate Na 2 CO 3 And (2) the nano-granular carbon-coated vanadium phosphate VPO4@C prepared in the step (3) and Mg prepared in the step (3) 3 (PO 4 ) 2 And 1mol of ammonium fluoride NH 4 F. 1/30mol of monoammonium phosphate is uniformly mixed in a solid phase ball milling mode, transferred into a graphite crucible, and then placed in a tube furnace to be kept at 700 ℃ under helium atmosphere for 8 hours, wherein the heating rate is 5 ℃/min; then the reaction product is placed in helium atmosphere and is rapidly cooled to room temperature for 1min at 25 ℃, and the Na doped with magnesium can be obtained after uniform grinding 1.1 V 0.9 Mg 0.1 PO 4 F material with 99.99% purity, designated material 7#.
The prepared electrode material 7# is assembled into a button cell of a sodium ion battery, and the capacities of the button cell at different multiplying powers of 0.2C, 1C, 2C, 5C and 10C are respectively as follows: 134mAh/g,126mAh/g,121mAh/g,113mAh/g and 108mAh/g. Due to the high purity of the material, the specific capacity of the battery at 0.2C is close to the theoretical specific capacity.
Comparative example 7 preparation of Na by sol-gel method 1.1 V 0.9 Mg 0.1 PO 4 F
2mol of citric acid C are added into a beaker 6 H 8 O 7 And 100mL deionized water, dissolve in a water bath at 85deg.C, set at 150r/min, then slowly add 0.9mol ammonium metavanadate NH into the beaker 4 VO 3 When the color of the solution changes from yellow to green to blue and no bubbles are generated, 1mol of ammonium fluoride NH4F and 1mol of ammonium dihydrogen phosphate NH are added in sequence 4 H 2 PO 4 Sodium carbonate Na 0.55mol 2 CO 3 1/30mol of magnesium acetate Mg (CH) 3 COO) 2 Continuously maintaining the temperature at 85 ℃ for water bath heating, placing the reaction solution in a 90 ℃ blast drying oven to remove residual moisture and residual gas after the reaction solution is in a gel state, completely drying the product, crushing and grinding, transferring the uniformly ground powder into a graphite crucible, placing the graphite crucible in a tube furnace, and preserving the heat for 5 hours under the helium atmosphere at the temperature of 350 ℃ and the heating rate of 5 ℃/min; taking out, carrying out secondary grinding, transferring the ground precursor into a graphite crucible again, placing the graphite crucible in a tube furnace, and preserving heat for 8 hours at 750 ℃ in helium atmosphere; then the reaction product is placed in helium atmosphere and is rapidly cooled to room temperature for 1min at 25 ℃, and the Na doped with magnesium can be obtained after uniform grinding 1.1 V 0.9 Mg 0.1 PO 4 And F, material. Since the precursor contains more vanadium oxide impurities, the purity is 90%, which is denoted as material G1.
The prepared electrode material G1 is assembled into a button cell of the sodium ion battery, and the prepared material FA1 contains more impurities, so that the capacity of the battery is lower, and the capacities of the battery under different multiplying powers of 0.2C, 1C, 2C, 5C and 10C are respectively as follows: 112mAh/g,107mAh/g,96mAh/g,85mAh/g,78mAh/g.
Comparative example 7-2 with VPO 4 Preparation of Na for precursor 1.1 V 0.9 Mg 0.1 PO 4 F
Step (1), 0.45mol of vanadium pentoxide V 2 O 5 0.9mol of monoammonium phosphate NH 4 H 2 PO 4 Uniformly mixing by solid-phase ball milling, transferring into a graphite crucible, and placing into a tubeIn a formula furnace, preserving heat for 5 hours at 750 ℃ under helium atmosphere, and obtaining vanadium phosphate VPO at a heating rate of 5 ℃/min 4 ；
Step (2), vanadium phosphate VPO 4 Transferring into a high-energy ball mill for treatment for 4 hours, setting the rotating speed to 400r/min, and obtaining the nano-granular vanadium phosphate VPO 4 The grain diameter is 50-80 nm;
step (3), 1/30mol of magnesium acetate Mg (CH 3 COO) 2 1/20mol of monoammonium phosphate NH 4 H 2 PO 4 After being evenly mixed by a solid-phase ball milling mode, the mixture is transferred into a graphite crucible and then placed into a tube furnace, and the mixture is preserved for 5 hours under the helium atmosphere at the temperature of 750 ℃ and the heating rate of 5 ℃/min, thus obtaining magnesium phosphate Mg 3 (PO 4 ) 2 ；
Step (4), 0.55mol of sodium carbonate Na 2 CO 3 And (2) nano-granular vanadium phosphate VPO4@C prepared in the step (3) and Mg prepared in the step (3) 3 (PO 4 ) 2 1mol of ammonium fluoride NH 4 F. 1/30mol of monoammonium phosphate and 0.2mol of citric acid C 6 H 8 O 7 After being evenly mixed by a solid-phase ball milling mode, the mixture is transferred into a graphite crucible and then placed in a tube furnace to be kept at 700 ℃ for 8 hours under helium atmosphere, and the heating rate is 5 ℃/min; then the reaction product is placed in helium atmosphere and is rapidly cooled to room temperature for 1min at 25 ℃, and the Na doped with magnesium can be obtained after uniform grinding 1.1 V 0.9 Mg 0.1 PO 4 F material with 99.99% purity was designated as material G1-2.
The prepared electrode material G1-2 is assembled into a button cell of the sodium ion battery, and as the prepared material G1-2 is coated with a carbon layer in the high-temperature sintering process, synthetic material particles are larger and are in um level, so that the capacity of the battery is lower than that of the embodiment, and the capacities of the battery under different multiplying powers of 0.2C, 1C, 2C, 5C and 10C are respectively: 126mAh/g,119mAh/g,109mAh/g,98mAh/g,90mAh/g.
Test case
Preparation of electrodes
1g of 5w% polyvinylidene fluoride (PVDF)/N-methylpyrrolidone (NMP) solution is firstly taken in a weighing bottle (specification phi 25 multiplied by 25 mm), and 0.8g of NMP is added and stirred uniformly to obtain a standby solution. 0.35g of the material powders prepared in examples 1 to 5 and comparative examples 1 to 5 (material 1#, material 2#, material 3#, material 4#, material 5# and material A, material B, material C, material D and material E) and 0.1g of Super P were respectively ground and mixed uniformly, and added to the solution for standby. After stirring for 5 hours, the mixture was knife-coated onto aluminum foil. The aluminum foil was dried in an oven at 65 ℃ for 12 hours. Then cutting the dried electrode into a wafer with the diameter of 14mm to serve as a positive plate for standby.
Battery assembly
The positive electrode of the half cell is the positive electrode plate prepared by the method, the negative electrode is a metal sodium plate, the diaphragm is a glass fiber membrane GF/C, and the electrolyte is 1.0mol L -1 NaClO of (C) 4 As a solute, EC/DEC (volume ratio 1:1) was used as a solvent, and a mixed solution of 5% fec additive was added. The assembly of the button half-cell was carried out in an argon-filled glove box (water/oxygen content less than 0.01 ppm), after encapsulation in the glove box, the cell was transferred out of the glove box and was allowed to stand in an oven at 40 ℃ for 24 hours for testing.
Battery testing
The charge and discharge test of the button cell is carried out by adopting a constant current voltage limiting mode. The test instrument used was the battery test system CT2100 developed by marchand electronics limited. The voltage range for half cell testing was set to 2-4.3V with a test temperature of 25 ℃.
Claims (10)
1. A process for the preparation of a polyanionic compound characterized by:
the polyanionic compound has a structure represented by formula I:
A 1+q (M 1-b N b ) y (XO e ) z D d a formula I;
in formula I:
a is at least one of Li, na and K;
m is selected from at least one of Fe, mn, ni, co, V, cr;
n is selected from at least one of Nb, Y, mg, ti, cu, zr, al;
x is selected from at least one of P, S, V, si, nb, mo, al, B;
d is at least one selected from F, OH, cl, br;
-0.2≤q≤3；0.9≤y≤2；0≤d≤4；1≤z≤3；1≤e≤4；0≤b≤0.1；
the preparation method of the polyanion compound comprises the following steps:
step (1), mixing raw materials I containing an M source, a carbon source and an X source, and performing heat treatment I in an inactive atmosphere I to obtain carbon-coated MXO e The method comprises the steps of carrying out a first treatment on the surface of the The time of the heat treatment I is 1-20 h;
step (2), the carbon-coated MXO obtained in the step (1) e Ball milling to obtain nano carbon coated MXO e ；
Step (3), mixing raw materials III containing N source and X source, and performing heat treatment III in an inactive atmosphere III to obtain the NXO e ；
Step (4) comprising the nanoscale carbon-coated MXO e The NXO e Mixing a raw material II of a source A, a source X and a source D, performing heat treatment II in an atmosphere II, and then cooling in the atmosphere II to obtain the polyanion compound; the time of the heat treatment II is 2-20 h.
2. The method according to claim 1, wherein,
the molar ratio of the total amount of the source A to the source X to the source D is (1+q), wherein z is D, and the z is calculated according to the molar amount of A in the source A, the molar amount of X in the source X and the molar amount of D in the source D respectively; the total amount of the X sources is the sum of the amount of the X sources in the step (1), the amount of the X sources in the step (3) and the amount of the X sources in the step (4);
in the step (1), the molar ratio of the M source to the X source is (1-b) X y: M; wherein 0<m is less than or equal to z;
in the step (3), the molar ratio of the N source to the X source is by; wherein n is 0.ltoreq.n < z;
in the step (4), the molar ratio of the D source to the X source is D (z-m-n), wherein n/(m+n) is more than or equal to 0 and less than or equal to 0.1.
3. The method according to claim 1, wherein,
the temperature of the heat treatment I is 500-1000 ℃, and the heating rate is 1-10 ℃ per minute.
4. The method according to claim 1, wherein,
when X is selected from P, B and M is selected from Mn, the temperature of the heat treatment II is 660-1200 ℃, and the molar ratio of the M source to the X source is 3:2, based on the molar amount of M in the M source and the molar amount of X in the X source;
when X is selected from P, B and M is selected from Fe, the temperature of the heat treatment II is 1000-1400 ℃, and the molar ratio of the M source to the X source is 1:1, based on the molar amount of M in the M source and the molar amount of X in the X source;
when X is selected from P, B and M is selected from one or more of Cr, the temperature of the heat treatment II is 500-1200 ℃, and the molar ratio of the M source to the X source is 1:1; based on the molar amount of M in the M source and the molar amount of X in the X source;
when X is selected from P, B and M is selected from one or more of Ni and Co, the temperature of the heat treatment II is 500-1200 ℃, and the molar ratio of the M source to the X source is 3:2; based on the molar amount of M in the M source and the molar amount of X in the X source;
when X is selected from P, B and M is selected from V, the temperature of the heat treatment II is 700-1200 ℃, and the molar ratio of the M source to the X source is 1:1, based on the molar amount of M in the M source and the molar amount of X in the X source;
When X is selected from S, si, mn, mo and M is selected from Mn, the temperature of the heat treatment II is 700-1200 ℃, and the molar ratio of the M source to the X source is 1:1, based on the molar amount of M in the M source and the molar amount of X in the X source;
when X is selected from S, si, mn, mo and M is selected from Fe, the temperature of the heat treatment II is 500-1000 ℃, and the molar ratio of the M source to the X source is 2:3, based on the molar amount of M in the M source and the molar amount of X in the X source;
when X is selected from S, si, mn, mo and M is selected from Cr, the temperature of the heat treatment II is 500-1000 ℃, and the molar ratio of the M source to the X source is 2:3, based on the molar amount of M in the M source and the molar amount of X in the X source;
when X is selected from S, si, mn, mo and M is selected from Ni and Co, the temperature of the heat treatment II is 500-1000 ℃, and the molar ratio of the M source to the X source is 1:1, based on the molar amount of M in the M source and the molar amount of X in the X source;
when X is selected from S, si, mn, mo and M is selected from V, the temperature of the heat treatment II is 700-1200 ℃, and the molar ratio of the M source to the X source is 2:3, based on the molar amount of M in the M source and the molar amount of X in the X source;
when X is selected from V, nb and Al, M is selected from Mn, the temperature of the heat treatment II is 700-1200 ℃, and the molar ratio of the M source to the X source is 1:2, based on the molar amount of M in the M source and the molar amount of X in the X source;
When X is selected from V, nb and Al, and M is selected from Fe, the temperature of the heat treatment II is 500-1000 ℃, and the molar ratio of the M source to the X source is 1:3, based on the molar amount of M in the M source and the molar amount of X in the X source;
when X is selected from V, nb and Al, M is selected from Cr, the temperature of the heat treatment II is 500-1000 ℃, and the molar ratio of the M source to the X source is 1:3, based on the molar amount of M in the M source and the molar amount of X in the X source;
when X is selected from V, nb and Al, M is selected from Ni and Co, the temperature of the heat treatment II is 500-1000 ℃, and the molar ratio of an M source to an X source is 1:2, based on the molar amount of M in the M source and the molar amount of X in the X source;
when X is selected from V, nb and Al, M is selected from V, the temperature of the heat treatment II is 700-1200 ℃, and the molar ratio of the M source to the X source is 1:3, based on the molar amount of M in the M source and the molar amount of X in the X source.
5. The method according to claim 1, wherein,
the time of the heat treatment III is 2-5 hours; the temperature of the heat treatment III is 600-1000 ℃, and the heating rate is 1-10 ℃ per minute.
6. The method according to claim 1, wherein,
in the step (1), the carbon source is at least one selected from citric acid, oxalic acid, ascorbic acid, glucose, sucrose, fructose and polyethylene glycol;
Preferably, the mass of the carbon source is 5% -40% of the total mass of the M source and the X source;
preferably, in the step (2), a high-energy ball mill is adopted for ball milling, the rotating speed is 200-800 r/min, and the ball milling treatment is carried out for 2-6 h;
preferably, in the step (2), the particle size of the nano particles is 1 nm-100 nm; preferably 50nm to 80nm;
preferably, in the step (4), the cooling time is 10 s-5 min, and the cooling time is 20-30 ℃;
preferably, the inactive atmosphere I, inactive atmosphere III are each independently selected from helium and/or nitrogen; the atmosphere II is selected from helium, nitrogen and H 2 At least one of them.
7. The method according to claim 1, wherein,
the source A, the source M, the source N, the source X and the source D are at least one selected from oxides, carbonates, hydroxides, oxalates, nitrates, phosphates, metal simple substances, chlorides, fluorides, bromides, sulfides and amides;
preferably, the method comprises the steps of,
the A source is selected from Li 2 O、Li 2 CO 3 、LiOH、LiH 2 PO 4 、Li 3 PO 4 、LiF、Na 2 CO 3 At least one of NaOH and KOH;
the M source is selected from Fe, fe 2 O 3 、Fe 3 O 4 、FeO、Co 3 O 4 、CoO、V 2 O 5 、Cr 2 O 3 、MnO、Mn 2 O 3 、MnO 2 、Mn 3 O 4 、Mn(CH 3 COO) 2 .4H 2 O, niO;
the N source is selected from Nb 2 O 5 、Y 2 O 3 、B 2 O 3 、TiO 2 、Cu 2 O、CuO、MgO、MgCO 3 、Mg(CH 3 COO) 2 At least one of (a) and (b);
the X source is selected from Nb 2 O 5 、V 2 O 5 、NH 4 H 2 PO 4 、(NH 4 ) 2 HPO 4 、H 3 PO 4 、P 2 O 5 、SiO 2 、Al 2 O 3 、MoO。
8. The polyanionic compound prepared by the preparation method according to any one of claims 1 to 7, wherein the purity of the compound is >99.9%.
9. Use of the polyanion compound according to claim 9 as positive electrode material in an alkali metal ion battery.
10. A positive electrode material comprising the polyanion-type compound produced by the production method according to any one of claims 1 to 7 or comprising the polyanion-type compound according to claim 8.
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