CN116692810A - 一种磷酸焦磷酸铁锰钠正极材料的制备方法 - Google Patents
一种磷酸焦磷酸铁锰钠正极材料的制备方法 Download PDFInfo
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- CN116692810A CN116692810A CN202310516491.4A CN202310516491A CN116692810A CN 116692810 A CN116692810 A CN 116692810A CN 202310516491 A CN202310516491 A CN 202310516491A CN 116692810 A CN116692810 A CN 116692810A
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- China
- Prior art keywords
- sodium
- pyrophosphate
- phosphate
- manganese
- positive electrode
- Prior art date
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- -1 sodium iron manganese phosphate pyrophosphate Chemical compound 0.000 title claims abstract description 18
- 239000007774 positive electrode material Substances 0.000 title claims description 45
- 239000011734 sodium Substances 0.000 claims abstract description 108
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 92
- 239000011572 manganese Substances 0.000 claims abstract description 69
- 238000000498 ball milling Methods 0.000 claims abstract description 60
- 239000000463 material Substances 0.000 claims abstract description 57
- 150000003839 salts Chemical class 0.000 claims abstract description 47
- 238000005303 weighing Methods 0.000 claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims abstract description 24
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002270 dispersing agent Substances 0.000 claims abstract description 15
- 238000001291 vacuum drying Methods 0.000 claims abstract description 12
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 239000010405 anode material Substances 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 238000000967 suction filtration Methods 0.000 claims abstract description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 43
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- UBYFFBZTJYKVKP-UHFFFAOYSA-J [Mn+4].[O-]P([O-])(=O)OP([O-])([O-])=O Chemical compound [Mn+4].[O-]P([O-])(=O)OP([O-])([O-])=O UBYFFBZTJYKVKP-UHFFFAOYSA-J 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 10
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 10
- 235000011187 glycerol Nutrition 0.000 claims description 10
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 229940062993 ferrous oxalate Drugs 0.000 claims description 7
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 7
- 239000001632 sodium acetate Substances 0.000 claims description 7
- 235000017281 sodium acetate Nutrition 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 239000005955 Ferric phosphate Substances 0.000 claims description 6
- 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 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 229940032958 ferric phosphate Drugs 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 6
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 6
- 229940071125 manganese acetate Drugs 0.000 claims description 6
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 229940116007 ferrous phosphate Drugs 0.000 claims description 5
- 229910000155 iron(II) phosphate Inorganic materials 0.000 claims description 5
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 4
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 4
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 4
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 239000011656 manganese carbonate Substances 0.000 claims description 3
- 235000006748 manganese carbonate Nutrition 0.000 claims description 3
- 229940093474 manganese carbonate Drugs 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 3
- HWPKGOGLCKPRLZ-UHFFFAOYSA-M monosodium citrate Chemical compound [Na+].OC(=O)CC(O)(C([O-])=O)CC(O)=O HWPKGOGLCKPRLZ-UHFFFAOYSA-M 0.000 claims description 3
- 239000002524 monosodium citrate Substances 0.000 claims description 3
- 235000018342 monosodium citrate Nutrition 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 3
- IEYGGTJEBHWPNO-UHFFFAOYSA-K sodium iron(2+) manganese(2+) phosphate Chemical compound [Na+].[Fe+2].P(=O)([O-])([O-])[O-].[Mn+2] IEYGGTJEBHWPNO-UHFFFAOYSA-K 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 229960002413 ferric citrate Drugs 0.000 claims description 2
- 229960005191 ferric oxide Drugs 0.000 claims description 2
- 235000001727 glucose Nutrition 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 235000021313 oleic acid Nutrition 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 abstract description 4
- UMZUVDAJYPZSCI-UHFFFAOYSA-K sodium [hydroxy(oxido)phosphoryl] phosphate manganese(2+) Chemical compound [O-]P([O-])(=O)OP(=O)([O-])O.[Mn+2].[Na+] UMZUVDAJYPZSCI-UHFFFAOYSA-K 0.000 abstract description 4
- 238000005245 sintering Methods 0.000 description 31
- 239000003814 drug Substances 0.000 description 17
- 229940079593 drug Drugs 0.000 description 16
- 239000011812 mixed powder Substances 0.000 description 15
- 239000002245 particle Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 229910052593 corundum Inorganic materials 0.000 description 9
- 239000010431 corundum Substances 0.000 description 9
- 238000007873 sieving Methods 0.000 description 9
- 238000001238 wet grinding Methods 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 238000009837 dry grinding Methods 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910015136 FeMn Inorganic materials 0.000 description 5
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910001415 sodium ion Inorganic materials 0.000 description 5
- HXANRRBZAUXOMS-UHFFFAOYSA-J sodium iron(2+) manganese(2+) phosphonato phosphate Chemical compound [O-]P([O-])(=O)OP(=O)([O-])[O-].[Na+].[Fe+2].[Mn+2] HXANRRBZAUXOMS-UHFFFAOYSA-J 0.000 description 5
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 230000001788 irregular Effects 0.000 description 4
- 239000006012 monoammonium phosphate Substances 0.000 description 4
- 229960004249 sodium acetate Drugs 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- XWQGIDJIEPIQBD-UHFFFAOYSA-J sodium;iron(3+);phosphonato phosphate Chemical compound [Na+].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O XWQGIDJIEPIQBD-UHFFFAOYSA-J 0.000 description 3
- 229910000616 Ferromanganese Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910020509 Na4Mn3 (PO4)2P2O7 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- GFORUURFPDRRRJ-UHFFFAOYSA-N [Na].[Mn] Chemical compound [Na].[Mn] GFORUURFPDRRRJ-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000011706 ferric diphosphate Substances 0.000 description 2
- 235000007144 ferric diphosphate Nutrition 0.000 description 2
- CADNYOZXMIKYPR-UHFFFAOYSA-B ferric pyrophosphate Chemical compound [Fe+3].[Fe+3].[Fe+3].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O CADNYOZXMIKYPR-UHFFFAOYSA-B 0.000 description 2
- 229940036404 ferric pyrophosphate Drugs 0.000 description 2
- 239000011645 ferric sodium diphosphate Substances 0.000 description 2
- 235000019851 ferric sodium diphosphate Nutrition 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- AWRQDLAZGAQUNZ-UHFFFAOYSA-K sodium;iron(2+);phosphate Chemical compound [Na+].[Fe+2].[O-]P([O-])([O-])=O AWRQDLAZGAQUNZ-UHFFFAOYSA-K 0.000 description 2
- HEVWJXJIIXJVKU-UHFFFAOYSA-K sodium;manganese(2+);phosphate Chemical compound [Na+].[Mn+2].[O-]P([O-])([O-])=O HEVWJXJIIXJVKU-UHFFFAOYSA-K 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
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Abstract
本发明公开了一种磷酸焦磷酸铁锰钠正极材料的制备方法,特点是包括以下步骤:1)称取钠源、铁源、锰源、磷源、碳源、高分子聚合物和分散剂加入行星球磨机中球磨0.5~15h,真空干燥得到前驱体材料,其中Na:Fe:Mn:P:C的摩尔比为4:3~x:x:4:(0~25),x=0~3;磷酸焦磷酸铁锰钠:高分子聚合物的质量比=(9.9~10.1):1;2)称取熔盐粉末加入球磨机中,使熔盐:前驱体的质量比=(0.2~5):1,球磨时长0.5~5h,将熔盐粉末和前驱体粉末球磨混合均匀后,在惰性气氛下进行热处理后,将烧结粉末置于溶剂中超声分散,通过抽滤后烘干得到纯净的多孔磷酸焦磷酸铁锰钠正极材料,优点高电压、优异倍率性能和循环性能。
Description
技术领域
本发明涉及磷酸焦磷酸铁锰钠正极材料,尤其是涉及一种磷酸焦磷酸铁锰钠正极材料的制备方法。
背景技术
随着人类社会经济的快速发展,新能源汽车和储能系统的需求与日俱增,对二次电池性能的要求越来越高。在所有二次电池中,锂离子电池发展较为成熟,但锂资源在全球范围内储量有限,分布不均,因此需要寻找新型电池作为锂离子电池的替代或补充。钠作为锂的同族元素,在地球中储量丰富、分布均匀、价格低廉,钠离子电池也有着更高的倍率性能、安全性能和高低温性能,发展和应用前景良好。在钠离子电池系统中,正极材料是影响电池能量密度的最关键因素。近年来,一类正极材料——磷酸焦磷酸铁钠Na4Fe3(PO4)2P2O7,因其结构稳定性强、倍率性能和循环性能优异,受到了学术界和工业界的广泛关注。
磷酸焦磷酸铁钠Na4Fe3(PO4)2P2O7综合了磷酸铁钠NaFePO4和焦磷酸铁钠Na2FeP2O7二者的优势,通过阴离子基团的诱导效应克服了磷酸铁钠电化学活性低的问题,具有三维钠离子扩散通道,电化学性能优于NaFePO4和Na2FeP2O7材料,但Na4Fe3(PO4)2P2O7材料的平台电压较低,仅为3.0V,为了提高Na4Fe3(PO4)2P2O7平台电压,人们通过使用Mn元素来部分取代Na4Fe3(PO4)2P2O7中的Fe元素,取得了良好的效果。但是普通球磨法制备的磷酸焦磷酸铁锰钠复合材料存在材料粒径增加、铁锰复合不均、极化现象、Mn溶解等问题导致材料的电化学性能急剧衰减,严重制约了Na4Fe3-xMnx(PO4)2P2O7材料的实际应用。
发明内容
本发明所要解决的技术问题是提供一种高电压、优异倍率性能和循环性能的磷酸焦磷酸铁锰钠正极材料的制备方法。
本发明解决上述技术问题所采用的技术方案为:一种磷酸焦磷酸铁锰钠正极材料的制备方法,包括以下步骤:
(1)称取钠源、铁源、锰源、磷源、碳源、高分子聚合物和分散剂加入球磨机中球磨0.5~15h,真空干燥得到前驱体材料,其中Na:Fe:Mn:P:C的摩尔比为4:3~x:x:4:(0~25),x=0~3;磷酸焦磷酸铁锰钠:高分子聚合物的质量比=(9.9~10.1):1;所述的分散剂选自去离子水、乙醇和丙酮中的一种;
(2)称取熔盐粉末加入球磨机中,使熔盐:前驱体的质量比=(0.2~5):1,球磨时长0.5~5h,将熔盐粉末和前驱体粉末球磨混合均匀后,在惰性气氛下进行热处理,热处理温度为450℃~600℃,煅烧时间为1~24h,然后将烧结粉末置于溶剂中超声分散以去除多余熔盐,通过抽滤后烘干得到纯净的多孔磷酸焦磷酸铁锰钠Na4Fe3-xMnx(PO4)2P2O7/C正极材料。
进一步,所述的钠源为磷酸二氢钠、磷酸氢二钠、磷酸钠、碳酸钠、碳酸氢钠、乙酸钠、柠檬酸二氢钠、草酸钠、海藻酸钠、焦磷酸钠中的一种或几种。
进一步,所述的铁源为硝酸铁、草酸亚铁、磷酸铁、磷酸亚铁、柠檬酸铁、三氧化二铁中的一种或几种。
进一步,所述的锰源为乙酸锰、硝酸锰、乙酰丙酮锰、碳酸锰、二氧化锰中的一种或几种。
进一步,所述的磷源为磷酸二氢铵、磷酸二氢钠、磷酸氢二铵、磷酸氢二钠、磷酸铁、磷酸亚铁中的一种或几种。
进一步,所述的碳源为柠檬酸、草酸、乙酸、抗坏血酸、酒石酸、油酸、葡萄糖中的一种或几种。
进一步,所述的高分子聚合物为聚乙烯吡咯烷酮、聚乙烯醇、聚乙二醇、聚丙烯腈、聚已丙酰胺中的一种或几种。
进一步,所述的熔盐为氢氧化钠、氢氧化钾、硝酸钠、硝酸钾中的一种或几种。
进一步,所述的超声分散用溶剂为去离子水、甘油、甲醇、乙醇中的一种或几种。
进一步,所述的惰性气氛为氩气、氦气、氖气和氮气中的一种或者几种。
与现有技术相比,本发明的优点在于:本发明一种磷酸焦磷酸铁锰钠正极材料的制备方法,其Na4Fe3-xMnx(PO4)2P2O7/C正极材料的烧结温度为450~600℃,选择熔点低于450℃,沸点高于600℃的无机盐作为前驱体材料的熔盐。烧结时,前驱体粉末在熔盐液相环境均质形核,保证了铁锰离子的均匀复合;熔盐烧结相比于固相烧结而言会产生数量更多的晶核,且消耗的能量抑制了晶核长大,使得颗粒粒径大大减小;熔盐的液态环境使得晶核均匀长大,高聚物在烧结时气化并造孔,得到大小均匀的近球形多孔颗粒,增大了活性材料与电解液的接触面积,缩短了钠离子传输距离;熔盐烧结对材料表面的重构作用抑制了Mn离子的溶解,有效提升了材料的倍率循环性能。烧结后多余的熔盐通过溶剂超声溶解,得到高纯的多孔磷酸焦磷酸铁锰钠Na4Fe3-xMnx(PO4)2P2O7/C正极材料。优点如下:
(1)本发明提供的熔盐辅助球磨法制备多孔磷酸焦磷酸铁锰钠Na4Fe3-xMnx(PO4)2P2O7/C正极材料的新方法,材料制备成本低、工作电压高、电化学性能优异、生产工艺简单,具有商业化和大规模生产的潜力。
(2)新工艺提出的熔盐辅助球磨法,使得前驱体粉末烧结时在熔盐液相环境均质形核,保证了铁锰离子的均匀复合;相比于常规球磨-焙烧工艺,新工艺烧结时产生更多数量的晶核,使得颗粒粒径大大减小。
(3)熔盐的液态环境使得晶核均匀长大,高聚物在烧结时气化并造孔,得到大小均匀的近球形多孔颗粒,增大了活性材料与电解液的接触面积,缩短了钠离子传输距离;熔盐烧结对材料表面的重构作用抑制了Mn离子的溶解,有效提升了材料的倍率循环性能。
综上所述,本发明一种磷酸焦磷酸铁锰钠正极材料的制备方法,通过熔盐辅助烧结协同高聚物造孔手段进行改性,解决了普通球磨法制备的Na4Fe3-xMnx(PO4)2P2O7/C正极材料存在的颗粒粒径大、铁锰分布不均、极化严重、Mn溶解等一系列问题,进而获得高电压、优异倍率性能和循环性能的多孔磷酸焦磷酸铁锰钠Na4Fe3-xMnx(PO4)2P2O7/C正极复合材料。
附图说明
图1为多孔磷酸焦磷酸铁锰钠Na4Fe3-xMnx(PO4)2P2O7/C(x=0~3)正极材料的制备原理示意图;
图2为实施例1的Na4Fe1.5Mn1.5(PO4)2P2O7/C材料XRD图谱;
图3为实施例1的Na4Fe1.5Mn1.5(PO4)2P2O7/C材料SEM图谱;
图4为对比例2的Na4Fe1.5Mn1.5(PO4)2P2O7/C材料XRD图谱;
图5为对比例2的Na4Fe1.5Mn1.5(PO4)2P2O7/C材料SEM图谱。
具体实施方式
以下结合附图实施例对本发明作进一步详细描述。
一、具体实施例
实施例1
熔盐法制备多孔磷酸焦磷酸铁锰钠Na4Fe1.5Mn1.5(PO4)2P2O7/C正极材料的方法,制备原理如图1所示,包括以下步骤:
1、按摩尔比Na:Fe:Mn:P=4:1.5:1.5:4称取乙酸钠、草酸亚铁、乙酸锰、磷酸二氢铵,选择葡萄糖为碳源(C6H12O6),按摩尔比Na4Fe1.5Mn1.5(PO4)2P2O7:C6H12O6=1:1称取,选择聚乙烯醇1788(PVA)为高分子聚合物添加剂,按质量比Na4Fe1.5Mn1.5(PO4)2P2O7:PVA=10:1称取,将上述原料按照比例称取后置于球磨罐中,选择无水乙醇为球磨分散剂,按球料比=15:1,转速300r/min,球磨湿磨12小时后,形成均一的面糊状,80℃真空干燥,得到前驱体材料;
2、向球磨罐加入熔盐氢氧化钠粉末,按质量比前驱体材料Na4Fe1.5Mn1.5(PO4)2P2O7:NaOH=1:3称取,球磨干磨1小时,将球和粉末进行过筛分离,使用刚玉管对混合粉末进行烧结,升温速率控制为3℃/min,于550℃下烧结10小时,热处理后冷却至室温,将混合粉末置于100ml甘油中超声分散1小时,抽滤后300℃处理1小时除去残留的甘油,得到纯净的磷酸焦磷酸铁锰钠Na4Fe1.5Mn1.5(PO4)2P2O7/C正极材料。
图2为实施例1的Na4Fe1.5Mn1.5(PO4)2P2O7/C材料XRD图谱;由图2可知多孔磷酸焦磷酸铁锰钠Na4Fe1.5Mn1.5(PO4)2P2O7/C正极材料的衍射峰和Na4Fe3(PO4)2P2O7的标准卡片、Na4Mn3(PO4)2P2O7的标准卡片完全重合,没有杂峰,表明通过熔盐法成功制备了纯净的Na4Fe1.5Mn1.5(PO4)2P2O7/C正极材料,熔盐和高分子聚合物添加剂的使用不会使材料产生新的杂相。
图3为实施例1的Na4Fe1.5Mn1.5(PO4)2P2O7/C材料SEM图谱;由图3和图5对比可知:通过熔盐法制备的Na4Fe1.5Mn1.5(PO4)2P2O7/C正极材料的形貌为纳米级多孔球形,表明高分子聚合物添加剂在高温下碳化分解造孔,增大了一次颗粒的比表面积;烧结时熔盐的液态环境成功调控了球磨的不规则形貌,没有二次颗粒团聚,近球形的一次颗粒表面光洁明亮,表明熔盐对材料的表面具有重构作用。
实施例2
熔盐法制备多孔磷酸焦磷酸铁锰钠Na4Fe2Mn(PO4)2P2O7/C正极材料的方法包括以下步骤:
1、按摩尔比Na:Fe:Mn:P=4:2:1:4称取柠檬酸二氢钠、硝酸铁、硝酸锰、磷酸二氢铵,选择柠檬酸为碳源(C6H8O7),按摩尔比Na4Fe2Mn(PO4)2P2O7:C6H8O7=1:1.5称取,选择聚乙烯吡咯烷酮(PVP)为高分子聚合物添加剂,按质量比Na4Fe2Mn(PO4)2P2O7:PVP=10:1称取,将上述药品按照比例称取后置于球磨罐中,混合均匀,选择丙酮为球磨分散剂,按球料比=14:1,转速250r/min,球磨湿磨15小时后形成均一的面糊状,80℃真空干燥,得到前驱体材料;
2、向球磨罐加入氢氧化钾粉末,按质量比Na4Fe2Mn(PO4)2P2O7:KOH=1:0.2称取,球磨干磨0.5小时,将球和粉末进行过筛分离,使用刚玉管对混合粉末进行烧结,控制升温速率为2℃/min,升温至500℃下烧结9小时,热处理后冷却至室温,将混合粉末置于100ml甘油中超声分散1小时,抽滤后300℃处理1小时除去残留的甘油,得到纯净的多孔磷酸焦磷酸铁锰钠Na4Fe2Mn(PO4)2P2O7/C正极材料。
实施例3
熔盐法制备多孔磷酸焦磷酸铁锰钠Na4FeMn2(PO4)2P2O7/C正极材料的方法包括以下步骤:
1、按摩尔比Na:Fe:Mn:P=4:1:2:4称取乙酸钠、磷酸亚铁、碳酸锰、磷酸二氢铵,选择酒石酸为碳源(C4H6O6),按摩尔比Na4FeMn2(PO4)2P2O7:C4H6O6=1:3称取,选择聚丙烯腈(PAN)为高分子聚合物添加剂,按质量比Na4FeMn2(PO4)2P2O7:PAN=10:1称取,将上述药品按照比例称取后置于球磨罐中,混合均匀;选择去离子水为球磨分散剂,按球料比=16:1,转速600r/min,球磨湿磨0.5小时后充分混合形成均一的面糊状,80℃真空干燥,得到前驱体材料;
2、向球磨罐加入氢氧化钠粉末,按质量比Na4FeMn2(PO4)2P2O7:NaOH=1:5称取,球磨干磨0.5小时,将球和粉末进行过筛分离,使用刚玉管对混合粉末进行烧结,控制升温速率为5℃/min,升温至450℃下烧结21小时,热处理后冷却至室温,将混合粉末置于100ml去离子水中超声分散1小时,抽滤后300℃处理1小时除去残留的水分,得到纯净的多孔磷酸焦磷酸铁锰钠Na4FeMn2(PO4)2P2O7正极材料。
实施例4
熔盐法制备多孔磷酸焦磷酸铁锰钠Na4Fe2.5Mn0.5(PO4)2P2O7/C正极材料的方法包括以下步骤:
1、按摩尔比Na:Fe:Mn:P=4:2.5:0.5:4称取海藻酸钠、草酸亚铁、乙酸锰、磷酸二氢铵,选择草酸为碳源(C2H2O4),按摩尔比Na4Fe2.5Mn0.5(PO4)2P2O7:C2H2O4=1:0.5称取,选择聚已丙酰胺(PAM)为高分子聚合物添加剂,按质量比Na4Fe2.5Mn0.5(PO4)2P2O7:PAM=10:1称取,将上述药品按照比例称取后置于球磨罐中,混合均匀;选择去离子水为球磨分散剂,按球料比=13:1,转速200r/min,球磨湿磨15小时后和药品粉末充分混合形成均一的面糊状,80℃真空干燥得到前驱体材料;
2、向球磨罐加入硝酸钠粉末,按质量比Na4Fe2.5Mn0.5(PO4)2P2O7:NaNO3=1:1称取,球磨干磨1小时,将球和粉末进行过筛分离,使用刚玉管对混合粉末进行烧结,控制升温速率为0.5℃/min,升温至600℃下烧结1小时,热处理后冷却至室温,将混合粉末置于100ml甲醇中超声分散1小时,抽滤后300℃处理1小时除去残留的甲醇,得到纯净的多孔磷酸焦磷酸铁锰钠Na4Fe2.5Mn0.5(PO4)2P2O7/C正极材料。
实施例5
熔盐法制备多孔磷酸焦磷酸铁锰钠Na4Fe0.5Mn2.5(PO4)2P2O7/C正极材料的方法包括以下步骤:
1、按摩尔比Na:Fe:Mn:P=4:0.5:2.5:4称取焦磷酸钠、磷酸铁、磷酸锰,选择抗坏血酸为碳源(C6H8O6),按摩尔比Na4Fe0.5Mn2.5(PO4)2P2O7:C6H8O6=1:2称取,选择聚乙烯吡咯烷酮(PVP)为高分子聚合物添加剂,按质量比Na4Fe0.5Mn2.5(PO4)2P2O7:PVP=10:1称取,将上述药品按照比例称取后置于球磨罐中,混合均匀;选择丙酮为球磨分散剂,按球料比=12:1,转速250r/min,球磨湿磨14小时后形成均一的面糊状,80℃真空干燥,得到前驱体材料;
2、向球磨罐加入硝酸钾粉末,按质量比Na4Fe0.5Mn2.5(PO4)2P2O7:KNO3=1:4称取,球磨干磨1小时,将球和粉末进行过筛分离,使用刚玉管对混合粉末进行烧结,控制升温速率为4℃/min,升温至575℃下烧结6小时,热处理后冷却至室温,将混合粉末置于100ml甲醇中超声分散1小时,抽滤后300℃处理1小时除去残留的甲醇,得到纯净的多孔磷酸焦磷酸铁锰钠Na4Fe0.5Mn2.5(PO4)2P2O7/C正极材料。
实施例6
熔盐法制备多孔磷酸焦磷酸铁锰钠Na4Fe3(PO4)2P2O7/C正极材料的方法包括以下步骤:
1、按摩尔比Na:Fe:P=4:3:4称取碳酸氢钠、硝酸铁、磷酸二氢铵,选择蔗糖为碳源(C12H22O11),按摩尔比Na4Fe3(PO4)2P2O7:C12H22O11=1:1称取,选择聚乙烯醇1788(PVA)为高分子聚合物添加剂,按质量比Na4Fe3(PO4)2P2O7:PVA=10:1称取,将上述药品按照比例称取后置于球磨罐中,混合均匀;选择无水乙醇为球磨分散剂,按球料比=15:1,转速300r/min,球磨湿磨12小时后形成均一的面糊状,80℃真空干燥得到前驱体材料;
2、向球磨罐加入氢氧化钠粉末,按质量比Na4Fe3(PO4)2P2O7:NaOH=1:3称取,球磨干磨1小时,将球和粉末进行过筛分离,使用刚玉管对混合粉末进行烧结,控制升温速率为3℃/min,升温至525℃下烧结15小时,热处理后冷却至室温,将混合粉末置于100ml甘油中超声分散1小时,抽滤后300℃处理1小时除去残留的甘油,得到纯净的多孔磷酸焦磷酸铁锰钠Na4Fe3(PO4)2P2O7/C正极材料。
二、对比例
对比例1
熔盐法制备无孔磷酸焦磷酸铁锰钠Na4Fe1.5Mn1.5(PO4)2P2O7/C正极材料的方法包括以下步骤:
1、按摩尔比Na:Fe:Mn:P=4:1.5:1.5:4称取乙酸钠、草酸亚铁、乙酸锰、磷酸二氢铵,选择葡萄糖为碳源(C6H12O6),按摩尔比Na4Fe1.5Mn1.5(PO4)2P2O7:C6H12O6=1:1称取,将上述药品按照比例称取后置于球磨罐中,混合均匀;选择无水乙醇为球磨分散剂,按球料比=15:1,转速300r/min,球磨湿磨12小时形成均一的面糊状,80℃真空干燥得到前驱体材料;
2、向球磨罐加入氢氧化钠粉末,按质量比Na4Fe1.5Mn1.5(PO4)2P2O7:NaOH=1:3称取,球磨干磨1小时,将球和粉末进行过筛分离,使用刚玉管对混合粉末进行烧结,控制升温速率为3℃/min,升温至550℃下烧结10小时,热处理后冷却至室温,将混合粉末置于100ml甘油中超声分散1小时,抽滤后300℃处理1小时除去残留的甘油,得到纯净的无孔磷酸焦磷酸铁锰钠Na4Fe1.5Mn1.5(PO4)2P2O7/C正极材料。
对比例2
无熔盐制备无孔磷酸焦磷酸铁锰钠Na4Fe1.5Mn1.5(PO4)2P2O7/C正极材料的方法包括以下步骤:
1、按摩尔比Na:Fe:Mn:P=4:1.5:1.5:4称取乙酸钠、草酸亚铁、乙酸锰、磷酸二氢铵,选择葡萄糖为碳源(C6H12O6),按摩尔比Na4Fe1.5Mn1.5(PO4)2P2O7:C6H12O6=1:1称取,将上述药品按照比例称取后置于球磨罐中,混合均匀;选择无水乙醇为球磨分散剂,按球料比=15:1,转速300r/min,球磨湿磨12小时后形成均一的面糊状,80℃真空干燥得到前驱体材料;
2、将前驱体材料球磨干磨1小时,将球和粉末进行过筛分离,使用刚玉管对混合粉末进行烧结,控制升温速率为3℃/min,升温至550℃下烧结10小时,热处理后冷却至室温,得到纯净的无孔磷酸焦磷酸铁锰钠Na4Fe1.5Mn1.5(PO4)2P2O7/C正极材料。(烧结过程没有熔盐参与,材料形貌不规则,粒径不均一)。
图4为对比例2的Na4Fe1.5Mn1.5(PO4)2P2O7/C材料XRD图谱;由图4可知无熔盐制备无孔Na4Fe1.5Mn1.5(PO4)2P2O7/C正极材料的衍射峰和Na4Fe3(PO4)2P2O7的标准卡片、Na4Mn3(PO4)2P2O7的标准卡片完全重合,没有杂峰,表明通过固相球磨法成功制备了纯净的Na4Fe1.5Mn1.5(PO4)2P2O7/C正极材料。(即实施例中的熔盐处理并没有改变材料的XRD衍射峰,材料均为纯相)
图5为对比例2的Na4Fe1.5Mn1.5(PO4)2P2O7/C材料SEM图谱;由图5和图3对比可知:通过固相球磨法制备的Na4Fe1.5Mn1.5(PO4)2P2O7/C正极材料的形貌为微米级不规则块状,表明固相球磨法合成的Na4Fe1.5Mn1.5(PO4)2P2O7/C正极材料没有固定的形貌;一次颗粒大小不均一,表面轮廓模糊,表明材料导电性较差;存在二次颗粒团聚的现象,不利于电解液的浸润和离子的扩散。
对比例3
无熔盐制备无孔磷酸焦磷酸铁钠Na4Fe3(PO4)2P2O7/C正极材料的方法包括以下步骤:
1、按摩尔比Na:Fe:P=4:3:4称取乙酸钠、草酸亚铁、磷酸二氢铵,选择葡萄糖为碳源(C6H12O6),按摩尔比Na4Fe3(PO4)2P2O7:C6H12O6=1:1称取,选择聚乙二醇20000(PEG)为球磨助磨剂,按质量比Na4Fe3(PO4)2P2O7:PEG=50:1称取。将上述药品按照比例称取后置于球磨罐中,混合均匀;选择无水乙醇为球磨分散剂,按质量比Na4Fe3(PO4)2P2O7:C2H5OH=1:1称取,置于球磨罐中,按球料比=15:1,转速300r/min,球磨湿磨12小时后形成均一的面糊状,80℃真空干燥得到前驱体材料;
2、将前驱体材料球磨干磨1小时,将球和粉末进行过筛分离,使用刚玉管对混合粉末进行烧结,300℃下烧结3小时,550℃下烧结10小时,升温速率3℃/min,热处理后冷却至室温,得到纯净的无孔磷酸焦磷酸铁钠Na4Fe3(PO4)2P2O7/C正极材料。(烧结过程没有熔盐参与,材料形貌不规则,粒径不均一)。
三、应用效果分析
电池的制备:以实施例1、2、3、4、5、6及对比例1、2、3制备的复合材料为正极活性材料,将其与乙炔黑(导电剂)、PVDF(聚偏二氟乙烯,粘接剂)按照8:1:1的质量比称取后,在研钵中研磨一段时间,使之混合均匀,加入N-甲基吡咯烷酮(NMP),不间断地研磨一段时间,最终得到均匀的黑色粘稠浆状物质。把研磨后得到的均匀浆料置于铝箔上,用刮刀将其均匀涂布成厚度均匀的薄膜。以金属钠片为对电极,玻璃纤维膜为隔膜,1mol/L的NaClO4/PC(碳酸丙烯酯)为电解液,在无水无氧的氩气气氛手套箱里组装成CR2032型扣式电池。其比容量、平均电压和循环性能见下表1所示:
表1不同样品比容量、平均电压和循环性能比较
由表1可知,熔盐法制备的多孔磷酸焦磷酸铁锰钠正极材料的0.1C首次放电比容量、0.1C 100圈循环容量保持率、1C首次放电比容量等电化学性能均高于普通固相法制备的无孔磷酸焦磷酸铁锰钠正极材料。且随着复合材料中锰含量的提升,材料工作电压显著提升,同时材料的放电容量和倍率循环性能没有明显下降,表明本技术发明有效解决了锰含量提升带来的材料电化学性能衰减难题。
上述说明并非对本发明的限制,本发明也并不限于上述举例。本技术领域的普通技术人员在本发明的实质范围内,做出的变化、改型、添加或替换,也应属于本发明的保护范围。
Claims (10)
1.一种磷酸焦磷酸铁锰钠正极材料的制备方法,其特征在于包括以下步骤:
(1)称取钠源、铁源、锰源、磷源、碳源、高分子聚合物和分散剂加入球磨机中球磨0.5~15h,真空干燥得到前驱体材料,其中Na:Fe:Mn:P:C的摩尔比为4:3~x:x:4:(0~25),x=0~3;磷酸焦磷酸铁锰钠:高分子聚合物的质量比=(9.9~10.1):1;所述的分散剂选自去离子水、乙醇和丙酮中的一种;
(2)称取熔盐粉末加入球磨机中,使熔盐:前驱体的质量比=(0.2~5):1,球磨时长0.5~5h,将熔盐粉末和前驱体粉末球磨混合均匀后,在惰性气氛下进行热处理,热处理温度为450℃~600℃,煅烧时间为1~24h,然后将烧结粉末置于溶剂中超声分散以去除多余熔盐,通过抽滤后烘干得到纯净的多孔磷酸焦磷酸铁锰钠Na4Fe3-xMnx(PO4)2P2O7/C正极材料。
2.根据权利要求1所述的一种磷酸焦磷酸铁锰钠正极材料的制备方法,其特征在于:所述的钠源为磷酸二氢钠、磷酸氢二钠、磷酸钠、碳酸钠、碳酸氢钠、乙酸钠、柠檬酸二氢钠、草酸钠、海藻酸钠、焦磷酸钠中的一种或几种。
3.根据权利要求1所述的一种磷酸焦磷酸铁锰钠正极材料的制备方法,其特征在于:所述的铁源为硝酸铁、草酸亚铁、磷酸铁、磷酸亚铁、柠檬酸铁、三氧化二铁中的一种或几种。
4.根据权利要求1所述的一种磷酸焦磷酸铁锰钠正极材料的制备方法,其特征在于:所述的锰源为乙酸锰、硝酸锰、乙酰丙酮锰、碳酸锰、二氧化锰中的一种或几种。
5.根据权利要求1所述的一种磷酸焦磷酸铁锰钠正极材料的制备方法,其特征在于:所述的磷源为磷酸二氢铵、磷酸二氢钠、磷酸氢二铵、磷酸氢二钠、磷酸铁、磷酸亚铁中的一种或几种。
6.根据权利要求1所述的一种磷酸焦磷酸铁锰钠正极材料的制备方法,其特征在于:所述的碳源为柠檬酸、草酸、乙酸、抗坏血酸、酒石酸、油酸、葡萄糖中的一种或几种。
7.根据权利要求1所述的一种磷酸焦磷酸铁锰钠正极材料的制备方法,其特征在于:所述的高分子聚合物为聚乙烯吡咯烷酮、聚乙烯醇、聚乙二醇、聚丙烯腈、聚已丙酰胺中的一种或几种。
8.根据权利要求1所述的一种磷酸焦磷酸铁锰钠正极材料的制备方法,其特征在于:所述的熔盐为氢氧化钠、氢氧化钾、硝酸钠、硝酸钾中的一种或几种。
9.根据权利要求1所述的一种磷酸焦磷酸铁锰钠正极材料的制备方法,其特征在于:所述的超声分散用溶剂为去离子水、甘油、甲醇、乙醇中的一种或几种。
10.根据权利要求1所述的一种磷酸焦磷酸铁锰钠正极材料的制备方法,其特征在于:所述的惰性气氛为氩气、氦气、氖气和氮气中的一种或者几种。
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