CN113845102A - Method for rapidly preparing high-quality fluorine-containing phosphate polyanion compound - Google Patents
Method for rapidly preparing high-quality fluorine-containing phosphate polyanion compound Download PDFInfo
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- CN113845102A CN113845102A CN202110660400.5A CN202110660400A CN113845102A CN 113845102 A CN113845102 A CN 113845102A CN 202110660400 A CN202110660400 A CN 202110660400A CN 113845102 A CN113845102 A CN 113845102A
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- Prior art keywords
- potassium
- sulfate
- fluorine
- phosphate
- quality
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000011737 fluorine Substances 0.000 title claims abstract description 32
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 29
- 150000001875 compounds Chemical class 0.000 title claims abstract description 19
- 229920000447 polyanionic polymer Polymers 0.000 title claims abstract description 14
- 229910019142 PO4 Inorganic materials 0.000 title claims description 10
- 239000010452 phosphate Substances 0.000 title claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000000654 additive Substances 0.000 claims abstract description 18
- 230000000996 additive effect Effects 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 238000000498 ball milling Methods 0.000 claims abstract description 13
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims abstract description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 20
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 13
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- 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
- 239000011591 potassium Substances 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 229960003975 potassium Drugs 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 239000011698 potassium fluoride Substances 0.000 claims description 5
- 235000003270 potassium fluoride Nutrition 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 4
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 4
- 235000011151 potassium sulphates Nutrition 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 claims description 2
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 claims description 2
- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-N 0.000 claims description 2
- PAJMKGZZBBTTOY-UHFFFAOYSA-N 2-[[2-hydroxy-1-(3-hydroxyoctyl)-2,3,3a,4,9,9a-hexahydro-1h-cyclopenta[g]naphthalen-5-yl]oxy]acetic acid Chemical compound C1=CC=C(OCC(O)=O)C2=C1CC1C(CCC(O)CCCCC)C(O)CC1C2 PAJMKGZZBBTTOY-UHFFFAOYSA-N 0.000 claims description 2
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 claims description 2
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 229910021550 Vanadium Chloride Inorganic materials 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- 229910000152 cobalt phosphate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-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
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 2
- 229940032950 ferric sulfate Drugs 0.000 claims description 2
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 claims description 2
- 229960001781 ferrous sulfate Drugs 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- YPJCVYYCWSFGRM-UHFFFAOYSA-H iron(3+);tricarbonate Chemical group [Fe+3].[Fe+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YPJCVYYCWSFGRM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 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 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- 229910000159 nickel phosphate Inorganic materials 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229940053662 nickel sulfate Drugs 0.000 claims description 2
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical group [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000001508 potassium citrate Substances 0.000 claims description 2
- 229960002635 potassium citrate Drugs 0.000 claims description 2
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 2
- 235000011082 potassium citrates Nutrition 0.000 claims description 2
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- OQZCJRJRGMMSGK-UHFFFAOYSA-M potassium metaphosphate Chemical compound [K+].[O-]P(=O)=O OQZCJRJRGMMSGK-UHFFFAOYSA-M 0.000 claims description 2
- 229940099402 potassium metaphosphate Drugs 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 229940093914 potassium sulfate Drugs 0.000 claims description 2
- CUNPJFGIODEJLQ-UHFFFAOYSA-M potassium;2,2,2-trifluoroacetate Chemical compound [K+].[O-]C(=O)C(F)(F)F CUNPJFGIODEJLQ-UHFFFAOYSA-M 0.000 claims description 2
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 claims description 2
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- 235000019798 tripotassium phosphate Nutrition 0.000 claims description 2
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 2
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 2
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 2
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 2
- KBQPEQMZFVCZKQ-UHFFFAOYSA-N [F].OP(O)(O)=O Chemical compound [F].OP(O)(O)=O KBQPEQMZFVCZKQ-UHFFFAOYSA-N 0.000 claims 1
- GQUJEMVIKWQAEH-UHFFFAOYSA-N titanium(III) oxide Chemical compound O=[Ti]O[Ti]=O GQUJEMVIKWQAEH-UHFFFAOYSA-N 0.000 claims 1
- 229910001414 potassium ion Inorganic materials 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000010406 cathode material Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 16
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 11
- 229940037179 potassium ion Drugs 0.000 description 11
- 238000005245 sintering Methods 0.000 description 10
- 239000012071 phase Substances 0.000 description 9
- 239000007774 positive electrode material Substances 0.000 description 8
- 239000007790 solid phase Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- 229910019205 PO4F Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 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 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/455—Phosphates containing halogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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 method for rapidly preparing a high-quality polyanion compound containing fluorophosphate, which comprises the steps of introducing a fluorine-containing carbon source additive into the synthesis of the polyanion material, and rapidly obtaining the high-quality polyanion material containing fluorine on a large scale through ball milling and calcination. The fluorine-containing carbon source additive can provide a fluorine-rich and reducing environment for the material in the high-temperature reaction process, and can also realize in-situ carbon coating on the material. The preparation method provided by the invention is simple in synthesis process and suitable for mass production of high-quality fluorine-containing phosphate potassium ion cathode materials.
Description
Technical Field
The invention belongs to the technical field of potassium ion battery anode materials, and particularly relates to a method for quickly preparing a high-quality fluorine-containing phosphate polyanion compound.
Background
Compared with the scarce lithium element, the content of the sodium element and the potassium element is abundant, which means that the content is inexhaustible. The development of potassium ion batteries and sodium ion batteries is a very promising research effort. Furthermore, K+Relative to Na+Has higher standard potential, when matched with a cathode to form a full battery, the potassium ion battery can provide a higher voltage platform, thereby increasing the energy density of the battery, so that the potassium ion battery can be used for chargingThe cell is considered to be a cheap high voltage battery system.
The polyanion compound is a general name of a series of compounds containing tetrahedral or octahedral anion structural units, and the structural units are connected into a three-dimensional network structure through strong covalent bonds and form more highly coordinated gaps occupied by other metal ions, so that the polyanion compound cathode material has a different crystalline phase structure from other cathode materials and various outstanding properties (such as good rate, stable cycle and the like) determined by the structure. Wherein the fluorophosphate polyanion-type compound is KMOxPO4F1-x(where M is a metal or nonmetal element: V, Cr, Mn, Ti, Nb, Co, Ni, Cu, Si, Sn, 0. ltoreq. x. ltoreq.1) is considered a potential potassium-ion battery positive electrode material for large-scale commercial application.
The following methods are generally used for preparing such polyanionic positive electrode materials: two-step carbothermic, sol-gel, and hydrothermal processes. The preparation method can effectively prepare the polyanionic anode material, but the preparation method is complicated and has high energy consumption, and the polyanionic anode material prepared by the method cannot realize large-scale high-quality preparation.
Disclosure of Invention
According to the invention, the fluorine-containing carbon source additive is added in the material synthesis process, and the additive serves as a fluorine source and also serves as a carbon source, so that a fluorine-rich and reducing environment is provided for the material in the high-temperature reaction process, and meanwhile, the in-situ carbon coating of the material can be realized. The invention is a one-step solid-phase sintering method, and the required compound raw material and the additive auxiliary agent are calcined in a high-temperature pyrolysis furnace, and the preparation method has the characteristics of simple process, easy control of reaction and low cost, can be used for large-scale continuous preparation, and is very suitable for large-scale production.
The invention aims to solve the technical problem of overcoming the defects and shortcomings in the background technology, and provides a simple method for preparing a fluorine-containing polyanion-type positive electrode material for a potassium ion battery in a large scale by adding an auxiliary agent in the material synthesis process.
The purpose of the invention is realized by the following steps:
(1) mixing a potassium source, a metal salt, a phosphorus source and a fluorine-containing carbon source additive according to a corresponding proportion, wherein the fluorine-containing carbon source additive can provide a fluorine-rich and reducing environment for the material in a high-temperature reaction process, and can realize in-situ carbon coating on the material;
(2) performing ball milling on the precursor powder obtained in the step (1);
(3) performing high-temperature calcination on the precursor powder in the step (2) after the ball milling is finished
(4) And (4) cooling the sample calcined in the step (3) along with the furnace to obtain the product.
In particular, the potassium source in step (1) may be one or more selected from potassium carbonate, potassium bicarbonate, potassium hydroxide, potassium chloride, tripotassium phosphate, potassium sulfate, potassium metaphosphate, potassium citrate, potassium ethoxide, potassium sulfate, potassium fluoride, potassium nitrate, potassium acetate, potassium metavanadate, potassium titanate, potassium manganate, potassium bifluoride, potassium pyrophosphate and potassium bisulfate; the metal salt can be selected from one or more of metal oxide salt, carbonate, nitrate, sulfate, phosphate or other metal salt; the phosphorus source is one or more than two of ammonium biphosphate, diammonium hydrogen phosphate, phosphoric acid, ammonium phosphate and phosphorus pentoxide; the fluorine-containing carbon source additive can be one or more than two of polytetrafluoroethylene, polyvinylidene fluoride, potassium trifluoroacetate and ammonium fluoride.
In particular, the metal oxide salt is selected from one or more of vanadium pentoxide, titanium dioxide, titanium oxide, ferric oxide, cobalt oxide, nickel oxide and manganese oxide; the carbonate is selected from one or more of iron carbonate, manganese carbonate, cobalt carbonate and nickel carbonate; the nitrate is selected from one or more of ferric nitrate, nickel nitrate, cobalt nitrate and manganese nitrate; the sulfate is selected from one or more of titanyl sulfate, ferrous sulfate, ferric sulfate, nickel sulfate, manganese sulfate and cobalt sulfate; the phosphate is selected from one or more of iron phosphate, nickel phosphate, cobalt phosphate and manganese phosphate, and the other metal salt is selected from one or more of ammonium metavanadate, vanadyl sulfate, vanadyl oxalate, vanadium chloride, vanadyl acetylacetonate, vanadium acetylacetonate, titanium acetylacetonate, tetrabutyl titanate and isopropyl titanate; the phosphorus source is ammonium biphosphate.
In particular, the metal oxide salt is vanadium pentoxide; the carbonate is ferric carbonate; the nitrate is ferric nitrate; the sulfate is titanium sulfate, and the phosphate is iron phosphate.
Particularly, the mass ratio of the fluorine-containing carbon source additive is 5-35%.
Particularly, the mass ratio of the fluorine-containing carbon source additive is 15-25%.
In particular, the rotation speed and time of the ball milling in the step (2) can be selected according to the target particle size of the target product.
Particularly, the rotation speed of the ball milling in the step (2) is 400 revolutions per minute, and the ball milling time is 6 hours.
In particular, the calcination temperature in the step (3) is 550-950 ℃.
In particular, the calcining temperature in the step (3) is 750 ℃, the calcining time is 2h, and the calcining speed is 10 ℃/min.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a graph showing KVPO prepared by one-step solid-phase sintering by adding polytetrafluoroethylene (PTFE as a fluorine source and a carbon source) in various proportions (0 wt%, 5 wt%, 15 wt%, 25 wt%, 35 wt%) in example 1 of the present invention4F polyanionic positive electrode material;
FIG. 2 shows KVPO prepared by calcining different temperature ranges (550 ℃, 650 ℃, 750 ℃, 850 ℃, 950 ℃) in one-step solid-phase sintering in example 1 of the present invention4F polyanionic positive electrode material;
FIG. 3 shows the results of example 1 of the present invention obtained by adding polytetrafluoroethylene (PTFE, as a fluorine source and carbon) in a proportion of 25 wt%Source) KVPO prepared by one-step solid phase sintering4F is a scanning electron microscope image of the polyanion type anode material;
FIG. 4 shows KVPO prepared in example 1 of the present invention4F is a cycle performance diagram in the potassium ion battery;
FIG. 5 shows KTiPO prepared by one-step solid phase sintering with different ratios (0 wt%, 5 wt%, 15 wt%, 25 wt%, 35 wt%) of polytetrafluoroethylene (PTFE as a fluorine source and a carbon source) in example 2 of the present invention4And F is a polyanionic positive electrode material.
FIG. 6 is a scanning electron microscope image of a KTiPO4F polyanionic positive electrode material prepared by one-step solid phase sintering by adding polytetrafluoroethylene (PTFE as a fluorine source and a carbon source) in a proportion of 25 wt% in example 2 of the present invention;
FIG. 7 shows KTiPO prepared in example 2 of the present invention4F cycle performance diagram in potassium ion battery.
Detailed Description
In order to facilitate understanding of the invention, the invention will be described more fully and in detail with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention. The preferred embodiments and materials described herein are exemplary only, and modifications and variations may be made without departing from the principles of the embodiments of the invention, which are also to be considered within the scope of the invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
The specific implementation mode of the invention is that auxiliary agents are added in the material synthesis process, and the polyanion type positive electrode material for the potassium ion battery is prepared by a one-step solid-phase sintering method.
Example 1
KVPO was prepared by controlling the proportions (0 wt%, 5 wt%, 15 wt%, 25 wt%, 35 wt%) of polytetrafluoroethylene (additive) in this example4F, specifically comprising the following steps:
(1) vanadium pentoxide, ammonium dihydrogen phosphate and potassium fluoride are taken as raw materials according to the element molar ratio K: v: p is 1: 1: 1, adding polytetrafluoroethylene powder with the mass ratio of 0 wt%, 5 wt%, 15 wt%, 25 wt% and 35 wt%, and ball-milling in a high-energy ball mill for 6 hours to obtain a precursor raw material which is uniformly mixed.
(2) And (3) putting the precursor raw material into a high-temperature sintering furnace, heating the precursor raw material from room temperature to 750 ℃, preserving the heat for 2 hours, cooling the precursor raw material along with the furnace, wherein the calcining atmosphere is argon, and the heating speed is 10 ℃/min. Taking out the powder, pulverizing, and grinding to obtain KVPO4And F, powder.
Example 2
KVPO was prepared by controlling the calcination temperature (550 deg.C, 650 deg.C, 750 deg.C, 850 deg.C, 950 deg.C) in this example4F, specifically comprising the following steps:
(1) vanadium pentoxide, ammonium dihydrogen phosphate and potassium fluoride are taken as raw materials according to the element molar ratio K: v: p is 1: 1: 1, adding polytetrafluoroethylene powder with the mass ratio of 15 wt%, and ball-milling for 6 hours in a high-energy ball mill to obtain a precursor raw material which is uniformly mixed.
(2) The precursor raw materials are put into a high-temperature sintering furnace, the temperature is respectively raised from room temperature to 550 ℃, 650 ℃, 750 ℃, 850 ℃ and 950 ℃, the heat is preserved for 2 hours, the raw materials are cooled along with the furnace, the calcining atmosphere is argon, and the temperature raising speed is 10 ℃/min. Taking out the powder, pulverizing, and grinding to obtain KVPO4And F, powder.
KVPO prepared by example 1 and example 24XRD and SEM results for F are shown in FIGS. 1-2 and 3. KVPO prepared in this example4F in potassium ion battery (half battery, porous carbon material for positive electrode, potassium sheet for negative electrode, KPF for electrolyte6in EC/DEC) (cycle performance test at 50 mA/g) As shown in FIG. 2, the top line represents the charge/discharge cycle efficiency, which reaches nearly 98% after 10 cyclesThe two curves are the charging specific capacity and the discharging specific capacity respectively, and after circulating for 50 circles, the capacity of the two curves is kept at 40 mAh/g. As is clear from FIG. 1, when PTFE (0 wt%) was not added, the phase of the material was not pure, and it was difficult to form KV because V having a pentavalent structure could not be reduced to V having a trivalent structureIIIPO4F. KVPO when 5 wt% PTFE is added4The F main phase begins to appear, when the addition amount reaches 15 to 25 weight percent, the phase is the purest and is high-purity KVPO4F. As can be seen from FIG. 2, when the calcination temperature is lower than 550 ℃, since PTFE is not completely decomposed, the reduction atmosphere provided is not enough to reduce V with pentavalent valence in the precursor to V with trivalent valence, and it is difficult to form KVIIIPO4F. KVPO when the calcining temperature reaches 650-850 DEG C4The major phase F began to appear, with the sample being purest at 750 ℃. When the temperature is continuously increased to 950 ℃, pure-phase KVPO can not be formed due to the volatilization of potassium element at high temperature4F。
Example 3
In the embodiment, KTiPO is prepared by regulating and controlling polytetrafluoroethylene with different proportions (0 wt%, 5 wt%, 15 wt%, 25 wt% and 35 wt%)4F, specifically comprising the following steps:
(1) titanium dioxide, ammonium dihydrogen phosphate and potassium fluoride are taken as raw materials according to the element molar ratio K: ti: p is 1: 1: 1, adding polytetrafluoroethylene powder with the mass ratio of 0 wt%, 5 wt%, 15 wt%, 25 wt% and 35 wt%, and ball-milling in a high-energy ball mill for 6 hours to obtain a precursor raw material which is uniformly mixed.
(2) And (2) putting the precursor raw material into a high-temperature sintering furnace, heating the precursor raw material from room temperature to 750 ℃, preserving the heat for 2 hours, cooling the precursor raw material along with the furnace, wherein the calcining atmosphere is argon, and the heating speed is 10 ℃ per minute. Taking out the powder, crushing and grinding uniformly to obtain KTiPO4And F, powder.
KTiPO prepared in this example4XRD and SEM results for F are shown in fig. 4 and 5. KTiPO prepared in this example4F in potassium ion battery (half battery, porous carbon material for positive electrode, potassium sheet for negative electrode, KPF for electrolyte6in EC/DEC) (cycle Performance test at 50mA/g Current Density) in FIG. 6, top line generationThe charge-discharge cycling efficiency is shown in the table, the following two curves are the charge specific capacity and the discharge specific capacity respectively, and the capacity of the battery is kept at 40mAh/g after 50 cycles of cycling. As can be seen, when PTFE (0 wt%) is not added, the phase of the material is not pure and is different from PDF card, mainly because tetravalent Ti can not be reduced to trivalent Ti, and KTi is difficult to formIIIPO4F. KTiPO when 5 wt% PTFE was added4The F main phase begins to appear, but at this time, a small amount of TiO2 is still present, and the degree of reduction is insufficient. When the addition amount reaches 15-25 wt%, the phase is purest and is pure KTiIIIPO4F。
In conclusion, the fluorine-containing carbon source additive is added in the material synthesis process, and the additive can be used as a carbon source, provides a reducing atmosphere in the material synthesis process to carry out in-situ carbon coating on the material, and also provides a fluorine-rich environment in the material synthesis process, so that the high-quality fluorine-containing polyanionic cathode material can be synthesized. The method is simple and easy to operate, low in cost and excellent in repeatability, can be used for effectively preparing the serial fluorine-containing polyanion-type anode materials, and can be used for easily and quickly realizing batch production.
The foregoing is considered as illustrative of the preferred embodiments of the invention and is not to be construed as limiting the invention in any way. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention should fall within the protection scope of the technical scheme of the present invention, unless the technical spirit of the present invention departs from the content of the technical scheme of the present invention.
Claims (10)
1. A method for rapidly preparing high-quality polyanion compounds containing fluorophosphate is characterized by comprising the following steps:
(1) mixing a potassium source, a metal salt, a phosphorus source and a fluorine-containing carbon source additive according to a corresponding proportion, wherein the fluorine-containing carbon source additive can provide a fluorine-rich and reducing environment for the material in a high-temperature reaction process, and can realize in-situ carbon coating on the material;
(2) performing ball milling on the precursor powder obtained in the step (1);
(3) performing high-temperature calcination on the precursor powder in the step (2) after the ball milling is finished
(4) And (4) cooling the sample calcined in the step (3) along with the furnace to obtain the product.
2. The method for rapidly preparing a high-quality polyanionic compound containing a fluorine phosphate according to claim 1, wherein the potassium source in the step (1) is selected from one or more of potassium carbonate, potassium bicarbonate, potassium hydroxide, potassium chloride, tripotassium phosphate, potassium sulfate, potassium metaphosphate, potassium citrate, potassium ethoxide, potassium sulfate, potassium fluoride, potassium nitrate, potassium acetate, potassium metavanadate, potassium titanate, potassium manganate, potassium bifluoride, potassium pyrophosphate, and potassium bisulfate; the metal salt can be selected from one or more of metal oxide salt, carbonate, nitrate, sulfate, phosphate or other metal salt; the phosphorus source is one or more than two of ammonium biphosphate, diammonium hydrogen phosphate, phosphoric acid, ammonium phosphate and phosphorus pentoxide; the fluorine-containing carbon source additive can be one or more than two of polytetrafluoroethylene, polyvinylidene fluoride, potassium trifluoroacetate and ammonium fluoride.
3. The method for rapidly preparing the high-quality polyanion compound containing fluorophosphate according to claim 2, wherein the metal oxide salt is selected from one or more of vanadium pentoxide, titanium dioxide, titanium sesquioxide, iron oxide, cobalt oxide, nickel oxide and manganese oxide; the carbonate is selected from one or more of iron carbonate, manganese carbonate, cobalt carbonate and nickel carbonate; the nitrate is selected from one or more of ferric nitrate, nickel nitrate, cobalt nitrate and manganese nitrate; the sulfate is selected from one or more of titanyl sulfate, ferrous sulfate, ferric sulfate, nickel sulfate, manganese sulfate and cobalt sulfate; the phosphate is selected from one or more of iron phosphate, nickel phosphate, cobalt phosphate and manganese phosphate, and the other metal salt is selected from one or more of ammonium metavanadate, vanadyl sulfate, vanadyl oxalate, vanadium chloride, vanadyl acetylacetonate, vanadium acetylacetonate, titanium acetylacetonate, tetrabutyl titanate and isopropyl titanate; the phosphorus source is ammonium biphosphate.
4. The method for rapidly preparing a high quality fluorophosphate polyanionic compound according to claim 3, wherein said metal oxide salt is vanadium pentoxide; the carbonate is ferric carbonate; the nitrate is ferric nitrate; the sulfate is titanium sulfate, and the phosphate is iron phosphate.
5. The method for rapidly preparing the high-quality fluorophosphate polyanionic compound according to claim 1, wherein the mass ratio of the fluorine-containing carbon source additive is 5-35%.
6. The method for rapidly preparing the high-quality fluorophosphate polyanionic compound according to claim 1 or 5, wherein the mass ratio of the fluorine-containing carbon source additive is 15-25%.
7. The method for rapidly preparing a high-quality fluorophosphate polyanion-based compound according to claim 1, wherein the rotating speed and time of the ball-milling in the step (2) can be selected according to the target particle size of the target product.
8. The method for rapidly preparing high-quality fluorophosphate polyanion-based compound according to claim 1 or 7, wherein the rotation speed of the ball mill in the step (2) is 400 rpm, and the ball milling time is 6 hours.
9. The method for rapidly preparing high quality fluorophosphate polyanionic compound according to claim 1, wherein the calcination temperature in step (3) is 550-950 ℃.
10. The method for rapidly preparing the high-quality polyanionic compound containing fluorophosphate according to claim 9, wherein the calcination temperature in the step (3) is 750 ℃, the calcination time is 2h, and the calcination speed is 10 ℃/min.
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| ZHAOMENG LIU: "Plum pudding model inspired KVPO4F@3DC as high-voltage and hyperstable cathode for potassium ion batteries", 《SCIENCE BULLETIN》, 6 April 2020 (2020-04-06), pages 1242 - 1251 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114572958A (en) * | 2022-03-04 | 2022-06-03 | 湖南大学 | Preparation method of fluorine-containing polyanion-type positive electrode material and fluorine-containing polyanion-type positive electrode material |
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