CN102306753A - Full solid phase preparation method of lithium ion positive electrode material lithium iron phosphate - Google Patents
Full solid phase preparation method of lithium ion positive electrode material lithium iron phosphate Download PDFInfo
- Publication number
- CN102306753A CN102306753A CN201110259971A CN201110259971A CN102306753A CN 102306753 A CN102306753 A CN 102306753A CN 201110259971 A CN201110259971 A CN 201110259971A CN 201110259971 A CN201110259971 A CN 201110259971A CN 102306753 A CN102306753 A CN 102306753A
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- CN
- China
- Prior art keywords
- solid phase
- lithium
- compound
- lithium ion
- mix
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000007790 solid phase Substances 0.000 title claims abstract description 44
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 25
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract 8
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000007774 positive electrode material Substances 0.000 title abstract 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 47
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- 238000005245 sintering Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 45
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 32
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 28
- 239000010405 anode material Substances 0.000 claims description 22
- 229910045601 alloy Inorganic materials 0.000 claims description 16
- 239000000956 alloy Substances 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 15
- 238000012545 processing Methods 0.000 claims description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 12
- 239000008246 gaseous mixture Substances 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- 229910052720 vanadium Inorganic materials 0.000 claims description 9
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 239000011790 ferrous sulphate Substances 0.000 claims description 7
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 7
- 239000004254 Ammonium phosphate Substances 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 6
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 6
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 claims description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 6
- 230000004927 fusion Effects 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 239000006230 acetylene black Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical group [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 239000005955 Ferric phosphate Substances 0.000 claims description 3
- 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 3
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 claims description 3
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 claims description 3
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 3
- ZLXPLDLEBORRPT-UHFFFAOYSA-M [NH4+].[Fe+].[O-]S([O-])(=O)=O Chemical compound [NH4+].[Fe+].[O-]S([O-])(=O)=O ZLXPLDLEBORRPT-UHFFFAOYSA-M 0.000 claims description 3
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 3
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical group [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 3
- 239000001639 calcium acetate Substances 0.000 claims description 3
- 229960005147 calcium acetate Drugs 0.000 claims description 3
- 235000011092 calcium acetate Nutrition 0.000 claims description 3
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 3
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000002134 carbon nanofiber Substances 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical group [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 229960004643 cupric oxide Drugs 0.000 claims description 3
- WCOATMADISNSBV-UHFFFAOYSA-K diacetyloxyalumanyl acetate Chemical group [Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WCOATMADISNSBV-UHFFFAOYSA-K 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 3
- 229940032958 ferric phosphate Drugs 0.000 claims description 3
- 239000011640 ferrous citrate Substances 0.000 claims description 3
- 235000019850 ferrous citrate Nutrition 0.000 claims description 3
- 229940116007 ferrous phosphate Drugs 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 229910000155 iron(II) phosphate Inorganic materials 0.000 claims description 3
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 3
- APVZWAOKZPNDNR-UHFFFAOYSA-L iron(ii) citrate Chemical compound [Fe+2].OC(=O)CC(O)(C([O-])=O)CC([O-])=O APVZWAOKZPNDNR-UHFFFAOYSA-L 0.000 claims description 3
- 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 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 3
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 claims description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical group [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 3
- 239000011654 magnesium acetate Substances 0.000 claims description 3
- 235000011285 magnesium acetate Nutrition 0.000 claims description 3
- 229940069446 magnesium acetate Drugs 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 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
- 229940099594 manganese dioxide Drugs 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 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
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 3
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 3
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 3
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- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 3
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
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- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 238000012360 testing method Methods 0.000 abstract description 10
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- 239000002245 particle Substances 0.000 abstract description 3
- 230000002441 reversible effect Effects 0.000 abstract description 3
- 238000005253 cladding Methods 0.000 abstract 1
- 239000002019 doping agent Substances 0.000 abstract 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 13
- 238000000498 ball milling Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 6
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 4
- 238000011031 large-scale manufacturing process Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- -1 purity is high Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
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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 full solid phase preparation method of lithium ion positive electrode material lithium iron phosphate and aims at improving the production efficiency of the lithium iron phosphate, lowering the preparation cost and improving the batch instability. The full solid phase preparation method of the lithium ion positive electrode material lithium iron phosphate comprises the following steps: carrying out solid phase mixing on a lithium source compound, an iron source and a phosphorous source compound, adding a carbon source substance, adding a dopant and sintering so as to get the lithium ion positive electrode material lithium iron phosphate. Compared with the prior art, according to the invention, the lithium iron phosphate adopting solid phase mixing, thinning and cladding has high purity, the particles are fine and uniform and can reach 50-200nm, the electric performance of the lithium iron phosphate is excellent, the reversible specific capacity is greater than 156mAh/g, the multiplying power performance is excellent, the production efficiency is improved by 15%, the cost is lowered by 12%, the variance of the specific capacity of the prepared material in parallel tests three times is less than 3%, and the batch is stable.
Description
Technical field
The present invention relates to a kind of preparation method's of cell positive material, particularly a kind of anode material for lithium-ion batteries preparation method.
Background technology
LiFePO4 is just progressively promoted the use of in fields such as portable electric appts, electric bicycle, electric automobile, accumulation power supplies as a kind of anode material for lithium-ion batteries that grew up in nearly 15 years.But; To use this material in enormous quantities in the huge industry of market potentials such as electrokinetic cell, energy-storage battery; The LiFePO4 of prior art also exists several difficult points to break through; For example: though the cost of raw material is low; But complicated process of preparation; Cause preparation cost too high, large-scale production batch between the problem of unstable properties need to solve.Preparation LiFePO4 prior art adopts wet method or liquid phase method, with more than one resolvability raw materials, is dissolved in deionized water, ethanol or acetone, carries out liquid-phase mixing and coats, and to obtain better mixing effect and covered effect, makes raw material reaction more abundant.But this process also has drawback, and the drying process cost after the liquid-phase mixing is higher, and efficient is also low, the difficult control of the uniformity coefficient of material, cause large-scale production batch between unstable properties.
Summary of the invention
The full method for preparing solid phase that the purpose of this invention is to provide a kind of lithium ion anode material LiFePO4, the technical problem that solve are to improve LiFePO4 production efficiency, reduce preparation cost, improve batch unsteadiness of large-scale production LiFePO4.
The present invention adopts following technical scheme: a kind of full method for preparing solid phase of lithium ion anode material LiFePO4; May further comprise the steps: the mol ratio 1～3.5: 1～3: 1～3 of, pressing lithium, iron, P elements; Li source compound, source of iron, P source compound solid phase mixing are obtained mixture; Rotating speed is 1～2000r/min's, and the time is 0.1～72 hour; Said Li source compound is more than one of lithia, lithium hydroxide, lithium phosphate, lithium carbonate, lithium nitrate, lithium dihydrogen phosphate, lithium formate and lithium acetate; Said source of iron is more than one in iron, ferric phosphate, ferrous sulfate, di-iron trioxide, ferrous oxide, tri-iron tetroxide, iron ammonium sulfate, ferrous sulfate, ferrous phosphate, ferrous ammonium phosphate, ferrous citrate and the frerrous chloride; Said P source compound is more than one in phosphorus pentoxide, phosphoric acid, ammonium dihydrogen phosphate, lithium dihydrogen phosphate, diammonium hydrogen phosphate, ferrous ammonium phosphate and the ammonium hydrogen phosphate salt; Two, press 0.01～20% of mixture quality, add carbon source material and mix the solid-phase mixture that obtains carbonaceous sources, rotating speed is 5～1000r/min, and the time is 0.1～72 hour; Carbon source material is more than one in glucose, sucrose, maltose, polyethylene glycol PEG, PVAC polyvinylalcohol, citric acid, acetylene black, carbon nano-tube and the carbon nano-fiber; Three, by 0.01～20% of the amount of substance of ferro element in the mixture of carbonaceous sources, add alloy and mix and obtain the solid phase presoma, rotating speed is 5～1000r/min, the time is 0.1～72 hour; Alloy is the simple substance of element manganese, cobalt, vanadium, nickel, aluminium, magnesium, calcium, zinc, silver, copper and in the compound more than one; Four, presoma is placed on sintering in the protective atmosphere; The oxygen volume content heats up with 1～20 ℃/min speed, at 500～850 ℃ of sintering 5-36 of temperature hours below 200ppm; Be cooled to normal temperature with 1～30 ℃/min speed, obtain the lithium ion anode material LiFePO4.
Method of the present invention is with the mixture thinning processing, and rotating speed is 1～5000r/min, and the time is 0.1～72 hour.
The compound of method manganese of the present invention is manganese acetate, manganese carbonate and manganese dioxide; The compound of said cobalt is cobalt acetate, cobalt carbonate and cobalt oxide; The compound of said vanadium is oxide hypovanadous oxide, vanadium trioxide, vanadium dioxide and the vanadic oxide of vanadium; The compound of said nickel is nickel acetate, nickelous carbonate and nickel oxide; The compound of said aluminium is aluminium acetate, aluminium carbonate and aluminium oxide; The compound of said magnesium is magnesium acetate, magnesium carbonate and magnesia; The compound of said calcium is calcium acetate, calcium carbonate, calcium bicarbonate and calcium oxide; The compound of said zinc is zinc acetate, zinc carbonate and zinc oxide; The compound of said silver is a silver nitrate; The compound of said copper is a cupric oxide, copper sulphate.
Method protective atmosphere of the present invention is more than one the gaseous mixture that is added with in more than one gaseous mixture or the argon gas that is added with in the gaseous mixture that is added with argon gas volume 0.5～3% hydrogen in the gaseous mixture that is added with nitrogen volume 0.5～3% hydrogen in nitrogen, argon gas, the nitrogen, the argon gas, the nitrogen in methane, ethane, ethene and the acetylene of nitrogen volume 0.5～4% in methane, ethane, ethene and the acetylene of argon gas volume 0.5～4%.
Method solid phase mixing of the present invention, thinning processing, interpolation carbon source material mix and add alloy and mix the employing agitating ball mill, and rotating speed is 5～500r/min, and the time is 1～24 hour.
Method solid phase mixing of the present invention, thinning processing, interpolation carbon source material mix and add alloy and mix the employing planetary ball mill, and rotating speed is 10～2000r/min, and the time is 1～72 hour.
Method solid phase mixing of the present invention, thinning processing, interpolation carbon source material mix and add alloy and mix the mechanical fusion machine of employing, and rotating speed is 800～1200r/min, and the time is 0.1～10 hour.
Method solid phase mixing of the present invention, thinning processing, interpolation carbon source material mix and add alloy and mix the employing mixer, and rotating speed 1～100r/min mixed 0.1～24 hour.
Method solid phase mixing of the present invention, interpolation carbon source material mix and add alloy and mix the employing machine mixer, rotating speed 5～1000r/min, and the time is 1～48 hour.
Method thinning processing of the present invention adopts pulverizer, and rotating speed is 100～5000r/min.
The present invention compared with prior art; Adopt the LiFePO4 of solid phase mixing, refinement, coating, purity is high, and particle is tiny and even; Can reach 50～200nm; The electrical property of LiFePO4 is excellent, and reversible specific capacity is greater than 156mAh/g, and high rate performance is excellent; Production efficiency improves 15%; Cost reduces the specific capacity variance of 12%, 3 prepared material of parallel test less than 3%, and is batch stable.
Description of drawings
Fig. 1 is the XRD figure of the embodiment of the invention 1.
Fig. 2 is the SEM figure of the embodiment of the invention 1.
Fig. 3 is the simulated battery 0.2C charging and discharging curve figure of sample A in the embodiment of the invention 1.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is done further explain.The full method for preparing solid phase of lithium ion anode material LiFePO4 of the present invention may further comprise the steps:
One, solid phase mixing, solid phase merge or the refinement of powder solid phase; Mol ratio 1～3.5: 1～3 in lithium, iron, P elements: 1～3 ratio; Source of iron, Li source compound, P source compound solid phase mixing are obtained mixture; Under normal temperature (20 ℃) condition; Put into the GSY-8 agitating ball mill of the prosperous swallow powder machinery of Wuxi City Co., Ltd; With the range of speeds of 5～500r/min, ball milling is 1～24 hour under the normal temperature
Or the GZ-120 machine mixer of Guangdong, Shanghai, Shanghai bright scientific instrument Co., Ltd, with the rotating speed of 5～1000r/min, normal temperature stirred 1～48 hour down,
Or the XXM planetary ball mill of the prosperous swallow powder machinery of Wuxi City Co., Ltd, rotating speed is 10～2000r/min, ball milling 1～72 hour,
Or the ZJ-30 type of Fuan, Wuxi powder equipment Co., Ltd machinery fusion machine, rotating speed is 800～1200r/min, merged 0.1～10 hour,
Or the GHJ-VI-500 mixer of the big Xiang machine-building in Jiangyin City Co., Ltd, rotating speed 1～100r/min mixed 0.1～24 hour.
Li source compound is more than one of lithia, lithium hydroxide, lithium phosphate, lithium carbonate, lithium nitrate, lithium dihydrogen phosphate, lithium formate and lithium acetate.
Source of iron is more than one in iron, Fe source compound ferric phosphate, ferrous sulfate, di-iron trioxide, ferrous oxide, tri-iron tetroxide, iron ammonium sulfate, ferrous sulfate, ferrous phosphate, ferrous ammonium phosphate, ferrous citrate and the frerrous chloride.
P source compound is more than one in phosphorus pentoxide, phosphoric acid, ammonium dihydrogen phosphate, lithium dihydrogen phosphate, diammonium hydrogen phosphate, ferrous ammonium phosphate and the ammonium hydrogen phosphate salt.
Two, thinning processing is carried out thinning processing under the solid phase environment, obtain the mixture of refinement; Under the normal temperature, mixture is put into the GSY-8 agitating ball mill of the prosperous swallow powder machinery of Wuxi City Co., Ltd, with the range of speeds of 5～500r/min; Ball milling is 1～24 hour under the normal temperature
Or the XXM planetary ball mill of the prosperous swallow powder machinery of Wuxi City Co., Ltd, rotating speed is 10～2000r/min, ball milling 1～72 hour,
Or the ZJ-30 type of Fuan, Wuxi powder equipment Co., Ltd machinery fusion machine, rotating speed is 800～1200r/min, merged 0.1～10 hour,
Or the GHJ-VI-500 mixer of the big Xiang machine-building in Jiangyin City Co., Ltd, rotating speed 1～100 commentaries on classics/min mixed 0.1～24 hour,
Or the WFJ-15 type pulverizer of the Feng Hua of Jiangyin City medicineization machinery Co., Ltd, grating disk rotating speed 100～5000r/min.
Three, add carbon source; By 0.01～20% of the mixture quality of refinement; Adding carbon source material mixes; Obtain the solid-phase mixture of carbonaceous sources; Under the normal temperature, put into the GSY-8 agitating ball mill of the prosperous swallow powder machinery of Wuxi City Co., Ltd, with the range of speeds of 5～500r/min; Ball milling is 1～24 hour under the normal temperature
Or the GZ-120 machine mixer of Guangdong, Shanghai, Shanghai bright scientific instrument Co., Ltd, with the range of speeds of 5～1000r/min, normal temperature stirred 1～48 hour down,
Or the XXM planetary ball mill of the prosperous swallow powder machinery of Wuxi City Co., Ltd, rotating speed is 10～2000r/min, ball milling 1～72 hour,
Or the ZJ-30 type of Fuan, Wuxi powder equipment Co., Ltd machinery fusion machine, rotating speed is 800～1200r/min, merged 0.1～10 hour,
Or the GHJ-VI-500 mixer of the big Xiang machine-building in Jiangyin City Co., Ltd, rotating speed 1～100 commentaries on classics/min mixed 0.1～24 hour, and control compounding substances granularity is 10～1000nm.
Carbon source material is more than one in glucose, sucrose, maltose, polyethylene glycol PEG, PVAC polyvinylalcohol, citric acid, acetylene black, carbon nano-tube and the carbon nano-fiber.
Four, mix; By 0.01～20% of the amount of substance (mol ratio) of ferro element in the solid-phase mixture of carbonaceous sources; In the mixture of carbonaceous sources, add alloy and mix and obtain the solid phase presoma; Mix the GSY-8 agitating ball mill that adopts the prosperous swallow powder machinery of Wuxi City Co., Ltd; Rotating speed with 5～500r/min; Ball milling is 1～24 hour under the normal temperature
Or the GZ-120 machine mixer of Guangdong, Shanghai, Shanghai bright scientific instrument Co., Ltd, with the range of speeds of 5～1000r/min, normal temperature stirred 1～48 hour down,
Or the XXM planetary ball mill of the prosperous swallow powder machinery of Wuxi City Co., Ltd, rotating speed is 10～2000r/min, ball milling 1～72 hour,
Or the ZJ-30 type of Fuan, Wuxi powder equipment Co., Ltd machinery fusion machine, rotating speed is 800～1200r/min, merged 0.1～10 hour,
Or the GHJ-VI-500 mixer of the big Xiang machine-building in Jiangyin City Co., Ltd, rotating speed 1～100 commentaries on classics/min mixed 0.1～24 hour.
Alloy is the simple substance of element manganese, cobalt, vanadium, nickel, aluminium, magnesium, calcium, zinc, silver, copper and in the compound more than one.
The compound of manganese is manganese acetate, manganese carbonate and manganese dioxide.
The compound of cobalt is cobalt acetate, cobalt carbonate and cobalt oxide.
The compound of vanadium is oxide hypovanadous oxide, vanadium trioxide, vanadium dioxide and the vanadic oxide of vanadium.
The compound of nickel is nickel acetate, nickelous carbonate and nickel oxide.
The compound of aluminium is aluminium acetate, aluminium carbonate and aluminium oxide.
The compound of magnesium is magnesium acetate, magnesium carbonate and magnesia.
The compound of calcium is calcium acetate, calcium carbonate, calcium bicarbonate and calcium oxide.
The compound of zinc is zinc acetate, zinc carbonate and zinc oxide.
The compound of silver is a silver nitrate.
The compound of copper is a cupric oxide, copper sulphate.
Five; Sintering; The good special stove of KTF type tube furnace or Nanjing that the solid phase presoma is placed on bright and beautiful stove industry equipment Co., Ltd before the Yixing City is already in the box type furnace of the HTF of Co., Ltd; Sintering in protective atmosphere; Protective atmosphere is a nitrogen; Argon gas; Be added with the gaseous mixture of nitrogen volume 0.5～3% hydrogen in the nitrogen; Be added with the gaseous mixture of argon gas volume 0.5～3% hydrogen in the argon gas; Be added with the methane of nitrogen volume 0.5～4% in the nitrogen; Ethane; Be added with the methane of argon gas volume 0.5～4% in the gaseous mixture of more than one in ethene and the acetylene or the argon gas; Ethane; The gaseous mixture of more than one in ethene and the acetylene; Flow 0.1～50L/min; The oxygen volume content is below 200ppm in the control stove; Heat up with 1～20 ℃/min speed; 500～850 ℃ of sintering of temperature 5～36 hours; Be cooled to normal temperature with 1～30 ℃/min speed, obtain the lithium ion anode material LiFePO4.
The LiFePO4 of method preparation of the present invention; Phase structure is analyzed at PANalytica X ' PERT PRO X-ray diffractometer (Holland); Graphite monochromator; The Cu target (λ=0.15406nm); 10 °/min of sweep speed; 10 °～90 ° of sweep limitss, XRD curve and XRD standard spectrogram (Reference code:01-081-1173) relatively are the LiFePO 4 material of olivine-type.Material sample surface topography, granular size are with FDAC S4800 sem observation.
Adopt following method to estimate the high rate performance and the capacity of the lithium ion anode material LiFePO4 of method preparation of the present invention; Lithium ion anode material LiFePO4, acetylene black, binding agent are pressed 90: 5: 5 mass ratio; Be applied on the aluminium foil, oven dry, anodal as simulated battery.Simulated battery is assembled in the glove box of argon shield and carries out, and negative pole is a metal lithium sheet, and barrier film is Celgard2400, and electrolyte is 1mol/L LiPF
6/ DMC+DEC (volume ratio is 1: 1); Form the CR2016 pattern and intend battery; Carry out the charge and discharge cycles experiment in 3.9～2.5V voltage range, charge-discharge test carries out on the new prestige battery detecting equipment CT-3008w-5V10mA-S1 of the Co., Ltd type battery testing system of Shenzhen.
The technological parameter of embodiment 1-13 is seen table 1.The electric performance test result sees table 2.
As shown in Figure 1, graphite monochromator, the Cu target (λ=0.15406nm); 10 °/min of sweep speed; 10 °～90 ° of sweep limitss, the XRD curve of embodiment 1 and XRD standard spectrogram (Reference code:01-081-1173) compare, and material is the LiFePO 4 material of olivine structural.
As shown in Figure 2, the stereoscan photograph of embodiment 1, the LiFePO4 particle is tiny and even, can reach nanoscale 50～200nm.
As shown in Figure 3, as positive pole, make button cell with the LiFePO 4 material of embodiment 1 preparation, carry out charge-discharge test, discharge capacity is 156mAh/g.
Comparative Examples 1 with lithium hydroxide, ferrous sulfate, phosphoric acid, is pressed the mol ratio 3: 1: 1 of lithium, iron, phosphorus, puts into agitating ball mill, adds deionized water, and making solid content of slurry is 35%, and with the rotating speed of 70r/min, ball milling is 8 hours under the normal temperature.Add manganese acetate, mass percent is 2%, and in agitating ball mill, with the rotating speed of 50r/min, ball milling is 1 hour under the normal temperature.Add mass percent in the mixture and be 1% carbon nano-tube, placed the planetary ball mill ball milling 1 hour, rotating speed is 50r/min.Centrifugal dehydration, 120 degree oven dry 12h in vacuum drying chamber, to moisture below 5000ppm.Take out material; Put into tube furnace; Logical nitrogen, flow 0.6L/min is warmed up to 600 ℃ with the speed of 5 ℃/min; Sintering 12 hours; Naturally be cooled to normal temperature, obtain LiFePO 4 of anode material, make the CR2016 pattern as stated above and intend battery; High rate performance and capacity are tested, and test result is seen table 2.Compare with the preparation time of Comparative Examples 1 with embodiment 1, embodiment 1 relatively sees table 3 with Comparative Examples 1 preparation time.
Table 1 embodiment 1-13 technology
The test result of table 2 embodiment 1-5 and Comparative Examples 1
| 0.2C/mAh/g | The first % of imitating | 0.5C/mAh/g | 1C/mAh/g | |
| Embodiment 1 | 156.089 | 97.9 | 152.066 | 146.231 |
| Embodiment 2 | 151.567 | 97.3 | 146.875 | 137.218 |
| Embodiment 3 | 143.921 | 94.9 | 138.185 | 134.029 |
| Embodiment 4 | 146.889 | 95.5 | 143.481 | 137.221 |
| Embodiment 5 | 150.352 | 97 | 143.133 | 134.223 |
| Comparative Examples 1 | 144.87 | 94.1 | 138.849 | 132.042 |
Table 3 preparation time and efficient contrast
Embodiment 1 has reduced 11.5h than the total time of Comparative Examples 1, and time efficiency improves 32%.
Adopt the scheme of embodiment 1, parallelly do three tests, the product that obtains is numbered A, B, C respectively, makes CR2016 pattern plan battery, and high rate performance and capacity are tested, and test result is seen table 4.
Table 4 electrochemical property test result contrast
Method of the present invention improves the efficient that LiFePO4 prepares production process, simplifies preparation technology's flow process, reduces preparation cost, better improves batch instability problem of large-scale production.Reversible specific capacity is greater than 156mAh/g, and electrical property is excellent.
Claims (10)
1. the full method for preparing solid phase of a lithium ion anode material LiFePO4; May further comprise the steps: the mol ratio 1～3.5: 1～3: 1～3 of, pressing lithium, iron, P elements; Li source compound, source of iron, P source compound solid phase mixing are obtained mixture; Rotating speed is 1～2000r/min's, and the time is 0.1～72 hour; Said Li source compound is more than one of lithia, lithium hydroxide, lithium phosphate, lithium carbonate, lithium nitrate, lithium dihydrogen phosphate, lithium formate and lithium acetate; Said source of iron is more than one in iron, ferric phosphate, ferrous sulfate, di-iron trioxide, ferrous oxide, tri-iron tetroxide, iron ammonium sulfate, ferrous sulfate, ferrous phosphate, ferrous ammonium phosphate, ferrous citrate and the frerrous chloride; Said P source compound is more than one in phosphorus pentoxide, phosphoric acid, ammonium dihydrogen phosphate, lithium dihydrogen phosphate, diammonium hydrogen phosphate, ferrous ammonium phosphate and the ammonium hydrogen phosphate salt; Two, press 0.01～20% of mixture quality, add carbon source material and mix the solid-phase mixture that obtains carbonaceous sources, rotating speed is 5～1000r/min, and the time is 0.1～72 hour; Carbon source material is more than one in glucose, sucrose, maltose, polyethylene glycol PEG, PVAC polyvinylalcohol, citric acid, acetylene black, carbon nano-tube and the carbon nano-fiber; Three, by 0.01～20% of the amount of substance of ferro element in the mixture of carbonaceous sources, add alloy and mix and obtain the solid phase presoma, rotating speed is 5～1000r/min, the time is 0.1～72 hour; Alloy is the simple substance of element manganese, cobalt, vanadium, nickel, aluminium, magnesium, calcium, zinc, silver, copper and in the compound more than one; Four, presoma is placed on sintering in the protective atmosphere; The oxygen volume content heats up with 1～20 ℃/min speed, at 500～850 ℃ of sintering 5-36 of temperature hours below 200ppm; Be cooled to normal temperature with 1～30 ℃/min speed, obtain the lithium ion anode material LiFePO4.
2. the full method for preparing solid phase of lithium ion anode material LiFePO4 according to claim 1 is characterized in that: with the mixture thinning processing, rotating speed is 1～5000r/min, and the time is 0.1～72 hour.
3. lithium ion anode material method preparing phosphate iron lithium according to claim 1 is characterized in that: the compound of said manganese is manganese acetate, manganese carbonate and manganese dioxide; The compound of said cobalt is cobalt acetate, cobalt carbonate and cobalt oxide; The compound of said vanadium is oxide hypovanadous oxide, vanadium trioxide, vanadium dioxide and the vanadic oxide of vanadium; The compound of said nickel is nickel acetate, nickelous carbonate and nickel oxide; The compound of said aluminium is aluminium acetate, aluminium carbonate and aluminium oxide; The compound of said magnesium is magnesium acetate, magnesium carbonate and magnesia; The compound of said calcium is calcium acetate, calcium carbonate, calcium bicarbonate and calcium oxide; The compound of said zinc is zinc acetate, zinc carbonate and zinc oxide; The compound of said silver is a silver nitrate; The compound of said copper is a cupric oxide, copper sulphate.
4. the full method for preparing solid phase of lithium ion anode material LiFePO4 according to claim 1 is characterized in that: said protective atmosphere is more than one the gaseous mixture that is added with in more than one gaseous mixture or the argon gas that is added with in the gaseous mixture that is added with argon gas volume 0.5～3% hydrogen in the gaseous mixture that is added with nitrogen volume 0.5～3% hydrogen in nitrogen, argon gas, the nitrogen, the argon gas, the nitrogen in methane, ethane, ethene and the acetylene of nitrogen volume 0.5～4% in methane, ethane, ethene and the acetylene of argon gas volume 0.5～4%.
5. the full method for preparing solid phase of lithium ion anode material LiFePO4 according to claim 1; It is characterized in that: said solid phase mixing, thinning processing, interpolation carbon source material mix and add alloy and mix the employing agitating ball mill; Rotating speed is 5～500r/min, and the time is 1～24 hour.
6. the full method for preparing solid phase of lithium ion anode material LiFePO4 according to claim 1; It is characterized in that: said solid phase mixing, thinning processing, interpolation carbon source material mix and add alloy and mix the employing planetary ball mill; Rotating speed is 10～2000r/min, and the time is 1～72 hour.
7. the full method for preparing solid phase of lithium ion anode material LiFePO4 according to claim 1; It is characterized in that: said solid phase mixing, thinning processing, interpolation carbon source material mix and add alloy and mix the mechanical fusion machine that adopts; Rotating speed is 800～1200r/min, and the time is 0.1～10 hour.
8. the full method for preparing solid phase of lithium ion anode material LiFePO4 according to claim 1; It is characterized in that: said solid phase mixing, thinning processing, interpolation carbon source material mix and add alloy and mix the employing mixer; Rotating speed 1～100r/min mixed 0.1～24 hour.
9. the full method for preparing solid phase of lithium ion anode material LiFePO4 according to claim 1; It is characterized in that: said solid phase mixing, interpolation carbon source material mix and add alloy and mix the employing machine mixer; Rotating speed 5～1000r/min, the time is 1～48 hour.
10. the full method for preparing solid phase of lithium ion anode material LiFePO4 according to claim 1 is characterized in that: said thinning processing adopts pulverizer, and rotating speed is 100～5000r/min.
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