CN103956468B - A kind of compound crystal formation bismuth phosphate lithium iron battery positive electrode and preparation method thereof - Google Patents
A kind of compound crystal formation bismuth phosphate lithium iron battery positive electrode and preparation method thereof Download PDFInfo
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- CN103956468B CN103956468B CN201410114255.0A CN201410114255A CN103956468B CN 103956468 B CN103956468 B CN 103956468B CN 201410114255 A CN201410114255 A CN 201410114255A CN 103956468 B CN103956468 B CN 103956468B
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- lithium
- crystal formation
- compound crystal
- iron
- bismuth
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- 239000013078 crystal Substances 0.000 title claims abstract description 102
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 98
- 150000001875 compounds Chemical class 0.000 title claims abstract description 83
- ZCZKVIWIVHHSOZ-UHFFFAOYSA-H bismuth lithium iron(2+) diphosphate Chemical compound [Fe+2].[Li+].P(=O)([O-])([O-])[O-].[Bi+3].P(=O)([O-])([O-])[O-] ZCZKVIWIVHHSOZ-UHFFFAOYSA-H 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 229910052493 LiFePO4 Inorganic materials 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 230000006835 compression Effects 0.000 claims abstract description 39
- 238000007906 compression Methods 0.000 claims abstract description 39
- 238000005245 sintering Methods 0.000 claims abstract description 31
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims abstract description 27
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000084 colloidal system Substances 0.000 claims abstract description 23
- 235000011837 pasties Nutrition 0.000 claims abstract description 17
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910000416 bismuth oxide Inorganic materials 0.000 claims abstract description 12
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000006185 dispersion Substances 0.000 claims abstract description 11
- 150000002500 ions Chemical class 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 26
- 239000008139 complexing agent Substances 0.000 claims description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 230000029087 digestion Effects 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 238000012423 maintenance Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000010008 shearing Methods 0.000 claims description 9
- 229910052797 bismuth Inorganic materials 0.000 claims description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-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
- 230000035882 stress Effects 0.000 claims description 8
- 241000196324 Embryophyta Species 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- 230000003064 anti-oxidating effect Effects 0.000 claims description 7
- 238000007664 blowing Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000011438 cord wood Substances 0.000 claims description 7
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical group Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000005955 Ferric phosphate Substances 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
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- 229940032958 ferric phosphate Drugs 0.000 claims description 4
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229920002907 Guar gum Polymers 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 229910052786 argon Inorganic materials 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 239000000665 guar gum Substances 0.000 claims description 3
- 229960002154 guar gum Drugs 0.000 claims description 3
- 235000010417 guar gum Nutrition 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 3
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 3
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 3
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052743 krypton Inorganic materials 0.000 claims description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- -1 iron salt ferric phosphate Chemical class 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 11
- 239000010405 anode material Substances 0.000 abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 230000008025 crystallization Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 19
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 8
- 229910010710 LiFePO Inorganic materials 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000003837 high-temperature calcination Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 3
- 230000001617 migratory effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ZVKRVGZVXQYLPZ-UHFFFAOYSA-N [Li].[V].P(O)(O)(O)=O Chemical compound [Li].[V].P(O)(O)(O)=O ZVKRVGZVXQYLPZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 241000446313 Lamella Species 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 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 description 1
- GOXBYKFTUFDRRB-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Fe+2].[Li+].[V+5] Chemical compound P(=O)([O-])([O-])[O-].[Fe+2].[Li+].[V+5] GOXBYKFTUFDRRB-UHFFFAOYSA-K 0.000 description 1
- 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 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- YWJVFBOUPMWANA-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YWJVFBOUPMWANA-UHFFFAOYSA-H 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 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 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000011712 cell development Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- RFGNMWINQUUNKG-UHFFFAOYSA-N iron phosphoric acid Chemical compound [Fe].OP(O)(O)=O RFGNMWINQUUNKG-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention discloses a kind of compound crystal formation bismuth phosphate lithium iron battery positive electrode, is by olivine-type LiFePO4 (LiFePO
4) with the bismuth oxide (δ-Bi of fluorite structure
2o
3) form a kind of on three dimensions, ion can the compound crystalline structure of fast transferring, consist of: Li
0.8-0.9fe
0.8-0.9bi
0.1-0.3pO
4.The preparation method of compound crystal formation bismuth phosphate iron lithium is provided further, it is characterized in that prefabricated pasty colloid thing by the high shear of conical screw extruder, high pressure, airtight successive reaction, one step completes dispersion, lures compound crystal into, compression sintering, thus obtains complete, even, the highdensity anode material for lithium-ion batteries of crystallization reaction.By compression sintering, manufacturing cycle is significantly shortened, make to prepare anode material of lithium battery more environmental protection and energy saving.
Description
Technical field
The present invention relates to battery material field, the bismuth phosphate lithium iron battery positive electrode being specifically related to a kind of compound crystal formation with and preparation method thereof.
Background technology
According to the consumption of automobile industry to oil and the pollution to air, electric automobile becomes the only way which must be passed alleviated consumption of petroleum and solve environmental pollution.The core developing electric motor car is then safety, efficiently secondary battery.At present, the main plumbic acid that uses and Ni-MH battery in electric motor car or hybrid electric vehicle, because useful life is short, easy contaminated environment, is progressively replaced by lithium battery safely and efficiently.Lithium ion battery is a kind of novel secondary energy-storage battery grown up the nineties in 20th century.Owing to there is high-energy, long-life, low consumption, nuisanceless, memory-less effect and the advantage such as self discharge is little, internal resistance is little, cost performance is high, pollution is few, be widely used in the fields such as mobile phone, notebook computer, video camera, digital camera, electric automobile.And to restrict one of bottleneck of lithium ion battery industrialization promotion be exactly positive electrode.At present, anode material for lithium-ion batteries mainly contains cobalt acid lithium, lithium nickelate, LiMn2O4 and LiFePO4 etc., wherein because cobalt is poisonous and resource-constrained, and lithium nickelate preparation difficulty, the factors such as the cycle performance of LiMn2O4 and high-temperature behavior difference, can only be used for small-sized lithium electricity positive electrode; And LiFePO4 (LiFePO
4) there is wide material sources, low price, Heat stability is good, no hygroscopicity, the advantage such as environmentally friendly, be applicable to large-scale development and use, be more suitable for the electric motor car of Large Copacity requirement.
LiFePO4 (the LiFePO of olivine-type structure
4) within 1997, to be in the news, there is reversible removal lithium embedded characteristic since, become one of study hotspot of current anode material for lithium-ion batteries with advantages such as its security performance is good, cycle performance is excellent, environmental friendliness, abundant raw material source.LiFePO4 (LiFePO
4) its theoretical specific capacity relatively high (170mAh/g), 3.4V (vs.Li/Li can be produced
+) voltage, especially there is the LiFePO4 (LiFePO of regular olivine-type
4) with and the FePO of Charging state
4cell parameter, belong to a kind of space group together, structurally extremely similar.Therefore, LiFePO4 (LiFePO
4) can the stability of holding structure in repeated charge process, circulating and reversible performance is high.There is good thermal stability, less moisture absorption and excellent charge-discharge performance, thus LiFePO under full-charge state
4be considered to the main flow direction of lithium-ion-power cell development.
But, LiFePO4 (LiFePO
4) as anode material of lithium battery, still existing defects, is mainly manifested in: 1, material conductivity is poor, LiFePO4 (LiFePO
4) in charge and discharge process, due to PO4 in crystal
3-limit Li
+mobile space, make Li
+embedding, de-process be only confined to two-dimentional removable space, and movable passageway is long, therefore, LiFePO
4electronics, ionic conductivity all lower, especially under the condition of heavy-current discharge, have larger capacitance loss; 2, LiFePO4 is due to special appearance, and tap density is little, and the electric energy stored by unit volume battery is less; 3, Fe in preparation
2+oxidizable one-tenth Fe
3+, be difficult to obtain single-phase LiFePO
4, purity is low, complicated process of preparation, needs long-time high-temperature calcination, and energy consumption is high, the cycle is long.
At present, LiFePO4 (LiFePO
4) mainly through controlling grain growth, prepare uniform particle diameter, tiny material, thus the ionic conduction performance of strengthening material.Synthesis LiFePO
4generally adopt high temperature solid-state method, as: Chinese invention patent CN101966986B discloses a kind of preparation method of lithium iron phosphate cathode material for lithium ion battery, lithium source, source of iron, phosphorus source and doped source material are placed in agitating ball mill and mix by the method, compound is joined in double screw extruder and carry out reactive extrursion, product will be extruded and be placed in inert atmosphere stove, at 600 ~ 800 DEG C, calcine 5-20 hour, obtain LiFePO 4 material.Chinese invention patent CN101764218A discloses a kind of preparation method of cathode material of lithium iron phosphate lithium-ion battery, and powdery source of iron, lithium source, phosphorus source are extruded pulverizing by the method in screw machine.The powder body material of regular crystal forms can not be obtained by this method, and complex process, need long-time high-temperature calcination.In order to improve LiFePO4 (LiFePO further
4) Practical Performance, people are studied its synthesis technique, find LiFePO
4particle radii have larger impact to electrode specific capacity.LiFePO
4particle radii are larger, Li
+solid-state diffusion distance longer, it is deviate from and embeds more difficult, LiFePO
4capacity more difficultly to give full play of.So, by reducing LiFePO
4the particle diameter of particle can improve LiFePO
4the chemical property of positive electrode.Such as: Chinese invention patent CN102709562A provides a kind of method utilizing Liquid preparation methods LiFePO4, this invention take di-iron trioxide as source of iron, with lithium hydroxide or lithium carbonate for lithium source, take phosphoric acid as phosphorus source, with glucose or sucrose for carbon source, control reaction temperature by solvent-thermal method, prepare LiFePO4 crystal.But hydro thermal method needs high temperature high voltage resistant equipment, the difficulty of suitability for industrialized production is comparatively large, and hydro thermal method easily generates metastable FePO simultaneously
4, affect the electrical property of product.Chinese invention patent CN101814600A provides a kind of preparation method of lithium iron phosphate serving as positive active material of lithium battery, adopt colloidal sol principle, with soluble ferric iron salt, lithium salts, phosphoric acid, complexing agent and doping metals source, carbon source predecessor for raw material, raw material made colloidal sol and concentrate, at 650 ~ 750 DEG C of temperature, then causing Self-propagating Sintering Synthetic olivine-type pure ferric phosphate lithium.With the LiFePO of sol-gel process synthesis
4have the advantages such as chemical uniformity is good, purity is high, particle is thin, but its main deficiency is that preparation technology is more complicated, and during gel drying, shrinkage is large, powder body material needs long-time high-temperature calcination.Chinese invention patent CN101906661B discloses a kind of ordered layered self-assembled nanostructured lithium iron phosphate polycrystalline powder and preparation method thereof, the particle of the 0.5-1 micron that the flaky lithium iron phosphate being about 20-40 nanometer by thickness is piled up layer by layer in order, be nano lamellar duct between adjacent two LiFePO4 lamellas, the formation of this structure is under the effect of surfactant double template, by the non-covalent bond effect of surfactant and forerunner's species, induce the nucleation of inorganic species, growth, overcome the arrangement of existing product LiFePO4 construction unit random, the shortcoming that degree of crystallinity is on the low side.The method is from the conductivity improving LiFePO4 in person, but the intrinsic conductivity of LiFePO4 does not improve.
On the other hand, occurred by Surface coating conductive carbon material, improved LiFePO4 (LiFePO by means such as amorphous phase doping, crystalline phase doping simultaneously
4) electronics, the ionic conductivity of material.Such as: Chinese invention patent CN102683702A discloses a kind of lithium iron phosphate preparation method of coated with uniform carbon, organic substance, ferric phosphate and Li source compound are placed in high-energy ball milling tank by this invention, add organic solvent, carry out wet ball grinding, by carbon cladding high conductivity, the chemical property of LiFePO4 effectively can be improved.Chinese invention patent CN102522550A discloses a kind of tantalum doped carbon-covering lithium iron phosphate and preparation method thereof, makes material electrochemical performance excellent by the doping of tantalum, and especially under high current density, capacity attenuation is minimum.Chinese invention patent CN103050698A discloses a kind of vanadium lithium iron phosphate anode material and preparation method thereof, the method is in order to overcome LiFePO4 and phosphoric acid vanadium lithium deficiency separately, utilize the mutual doping in LiFePO4 and phosphoric acid vanadium lithium of vanadium and iron to form a kind of composite crystalline structure simultaneously with olivine-type LiFePO4 and monoclinic lithium vanadium phosphate, thus promote the conductivity of material.But because the crystal defect of doping property does not form complete crystal formation, therefore Li
+migration be still confined to the two-dimensional space of olivine-type, especially in order to make stably-doped and crystal grain is regular, usually need to calcine 5-20 hour under the hot conditions of 500-800 DEG C, needing to consume a large amount of energy.
According to above-mentioned, the LiFePO4 (LiFePO of olivine-type structure
4) there is stable structure and higher specific capacity, circulating and reversible performance is high, is suitable for the positive electrode of lithium battery, but, due to olivine-type structure LiFePO4 (LiFePO
4) self-defect, PO4 in structure
3-limit Li
+mobile space, and movable passageway is longer, have impact on Large Copacity fast charging and discharging.Although improved by improvement preparation method and doping at present, the intrinsic conductivity of LiFePO4 cannot obtain the change of essence.In addition, there is reaction not exclusively in existing preparation method's solid phase method, the defect of crystallization irregularity, liquid phase method exists reaction process complexity, the defect of severe reaction conditions.And calcine 5-20 hour under usually needing the hot conditions of 500-800 DEG C, calcined for a long time by high temperature and obtain complete crystal formation, need to consume a large amount of energy.Finally cause current LiFePO4 (LiFePO
4) density is little, Fe in synthesis
2+oxidizable one-tenth Fe
3+, be difficult to obtain single-phase LiFePO
4, purity is low, and manufacturing cost continues to make friends with.
Summary of the invention
Li is there is as anode material for lithium-ion batteries for existing LiFePO4
+embedding, de-process be only confined to two-dimensional movement space, and the fault of construction that movable passageway is long, and have in LiFePO4 preparation that the high-temperature calcination cycle is long, product density is little, Fe in synthesis
2+oxidizable one-tenth Fe
3+, be difficult to obtain single-phase LiFePO
4, the defect such as purity is low, manufacturing cost is high.The invention provides a kind of by olivine-type LiFePO4 (LiFePO
4) with the bismuth oxide (δ-Bi of fluorite structure
2o
3) anode material for lithium-ion batteries of compound crystal formation that formed, this compound crystal formation is bismuth phosphate iron lithium, due to Bi
3+the lone pair electrons of polarization, Bi
2o
3between ion, bond energy is lower, and the sky of its lattice is supported oxygen position and improve ionic mobility in olivine-type LiFePO4 lattice, the Li thus contracting has been broken
+embedding, de-passage, Li
+migratory movement expanded range to three-dimensional, avoid the capacitance loss that LiFePO4 causes because grain particles is large, uneven.
Further aim of the present invention is to provide a kind of preparation method of compound crystal formation bismuth phosphate iron lithium, prefabricated pasty colloid thing by the high shear of conical screw extruder, high pressure, airtight successive reaction Fast Compression sintering synthesis compound crystal formation bismuth phosphate iron lithium, thus is obtained complete, even, the highdensity anode material for lithium-ion batteries of crystallization reaction by its feature.
Concrete summary of the invention is as follows:
A kind of compound crystal formation of the present invention bismuth phosphate lithium iron battery positive electrode, is characterized in that: by olivine-type LiFePO4 (LiFePO
4) with the bismuth oxide (δ-Bi of fluorite structure
2o
3) form a kind of on three dimensions, ion can the compound crystalline structure of fast transferring.Consist of: Li
0.8-0.9fe
0.8-0.9bi
0.1-0.3pO
4.
A preparation method for compound crystal formation bismuth phosphate lithium iron battery positive electrode, comprises following concrete steps:
1) in high-speed mixer by lithium source, source of iron, bismuth source, phosphorus source in molar ratio Li:Fe:Bi:P=0.8-0.9:0.8-0.9:0.1-0.3:1 mixing, and add the hydrosol, addition is the 10-20% of lithium source, source of iron, bismuth source, phosphorus source gross mass, add crystal formation complexing agent simultaneously, addition is the 0.2-1% of lithium source, source of iron, bismuth source, phosphorus source gross mass, and obtains pasty colloid pre-reaction body with the speed high-speed stirred of 500-1000rpm dispersion 10-30min;
2) the pasty colloid pre-reaction body obtained in step 1) is pumped into conical screw extruder, screw extruder is by carrying screwing element, thread engagement element, compression screwing element with cordwood arrangement on mandrel, composition conveying dryer section, shear homogenizing zone, compression sintering section three part, control extruder temperature: conveying dryer section 120-160 DEG C, shear homogenizing zone 180-280 DEG C, compression sintering section 300-360 DEG C, screw rod produces continuous shear stress homogenizing under the rotating condition of 200-400rpm, by luring into of the strong shearing of screw extruder and crystal formation complexing agent, the pre-colloid of paste forms compound crystal formation bismuth phosphate iron lithium fast, in order to anti-oxidation, screw extruder is in conveying dryer section, shear homogenizing zone, compression sintering section all arranges devolatilization vacuum plant, ensure that reaction is carried out under anaerobic,
3) by step 2) in the compound crystal formation bismuth phosphate iron lithium that obtains send into airtight digestion tank, digestion tank arranges high pressure and inert gas maintenance, ageing maintenance 1-2 hour, and then blowing cools naturally;
4) cooling material step 3) obtained drops into eddy airstream pulverizer, obtains the compound crystal formation bismuth phosphate iron lithium particle that granular size is 100-200nm, this particle and compound crystal formation bismuth phosphate lithium iron battery positive electrode of the present invention.
In above-mentioned preparation method, the lithium source described in step 1) is at least one in Acidic Liquid in soluble phosphoric acid hydrogen two lithium, lithium carbonate, lithium hydroxide, lithium dihydrogen phosphate; Described source of iron is trivalent iron salt, preferably phosphoric acid iron, iron oxide, iron chloride, ferric nitrate; Described bismuth source is bismuth nitrate; Described phosphorus source is at least one in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid; At least one in the hydroxypropyl methyl cellulose ether of the described hydrosol to be concentration be 10-15%, guar gum, sesbania gum, CMS glue; Described crystal formation complexing agent is triethanolamine.
In above-mentioned preparation method, step 2) described in conical screw extruder screw draw ratio 56/1, ensure that the reaction time of material in extruder maintains 20-30min, utilize conical screw extruder to make colloid pre-reaction body one step complete dispersion, lure compound crystal into, compression sintering, form olivine-type LiFePO4 (LiFePO
4) and the bismuth oxide (δ-Bi of fluorite structure
2o
3) compound crystal formation.Owing to adopting continuous shear stress and compression sintering, not only reduce reaction temperature, and shorten the reaction time, especially owing to be sheared and compression affects, compound crystal formation bismuth phosphate iron lithium is the superposition in stratiform in forming process, the compound crystal formation bismuth phosphate iron lithium material appearance obtained is regular, and packing is high.
In above-mentioned preparation method, step 2) described in conical screw extruder adopt Electromagnetic Heating, realize the even heated fast of material, reach stable reaction.
In above-mentioned preparation method, step 2) described in conical screw extruder to arrange devolatilization Vacuum Pressure be 1.5-2.8MPa.
In above-mentioned preparation method, digestion tank described in step 3) arranges the pressure of 5-10MPa, and described inert gas can select helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), nitrogen (N2).
In above-mentioned preparation method, the eddy airstream pulverizer described in step 4) arranges circulation classification machine, the gradation reaching 100-200nm requirement can be collected.
A kind of compound crystal formation of the present invention bismuth phosphate lithium iron battery positive electrode and preparation method thereof is by olivine-type LiFePO4 (LiFePO
4) with the bismuth oxide (δ-Bi of fluorite structure
2o
3) form a kind of on three dimensions, ion can the compound crystalline structure of fast transferring, consist of: Li
0.8-0.9fe
0.8-0.9bi
0.1-0.3pO
4.By at the shearing homogenizing of conical screw extruder and compression sintering, under colloid, crystal formation complexing agent is utilized to make the bismuth oxide (δ-Bi of fluorite structure
2o
3) lattice is compounded in olivine-type LiFePO4 lattice, the bismuth oxide (δ-Bi of fluorite structure
2o
3) in crystal structure, due to Bi
3+form compact reactor cumuliformis, whole octahedral interstices is not all filled, that is 8 O
2-between define a cavity, structure comparison is open, for ion diffuse provides stable passage.Bismuth oxide (δ-the Bi of fluorite structure
2o
3) sky support oxygen position and not only improve olivine-type LiFePO4 lattice intermediate ion mobility, and compound crystalline structure makes Li
+migratory movement expanded range to three-dimensional, the Li thus contracting has been broken
+embedding, de-passage, avoid the capacitance loss that LiFePO4 causes because grain particles is large, uneven.Further, in conical screw extruder, owing to being sheared and compressing, compound crystal formation bismuth phosphate iron lithium is the superposition in stratiform in forming process, and the compound crystal formation bismuth phosphate iron lithium material appearance obtained is regular, and packing, tap density can reach 2.0g/cm
3above, reaction efficiency is high.The method not only reacts even, and calcines for a long time without the need to other high temperature, and manufacturing cycle significantly shortens, and makes to prepare anode material of lithium battery more environmental protection and energy saving.
Accompanying drawing explanation
Fig. 1 is the process flow diagram that a kind of compound crystal formation of the present invention bismuth phosphate lithium iron battery positive electrode adopts.
Fig. 2 is the XRD collection of illustrative plates of embodiment 1 gained compound crystal formation bismuth phosphate iron lithium.
Fig. 3 is the SEM photo of embodiment 1 gained compound crystal formation bismuth phosphate iron lithium.
A kind of compound crystal formation of the present invention bismuth phosphate lithium iron battery positive electrode and preparation method thereof, compared with existing lithium iron phosphate positive material technology, its outstanding feature is:
1, a kind of compound crystal formation of the present invention bismuth phosphate lithium iron battery positive electrode, is by olivine-type LiFePO4 (LiFePO
4) with the bismuth oxide (δ-Bi of fluorite structure
2o
3) the compound crystal formation anode material for lithium-ion batteries that formed, this compound crystal formation is bismuth phosphate iron lithium, due to Bi
3+the lone pair electrons of polarization, the sky of its lattice is supported oxygen position and improve ionic mobility in olivine-type LiFePO4 lattice, the Li thus contracting has been broken
+embedding, de-passage, make Li
+migratory movement expanded range to three-dimensional, avoid the capacitance loss that LiFePO4 causes because grain particles is large, uneven.
2, a kind of compound crystal formation of the present invention bismuth phosphate lithium iron battery positive electrode, lures by what use crystal formation complexing agent the compound achieving olivine-type structure and fluorite structure into, thus changes the fault of construction of LiFePO4 existence.
3, the preparation method of a kind of compound crystal formation of the present invention bismuth phosphate lithium iron battery positive electrode, adopt colloid pre-reaction body at the continuous confined reaction of conical screw, one step completes dispersion, lures compound crystal into, compression sintering, not only reduce reaction temperature, 200-360 DEG C is reduced to by original 600-800 DEG C, and significantly shorten the reaction time, foreshorten to 20-30 minute by original 5-20 hour.
4, the preparation method of a kind of compound crystal formation of the present invention bismuth phosphate lithium iron battery positive electrode, not only reaction efficiency high, react completely, purity is high, crystallization is even, crystal grain is tiny, and be subject to shearing and the compression of continuous uniform, grain growth rule, superpose in stratiform, appearance is regular, and its tap density can reach 2.0g/cm
3above.
5, the preparation method of a kind of compound crystal formation of the present invention bismuth phosphate lithium iron battery positive electrode, production efficiency is high, equipment investment is low, can continuous operation, easy to implement with control, low, the without sewage discharge of energy consumption, be beneficial to suitability for industrialized production.
Embodiment
Following embodiment, is described in further detail foregoing of the present invention again.But this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following example.Without departing from the idea case in the present invention described above, the various replacement made according to ordinary skill knowledge and customary means or change, all should comprise within the scope of the invention.
embodiment 1
1) in high-speed mixer, phosphoric acid hydrogen two lithium, iron oxide, bismuth nitrate, phosphoric acid are pressed effective element mol ratio Li:Fe:Bi:P=0.8:0.9:0.15:1 and mixed, and add the sesbania gum of gross mass 10%, add the crystal formation complexing agent triethanolamine of gross mass 0.2% simultaneously, and obtain pasty colloid pre-reaction body with the speed high-speed stirred of 500rpm dispersion 30min;
2) the pasty colloid pre-reaction body obtained in step 1) is pumped into conical screw extruder, screw extruder is by carrying screwing element, thread engagement element, compression screwing element with cordwood arrangement on mandrel, composition conveying dryer section, shear homogenizing zone, compression sintering section three part, control extruder temperature: conveying dryer section 160 DEG C, shear homogenizing zone 200 DEG C, compression sintering section 300 DEG C, screw rod produces continuous shear stress homogenizing under the rotating condition of 200rpm, by luring into of the strong shearing of screw extruder and crystal formation complexing agent, pasty colloid pre-reaction body forms compound crystal formation bismuth phosphate iron lithium fast, in order to anti-oxidation, screw extruder is in conveying dryer section, shear homogenizing zone, compression sintering section all arranges devolatilization vacuum plant, devolatilization Vacuum Pressure is 1.5MPa, ensure that reaction is carried out under anaerobic,
3) by step 2) in the compound crystal formation bismuth phosphate iron lithium that obtains send into airtight digestion tank, digestion tank arranges pressure and the nitrogen maintenance of 5MPa, ageing 1 hour, and then blowing cools naturally;
4) cooling material step 3) obtained drops into eddy airstream pulverizer, obtains the compound crystal formation bismuth phosphate iron lithium particle that granular size is 100-200nm, this particle and compound crystal formation bismuth phosphate lithium iron battery positive electrode of the present invention.
By detecting: as Fig. 2 carries out X-ray diffraction phenetic analysis, the compound crystal formation bismuth phosphate iron lithium material structure of gained is not exclusively same as olivine-type structure, but occurring identical bimodal, symbolizing the bismuth oxide (δ-Bi of fluorite structure
2o
3) lattice is compounded in olivine-type LiFePO4 lattice and forms a kind of new compound crystal formation.By Fig. 3 scanning electron microscopic observation, bismuth phosphate iron lithium particle size is even, and particle diameter is about 100-200nm.Tap density 2.1g/cm
3, room temperature first discharge specific capacity (1C) > 155mAh/g.
embodiment 2
1) in high-speed mixer, lithium carbonate, iron chloride, bismuth nitrate, diammonium hydrogen phosphate are pressed effective element mol ratio Li:Fe:Bi:P=0.8:0.8:0.3:1 and mixed, and add 15% CMS glue of gross mass, add the crystal formation complexing agent triethanolamine of 0.5% of gross mass simultaneously, and obtain pasty colloid pre-reaction body with the speed high-speed stirred of 1000rpm dispersion 10min;
2) the paste pre-reaction body obtained in step 1) is pumped into conical screw extruder, screw extruder is by carrying screwing element, thread engagement element, compression screwing element with cordwood arrangement on mandrel, composition conveying dryer section, shear homogenizing zone, compression sintering section three part, control extruder temperature: conveying dryer section 120 DEG C, shear homogenizing zone 180 DEG C, compression sintering section 300 DEG C, screw rod produces continuous shear stress homogenizing under the rotating condition of 400rpm, by luring into of the strong shearing of screw extruder and crystal formation complexing agent, the pre-colloid reaction body of paste forms compound crystal formation bismuth phosphate iron lithium fast, in order to anti-oxidation, screw extruder is in conveying dryer section, shear homogenizing zone, compression sintering section all arranges devolatilization vacuum plant, devolatilization Vacuum Pressure is 2.5MPa, ensure that reaction is carried out under anaerobic,
3) by step 2) in the compound crystal formation bismuth phosphate iron lithium that obtains send into airtight digestion tank, digestion tank arranges pressure and the argon gas maintenance of 8MPa, ageing 1.5 hours, and then blowing cools naturally;
4) cooling material step 3) obtained drops into eddy airstream pulverizer, obtains the compound crystal formation bismuth phosphate iron lithium particle that granular size is 100-200nm, this particle and compound crystal formation bismuth phosphate lithium iron battery positive electrode of the present invention.
After testing: the tap density of compound crystal formation bismuth phosphate iron lithium material is 2.0g/cm
3, under 1C, the room temperature first discharge specific capacity > 163mAh/g of material.Under 5C, the room temperature first discharge specific capacity > 159mAh/g of material, after 200 5C charge and discharge cycles, the electric specific capacity > 158mAh/g of material, without obviously decaying.
embodiment 3
1) in high-speed mixer, lithium dihydrogen phosphate, ferric nitrate, bismuth nitrate, ammonium dihydrogen phosphate are pressed effective element mol ratio Li:Fe:Bi:P=0.8:0.8:0.2:1 and mixed, and add 20% guar gum of gross mass, add the crystal formation complexing agent triethanolamine of 1% of gross mass simultaneously, and obtain pasty colloid pre-reaction body with the speed high-speed stirred of 800rpm dispersion 20min;
2) the paste pre-reaction body obtained in step 1) is pumped into screw extruder, screw extruder is by carrying screwing element, thread engagement element, compression screwing element with cordwood arrangement on mandrel, composition conveying dryer section, shear homogenizing zone, compression sintering section three part, control extruder temperature: conveying dryer section 150 DEG C, shear homogenizing zone 200 DEG C, compression sintering section 360 DEG C, screw rod produces continuous shear stress homogenizing under the rotating condition of 400rpm, by luring into of the strong shearing of screw extruder and crystal formation complexing agent, pasty colloid pre-reaction body forms compound crystal formation bismuth phosphate iron lithium fast, in order to anti-oxidation, screw extruder is in conveying dryer section, shear homogenizing zone, compression sintering section all arranges devolatilization vacuum plant, devolatilization Vacuum Pressure is 2.8MPa, ensure that reaction is carried out under anaerobic,
3) by step 2) in the compound crystal formation bismuth phosphate iron lithium that obtains send into airtight digestion tank, digestion tank arranges pressure and the helium maintenance of 9MPa, ageing 2 hours, and then blowing cools naturally;
4) cooling material step 3) obtained drops into eddy airstream pulverizer, obtains the compound crystal formation bismuth phosphate iron lithium particle that granular size is 100-200nm, this particle and compound crystal formation bismuth phosphate lithium iron battery positive electrode of the present invention.
After testing: the tap density of compound crystal formation bismuth phosphate iron lithium material is 2.2g/cm
3, under 1C, the room temperature first discharge specific capacity > 159mAh/g of material.
embodiment 4
1) in high-speed mixer, lithium hydroxide, ferric nitrate, bismuth nitrate, phosphoric acid are pressed effective element mol ratio Li:Fe:Bi:P=0.9:0.8:0.1:1 and mixed, and add 10% hydroxypropyl methyl cellulose ether of gross mass, add the crystal formation complexing agent triethanolamine of 0.4% of gross mass simultaneously, and obtain pasty colloid pre-reaction body with the speed high-speed stirred of 500rpm dispersion 20min;
2) the paste pre-reaction body obtained in step 1) is pumped into conical screw extruder, screw extruder is by carrying screwing element, thread engagement element, compression screwing element with cordwood arrangement on mandrel, composition conveying dryer section, shear homogenizing zone, compression sintering section three part, control extruder temperature: conveying dryer section 130 DEG C, shear homogenizing zone 250 DEG C, compression sintering section 350 DEG C, screw rod produces continuous shear stress homogenizing under the rotating condition of 350rpm, by luring into of the strong shearing of screw extruder and crystal formation complexing agent, pasty colloid pre-reaction body forms compound crystal formation bismuth phosphate iron lithium fast, in order to anti-oxidation, screw extruder is in conveying dryer section, shear homogenizing zone, compression sintering section all arranges devolatilization vacuum plant, devolatilization Vacuum Pressure is 2.0MPa, ensure that reaction is carried out under anaerobic,
3) by step 2) in the compound crystal formation bismuth phosphate iron lithium that obtains send into airtight digestion tank, digestion tank arranges pressure and the neon maintenance of 10MPa, ageing 2 hours, and then blowing cools naturally;
4) cooling material step 3) obtained drops into eddy airstream pulverizer, obtains the compound crystal formation bismuth phosphate iron lithium particle that granular size is 100-200nm, this particle and compound crystal formation bismuth phosphate lithium iron battery positive electrode of the present invention.
After testing: the tap density of compound crystal formation bismuth phosphate iron lithium material is 2.0g/cm
3, under 1C, the room temperature first discharge specific capacity > 160mAh/g of material.
embodiment 5
1) in high-speed mixer, lithium carbonate, ferric phosphate, bismuth nitrate, diammonium hydrogen phosphate are pressed effective element mol ratio Li:Fe:Bi:P=0.8:0.8:0.3:1 and mixed, and add 15% sesbania gum of gross mass, add the crystal formation complexing agent triethanolamine of 1% of gross mass simultaneously, and obtain pasty colloid pre-reaction body with the speed high-speed stirred of 1000rpm dispersion 30min;
2) the paste pre-reaction body obtained in step 1) is pumped into conical screw extruder, screw extruder is by carrying screwing element, thread engagement element, compression screwing element with cordwood arrangement on mandrel, composition conveying dryer section, shear homogenizing zone, compression sintering section three part, control extruder temperature: conveying dryer section 150 DEG C, shear homogenizing zone 260 DEG C, compression sintering section 350 DEG C, screw rod produces continuous shear stress homogenizing under the rotating condition of 400rpm, by luring into of the strong shearing of screw extruder and crystal formation complexing agent, pasty colloid pre-reaction body forms compound crystal formation bismuth phosphate iron lithium fast, in order to anti-oxidation, screw extruder is in conveying dryer section, shear homogenizing zone, compression sintering section all arranges devolatilization vacuum plant, devolatilization Vacuum Pressure is 1.5MPa, ensure that reaction is carried out under anaerobic,
3) by step 2) in the compound crystal formation bismuth phosphate iron lithium that obtains send into airtight digestion tank, digestion tank arranges pressure and the xenon maintenance of 5MPa, ageing 1 hour, and then blowing cools naturally;
4) cooling material step 3) obtained drops into eddy airstream pulverizer, obtains the compound crystal formation bismuth phosphate iron lithium particle that granular size is 100-200nm, this particle and compound crystal formation bismuth phosphate lithium iron battery positive electrode of the present invention.
After testing: the tap density of compound crystal formation bismuth phosphate iron lithium material is 2.1g/cm
3, under 1C, the room temperature first discharge specific capacity > 161mAh/g of material.
Claims (8)
1. a compound crystal formation bismuth phosphate lithium iron battery positive electrode, is characterized in that: by olivine-type LiFePO4 (LiFePO
4) with the bismuth oxide (δ-Bi of fluorite structure
2o
3) form a kind of on three dimensions, ion can the compound crystalline structure of fast transferring, consist of: Li
xfe
ybi
zpO4, wherein 0.8≤x≤0.9,0.8≤y≤0.9,0.1≤z≤0.3.
2. a preparation method for compound crystal formation bismuth phosphate lithium iron battery positive electrode, comprises following concrete steps:
1) lithium source, source of iron, bismuth source, phosphorus source are mixed to get the mixture of mol ratio Li:Fe:Bi:P=0.8-0.9:0.8-0.9:0.1-0.3:1 in high-speed mixer, and add the hydrosol, addition is the 10-20% of lithium source, source of iron, bismuth source, phosphorus source gross mass, add crystal formation complexing agent simultaneously, addition is the 0.2-1% of lithium source, source of iron, bismuth source, phosphorus source gross mass, and obtains pasty colloid pre-reaction body with the speed high-speed stirred of 500-1000rpm dispersion 10-30min;
2) the pasty colloid pre-reaction body obtained in step 1) is pumped into conical screw extruder, screw extruder is by carrying screwing element, thread engagement element, compression screwing element with cordwood arrangement on mandrel, composition conveying dryer section, shear homogenizing zone, compression sintering section three part, control extruder temperature: conveying dryer section 120-160 DEG C, shear homogenizing zone 180-280 DEG C, compression sintering section 300-360 DEG C, screw rod produces continuous shear stress homogenizing under the rotating condition of 200-400rpm, by the strong shearing of screw extruder, luring into of compression sintering and crystal formation complexing agent, pasty colloid pre-reaction body forms compound crystal formation bismuth phosphate iron lithium fast, in order to anti-oxidation, screw extruder is in conveying dryer section, shear homogenizing zone, compression sintering section all arranges devolatilization vacuum plant, ensure that reaction is carried out under anaerobic, colloid pre-reaction body one step is made to complete dispersion, lure compound crystal into, compression sintering, form olivine-type LiFePO4 (LiFePO
4) and the bismuth oxide (δ-Bi of fluorite structure
2o
3) compound crystal formation,
3) by step 2) in the compound crystal formation bismuth phosphate iron lithium that obtains send into airtight digestion tank, digestion tank arranges high pressure and helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), nitrogen (N
2) in a kind of gas maintenance, ageing maintenance 1-2 hour, then blowing cools naturally;
4) cooling material step 3) obtained drops into eddy airstream pulverizer, obtains the compound crystal formation bismuth phosphate iron lithium particle that granular size is 100-200nm, this particle and compound crystal formation bismuth phosphate lithium iron battery positive electrode of the present invention.
3. the preparation method of a kind of compound crystal formation bismuth phosphate lithium iron battery positive electrode as claimed in claim 2, the lithium source that it is characterized in that described in step 1) is at least one in Acidic Liquid in soluble phosphoric acid hydrogen two lithium, lithium carbonate, lithium hydroxide, lithium dihydrogen phosphate; Described source of iron is at least one in trivalent iron salt ferric phosphate, iron oxide, iron chloride, ferric nitrate; Described bismuth source is bismuth nitrate; Described phosphorus source is at least one in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid; At least one in the hydroxypropyl methyl cellulose ether of the described hydrosol to be mass concentration be 10-15%, guar gum, sesbania gum, CMS glue; Described crystal formation complexing agent is triethanolamine.
4. the preparation method of a kind of compound crystal formation bismuth phosphate lithium iron battery positive electrode as claimed in claim 2, it is characterized in that step 2) described in conical screw extruder screw draw ratio 56/1, ensure the reaction time of material in extruder maintain 20-30min.
5. the preparation method of a kind of compound crystal formation bismuth phosphate lithium iron battery positive electrode as claimed in claim 2, is characterized in that step 2) described in conical screw extruder adopt Electromagnetic Heating, realize the even heated fast of material, reach stable reaction.
6. the preparation method of a kind of compound crystal formation bismuth phosphate lithium iron battery positive electrode as claimed in claim 2, is characterized in that step 2) described in conical screw extruder to arrange devolatilization Vacuum Pressure be 1.5-2.8MPa.
7. the preparation method of a kind of compound crystal formation bismuth phosphate lithium iron battery positive electrode as claimed in claim 2, is characterized in that the digestion tank described in step 3) arranges the pressure of 5-10MPa.
8. the preparation method of a kind of compound crystal formation bismuth phosphate lithium iron battery positive electrode as claimed in claim 2, is characterized in that the eddy airstream pulverizer described in step 4) arranges circulation classification machine, the gradation reaching 100-200nm requirement can be collected.
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