CN107093732B - A kind of lithium iron phosphate/carbon nano-tube nano composite material and preparation method for anode material of lithium battery - Google Patents
A kind of lithium iron phosphate/carbon nano-tube nano composite material and preparation method for anode material of lithium battery Download PDFInfo
- Publication number
- CN107093732B CN107093732B CN201710326942.2A CN201710326942A CN107093732B CN 107093732 B CN107093732 B CN 107093732B CN 201710326942 A CN201710326942 A CN 201710326942A CN 107093732 B CN107093732 B CN 107093732B
- Authority
- CN
- China
- Prior art keywords
- lithium
- phosphate
- carbon
- lifepo4
- iron
- 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.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 85
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 85
- 239000000463 material Substances 0.000 title claims abstract description 59
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 51
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 27
- 239000010405 anode material Substances 0.000 title claims abstract description 12
- 229910052493 LiFePO4 Inorganic materials 0.000 claims abstract description 75
- 239000003054 catalyst Substances 0.000 claims abstract description 68
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 49
- 239000002002 slurry Substances 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 28
- 229910001386 lithium phosphate Inorganic materials 0.000 claims abstract description 26
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000005507 spraying Methods 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 238000010792 warming Methods 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 87
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 58
- 229910052742 iron Inorganic materials 0.000 claims description 38
- 238000000889 atomisation Methods 0.000 claims description 30
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 29
- 229910052750 molybdenum Inorganic materials 0.000 claims description 29
- 239000011733 molybdenum Substances 0.000 claims description 29
- 229910052759 nickel Inorganic materials 0.000 claims description 29
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 16
- 239000011777 magnesium Substances 0.000 claims description 16
- 229910052749 magnesium Inorganic materials 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000012159 carrier gas Substances 0.000 claims description 11
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims description 11
- 159000000002 lithium salts Chemical class 0.000 claims description 11
- 159000000003 magnesium salts Chemical class 0.000 claims description 11
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- 239000005955 Ferric phosphate Substances 0.000 claims description 8
- 229940032958 ferric phosphate Drugs 0.000 claims description 8
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 8
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 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
- 230000035484 reaction time Effects 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 229960004756 ethanol Drugs 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- 229940056319 ferrosoferric oxide Drugs 0.000 claims description 3
- 229940062993 ferrous oxalate Drugs 0.000 claims description 3
- 229940116007 ferrous phosphate Drugs 0.000 claims description 3
- 229960001781 ferrous sulfate Drugs 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 229960003284 iron Drugs 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000155 iron(II) phosphate Inorganic materials 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 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
- 150000003891 oxalate salts Chemical class 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000010450 olivine Substances 0.000 claims description 2
- 229910052609 olivine Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 239000012018 catalyst precursor Substances 0.000 abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- 239000011261 inert gas Substances 0.000 abstract description 3
- 230000001413 cellular effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 15
- 238000007599 discharging Methods 0.000 description 11
- 238000005253 cladding Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- -1 carbon nano tube compound Chemical class 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 238000005457 optimization Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000002708 enhancing effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- ZSYNKHJUSDFTCQ-UHFFFAOYSA-N [Li].[Fe].P(O)(O)(O)=O Chemical compound [Li].[Fe].P(O)(O)(O)=O ZSYNKHJUSDFTCQ-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000004050 hot filament vapor deposition Methods 0.000 description 2
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 2
- 150000002680 magnesium Chemical class 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 240000007817 Olea europaea Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 235000014786 phosphorus Nutrition 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000009466 transformation Effects 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
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to a kind of lithium iron phosphate/carbon nano-tube nano composite material and preparation methods for anode material of lithium battery, the composite material is made of LiFePO4 core and carbon nanotube shell, it specifically prepares by the following method: ferric lithium phosphate precursor and catalyst precursor is stirred in a solvent, and pH value is adjusted with alkali, it is added in hydrothermal reaction kettle and is warming up to 500 DEG C of reaction 12h, catalyst is made and loads LiFePO4 slurry；Then catalyst load LiFePO4 slurry is atomized above CVD by spraying apparatus, gaseous carbon sources, which are catalyzed, under high temperature and inert gas is coated on LiFePO4 surface for carbon nanotube, obtains lithium iron phosphate/carbon nano-tube nano composite material.The chemical properties such as material electric conductivity with higher, specific capacity and multiplying power property, can be widely used for the positive electrode of electric vehicle lithium battery, cellular li-ion battery etc..
Description
Technical field
The present invention relates to a kind of anode material of lithium battery more particularly to a kind of ferric phosphates for anode material of lithium battery
Lithium/carbon nanotube composite materials and preparation method thereof.
Background technique
The LiFePO4 of olivine-type is because its raw material sources is abundant, price is cheap, thermal stability is good, and cycle performance is excellent etc.
Advantage is considered as a kind of Olivine-type Cathode Material in Li-ion Batteries with broad prospect of application, and is applied to power battery or storage
It can battery.And the raising with people to electric car, mobile phone fast charge demand, lithium ion battery need to have higher multiplying power, mesh
It is preceding to be difficult to realize because LiFePO4 conductivity is lower.
For the electric conductivity for improving LiFePO4, carbon-coated method is widely used at present, on the one hand can improve ferric phosphate
The electric conductivity of lithium, while growing up for LiFePO4 crystal grain can be prevented under the conditions of solid phase high―temperature nuclei, it is conducive to nano-scale powder
Preparation, to realize the high magnification of lithium ion battery.Chinese patent CN101636861A, US2010/0297496A1 and
CN1186835C adds carbon source presoma reheating solution into ferric lithium phosphate precursor using the method for physical mixed and forms carbon coating
Layer, but pyrolysis carbon material electric conductivity due to crystallinity difference itself is bad, phosphorus can be reduced by increasing raising electric conductivity by carbon content
The chemical property of sour iron lithium.
Chinese patent CN101442126A and CN101533904A are introducing catalytic component using chemical vapour deposition technique
The step of doping, generates carbon nanotube, but the physics mode of ball milling mixing is difficult to ensure that catalyst is uniformly distributed, and fixed bed
Chemical gaseous phase deposition also causes nano-carbon layer deposition uneven.In addition, this method will can make when introducing catalyst with water and oxygen, water
Lithium in LiFePO4 generates LiOH and Li2CO3, oxygen can be such that LiFePO4 aoxidizes, to generate negative shadow to LiFePO4
It rings.The ferric lithium phosphate precursor powder, catalyst and the liquid carbon source that prepare are uniformly mixed by Chinese patent CN102427130B
Slurry is made, by feeding to high temperature reaction stove by spraying, generates lithium iron phosphate/carbon nano tube compound material, this method exists
Following problems: 1. liquid carbon source just facilitates under higher content enters reacting furnace by spraying, and liquid carbon source is because cannot be with catalyst
It comes into full contact with and is easy to generate carbon coating layer and non-carbonic nanotube, the electric conductivity of carbon can not show a candle to carbon nanotube, to influence ferric phosphate
The chemical property of lithium；2. simply ferric lithium phosphate precursor powder, catalyst and liquid carbon source physical blending are difficult to realize
To effective cladding of LiFePO4, carbon or carbon nanotube are possible in a free form the carbon or carbon nanotube that liquid carbon source generates
In the presence of exposed LiFePO4 affects the promotion of electrochemical performances of lithium iron phosphate because electric conductivity is not good enough.
From the foregoing, it will be observed that current lithium iron phosphate/carbon nano-tube nano composite material has the disadvantage in that 1. catalyst and carbon
Source contact is uneven, and the carbon generated is caused to increase, electric conductivity decline, to influence the chemical property of material；2. introducing catalysis
When agent, bring water can make the lithium in LiFePO4 generate LiOH and Li2CO3, bring oxygen can be such that LiFePO4 aoxidizes,
To have a negative impact to LiFePO4；3. liquid carbon source with catalyst due to cannot come into full contact with easy generation carbon coating layer
The electric conductivity of non-carbonic nanotube, carbon can not show a candle to carbon nanotube, to influence the chemical property of LiFePO4；4. carbon or carbon nanometer
Pipe is possible to exist in a free form, and exposed LiFePO4 affects electrochemical performances of lithium iron phosphate because electric conductivity is not good enough
It is promoted.
Summary of the invention
The object of the present invention is to provide a kind of lithium iron phosphate/carbon nano-tube nano composite material of anode material of lithium battery and
Preparation method, contacts that uneven, carbon nanotube transformation efficiency is low, can bring when introducing catalyst to solve catalyst with carbon source
Water and oxygen, carbon nanotube coat incomplete and non-uniform problem, effectively improve lithium iron phosphate/carbon nano-tube nano composite wood
The chemical properties such as electric conductivity, specific capacity and the multiplying power property of material.
In order to solve the above technical problems, the present invention provides a kind of lithium iron phosphate/carbon nanometer for anode material of lithium battery
Pipe nanocomposite, the composite material are made of LiFePO4 core and carbon nanotube shell, and wherein lithium iron phosphate particles are olive
Stone structure, aggregate particle size are 0.2 micron -10 microns；The carbon nanotube is wrapped in LiFePO4 surface, the pipe of carbon nanotube
Diameter is 2 nanometers -20 nanometers, and the internal diameter of carbon nanotube is 1 nanometer -10 nanometers, and the length of the carbon nanotube is 100 nanometer -1000
Nanometer.
The core-shell structure of lithium iron phosphate/carbon nanotube realizes carbon nanotube to the cladding of LiFePO4, improves it and leads
Electrical property and chemical property.In addition, the size of LiFePO4 and carbon nanotube affects the performance of material: LiFePO4 partial size mistake
Conference coat carbon nanotube can not completely, and partial size is too small and the easy reunion of LiFePO4 is caused to be difficult to disperse to influence uniformly
Cladding；Carbon nanotube is slightly difficult to very much coat up, too thin to be difficult to coat completely with too short, too long to be easy to be free in LiFePO4
Surface all influences the effect of cladding.
Preferably, the aggregate particle size of the lithium iron phosphate particles is 0.5 micron -5 microns, and the pipe of the carbon nanotube
Diameter is 3 nanometers -10 nanometers, and internal diameter is 2 nanometers -6 nanometers, and the length of carbon nanotube is 200 nanometers -800 nanometers.
Preferably, the aggregate particle size of the lithium iron phosphate particles is 1 micron -3 microns, and the caliber of the carbon nanotube
It is 4 nanometers -6 nanometers, internal diameter is 3 nanometers -5 nanometers, and the length of carbon nanotube is 400 nanometers -600 nanometers.
Realize that above-mentioned purpose, the present invention provide a kind of manufacture aforementioned phosphate iron lithium/carbon nanotube composite materials system
Preparation Method includes the following steps:
Step (1): the preparation of catalyst load LiFePO4 slurry
By lithium salts, microcosmic salt, molysite, Li:P:Fe=1:1:1 is weighed in molar ratio, at the same be added iron, nickel, molybdenum, in magnesium salts
One or more catalyst precursors, iron, nickel molar content be 2%-20%, the molar content of molybdenum is 2%-15%, magnesium
Molar content is 25%-90%,；Each component is stirred in a solvent, and adjusts pH value with alkali, is then added to water
It is warming up to 300 DEG C of -800 DEG C of reaction 1h-24h in thermal response kettle, catalyst is made and loads LiFePO4 slurry；
Step (2): the preparation of lithium iron phosphate/carbon nano-tube nano composite material
Catalyst load LiFePO4 slurry is atomized above chemical vapor depsotition equipment (CVD) by spraying apparatus,
Size droplet diameter after atomization is 1 micron -100 microns, and the drop after atomization enters high temperature reaction zone, and temperature is 600 DEG C -700 DEG C,
Make carrier gas using indifferent gas and is passed through one or more of hydrogen, nitrogen, methane, ethyl alcohol, acetylene, ethylene below CVD as carbon
The flow that is passed through in source, carbon source is 200SCCM-4000SCCM, and control catalyst load ferric lithium phosphate precursor slurry is in CVD high temperature
Area residence time 2h-8h, the reaction time of CVD process is controlled by high pressure draught obtains phosphoric acid below 20s-20min, CVD
Iron lithium/carbon nanotube composite materials.
During the reaction, atomized drop is too small, and spraying apparatus cannot achieve；Atomized drop is excessive, the ferric phosphate of generation
Lithium particle is excessive, to influence the cladding of carbon nanotube.Meanwhile reaction temperature is too low, the reaction time is too short, is unfavorable for the shadow that is carbonized
Ring the generation of carbon nanotube；Reaction temperature is excessively high, the reaction time is too long, and energy consumption is excessive.It is unfavorable in addition, the flow of carbon source is too fast
The generation and cladding of carbon nanotube, flow influence production efficiency slowly excessively.
As optimization design, the ferric lithium phosphate precursor salt is divided into lithium source, source of iron and phosphorus source three classes, and wherein lithium source is
At least one of Li source compounds such as lithium hydroxide, lithium carbonate, lithium phosphate, lithium oxalate, lithium acetate；Source of iron is three oxidations two
At least one of iron, ferroso-ferric oxide, ferric phosphate, ferrous phosphate, ferrous oxalate, ferrous sulfate；Phosphorus source is phosphoric acid, di(2-ethylhexyl)phosphate
Any one in the P source compounds such as hydrogen ammonium, diammonium hydrogen phosphate, ammonium phosphate, ferric phosphate.
As optimization design, the solvent is at least one of dehydrated alcohol, methanol, acetone, propyl alcohol, is born with catalyst
The solid-to-liquid ratio for carrying ferric lithium phosphate precursor is 6%-65%；The precursor material of the catalyst is divided into iron, nickel, molybdenum, four class of magnesium,
Specially oxide, hydroxide, halide, sulfate, carbonate, nitrate, phosphate, acetate, oxalates, fatty acid
At least one of salt, Metallocenic compound, metal carbonyl.
As optimization design, the alkali be at least one of ammonia, urea, sodium carbonate, sodium bicarbonate, ammonium hydrogen carbonate, and
Mass percent shared by the catalytic component is 0.6%-4%；The CVD refers to chemical vapor deposition process and its improves enhancing
Technique, including CVD, PECVD, LPCVD, HPD-CVD, HFCVD, microwave plasma enhancing chemical vapor deposition process in one
Kind；The inert atmosphere includes at least one of nitrogen, argon gas, helium.
As optimization design, iron in the step (1), nickel molar content be 5-15%, and the molar content of molybdenum is
4%-12%, the molar content of magnesium are 40%-85%；And the size droplet diameter after step (2) atomization is 5 microns -20 microns,
It is 600 DEG C -700 DEG C that drop after atomization, which enters high temperature reaction zone temperature, and the flow that is passed through of carbon source is 500SCCM-
2000SCCM, and controlling catalyst load ferric lithium phosphate precursor slurry in the high-temperature region CVD residence time is 3h-6h.
As optimization design, iron in the step (1), nickel molar content be 8-13%, and the molar content of molybdenum is
8%-12%, the molar content of magnesium are 75%-82%；And the size droplet diameter after step (2) atomization is 8 microns -12 microns,
It is 650 DEG C -680 DEG C that drop after atomization, which enters high temperature reaction zone temperature, and the flow that is passed through of carbon source is 800SCCM-
1000SCCM, and controlling catalyst load ferric lithium phosphate precursor slurry in the high-temperature region CVD residence time is 4h-5h.
Lithium iron phosphate/carbon nano-tube nano composite material of the invention has the advantage that
1. the present invention is that carbon nanotube is shell, LiFePO4 is the nanocomposite of core, and carbon nanotube is to LiFePO4
Complete cladding, avoid the exposed of insulating properties LiFePO4, improve the electric conductivity of material；
2. the hydro-thermal reaction in the present invention is conducive to generate the catalyst uniform load LiFePO4 of Nano grade, make to be catalyzed
Agent can come into full contact on the surface of LiFePO4 with carbon source, not only make the high conversion rate of carbon nanotube, but also carbon nanotube is to phosphorus
The cladding of sour iron lithium is spent completely and the uniformity is high, to improve the electric conductivity of LiFePO4；
3. the present invention can not only be come into full contact with using gas as carbon source with catalyst and LiFePO4, and can be kept away
The generation for exempting from carbon, improves the conversion ratio of carbon nanotube, to improve the electric conductivity of LiFePO4；
4. entire CVD technique of the invention uses inert gas, oxygen is avoided, moisture receives lithium iron phosphate/carbon nanotube
The negative effect of nano composite material.
Specific embodiment
The present invention discloses a kind of lithium iron phosphate/carbon nano-tube nano composite material for anode material of lithium battery, this is multiple
Condensation material is made of LiFePO4 core and carbon nanotube shell, in which: lithium iron phosphate particles are olivine structural, and aggregate particle size is
0.2 micron -10 microns, preferably 0.5 micron -5 microns, more preferable 1 micron -3 microns, LiFePO4 partial size, which crosses conference, makes carbon nanometer
Pipe can not be coated completely, and partial size is too small and the easy reunion of LiFePO4 is caused to be difficult to disperse to influence uniformly to coat.Carbon nanometer
Pipe is wrapped in the surface of LiFePO4, and the caliber of carbon nanotube is 2 nanometers -20 nanometers, and preferably 3 nanometers -10 nanometers, more preferable 3
- 6 nanometers of nanometer, internal diameter are 1 nanometer -10 nanometers, and preferably 2 nanometers -6 nanometers, more preferable 3 nanometers -5 nanometers, length is received for 100
Rice -1000 nanometers, preferably 200 nanometers -800 nanometers, more preferable 400 nanometers -600 nanometers, the carbon nanotube of suitable dimension all without
Method is realized to the complete cladding of LiFePO4, is slightly difficult to very much coat up, too thin to be difficult to coat too long easy trip completely with too short
From the effect on the surface of LiFePO4, all influencing cladding.
Invention additionally discloses a kind of lithium iron phosphate/carbon nano-tube nano composite materials for manufacturing aforementioned anode material of lithium battery
Preparation method, include the following steps:
Step (1): the preparation of catalyst load LiFePO4 slurry
By lithium salts, microcosmic salt, molysite, Li:P:Fe=1:1:1 is weighed in molar ratio, at the same be added iron, nickel, molybdenum, in magnesium salts
One or more catalyst precursors, iron, nickel molar content be 2%-20%, the molar content of molybdenum is 2%-15%, magnesium
Molar content is 25%-90%,；Each component is stirred in a solvent, and adjusts pH value with alkali, is then added to water
It is warming up to 300 DEG C of -800 DEG C of reaction 1h-24h in thermal response kettle, catalyst is made and loads LiFePO4 slurry；
Step (2): the preparation of lithium iron phosphate/carbon nano-tube nano composite material
Catalyst load LiFePO4 slurry is atomized above chemical vapor depsotition equipment (CVD) by spraying apparatus,
Size droplet diameter after atomization is 1 micron -100 microns, and the drop after atomization enters high temperature reaction zone, and temperature is 600 DEG C -700 DEG C,
Make carrier gas using indifferent gas and is passed through one or more of hydrogen, nitrogen, methane, ethyl alcohol, acetylene, ethylene below CVD as carbon
The flow that is passed through in source, carbon source is 200SCCM-4000SCCM, and control catalyst load ferric lithium phosphate precursor slurry is in CVD high temperature
Area residence time 2h-8h, the reaction time of CVD process is controlled by high pressure draught obtains phosphoric acid below 20s-20min, CVD
Iron lithium/carbon nanotube composite materials.
Ferric lithium phosphate precursor salt is divided into lithium source, source of iron and phosphorus source three classes, wherein lithium source be lithium hydroxide, lithium carbonate,
At least one of Li source compounds such as lithium phosphate, lithium oxalate, lithium acetate；Source of iron is di-iron trioxide, ferroso-ferric oxide, phosphoric acid
At least one of iron, ferrous phosphate, ferrous oxalate, ferrous sulfate；Phosphorus source is phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphorus
Any one in the P source compounds such as sour ammonium, ferric phosphate.
Solvent is at least one of dehydrated alcohol, methanol, acetone, propyl alcohol, loads ferric lithium phosphate precursor with catalyst
Solid-to-liquid ratio be 6%-65%；The precursor material of catalyst is divided into iron, nickel, molybdenum, four class of magnesium, specially oxide, hydroxide
Object, halide, sulfate, carbonate, nitrate, phosphate, acetate, oxalates, fatty acid salt, Metallocenic compound, gold
Belong at least one of carbonyls.
Alkali is at least one of ammonia, urea, sodium carbonate, sodium bicarbonate, ammonium hydrogen carbonate, and quality shared by catalytic component
Percentage is 0.6%-4%；CVD refer to chemical vapor deposition process and its improve enhancing technique, including CVD, PECVD,
One of LPCVD, HPD-CVD, HFCVD, microwave plasma enhancing chemical vapor deposition process；Inert atmosphere include nitrogen,
At least one of argon gas, helium.
Iron in step (1), nickel molar content be 5-15%, and the molar content of molybdenum is 4%-12%, and magnesium mole contains
Amount is 40%-85%；And the size droplet diameter after step (2) atomization is 5 microns -20 microns, it is anti-that the drop after atomization enters high temperature
Answering area's temperature is 600 DEG C -700 DEG C, and the flow that is passed through of carbon source is 500SCCM-2000SCCM, and controls catalyst and load phosphoric acid
Iron lithium precursor pulp is 3h-6h in the high-temperature region CVD residence time.
Iron in step (1), nickel molar content be 8-13%, and the molar content of molybdenum is 8%-12%, and magnesium mole contains
Amount is 75%-82%；And the size droplet diameter after step (2) atomization is 8 microns -12 microns, it is anti-that the drop after atomization enters high temperature
Answering area's temperature is 650 DEG C -680 DEG C, and the flow that is passed through of carbon source is 800SCCM-1000SCCM, and controls catalyst and load phosphoric acid
Iron lithium precursor pulp is 4h-5h in the high-temperature region CVD residence time.
After the preparation of lithium iron phosphate/carbon nano-tube nano pipe nanocomposite, button half-cell is made as follows
And test specific capacity and multiplying power property: lithium iron phosphate/carbon nanotube and PVDF being weighed with the mass ratio of 90:10, after mixed pulp
Film, drying, compacting, punching, a pour lithium slice is cathode in vacuum glove box, to be dissolved in volume ratio as the carbonic acid second of 1:1
Lithium hexafluoro phosphate in ester and methyl carbonate is electrolyte, and polypropylene microporous film is diaphragm, forms 2032 button cells, and adopt
Carry out constant current constant voltage charge-discharge test with new prestige battery controlled testing instrument, by voltage be 4.2V-2.0V.
Embodiment 1:
Step (1): the preparation of catalyst load LiFePO4 slurry
By lithium salts, microcosmic salt, molysite, Li:P:Fe=1:1:1 is weighed in molar ratio, at the same be added iron, nickel, molybdenum, in magnesium salts
One or more catalyst precursors, iron, nickel molar content be 13%, the molar content of molybdenum is 12%, the molar content of magnesium
It is 75%, each component is stirred in a solvent, and adjust pH value with alkali, is then added in hydrothermal reaction kettle and heats up
To 800 DEG C of reaction 1h, catalyst is made and loads LiFePO4 slurry.
Step (2): the preparation of lithium iron phosphate/carbon nano-tube nano composite material
Catalyst load LiFePO4 slurry is atomized above CVD by spraying apparatus, the size droplet diameter after atomization is 1
Micron, the drop after atomization enter high temperature reaction zone, and temperature is 600 DEG C, make carrier gas with indifferent gas and are passed through ethyl alcohol work below CVD
For carbon source, being passed through flow is 4000SCCM, and control catalyst load ferric lithium phosphate precursor slurry is when the high-temperature region CVD stops
Between 8h, obtain lithium iron phosphate/carbon nano-tube nano composite material below CVD.
Charge-discharge test under 6C multiplying power is carried out using the material, circulation still keeps discharge capacity to reach 135mAh/g after 30 weeks,
Discharging efficiency is maintained at 97% or more, has excellent multiplying power property.
Embodiment 2:
Step (1): the preparation of catalyst load LiFePO4 slurry
By lithium salts, microcosmic salt, molysite, Li:P:Fe=1:1:1 is weighed in molar ratio, at the same be added iron, nickel, molybdenum, in magnesium salts
One or more catalyst precursors, iron, nickel molar content be 8%, the molar content of molybdenum is 10%, and the molar content of magnesium is
82%, each component is stirred, and adjust pH value with alkali in a solvent, is then added in hydrothermal reaction kettle and is warming up to
300 DEG C of reactions for 24 hours, are made catalyst and load LiFePO4 slurry.
Step (2): the preparation of lithium iron phosphate/carbon nano-tube nano composite material
Catalyst load LiFePO4 slurry is atomized above CVD by spraying apparatus, the size droplet diameter after atomization is
100 microns, the drop after atomization enters high temperature reaction zone, and temperature is 700 DEG C, makees carrier gas with indifferent gas and is passed through hydrogen below CVD
For gas as carbon source, being passed through flow is 200SCCM, and control catalyst load ferric lithium phosphate precursor slurry is stopped in the high-temperature region CVD
Time 2h, obtain lithium iron phosphate/carbon nano-tube nano composite material below CVD.
Charge-discharge test under 6C multiplying power is carried out using the material, circulation still keeps discharge capacity to reach 140mAh/g after 30 weeks,
Discharging efficiency is maintained at 98% or more, has excellent multiplying power property.
Embodiment 3:
Step (1): the preparation of catalyst load LiFePO4 slurry
By lithium salts, microcosmic salt, molysite, Li:P:Fe=1:1:1 is weighed in molar ratio, at the same be added iron, nickel, molybdenum, in magnesium salts
One or more catalyst precursors, iron, nickel molar content be 10%, the molar content of molybdenum is 10%, the molar content of magnesium
It is 80%, each component is stirred in a solvent, and adjust pH value with alkali, is then added in hydrothermal reaction kettle and heats up
To 600 DEG C of reaction 10h, catalyst is made and loads LiFePO4 slurry.
Step (2): the preparation of lithium iron phosphate/carbon nano-tube nano composite material
Catalyst load LiFePO4 slurry is atomized above CVD by spraying apparatus, the size droplet diameter after atomization is
10 microns, the drop after atomization enters high temperature reaction zone, and temperature is 660 DEG C, makees carrier gas with indifferent gas and is passed through methane below CVD
As carbon source, being passed through flow is 1000SCCM, and control catalyst load ferric lithium phosphate precursor slurry is stopped in the high-temperature region CVD
Lithium iron phosphate/carbon nano-tube nano composite material is obtained below time 4h, CVD.
Charge-discharge test under 6C multiplying power is carried out using the material, circulation still keeps discharge capacity to reach 145mAh/g after 30 weeks,
Discharging efficiency is maintained at 99% or more, has excellent multiplying power property.
Embodiment 4:
Step (1): the preparation of catalyst load LiFePO4 slurry
By lithium salts, microcosmic salt, molysite, Li:P:Fe=1:1:1 is weighed in molar ratio, at the same be added iron, nickel, molybdenum, in magnesium salts
One or more catalyst precursors, iron, nickel molar content be 8%, the molar content of molybdenum is 11%, and the molar content of magnesium is
81%, each component is stirred, and adjust pH value with alkali in a solvent, is then added in hydrothermal reaction kettle and is warming up to
500 DEG C of reaction 12h are made catalyst and load LiFePO4 slurry.
Step (2): the preparation of lithium iron phosphate/carbon nano-tube nano composite material
Catalyst load LiFePO4 slurry is atomized above CVD by spraying apparatus, the size droplet diameter after atomization is
11 microns, the drop after atomization enters high temperature reaction zone, and temperature is 670 DEG C, makees carrier gas with indifferent gas and is passed through methane below CVD
As carbon source, being passed through flow is 900SCCM, and control catalyst load ferric lithium phosphate precursor slurry is stopped in the high-temperature region CVD
Lithium iron phosphate/carbon nano-tube nano composite material is obtained below time 5h, CVD.
Charge-discharge test under 6C multiplying power is carried out using the material, circulation still keeps discharge capacity to reach 142mAh/g after 30 weeks,
Discharging efficiency is maintained at 99% or more, has excellent multiplying power property.
Embodiment 5:
Step (1): the preparation of catalyst load LiFePO4 slurry
By lithium salts, microcosmic salt, molysite, Li:P:Fe=1:1:1 is weighed in molar ratio, at the same be added iron, nickel, molybdenum, in magnesium salts
One or more catalyst precursors, iron, nickel molar content be 12%, the molar content of molybdenum is 10%, the molar content of magnesium
It is 78%, each component is stirred in a solvent, and adjust pH value with alkali, is then added in hydrothermal reaction kettle and heats up
To 500 DEG C of reaction 12h, catalyst is made and loads LiFePO4 slurry.
Step (2): the preparation of lithium iron phosphate/carbon nano-tube nano composite material
Catalyst load LiFePO4 slurry is atomized above CVD by spraying apparatus, the size droplet diameter after atomization is
11 microns, the drop after atomization enters high temperature reaction zone, and temperature is 670 DEG C, makees carrier gas with indifferent gas and is passed through ethylene below CVD
As carbon source, being passed through flow is 1000SCCM, and control catalyst load ferric lithium phosphate precursor slurry is stopped in the high-temperature region CVD
Lithium iron phosphate/carbon nano-tube nano composite material is obtained below time 4h, CVD.
Charge-discharge test under 6C multiplying power is carried out using the material, circulation still keeps discharge capacity to reach 149mAh/g after 30 weeks,
Discharging efficiency is maintained at 99% or more, has excellent multiplying power property.
Embodiment 6:
Step (1): the preparation of catalyst load LiFePO4 slurry
By lithium salts, microcosmic salt, molysite, Li:P:Fe=1:1:1 is weighed in molar ratio, at the same be added iron, nickel, molybdenum, in magnesium salts
One or more catalyst precursors, iron, nickel molar content be 18%, the molar content of molybdenum is 12%, the molar content of magnesium
It is 70%, each component is stirred in a solvent, and adjust pH value with alkali, is then added in hydrothermal reaction kettle and heats up
To 600 DEG C of reaction 8h, catalyst is made and loads LiFePO4 slurry.
Step (2): the preparation of lithium iron phosphate/carbon nano-tube nano composite material
Catalyst load LiFePO4 slurry is atomized above CVD by spraying apparatus, the size droplet diameter after atomization is
20 microns, the drop after atomization enters high temperature reaction zone, and temperature is 660 DEG C, makees carrier gas with indifferent gas and is passed through ethylene below CVD
As carbon source, being passed through flow is 2000SCCM, and control catalyst load ferric lithium phosphate precursor slurry is stopped in the high-temperature region CVD
Lithium iron phosphate/carbon nano-tube nano composite material is obtained below time 3h, CVD.
Charge-discharge test under 6C multiplying power is carried out using the material, circulation still keeps discharge capacity to reach 156mAh/g after 30 weeks,
Discharging efficiency is maintained at 98% or more, has excellent multiplying power property.
Embodiment 7:
Step (1): the preparation of catalyst load LiFePO4 slurry
By lithium salts, microcosmic salt, molysite, Li:P:Fe=1:1:1 is weighed in molar ratio, at the same be added iron, nickel, molybdenum, in magnesium salts
One or more catalyst precursors, iron, nickel molar content be 10%, the molar content of molybdenum is 10%, the molar content of magnesium
It is 80%, each component is stirred in a solvent, and adjust pH value with alkali, is then added in hydrothermal reaction kettle and heats up
To 700 DEG C of reaction 4h, catalyst is made and loads LiFePO4 slurry.
Step (2): the preparation of lithium iron phosphate/carbon nano-tube nano composite material
Catalyst load LiFePO4 slurry is atomized above CVD by spraying apparatus, the size droplet diameter after atomization is
20 microns, the drop after atomization enters high temperature reaction zone, and temperature is 700 DEG C, makees carrier gas with indifferent gas and is passed through ethylene below CVD
As carbon source, being passed through flow is 1800SCCM, and control catalyst load ferric lithium phosphate precursor slurry is stopped in the high-temperature region CVD
Lithium iron phosphate/carbon nano-tube nano composite material is obtained below time 4h, CVD.
Charge-discharge test under 6C multiplying power is carried out using the material, circulation still keeps discharge capacity to reach 153mAh/g after 30 weeks,
Discharging efficiency is maintained at 98% or more, has excellent multiplying power property.
Embodiment 8:
Step (1): the preparation of catalyst load LiFePO4 slurry
By lithium salts, microcosmic salt, molysite, Li:P:Fe=1:1:1 is weighed in molar ratio, at the same be added iron, nickel, molybdenum, in magnesium salts
One or more catalyst precursors, iron, nickel molar content be 10%, the molar content of molybdenum is 10%, the molar content of magnesium
It is 80%, each component is stirred in a solvent, and adjust pH value with alkali, is then added in hydrothermal reaction kettle and heats up
To 600 DEG C of reaction 8h, catalyst is made and loads LiFePO4 slurry.
Step (2): the preparation of lithium iron phosphate/carbon nano-tube nano composite material
Catalyst load LiFePO4 slurry is atomized above CVD by spraying apparatus, the size droplet diameter after atomization is
20 microns, the drop after atomization enters high temperature reaction zone, and temperature is 660 DEG C, makees carrier gas with indifferent gas and is passed through ethylene below CVD
As carbon source, being passed through flow is 2000SCCM, and control catalyst load ferric lithium phosphate precursor slurry is stopped in the high-temperature region CVD
Lithium iron phosphate/carbon nano-tube nano composite material is obtained below time 3h, CVD.
Charge-discharge test under 6C multiplying power is carried out using the material, circulation still keeps discharge capacity to reach 156mAh/g after 30 weeks,
Discharging efficiency is maintained at 98% or more, has excellent multiplying power property.
Comparative example 1:
Referring to embodiment 3, LiFePO4 is directly mixed with carbon nanotube.
Charge-discharge test under 6C multiplying power is carried out using the material, circulation still keeps discharge capacity to reach 105mAh/g after 30 weeks,
Discharging efficiency is maintained at 82% or less.
Comparative example 2:
Referring to embodiment 3, changes gaseous carbon source into liquid carbon source, obtain lithium iron phosphate/carbon nano tube compound material.
Charge-discharge test under 6C multiplying power is carried out using the material, circulation still keeps discharge capacity to reach 115mAh/g after 30 weeks,
Discharging efficiency is maintained at 83% or less.
Comparative example 3:
Referring to embodiment 3, hydro-thermal reaction is removed, lithium iron phosphate/carbon nano tube compound material is obtained.
Charge-discharge test under 6C multiplying power is carried out using the material, circulation still keeps discharge capacity to reach 108mAh/g after 30 weeks,
Discharging efficiency is maintained at 82% or less.
Comparative example 4:
Referring to embodiment 3, changes inert gas into oxygen and vapor, obtain lithium iron phosphate/carbon nano tube compound material.
Charge-discharge test under 6C multiplying power is carried out using the material, circulation still keeps discharge capacity up to 68mAh/g, puts after 30 weeks
Electrical efficiency is maintained at 57% or less.
It is to be provided for the embodiments of the invention lithium iron phosphate/carbon nano-tube nano composite material and preparation method above
It is discussed in detail.Principle and implementation of the present invention are described for specific embodiment used herein, and embodiment is said
It is bright to be merely used to help understand method and its core concept of the invention, the foregoing is merely presently preferred embodiments of the present invention and
, it is not intended to limit the invention, any modifications, equivalent replacements, and improvements done within the spirit and principles of the present invention
Deng should all be included in the protection scope of the present invention.
Claims (3)
1. a kind of preparation method of lithium iron phosphate/carbon nano-tube nano composite material of manufacture for anode material of lithium battery, should
Composite material is made of LiFePO4 core and carbon nanotube shell, and wherein lithium iron phosphate particles are olivine structural, aggregate particle size
It is 0.2 micron -10 microns；The carbon nanotube is wrapped in LiFePO4 surface, and the caliber of carbon nanotube is 2 nanometers -20 nanometers,
The internal diameter of carbon nanotube is 1 nanometer -10 nanometers, and the length of the carbon nanotube is 100 nanometers -1000 nanometers, it is characterised in that packet
Include following steps:
Step (1): the preparation of catalyst load LiFePO4 slurry
By lithium salts, microcosmic salt, molysite, Li:P:Fe=1:1:1 is weighed in molar ratio, while iron, nickel, molybdenum, a kind of in magnesium salts is added
Or multiple catalysts presoma, iron, nickel molar content be 2%-20%, the molar content of molybdenum is 2%-15%, mole of magnesium
Content is 25%-90%；Each component is stirred in a solvent, and adjusts pH value with alkali, it is anti-to be then added to hydro-thermal
It answers and is warming up to 300 DEG C of -800 DEG C of reaction 1h-24h in kettle, catalyst is made and loads LiFePO4 slurry；
Step (2): the preparation of lithium iron phosphate/carbon nano-tube nano composite material
Catalyst load LiFePO4 slurry is atomized above chemical vapor depsotition equipment (CVD) by spraying apparatus, atomization
Size droplet diameter afterwards is 1 micron -100 microns, and the drop after atomization enters high temperature reaction zone, and temperature is 600 DEG C -700 DEG C, with lazy
Property gas make carrier gas and be passed through one or more of methane, ethyl alcohol, acetylene, ethylene below CVD as carbon source, carbon source is passed through stream
Amount is 200SCCM-4000SCCM, and control catalyst load ferric lithium phosphate precursor slurry is in the high-temperature region CVD residence time 2h-
The reaction time of 8h, CVD process is controlled by high pressure draught in 20s-20min, and the lower section CVD obtains lithium iron phosphate/carbon nanotube and receives
Nano composite material.
2. a kind of lithium iron phosphate/carbon nano-tube nano composite material for anode material of lithium battery according to claim 1
Preparation method, it is characterised in that: the ferric lithium phosphate precursor salt is divided into lithium source, source of iron and phosphorus source three classes, wherein lithium source
For at least one of Li source compounds such as lithium hydroxide, lithium carbonate, lithium phosphate, lithium oxalate, lithium acetate；Source of iron is three oxidations two
At least one of iron, ferroso-ferric oxide, ferric phosphate, ferrous phosphate, ferrous oxalate, ferrous sulfate；Phosphorus source is phosphoric acid, di(2-ethylhexyl)phosphate
Hydrogen ammonium, diammonium hydrogen phosphate, ammonium phosphate, any one in ferric phosphate P source compound.
3. a kind of lithium iron phosphate/carbon nano-tube nano composite material for anode material of lithium battery according to claim 1
Preparation method, it is characterised in that: the solvent be at least one of dehydrated alcohol, methanol, acetone, propyl alcohol, with catalyst
The solid-to-liquid ratio for loading ferric lithium phosphate precursor is 6%-65%；The precursor material of the catalyst is divided into iron, nickel, molybdenum, magnesium four
Class, specially oxide, hydroxide, halide, sulfate, carbonate, nitrate, phosphate, acetate, oxalates, rouge
At least one of fat hydrochlorate, Metallocenic compound, metal carbonyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710326942.2A CN107093732B (en) | 2017-05-10 | 2017-05-10 | A kind of lithium iron phosphate/carbon nano-tube nano composite material and preparation method for anode material of lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710326942.2A CN107093732B (en) | 2017-05-10 | 2017-05-10 | A kind of lithium iron phosphate/carbon nano-tube nano composite material and preparation method for anode material of lithium battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107093732A CN107093732A (en) | 2017-08-25 |
| CN107093732B true CN107093732B (en) | 2019-11-08 |
Family
ID=59638447
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710326942.2A Active CN107093732B (en) | 2017-05-10 | 2017-05-10 | A kind of lithium iron phosphate/carbon nano-tube nano composite material and preparation method for anode material of lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107093732B (en) |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2964898T3 (en) | 2015-12-16 | 2024-04-10 | 6K Inc | Spheroidal dehydrogenated metals and metal alloy particles |
| US10987735B2 (en) | 2015-12-16 | 2021-04-27 | 6K Inc. | Spheroidal titanium metallic powders with custom microstructures |
| CN108232180A (en) * | 2017-12-19 | 2018-06-29 | 刘博文 | A kind of graphene/titanium dioxide/LiFePO4 aeroge cell positive material and preparation method thereof |
| EP3810358A1 (en) | 2018-06-19 | 2021-04-28 | 6K Inc. | Process for producing spheroidized powder from feedstock materials |
| CN109659531A (en) * | 2018-12-17 | 2019-04-19 | 中科廊坊过程工程研究院 | A kind of nickel cobalt lithium aluminate composite positive pole and its preparation method and application |
| CN114007782A (en) | 2019-04-30 | 2022-02-01 | 6K有限公司 | Mechanically alloyed powder feedstock |
| ES2994209T3 (en) | 2019-11-18 | 2025-01-20 | 6K Inc | Unique feedstocks for spherical powders and methods of manufacturing |
| US11590568B2 (en) | 2019-12-19 | 2023-02-28 | 6K Inc. | Process for producing spheroidized powder from feedstock materials |
| KR20230029836A (en) | 2020-06-25 | 2023-03-03 | 6케이 인크. | Microcomposite alloy structure |
| CN111740104B (en) * | 2020-07-01 | 2021-07-16 | 中南大学 | A kind of preparation method of lithium iron manganese phosphate/carbon nanotube composite cathode material |
| CN111725516B (en) * | 2020-07-01 | 2023-05-05 | 中南大学 | LiFePO 4 Preparation method of CNTs composite positive electrode material |
| CN111740115B (en) * | 2020-07-01 | 2021-07-16 | 中南大学 | A kind of preparation method of lithium iron phosphate/carbon nanotube composite cathode material |
| CN111740113B (en) * | 2020-07-01 | 2021-07-16 | 中南大学 | Preparation method of lithium iron phosphate/carbon nanotube composite cathode material |
| CN111732088B (en) * | 2020-07-01 | 2021-11-16 | 中南大学 | A lithium iron phosphate precursor/carbon nanotube composite material |
| CN111740112B (en) * | 2020-07-01 | 2021-07-20 | 中南大学 | A kind of preparation method of lithium iron phosphate/carbon nanotube composite cathode material |
| KR102811425B1 (en) | 2020-09-24 | 2025-05-26 | 6케이 인크. | Systems, devices and methods for initiating plasma |
| WO2022094528A1 (en) | 2020-10-30 | 2022-05-05 | 6K Inc. | Systems and methods for synthesis of spheroidized metal powders |
| AU2022206483A1 (en) | 2021-01-11 | 2023-08-31 | 6K Inc. | Methods and systems for reclamation of li-ion cathode materials using microwave plasma processing |
| EP4313449A1 (en) | 2021-03-31 | 2024-02-07 | 6K Inc. | Systems and methods for additive manufacturing of metal nitride ceramics |
| US12261023B2 (en) | 2022-05-23 | 2025-03-25 | 6K Inc. | Microwave plasma apparatus and methods for processing materials using an interior liner |
| CN115000347B (en) * | 2022-05-26 | 2024-06-25 | 广东奥德迈新能源有限责任公司 | Modified lithium iron oxide positive electrode plate, battery containing modified lithium iron oxide positive electrode plate and preparation method of modified lithium iron oxide positive electrode plate |
| US12040162B2 (en) | 2022-06-09 | 2024-07-16 | 6K Inc. | Plasma apparatus and methods for processing feed material utilizing an upstream swirl module and composite gas flows |
| WO2024044498A1 (en) | 2022-08-25 | 2024-02-29 | 6K Inc. | Plasma apparatus and methods for processing feed material utilizing a powder ingress preventor (pip) |
| US12195338B2 (en) | 2022-12-15 | 2025-01-14 | 6K Inc. | Systems, methods, and device for pyrolysis of methane in a microwave plasma for hydrogen and structured carbon powder production |
| WO2024234146A1 (en) * | 2023-05-12 | 2024-11-21 | 广东邦普循环科技有限公司 | Preparation method for composite electrode material and use thereof |
| KR102686823B1 (en) * | 2024-02-01 | 2024-07-19 | 양효식 | Positive electrode for secondary battery, method of manufacturing the same, and secondary battery containing the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102427130A (en) * | 2011-03-23 | 2012-04-25 | 上海中兴派能能源科技有限公司 | Lithium iron phosphate-carbon nanotube composite material, preparation method, and application thereof |
| CN105789620A (en) * | 2014-12-23 | 2016-07-20 | 深圳市比克电池有限公司 | Preparation method of lithium iron phosphate cathode material and lithium iron phosphate cathode material |
-
2017
- 2017-05-10 CN CN201710326942.2A patent/CN107093732B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102427130A (en) * | 2011-03-23 | 2012-04-25 | 上海中兴派能能源科技有限公司 | Lithium iron phosphate-carbon nanotube composite material, preparation method, and application thereof |
| CN105789620A (en) * | 2014-12-23 | 2016-07-20 | 深圳市比克电池有限公司 | Preparation method of lithium iron phosphate cathode material and lithium iron phosphate cathode material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107093732A (en) | 2017-08-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107093732B (en) | A kind of lithium iron phosphate/carbon nano-tube nano composite material and preparation method for anode material of lithium battery | |
| US20230322557A1 (en) | Method for preparing lithium manganese iron phosphate, cathode material, and lithium-ion battery | |
| CN102427130B (en) | Lithium iron phosphate-carbon nanotube composite material, preparation method, and application thereof | |
| Jiang et al. | Enhanced electrochemical performances of FeO x–graphene nanocomposites as anode materials for alkaline nickel–iron batteries | |
| CN108232145A (en) | A kind of space buffer, the silicon oxide composite material and preparation method thereof of elements doped lithium, lithium ion battery | |
| CN101442126B (en) | Carbon nanotube key joint lithium iron phosphate composite electrode material and preparation method thereof | |
| CN101339991B (en) | Composite coating modified high tap density lithium ion battery positive electrode material and its preparation method and application | |
| US20250388469A1 (en) | Phosphate precursor and preparation method therefor, cathode material and preparation therefor, cathode sheet and secondary battery | |
| CN111020749B (en) | Cobalt-loaded hollow carbon nanofiber composite catalyst and preparation method and application thereof | |
| CN109037659A (en) | A kind of preparation method of bilayer carbon-coated LiFePO 4 for lithium ion batteries material | |
| CN115377605B (en) | Hollow metal oxide-metal phosphide heterojunction material and preparation method and application thereof | |
| CN101834288A (en) | Lithium iron phosphate/nano carbon composite material and preparation method thereof | |
| CN107464938A (en) | A kind of molybdenum carbide/carbon composite with core shell structure and preparation method thereof and the application in lithium-air battery | |
| CN114300661A (en) | Lithium iron phosphate-lithium vanadium phosphate composite cathode material and preparation method and application thereof | |
| CN112744872A (en) | Liquid-phase phosphorus element doping modification preparation method of high-nickel anode material | |
| CN107887583A (en) | A kind of doped lithium iron phosphate anode material and preparation method thereof | |
| JP2014201459A (en) | Method for producing lithium iron phosphate | |
| CN106450300A (en) | Na2Fe2P2O7 material with flower-like structure and preparation method and application thereof | |
| CN111740104A (en) | A kind of preparation method of lithium iron manganese phosphate/carbon nanotube composite cathode material | |
| CN103094551A (en) | Graphite/manganous oxide composite electrode material and preparation method thereof | |
| CN102867956A (en) | Preparation method of electro-chemical active material | |
| CN114956193B (en) | Preparation method and application of positive electrode active material | |
| CN113460983B (en) | Self-supporting transition metal phosphide/carbon composite material film, preparation method and application thereof, and battery | |
| CN118738337B (en) | Silicon-carbon coated lithium iron phosphate positive electrode material, preparation method thereof, positive electrode plate, lithium ion battery and electric equipment | |
| CN118771385B (en) | Negative electrode material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhu Liangyuan Inventor after: Peng Xiaoxiong Inventor before: Peng Xiao Xiong |
|
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20191012 Address after: 344000 Jiangxi province Fuzhou City Jinchao Economic Development Zone, hi tech Industrial Park Applicant after: Jiangxi Dibico Co., Ltd. Address before: 404300, No. two, Xiangshan Road, 11 Zhong Zhou Town, Chongqing, Zhongxian, No. 33-1, attached 2 Applicant before: Peng Xiao Xiong |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Lithium iron phosphate / carbon nanotube nanocomposite for lithium battery cathode material and its preparation method Effective date of registration: 20201217 Granted publication date: 20191108 Pledgee: Fuzhou hi tech Zone Industry and technology Financing Guarantee Co., Ltd Pledgor: Jiangxi DBK Corporation Co.,Ltd. Registration number: Y2020360000110 |