CN102447096B - Lithium iron vanadium phosphate solid solution as lithium ion battery anode material and preparation method and application thereof - Google Patents
Lithium iron vanadium phosphate solid solution as lithium ion battery anode material and preparation method and application thereof Download PDFInfo
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- CN102447096B CN102447096B CN201010299519.6A CN201010299519A CN102447096B CN 102447096 B CN102447096 B CN 102447096B CN 201010299519 A CN201010299519 A CN 201010299519A CN 102447096 B CN102447096 B CN 102447096B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 239000010405 anode material Substances 0.000 title claims abstract description 42
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 35
- 239000006104 solid solution Substances 0.000 title claims abstract description 29
- 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 title abstract 5
- 239000000463 material Substances 0.000 claims abstract description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 57
- 238000001035 drying Methods 0.000 claims description 52
- 239000002243 precursor Substances 0.000 claims description 50
- 238000010438 heat treatment Methods 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 33
- 239000000126 substance Substances 0.000 claims description 30
- 229910052799 carbon Inorganic materials 0.000 claims description 26
- 239000012298 atmosphere Substances 0.000 claims description 24
- 238000000889 atomisation Methods 0.000 claims description 23
- 238000012545 processing Methods 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 23
- 239000002002 slurry Substances 0.000 claims description 21
- 239000013078 crystal Substances 0.000 claims description 20
- 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 18
- 239000010450 olivine Substances 0.000 claims description 17
- 229910052609 olivine Inorganic materials 0.000 claims description 17
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 14
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 13
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 13
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 13
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- CUBUBDGUWYJRRD-UHFFFAOYSA-E [Li+].[Fe+2].P(=O)([O-])([O-])[O-].[Li+].[V+5].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-] Chemical compound [Li+].[Fe+2].P(=O)([O-])([O-])[O-].[Li+].[V+5].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-] CUBUBDGUWYJRRD-UHFFFAOYSA-E 0.000 claims description 12
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 10
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 230000008569 process Effects 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 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 229940062993 ferrous oxalate Drugs 0.000 claims description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 4
- 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 abstract 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract 2
- 238000001228 spectrum Methods 0.000 description 36
- 239000000843 powder Substances 0.000 description 33
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- 239000007789 gas Substances 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000000203 mixture Substances 0.000 description 16
- 238000005507 spraying Methods 0.000 description 15
- 239000011159 matrix material Substances 0.000 description 14
- 239000007921 spray Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 229910052786 argon Inorganic materials 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 239000012535 impurity Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000003595 mist Substances 0.000 description 9
- 239000006199 nebulizer Substances 0.000 description 9
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 7
- 229930006000 Sucrose Natural products 0.000 description 6
- TXVRYPGVUXGNNW-UHFFFAOYSA-N [Li].[Fe].[V].P(O)(O)(O)=O Chemical compound [Li].[Fe].[V].P(O)(O)(O)=O TXVRYPGVUXGNNW-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000005720 sucrose Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 229910010710 LiFePO Inorganic materials 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 4
- 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 4
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- -1 octadecyl dimethyl benzyl Chemical group 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910013553 LiNO Inorganic materials 0.000 description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 2
- 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 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 125000000185 sucrose group Chemical group 0.000 description 2
- ZPOLNCDBPYJDSE-UHFFFAOYSA-N 3-[4-[bis(2-chloroethyl)amino]phenyl]-2-formamidopropanoic acid Chemical compound O=CNC(C(=O)O)CC1=CC=C(N(CCCl)CCCl)C=C1 ZPOLNCDBPYJDSE-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 229910012425 Li3Fe2 (PO4)3 Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015118 LiMO Inorganic materials 0.000 description 1
- 229910013086 LiNiPO Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000002228 NASICON Substances 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a lithium iron vanadium phosphate solid solution as a lithium ion battery anode material, and a preparation method and application thereof, and belongs to the technical field of battery materials. The invention provides a lithium ion battery anode material lithium vanadium iron phosphate solid solution, which integrates the advantages of lithium iron phosphate and lithium vanadium phosphate, overcomes the defects of the prior single lithium iron phosphate as a main body and the prior lithium vanadium phosphate as a main body, and has the advantages of good cyclicity, superior rate capability, high specific capacity, high safety and the like. The invention also provides a preparation method of the lithium vanadium iron phosphate solid solution of the lithium ion battery anode material and application of the lithium vanadium iron phosphate solid solution to the lithium ion battery anode material with high multiplying power and high capacity.
Description
Technical field
The present invention relates to battery material technical field, particularly relate to anode material for lithium ion battery and its preparation method and application.
Background technology
Lithium ion battery is secondary cell of new generation after cadmium nickel, Ni-MH battery.Wherein, positive electrode is most important for the important performance such as operating voltage, specific energy, cycle life that improves lithium ion battery.That conventional is LiCoO at present
2, LiMn
2o
4and LiNiO
2.But cobalt resource lacks, and has limited LiCoO
2application, LiNiO
2difficult synthetic, in charge and discharge process, there is obvious exothermic reaction, may cause safety problem, LiMn
2o
4while working near 50 ℃, capacity attenuation is very fast, and this is the factor of its development of restriction.Therefore finding the better new material of cost performance becomes the emphasis of research.
1997, the John B.Goodenough of texas,U.S university etc. were in U.S. Pat 5,910, report take olivine structural as main one dimension tunnel structure positive electrode LiFePO in 382 (being WO1997040541)
4there is good charge and discharge platform, security performance and cycle performance.But, due to PO
4tetrahedron is positioned at FeO
6between layer, adjacent FeO
6octahedra by summit link altogether, with layer structure (LiMO
2, M=Co, Ni) and spinel structure (LiM
2o
4, M=Mn) and the middle MO of rib altogether that exists
6octahedra continuous structure difference, the octahedron on summit has relatively low ionic conductance altogether, and this has hindered Li to a certain extent
+diffusion motion.Therefore, there is the positive electrode LiFePO of one dimension tunnel structure
4can only allow Li
+move in one direction, its one dimension ion channel is easy to be subject to the impact of impurity or dislocation etc. in lattice and is blocked, makes LiFePO
4electric conductivity and current ratio characteristic poor.
For olivine structural LiFePO
4electric conductivity and the poor feature of current ratio characteristic, researcher adopts the mode of preparing solid solution compound or preparing doped compound to improve LiFePO
4chemical property.Wherein, solid solution compound is mainly with olivine structural LiFePO
4for basis, with other olivine structural compound Ls iCoPO
4, LiNiPO
4, LiMnPO
4form solid solution, its chemical formula is LiFe
xm
ypO
4(0 < x < 1,0 < y < 1, x+y=1), M element is divalent state Co, Ni or Mn (in Table 1).In addition, M2 position (being Fe position) doping is also a kind of positive electrode LiFePO that improves
4the common technique means of chemical property, the chemical formula of doping afterproduct is LiFe
xm
ypO
4(0.8≤x <, 1,0 < y≤0.2, x+y=1), wherein M element mainly contains Mg
2+, Ca
2+, Sn
2+, Zn
2+, V
3+, Cr
3+, Mo
3+, Zr
4+, Ti
4+, Nb
5+, W
6+deng.Compound L iFe after this doping
xm
ypO
4, the span of x is generally not less than 0.8, and its structure is still olivine structural LiFePO
4(in Table 1).
There is the three-dimensional frame structure positive electrode Li of NASCION structure
3v
2(PO
4)
3also can be used as anode material for lithium-ion batteries.Due to the Li in NASICON structure
3v
2(PO
4)
3in all cations all pass through very strong covalent bond and P
5+form stable (PO
4)
3-polyanion group, therefore the oxygen in lattice is difficult for losing, and has stable macroscopic property, even the Li deviating from
+when being greater than 1 with transition metal atoms mol ratio, still there is unusual stability.In addition, due to Li
3v
2(PO
4)
3middle PO
4tetrahedron and VO
6octahedron forms three-dimensional framework structure by sharing nonadjacent oxygen atom, wherein, and each VO
6around octahedra, there are 6 PO
4tetrahedron, and each PO
4tetrahedron has 4 VO around
6octahedron, so just with A
2b
3(wherein A=VO
6, B=PO
4) be unit form three-dimensional frame structure, in each monocrystalline by 4 A
2b
3cell formation, Li
3v
2(PO
4)
3in the lithium ion deintercalation well of each unit, be more conducive to Li
+deintercalation, therefore Li
3v
2(PO
4)
3there is excellent electric conductivity and high rate capability.But, when there being 3mol Li
+while carrying out deintercalation, although its theoretical specific capacity can reach 197.3mAh/g, cycle performance is poor, and decay is serious.
Due to NASCION structure Li
3v
2(PO
4)
3shortcoming, researcher adopts the mode of preparing solid solution compound or preparing doped compound to improve Li
3v
2(PO
4)
3chemical property.Wherein, solid solution compound is mainly with NASCION structure Li
3v
2(PO
4)
3for basis, with other NASCION structural compounds, be mainly Li
3fe
2(PO
4)
3form solid solution, its chemical formula is Li
3fe
xv
y(PO
4)
3(0 < x < 2,0 < y < 2, x+y=2), Fe is+3 valence states, V is+3 valence states (in Table 1).In addition M2 position (being V position) Li doped,
3v
2(PO
4)
3positive electrode, i.e. Li
3m
xv
y(PO
4)
3(0 < x≤0.2,1.8≤y < 2, x+y=2) is also a kind of positive electrode Li that improves
3v
2(PO
4)
3the common technique means of chemical property, wherein M element mainly contains Mg
2+, Fe
2+, Ti
4+, Zr
4+deng (in Table 1).Compound L i after this doping
3m
xv
y(PO
4)
3, being mainly NASCION structure, the span of x is not more than 0.2, and its matrix is still NASCION structure Li
3v
2(PO
4)
3.But also do not collect at present LiFePO
4and Li
3v
2(PO
4)
3advantage is avoided the material of both shortcomings.
Table 1 olivine structural positive electrode LiFePO
4with NASCION structure Li
3v
2(PO
4)
3patents and document
Summary of the invention
The object of the invention is to overcome single LiFePO in the past
4for main body electric conductivity with current ratio characteristic is poor and single Li
3v
2(PO
4)
3for main body cycle performance is poor, the serious defect that decays, a kind of ion battery anode material vanadium lithium phosphate iron lithium solid solution is provided, this material has that cyclicity is good, the superior specific capacity of high rate performance is high and the advantage such as fail safe is high.
The invention provides a kind of preparation method of ion battery anode material vanadium lithium phosphate iron lithium solid solution.
The invention provides the application of ion battery anode material vanadium lithium phosphate iron lithium solid solution on the anode material for lithium-ion batteries of high magnification, high power capacity.
Object of the present invention realizes in the following manner:
A kind of ion battery anode material vanadium lithium phosphate iron lithium solid solution, it consists of: LiFe
xv
ypO
4, it is characterized in that: x, y represent molar percentage, span is 0 < x < 1,0 < y < 2/3, and 2x+3y=2, the chemical valence of Fe is+divalent state that the chemical valence of V is+3 valence states.
Its crystal structure is between olivine structural and NASCION structure.
It can carry out C element doping, the content of carbon accounts for the 1-30wt% of matrix total amount, preferred carbon content accounts for the 1-5wt% of matrix total amount, its carbon source material is carbonaceous organic material or water-insoluble carbon source, as sucrose, water soluble starch, polyethylene glycol, citric acid, carbon black, carbon nano-tube or carbon fiber.
The invention provides phosphoric acid vanadium iron lithium solid solution is prepared by the following method, its main preparation methods has solid phase method, microwave method, sol-gal process, hydro thermal method, the precipitation method, solvent-thermal method, fuse salt growth method, spray pyrolysis, atomization drying carbothermic method etc., the preferred atomization drying carbothermic method of the present invention and solid phase method.
The present invention illustrates the preparation method of phosphoric acid vanadium iron lithium solid solution as an example of atomization drying carbothermic method and solid phase method example, but is not limited to this.
Atomization drying carbothermic method specifically comprises the steps:
The processing that homogenizes of step 1, raw material: according to stoichiometric proportion by lithium source, source of iron, phosphorus source, vanadium source and/or carbon source and/or dispersant is water-soluble or ethanol in be mixed with slurries or solution, and homogenize and process as precursor liquid A; When having the material of water insoluble or ethanol, need to add dispersant;
Step 3, heat treatment: precursor B is placed in to sintering furnace, and at nonoxidizing atmosphere, 600~800 ℃, heating, makes anode material for lithium ion battery.Preferably 700 ℃ and 750 ℃ of heating-up temperatures, be 4~36 hours heating time, is preferably 12 hours.
Wherein, described lithium source is
liAc2H
2o or LiNO
3; Described source of iron is Fe, Fe
2o
3, Fe (NO
3)
39H
2o or Fe
2(C
2o
4)
3; Described phosphorus source is H
3pO
4, NH
4h
2pO
4or (NH
4)
2hPO
4; Vanadium source compound used is V
2o
5or NH
4vO
3; Described carbon source is sucrose, water soluble starch, polyethylene glycol, citric acid, carbon black, acetylene black, carbon nano-tube or carbon fiber; Described dispersant be nonionic surface active agent as hexadecyltrimethylammonium chloride, tween series, NPE etc., or cationic surface active agent is as cetyl trimethyl quaternary ammonium bromides, octadecyl dimethyl benzyl aliquat, cetyl methyl amine etc.
The described processing means that homogenize are high-speed stirred, sand milling, ball milling or mediate and mix.
In described presoma preparation process, drying means is atomization drying method.
Sintering furnace in described heat treatment step is common external heat high-temperature atmosphere furnace, electric heat source stove, coking furnace or pyrolysis furnace; Nonoxidizing atmosphere in described heat treatment step is the mist of argon gas, nitrogen, CO (carbon monoxide converter) gas or hydrogen and argon gas or nitrogen.
The consumption of described carbon source is the 1-30wt% that the content of carbon accounts for matrix total amount.
The consumption of described dispersant is 5.0~10.0g/1000ml solution.
Solid phase method is with conventional solid phase synthesis process, with reference to Chinese patent CN1581537, CN1762798, CN1767238, specifically comprises the steps:
Wherein, described lithium source
liAc2H
2o or LiNO
3; Described source of iron is Fe, Fe
2o
3, Fe (NO
3)
39H
2o, FePO
4, FeC
2o
4or Fe
2(C
2o
4)
3; Described phosphorus source is H
3pO
4, NH
4h
2pO
4or (NH
4)
2hPO
4; Vanadium source compound used is V
2o
5or NH
4vO
3; Described carbon source is sucrose, water soluble starch, polyethylene glycol, citric acid, carbon black, carbon nano-tube or carbon fiber etc.
Sintering furnace in described heat treatment step is common external heat high-temperature atmosphere furnace, electric heat source stove, coking furnace or pyrolysis furnace; Nonoxidizing atmosphere in described heat treatment step is the mist of argon gas, hydrogen, nitrogen, CO (carbon monoxide converter) gas or hydrogen and argon gas or nitrogen.
The consumption of described carbon source is the 1-30wt% that the content of carbon accounts for matrix total amount.
Phosphoric acid vanadium iron lithium solid solution provided by the invention can be used as positive electrode active materials and uses in secondary lithium battery.This class secondary cell is applicable to various mobile electronic devices or mobile driven by energy equipment as electric automobile, hybrid electric vehicle, and the accumulation power supplies such as aerospace field, artificial satellite and region electronics synthesis information system etc., and be not limited to this.
The advantage of phosphoric acid vanadium iron lithium solid solution of the present invention is:
Phosphoric acid vanadium iron lithium solid solution of the present invention, as can charging-discharging lithium ion battery positive electrode, has that cyclicity is good, safe, high rate performance is superior and specific capacity advantages of higher, can be mainly used in the lithium ion battery of high magnification, high power capacity.The present invention integrates LiFePO4 and phosphoric acid vanadium lithium advantage, and to have overcome single LiFePO4 be in the past the defect that main body and phosphoric acid vanadium lithium are main body, take novel solid solution phosphoric acid vanadium iron lithium as main body, is the choosing of preparing the ideal of high power capacity, high power battery.
The present invention's dried carbon thermal reduction of preferably spraying is prepared precursor liquid by soft chemical method, can make to reach between raw material the mixing of atomic level, overcome the defect that the method Raws such as solid phase method can not fully contact, and obtained that particle size is controlled, the material of even particle size distribution.The method technique is simple, can continuity operate, and is easy to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 LiFe
xv
ypO
4the X-ray diffractogram of (0 < x < 1,0 < y < 2/3,2x+3y=2)
Fig. 2 LiFe
xv
ypO
4the x-ray photoelectron energy spectrogram of (0 < x < 1,0 < y < 2/3,2x+3y=2), demonstrates the electron binding energy of Fe, V element
Fig. 3 embodiment 1 particle size distribution figure
Fig. 4 embodiment 1 first charge-discharge figure
Fig. 5 embodiment 4 first charge-discharge figure
Fig. 6 embodiment 6 particulate scan Electronic Speculum figure
Cycle performance figure under Fig. 7 embodiment 6 different multiplying
Fig. 8 embodiment 9 first charge-discharge figure
Embodiment
Below by specific embodiment, with atomization drying carbothermic method and solid phase method, further illustrate the present invention, but these embodiment are not used for limiting protection scope of the present invention.
X gets 0.1, preparation LiFe
0.1v
0.6pO
4positive electrode.Atomization drying carbothermic method.
Step 3, heat treatment: this precursor B is placed in to high-temperature atmosphere furnace, and under nitrogen atmosphere, heat treatment 12h at 700 ℃, obtains anode material for lithium ion battery LiFe
0.1v
0.6pO
4/ C, this material is black powder.Its X ray diffracting spectrum (XRD) is shown in Fig. 1, shows not have other impurity, has obtained complete crystal, and crystal structure is between olivine structural and NASCION structure.Its x-ray photoelectron power spectrum (XPS) is shown in Fig. 2, shows that the chemical valence of Fe is+divalent state, and the chemical valence of V is+3 valence states.Laser particle analyzer is measured and is shown that average grain diameter is in 20 μ m left and right (seeing Fig. 3).
Simulated battery is made: by the LiFe obtaining
0.1v
0.6pO
4the n-formyl sarcolysine base pyrrolidone solution of/C and acetylene black and 10% Kynoar (PVDF) is mixed into slurry at normal temperatures and pressures, evenly be coated in aluminum substrates, then 80 ℃ of vacuumizes 12 hours, be cut into the electrode slice of 1X1cm as the positive pole of simulated battery, the negative pole of simulated battery is used lithium sheet, and electrolyte is 1mol LiPF
6/ EC+DMC+DEC.Positive pole, negative pole, electrolyte, barrier film are assembled into simulated battery in the glove box of argon shield.
Simulated battery electrochemical property test: carry out electrochemical property test discharging and recharging on instrument, discharge and recharge test with C/10, first charge-discharge amount reaches 112mAh/g (seeing Fig. 4).
X gets 0.2, preparation LiFe
0.2v
0.53pO
4positive electrode.Solid phase method.
Embodiment 3
X gets 0.3, preparation LiFe
0.3v
0.47pO
4positive electrode.Atomization drying carbothermic method.
Step 3, heat treatment: this precursor B is placed in to high-temperature atmosphere furnace, and under argon gas atmosphere, heat treatment 12h at 700 ℃, obtains anode material for lithium ion battery LiFe
0.3v
0.47pO
4/ C, this material is black powder.Its X ray diffracting spectrum (XRD) is shown in Fig. 1, shows not have other impurity, has obtained complete crystal, and crystal structure is between olivine structural and NASCION structure.Its x-ray photoelectron power spectrum (XPS) is shown in Fig. 2, shows that the chemical valence of Fe is+divalent state, and the chemical valence of V is+3 valence states.
Embodiment 4
X gets 0.4, preparation LiFe
0.4v
0.4pO
4positive electrode.Solid phase method.
Simulated battery making and electrochemical property test step are as implemented as described in 1.Under C/10, first charge-discharge amount reaches 137mAh/g (seeing Fig. 5), has good cycle performance.
X gets 0.5, preparation LiFe
0.5v
0.34pO
4positive electrode.Atomization drying carbothermic method.
Step 3, heat treatment: this precursor B is placed in to high-temperature atmosphere furnace, and under argon gas atmosphere, heat treatment 36h at 600 ℃, obtains anode material for lithium ion battery LiFe
0.5v
0.34pO
4/ C, this material is black powder.Its X ray diffracting spectrum (XRD) is shown in Fig. 1, shows not have other impurity, has obtained complete crystal, and crystal structure is between olivine structural and NASCION structure.Its x-ray photoelectron power spectrum (XPS) is shown in Fig. 2, shows that the chemical valence of Fe is+divalent state, and the chemical valence of V is+3 valence states.
Embodiment 6
X gets 0.6, preparation LiFe
0.6v
0.27pO
4positive electrode.Atomization drying carbothermic method.
Step 3, heat treatment: this precursor B is placed in to high-temperature atmosphere furnace, and under nitrogen atmosphere, heat treatment 4h at 800 ℃, obtains anode material for lithium ion battery LiFe
0.6v
0.27pO
4/ C, this material is black powder.Its X ray diffracting spectrum (XRD) is shown in Fig. 1, shows not have other impurity, has obtained complete crystal, and crystal structure is between olivine structural and NASCION structure.Its x-ray photoelectron power spectrum (XPS) is shown in Fig. 2, shows that the chemical valence of Fe is+divalent state, and the chemical valence of V is+3 valence states.Laser particle analyzer is measured and is shown that average grain diameter is in 20 μ m left and right.Scanning electron microscopy (seeing Fig. 6) shows, the LiFe obtaining
0.6v
0.27pO
4/ C powder body material is spherical in shape.
Simulated battery making and electrochemical property test step are as implemented as described in 1.Under C/10, first charge-discharge amount reaches 151mAh/g, has good cycle performance (seeing Fig. 7).
Embodiment 7
X gets 0.7, preparation LiFe
0.7v
0.2pO
4positive electrode.Atomization drying carbothermic method.
Step 3, heat treatment: this precursor B is placed in to high-temperature atmosphere furnace, and under nitrogen atmosphere, heat treatment 12h at 750 ℃, obtains anode material for lithium ion battery LiFe
0.7v
0.2pO
4/ C, this material is black powder.Its X ray diffracting spectrum (XRD) is shown in Fig. 1, shows not have other impurity, has obtained complete crystal, and crystal structure is between olivine structural and NASCION structure.Its x-ray photoelectron power spectrum (XPS) is shown in Fig. 2, shows that the chemical valence of Fe is+divalent state, and the chemical valence of V is+3 valence states.
X gets 0.8, preparation LiFe
0.8v
0.14pO
4positive electrode.Atomization drying carbothermic method.
Step 3, heat treatment: this precursor B is placed in to high-temperature atmosphere furnace, and under nitrogen atmosphere, heat treatment 12h at 700 ℃, obtains anode material for lithium ion battery LiFe
0.8v
0.14pO
4/ C, this material is black powder.Its X ray diffracting spectrum (XRD) is shown in Fig. 1, shows not have other impurity, has obtained complete crystal, and crystal structure is between olivine structural and NASCION structure.Its x-ray photoelectron power spectrum (XPS) is shown in Fig. 2, shows that the chemical valence of Fe is+divalent state, and the chemical valence of V is+3 valence states.
X gets 0.9, preparation LiFe
0.9v
0.07pO
4positive electrode.Atomization drying carbothermic method.
Step 3, heat treatment: this precursor B is placed in to high-temperature atmosphere furnace, and under nitrogen atmosphere, heat treatment 10h at 700 ℃, obtains anode material for lithium ion battery LiFe
0.9v
0.07pO
4/ C, this material is black powder.Its X ray diffracting spectrum (XRD) is shown in Fig. 1, shows not have other impurity, has obtained complete crystal, and crystal structure is between olivine structural and NASCION structure.Its x-ray photoelectron power spectrum (XPS) is shown in Fig. 2, shows that the chemical valence of Fe is+divalent state, and the chemical valence of V is+3 valence states.
Simulated battery making and electrochemical property test step are as implemented as described in 1.Under C/10, first charge-discharge amount reaches 124mAh/g (seeing Fig. 8).
X gets 0.1, preparation LiFe
0.1v
0.6pO
4positive electrode.Atomization drying carbothermic method.
Step 3, heat treatment: this precursor B is placed in to high-temperature atmosphere furnace, and under hydrogen and nitrogen mixture body, heat treatment 12h at 700 ℃, obtains anode material for lithium ion battery LiFe
0.1v
0.6pO
4, this material is black powder.Its X ray diffracting spectrum (XRD) is shown in Fig. 1, and its x-ray photoelectron power spectrum (XPS) is shown in Fig. 2.
Embodiment 11
X gets 0.2, preparation LiFe
0.2v
0.53pO
4positive electrode.Solid phase method.
X gets 0.3, preparation LiFe
0.3v
0.47pO
4positive electrode.Atomization drying carbothermic method.
Step 3, heat treatment: this precursor B is placed in to high-temperature atmosphere furnace, and under the mist of hydrogen and argon gas, heat treatment 12h at 700 ℃, obtains anode material for lithium ion battery LiFe
0.3v
0.47pO
4, this material is black powder.Its X ray diffracting spectrum (XRD) is shown in Fig. 1, and its x-ray photoelectron power spectrum (XPS) is shown in Fig. 2.
X gets 0.4, preparation LiFe
0.4v
0.4pO
4positive electrode.Solid phase method.
Embodiment 14
X gets 0.5, preparation LiFe
0.5v
0.34pO
4positive electrode.Atomization drying carbothermic method.
Step 3, heat treatment: this precursor B is placed in to high-temperature atmosphere furnace, and under the mist of hydrogen and argon gas, heat treatment 36h at 600 ℃, obtains anode material for lithium ion battery LiFe
0.5v
0.34pO
4, this material is black powder.Its X ray diffracting spectrum (XRD) is shown in Fig. 1, and its x-ray photoelectron power spectrum (XPS) is shown in Fig. 2.
X gets 0.6, preparation LiFe
0.6v
0.27pO
4positive electrode.Atomization drying carbothermic method.
Step 3, heat treatment: this precursor B is placed in to high-temperature atmosphere furnace, and under the gaseous mixture of hydrogen and argon gas, heat treatment 4h at 800 ℃, obtains anode material for lithium ion battery LiFe
0.6v
0.27pO
4, this material is black powder.Its X ray diffracting spectrum (XRD) is shown in Fig. 1, and its x-ray photoelectron power spectrum (XPS) is shown in Fig. 2.
Embodiment 16
X gets 0.7, preparation LiFe
0.7v
0.2pO
4positive electrode.Atomization drying carbothermic method.
Step 3, heat treatment: this precursor B is placed in to high-temperature atmosphere furnace, and under the mist of hydrogen and nitrogen, heat treatment 12h at 800 ℃, obtains anode material for lithium ion battery LiFe
0.7v
0.2pO
4, this material is black powder.Its X ray diffracting spectrum (XRD) is shown in Fig. 1, and its x-ray photoelectron power spectrum (XPS) is shown in Fig. 2.
Embodiment 17
X gets 0.8, preparation LiFe
0.8v
0.14pO
4positive electrode.Atomization drying carbothermic method.
Step 3, heat treatment: this precursor B is placed in to high-temperature atmosphere furnace, and under the mist of hydrogen and nitrogen, heat treatment 12h at 700 ℃, obtains anode material for lithium ion battery LiFe
0.8v
0.14PO
4, this material is black powder.Its X ray diffracting spectrum (XRD) is shown in Fig. 1, and its x-ray photoelectron power spectrum (XPS) is shown in Fig. 2.
Embodiment 18
X gets 0.9, preparation LiFe
0.9v
0.07pO
4positive electrode.Atomization drying carbothermic method.
Step 3, heat treatment: this precursor B is placed in to high-temperature atmosphere furnace, and under the mist of hydrogen and nitrogen, heat treatment 10h at 700 ℃, obtains anode material for lithium ion battery LiFe
0.9v
0.07pO
4, this material is black powder.Its X ray diffracting spectrum (XRD) is shown in Fig. 1, and its x-ray photoelectron power spectrum (XPS) is shown in Fig. 2.
Claims (7)
1. an ion battery anode material vanadium lithium phosphate iron lithium solid solution, it consists of: LiFe
xv
yp0
4, x, y represent molar percentage, 0<x<1,0<y<2/3, and 2x+3y=2, the chemical valence of Fe is+divalent state, the chemical valence of V is+3 valence states, and its crystal structure is between olivine and NASCION.
2. ion battery anode material vanadium lithium phosphate iron lithium solid solution according to claim 1, is characterized in that Li source compound used is lithium hydroxide, lithium carbonate, lithium acetate or lithium nitrate; Source of iron used is iron oxide, ferric nitrate or ferrous oxalate; Vanadium source compound used is ammonium metavanadate; P source compound used is phosphoric acid, ammonium dihydrogen phosphate or diammonium hydrogen phosphate.
3. ion battery anode material vanadium lithium phosphate iron lithium solid solution according to claim 1, is characterized in that carrying out carbon doping, and the content of carbon accounts for LiFe
xv
ypO
4the 1-5wt% of/C total amount.
4. a preparation method for ion battery anode material vanadium lithium phosphate iron lithium solid solution claimed in claim 1, is characterized in that using atomization drying carbothermic method or solid phase method.
5. the preparation method of ion battery anode material vanadium lithium phosphate iron lithium solid solution according to claim 4, is characterized in that using atomization drying carbothermic method to carry out according to following steps:
The processing that homogenizes of step 1, raw material: according to stoichiometric proportion by lithium source, source of iron, phosphorus source, vanadium source, carbon source and dispersant is water-soluble or ethanol in be mixed with slurries or solution, and homogenize and process as precursor liquid A; When having the material of water insoluble or ethanol, need to add dispersant;
Step 2, precursor preparation: the precursor liquid A after treatment that will homogenize carries out atomization drying, obtains precursor B;
Step 3, heat treatment: precursor B is placed in to sintering furnace, and at nonoxidizing atmosphere, 600~800 ℃, heating, 4~36 hours heating times, makes anode material for lithium ion battery.
6. the preparation method of ion battery anode material vanadium lithium phosphate iron lithium solid solution according to claim 4, is characterized in that using solid phase method to carry out according to following steps:
Step 1, the raw material processing that homogenizes: by lithium source, source of iron, phosphorus source, vanadium source and carbon source, add water or ethanol according to stoichiometric proportion, be placed in grinding in ball grinder and obtain precursor A;
Step 2, heat treatment: this precursor A is placed in to sintering furnace, and at nonoxidizing atmosphere, 600~800 ℃, heating, makes anode material for lithium ion battery.
7. an application for ion battery anode material vanadium lithium phosphate iron lithium solid solution claimed in claim 1, for secondary lithium battery.
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CN103050698A (en) * | 2013-01-15 | 2013-04-17 | 四川大学 | Vanadium lithium iron phosphate anode material and preparation method thereof |
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CN105226275A (en) * | 2015-07-15 | 2016-01-06 | 徐茂龙 | A kind of modification fluorophosphoric acid vanadium lithium anode material of lithium battery and preparation method thereof |
CN107146877B (en) * | 2017-05-03 | 2021-02-19 | 武汉理工大学 | Preparation method of fluoxaphosphate lithium ion battery material, positive plate and lithium ion battery |
CN107579304A (en) * | 2017-09-06 | 2018-01-12 | 湖南省正源储能材料与器件研究所 | A kind of method that phosphoric acid vanadium iron lithium is prepared in the anode pole piece from waste lithium iron phosphate |
CN113060717A (en) * | 2021-03-26 | 2021-07-02 | 天津斯科兰德科技有限公司 | Preparation method of lithium iron vanadium phosphate positive electrode material |
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