CN1635648A - Method for preparing high-density spherical ferric lithium phosphate as anode material of lithium-ion battery - Google Patents
Method for preparing high-density spherical ferric lithium phosphate as anode material of lithium-ion battery Download PDFInfo
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- CN1635648A CN1635648A CNA2004101034853A CN200410103485A CN1635648A CN 1635648 A CN1635648 A CN 1635648A CN A2004101034853 A CNA2004101034853 A CN A2004101034853A CN 200410103485 A CN200410103485 A CN 200410103485A CN 1635648 A CN1635648 A CN 1635648A
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- Prior art keywords
- lithium
- ferric
- phosphate
- aqueous solution
- ion battery
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 17
- 239000010405 anode material Substances 0.000 title claims description 15
- 229910001386 lithium phosphate Inorganic materials 0.000 title claims description 12
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 title claims description 12
- 238000000034 method Methods 0.000 title abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 41
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 30
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 18
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 18
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 18
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 15
- 239000011574 phosphorus Substances 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 5
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000003595 mist Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 150000002505 iron Chemical class 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 7
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 7
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 229930006000 Sucrose Natural products 0.000 claims description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 6
- 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 6
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 5
- -1 metals compound Chemical class 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 238000010348 incorporation Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 27
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract 1
- 150000002736 metal compounds Chemical class 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 29
- 150000001875 compounds Chemical class 0.000 description 12
- 239000010955 niobium Substances 0.000 description 12
- 238000000498 ball milling Methods 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 239000011268 mixed slurry Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- 229910015645 LiMn Inorganic materials 0.000 description 3
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 3
- 235000019801 trisodium phosphate Nutrition 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 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
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 229940062993 ferrous oxalate Drugs 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- H01M4/58—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
- 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
-
- 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)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
This invention discloses the method for preparing high-density spherical lithium ferric phosphate used as the positive material of lithium ion cell, which contains synthesizing the ferric iron salt aqueous solution, phosphorus source aqueous solution and alkali aqueous solution to form spherical or spheroid ferric phosphate precursor, uniformly mixed with lithium source, carbon source and doped metal compound after being washed and dried, high temperature heat treating at 600-900 degree centigrade for 8-48 hr under inertia or reducing atmosphere protection to obtain lithium ferric phosphate with mean grain size of 7-12 micrometer,2.0-2.2g/cm3 of tap density, high buck density of 140-155mAh/g first discharge ratio capacity at normal temperature, and high volume ratio capacity.
Description
Technical field
The invention belongs to the energy and material technical field.Be particularly related to a kind of preparation method of high-density spherical ferric lithium phosphate as anode material of lithium-ion battery.
Background technology
Lithium ion battery is the green high-capacity battery of a new generation, numerous advantages such as have that voltage height, energy density are big, good cycle, self discharge are little, memory-less effect, operating temperature range are wide, be widely used in mobile phone, notebook computer, UPS, video camera, various portable power tool, electronic instrument, weaponry etc., in electric automobile, also have a good application prospect, be considered to be in 21st century national economy and the significant new high-tech product of people's lives.
Positive electrode is the important component part of lithium ion battery.At present, the maximum positive electrode of research is LiCoO
2, LiNiO
2, LiMn
2O
4LiCoO
2Be the positive electrode of unique large-scale commercial, the research comparative maturity, high comprehensive performance, but cost an arm and a leg, capacity is lower, and toxicity is bigger, has certain safety issue, and expectation will be replaced by the new material of high-performance and low-cost.LiNiO
2Cost is lower, and capacity is higher, but the preparation difficulty, there are comparatively serious safety problem in the consistency of material property and poor reproducibility.Spinelle LiMn
2O
4Cost is low, and fail safe is good, but cycle performance especially high temperature cyclic performance is poor, certain dissolubility is arranged in electrolyte, storge quality is poor.The research and development novel anode material becomes current focus.
LiFePO4 (the LiFePO of quadrature olivine structural
4) positive electrode becomes new research focus both at home and abroad gradually.Primary Study shows that this novel anode material has been concentrated LiCoO
2, LiNiO
2, LiMn
2O
4Advantage separately Deng material: do not contain noble element, raw material cheapness, resource are greatly abundant; Operating voltage moderate (3.4V); Platform identity is good, and voltage pole is (can match in excellence or beauty with stabilized voltage power supply) steadily; Theoretical capacity big (170mAh/g); Stability Analysis of Structures, security performance splendid (O and P make material be difficult to analyse oxygen and decompose with the strong covalent bond strong bonded); High-temperature behavior and good cycle; Volume-diminished during charging, the bulk effect when cooperating with carbon negative pole material is good; Good with most of electrolyte system compatibilities, storge quality is good; Nontoxic, be real green material.
Yet there are two significant disadvantages in LiFePO4, the one, and conductivity is low, causes high-rate charge-discharge capability poor, and actual specific capacity is low; The 2nd, bulk density is low, causes volume and capacity ratio low.These two shortcomings have hindered the practical application of this material.Current, people's research attentiveness concentrates on and solves low this field of LiFePO4 conductivity, and has obtained major progress.The corrective measure of taking mainly contains:
(1) mixes conductive carbon material or conductive metal particle toward the LiFePO4 granule interior,, improve the electronic conductivity of material perhaps toward LiFePO4 particle surface coated with conductive material with carbon element.
(2) in the LiFePO4 lattice, mix the small amount of impurities metal ion, as Mg
2+, Al
3+, Ti
4+, Zr
4+, Nb
5+, replace a part of Li
+The position, thereby make the LiFePO4 intrinsic semiconductor change n type or p N-type semiconductor N into, significantly improved the electronic conductivity of material.
(3) in LiFePO4, mix Mn
2+Deng impurity element, replace a part of Fe
2+The position, increase the cell parameter of LiFePO4, improve the lithium ion conductivity of material.
(4) adopt new technologies such as sol-gal process, liquid phase synthesizing method, reduce the size of LiFePO4 crystal grain, even the synthesis of nano LiFePO4, Li shortened as far as possible
+Diffusion length, improved the lithium ion conductivity and the stock utilization of material on apparent.
Yet the shortcoming that the LiFePO4 bulk density is low is subjected to people's ignorance and avoidance always, is not resolved as yet, has hindered the practical application of material.The solid density of cobalt acid lithium is 5.1g/cm
3, the tap density of commodity cobalt acid lithium is generally 2.0-2.4g/cm
3And the solid density of LiFePO4 only is 3.6g/cm
3, itself is just much lower than cobalt acid lithium.For improving conductivity, people mix conductive carbon material, have significantly reduced the bulk density of material again, make the tap density of general carbon dope LiFePO4 have only 1.0g/cm
3So low bulk density makes that the volume and capacity ratio of LiFePO4 is more much lower than the sour lithium of cobalt, and the battery volume of making will be very huge, not only have no advantage and can say, and be difficult to be applied to reality.Therefore, the bulk density of raising LiFePO4 and volume and capacity ratio have the decision meaning to the practicability of LiFePO4.
The bulk density of powder body material and the pattern of powder granule, particle diameter and distribution thereof are closely related.The lithium iron phosphate positive material of having reported both at home and abroad all is made up of random sheet or granular solid matter at present, and bulk density is low.The LiFePO 4 powder material of being made up of the spheric granules of rule will have higher bulk density.Moreover, spherical product also has excellent flowability, dispersiveness and processability, very helps making the coating of positive electrode slurry and electrode slice, improves the electrode slice quality.In addition, with respect to random particle, the spheric granules surface ratio of rule is easier to coat complete, even, firm decorative layer, so spherical LiFePO 4 more is hopeful further to improve combination property by finishing.Up to now, spherical LiFePO 4 is not seen bibliographical information as yet.
Summary of the invention
The purpose of this invention is to provide that a kind of technology is simple, with low cost, the preparation method of the high-density spherical ferric lithium phosphate as anode material of lithium-ion battery that is suitable for suitability for industrialized production; it is characterized in that; earlier with the trivalent iron salt aqueous solution, the phosphorus source aqueous solution, aqueous alkali reaction synthesizing spherical or class ball shape ferric phosphate presoma; evenly mix with lithium source, carbon source, doping metals compound the dry back of washing; under inertia or protection of reducing atmosphere, obtained LiFePO4 in high-temperature heat treatment 8-48 hour through 600-900 ℃.The gained LiFePO 4 powder is made up of sphere or spherical particle, bulk density height, good conductivity, specific capacity height.
Described trivalent iron salt is one or more in ferric nitrate, ferric trichloride and the ferric sulfate, and the concentration of iron is the 0.2-3 mol in the aqueous solution.
Described phosphorus source is one or more in phosphoric acid, ammonium dihydrogen phosphate, the tertiary sodium phosphate, and the concentration of phosphorus is the 0.2-3 mol in the aqueous solution.
Described alkali is one or more in ammonia, the NaOH, and the concentration of alkali is the 2-10 mol in the aqueous solution.
In the process of described synthesizing spherical or class ball shape ferric phosphate presoma, the flow of the control trivalent iron salt aqueous solution and the phosphorus source aqueous solution makes Fe
3+With PO
4 3-Reaction with same mole; Regulate the flow of aqueous alkali simultaneously, the pH value of control reactor internal reaction liquid is 1-5.5.
Described lithium source is a lithium carbonate, and consumption is a lithium: iron: phosphorus=1: 1: 1 (mol ratio).
Described carbon source is selected from one or more in sucrose, the glucose, and consumption is the 0.5-15wt% of LiFePO4.
Described doping metals compound is selected from one or more in magnesium nitrate, aluminum nitrate, titanium dioxide, zirconium dioxide, the niobium pentaoxide, and the incorporation of metallic element is the 0.005-0.02 of lithium (mol ratio).
Described inertia or reducing atmosphere source of the gas are the mist of nitrogen and hydrogen, the mist of 90% nitrogen+10% hydrogen preferably, gas flow be the 0.1-10 liter/minute.
The invention has the beneficial effects as follows that it is 7-12 μ m that this preparation method prepares average grain diameter, tap density can reach 2.0-2.2g/cm
3, first discharge specific capacity can reach the high-bulk-density of 140-155mAh/g, the lithium ion battery anode material spherical LiFePO 4 of high-volume and capacity ratio under the room temperature.
Embodiment
Specific implementation method of the present invention comprises following each step successively:
1. compound concentration is the trivalent iron salt aqueous solution of 0.2-3 mol.
2. compound concentration is the phosphorus source aqueous solution of 0.2-3 mol.
3. compound concentration is the aqueous alkali of 2-10 mol.
4. the above-mentioned trivalent iron salt aqueous solution, the phosphorus source aqueous solution, aqueous alkali are input to respectively continuously with pump in the reactor of band stirring, the flow of the control trivalent iron salt aqueous solution and the phosphorus source aqueous solution makes Fe
3+With PO
4 3-Reaction with same mole; Regulate the flow of aqueous alkali simultaneously, the pH value of control reactor internal reaction liquid is 1-5.5, and control reaction temperature is 35-65 ℃, and the mixed material nature overflow in the reactor is discharged.
5. step (4) gained material is changed over to and carries out Separation of Solid and Liquid in the solid-liquid separator, with the solid product of deionized water washing Separation of Solid and Liquid gained to the pH value of washings greater than till 6; Product after the washing in 80-100 ℃ of dry 2-4 hour, gets ball shape ferric phosphate in drier.
6. with mass ratio 1: 1 lithium carbonate is mixed with deionized water, and in ball mill, made slurry in ball milling 2-4 hour.
7. in Li: Fe: P=1: the ratio of 1: 1 (mol ratio) takes by weighing step (5) gained ball shape ferric phosphate and step (6) gained lithium source slurry mixes.
8. step (7) products therefrom is placed stove, under inertia or protection of reducing atmosphere, be warming up to 600-900 ℃, constant temperature 8-48 hour, natural cooling in stove obtained spherical LiFePO 4.
In above-mentioned preparation method, the described trivalent iron salt of step (1) is one or more in ferric nitrate, ferric trichloride, the ferric sulfate.
In above-mentioned preparation method, the described phosphorus of step (2) source is one or more in phosphoric acid, ammonium dihydrogen phosphate, the tertiary sodium phosphate.
In above-mentioned preparation method, the described alkali of step (3) is one or more in ammonia, the NaOH.
In above-mentioned preparation method, can mix metallic compound simultaneously during step (6) preparation lithium carbonate slurry, described doping metals compound is selected from one or more in magnesium nitrate, aluminum nitrate, titanium dioxide, zirconium dioxide, the niobium pentaoxide, and the incorporation of metallic element is the 0.005-0.02 of lithium (mol ratio).
In above-mentioned preparation method, can mix carbon source simultaneously during step (6) preparation lithium carbonate slurry, be selected from a kind of in sucrose, the glucose or several, its consumption is the 0.5-15wt% of LiFePO4.
In above-mentioned preparation method, described inertia of step (7) or reducing atmosphere source of the gas are the mist of nitrogen and hydrogen, the mist of 90% nitrogen+10% hydrogen preferably, gas flow be the 0.1-10 liter/minute.
Introduce embodiments of the invention below:
Embodiment 1
Compound concentration is the iron nitrate aqueous solution of 2 mol, and compound concentration is the phosphate aqueous solution of 2 mol, and compound concentration is the ammonia spirit of 6 mol.Respectively iron nitrate aqueous solution, phosphate aqueous solution, ammonia spirit are input to measuring pump in the reactor of 3 liter capacities that filled with deionized water in advance and react, the flow of control iron nitrate aqueous solution and phosphate aqueous solution is 120 milliliters/hour, regulate the flow of ammonia spirit, the pH value of control reactor internal reaction liquid is 4.0 ± 0.1.The control reactor temperature is 50 ℃.Mixed material nature overflow in the reactor enters in the pans.After the continuous feed 20 hours, stop charging, the material in the reactor is discharged, carry out Separation of Solid and Liquid with centrifuge.With 60 ℃ deionized waters washing solid products to the pH value of washings greater than till 6.With the product after the washing in drying box in 90 ℃ dry 3 hours down, obtain ball shape ferric phosphate (FePO
4.2H
2O).Take by weighing 18.5 gram lithium carbonate (Li
2CO
3), 9 gram sucrose and measure 20 milliliters of deionized waters, place the ball mill ball milling to stop after 3 hours.Take by weighing the above-mentioned ferric phosphate that makes of 93.5 grams, place the lithium carbonate slurry behind the ball milling, slowly stirred 10 minutes, obtain mixed slurry.Mixed slurry is put into alumina crucible, speed by 200 ℃/hour in tube furnace is warming up to 800 ℃, constant temperature 16 hours, stop heating, in stove, naturally cool to room temperature, continue to feed the mist of 90% nitrogen+10% hydrogen in this process in the tube furnace, gas flow is 1 liter/minute, obtains spherical LiFePO 4 (LiFePO
4) product.Recording this product average grain diameter is 8-10 μ m, and tap density is 2.08g/cm
3With the lithium sheet is negative pole, and recording this LiFePO4 first discharge specific capacity at room temperature is 145mAh/g.
Embodiment 2
Compound concentration is the ferric chloride aqueous solutions of 1 mol, and compound concentration is the ammonium dihydrogen phosphate aqueous solution of 1 mol, and compound concentration is the sodium hydrate aqueous solution of 3 mol.Respectively ferric chloride aqueous solutions, ammonium dihydrogen phosphate aqueous solution, sodium hydrate aqueous solution are input to measuring pump in the reactor of 3 liter capacities that filled with deionized water in advance and react, the flow of control ferric chloride aqueous solutions and ammonium dihydrogen phosphate aqueous solution is 120 milliliters/hour, regulate the flow of sodium hydrate aqueous solution, the pH value of control reactor internal reaction liquid is 4.0 ± 0.1.The control reactor temperature is 50 ℃.Mixed material nature overflow in the reactor enters in the pans.After the continuous feed 20 hours, stop charging, the material in the reactor is discharged, carry out Separation of Solid and Liquid with centrifuge.With 60 ℃ deionized waters washing solid products to the pH value of washings greater than till 6.With the product after the washing in drying box in 90 ℃ dry 3 hours down, obtain ball shape ferric phosphate (FePO
4.2H
2O).Take by weighing 18.5 gram lithium carbonate (Li
2CO
3), 9 gram glucose and measure 20 milliliters of deionized waters, place the ball mill ball milling to stop after 3 hours.Take by weighing the above-mentioned ferric phosphate that makes of 93.5 grams, place the lithium carbonate slurry behind the ball milling, slowly stirred 10 minutes, obtain mixed slurry.Mixed slurry is put into alumina crucible, speed by 200 ℃/hour in tube furnace is warming up to 800 ℃, constant temperature 16 hours, stop heating, in stove, naturally cool to room temperature, continue to feed the mist of 90% nitrogen+109% hydrogen in this process in the tube furnace, gas flow is 1 liter/minute, obtains spherical LiFePO 4 (LiFePO
4) product.Recording this product average grain diameter is 8-10 μ m, and tap density is 2.03g/cm
3With the lithium sheet is negative pole, and recording this LiFePO4 first discharge specific capacity at room temperature is 142mAh/g.
Embodiment 3
Compound concentration is the ferric sulfate aqueous solution of 0.5 mol, and compound concentration is the trisodium phosphate aqueous solution of 1 mol, and compound concentration is the ammonia spirit of 6 mol.Respectively ferric sulfate aqueous solution, trisodium phosphate aqueous solution, ammonia spirit are input to measuring pump in the reactor of 3 liter capacities that filled with deionized water in advance and react, the flow of control ferric sulfate aqueous solution and trisodium phosphate aqueous solution is 120 milliliters/hour, regulate the flow of ammonia spirit, the pH value of control reactor internal reaction liquid is 4.0 ± 0.1.The control reactor temperature is 50 ℃.Mixed material nature overflow in the reactor enters in the pans.After the continuous feed 20 hours, stop charging, the material in the reactor is discharged, carry out Separation of Solid and Liquid with centrifuge.With 60 ℃ deionized waters washing solid products to the pH value of washings greater than till 6.With the product after the washing in drying box in 90 ℃ dry 3 hours down, obtain ball shape ferric phosphate (FePO
4.2H
2O).Take by weighing 18.5 gram lithium carbonate (Li
2CO
3), 9 gram sucrose and measure 20 milliliters of deionized waters, place the ball mill ball milling to stop after 3 hours.Take by weighing the above-mentioned ferric phosphate that makes of 93.5 grams, place the lithium carbonate slurry behind the ball milling, slowly stirred 10 minutes, obtain mixed slurry.Mixed slurry is put into alumina crucible, speed by 200 ℃/hour in tube furnace is warming up to 800 ℃, constant temperature 16 hours, stop heating, in stove, naturally cool to room temperature, continue to feed the mist of 90% nitrogen+10% hydrogen in this process in the tube furnace, gas flow is 1 liter/minute, obtains spherical LiFePO 4 (LiFePO
4) product.Recording this product average grain diameter is 8-10 μ m, and tap density is 2.05g/cm
3With the lithium sheet is negative pole, and recording this LiFePO4 first discharge specific capacity at room temperature is 140mAh/g.
Embodiment 4
Prepare ball shape ferric phosphate by embodiment 1 identical condition.Take by weighing 18.3 gram lithium carbonate (Li
2CO
3), 9 gram sucrose, 0.665 gram niobium pentaoxide (Nb
2O
5) and measure 20 milliliters of deionized waters, place the ball mill ball milling to stop after 3 hours.Take by weighing the above-mentioned ferric phosphate that makes of 93.5 grams, place the lithium carbonate slurry behind the ball milling, slowly stirred 10 minutes, obtain mixed slurry.Mixed slurry is put into alumina crucible, speed by 200 ℃/hour in tube furnace is warming up to 800 ℃, constant temperature 16 hours, stop heating, in stove, naturally cool to room temperature, continue to feed the mist of 90% nitrogen+10% hydrogen in this process in the tube furnace, gas flow is 1 liter/minute, obtains mixing the spherical LiFePO 4 (Li of niobium and an amount of carbon dope
0.99Nb
0.01FePO
4) product.Recording this product average grain diameter is 8-10 μ m, and tap density is 2.10g/cm
3With the lithium sheet is negative pole, and recording this LiFePO4 first discharge specific capacity at room temperature is 155mAh/g.
Embodiment 5
With 0.41 gram titanium dioxide (TiO
2) replace 0.665 among the embodiment 4 to restrain niobium pentaoxide (Nb
2O
5), other condition obtains mixing the spherical LiFePO 4 (Li of titanium and an amount of carbon dope with embodiment 4
0.99Ti
0.01FePO
4) product.Recording this product average grain diameter is 8-10 μ m, and tap density is 2.09g/cm
3With the lithium sheet is negative pole, and recording this LiFePO4 first discharge specific capacity at room temperature is 150mAh/g.
Embodiment 6
With 0.62 gram zirconium dioxide (ZrO
2) replace 0.665 among the embodiment 4 to restrain niobium pentaoxide (Nb
2O
5), other condition obtains mixing the spherical LiFePO 4 (Li of zirconium and an amount of carbon dope with embodiment 4
0.99Zr
0.01FePO
4) product.Recording this product average grain diameter is 8-10 μ m, and tap density is 2.08g/cm
3With the lithium sheet is negative pole, and recording this LiFePO4 first discharge specific capacity at room temperature is 150mAh/g.
Embodiment 7
With 1.28 gram magnesium nitrate (Mg (NO
3)
2.6H
2O) replace 0.665 among the embodiment 4 to restrain niobium pentaoxide (Nb
2O
5), other condition obtains mixing the spherical LiFePO 4 (Li of magnesium and an amount of carbon dope with embodiment 4
0.99Mg
0.01FePO
4) product.Recording this product average grain diameter is 8-10 μ m, and tap density is 2.03g/cm
3With the lithium sheet is negative pole, and recording this LiFePO4 first discharge specific capacity at room temperature is 150mAh/g.
Embodiment 8
With 1.88 gram aluminum nitrate (Al (NO
3)
3.9H
2O) replace 0.665 among the embodiment 4 to restrain niobium pentaoxide (Nb
2O
5), other condition obtains mixing the spherical LiFePO 4 (Li of aluminium and an amount of carbon dope with embodiment 4
0.99Al
0.01FePO
4) product.Recording this product average grain diameter is 8-10 μ m, and tap density is 2.01g/cm
3With the lithium sheet is negative pole, and recording this LiFePO4 first discharge specific capacity at room temperature is 150mAh/g.
Embodiment 9
Heat treatment temperature is 900 ℃, constant temperature 48 hours, and other condition obtains mixing the spherical LiFePO 4 (Li of niobium and an amount of carbon dope with embodiment 4
0.99Nb
0.01FePO
4) product.Recording this product average grain diameter is 7-9 μ m, and tap density is 2.20g/cm
3With the lithium sheet is negative pole, and recording this LiFePO4 first discharge specific capacity at room temperature is 140mAh/g.
Embodiment 10
Heat treatment temperature is 600 ℃, constant temperature 8 hours, and other condition obtains mixing the spherical LiFePO 4 (Li of niobium and an amount of carbon dope with embodiment 4
0.99Nb
0.01FePO
4) product.Recording this product average grain diameter is 10-12 μ m, and tap density is 2.0g/cm
3With the lithium sheet is negative pole, and recording this LiFePO4 first discharge specific capacity at room temperature is 140mAh/g.
Comparing embodiment 1
Adopt traditional mechanical mixture-high-temperature solid phase reaction method to prepare the non-ball shape ferric phosphate lithium.Take by weighing 18.5 gram lithium carbonate (Li
2CO
3), 90 gram ferrous oxalate (FeC
2O
4.2H
2O), 59.5 gram ammonium dihydrogen phosphate (NH
4H
2PO
4), 9 the gram acetylene blacks, place the ball mill ball milling to stop after 24 hours.Mixed material is put into alumina crucible, speed by 200 ℃/hour in tube furnace is warming up to 800 ℃, constant temperature 16 hours, stop heating, in stove, naturally cool to room temperature, continue to feed the mist of 90% nitrogen+10% hydrogen in this process in the tube furnace, gas flow is 1 liter/minute, obtains non-ball shape ferric phosphate lithium (LiFePO
4) product.Recording this product average grain diameter is 5-7 μ m, and tap density is 1.08g/cm
3With the lithium sheet is negative pole, and recording this LiFePO4 first discharge specific capacity at room temperature is 119mAh/g.
Claims (8)
1. the preparation method of a high-density spherical ferric lithium phosphate as anode material of lithium-ion battery, it is characterized in that: be the trivalent iron salt aqueous solution of 0.2-3 mol with concentration earlier, concentration is the phosphorus source aqueous solution of 0.2-3 mol, concentration is that the aqueous alkali of 2-10 mol mixes, the flow of the control trivalent iron salt aqueous solution and the phosphorus source aqueous solution makes Fe
3+With PO
4 3-Reaction with same mole; Regulate the flow of aqueous alkali simultaneously; the pH value of control reactor internal reaction liquid is 1-5.5; reaction synthesizing spherical or class ball shape ferric phosphate presoma; lithium in phosphorus source, lithium source and the carbon source is pressed in the dry back of washing: iron: the consumption of phosphorus=1: 1: 1 (mol ratio); with the incorporation of metallic element in the doping metals compound be that the ratio of the 0.005-0.02 (mol ratio) of lithium is evenly mixed; under inertia or protection of reducing atmosphere, obtained spherical LiFePO 4 in high-temperature heat treatment 8-48 hour through 600-900 ℃.
2. according to the preparation method of the described high-density spherical ferric lithium phosphate as anode material of lithium-ion battery of claim 1, it is characterized in that: described trivalent iron salt is one or more in ferric nitrate, ferric trichloride and the ferric sulfate.
3. according to the preparation method of the described high-density spherical ferric lithium phosphate as anode material of lithium-ion battery of claim 1, it is characterized in that: described phosphorus source is one or more in phosphoric acid, ammonium dihydrogen phosphate, the tertiary sodium phosphate.
4. according to the preparation method of the described high-density spherical ferric lithium phosphate as anode material of lithium-ion battery of claim 1, it is characterized in that: described alkali is one or both in ammonia, the NaOH.
5. according to the preparation method of the described high-density spherical ferric lithium phosphate as anode material of lithium-ion battery of claim 1, it is characterized in that: described lithium source is a lithium carbonate.
6. according to the preparation method of the described high-density spherical ferric lithium phosphate as anode material of lithium-ion battery of claim 1, it is characterized in that: described carbon source is selected from one or both in sucrose, the glucose, and consumption is the 0.5-15wt% of LiFePO4.
7. according to the preparation method of the described high-density spherical ferric lithium phosphate as anode material of lithium-ion battery of claim 1, it is characterized in that: described doping metals compound is selected from one or more in magnesium nitrate, aluminum nitrate, titanium dioxide, zirconium dioxide, the niobium pentaoxide.
8. according to the preparation method of the described high-density spherical ferric lithium phosphate as anode material of lithium-ion battery of claim 1, it is characterized in that: described inertia or reducing atmosphere source of the gas are the mist of nitrogen and hydrogen, the mist of 90% nitrogen+10% hydrogen preferably, gas flow be the 0.1-10 liter/minute.
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| CN102255078B (en) * | 2011-05-27 | 2012-07-18 | 丁建民 | Coordinated method for preparing nanometer spherical iron phosphate and then using carbon fusion method to prepare nanometer spherical lithium iron phosphate |
| CN102255078A (en) * | 2011-05-27 | 2011-11-23 | 丁建民 | Coordinated method for preparing nanometer spherical iron phosphate and then using carbon fusion method to prepare nanometer spherical lithium iron phosphate |
| CN102244246A (en) * | 2011-06-09 | 2011-11-16 | 大连交通大学 | Preparation method of lithium iron phosphate/carbon composite material |
| CN102244246B (en) * | 2011-06-09 | 2013-07-31 | 大连交通大学 | Preparation method of lithium iron phosphate/carbon composite material |
| CN102856545A (en) * | 2012-09-11 | 2013-01-02 | 清华大学 | Preparation method of micro-nano-grade metal-ion-doped lithium iron phosphate anode material |
| CN102916179B (en) * | 2012-09-29 | 2015-02-11 | 杭州金马能源科技有限公司 | Method for manufacturing industrialized high-energy lithium iron phosphate material |
| CN102916179A (en) * | 2012-09-29 | 2013-02-06 | 杭州金马能源科技有限公司 | Method for manufacturing industrialized high-energy lithium iron phosphate material |
| CN104752718A (en) * | 2013-12-27 | 2015-07-01 | 比亚迪股份有限公司 | LiMnxFe1-xPO4 positive electrode active material and preparation method thereof |
| CN113659132A (en) * | 2021-07-09 | 2021-11-16 | 江苏乐能电池股份有限公司 | Preparation method of high-performance nanoscale lithium iron phosphate cathode material |
| CN114171740B (en) * | 2021-11-04 | 2024-01-30 | 江苏涛立电子新材料有限公司 | Preparation method of nano lithium iron phosphate positive electrode material and lithium ion battery |
| CN114171740A (en) * | 2021-11-04 | 2022-03-11 | 江苏涛立电子新材料有限公司 | Preparation method of nano lithium iron phosphate cathode material and lithium ion battery |
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