CN1305148C - Method for preparing high-density spherical lithium iron phosphate and lithium iron manganese phosphate - Google Patents
Method for preparing high-density spherical lithium iron phosphate and lithium iron manganese phosphate Download PDFInfo
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- CN1305148C CN1305148C CNB2005100020129A CN200510002012A CN1305148C CN 1305148 C CN1305148 C CN 1305148C CN B2005100020129 A CNB2005100020129 A CN B2005100020129A CN 200510002012 A CN200510002012 A CN 200510002012A CN 1305148 C CN1305148 C CN 1305148C
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- phosphate
- lithium iron
- lithium
- manganese
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- 238000000034 method Methods 0.000 title claims abstract description 22
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title abstract description 10
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 title abstract 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 40
- 239000011574 phosphorus Substances 0.000 claims abstract description 40
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 37
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 37
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 37
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 37
- 238000002360 preparation method Methods 0.000 claims abstract description 27
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 19
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 19
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 19
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 19
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 12
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 claims abstract description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 54
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 52
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 49
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 44
- 239000007864 aqueous solution Substances 0.000 claims description 38
- 239000008139 complexing agent Substances 0.000 claims description 38
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 37
- 229910052744 lithium Inorganic materials 0.000 claims description 37
- 239000011572 manganese Substances 0.000 claims description 34
- 229910021529 ammonia Inorganic materials 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 23
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 22
- 229910052742 iron Inorganic materials 0.000 claims description 21
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 claims description 20
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 19
- 229910052748 manganese Inorganic materials 0.000 claims description 19
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 17
- 239000012295 chemical reaction liquid Substances 0.000 claims description 16
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 14
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 14
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 11
- 239000004254 Ammonium phosphate Substances 0.000 claims description 10
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 10
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 10
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 10
- 230000002194 synthesizing effect Effects 0.000 claims description 10
- 239000011975 tartaric acid Substances 0.000 claims description 10
- 235000002906 tartaric acid Nutrition 0.000 claims description 10
- 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
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 7
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 7
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract 3
- 239000010406 cathode material Substances 0.000 abstract 2
- 239000002738 chelating agent Substances 0.000 abstract 1
- 229940116007 ferrous phosphate Drugs 0.000 abstract 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 abstract 1
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 abstract 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 24
- 239000000047 product Substances 0.000 description 23
- 239000007787 solid Substances 0.000 description 15
- 239000007788 liquid Substances 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000000926 separation method Methods 0.000 description 12
- 238000000498 ball milling Methods 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 235000014786 phosphorus Nutrition 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000011268 mixed slurry Substances 0.000 description 8
- 235000011007 phosphoric acid Nutrition 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 239000010405 anode material Substances 0.000 description 6
- 235000015165 citric acid Nutrition 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910011570 LiFe 1-x Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000002505 iron Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 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
- 239000002253 acid Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- 229910010710 LiFePO Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000001816 cooling Methods 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
- 238000004519 manufacturing process Methods 0.000 description 2
- -1 metals compound Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 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
- 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
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229940032958 ferric phosphate Drugs 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
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 230000001681 protective effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention discloses a method for preparing high-density spherical lithium iron phosphate and lithium iron manganese phosphate for the cathode materials of lithium ion batteries, which belongs to the technical field of the preparation of energy materials. The method for preparing high-density spherical lithium iron phosphate and lithium iron manganese phosphate comprises the following steps: ferrous sulfate, a phosphorus source and chelating agent or manganese sulfate are proportionally mixed to prepare mixture water solution; the mixture water solution is reacted with ammonium solution to synthesize a spherical ferrous phosphate ammonium or manganese phosphate ferrous ammonium precursor; after the precursor is washed and dried, the precursor and lithium carbonate are uniformly mixed according to the mol ratio of 1: 1; the lithium iron phosphate and the lithium iron manganese phosphate are obtained by a heat treatment with the high temperature of 600 to 900 DEG C for from 8 to 48 hours. The method for preparing high-density spherical lithium iron phosphate and lithium iron manganese phosphate can prepare the spherical lithium iron phosphate and the lithium iron manganese phosphate with high bulk density and high volume ratio capacity for the cathode materials of lithium ion batteries, the average particle diameter of the lithium iron phosphate and the lithium iron manganese phosphate is from 7 to 12 mu m, the tap density of the lithium iron phosphate and the lithium iron manganese phosphate can reach from 2.0 to 2.2 g/cm<3>, and under ordinary temperature, the first discharge ratio capacity of the lithium iron phosphate and the lithium iron manganese phosphate can reach from 145 to 160 mAh/g.
Description
Technical field
The invention belongs to the energy and material technical field.Be particularly related to a kind of preparation method who is used for the high-density spherical ferric lithium phosphate and the iron manganese phosphate for lithium of anode material for lithium-ion batteries.
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
4, LiCoO
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, synthetic iron manganese phosphate for lithium (LiFe
1-xMn
xPO
4, 0 (x≤0.4).
(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～.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.
In application number is 200410103485.3 patent of invention " preparation method of high-density spherical ferric lithium phosphate as anode material of lithium-ion battery "; a kind of preparation method of high-density spherical ferric lithium phosphate is disclosed; this method is 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 8～48 hours through 600～900 ℃ of high-temperature heat treatment.The LiFePO4 average grain diameter that this method is prepared is 7～12 μ m, and tap density can reach 2.0～2.2g/cm
3, first discharge specific capacity can reach 140～155mAh/g under the room temperature.In application number is 200510000167.9 patent of invention " a kind of preparation method of high-density spherical ferric lithium phosphate ", a kind of preparation method of high-density spherical ferric lithium phosphate is disclosed, this method is to be raw material with trivalent iron salt ferric nitrate, phosphoric acid, lithium acetate, obtains spherical LiFePO 4 by sol-gal process.The LiFePO4 average grain diameter that this method is prepared is 5～8 μ m, and tap density can reach 1.8～2.0g/cm
3, first discharge specific capacity can reach 140～160mAh/g under the room temperature.
It is feedstock production high-density spherical ferric lithium phosphate (LiFePO that the present invention proposes with the divalent iron salt
4) and mix manganese derivative----iron manganese phosphate for lithium (LiFe
1-xMn
xPO
4, 0＜x≤0.4) method.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method who is used for the high-density spherical ferric lithium phosphate and the iron manganese phosphate for lithium of anode material for lithium-ion batteries that technology is simple, with low cost, be suitable for suitability for industrialized production, it is characterized in that, earlier with ferrous sulfate (FeSO
47H
2O), phosphorus source, complexing agent be made into mixture aqueous solution after mixing in proportion, again with ammonia spirit reaction synthesizing spherical ferrous ammonium phosphate (NH
4FePO
4H
2O) presoma, evenly mix with mol ratio with lithium carbonate at 1: 1 the dry back of washing, under the nitrogen atmosphere protection, obtained LiFePO4 in 8～48 hours through 600～900 ℃ of high-temperature heat treatment.The gained LiFePO 4 powder is a spheric granules, bulk density height, good conductivity, specific capacity height.
The concentration of iron is 0.2～2 mol in described ferrous sulfate, phosphorus source, the complexing agent mixed aqueous solution.
Phosphorus source in described ferrous sulfate, phosphorus source, the complexing agent mixed aqueous solution is one or more in phosphoric acid, ammonium dihydrogen phosphate and the diammonium hydrogen phosphate, and the concentration of phosphorus is phosphorus in molar ratio in the aqueous solution: iron=1.1～2: 1.
Complexing agent in described ferrous sulfate, phosphorus source, the complexing agent mixed aqueous solution is one or more in citric acid and the tartaric acid, and the concentration of complexing agent is complexing agent in molar ratio in the aqueous solution: iron=0.1 or 0.2: 1.
The concentration of described ammonia spirit is 2～10 mol.
At synthesizing spherical ferrous ammonium phosphate (NH
4FePO
4H
2O) in the process of presoma, the temperature of control reactor internal reaction liquid is 45～90 ℃.The flow that constant ferrous sulfate, phosphorus source, complexing agent mixed aqueous solution are 120 milliliters/hour is regulated the flow of ammonia spirit simultaneously, and the pH value that makes reactor internal reaction liquid is 5.0～8.0.
What the present invention provided a kind of high-density spherical ferric lithium phosphate simultaneously mixes manganese derivative---iron manganese phosphate for lithium LiFe
1-xMn
xPO
4The preparation method; 0＜x≤0.4 wherein; it is characterized in that; earlier ferrous sulfate, manganese sulfate, phosphorus source, complexing agent are made into mixture aqueous solution after mixing in proportion, with ammonia spirit reaction synthesizing spherical manganese phosphate ferrous ammonium presoma, evenly mix with mol ratio with lithium carbonate at 1: 1 the dry back of washing again; under the nitrogen atmosphere protection, obtained iron manganese phosphate for lithium in 8～48 hours through 600～900 ℃ of high-temperature heat treatment.Gained iron manganese phosphate powder for lithium is a spheric granules, bulk density height, good conductivity, specific capacity height.
The total concentration of iron and manganese is 0.2～2 mol in described ferrous sulfate, manganese sulfate, phosphorus source, the complexing agent mixed aqueous solution, wherein by mole percentage 0＜manganese/(iron+manganese)≤40%.
Phosphorus source in described ferrous sulfate, manganese sulfate, phosphorus source, the complexing agent mixed aqueous solution is one or more in phosphoric acid, ammonium dihydrogen phosphate and the diammonium hydrogen phosphate, and the mol ratio concentration of phosphorus is phosphorus in the aqueous solution: (iron+manganese)=1.1～2: 1.
Complexing agent in described ferrous sulfate, manganese sulfate, phosphorus source, the complexing agent mixed aqueous solution is one or more in citric acid, the tartaric acid, and the mol ratio concentration of complexing agent is complexing agent in the aqueous solution: (iron+manganese)=0.1: 1.
The concentration of described ammonia spirit is 2～10 mol.
At synthesizing spherical manganese phosphate ferrous ammonium (NH
4Fe
1-xMn
xPO
4H
2O) in the process of presoma, the temperature of control reactor internal reaction liquid is 45～90 ℃.The flow that constant ferrous sulfate, manganese sulfate, phosphorus source, complexing agent mixed aqueous solution are 120 milliliters/hour is regulated the flow of ammonia spirit simultaneously, and the pH value that makes reactor internal reaction liquid is 5.0～8.0.
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 145～160mAh/g, the lithium ion battery anode material spherical LiFePO 4 and the iron manganese phosphate for lithium of high-volume and capacity ratio under the room temperature.Compare with the trivalent iron salt route; the present invention utilizes divalent iron salt to be raw material; raw material sources are more extensive; be easy to improve material lithium ion conductivity and actual capacity by mixing manganese; need not a large amount of carbon source reduction ferric ions during heat treatment; protective atmosphere is required to reduce, have certain advantage, very with practical value.
Embodiment
Preparation high-density spherical ferric lithium phosphate (LiFePO
4) specific implementation method comprise following each step successively:
1. prepare ferrous sulfate, phosphorus source, complexing agent mixed aqueous solution, be 0.2～2 mol with concentration of iron earlier, phosphorus concentration is phosphorus in molar ratio: iron=1.1～2.0: 1, and complexing agent concentration is complexing agent in molar ratio: ferrous sulfate, phosphorus source, the complexing agent mixed aqueous solution of iron=0.1 or 0.2: 1;
2. compound concentration is the ammonia spirit of 2～10 mol.
3. with above-mentioned ferrous sulfate, phosphorus source, complexing agent mixed aqueous solution, ammonia spirit is input to respectively continuously with pump in the reactor of band stirring, and the temperature of control reactor internal reaction liquid is 45～90 ℃.The flow that constant ferrous sulfate, phosphorus source, complexing agent mixed aqueous solution are 120 milliliters/hour is regulated the flow of ammonia spirit simultaneously, and the pH value that makes reactor internal reaction liquid is 5.0～8.0.Mixed material nature overflow in the reactor is discharged.
4. step (3) gained material is changed over to and carry 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, until using BaCl
2Can not detect the SO in the washings
4 2-Till.Product after the washing in drier in 80～100 ℃ of dryings 2～4 hours, spherical ferrous ammonium phosphate.
5. with mass ratio 1: 1 lithium carbonate is mixed with deionized water, and ball milling was made slurry in 2～4 hours in ball mill.
6. in Li: Fe: P=1: 1: 1 mol ratio ratio takes by weighing spherical ferrous ammonium phosphate of step (4) gained and step (5) gained lithium source slurry and mixes.
7. step (6) products therefrom is placed stove, under the nitrogen atmosphere protection, be warming up to 600～900 ℃, constant temperature 8～48 hours, natural cooling in stove obtains spherical LiFePO 4.
In above-mentioned preparation method's step (1), described phosphorus source is one or more in phosphoric acid, ammonium dihydrogen phosphate, the diammonium hydrogen phosphate.
In above-mentioned preparation method's step (1), described complexing agent is one or more in citric acid, the tartaric acid.
The preparation high-density spherical ferric lithium phosphate mix manganese derivative---iron manganese phosphate for lithium (LiFe
1-xMn
xPO
4, 0＜x≤0.4) specific implementation method comprise following each step successively:
1. prepare ferrous sulfate, manganese sulfate, phosphorus source, complexing agent mixed aqueous solution, wherein the total concentration of iron and manganese is 0.2～2 mol, wherein by mole percentage 0＜manganese/(iron+manganese)≤40%, phosphorus concentration is phosphorus in molar ratio: (iron+manganese)=1.1～2.0: 1, and complexing agent concentration is complexing agent in molar ratio: ferrous sulfate, manganese sulfate, phosphorus source, the complexing agent mixed aqueous solution of (iron+manganese)=0.1: 1
2. compound concentration is the ammonia spirit of 2～10 mol.
3. with above-mentioned ferrous sulfate, manganese sulfate, phosphorus source, complexing agent mixed aqueous solution, ammonia spirit is input to respectively continuously with pump in the reactor of band stirring, and the temperature of control reactor internal reaction liquid is 45～90 ℃.The flow that constant ferrous sulfate, manganese sulfate, phosphorus source, complexing agent mixed aqueous solution are 120 milliliters/hour is regulated the flow of ammonia spirit simultaneously, and the pH value that makes reactor internal reaction liquid is 5.0～8.0.Mixed material nature overflow in the reactor is discharged.
4. step (3) gained material is changed over to and carry 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, until using BaCl
2Can not detect the SO in the washings
4 2-Till.Product after the washing in 80～100 ℃ of dryings 2～4 hours, obtains spherical manganese phosphate ferrous ammonium (NH in drier
4Fe
1-xMn
xPO
4H
2O, 0＜x≤0.4).
5. with mass ratio 1: 1 lithium carbonate is mixed with deionized water, and ball milling was made slurry in 2～4 hours in ball mill.
6. in Li: (Fe+Mn): P=1: 1: 1 mol ratio ratio takes by weighing spherical manganese phosphate ferrous ammonium of step (4) gained and step (5) gained lithium source slurry and mixes.
7. step (6) products therefrom is placed stove, under the nitrogen atmosphere protection, be warming up to 600～900 ℃, constant temperature 8～48 hours, natural cooling in stove obtains spherical iron manganese phosphate for lithium (LiFe
1-xMn
xPO
4, 0＜x≤0.4).
In above-mentioned preparation method, the described phosphorus of step (1) source is one or more in phosphoric acid, ammonium dihydrogen phosphate and the diammonium hydrogen phosphate.
In above-mentioned preparation method's step (1), described complexing agent is one or more in citric acid and the tartaric acid.
Introduce embodiments of the invention below:
Embodiment 1
Preparation ferrous sulfate, phosphoric acid, citric acid mixed aqueous solution, wherein ferrous sulfate concentration is that 1.5 mol, phosphoric acid concentration are that 2.25 mol, citric acid concentration are 0.15 mol.Compound concentration is the ammonia spirit of 10 mol.Respectively ferrous sulfate, phosphoric acid, citric acid mixed aqueous solution and 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 ferrous sulfate, phosphoric acid, citric acid mixed aqueous solution is 120 milliliters/hour, regulate the flow of ammonia spirit, the pH value of control reactor internal reaction liquid is 5.0 ± 0.1.The control reactor temperature is 80 ℃.Mixed material nature overflow in the reactor enters in the pans.After the continuous feed 30 hours, stop charging, the material in the reactor is discharged, carry out Separation of Solid and Liquid with centrifuge.With the solid product of 60 ℃ deionized water washing Separation of Solid and Liquid gained, until using BaCl
2Can not detect the SO in the washings
4 2-Till.With the product after the washing in drying box in 80 ℃ dry 3 hours down, obtain spherical ferrous ammonium phosphate.Take by weighing 18.5 gram lithium carbonate (Li
2CO
3) and measure 18.5 milliliters of deionized waters, place the ball mill ball milling to stop after 3 hours.Take by weighing the above-mentioned ferrous ammonium 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 in the tube furnace to feed nitrogen in this process, gas flow is 1 liter/minute, obtains the spherical 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 150mAh/g.
Embodiment 2
Preparation ferrous sulfate, ammonium dihydrogen phosphate, tartaric acid mixed aqueous solution, wherein ferrous sulfate concentration is that 0.5 mol, biphosphate ammonium concentration are that 0.6 mol, tartaric acid concentration are 0.1 mol.Compound concentration is the ammonia spirit of 2 mol.Respectively ferrous sulfate, phosphoric acid, tartaric acid mixed aqueous solution and 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 ferrous sulfate, phosphoric acid, tartaric acid mixed aqueous solution is 120 milliliters/hour, regulate the flow of ammonia spirit, the pH value of control reactor internal reaction liquid is 6.5 ± 0.1.The control reactor temperature is 70 ℃.Mixed material nature overflow in the reactor enters in the pans.After the continuous feed 30 hours, stop charging, the material in the reactor is discharged, carry out Separation of Solid and Liquid with centrifuge.With the solid product of 60 ℃ deionized water washing Separation of Solid and Liquid gained, until using BaCl
2Can not detect the SO in the washings
4 2-Till.With the product after the washing in drying box in 80 ℃ dry 3 hours down, obtain spherical ferrous ammonium phosphate.Take by weighing 18.5 gram lithium carbonate (Li
2O
3) and measure 18.5 milliliters of deionized waters, place the ball mill ball milling to stop after 3 hours.Take by weighing the above-mentioned ferrous ammonium 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 in the tube furnace to feed nitrogen in this process, gas flow is 1 liter/minute, obtains the spherical LiFePO 4 product.Recording this product average grain diameter is 7-9 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 3
Replace the phosphoric acid of 2.25 mol with the diammonium hydrogen phosphate of 2.25 mol, prepare spherical LiFePO 4 by embodiment 1 identical condition.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 150mAh/g.
Embodiment 4
Preparation ferrous sulfate, manganese sulfate, phosphoric acid, citric acid mixed aqueous solution, wherein ferrous sulfate concentration is that 1.2 mol, manganese sulfate concentration are that 0.3 mol, phosphoric acid concentration are that 2.25 mol, citric acid concentration are 0.15 mol.Compound concentration is the ammonia spirit of 8 mol.Respectively ferrous sulfate, manganese sulfate, phosphoric acid, citric acid mixed aqueous solution and 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 ferrous sulfate, manganese sulfate, phosphoric acid, citric acid mixed aqueous solution is 120 milliliters/hour, regulate the flow of ammonia spirit, the pH value of control reactor internal reaction liquid is 7.0 ± 0.1.The control reactor temperature is 80 ℃.Mixed material nature overflow in the reactor enters in the pans.After the continuous feed 30 hours, stop charging, the material in the reactor is discharged, carry out Separation of Solid and Liquid with centrifuge.With the solid product of 60 ℃ deionized water washing Separation of Solid and Liquid gained, until using BaCl
2Can not detect the SO in the washings
4 2-Till.With the product after the washing in drying box in 80 ℃ dry 3 hours down, obtain spherical manganese phosphate ferrous ammonium (NH
4Fe
0.8Mn
0.2PO
4H
2O).Take by weighing 18.5 gram lithium carbonate (Li
2CO
3) and measure 18.5 milliliters of deionized waters, place the ball mill ball milling to stop after 3 hours.Take by weighing the above-mentioned manganese phosphate ferrous ammonium 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 in the tube furnace to feed nitrogen in this process, gas flow is 1 liter/minute, obtains spherical iron manganese phosphate for lithium (LiFe
0.8Mn
0.2PO
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 iron manganese phosphate for lithium first discharge specific capacity at room temperature is 155mAh/g.
Embodiment 5
Preparation ferrous sulfate, manganese sulfate, phosphoric acid, citric acid mixed aqueous solution, wherein ferrous sulfate concentration is that 0.9 mol, manganese sulfate concentration are that 0.6 mol, phosphoric acid concentration are that 2.25 mol, citric acid concentration are 0.15 mol.Compound concentration is the ammonia spirit of 6 mol.Respectively ferrous sulfate, manganese sulfate, phosphoric acid, citric acid mixed aqueous solution and 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 ferrous sulfate, manganese sulfate, phosphoric acid, citric acid mixed aqueous solution is 120 milliliters/hour, regulate the flow of ammonia spirit, the pH value of control reactor internal reaction liquid is 8.0 ± 0.1.The control reactor temperature is 80 ℃.Mixed material nature overflow in the reactor enters in the pans.After the continuous feed 30 hours, stop charging, the material in the reactor is discharged, carry out Separation of Solid and Liquid with centrifuge.With the solid product of 60 ℃ deionized water washing Separation of Solid and Liquid gained, until using BaCl
2Can not detect the SO in the washings
4 2-Till.With the product after the washing in drying box in 80 ℃ dry 3 hours down, obtain spherical manganese phosphate ferrous ammonium (NH
4Fe
0.6Mn
0.4PO
4H
2O).Take by weighing 18.5 gram lithium carbonate (Li
2CO
3) and measure 18.5 milliliters of deionized waters, place the ball mill ball milling to stop after 3 hours.Take by weighing the above-mentioned manganese phosphate ferrous ammonium 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 in the tube furnace to feed nitrogen in this process, gas flow is 1 liter/minute, obtains spherical iron manganese phosphate for lithium (LiFe
0.6Mn
0.4PO
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 iron manganese phosphate for lithium first discharge specific capacity at room temperature is 160mAh/g.
Embodiment 6
Heat treatment temperature is 900 ℃, constant temperature 48 hours, and other condition obtains spherical iron manganese phosphate for lithium (LiFe with embodiment 5
0.6Mn
0.4PO
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 iron manganese phosphate for lithium first discharge specific capacity at room temperature is 147mAh/g.
Embodiment 7
Heat treatment temperature is 600 ℃, constant temperature 8 hours, and other condition obtains spherical iron manganese phosphate for lithium (LiFe with embodiment 5
0.6Mn
0.4PO
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 iron manganese phosphate for lithium first discharge specific capacity at room temperature is 150mAh/g.
Claims (6)
1. the preparation method of a high-density spherical ferric lithium phosphate, it is characterized in that: be 0.2～2 mol with concentration of iron earlier, phosphorus concentration is phosphorus in molar ratio: iron=1.1～2.0: 1, complexing agent concentration is complexing agent in molar ratio: the ferrous sulfate of iron=0.1 or 0.2: 1, the phosphorus source, complexing agent mixed aqueous solution and concentration are the ammonia spirit reaction synthesizing spherical ferrous ammonium phosphate presoma of 2～10 mol, evenly mix with mol ratio with lithium carbonate at 1: 1 the dry back of washing, under the nitrogen atmosphere protection, obtained spherical LiFePO 4 in 8～48 hours through 600～900 ℃ of high-temperature heat treatment; Wherein the phosphorus source is one or more in phosphoric acid, ammonium dihydrogen phosphate and the diammonium hydrogen phosphate.
2. the preparation method of a high-density spherical iron manganese phosphate for lithium, it is characterized in that: the total concentration with iron and manganese is 0.2～2 mol earlier, wherein by mole percentage 0＜manganese/(iron+manganese)≤40%, phosphorus concentration is phosphorus in molar ratio: (iron+manganese)=1.1～2.0: 1, complexing agent concentration is complexing agent in molar ratio: the ferrous sulfate of (iron+manganese)=0.1: 1, manganese sulfate, the phosphorus source, complexing agent mixed aqueous solution and concentration are the ammonia spirit reaction synthesizing spherical manganese phosphate ferrous ammonium presoma of 2～10 mol, evenly mix with mol ratio with lithium carbonate at 1: 1 the dry back of washing, under the nitrogen atmosphere protection, obtained spherical iron manganese phosphate for lithium in 8～48 hours through 600～900 ℃ of high-temperature heat treatment; Described phosphorus source is one or more in phosphoric acid, ammonium dihydrogen phosphate and the diammonium hydrogen phosphate.
3. according to the preparation method of the described high-density spherical ferric lithium phosphate of claim 1, it is characterized in that: described complexing agent is one or more in citric acid and the tartaric acid.
4. according to the preparation method of the described high-density spherical iron manganese phosphate for lithium of claim 2, it is characterized in that: described complexing agent is one or more in citric acid and the tartaric acid.
5. according to the preparation method of the described high-density spherical ferric lithium phosphate of claim 1, it is characterized in that: in the process of described synthesizing spherical ferrous ammonium phosphate presoma, the temperature of control reactor internal reaction liquid is 45～90 ℃, and the pH value of control reactor internal reaction liquid is 5.0～8.0.
6. according to the preparation method of the described high-density spherical iron manganese phosphate for lithium of claim 2, it is characterized in that: in the process of described synthesizing spherical manganese phosphate ferrous ammonium presoma, the temperature of control reactor internal reaction liquid is 45～90 ℃, and the pH value of control reactor internal reaction liquid is 5.0～8.0.
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| CN100418255C (en) * | 2005-12-23 | 2008-09-10 | 清华大学 | Method for preparing lithium enriched lithium ion phosphate powder |
| CN100371239C (en) * | 2006-03-20 | 2008-02-27 | 清华大学 | Method for preparing high density lithium ferric phosphate by microwave heating |
| CN100361893C (en) * | 2006-03-30 | 2008-01-16 | 上海交通大学 | Method of preparing carbon cladded ferrous lithium phosphate by using ironic phosphate |
| CN101559340B (en) * | 2009-05-18 | 2012-01-25 | 中国科学院长春应用化学研究所 | Method for preparing non-agglomerate nanometer material |
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| CN113942990B (en) * | 2021-08-25 | 2023-06-20 | 北京当升材料科技股份有限公司 | Lithium iron manganese phosphate precursor, lithium iron manganese phosphate positive electrode material, preparation method of lithium iron manganese phosphate positive electrode material, electrode, and lithium ion battery |
| CN114649530A (en) * | 2022-03-28 | 2022-06-21 | 湖北云翔聚能新能源科技有限公司 | Preparation method of nanometer lithium manganese iron phosphate material of vanadium-titanium doped composite carbon nanotube and nanometer lithium manganese iron phosphate material |
| CN114933292B (en) * | 2022-05-25 | 2023-08-11 | 广东邦普循环科技有限公司 | Preparation method and application of lithium iron phosphate |
| CN115020664B (en) * | 2022-06-17 | 2024-04-05 | 蜂巢能源科技股份有限公司 | Lithium iron manganese phosphate positive electrode material, and preparation method and application thereof |
| CN115057426B (en) * | 2022-06-17 | 2024-02-13 | 德阳川发龙蟒新材料有限公司 | Preparation method of high-magnification and high-compaction lithium manganese iron phosphate |
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