CN104051732A - Method for preparing lithium iron phosphate by clathration technology - Google Patents
Method for preparing lithium iron phosphate by clathration technology Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 59
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 9
- 238000005516 engineering process Methods 0.000 title abstract description 3
- 239000013078 crystal Substances 0.000 claims abstract description 26
- 238000000137 annealing Methods 0.000 claims abstract description 13
- 238000003763 carbonization Methods 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 109
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 40
- 239000002243 precursor Substances 0.000 claims description 38
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 19
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 18
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000001038 titanium pigment Substances 0.000 claims description 13
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 12
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 10
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 6
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 claims description 4
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- WSSMOXHYUFMBLS-UHFFFAOYSA-L iron dichloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Fe+2] WSSMOXHYUFMBLS-UHFFFAOYSA-L 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 235000011007 phosphoric acid Nutrition 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 28
- 239000002245 particle Substances 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 abstract 2
- 239000011248 coating agent Substances 0.000 abstract 2
- 238000000576 coating method Methods 0.000 abstract 2
- 229920000858 Cyclodextrin Polymers 0.000 abstract 1
- 239000001116 FEMA 4028 Substances 0.000 abstract 1
- 238000005054 agglomeration Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 abstract 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 abstract 1
- 229960004853 betadex Drugs 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 37
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000010450 olivine Substances 0.000 description 2
- 229910052609 olivine Inorganic materials 0.000 description 2
- -1 phosphoric acid hydrogen iron complex Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 229910003321 CoFe Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910013275 LiMPO Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- KVCWSJZUKMSPLM-UHFFFAOYSA-N O.O[PH2]=O Chemical compound O.O[PH2]=O KVCWSJZUKMSPLM-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005256 carbonitriding Methods 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a method for preparing lithium iron phosphate by a clathration technology. The method comprises the following steps of carrying out lithium iron phosphate crystal clathration by beta-cyclodextrin or hydroquinone as a clathrate and then carrying out carbonization annealing heat-treatment. The method has two good implementation methods and can realize clathration of lithium iron phosphate crystals in two stages. The method solves the problems of nonuniform and untight coating and realizes molecular grade clathration carbonization. The method effectively solves the problem of molecular agglomeration of lithium iron phosphate in synthesis and realizes refinement of secondary subgrain sizes. The lithium iron phosphate material obtained by the method has good nanometer particle size distribution and has an average particle size less than 1 micron. The lithium iron phosphate material has good conductive performances, realizes uniform and complete surface carbon coating, and has stable performances and gram volume of 163mAH. The method is simple and easy and is convenient for large-scale production.
Description
Technical field
The present invention relates to chemical synthetic material field, relate to specifically a kind of method of preparing high-quality lithium ion secondary battery anode material ferric lithium phosphate crystal with clathrate process.
Background technology
NTT from Japan in 1996 discloses AyMPO first
4(A is alkali metal, and M is both combinations of CoFe: LiFeCOPO
4) the anode material of lithium battery of olivine structural after, the Research Groups such as the vertical John.B.Goodenough of university of Texas, USA in 1997, have reported LiFePO
4olivine structural (LiMPO
4), European has also found the LiFePO of natural olivine structural
4.LiFePO
4also be found to have commercialization secondary battery material lithium as sour in cobalt, lithium nickelate, the superior function that the materials such as ternary are incomparable.This material possesses raw material wide material sources, cheap, memory-less effect, has extended cycle life, and security performance is good, and high-temperature behavior is good, not containing heavy metal, and the series of advantages such as non-environmental-pollution.
Although LiFePO
4have plurality of advantages, but exist defect yet, material self-conductive performance is not good, causes cryogenic property and high-rate discharge ability poor etc., and existence that should these problems has also caused various countries scientists' research energetically.In order to change the electric conductivity of material, American has proposed the coated method that changes material conductivity of carbon.Yet LiFePO4 molecule is so little, how the molecule of Nano grade, be coated evenly, rather than the bag having wrapped is very thick, and the part material electric conductivity not being coated to is still bad, affects the performance of material monolithic performance.
Summary of the invention
The present invention is by the research that becomes more meticulous to synthesis technique, invent a kind of method of preparing LiFePO4 with clathrate process, LiFePO4 crystalline material prepared by the method, evenly coated, chemical property is good, batch stable and consistent, and multiplying power discharging property is good, good processability, can be competent at the high requirement of electrokinetic cell to positive electrode.
The invention provides a kind of method of preparing LiFePO4 with clathrate process, it is characterized in that comprising the following steps:
1. by titanium pigment source compound, Fe source compound, Li source compound and inclusion compound, within 1: 1: 2 in molar ratio～3.6: 1, weigh, then supersaturation is dissolved in deionized water or distilled water, forms respectively P source compound solution, Fe source compound solution, Li source compound solution, inclusion complex in solution;
2. described P source compound solution is added to autoclave, make autoclave be warming up to 50-110 ℃, then slowly in autoclave, add described Fe source compound solution, in autoclave, pass into inert gas, then slowly in autoclave, add Li source compound solution, finally slowly in autoclave, add inclusion complex in solution, then sealing autoclave, setting high pressure temperature in the kettle is warming up to 120-260 ℃ with the speed of 1-10 ℃/min, set autoclave pressure at 0.2-4.7MPa, start to carry out inclusion process, whole inclusion process all ceaselessly disperses to stir, whole inclusion process continues 4-15 hour, inclusion process is complete, setting high pressure temperature in the kettle is cooled to normal temperature with the speed of 1-20 ℃/min, again autoclave contents is carried out to Separation of Solid and Liquid, after isolated solid is washed, low temperature or vacuumize again, obtain LiFePO4 inclusion compound crystal.
Further, the LiFePO4 inclusion compound crystal of acquisition is added in inert atmosphere protection or vacuum furnace, carry out high temperature cabonization annealing, carbonization annealing temperature is controlled at 600-800 ℃, and constant temperature time was controlled between 4-6 hours.
Further, described inclusion compound is beta-schardinger dextrin-or hydroquinones.
Further, described titanium pigment source compound is phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, lithium dihydrogen phosphate, phosphoric acid hydrogen two lithiums, described soluble iron source compound is green vitriol, Iron dichloride tetrahydrate, ferrous acetate, and described solubility Li source compound is a hydronium(ion) oxidation lithium, lithium chloride, lithium nitrate, lithium dihydrogen phosphate, lithium acetate and phosphoric acid hydrogen two lithiums.
The present invention has effectively solved coated inhomogeneous, not tight problem, reaches the inclusion carbonization of molecular level.Effectively solved the LiFePO4 problem that molecule is reunited in building-up process, refinement secondary Domain size.The synthetic LiFePO 4 material of this technique has good nano particle size and distributes, and particle mean size is less than 1um.Have good electric conductivity, material with carbon-coated surface is complete evenly simultaneously, stable performance, and gram volume is up to 163mAH.Method is simple, is convenient to large-scale production.
Accompanying drawing explanation
Fig. 1 is the gram volume resolution chart of the prepared LiFePO 4 material of the present invention;
Fig. 2 is the multiplying power resolution chart of the prepared LiFePO 4 material of the present invention;
Fig. 3 is the cycle performance resolution chart of the prepared LiFePO 4 material of the present invention;
Fig. 4 is the particle size distribution figure of the prepared LiFePO 4 material of the present invention;
Fig. 5 is the XRD figure of the prepared LiFePO 4 material of the present invention.
Embodiment
Embodiment mono-:
The invention provides a kind of method of preparing LiFePO4 with clathrate process, it is characterized in that comprising the following steps:
1. by titanium pigment source compound, Fe source compound, Li source compound and inclusion compound, within 1: 1: 2 in molar ratio～3.6: 1, weigh, then supersaturation is dissolved in deionized water or distilled water, forms respectively P source compound solution, Fe source compound solution, Li source compound solution, inclusion complex in solution;
2. described P source compound solution is added to autoclave, make autoclave be warming up to 50-110 ℃, then slowly in autoclave, add described Fe source compound solution, in autoclave, pass into inert gas, then slowly in autoclave, add Li source compound solution, finally slowly in autoclave, add inclusion complex in solution, then sealing autoclave, setting high pressure temperature in the kettle is warming up to 120-260 ℃ with the speed of 1-10 ℃/min, set autoclave pressure at 0.2-4.7MPa, start to carry out inclusion process, whole inclusion process all ceaselessly disperses to stir, whole inclusion process continues 4-15 hour, inclusion process is complete, setting high pressure temperature in the kettle is cooled to normal temperature with the speed of 1-20 ℃/min, again autoclave contents is carried out to Separation of Solid and Liquid, after isolated solid is washed, low temperature or vacuumize again, obtain LiFePO4 inclusion compound crystal.
Further, the LiFePO4 inclusion compound crystal of acquisition is added in inert atmosphere protection or vacuum furnace, carry out high temperature cabonization annealing, carbonization annealing temperature is controlled at 600-800 ℃, and constant temperature time was controlled between 4-6 hours.
Further, described inclusion compound is beta-schardinger dextrin-or hydroquinones.
Further, described titanium pigment source compound is phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, lithium dihydrogen phosphate, phosphoric acid hydrogen two lithiums, described soluble iron source compound is green vitriol, Iron dichloride tetrahydrate, ferrous acetate, and described solubility Li source compound is a hydronium(ion) oxidation lithium, lithium chloride, lithium nitrate, lithium dihydrogen phosphate, lithium acetate and phosphoric acid hydrogen two lithiums.Preferred compositions has: for example lithium nitrate and ferrous sulfate add diammonium hydrogen phosphate combination, also has lithium acetate and frerrous chloride to add the LiFePO4 inclusion compound crystal that ammonium phosphate all can be prepared by following process.
Embodiment bis-
A method of preparing LiFePO4 with clathrate process, is characterized in that comprising the following steps:
1. weigh first in molar ratio titanium pigment source compound, Fe source compound and Li source compound, load weighted titanium pigment source compound, Fe source compound and Li source compound supersaturation are dissolved in deionized water or distilled water, form respectively P source compound precursor solution, Fe source compound precursor solution and the Li source compound precursor solution of molecular level, then adopt hydro thermal method to make described P source compound precursor solution, Fe source compound precursor solution and Li source compound precursor solution synthesizing iron lithium phosphate presoma in autoclave;
2. autoclave contents is carried out to Separation of Solid and Liquid, gained solid is ferric lithium phosphate precursor to be washed, ferric lithium phosphate precursor isolated to be washed is washed, keep the percentage by weight of water in the ferric lithium phosphate precursor after washing 30-80%, after washing, form ferric lithium phosphate precursor suspension-turbid liquid, then in ferric lithium phosphate precursor suspension-turbid liquid, add inclusion compound, the inclusion compound adding and the mol ratio of ferric lithium phosphate precursor are 1-2.5: 1, inclusion compound supersaturation is dissolved in ferric lithium phosphate precursor suspension-turbid liquid, and then the ferric lithium phosphate precursor suspension-turbid liquid that has dissolved inclusion compound is undertaken by ultrasonic dispersion machine after the ultrasonic peptizaiton of 4-20 hour, form LiFePO4 inclusion compound crystal, out by solid-liquid separating equipment by LiFePO4 inclusion compound crystal separation finally.
Further, the LiFePO4 inclusion compound crystal of acquisition is added in inert atmosphere protection or vacuum furnace, carry out high temperature cabonization annealing, carbonization annealing temperature is controlled at 600-800 ℃, and constant temperature time was controlled between 4-6 hours.
Further, described inclusion compound is beta-schardinger dextrin-or hydroquinones.
Further, described titanium pigment source compound is phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, lithium dihydrogen phosphate, phosphoric acid hydrogen two lithiums, described soluble iron source compound is green vitriol, Iron dichloride tetrahydrate, ferrous acetate, and described solubility Li source compound is a hydronium(ion) oxidation lithium, lithium chloride, lithium nitrate, lithium dihydrogen phosphate, lithium acetate and phosphoric acid hydrogen two lithiums.Preferred compositions has: for example lithium nitrate and ferrous sulfate add diammonium hydrogen phosphate combination, also has lithium acetate and frerrous chloride to add the LiFePO4 inclusion compound crystal that ammonium phosphate all can be prepared by following process.
Described hydro thermal method refers to: Hydrothermal Synthesis LiFePO4 crystal precursor, first by titanium pigment source compound, Fe source compound and Li source compound, 1: 1: 2 in molar ratio～3.6 weigh, then by load weighted titanium pigment source compound, Fe source compound and Li source compound supersaturation are dissolved in deionized water or distilled water, form respectively the P source compound precursor solution of molecular level, Fe source compound precursor solution and Li source compound precursor solution, then described P source compound precursor solution is added in autoclave, after making high pressure temperature in the kettle rise to 50 ~ 110 ℃, then slowly add described Fe source compound precursor solution, make P source compound precursor solution and Fe source compound precursor solution in autoclave, form the ferrous Fe of intermediate hypophosphite monohydrate
3(PO
4)
28H
2o and phosphoric acid hydrogen iron complex, then after passing into inert gas in described autoclave, in described autoclave, add described Li source compound precursor solution again, then in autoclave, start temperature reaction, controlling heating rate makes high pressure temperature in the kettle rise to 120-260 ℃ at 1-10 ℃/min, pressure in autoclave is controlled at 0.2-4.7MPa, in whole temperature reaction process, solution in autoclave is not stopped to stir, whole temperature reaction process continues 4-15 hour, after temperature reaction, controlling rate of temperature fall is down to after normal temperature at 1-20 ℃/min, make the solution in autoclave introduce solid-liquid separating equipment by baiting valve and drainage pump, isolated solid is fully washed after washing away surface deposits and impurity and obtains pure LiFePO4 crystal presoma,
Embodiment tri-
(1) it is 1: 1: 3, in molar ratio: 1 takes green vitriol, phosphoric acid, a hydronium(ion) oxidation lithium and beta-schardinger dextrin-dissolves respectively, 10% of the quality that solid content gross mass is aqueous solvent.
(2), add autoclave to make the two mix powerful high-speed stirred phosphoric acid solution and green vitriol solution; then lithium hydroxide solution is slowly added to autoclave; pass into inert protective gas; finally add beta-schardinger dextrin-sealed reactor; start to heat up, heating rate is 3 ℃/min left and right, rises to 220 ℃; temperature of reaction system is remained on to 220 ℃, and system pressure is controlled at 1.6MPa.Constant temperature time is controlled at 8 hours.
(3), reaction is separated with centrifugation or suction filtration by solid-liquid after finishing.Solid after separation obtains LiFePO4 inclusion compound crystal presoma through washing.
(4), LiFePO4 crystal inclusion compound presoma is added in inert atmosphere protection or vacuum furnace, carry out high temperature cabonization annealing, carbonization annealing temperature is controlled at 600 ℃, and constant temperature time is controlled at can produce the LiFePO4 crystal being coated for 4 hours.
Example four
(1) be, in molar ratio take green vitriol, phosphoric acid at 1: 1: 3, a hydronium(ion) oxidation lithium dissolves respectively, 15% of the quality that solid content gross mass is aqueous solvent.
(2), add autoclave to make the two mix powerful high-speed stirred phosphoric acid and green vitriol solution, pass into protective gas, then lithium hydroxide solution is slowly added to autoclave.Sealed reactor, starts to heat up, and heating rate is 3 ℃/min left and right, rises to 220 ℃, and temperature of reaction system is remained on to 220 ℃, and system pressure is controlled at 1.6MPa.Constant temperature time is controlled at 6 hours.
(3), reaction is separated with centrifugation or suction filtration by solid-liquid after finishing.Solid after separation obtains LiFePO4 crystal presoma through washing.
(4), the LiFePO4 water content after control washing is in 60% left and right.
(5), add the LiFePO4 crystal presoma mole inclusion compound hydroquinones of 1: 1, supersaturation is dissolved in ferric lithium phosphate precursor suspension-turbid liquid.
(6), by physical and chemical effect, inclusion process is completed under saturated solution and the interactional mechanism of ultrasonic dispersion.
(7), clathrate process completes final vacuum or low temperature drying LiFePO4 inclusion compound crystal.
(8), LiFePO4 inclusion compound crystal is added in inert atmosphere protection or vacuum furnace, carry out high temperature cabonization annealing, carbonization annealing temperature is controlled at 700 ℃, and constant temperature time is controlled at 5 hours can produce coated perfect LiFePO4 crystal.
Detect and analyze:
The detection of entrusting the global group in Xinxiang to do, the preparation-obtained LiFePO 4 material of preparation method by the LiFePO 4 material of a kind of carbo-nitriding provided by the present invention, after testing, the theoretical gram volume of LiFePO4 is 170mAH/g, LiFePO 4 material prepared by this method can be stablized and accomplishes 163mAH/g, specifically referring to gram volume resolution chart accompanying drawing 1; The high rate performance of LiFePO 4 material prepared by this method, the standard of European Union be that 1C charges and discharge and is not less than 130mAH/g, the domestic good 1C that can reach relatively doing at present charges and discharge 135mAH/g, and LiFePO 4 material prepared by this method, data are that 1C charges and discharge 154mAH/g left and right after testing, specifically referring to multiplying power resolution chart accompanying drawing 2; In addition, the lattice stability of LiFePO 4 material prepared by this method embodies by cycle performance, current provided figure be 50 times undamped, specifically referring to Fig. 3; Have, the physical property of this LiFePO 4 material material, can direct-detection, comprises granularity again, can detect by laser fineness gage, and I am Fig. 4 with particle size distribution figure; As for this synthetic powder body material, be the purity of target product LiFePO4 and this product, can carry out check analysis by XRD collection of illustrative plates, I am also Fig. 5 with XRD figure; Finally, batch stability of this LiFePO 4 material, by according to the same method of this technique, same condition, repeats 10 tests, detects gram volume all between 158-163 mAH/g, fluctuation is in 3% left and right, and we think that a batch stability consistency is controlled.
Claims (5)
1. with clathrate process, prepare a method for LiFePO4, it is characterized in that comprising the following steps:
1. by titanium pigment source compound, Fe source compound, Li source compound and inclusion compound, within 1: 1: 2 in molar ratio～3.6: 1, weigh, then supersaturation is dissolved in deionized water or distilled water, forms respectively P source compound solution, Fe source compound solution, Li source compound solution, inclusion complex in solution;
2. described P source compound solution is added to autoclave, make autoclave be warming up to 50-110 ℃, then slowly in autoclave, add described Fe source compound solution, in autoclave, pass into inert gas, then slowly in autoclave, add Li source compound solution, finally slowly in autoclave, add inclusion complex in solution, then sealing autoclave, setting high pressure temperature in the kettle is warming up to 120-260 ℃ with the speed of 1-10 ℃/min, set autoclave pressure at 0.2-4.7MPa, start to carry out inclusion process, whole inclusion process all ceaselessly disperses to stir, whole inclusion process continues 4-15 hour, inclusion process is complete, setting high pressure temperature in the kettle is cooled to normal temperature with the speed of 1-20 ℃/min, again autoclave contents is carried out to Separation of Solid and Liquid, after isolated solid is washed, low temperature or vacuumize again, obtain LiFePO4 inclusion compound crystal.
2. a kind of method of preparing LiFePO4 with clathrate process as claimed in claim 1, is characterized in that comprising the following steps:
1. weigh first in molar ratio titanium pigment source compound, Fe source compound and Li source compound, load weighted titanium pigment source compound, Fe source compound and Li source compound supersaturation are dissolved in deionized water or distilled water, form respectively P source compound precursor solution, Fe source compound precursor solution and the Li source compound precursor solution of molecular level, then adopt hydro thermal method to make described P source compound precursor solution, Fe source compound precursor solution and Li source compound precursor solution synthesizing iron lithium phosphate presoma in autoclave;
2. autoclave contents is carried out to Separation of Solid and Liquid, gained solid is ferric lithium phosphate precursor to be washed, ferric lithium phosphate precursor isolated to be washed is washed, keep the percentage by weight of water in the ferric lithium phosphate precursor after washing 30-80%, after washing, form ferric lithium phosphate precursor suspension-turbid liquid, then in ferric lithium phosphate precursor suspension-turbid liquid, add inclusion compound, the inclusion compound adding and the mol ratio of ferric lithium phosphate precursor are 1-2.5: 1, inclusion compound supersaturation is dissolved in ferric lithium phosphate precursor suspension-turbid liquid, and then the ferric lithium phosphate precursor suspension-turbid liquid that has dissolved inclusion compound is undertaken by ultrasonic dispersion machine after the ultrasonic peptizaiton of 4-20 hour, form LiFePO4 inclusion compound crystal, out by solid-liquid separating equipment by LiFePO4 inclusion compound crystal separation finally.
3. a kind of method of preparing LiFePO4 with clathrate process as claimed in claim 1 or 2; it is characterized in that: the LiFePO4 inclusion compound crystal of acquisition is added in inert atmosphere protection or vacuum furnace; carry out high temperature cabonization annealing; carbonization annealing temperature is controlled at 600-800 ℃, and constant temperature time was controlled between 4-6 hours.
4. a kind of method of preparing LiFePO4 with clathrate process as claimed in claim 1 or 2, is characterized in that: described inclusion compound is beta-schardinger dextrin-or hydroquinones.
5. a kind of method of preparing LiFePO4 with clathrate process as claimed in claim 1 or 2, it is characterized in that: described titanium pigment source compound is phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, lithium dihydrogen phosphate, phosphoric acid hydrogen two lithiums, described soluble iron source compound is green vitriol, Iron dichloride tetrahydrate, ferrous acetate, and described solubility Li source compound is a hydronium(ion) oxidation lithium, lithium chloride, lithium nitrate, lithium dihydrogen phosphate, lithium acetate and phosphoric acid hydrogen two lithiums.
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