CN104051732B - A kind of clathrate process prepares the method for LiFePO4 - Google Patents
A kind of clathrate process prepares the method for LiFePO4 Download PDFInfo
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- CN104051732B CN104051732B CN201410141267.2A CN201410141267A CN104051732B CN 104051732 B CN104051732 B CN 104051732B CN 201410141267 A CN201410141267 A CN 201410141267A CN 104051732 B CN104051732 B CN 104051732B
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- source compound
- clathrate
- lifepo4
- autoclave
- lithium
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- 238000000034 method Methods 0.000 title claims abstract description 56
- 229910052493 LiFePO4 Inorganic materials 0.000 title claims abstract description 46
- 239000013078 crystal Substances 0.000 claims abstract description 24
- 238000000137 annealing Methods 0.000 claims abstract description 15
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003763 carbonization Methods 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims description 75
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 41
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 34
- 239000002243 precursor Substances 0.000 claims description 32
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 19
- 229910052744 lithium Inorganic materials 0.000 claims description 19
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 16
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid 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
- 239000001038 titanium pigment Substances 0.000 claims description 11
- 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
- 239000007787 solid Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000005696 Diammonium phosphate Substances 0.000 claims description 6
- 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
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 6
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 claims description 6
- 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
- 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
- 229910052756 noble gas Inorganic materials 0.000 claims description 4
- 235000011007 phosphoric acid Nutrition 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 150000002506 iron compounds Chemical class 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 27
- 229910010707 LiFePO 4 Inorganic materials 0.000 abstract description 13
- 238000005253 cladding Methods 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 229920000858 Cyclodextrin Polymers 0.000 abstract description 2
- 239000001116 FEMA 4028 Substances 0.000 abstract description 2
- 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 description 2
- 235000011175 beta-cyclodextrine Nutrition 0.000 abstract description 2
- 229960004853 betadex Drugs 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 238000007669 thermal treatment Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000006193 liquid solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004254 Ammonium phosphate Substances 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
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000010450 olivine Substances 0.000 description 2
- 229910052609 olivine Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000002360 preparation method 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
- 229910001305 LiMPO4 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 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
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 phosphoric acid hydrogen iron complex Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 238000001228 spectrum Methods 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
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- 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 present invention relates to a kind of method that clathrate process prepares LiFePO4.The present invention passes through clathrate beta cyclodextrin or hydroquinone, and LiFePO4 crystal is carried out molecule inclusion, carries out carbonization annealing process of thermal treatment after inclusion.This technique has two kinds of good implementation methods, two stages, LiFePO4 crystal can be carried out inclusion.This technique effectively solves cladding, uneven, the most tight problem, reaches the inclusion carbonization of molecular level.Effectively solve the problem that LiFePO4 is reunited at building-up process Middle molecule, refine secondary Domain size.The LiFePO 4 material of this technique synthesis has the distribution of good nano particle size, and particle mean size is less than 1um.Having good electric conductivity, material with carbon-coated surface is completely uniform, and stable performance, gram volume is up to 163mAH simultaneously.Method is simple, it is simple to large-scale production.
Description
Technical field
The present invention relates to chemical synthetic material field, in particular relate to one clathrate process and prepare high-quality lithium ion
The method of secondary battery anode material ferric lithium phosphate crystal.
Background technology
AyMPO is disclosed first from the NTT of Japan in 19964(A is alkali metal, and M is the combination of both CoFe: LiFeCOPO4)
Olivine structural anode material of lithium battery after, within 1997, Texas, USA founds university John.B.Goodenough
Deng research group, it has been reported that LiFePO4Olivine structural (LiMPO4), European have also discovered natural olivine structural
LiFePO4。LiFePO4Also be found to have commercialization secondary battery material such as cobalt acid lithium, lithium nickelate, the material such as ternary without
The superior function of method analogy.This material possesses that raw material sources is extensive, cheap, memory-less effect, has extended cycle life, safety
Performance is good, and high-temperature behavior is good, without series of advantages such as heavy metal, non-environmental-pollutions.
Although LiFePO4Having plurality of advantages, but there is also defect, material self-conductive performance is the best, causes low temperature properties
The existence of these problems can be answered also to have caused the research energetically of various countries scientist with high-rate discharge ability difference etc..In order to change
The electric conductivity of material, American proposes the method that carbon cladding changes material conductivity.But LiFePO4 molecule is so
Little, the molecule of Nano grade, the bag how being evenly coated rather than having wrapped the thickest, the portion of material electric conductivity not being coated to
Can be the most bad, affect the performance of material overall performance.
Summary of the invention
The present invention, by the research that becomes more meticulous synthesis technique, invents a kind of clathrate process and prepares the side of LiFePO4
Method, LiFePO4 crystalline material prepared by the method, it is evenly coated, chemical property is good, batch stable and consistent, multiplying power discharging
Can be good, good processability, it is possible to the competent electrokinetic cell high requirement to positive electrode.
The present invention provides a kind of method that clathrate process prepares LiFePO4, it is characterized in that comprising the following steps:
1. by titanium pigment source compound, Fe source compound, Li source compound and clathrate, in molar ratio 1: 1: 2～3.6
: 1 weighs, and during then supersaturation is dissolved in deionized water or distilled water, forms P source compound solution, Fe source compound respectively molten
Liquid, Li source compound solution, inclusion complex in solution；
2. phosphorus source compound solution is added autoclave, make autoclave be warming up to 50-110 DEG C, then slowly to height
Add described Fe source compound solution in pressure still, in autoclave, be passed through noble gas, in autoclave, then slowly add lithium
Source compound solution, last slowly addition inclusion complex in solution, then sealing autoclave in autoclave, set high pressure temperature in the kettle
With the ramp of 1-10 DEG C/min to 120-260 DEG C, set autoclave pressure at 0.2-4.7MPa, proceed by inclusion mistake
Journey, whole inclusion process the most ceaselessly disperse stirring, whole inclusion process continue 4-15 hour, inclusion process is complete, if
Determine high pressure temperature in the kettle and be cooled to room temperature with the speed of 1-20 DEG C/min, then autoclave contents is carried out solid-liquid separation, will divide
After the solid separated out washs, then low temperature or vacuum drying, it is thus achieved that LiFePO4 clathrate crystal.
Further, the LiFePO4 clathrate crystal obtained is added in inert atmosphere protection or vacuum drying oven, carries out height
Temperature carbonization annealing, carbonization annealing temperature controls at 600 800 DEG C, and constant temperature time controlled between 46 hours.
Further, described clathrate is beta-schardinger dextrin-or hydroquinone.
Further, described titanium pigment source compound be phosphoric acid, diammonium phosphate, ammonium dihydrogen phosphate, lithium dihydrogen phosphate,
Phosphoric acid hydrogen two lithium, described soluble iron source compound is green vitriol, Iron dichloride tetrahydrate, ferrous acetate, described
Solubility Li source compound is a hydronium(ion) lithium oxide, lithium chloride, lithium nitrate, lithium dihydrogen phosphate, Quilonorm (SKB) and phosphoric acid hydrogen two lithium.
The present invention effectively solves the problem that cladding is uneven, the most tight, reaches the inclusion carbonization of molecular level.Effectively
Solve the problem that LiFePO4 is reunited at building-up process Middle molecule, refine secondary Domain size.The phosphoric acid of this technique synthesis
Ferrum lithium material has the distribution of good nano particle size, and particle mean size is less than 1um.There is good electric conductivity, surface carbon simultaneously
Cladding is complete uniformly, and stable performance, gram volume is up to 163mAH.Method is simple, it is simple to large-scale production.
Accompanying drawing explanation
Fig. 1 is the gram volume test figure of the LiFePO 4 material prepared by the present invention；
Fig. 2 is the multiplying power test figure of the LiFePO 4 material prepared by the present invention；
Fig. 3 is the cycle performance test figure of the LiFePO 4 material prepared by the present invention；
Fig. 4 is the particle size distribution figure of the LiFePO 4 material prepared by the present invention；
Fig. 5 is the XRD figure of the LiFePO 4 material prepared by the present invention.
Detailed description of the invention
Embodiment one:
The present invention provides a kind of method that clathrate process prepares LiFePO4, it is characterized in that comprising the following steps:
1. by titanium pigment source compound, Fe source compound, Li source compound and clathrate, in molar ratio 1: 1: 2～3.6
: 1 weighs, and during then supersaturation is dissolved in deionized water or distilled water, forms P source compound solution, Fe source compound respectively molten
Liquid, Li source compound solution, inclusion complex in solution；
2. phosphorus source compound solution is added autoclave, make autoclave be warming up to 50-110 DEG C, then slowly to height
Add described Fe source compound solution in pressure still, in autoclave, be passed through noble gas, in autoclave, then slowly add lithium
Source compound solution, last slowly addition inclusion complex in solution, then sealing autoclave in autoclave, set high pressure temperature in the kettle
With the ramp of 1-10 DEG C/min to 120-260 DEG C, set autoclave pressure at 0.2-4.7MPa, proceed by inclusion mistake
Journey, whole inclusion process the most ceaselessly disperse stirring, whole inclusion process continue 4-15 hour, inclusion process is complete, if
Determine high pressure temperature in the kettle and be cooled to room temperature with the speed of 1-20 DEG C/min, then autoclave contents is carried out solid-liquid separation, will divide
After the solid separated out washs, then low temperature or vacuum drying, it is thus achieved that LiFePO4 clathrate crystal.
Further, the LiFePO4 clathrate crystal obtained is added in inert atmosphere protection or vacuum drying oven, carries out height
Temperature carbonization annealing, carbonization annealing temperature controls at 600 800 DEG C, and constant temperature time controlled between 46 hours.
Further, described clathrate is beta-schardinger dextrin-or hydroquinone.
Further, described titanium pigment source compound be phosphoric acid, diammonium phosphate, ammonium dihydrogen phosphate, lithium dihydrogen phosphate,
Phosphoric acid hydrogen two lithium, described soluble iron source compound is green vitriol, Iron dichloride tetrahydrate, ferrous acetate, described
Solubility Li source compound is a hydronium(ion) lithium oxide, lithium chloride, lithium nitrate, lithium dihydrogen phosphate, Quilonorm (SKB) and phosphoric acid hydrogen two lithium.
It is preferably in combination with: such as lithium nitrate and ferrous sulfate add diammonium phosphate combination, and also Quilonorm (SKB) and ferrous chloride add ammonium phosphate
The LiFePO4 clathrate crystal all can prepared by following process.
Embodiment two
A kind of clathrate process prepares the method for LiFePO4, it is characterized in that comprising the following steps:
Weigh titanium pigment source compound, Fe source compound and Li source compound the most in molar ratio, by load weighted
Titanium pigment source compound, Fe source compound and Li source compound supersaturation are dissolved in deionized water or distilled water, respectively shape
Become the P source compound precursor solution of molecular level, Fe source compound precursor solution and Li source compound precursor solution, so
Rear employing hydro-thermal method makes phosphorus source compound precursor solution, Fe source compound precursor solution and Li source compound presoma
Solution is synthesizing iron lithium phosphate presoma in autoclave；
2. autoclave contents carries out solid-liquid separation, and gained solid is ferric lithium phosphate precursor to be washed, and will isolate
Ferric lithium phosphate precursor to be washed wash, keep the percentage by weight of water in the ferric lithium phosphate precursor after washing to exist
30 80%, form ferric lithium phosphate precursor suspension after washing, in ferric lithium phosphate precursor suspension, then add inclusion
Thing, the clathrate of addition and the mol ratio of ferric lithium phosphate precursor are 1-2.5: 1, before clathrate supersaturation is dissolved in LiFePO4
Drive in body suspension, the most again the ferric lithium phosphate precursor suspension having dissolved clathrate is carried out 4-20 by ultrasonic disperse machine
Hour ultrasonic disperse effect after, formed LiFePO4 clathrate crystal, finally by solid-liquid separating equipment by LiFePO4 bag
Solvate crystal is separated.
Further, the LiFePO4 clathrate crystal obtained is added in inert atmosphere protection or vacuum drying oven, carries out height
Temperature carbonization annealing, carbonization annealing temperature controls at 600 800 DEG C, and constant temperature time controlled between 46 hours.
Further, described clathrate is beta-schardinger dextrin-or hydroquinone.
Further, described titanium pigment source compound be phosphoric acid, diammonium phosphate, ammonium dihydrogen phosphate, lithium dihydrogen phosphate,
Phosphoric acid hydrogen two lithium, described soluble iron source compound is green vitriol, Iron dichloride tetrahydrate, ferrous acetate, described
Solubility Li source compound is a hydronium(ion) lithium oxide, lithium chloride, lithium nitrate, lithium dihydrogen phosphate, Quilonorm (SKB) and phosphoric acid hydrogen two lithium.
It is preferably in combination with: such as lithium nitrate and ferrous sulfate add diammonium phosphate combination, and also Quilonorm (SKB) and ferrous chloride add ammonium phosphate
The LiFePO4 clathrate crystal all can prepared by following process.
Described hydro-thermal method refers to: Hydrothermal Synthesis LiFePO4 crystal precursor, first by titanium pigment source compound, source of iron
Compound and Li source compound, 1: 1: 2～3.6 weigh, then by load weighted titanium pigment source compound, source of iron in molar ratio
Compound and Li source compound supersaturation are dissolved in deionized water or distilled water, before forming the P source compound of molecular level respectively
Drive liquid solution, Fe source compound precursor solution and Li source compound precursor solution, then by phosphorus source compound forerunner
Liquid solution adds in autoclave, makes high pressure temperature in the kettle rise to 50 ~ 110 DEG C and is followed by slowly added to described Fe source compound forerunner
Liquid solution, makes P source compound precursor solution and Fe source compound precursor solution form intermediate hydration phosphorus in autoclave
The ferrous Fe of acid3(PO4)2•8H2O and phosphoric acid hydrogen iron complex, be then passed through after noble gas again to described in described autoclave
Add described Li source compound precursor solution in autoclave, then in autoclave, start to warm up reaction, control heating rate and exist
1-10 DEG C/min makes high pressure temperature in the kettle rise to 120-260 DEG C, the Stress control in autoclave at 0.2-4.7MPa, whole intensification
Solution in autoclave does not stop in course of reaction stirring, and whole temperature reaction process continues 4-15 hour, and temperature reaction is complete
After, control rate of temperature fall, after 1-20 DEG C/min is down to room temperature, makes the solution in autoclave be introduced by baiting valve and drainage pump
Solid-liquid separating equipment, fully washs isolated solid and obtains pure LiFePO4 crystalline substance after washing away surface deposits and impurity
Body presoma；
Embodiment three
(1), be in molar ratio 1: 1: 3: 1 weigh green vitriol, phosphoric acid, a hydronium(ion) lithium oxide and β-
Cyclodextrin dissolves respectively, and solid content gross mass is the 10% of the quality of aqueous solvent.
(2), by phosphoric acid solution and green vitriol solution add autoclave and make the two mixing strength high-speed stirred, so
After lithium hydroxide solution is slowly added to autoclave, be passed through inert protective gas, be eventually adding beta-schardinger dextrin-sealed reactor, open
Beginning to heat up, heating rate is 3 DEG C/about min, rises to 220 DEG C, and temperature of reaction system is maintained at 220 DEG C, and system pressure controls
At 1.6MPa.Constant temperature time controlled at 8 hours.
(3) after, reaction terminates, solid-liquid centrifugation or sucking filtration are separated.Solid after separation is scrubbed obtains phosphoric acid
Ferrum lithium clathrate crystal presoma.
(4), LiFePO4 crystal inclusion compound presoma is added in inert atmosphere protection or vacuum drying oven, carry out high temperature cabonization
Annealing, carbonization annealing temperature controls at 600 DEG C, and it is brilliant that constant temperature time controlled to produce the LiFePO4 being coated with at 4 hours
Body.
Example four
(1) it is, that 1: 1: 3 to weigh green vitriol, phosphoric acid, a hydronium(ion) lithium oxide respectively the most molten in molar ratio
Solving, solid content gross mass is the 15% of the quality of aqueous solvent.
(2), by phosphoric acid and green vitriol solution add autoclave and make the two mixing strength high-speed stirred, be passed through guarantor
Protect gas, then lithium hydroxide solution is slowly added to autoclave.Sealed reactor, starts to warm up, and heating rate is 3 DEG C/min
Left and right, rises to 220 DEG C, and temperature of reaction system is maintained at 220 DEG C, and system pressure controls at 1.6MPa.Constant temperature time controls 6
Hour.
(3) after, reaction terminates, solid-liquid centrifugation or sucking filtration are separated.Solid after separation is scrubbed obtains phosphoric acid
Ferrum crystalline lithium presoma.
(4) the LiFePO4 water content after washing, is controlled about 60%.
(5), add LiFePO4 crystal presoma mole 1: 1 clathrate hydroquinone, supersaturation is dissolved in phosphoric acid
In ferrum lithium presoma suspension.
(6), inclusion process is made to complete under the mechanism that saturated solution and ultrasonic disperse interact by physical and chemical effect.
(7), clathrate process completes final vacuum or cold drying LiFePO4 clathrate crystal.
(8), LiFePO4 clathrate crystal is added in inert atmosphere protection or vacuum drying oven, carries out high temperature cabonization annealing,
Carbonization annealing temperature controls at 700 DEG C, and constant temperature time controlled to produce the perfect LiFePO4 crystal of cladding at 5 hours.
Detection is analyzed:
Entrust the detection that the global group in Xinxiang does, by the LiFePO 4 material of a kind of carbo-nitriding provided by the present invention
The preparation-obtained LiFePO 4 material of preparation method, after testing, the theoretical gram volume of LiFePO4 is 170mAH/g, this method
The LiFePO 4 material of preparation can stably accomplish 163mAH/g, tests figure accompanying drawing 1 referring specifically to gram volume；Phosphorus prepared by this method
The high rate performance of acid ferrum lithium material, the standard of European Union is that 1C charge and discharge is not less than 130mAH/g, domestic relatively do at present good
Can reach 1C charge and discharge 135mAH/g, and LiFePO 4 material prepared by this method, data are 1C charge and discharge 154mAH/g after testing
Left and right, tests figure accompanying drawing 2 referring specifically to multiplying power；It addition, the lattice stability of LiFePO 4 material prepared by this method is to pass through
Cycle performance embodies, the figure provided at present be 50 times undamped, referring specifically to Fig. 3；Further, this LiFePO 4 material material
The physical property of material, can directly be detected, including granularity, can be detected by laser fineness gage, and I divides with granularity
Butut i.e. Fig. 4；It is the purity of target product LiFePO4 and this product as this powder body material synthesized, Ke Yitong
Crossing XRD figure spectrum and carry out check analysis, I am also with XRD figure i.e. Fig. 5；Finally, the lot stability of this LiFePO 4 material, by pressing
According to the method that this technique is same, same condition, be repeated 10 times test, detection gram volume all between 158-163 mAH/g, ripple
Move about 3%, it is believed that lot stability concordance is controlled.
Claims (3)
1. the method preparing LiFePO4 with clathrate process, is characterized in that comprising the following steps:
1. by titanium pigment source compound, Fe source compound, Li source compound and clathrate, in molar ratio 1: 1: (2～3.6): 1
Weigh, during then supersaturation is dissolved in deionized water or distilled water, form P source compound solution, Fe source compound respectively molten
Liquid, Li source compound solution, inclusion complex in solution；Described clathrate is beta-schardinger dextrin-or hydroquinone；
2. phosphorus source compound solution is added autoclave, make autoclave be warming up to 50-110 DEG C, then slowly to autoclave
Interior addition described Fe source compound solution, is passed through noble gas in autoclave, then slowly adds lithium source in autoclave
Polymer solution, last slowly addition inclusion complex in solution, then sealing autoclave in autoclave, set high pressure temperature in the kettle with 1-
The ramp of 10 DEG C/min is to 120-260 DEG C, and setting autoclave pressure, at 0.2-4.7MPa, proceeds by inclusion process, whole
Individual inclusion process the most ceaselessly disperses stirring, and whole inclusion process continues 4-15 hour, and inclusion process is complete, sets high pressure
Temperature in the kettle is cooled to room temperature with the speed of 1-20 DEG C/min, then autoclave contents is carried out solid-liquid separation, by isolated
After solid washs, then low temperature or vacuum drying, it is thus achieved that LiFePO4 clathrate crystal；The LiFePO4 clathrate that will obtain
Crystal adds in inert atmosphere protection or vacuum drying oven, carries out high temperature cabonization annealing, and carbonization annealing temperature controls at 600 800 DEG C,
Constant temperature time controlled between 46 hours.
2. the method preparing LiFePO4 with clathrate process, is characterized in that comprising the following steps:
Weigh titanium pigment source compound, Fe source compound and Li source compound the most in molar ratio, by load weighted solvable
Property P source compound, Fe source compound and Li source compound supersaturation be dissolved in deionized water or distilled water, formed respectively point
The P source compound precursor solution of sub-level, Fe source compound precursor solution and Li source compound precursor solution, then adopt
Phosphorus source compound precursor solution, Fe source compound precursor solution and Li source compound precursor solution is made by hydro-thermal method
Synthesizing iron lithium phosphate presoma in autoclave；
2. autoclave contents carries out solid-liquid separation, and gained solid is ferric lithium phosphate precursor to be washed, and treats isolated
Washing ferric lithium phosphate precursor washs, and in the ferric lithium phosphate precursor after holding washing, the percentage by weight of water is 30
80%, form ferric lithium phosphate precursor suspension after washing, in ferric lithium phosphate precursor suspension, then add clathrate, institute
Stating clathrate is beta-schardinger dextrin-or hydroquinone, and the clathrate of addition and the mol ratio of ferric lithium phosphate precursor are (1-2.5): 1,
Clathrate supersaturation is dissolved in ferric lithium phosphate precursor suspension, will dissolve the ferric lithium phosphate precursor of clathrate the most again
After suspension carries out the ultrasonic disperse effect of 4-20 hour by ultrasonic disperse machine, form LiFePO4 clathrate crystal, finally
By solid-liquid separating equipment, LiFePO4 clathrate crystal is separated；The LiFePO4 clathrate crystal obtained is added lazy
In property atmosphere protection or vacuum drying oven, carrying out high temperature cabonization annealing, carbonization annealing temperature controls at 600 800 DEG C, constant temperature time control
System is between 46 hours.
A kind of clathrate process prepares the method for LiFePO4, it is characterized in that: described solvable
Property P source compound is phosphoric acid, diammonium phosphate, ammonium dihydrogen phosphate, lithium dihydrogen phosphate, phosphoric acid hydrogen two lithium, described solubility source of iron
Compound is green vitriol, Iron dichloride tetrahydrate, ferrous acetate, and described solubility Li source compound is a hydronium(ion)
Lithium oxide, lithium chloride, lithium nitrate, lithium dihydrogen phosphate, Quilonorm (SKB) and phosphoric acid hydrogen two lithium.
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