CN1298621C - Method for preparing Li Fe PO4 ball shape powder - Google Patents
Method for preparing Li Fe PO4 ball shape powder Download PDFInfo
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- CN1298621C CN1298621C CNB2004100989424A CN200410098942A CN1298621C CN 1298621 C CN1298621 C CN 1298621C CN B2004100989424 A CNB2004100989424 A CN B2004100989424A CN 200410098942 A CN200410098942 A CN 200410098942A CN 1298621 C CN1298621 C CN 1298621C
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- 239000000843 powder Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 31
- 238000002360 preparation method Methods 0.000 claims abstract description 27
- 239000012298 atmosphere Substances 0.000 claims abstract description 25
- 238000000498 ball milling Methods 0.000 claims abstract description 22
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims abstract description 20
- 239000011858 nanopowder Substances 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims abstract description 6
- 239000011164 primary particle Substances 0.000 claims abstract description 5
- 239000006229 carbon black Substances 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002203 pretreatment Methods 0.000 claims description 17
- 238000005303 weighing Methods 0.000 claims description 17
- 229910010710 LiFePO Inorganic materials 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000003595 mist Substances 0.000 claims description 11
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- ZDYUUBIMAGBMPY-UHFFFAOYSA-N oxalic acid;hydrate Chemical class O.OC(=O)C(O)=O ZDYUUBIMAGBMPY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052573 porcelain Inorganic materials 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000002019 doping agent Substances 0.000 claims description 4
- 238000005336 cracking Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000010304 firing Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 abstract 2
- 239000011230 binding agent Substances 0.000 abstract 1
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 229910021385 hard carbon Inorganic materials 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- GQCUKJLDVJKUKF-UHFFFAOYSA-N magnesium;oxalic acid;hydrate Chemical compound O.[Mg].OC(=O)C(O)=O GQCUKJLDVJKUKF-UHFFFAOYSA-N 0.000 description 4
- 229920002994 synthetic fiber Polymers 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
一种LiFePO4球形粉体的制备方法，包括预合成掺杂或者空白LiFePO4纳米粉体A，粉体A与粘合剂、分散剂、水混合球磨得到浆料B；将浆料B喷雾造粒并干燥，在还原气氛下处理，最后将处理得到的粉体在还原或者惰性气氛烧成，即得到碳黑包覆的具有纳米级一次粒径的球形LiFePO4粉体。本发明的制备过程时间短、烧成温度低、能耗低、制备的多晶LiFePO4粉体粒径分布窄，并且呈球形形态、得到的硬性碳包覆的LiFePO4粉体无需进行后期的包覆处理即可改善材料的电子导电性能。材料粉体粒径可调，材料制备过程简单，流程时间短暂，材料产率较高。
A preparation method of LiFePO4 spherical powder, comprising pre-synthesizing doped or blank LiFePO4 nano-powder A, mixing powder A with binder, dispersant, water and ball milling to obtain slurry B; spraying slurry B Granulated and dried, treated in a reducing atmosphere, and finally fired in a reducing or inert atmosphere to obtain a carbon black-coated spherical LiFePO 4 powder with a nanoscale primary particle size. The preparation time of the present invention is short, the firing temperature is low, the energy consumption is low, the particle size distribution of the prepared polycrystalline LiFePO 4 powder is narrow, and it is in a spherical shape, and the obtained hard carbon-coated LiFePO 4 powder does not need to be processed in the later stage. The coating treatment can improve the electronic conductivity of the material. The particle size of the material powder is adjustable, the material preparation process is simple, the process time is short, and the material yield is high.
Description
Technical field
The present invention relates to a kind of high electrochemical performance secondary lithium battery or power source battery anode material spherical LiFePO
4The preparation method of powder belongs to material science.
Background technology
LiFePO
4That material has is cheap, nontoxic, nonhygroscopic, Environmental compatibility is fine, rich in mineral resources, characteristics such as capacity is higher (theoretical capacity is 170mAh/g, and energy density is 550Wh/Kg), stability is fine.It is a kind of positive electrode material equivalent material of tool potentiality.Be with a wide range of applications and the very big market requirement.Existing several synthetic methods are arranged at present:
1) solid phase method, JP2000294238, are calcined under inert atmosphere as raw material with Ferrox, Secondary ammonium phosphate and Quilonum Retard.EP1193784 is with Fe
3(PO
4)
2And Li
3PO
4As raw material and add hydrocarbon polymer and carry out solid phase synthesis; This method synthetic material granule is thick, and form is irregular, and material electrochemical performance is low.
2) sol-gel method, publication number: CN1410349 is with Fe (Ac)
2, FeSO
4, 7H
2O, Ba (Ac)
2And organic acid is a raw material; Technology is comparatively complicated, the improper easy introducing Ba of process control
2+, Fe
3+Deng impurity.
3) reversed phase lithium inserting process, publication number: CN1469499, with normal heptane-ST80 system, the microreactor synthesis of nano FePO that utilizes micro emulsion to form
4, utilize LiI to insert lithium then.This method technical process complexity, the flow process time is longer.
4) spray-drying process, S.L.Bewlay, K.Konstantinov, G.X.Wang, Materials Letters, 58 (11), 2004,1788.This method is mainly utilized and is contained Li
+, Fe
2+And PO
4 3-Isoionic nitrate solution is as spray-dired slip, and spray-dried back is as the presoma of synthetic materials.This technology can obtain the material of controllable grain size, and technology is simple, but causes the oxidation of ferrous ion in the building-up process easily, is unfavorable for the improvement of material property.And, require very high to processing unit owing to contain strong acid in the solution.
5) coprecipitation method, G.Arnold, J.Garche, R.Hemmer, et al.Journal of Power Sources 2003,119-121:247.This method is introduced impurity easily, is unfavorable for the improvement of material electrochemical performance.
6) emulsion desiccating method S.T.Myung, S.Komaba, R.Takagai, et al., Chemistry Letters, 32 (7), 2003,566.This method complicated process of preparation, the flow process time is longer.
7) hydrothermal method, Yang S.F, Zavalij P.Y et al.electrochemistry communications.3,2001,505.This side is unfavorable for the improvement of material electrochemical performance.
Summary of the invention
The object of the invention provides a kind of LiFePO
4The preparation method of spherical powder, this method can solve the density of material of conventional preparation method preparation little and specific surface area is little and the problem of poorly conductive can to have crystallinity in fairly large preparation down good, powder is a spherical morphology, narrowly distributing, and the purity height (removes LiFePO
4Do not have dephasign outward with the rigid carbon that coats), the material good conductivity, specific surface area is big, and has the LiFePO of bigger mass density
4Spherical powder, this powder also helps LiFePO
4The manufacture craft of material cell.
A kind of LiFePO
4The preparation method of spherical powder, this method may further comprise the steps:
The 1st step: pre-synthesizing blender or blank LiFePO
4Nano-powder A
, Quilonum Retard ferrous with 2 oxalic acid hydrates, primary ammonium phosphate are that main precursor takes by weighing some according to 1: 0.5: 1 mole of proportioning; If the adulterated LiFePO of preparation
4Material is that 0～0.8at% takes by weighing dopant according to atomic percentage conc then; With the above material that takes by weighing is the ball-milling medium ball milling with the dehydrated alcohol, through pre-treatment 8～16 hours in 300～400 ℃ of following inert atmospheres or reducing atmosphere after the cryodrying, obtains nano-powder A;
The 2nd step: according to nano-powder A: tackiness agent: dispersion agent: water=(60～65kg): (6～6.5kg): (720～780mL): (54～58.5L) mixed, ball milling obtains having good fluidity and the stable slurry B that is suitable for mist projection granulating;
The 3rd step: use slurry B, mist projection granulating as requested in the mist projection granulating tower obtains the spherical powder of different-grain diameter;
The 4th step: with the porcelain boat of packing into after the 3rd spherical powder drying that obtains of step, 400 ℃ of pre-treatment are 2～8 hours under reducing atmosphere or inert atmosphere, and powder is cracking lentamente in this atmosphere;
The 5th step: the 4th powder that obtains of step is burnt till in reduction or the inert atmosphere down at 550～850 ℃, be incubated 8～36 hours, promptly obtain the spherical LiFePO with nano level primary particle size of carbon black coating
4Powder.
With above step, if the adulterated LiFePO of preparation
4Material is that 0～0.8at% takes by weighing dopant according to atomic percentage conc then, and its doping way can be singly to mix, and also can be two mixing or the mixed doping of more hotchpotchs.Its dopant can be as 2 oxalic acid hydrate magnesium, many materials such as aluminum isopropylate.
Principle of the present invention is: synthetic in advance LiFePO
4Powder A can improve powder ferrous ion anti-oxidant in the technical process process; Pre-synthetic nano-powder is difficult in calcination process that after organism coats particle takes place grows up, thereby has kept material to have nano level primary particle size; Utilize atomizing granulating technology to make nanoparticle agglomerates become needed bead form, guaranteed that material has bigger specific surface area and bigger powder density; Utilize polymer substance (dispersion agent and the tackiness agent) carbon black that cracking forms in inertia or reducing atmosphere effectively to solve LiFePO
4The problem that the material electronics specific conductivity is low.
Beneficial effect of the present invention: preparation process time of the present invention is short, firing temperature is low, energy consumption is low, the polycrystalline LiFePO of preparation
4The diameter of particle narrowly distributing, and form spherical in shape, directly under inertia or reducing atmosphere, burn till, the LiFePO that rigid carbon coats can be obtained
4Powder.Therefore also need not to carry out the coating in later stage and handle the electronic conductivity that can improve material.Synthetic materials has nano level primary particle size, has guaranteed that material has bigger specific surface area; Synthetic materials has bigger density, is fit to the making of lithium ion battery, and adjustable between 550 ℃～850 ℃ of the synthesis temperatures, the material diameter of particle is adjustable, and the material preparation process is simple, and the flow process time is of short duration, and the material productive rate is higher.
Description of drawings
Figure (1) is the XRD figure spectrum of pre-treatment powder A1, wherein (200), and (101), (210), (011), (111), (211), (301), (311), (121), (410), (401), diffraction peaks such as (022) is LiFePO
4The characteristic peak of material.
Figure (2) is to use the XRD diffractogram of the powder of preparation among present method embodiment 1.
Figure (3) is to use the SEM figure of the powder of preparation among present method embodiment 1.
Figure (4) is to use the XRD diffractogram of the powder of preparation among present method embodiment 2.
Figure (5) is to use the SEM figure of the powder of preparation among present method embodiment 2.
Figure (6) is to use the XRD diffractogram of the powder of preparation among present method embodiment 3.
Figure (7) is to use the SEM figure of the powder of preparation among present method embodiment 3.
Figure (8) is to use the XRD diffractogram of the powder of preparation among present method embodiment 4.
Figure (9) is to use the SEM figure of the powder of preparation among present method embodiment 4.
Figure (10) is to use the XRD diffractogram of the powder of preparation among present method embodiment 5.
Embodiment
Below by embodiment, further illustrate the present invention.
Embodiment 1: pre-burning LiFePO
4Presoma: according to 1: 0.5: 1 mole of proportioning take by weighing that 2 oxalic acid hydrates are ferrous, Quilonum Retard, primary ammonium phosphate, be ball-milling medium with the dehydrated alcohol with mixture ball milling 4 hours; Through after the cryodrying in 300 ℃ of following inert atmospheres or reducing atmosphere pre-treatment can obtain solid matter pre-treatment powder A1 in 8 hours, figure (1) is the XRD figure of pre-treatment powder A1 spectrum.Take by weighing 6 kilograms of A1,0.6 kilogram of PVA, 5.4 liters of deionized waters, 72 milliliters of dispersion agents place container, and ball milling is 48 hours on the mill that rolls, and can obtain slip mobile and that have good stability.Slip is sent in the mist projection granulating tower, and input speed is controlled at 12 ± 2ml/min, and the nozzle air current amount is 0.08～0.1Mpa by compressed-air actuated pressure-controlling, and temperature of inlet air is about 300 ℃, and temperature out is 100～130 ℃.Collect dried powder, and powder has been put into porcelain boat, inserted in the atmosphere furnace under nitrogen atmosphere 400 ℃ of pre-treatment 2 hours, obtained the black LiFePO of good fluidity then 550 ℃ of insulations in 8 hours
4Spherical powder.As Fig. 2, shown in Figure 3, figure (2) is to use the XRD diffractogram of the powder for preparing in this example of present method, and figure (3) is to use the SEM figure of the powder for preparing in this example of present method.
Embodiment 2: pre-burning LiFePO
4Presoma: according to the mole proportioning take by weighing that 2 oxalic acid hydrates are ferrous, Quilonum Retard, primary ammonium phosphate, and add the 2 oxalic acid hydrate magnesium of 0.8at%; With the dehydrated alcohol ball-milling medium with mixture ball milling 8 hours; Through after the cryodrying in 400 ℃ of following inert atmospheres or reducing atmosphere pre-treatment can obtain solid matter A2 in 16 hours; Take by weighing solid matter A26.5 kilogram, 0.65 kilogram of PVA, 5.85 liters of deionized waters, 78 milliliters of dispersion agents place container, and ball milling is 4 days on the mill that rolls, and can obtain slip mobile and that have good stability; Slip is sent in the mist projection granulating tower, and input speed is controlled at 12 ± 2ml/min, and the nozzle air current amount is 0.08～0.1Mpa by compressed-air actuated pressure-controlling, and temperature of inlet air is about 300 ℃, and temperature out is 100～130 ℃; Collect dried powder, and powder has been put into porcelain boat, inserted in the atmosphere furnace under nitrogen atmosphere 400 ℃ of pre-treatment 8 hours, obtained the black LiFePO of good fluidity then 850 ℃ of insulations in 36 hours
4Spherical powder.As Fig. 4, shown in Figure 5, figure (4) is to use the XRD diffractogram of the powder for preparing in this example of present method, and figure (5) is to use the SEM figure of the powder for preparing in this example of present method.
Embodiment 3: pre-burning LiFePO
4Presoma: according to the mole proportioning take by weighing that 2 oxalic acid hydrates are ferrous, Quilonum Retard, primary ammonium phosphate, and add the aluminum isopropylate of 0.4at%.With the dehydrated alcohol ball-milling medium with mixture ball milling 6 hours.Through after the cryodrying in 350 ℃ of following inert atmospheres or reducing atmosphere pre-treatment can obtain solid matter A3 in 10 hours.Take by weighing solid matter A36.2 kilogram, 0.62 kilogram of PVA, 5.25 liters of deionized waters, 73 milliliters of dispersion agents place container, and ball milling is 3 days on the mill that rolls, and can obtain slip mobile and that have good stability.Slip is sent in the mist projection granulating tower, and input speed is controlled at 12 ± 2ml/min, and the nozzle air current amount is 0.08～0.1Mpa by compressed-air actuated pressure-controlling, and temperature of inlet air is about 300 ℃, and temperature out is 100～130 ℃.Collect dried powder, and powder has been put into porcelain boat, inserted in the atmosphere furnace under nitrogen atmosphere 400 ℃ of pre-treatment 4 hours, obtained the black LiFePO of good fluidity then 700 ℃ of insulations in 16 hours
4Spherical powder.As Fig. 6, shown in Figure 7, figure (6) is to use the XRD diffractogram of the powder for preparing in this example of present method, and figure (7) is to use the SEM figure of the powder for preparing in this example of present method.
Embodiment 4: first pre-burning LiFePO
4Presoma: according to the mole proportioning take by weighing that 2 oxalic acid hydrates are ferrous, Quilonum Retard, primary ammonium phosphate, and add aluminum isopropylate and the 0.4at%2 oxalic acid hydrate magnesium of 0.4at%; With the dehydrated alcohol ball-milling medium with mixture ball milling 4 hours; Through after the cryodrying in 400 ℃ of following inert atmospheres or reducing atmosphere pre-treatment can obtain solid matter A4 in 8 hours; Take by weighing 6 kilograms of A4,0.6 kilogram of PVA, 5.4 liters of deionized waters, 72 milliliters of dispersion agents place container, and ball milling is 48 hours on the mill that rolls, and can obtain slip mobile and that have good stability.Slip is sent in the mist projection granulating tower, and input speed is controlled at 12 ± 2ml/min, and the nozzle air current amount is 0.08～0.1Mpa by compressed-air actuated pressure-controlling, and temperature of inlet air is about 300 ℃, and temperature out is 100～130 ℃.Collect dried powder, and powder has been put into porcelain boat, inserted in the atmosphere furnace under nitrogen atmosphere 400 ℃ of pre-treatment 4 hours, obtained the black LiFePO of good fluidity then 800 ℃ of insulations in 8 hours
4Spherical powder.As Fig. 8, shown in Figure 9, figure (8) is to use the XRD diffractogram of the powder for preparing in this example of present method, and figure (9) is to use the SEM figure of the powder for preparing in this example of present method.
Embodiment 5: pre-burning LiFePO
4Presoma: according to the mole proportioning take by weighing that 2 oxalic acid hydrates are ferrous, Quilonum Retard, primary ammonium phosphate, and add the 2 oxalic acid hydrate magnesium of 0.3at%; With the dehydrated alcohol ball-milling medium with mixture ball milling 8 hours; Through after the cryodrying in 400 ℃ of following inert atmospheres or reducing atmosphere pre-treatment can obtain solid matter A2 in 10 hours; Take by weighing 6.5 kilograms of solid matter A2,0.6 kilogram of PVA, 5.6 liters of deionized waters, 82 milliliters of dispersion agents place container, and ball milling is 50 hours on the mill that rolls, and can obtain slip mobile and that have good stability; Slip is sent in the mist projection granulating tower, and input speed is controlled at 12 ± 2ml/min, and the nozzle air current amount is 0.08～0.1Mpa by compressed-air actuated pressure-controlling, and temperature of inlet air is about 300 ℃, and temperature out is 100～130 ℃; Collect dried powder, and powder has been put into porcelain boat, inserted in the atmosphere furnace under nitrogen atmosphere 400 ℃ of pre-treatment 2 hours, obtained the black LiFePO of good fluidity then 650 ℃ of insulations in 24 hours
4Spherical powder.As shown in figure 10, figure (10) is to use the XRD diffractogram of the powder for preparing in this example of present method.
Although the present invention is described in each preferred embodiment, but the heat of this area white silk technician understands the present invention easily and is not limited to foregoing description, it can be changed in multiple other modes or be improved, and does not break away from the spirit and scope of illustrating in the claim of the present invention.
Claims (1)
1, a kind of LiFePO
4The preparation method of spherical powder is characterized in that, this method may further comprise the steps:
The 1st step: synthetic in advance LiFePO
4Nano-powder A
, Quilonum Retard ferrous with 2 oxalic acid hydrates, primary ammonium phosphate are that main precursor takes by weighing some according to 1: 0.5: 1 mole of proportioning; If the adulterated LiFePO of preparation
4Material is that 0～0.8at% takes by weighing dopant according to atomic percentage conc then; Is the ball-milling medium ball milling with the above material that takes by weighing with the dehydrated alcohol, and after cryodrying, pre-treatment is 8～16 hours in 300～400 ℃ of following inert atmospheres or reducing atmosphere, obtains nano-powder A;
The 2nd step: according to nano-powder A: tackiness agent: dispersion agent: water=(60～65kg): (6～6.5kg): (720～780mL): (54～58.5L) mixed, ball milling obtains having good fluidity and the stable slurry B that is suitable for mist projection granulating;
The 3rd step: use slurry B, mist projection granulating as requested in the mist projection granulating tower obtains the spherical powder of different-grain diameter;
The 4th step: with the porcelain boat of packing into after the 3rd spherical powder drying that obtains of step, 400 ℃ of pre-treatment are 2～8 hours under reducing atmosphere or inert atmosphere, and powder is cracking lentamente in this atmosphere;
The 5th step: the 4th powder that obtains of step is burnt till in reduction or the inert atmosphere down at 550～850 ℃, be incubated 8～36 hours, promptly obtain the spherical LiFePO with nano level primary particle size of carbon black coating
4Powder.
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|---|---|---|---|
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|---|---|---|---|
| CNB2004100989424A CN1298621C (en) | 2004-12-17 | 2004-12-17 | Method for preparing Li Fe PO4 ball shape powder |
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| CN1298621C true CN1298621C (en) | 2007-02-07 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102593446A (en) * | 2012-02-22 | 2012-07-18 | 清华大学 | Method for preparing active electrode material of lithium ion battery |
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| TWI483448B (en) * | 2013-10-07 | 2015-05-01 | Formosa Biomedical Technology Corp | Process for producing spherical lfp/c or lfpo/c composite material through spray drying method and use the same |
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| CN111252751B (en) * | 2018-12-03 | 2023-01-10 | 成都市银隆新能源有限公司 | Microfluidic droplet forming structural component and method for preparing solid spherical lithium iron phosphate |
| CN114824253B (en) * | 2022-04-24 | 2024-03-15 | 中南大学 | Granulating method for spherical particles of lithium ion battery anode material |
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