CN102275887A - Preparation method of high capacity high compacted density lithium iron phosphate material and product thereof - Google Patents
Preparation method of high capacity high compacted density lithium iron phosphate material and product thereof Download PDFInfo
- Publication number
- CN102275887A CN102275887A CN2011100090201A CN201110009020A CN102275887A CN 102275887 A CN102275887 A CN 102275887A CN 2011100090201 A CN2011100090201 A CN 2011100090201A CN 201110009020 A CN201110009020 A CN 201110009020A CN 102275887 A CN102275887 A CN 102275887A
- Authority
- CN
- China
- Prior art keywords
- preparation
- compacted density
- source
- product
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention, belonging to the field of lithium ion batteries cathode materials, discloses a preparation method of a high capacity high compacted density lithium iron phosphate material, comprising the following steps: (1) mixing lithium source, Fe3+ source, phosphate, doping agent and organic carbon source, then carrying out spray granulation; (2) preparing a pre-sintered product; (3) mixing the pre-sintered product with inorganic carbon source for sand milling, then carrying out spray drying to obtain secondary spray powder; (4) heating the secondary spray powder under vacuum condition orin a protective atmosphere, and sintering at constant temperature; and (5) carrying out secondary ball milling or air-flow grinding on the sintered semi-finished product to obtain a lithium iron phosphate product. The method solves the problems of the increase of product cost caused by using divalent iron source, difficult coating and low compacted density of pole pieces, and has the characteristics of low product cost, good processability, good conductive property, and good electrochemical performance of the prepared pole pieces.
Description
Technical field
The invention belongs to the anode material for lithium-ion batteries field, specifically provide preparation method of a kind of heavy body high compacted density LiFePO 4 material and products thereof.
Background technology
Lithium ion battery is as the new generation of green high tension battery, advantage such as have that voltage height, energy density are big, good cycle, self-discharge are little, memory-less effect, operating temperature range are wide and being widely used.Iron lithium phosphate is as anode material for lithium-ion batteries of new generation, cheap because of it, theoretical capacity higher (about 170mAh/g), stable operating voltage, asepsis environment-protecting, Stability Analysis of Structures, security is good, the cycle life of Heat stability is good and overlength and become the focus of current research, is one of best positive electrode material of power train in vehicle application power supply.
The main method of current synthesizing iron lithium phosphate has high-temperature solid phase reaction method, liquid-phase coprecipitation, hydrothermal method, the liquid-phase oxidation reduction method, solid phase microwave sintering method and mechanical ball milling method etc., but the easiest realization is industrial to be high-temperature solid phase reaction method, and other method successfully is used for the report that yet there are no of iron lithium phosphate production.As Chinese patent literature CN1581537A, CN1753216 A, CN1762798 A, CN1767238 A and foreign literature [J] A.Yamada et.al. Journal of the electrochemical Society; Vol148; A960-A967 (2001); the disclosed method of US Pat.5910382; be with ferrous salt; mix with phosphoric acid salt and lithium salts or lithium hydroxide, under inert atmosphere protection through 300-350 ℃ and 500-800 ℃ of segmentation roasting synthesizing iron lithium phosphate.The advantage of ferrous salt solid phase method is that technology is simple, synthetic material discharging gram volume height, easily realize industrialization, but divalence source of iron price is more expensive, and owing to need prevent the oxidation of divalence source of iron, complicated process of preparation, it often is solvent with the organism, product purity is wayward, thereby cost is increased, and general sintering time is all more than 25 hours.The tap density of material is lower behind the sintering, and tap density is generally less than 1.0 g/cm
3, powder body compacted density is usually less than 2.2g/m
3And when making battery plate, the coating difficulty, easy dry linting, the pole piece compacted density has only 2.15g/m
3About, volume and capacity ratio is lower.The then at first employing " carbothermic method " of Valence company (US6528033, US2004/0151649), with Fe
2O
3Be source of iron, in mixed solvent, behind the combination drying, utilize the reductibility of carbon under the high temperature with monometallic, magnesium hydroxide, inorganic carbon, sintering synthesizing iron lithium phosphate in inert atmosphere.The iron lithium phosphate that adopts this method production causes the material discharging gram volume not high owing to being carbon source with the inorganic carbon, and the 0.1C discharge is the highest to be had only about 135mAh/g.Chinese patent literature CN101597048A is except increasing mixing operation, and other and Valence patent are basic identical.People are that carbon source prepare iron lithium phosphate/LiFePO 4 with ferric ion as raw material and organic carbon by improving employing.Adopt a step solid phase method as the preparation method among the Chinese patent literature CN1564343A, with a certain proportion of lithium salts, Fe
3+Compound and phosphoric acid salt mix, and then with mixture pyrolysis in inert atmosphere, add a certain amount of high molecular polymer before the pyrolysis, obtain ferrous phosphate base lithium salts-carbon anode composite material.Owing to adopt high molecular polymer, particularly the product of plastic-like such as polyethylene or polypropylene carries out dry grinding as additive among this preparation method, and raw material mixes inhomogeneous, and particle is bigger, and dephasign is more, thereby causes product performance relatively poor.
Though in occupation of domestic and international certain market, their product gram volume is low to be a very big defective with the iron lithium phosphate product of ferric iron preparation for Taiwan Chang Yuan science and technology and U.S. Valence at present.This defective exposes undoubtedly in face of with the heavy body iron lithium phosphate product of ferrous iron preparation in U.S. A123 and Canadian Phostech company, causes share of market to be extruded gradually.
Summary of the invention
The present invention is directed to prior art adopts the divalence source of iron to cause product cost to increase, be coated with difficulty and the not high defective of pole piece compacted density, it is the preparation method of the lithium ion battery anode material lithium iron phosphate of raw material that a kind of ferric iron source that adopts is provided, the product of producing is processed easily, pole piece compacted density height, this preparation method's technology is simple simultaneously, greatly reduces production cost.
The not high defective of LiFePO 4 material discharge gram volume that the present invention also adopts ferric oxide, hydrous iron oxide to prepare as source of iron at prior art, a kind of anode material for lithium-ion batteries heavy body method preparing phosphate iron lithium is provided, preparation method of the present invention carries out elite to ferric raw material, the iron lithium phosphate product loading capacity height of producing.
The present invention also adopts ferric oxide, hydrous iron oxide as source of iron at prior art, with organic compound as carbon source, the iron lithium phosphate second particle for preparing is reunited, be difficult for pulverizing, thereby cause powder body compacted density not high, the defective that the pole piece compacted density is lower, a kind of preparation method of lithium ion battery anode material lithium iron phosphate is provided, the specific addition means that the present invention adopts inorganic carbon source and organic carbon source to combine, the LiFePO 4 material of producing have powder body compacted density and the high good characteristics of pole piece compacted density.
The present invention also adopts high molecular polymer to carry out dry grinding as additive at prior art and causes the relatively poor defective of product performance, a kind of preparation method of lithium ion battery anode material lithium iron phosphate is provided, preparation method of the present invention adopts additive and a small amount of solvent to carry out uniform mixing, dephasign is few, and product performance are better.
The present invention also prepares the defective of lithium ion battery anode material lithium iron phosphate at methods such as available technology adopting liquid phase deposition, hydrothermal method, mechanical ball milling methods, a kind of low-cost preparation method of lithium ion battery anode material lithium iron phosphate is provided, this preparation method's production cost is low, be fit to big suitability for industrialized production, processing parameter is controlled easily, the batch good stability, prepared product has good pole piece processing characteristics, conductivity and chemical property.
For realizing purpose of the present invention, the contriver provides following technical scheme:
A kind of preparation method of heavy body high compacted density LiFePO 4 material comprises that the following step poly-:
(1) with lithium source, Fe
3+Source, phosphoric acid salt, doping agent and organic carbon source carry out proportioning, obtain mixed slurry behind the wet ball grinding 2-5h, and mixed slurry obtains the powder of spraying through mist projection granulating then, and wherein, the mol ratio of Li:Fe:P is 1:(0.95 ~ 1.0): 1; The add-on of described organic carbon source is Fe
3+16 ~ 20% of source quality,
(2) powder of will spraying is a heat treated in 10 ~ 30 liters/minute the protective atmosphere at vacuum condition or at flow velocity, and temperature rise rate is 2 ~ 5 ℃/minute, and thermal treatment temp is 400 ~ 500 ℃; pre-burning 2 ~ 5h under the constant temperature; drop to room temperature with 1 ~ 3 ℃/minute speed then, obtain the pre-burning product
(3) with pre-burning product and inorganic carbon source mixed sand mill 1 ~ 3h, spray-dried again, obtain secondary spraying powder,
(4) secondary is sprayed powder is a heat treated in 10 ~ 30 liters/minute the protective atmosphere at vacuum condition or at flow velocity, temperature rise rate is 2 ~ 5 ℃/minute, thermal treatment temp is 650 ~ 800 ℃, and sintering 4 ~ 7h under the constant temperature drops to room temperature with 2 ~ 5 ℃/minute speed then;
(5) with the work in-process behind the above-mentioned sintering by after secondary ball milling or the airflow milling, obtain the iron lithium phosphate product.
The ferric iron source that the present invention proposes to use special stipulation specific surface area and particular size to require is raw material, the advantage and the strong characteristics of inorganic superfine graphite carbon dust electric conductivity that adopt organic carbon original position carbon to coat, adopt secondary spraying agglomerating technology, prepare the iron lithium phosphate product of high powder body compacted density, high pole piece compacted density and heavy body.
The sintering whole process of step among the present invention (2) and step (4) is all carried out under inert atmosphere or under the vacuum condition; any can all can use in the Equipment for Heating Processing of even heating under the atmosphere protection in sintering process is as vacuum oven, box-type furnace, continuous tunnel furnace, rotary atmosphere furnace, bell jar stove, tube furnace, shuttle-type stove or pushed bat kiln etc.Protective atmosphere in described step (2) or (4) is one or more in nitrogen atmosphere, argon gas atmosphere and the hydrogen atmosphere.
As preferred version, according to the preparation method of heavy body high compacted density LiFePO 4 material of the present invention, wherein, the lithium source in the described step (1) is one or both in Quilonum Retard or the monohydrate lithium hydroxide; Dispersion agent in the wet ball grinding is a deionized water.Wherein, monohydrate lithium hydroxide is the preferred lithium source.
As preferred version, according to the preparation method of heavy body high compacted density LiFePO 4 material of the present invention, wherein, the Fe in the described step (1)
3+The source is one or both in ferric oxide or the hydrous iron oxide.Wherein, hydrous iron oxide is preferred source of iron.
As preferred version, according to the preparation method of heavy body high compacted density LiFePO 4 material of the present invention, wherein, the specific surface area of described ferric oxide needs greater than 6m
2/ g and particulate primary particle size are less than 100nm; The specific surface area of described hydrous iron oxide needs greater than 40m
2/ g and particulate primary particle size are less than 100nm.
As preferred version, according to the preparation method of heavy body high compacted density LiFePO 4 material of the present invention, wherein, the organic carbon source in the described step (1) is one or both in sucrose or the glucose.
As preferred version, according to the preparation method of heavy body high compacted density LiFePO 4 material of the present invention, wherein, in the described step (1): the solid content in the wet ball grinding is 20 ~ 50wt%, behind the ball milling 2-5h, the particle diameter of mixed slurry is D50=200 ~ 600nm; Adopt centrifugal spray dryer in the mist projection granulating, its inlet temperature is 180 ~ 260 ℃, and temperature out is 90 ~ 110 ℃.
As preferred version, according to the preparation method of heavy body high compacted density LiFePO 4 material of the present invention, wherein, the inorganic carbon source in the described step (3) is that specific surface area is 400 ~ 1000m
2The hyperfine carbon dust 1 of/g and specific surface area are 60 ~ 120m
2The mixing carbon dust of the hyperfine carbon dust 2 of/g, wherein, the part by weight of described hyperfine carbon dust 1 in mixing carbon dust is 20 ~ 40%, the weight of described inorganic carbon source is 2 ~ 6% of pre-burning product weight.
As preferred version, preparation method according to heavy body high compacted density LiFePO 4 material of the present invention, wherein, in the described step (3): dispersion agent is the mixed solvent of deionized water and dehydrated alcohol in the mixing sand milling, wherein, the part by weight of dehydrated alcohol in mixed solvent is 1 ~ 10%, behind wet ball grinding 1 ~ 3h, the compound particle diameter is D50=100 ~ 300nm, and the solid content in the wet ball grinding is 20 ~ 40wt%; Adopt centrifugal spray dryer in the spraying drying, its temperature in is 290 ~ 320 ℃, and temperature out is 110 ~ 120 ℃.
As preferred version, preparation method according to heavy body high compacted density LiFePO 4 material of the present invention, wherein, doping agent in the described step (1) is a kind of in titanium dioxide, magnesium hydroxide, Niobium Pentxoxide or the manganese acetate, the dopant metal ion carries out the iron position and mixes in iron lithium phosphate, the quality of doping agent is with respect to Fe
3+The summation of the quality of source and doping agent, its ratio is no more than 3%.
The product that the present invention also provides the preparation method of heavy body high compacted density LiFePO 4 material recited above to obtain, described product are iron lithium phosphate, and this iron lithium phosphate is LiFe
1-xM
xPO
4/ C matrix material, promptly described iron lithium phosphate is the composite particulate material of lithium iron phosphate and carbon coating layer, composite particulate material is elliposoidal, wherein M=Mg, Ti, Mn or Nb metal, 0≤x≤0.02; The particle diameter of matrix material is D50=1-4 μ m, and specific surface area is 11-25m
2/ g, powder body compacted density are 2.3-2.5g/cm
3This LiFe
1-xM
xPO
4/ C matrix material comprises the composition of following mass percent: C:2 ~ 6%, and all the other are LiFe
1-xM
xPO
4According to this area universal method, utilize the compacted density of the electrode plates of this Composite Preparation can reach 2.2-2.4g/cm
3, experiment shows that matrix material of the present invention can be assembled into the higher battery of heavy body, high magnification and voltage platform.
Compared with prior art, the present invention has the following advantages:
(1), to adopt the stable ferric iron of cheap chemical property be source of iron in the present invention, reduced production cost; Solved that the easy oxidation of ferrous salt causes the impure problem of product and the ferrous iron tap density is not high, powder body compacted density and the not high shortcoming of electrode plates compacted density.
(2), to propose first with the hydrous iron oxide be that source of iron prepares iron lithium phosphate in the present invention, and adopt three oxygen two of special stipulation specific surface area and size to change iron and hydrous iron oxide, having overcome is the not high defective of LiFePO 4 material loading capacity of source of iron preparation with the ferric oxide both at home and abroad, and can reach divalence source of iron and tertiary iron phosphate is the iron lithium phosphate discharge gram volume of source of iron preparation.
(3), the present invention adopts the secondary spray art, not only having overcome ferric iron adopts the organic carbon source product particle of once spraying behind the sintering big, powder body compacted density and the not high shortcoming of pole piece compacted density, and what is more important is by the spraying of inorganic carbon secondary, increase carbon and coat homogeneity, simultaneously pre-imitation frosted glass particulate granularity can be become evenly tiny, help the material reaction evenly, shorten secondary high temperature sintering reaction required time, and utilize the high characteristics of this graphitized carbon specific conductivity of inorganic carbon, conductive carbon between the enhanced granule connects, stable performance.
(4), the present invention is by the secondary spray art, the powder of directly will spray dress burns, and has avoided CN101597048A and U.S. Valence patent that the powder of spraying is carried out the loaded down with trivial details technical process that briquetting refills burning, enhances productivity.
(5), the processing parameter that adopts of the preparation method of lithium ion battery anode material lithium iron phosphate of the present invention controls easily, technology stability is good, and is with low cost, realizes easily producing in enormous quantities.
(6), the lithium ion battery anode material lithium iron phosphate of preparation method's preparation of the present invention has purposes widely, adopt the lithium ion battery security energy of this positive electrode material preparation good, cost is low, can be used for fields such as electric bicycle, battery-operated motor cycle, electromobile, mine lamp, scooter, notebook computer, power tool and some unconventional removable power supplys.
Description of drawings
Fig. 1 is the X-ray diffracting spectrum of the prepared lithium ion battery anode material lithium iron phosphate of embodiment 1.
Fig. 2 is embodiment 1 prepared material is tested gained on the laser particle size distribution instrument a particle size distribution figure.
Fig. 3 is the simulation button cell of the prepared lithium ion battery anode material lithium iron phosphate of embodiment 1, in voltage is the 2.5-4.15V scope, and when envrionment temperature is 23 ± 2 ℃, discharge curve under the different charge-discharge magnifications.
Fig. 4 is the SEM figure of the prepared lithium ion battery anode material lithium iron phosphate of embodiment 3.
Fig. 5 is the simulation button cell of the prepared lithium ion battery anode material lithium iron phosphate of embodiment 3, is 23 ± 2 ℃ at probe temperature, when voltage range is 2.5-4.15V, discharge curve under the different charge-discharge magnifications, charge-discharge magnification is respectively 0.2C, 1C, 2C, 3C.
Fig. 6 is the prepared prepared 2Ah liquid flexible packed lithium battery of lithium ion battery anode material lithium iron phosphate of embodiment 3, is 23 ± 2 ℃ at probe temperature, when voltage range is 2.0-3.65V, and the high rate performance figure under the different multiplying discharging condition.
Fig. 7 is that the 1C of the prepared 10Ah liquid flexible packed lithium battery of the prepared lithium ion battery anode material lithium iron phosphate of embodiment 4 charges and discharge cycle performance figure, and voltage range is 23 ± 2 ℃ for the 2.0-3.65V probe temperature.
Embodiment
Below in conjunction with embodiment, be described more specifically content of the present invention.Should be appreciated that enforcement of the present invention is not limited to the following examples, all will fall into protection domain of the present invention any pro forma accommodation and/or the change that the present invention made.
In the present invention, if not refer in particular to, all equipment and raw material etc. all can be buied from market or the industry is commonly used.Method among the following embodiment if no special instructions, is the ordinary method of this area.
Embodiment 1:
With 3080 gram monohydrate lithium hydroxides, 6209 gram hydrous iron oxide (specific surface area 100m
2/ g and particulate primary particle size are less than 100nm), 8444 gram primary ammonium phosphates, 117 gram titanium dioxide and 1046 gram sucrose mix, put into the wet method agitating ball mill, add water 30kg, add 200 kilograms of zirconia balls, ball milling mixed after 5 hours, obtained the mixed slurry that particle diameter is D50=200-600nm, then with the mixed slurry centrifugal spray dryer, in temperature in is 200 ℃, and temperature out is under 100 ℃ of conditions, obtains the powder of spraying; The powder of should spraying is put into the atmosphere protection stove, under 10 liters/minute nitrogen atmosphere, is warmed up to 400 ℃ of constant temperature 2h with 3 ℃/minute speed, drops to room temperature with 2 ℃/minute speed then, obtains the pre-burning product.With 14kg pre-burning product, 56g specific surface area is 770m
2The hyperfine carbon dust 1 of/g and 224g specific surface area are 62m
2The hyperfine carbon dust 2 of/g, put into the wet method agitating ball mill, after adding 22kg deionized water and 1kg dehydrated alcohol mixing and ball milling 1h, obtain the compound that particle diameter is D50=100-300nm, then with the compound centrifugal spray dryer, in temperature in is 320 ℃, and temperature out is under 120 ℃ of conditions, obtains secondary spraying powder; The secondary powder of spraying is put into the atmosphere protection stove, under 10 liters/minute nitrogen atmosphere, be warmed up to 650 ℃ of constant temperature 7h, drop to room temperature with 2 ℃/minute speed then, obtain sintered products with 3 ℃/minute speed.With the direct stage treatment on airflow milling of sintered products, obtain evengranular iron lithium phosphate.
Record that carbon content is 2.0% in the present embodiment LiFePO 4 material, tap density is 1.41g/cm
3, specific surface area is 11.3m
2/ g, powder body compacted density are 2.46g/cm
3(1.5t/cm
2Pressure), the battery plate compacted density is 2.36g/cm
3The XRD spectra of present embodiment LiFePO 4 material is seen Fig. 1, and the reference standard card is the intact peridotites iron lithium phosphate of crystal formation, does not observe the diffraction peak of carbon, shows that carbon exists with amorphous carbon.
Record present embodiment positive electrode material size-grade distribution as shown in Figure 2.As seen from Figure 2, the iron lithium phosphate second particle of the present invention's preparation is evenly tiny, the D10=0.56 micron, and the D50=1.74 micron, the D90=4.92 micron, size-grade distribution is normal state.
Take by weighing the positive electrode material of embodiment 1 gained respectively with the mass ratio of 82:8:10: acetylene black: PVDF, make electrode after grinding evenly, negative pole is selected metal lithium sheet for use, and electrolytic solution is for being dissolved in the LiPF of the 1.0mol/L in ethyl-carbonate+carbonic acid diethyl vinegar (volume ratio 1:1) mixed solvent
6, barrier film is a polypropylene microporous film, is assembled into button cell.Fig. 3 is that above-mentioned button cell is 23 ± 2 ℃ at probe temperature, and voltage range is 2.5-4.15V, and charge-discharge magnification is the charging and discharging curve figure under 0.2C, the 1C.When 0.2C discharged, the reversible gram volume of material can reach 160mAh/g, and reversible gram volume is 144mAh/g during the 1C discharge.Thereby show the lithium ion battery anode material lithium iron phosphate gram volume height that adopts the present invention's preparation, discharge platform is stable, superior performance.
With 3080 gram monohydrate lithium hydroxides, 6394 gram hydrous iron oxide (specific surface area 100m
2/ g and particulate primary particle size are less than 100nm), 8444 gram primary ammonium phosphates, 64 gram magnesium hydroxides and 1046 gram sucrose mix, put into the wet method agitating ball mill, add water 30kg, add 200 kilograms of zirconia balls, ball milling mixed after 2 hours, obtained the mixed slurry that particle diameter is D50=200-600nm, then with the mixed slurry centrifugal spray dryer, in temperature in is 230 ℃, and temperature out is under 100 ℃ of conditions, obtains the powder of spraying; The powder of should spraying is put into the atmosphere protection stove, under 10 liters/minute nitrogen atmosphere, is warmed up to 400 ℃ of constant temperature 4h with 5 ℃/minute speed, drops to room temperature with 3 ℃/minute speed then, obtains the pre-burning product.With 14kg pre-burning product, 252g specific surface area is 770m
2The hyperfine carbon dust 1 of/g and 588g specific surface area are 62m
2The hyperfine carbon dust 2 of/g, put into the wet method agitating ball mill, after adding 22kg deionized water and 2.4kg dehydrated alcohol mixing and ball milling 3h, obtain the compound that particle diameter is D50=100-300nm, then with the compound centrifugal spray dryer, in temperature in is 290 ℃, and temperature out is under 110 ℃ of conditions, obtains secondary spraying powder; The secondary powder of spraying is put into the atmosphere protection stove, under 30 liters/minute nitrogen atmosphere, be warmed up to 750 ℃ of constant temperature 5h, drop to room temperature with 3 ℃/minute speed then, obtain sintered products with 3 ℃/minute speed.With the direct stage treatment on airflow milling of sintered products, obtain evengranular iron lithium phosphate.
Record that carbon content is 6.0% in the present embodiment LiFePO 4 material, tap density is 1.19g/cm
3, specific surface area is 16.8m
2/ g, powder body compacted density are 2.30g/cm
3(1.5t/cm
2Pressure), the battery plate compacted density is 2.25g/cm
3Adopting the button cell of the lithium iron phosphate positive material assembling of present embodiment preparation is 23 ± 2 ℃ at probe temperature, and when voltage range was 2.5-4.15V, the reversible gram volume of material reached 165mAh/g during the 0.2C discharge, and reversible gram volume is 149mAh/g during the 1C discharge.
With 3080 gram monohydrate lithium hydroxides, 5746 gram ferric oxide (specific surface area 10m
2/ g and particulate primary particle size are less than 100nm), 8444 gram primary ammonium phosphates, 97.6 gram Niobium Pentxoxides and 1060 gram sucrose mix, put into the wet method agitating ball mill, add water 30kg, add 200 kilograms of zirconia balls, ball milling mixed after 2 hours, obtained the mixed slurry that particle diameter is D50=200-600nm, then with the mixed slurry centrifugal spray dryer, in temperature in is 220 ℃, and temperature out is under 95 ℃ of conditions, obtains the powder of spraying; The powder of should spraying is put into the atmosphere protection stove, under 20 liters/minute nitrogen atmosphere, is warmed up to 400 ℃ of constant temperature 2h with 3 ℃/minute speed, drops to room temperature with 2 ℃/minute speed then, obtains the pre-burning product.With 14kg pre-burning product, 54.6g specific surface area is 770m
2The hyperfine carbon dust 1 of/g and 218.4g specific surface area are 62m
2The hyperfine carbon dust 2 of/g, put into the wet method agitating ball mill, after adding 22kg deionized water and 1.8kg dehydrated alcohol mixing and ball milling 2h, obtain the compound that particle diameter is D50=100-300nm, then with the compound centrifugal spray dryer, in temperature in is 300 ℃, and temperature out is under 120 ℃ of conditions, obtains secondary spraying powder; The secondary powder of spraying is put into the atmosphere protection stove, under 15 liters/minute nitrogen atmosphere, be warmed up to 700 ℃ of constant temperature 6h, drop to room temperature with 2 ℃/minute speed then, obtain sintered products with 3 ℃/minute speed.With the direct stage treatment on airflow milling of sintered products, obtain evengranular iron lithium phosphate.
Record that carbon content is 3.8% in the present embodiment LiFePO 4 material, tap density is 1.25g/cm
3, specific surface area is 14.9m
2/ g, powder body compacted density are 2.35g/cm
3(1.5t/cm
2Pressure), the battery plate compacted density is 2.33g/cm
3The iron lithium phosphate product sem photograph that Fig. 4 makes for present embodiment, carbon is coated on the iron lithium phosphate surface very uniformly as can be seen from Figure 4, and the iron lithium phosphate particle is linked together.Fig. 5 is the charging and discharging curve figure of iron lithium phosphate button cell under different charge-discharge magnifications of present embodiment, and the condition that wherein discharges and recharges is that voltage range is 2.5-4.15V, and charge-discharge magnification is respectively 0.2C, 1C, 2C, 3C, and probe temperature is 23 ± 2 ℃; When 0.2C discharged, the reversible gram volume of material can reach 151mAh/g, and reversible gram volume is 140mAh/g during the 1C discharge, and reversible gram volume is 132mAh/g during the 2C discharge, and reversible gram volume is 127mAh/g during the 3C discharge.Fig. 6 is the discharge curve of 2Ah flexible-packed battery under the different multiplying condition of present embodiment iron lithium phosphate product, and wherein charging and discharging voltage is 2.0-3.65V by scope, and probe temperature is 23 ± 2 ℃, and the single face area density is 150g/m
2, the pole piece compacted density is 2.33g/cm
3, the multiplying power discharging curve under the different charge-discharge magnifications (all the other all are the 1C chargings for 0.2C/0.2C, 0.5C/0.5C).This 2Ah liquid flexible packed lithium battery platform voltage is higher as can be seen from Figure 6, and threshold voltage is 3.22V among the 1C, and threshold voltage is 2.83V among the 10C, and multiplying power discharging property and good, and the 10C capacity is 92.1% of a 0.2C capacity.Thereby show that the lithium ion battery anode material lithium iron phosphate that adopts preparation of the present invention can be assembled into the higher battery of heavy body, high magnification and voltage platform.
Embodiment 4
With 3694 gram Quilonum Retards, 7900 gram ferric oxide (specific surface area 10m
2/ g and particulate primary particle size are less than 100nm), 11498 gram primary ammonium phosphates, 245 gram four hydration manganese acetates and 1580 gram glucose mix, put into the wet method agitating ball mill, add water 30kg, add 200 kilograms of zirconia balls, ball milling mixed after 2 hours, obtained the mixed slurry that particle diameter is D50=200-600nm, then with the mixed slurry centrifugal spray dryer, in temperature in is 250 ℃, and temperature out is under 110 ℃ of conditions, obtains the powder of spraying; The powder of should spraying is put into the atmosphere protection stove, under 10 liters/minute nitrogen atmosphere, is warmed up to 500 ℃ of constant temperature 2h with 3 ℃/minute speed, drops to room temperature with 2 ℃/minute speed then, obtains the pre-burning product.With 14kg pre-burning product, 306g specific surface area is 770m
2The hyperfine carbon dust 1 of/g and 459g specific surface area are 62m
2The hyperfine carbon dust 2 of/g, put into the wet method agitating ball mill, after adding 22kg deionized water and 2kg dehydrated alcohol mixing and ball milling 3h, obtain the compound that particle diameter is D50=100-300nm, then with the compound centrifugal spray dryer, in temperature in is 320 ℃, and temperature out is under 120 ℃ of conditions, obtains secondary spraying powder; The secondary powder of spraying is put into the atmosphere protection stove, under 10 liters/minute nitrogen atmosphere, be warmed up to 750 ℃ of constant temperature 4.5h, drop to room temperature with 2 ℃/minute speed then, obtain sintered products with 3 ℃/minute speed.With the direct stage treatment on airflow milling of sintered products, obtain evengranular iron lithium phosphate.
The carbon content that records the present embodiment LiFePO 4 material is 5.2%, and tap density is 1.23g/cm
3, specific surface area is 15.7m
2/ g, powder body compacted density are 2.38g/cm
3(1.5t/cm
2Pressure), the battery plate compacted density is 2.31g/cm
3, send lithium ion battery factory to be prepared into electrode slice the gained material and be assembled into the 10Ah flexible-packed battery.Fig. 7 is the cycle performance graphic representation that the 10Ah flexible-packed battery of present embodiment iron lithium phosphate product discharges and recharges at 1C, and wherein charging and discharging voltage is 2.0-3.65V by scope, and probe temperature is 23 ± 2 ℃, and the single face area density is 130g/m
2, the pole piece compacted density is 2.31g/cm
3The result of Fig. 7 shows, adopts the 10Ah liquid flexible packed lithium battery of the lithium ion battery anode material lithium iron phosphate assembling of preparation method's preparation of the present invention, and cycle performance is very excellent, and it is 90% that 1C charges and discharge 2149 capability retentions.
Comparative example 1
Than embodiment 1, with 3080 gram monohydrate lithium hydroxides, 6209 gram hydrous iron oxide (specific surface area 100m
2/ g and particulate primary particle size are less than 100nm), 8444 gram primary ammonium phosphates, 117 gram titanium dioxide and 1590 gram sucrose mix, put into the wet method agitating ball mill, add water 30kg, add 200 kilograms of zirconia balls, ball milling mixed after 5 hours, used drying machine with centrifugal spray, was 200 ℃ in temperature in, temperature out is under 100 ℃ of conditions, obtains the powder of spraying; The powder of should spraying is put into the atmosphere protection stove, under 10 liters/minute nitrogen atmosphere, is warmed up to 400 ℃ of constant temperature 2h with 3 ℃/minute speed, drops to room temperature with 2 ℃/minute speed then, obtains the pre-burning product.With putting into the atmosphere protection stove after the fragmentation of pre-burning product, under 10 liters/minute nitrogen atmosphere, be warmed up to 650 ℃ of constant temperature 7h with 3 ℃/minute speed, drop to room temperature with 2 ℃/minute speed then, obtain sintered products.With the direct stage treatment on airflow milling of sintered products, obtain evengranular iron lithium phosphate.Record that carbon content is 2.0% in the material, tap density is 1.31g/cm
3, specific surface area is 15.6m
2/ g, powder body compacted density are 2.25g/cm
3(1.5t/cm
2Pressure), the battery plate compacted density is 2.21g/cm
3Button cell is 23 ± 2 ℃ at probe temperature, and when voltage range was 2.5-4.15V, during the 0.2C discharge, the reversible gram volume of material can reach 145mAh/g, and reversible gram volume is 130mAh/g during the 1C discharge.
Comparative example 2
Than embodiment 2, with 3080 gram monohydrate lithium hydroxides, 6394 gram hydrous iron oxide (specific surface area 100m
2/ g and particulate primary particle size are less than 100nm), 8444 gram primary ammonium phosphates, 64 gram magnesium hydroxides, 237g specific surface areas are 770m
2The hyperfine carbon dust 1 of/g and 948g specific surface area are 62m
2The hyperfine carbon dust 2 of/g mixes, and puts into the wet method agitating ball mill, adds water 30kg and dehydrated alcohol 3.3kg, add 200 kilograms of zirconia balls, ball milling mixed after 3 hours, used drying machine with centrifugal spray, in temperature in is 290 ℃, and temperature out is under 110 ℃ of conditions, obtains the powder of spraying; The powder of should spraying is put into the atmosphere protection stove, under 30 liters/minute nitrogen atmosphere, is warmed up to 750 ℃ of constant temperature 5h with 3 ℃/minute speed, drops to room temperature with 3 ℃/minute speed then, obtains sintered products.Record that carbon content is 6.0% in the material, tap density is 1.23g/cm
3, specific surface area is 13.8m
2/ g, powder body compacted density are 2.45g/cm
3(1.5t/cm
2Pressure), the battery plate compacted density is 2.38g/cm
3Button cell is 23 ± 2 ℃ at probe temperature, and when voltage range was 2.5-4.15V, the reversible gram volume of material reached 135mAh/g during the 0.2C discharge, and reversible gram volume is 125mAh/g during the 1C discharge.
Above preferred embodiment just is used for description and interpretation content of the present invention, does not constitute the restriction to content of the present invention.Although the contriver has done in more detail the present invention and has enumerated, but, the content that those skilled in the art is disclosed according to summary of the invention part and embodiment, can make various modifications or/and to replenish or adopt similar mode to substitute be obvious to described specific embodiment, and can realize technique effect of the present invention, therefore, give unnecessary details no longer one by one herein.The term that occurs among the present invention is used for the elaboration of technical solution of the present invention and understanding are not construed as limiting the invention.
Claims (10)
1. the preparation method of a heavy body high compacted density LiFePO 4 material is characterized in that, described preparation method comprises that the following step poly-:
(1) with lithium source, Fe
3+Source, phosphoric acid salt, doping agent and organic carbon source carry out proportioning, obtain mixed slurry behind the wet ball grinding 2-5h, and mixed slurry obtains the powder of spraying through mist projection granulating then, and wherein, the mol ratio of Li:Fe:P is 1:(0.95 ~ 1.0): 1; The add-on of described organic carbon source is Fe
3+16 ~ 20% of source quality,
(2) powder of will spraying is a heat treated in 10 ~ 30 liters/minute the protective atmosphere at vacuum condition or at flow velocity, and temperature rise rate is 2 ~ 5 ℃/minute, and thermal treatment temp is 400 ~ 500 ℃; pre-burning 2 ~ 5h under the constant temperature; drop to room temperature with 1 ~ 3 ℃/minute speed then, obtain the pre-burning product
(3) with pre-burning product and inorganic carbon source mixed sand mill 1 ~ 3h, spray-dried again, obtain secondary spraying powder,
(4) secondary is sprayed powder is a heat treated in 10 ~ 30 liters/minute the protective atmosphere at vacuum condition or at flow velocity, temperature rise rate is 2 ~ 5 ℃/minute, thermal treatment temp is 650 ~ 800 ℃, and sintering 4 ~ 7h under the constant temperature drops to room temperature with 2 ~ 5 ℃/minute speed then;
(5) with the work in-process behind the above-mentioned sintering by after secondary ball milling or the airflow milling, obtain the iron lithium phosphate product.
2. the preparation method of heavy body high compacted density LiFePO 4 material according to claim 1 is characterized in that, the lithium source in the described step (1) is one or both in Quilonum Retard or the monohydrate lithium hydroxide; Dispersion agent in the wet ball grinding is a deionized water.
3. the preparation method of heavy body high compacted density LiFePO 4 material according to claim 1 is characterized in that, the Fe in the described step (1)
3+The source is one or both in ferric oxide or the hydrous iron oxide.
4. the preparation method of heavy body high compacted density LiFePO 4 material according to claim 3 is characterized in that, the specific surface area of described ferric oxide needs greater than 6m
2/ g and particulate primary particle size are less than 100nm; The specific surface area of described hydrous iron oxide needs greater than 40m
2/ g and particulate primary particle size are less than 100nm.
5. the preparation method of heavy body high compacted density LiFePO 4 material according to claim 1 is characterized in that, the organic carbon source in the described step (1) is one or both in sucrose or the glucose.
6. the preparation method of heavy body high compacted density LiFePO 4 material according to claim 1, it is characterized in that, in the described step (1): the solid content in the wet ball grinding is 20 ~ 50wt%, and behind the ball milling 2-5h, the particle diameter of mixed slurry is D50=200 ~ 600nm; Adopt centrifugal spray dryer in the mist projection granulating, its inlet temperature is 180 ~ 260 ℃, and temperature out is 90 ~ 110 ℃.
7. the preparation method of heavy body high compacted density LiFePO 4 material according to claim 1 is characterized in that, the inorganic carbon source in the described step (3) is that specific surface area is 400 ~ 1000m
2The hyperfine carbon dust 1 of/g and specific surface area are 60 ~ 120m
2The mixing carbon dust of the hyperfine carbon dust 2 of/g, wherein, the part by weight of described hyperfine carbon dust 1 in mixing carbon dust is 20 ~ 40%, the weight of described inorganic carbon source is 2 ~ 6% of pre-burning product weight.
8. the preparation method of heavy body high compacted density LiFePO 4 material according to claim 1, it is characterized in that, in the described step (3): dispersion agent is the mixed solvent of deionized water and dehydrated alcohol in the mixing sand milling, wherein, the part by weight of dehydrated alcohol in mixed solvent is 1 ~ 10%, behind wet ball grinding 1 ~ 3h, the compound particle diameter is D50=100 ~ 300nm, and the solid content in the wet ball grinding is 20 ~ 40wt%; Adopt centrifugal spray dryer in the spraying drying, its temperature in is 290 ~ 320 ℃, and temperature out is 110 ~ 120 ℃.
9. the preparation method of heavy body high compacted density LiFePO 4 material according to claim 1, it is characterized in that, doping agent in the described step (1) is a kind of in titanium dioxide, magnesium hydroxide, Niobium Pentxoxide or the manganese acetate, and the quality of doping agent is with respect to Fe
3+The summation of the quality of source and doping agent, its ratio is no more than 3%.
10. a product that is obtained by the preparation method of the arbitrary described heavy body high compacted density LiFePO 4 material of claim 1-9 is characterized in that described product is an iron lithium phosphate, and this iron lithium phosphate is LiFe
1-xM
xPO
4/ C matrix material, wherein M=Mg, Ti, Mn or Nb metal, 0≤x≤0.02; The particle diameter of matrix material is D50=1-4 μ m, and specific surface area is 11-25m
2/ g, powder body compacted density are 2.3-2.5g/cm
3This LiFe
1-xM
xPO
4/ C matrix material comprises the composition of following mass percent: C:2 ~ 6%, and all the other are LiFe
1-xM
xPO
4
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100090201A CN102275887A (en) | 2011-01-17 | 2011-01-17 | Preparation method of high capacity high compacted density lithium iron phosphate material and product thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100090201A CN102275887A (en) | 2011-01-17 | 2011-01-17 | Preparation method of high capacity high compacted density lithium iron phosphate material and product thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102275887A true CN102275887A (en) | 2011-12-14 |
Family
ID=45101691
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100090201A Pending CN102275887A (en) | 2011-01-17 | 2011-01-17 | Preparation method of high capacity high compacted density lithium iron phosphate material and product thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102275887A (en) |
Cited By (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102623701A (en) * | 2012-01-13 | 2012-08-01 | 厦门钨业股份有限公司 | Preparation method for low-temperature nanometer lithium iron phosphate cathode material |
| CN102820470A (en) * | 2012-07-20 | 2012-12-12 | 合肥国轩高科动力能源有限公司 | Method for controllably synthesizing lithium iron phosphate as positive electrode material of lithium ion battery |
| CN102969502A (en) * | 2012-11-26 | 2013-03-13 | 厦门钨业股份有限公司 | Preparation method of high-vibration-compaction low-specific-surface-area lithium iron phosphate made by positive pole material |
| CN103022476A (en) * | 2012-12-24 | 2013-04-03 | 湖南长远锂科有限公司 | Preparation method of high-nickel-content anode material for lithium ion battery |
| CN104282887A (en) * | 2014-10-14 | 2015-01-14 | 江苏华东锂电技术研究院有限公司 | Carbon coating method for electrode active material of lithium ion battery |
| CN104319380A (en) * | 2014-11-13 | 2015-01-28 | 四川浩普瑞新能源材料有限公司 | Composite LiFePO4/C cathode material for lithium ion battery and preparation method for composite LiFePO4/C cathode material |
| CN104858020A (en) * | 2015-05-27 | 2015-08-26 | 李朝林 | Vacuum ball milling method for improving compaction density of lithium iron phosphate material |
| CN105261738A (en) * | 2015-10-20 | 2016-01-20 | 四川科能锂电有限公司 | Preparation method of lithium iron phosphate |
| CN105253870A (en) * | 2015-10-20 | 2016-01-20 | 四川科能锂电有限公司 | Production process of lithium iron phosphate |
| CN105336929A (en) * | 2015-10-15 | 2016-02-17 | 福建师范大学 | Method for preparing spherical carbon-coated lithium iron phosphate positive electrode material through atomization method |
| CN105449201A (en) * | 2015-01-28 | 2016-03-30 | 万向A一二三系统有限公司 | Preparation method of power-type high-tap density lithium iron phosphate composite material |
| CN105609764A (en) * | 2015-12-24 | 2016-05-25 | 郑春燕 | High-stability rare earth-lithium iron phosphate composite electrode material |
| CN105870420A (en) * | 2016-05-27 | 2016-08-17 | 天津巴莫科技股份有限公司 | Lithium-manganese-phosphate anode material for lithium-ion power battery and preparing method thereof |
| CN106207170A (en) * | 2016-08-15 | 2016-12-07 | 海宁永欣科技咨询有限公司 | A kind of production technology of nanometer lithium iron phosphate cathode material |
| TWI570245B (en) * | 2015-11-19 | 2017-02-11 | Taiwan Powder Technologies Co Ltd | A method for preparing a porous spherical iron-based alloy powder by a reduction reaction, the powder and the powder are prepared Sintered body |
| CN106450289A (en) * | 2016-08-17 | 2017-02-22 | 中信大锰矿业有限责任公司大新锰矿分公司 | High-voltage lithium cobalt oxide positive electrode material and preparation method therefor |
| CN106785058A (en) * | 2016-12-07 | 2017-05-31 | 深圳市朗泰沣电子有限公司 | A kind of preparation method of high-energy-density long-life ferric phosphate lithium cell |
| CN106744780A (en) * | 2017-03-22 | 2017-05-31 | 广东光华科技股份有限公司 | A kind of preparation method of high-pressure solid lithium ion battery anode material lithium iron phosphate |
| CN107572495A (en) * | 2017-09-10 | 2018-01-12 | 绵阳梨坪科技有限公司 | The technique that a kind of homogeneous grain diameter combination mechanical alloying prepares LiFePO4 |
| CN108963199A (en) * | 2017-05-19 | 2018-12-07 | 株式会社东芝 | Electrode for secondary battery, secondary cell, battery pack and vehicle |
| CN109650366A (en) * | 2018-11-22 | 2019-04-19 | 湖北融通高科先进材料有限公司 | A kind of LiFePO4 and preparation method thereof |
| CN109755518A (en) * | 2018-12-29 | 2019-05-14 | 浙江南都电源动力股份有限公司 | The preparation method of carbon-coated LiFePO 4 for lithium ion batteries material |
| CN111392705A (en) * | 2020-02-25 | 2020-07-10 | 东莞东阳光科研发有限公司 | Preparation method of high-compaction lithium iron phosphate |
| CN112768688A (en) * | 2019-11-05 | 2021-05-07 | 贝特瑞（天津）纳米材料制造有限公司 | Lithium iron phosphate material, preparation method thereof and lithium ion battery |
| WO2021248181A1 (en) * | 2020-06-09 | 2021-12-16 | VSPC Ltd | Method for making lithium metal phosphates |
| CN114335478A (en) * | 2021-12-31 | 2022-04-12 | 四川大学 | Magnesium-doped lithium iron phosphate/carbon composite microsphere with high tap density as well as preparation method and application thereof |
| CN115196612A (en) * | 2022-09-01 | 2022-10-18 | 中国长江三峡集团有限公司 | Lithium iron phosphate anode material, preparation method thereof and lithium ion battery anode plate |
| CN115231543A (en) * | 2022-08-02 | 2022-10-25 | 湖北融通高科先进材料有限公司 | Preparation method of multi-carbon-coated high-compaction lithium iron manganese phosphate |
| CN116354326A (en) * | 2023-02-28 | 2023-06-30 | 中南大学 | A kind of preparation method of lithium iron phosphate lithium ion battery cathode material |
| CN117550578A (en) * | 2023-11-15 | 2024-02-13 | 银贮(宁波)科技有限公司 | Spherical lithium iron phosphate and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1648036A (en) * | 2004-12-17 | 2005-08-03 | 清华大学 | A kind of preparation method of LiFePO4 spherical powder |
| CN101190785A (en) * | 2006-11-24 | 2008-06-04 | 横店集团东磁股份有限公司 | Preparation method and product of lithium iron phosphate cathode material for lithium ion battery |
| CN101200289A (en) * | 2006-12-15 | 2008-06-18 | 中国电子科技集团公司第十八研究所 | Lithium ferric phosphate material and method for making same |
| CN101339995A (en) * | 2008-08-12 | 2009-01-07 | 中国兵器工业第二一三研究所 | Preparation of lithium iron phosphate positive electrode material for lithium ion power cell |
-
2011
- 2011-01-17 CN CN2011100090201A patent/CN102275887A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1648036A (en) * | 2004-12-17 | 2005-08-03 | 清华大学 | A kind of preparation method of LiFePO4 spherical powder |
| CN101190785A (en) * | 2006-11-24 | 2008-06-04 | 横店集团东磁股份有限公司 | Preparation method and product of lithium iron phosphate cathode material for lithium ion battery |
| CN101200289A (en) * | 2006-12-15 | 2008-06-18 | 中国电子科技集团公司第十八研究所 | Lithium ferric phosphate material and method for making same |
| CN101339995A (en) * | 2008-08-12 | 2009-01-07 | 中国兵器工业第二一三研究所 | Preparation of lithium iron phosphate positive electrode material for lithium ion power cell |
Cited By (41)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102623701A (en) * | 2012-01-13 | 2012-08-01 | 厦门钨业股份有限公司 | Preparation method for low-temperature nanometer lithium iron phosphate cathode material |
| CN102623701B (en) * | 2012-01-13 | 2014-08-06 | 厦门钨业股份有限公司 | Preparation method for low-temperature nanometer lithium iron phosphate cathode material |
| CN102820470A (en) * | 2012-07-20 | 2012-12-12 | 合肥国轩高科动力能源有限公司 | Method for controllably synthesizing lithium iron phosphate as positive electrode material of lithium ion battery |
| CN102969502B (en) * | 2012-11-26 | 2015-04-08 | 厦门钨业股份有限公司 | Preparation method of high-vibration-compaction low-specific-surface-area lithium iron phosphate made by positive pole material |
| CN102969502A (en) * | 2012-11-26 | 2013-03-13 | 厦门钨业股份有限公司 | Preparation method of high-vibration-compaction low-specific-surface-area lithium iron phosphate made by positive pole material |
| CN103022476B (en) * | 2012-12-24 | 2015-09-09 | 湖南长远锂科有限公司 | A kind of preparation method of high nickel content anode material for lithium-ion batteries |
| CN103022476A (en) * | 2012-12-24 | 2013-04-03 | 湖南长远锂科有限公司 | Preparation method of high-nickel-content anode material for lithium ion battery |
| CN104282887A (en) * | 2014-10-14 | 2015-01-14 | 江苏华东锂电技术研究院有限公司 | Carbon coating method for electrode active material of lithium ion battery |
| CN104319380A (en) * | 2014-11-13 | 2015-01-28 | 四川浩普瑞新能源材料有限公司 | Composite LiFePO4/C cathode material for lithium ion battery and preparation method for composite LiFePO4/C cathode material |
| CN104319380B (en) * | 2014-11-13 | 2016-07-20 | 四川浩普瑞新能源材料有限公司 | A kind of lithium ion battery LiFePO4/ C composite positive pole and preparation method thereof |
| CN105449201B (en) * | 2015-01-28 | 2018-06-22 | 万向一二三股份公司 | A kind of preparation method of power-type high vibration high density lithium iron phosphate composite material |
| CN105449201A (en) * | 2015-01-28 | 2016-03-30 | 万向A一二三系统有限公司 | Preparation method of power-type high-tap density lithium iron phosphate composite material |
| CN104858020A (en) * | 2015-05-27 | 2015-08-26 | 李朝林 | Vacuum ball milling method for improving compaction density of lithium iron phosphate material |
| CN104858020B (en) * | 2015-05-27 | 2018-01-12 | 东莞理工学院 | A kind of vacuum ball grinding method for improving LiFePO 4 material compacted density |
| CN105336929A (en) * | 2015-10-15 | 2016-02-17 | 福建师范大学 | Method for preparing spherical carbon-coated lithium iron phosphate positive electrode material through atomization method |
| CN105336929B (en) * | 2015-10-15 | 2017-11-10 | 福建师范大学 | A kind of method that atomization prepares spherical carbon-coated LiFePO 4 for lithium ion batteries positive electrode |
| CN105253870A (en) * | 2015-10-20 | 2016-01-20 | 四川科能锂电有限公司 | Production process of lithium iron phosphate |
| CN105261738A (en) * | 2015-10-20 | 2016-01-20 | 四川科能锂电有限公司 | Preparation method of lithium iron phosphate |
| TWI570245B (en) * | 2015-11-19 | 2017-02-11 | Taiwan Powder Technologies Co Ltd | A method for preparing a porous spherical iron-based alloy powder by a reduction reaction, the powder and the powder are prepared Sintered body |
| CN105609764A (en) * | 2015-12-24 | 2016-05-25 | 郑春燕 | High-stability rare earth-lithium iron phosphate composite electrode material |
| CN105870420A (en) * | 2016-05-27 | 2016-08-17 | 天津巴莫科技股份有限公司 | Lithium-manganese-phosphate anode material for lithium-ion power battery and preparing method thereof |
| CN105870420B (en) * | 2016-05-27 | 2018-06-19 | 天津巴莫科技股份有限公司 | A kind of lithium-ion-power cell manganese-lithium phosphate anode material and preparation method thereof |
| CN106207170A (en) * | 2016-08-15 | 2016-12-07 | 海宁永欣科技咨询有限公司 | A kind of production technology of nanometer lithium iron phosphate cathode material |
| CN106207170B (en) * | 2016-08-15 | 2018-11-02 | 武汉联德化学品有限公司 | A kind of production technology of nanometer lithium iron phosphate cathode material |
| CN106450289A (en) * | 2016-08-17 | 2017-02-22 | 中信大锰矿业有限责任公司大新锰矿分公司 | High-voltage lithium cobalt oxide positive electrode material and preparation method therefor |
| CN106785058A (en) * | 2016-12-07 | 2017-05-31 | 深圳市朗泰沣电子有限公司 | A kind of preparation method of high-energy-density long-life ferric phosphate lithium cell |
| CN106744780A (en) * | 2017-03-22 | 2017-05-31 | 广东光华科技股份有限公司 | A kind of preparation method of high-pressure solid lithium ion battery anode material lithium iron phosphate |
| CN108963199A (en) * | 2017-05-19 | 2018-12-07 | 株式会社东芝 | Electrode for secondary battery, secondary cell, battery pack and vehicle |
| CN107572495A (en) * | 2017-09-10 | 2018-01-12 | 绵阳梨坪科技有限公司 | The technique that a kind of homogeneous grain diameter combination mechanical alloying prepares LiFePO4 |
| CN109650366A (en) * | 2018-11-22 | 2019-04-19 | 湖北融通高科先进材料有限公司 | A kind of LiFePO4 and preparation method thereof |
| CN109755518A (en) * | 2018-12-29 | 2019-05-14 | 浙江南都电源动力股份有限公司 | The preparation method of carbon-coated LiFePO 4 for lithium ion batteries material |
| CN112768688A (en) * | 2019-11-05 | 2021-05-07 | 贝特瑞（天津）纳米材料制造有限公司 | Lithium iron phosphate material, preparation method thereof and lithium ion battery |
| CN111392705A (en) * | 2020-02-25 | 2020-07-10 | 东莞东阳光科研发有限公司 | Preparation method of high-compaction lithium iron phosphate |
| CN111392705B (en) * | 2020-02-25 | 2021-11-12 | 东莞东阳光科研发有限公司 | Preparation method of high-compaction lithium iron phosphate |
| WO2021248181A1 (en) * | 2020-06-09 | 2021-12-16 | VSPC Ltd | Method for making lithium metal phosphates |
| CN114335478A (en) * | 2021-12-31 | 2022-04-12 | 四川大学 | Magnesium-doped lithium iron phosphate/carbon composite microsphere with high tap density as well as preparation method and application thereof |
| CN115231543A (en) * | 2022-08-02 | 2022-10-25 | 湖北融通高科先进材料有限公司 | Preparation method of multi-carbon-coated high-compaction lithium iron manganese phosphate |
| CN115196612A (en) * | 2022-09-01 | 2022-10-18 | 中国长江三峡集团有限公司 | Lithium iron phosphate anode material, preparation method thereof and lithium ion battery anode plate |
| CN115196612B (en) * | 2022-09-01 | 2023-05-16 | 中国长江三峡集团有限公司 | Lithium iron phosphate positive electrode material, preparation method thereof and lithium ion battery positive electrode sheet |
| CN116354326A (en) * | 2023-02-28 | 2023-06-30 | 中南大学 | A kind of preparation method of lithium iron phosphate lithium ion battery cathode material |
| CN117550578A (en) * | 2023-11-15 | 2024-02-13 | 银贮(宁波)科技有限公司 | Spherical lithium iron phosphate and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102275887A (en) | Preparation method of high capacity high compacted density lithium iron phosphate material and product thereof | |
| CN101284681B (en) | Super-size and high-density lithium cobalt oxide and method for preparing the same | |
| CN100530780C (en) | Composite lithium titanate electrode material and preparation method thereof | |
| CN101966986B (en) | Preparation method of lithium iron phosphate cathode material for lithium ion battery | |
| CN101540394B (en) | Method for preparing lithium ferrosilicon silicate of lithium-ion battery cathode material | |
| CN100491239C (en) | Preparation method and product of lithium iron phosphate cathode material for lithium ion battery | |
| CN101630739B (en) | Preparation method of modified doping lithium ferric phosphate | |
| CN104752718B (en) | A kind of LiMnxFe1‑xPO4Positive electrode active materials and preparation method thereof | |
| CN101591012B (en) | Preparation method of lithium iron phosphate as cathode material of lithium ion battery | |
| CN111952590A (en) | Lithium ion battery positive electrode material for improving safety and cycle performance and preparation method thereof | |
| CN106410182B (en) | A kind of preparation method of high compaction density micron-scale single crystal ternary positive electrode material | |
| CN109607505A (en) | A kind of preparation method for the LiFePO4 improving cryogenic property | |
| CN109873140B (en) | Graphene composite ternary cathode material of lithium ion battery and preparation method of graphene composite ternary cathode material | |
| CN101481106A (en) | Oxygen-containing vacancy and Fe site doped lithium ferric phosphate and rapid solid-phase sintering method thereof | |
| CN102745663B (en) | Method for preparing lithium iron phosphate material | |
| CN101734637A (en) | A kind of preparation method of positive electrode material lithium vanadium phosphate powder for lithium ion battery | |
| CN101152959A (en) | Preparation method of lithium iron phosphate composite oxide | |
| CN101764226B (en) | Oxygen vacancy-contained and Fe site-doped lithium ferric phosphate and rapid solid-phase sintering method thereof | |
| KR101443359B1 (en) | Manufacturing method of nickel rich lithium-nickel-cobalt-manganese composite oxide, nickel rich lithium-nickel-cobalt-manganese composite oxide made by the same, and lithium ion batteries containing the same | |
| CN103296257A (en) | Preparation method of modified lithium titanate negative material of lithium-ion battery | |
| CN100564250C (en) | The microwave fast solid phase sintering method of lithium ion battery anode material lithium iron phosphate | |
| CN112151797A (en) | Lithium-rich manganese-based positive electrode material coated by multi-metal composite oxide and preparation method thereof | |
| CN104009234B (en) | The method of microwave method synthesis of anode material of lithium-ion battery iron manganese phosphate for lithium | |
| CN113072051A (en) | Post-treatment method of phosphate system anode material | |
| CN106602059A (en) | Preparation method of water system lithium ion battery material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20111214 |