CN102013484A - Preparation method of spherical lithium iron phosphate - Google Patents
Preparation method of spherical lithium iron phosphate Download PDFInfo
- Publication number
- CN102013484A CN102013484A CN2010105608829A CN201010560882A CN102013484A CN 102013484 A CN102013484 A CN 102013484A CN 2010105608829 A CN2010105608829 A CN 2010105608829A CN 201010560882 A CN201010560882 A CN 201010560882A CN 102013484 A CN102013484 A CN 102013484A
- Authority
- CN
- China
- Prior art keywords
- preparation
- spherical
- mixed solution
- presoma
- iron phosphate
- 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 discloses a preparation method of spherical lithium iron phosphate, relating to a preparation method of spherical lithium iron phosphate serving as an anode material of a lithium ion battery. The molecular formula of the spherical doped lithium iron phosphate/carbon compound powder is as follows: Li(1-x)MxFe(1-y)M'yPO4/C, wherein M and M' represent doped ions. The preparation method is characterized in that lithium dihydrogen orthophosphate and ferric nitrate are used as raw materials in the preparation process; the doped metal ion salts and a carbon source are added in the raw materials weighed based on a stoichiometric proportion; the raw materials are added in deionized water; the prepared mixing solution is subject to spray drying to obtain a precursor; and the precursor is ground and then calcined under the inert atmosphere or weak reducing atmosphere to obtain the spherical doped lithium iron phosphate/carbon compound powder. The method provided by the invention can be used for synthesizing the lithium iron phosphate material with an appearance like a spheroid and good electrochemical performance. The technology process is simple.
Description
Technical field
A kind of preparation method of spherical LiFePO 4 relates to a kind of lithium ion battery ball positive electrode shape method preparing phosphate iron lithium.
Background technology
Anode material for lithium-ion batteries is the important component part of lithium ion battery, and it is the key factor of fail safe, capacity and the price of decision battery.LiCoO
2Be the anode material for lithium-ion batteries of present main flow, it have be easy to synthesize, operating voltage height, charging/discharging voltage steadily, be fit to advantages such as high current charge-discharge, specific energy height, good cycle.But LiCoO
2Poor heat stability, there is safety problem in battery, and cobalt costs an arm and a leg, and inadequate resource has begun to restrict the development of lithium-ion-power cell industry.And anode material for lithium-ion batteries of new generation-olivine-type LiFePO4 is the research forward position of anode material for lithium-ion batteries in recent years, compares other positive electrode and has abundant raw material, cheap, environmentally friendly, discharging voltage balance and LiPF
6Advantages such as electrolyte coupling, high fail safe and thermal stability are for the development of high-capacity lithium-ion power battery has represented the broad space.
LiFePO4 is the earliest by propositions such as Goodenough, and it has 170mAh/g theoretical capacity and 3.5V discharge voltage, but its conduction rate variance (10
-9S/cm).LiFePO4 is carried out the electric conductivity that a large amount of study on the modification improves LiFePO4 both at home and abroad in recent years, mainly comprised modes such as control granular size and pattern, carbon coating, metal ion mixing.In order to realize the industrialization of lithium iron phosphate positive material, carbon coated and doped metal ion collaborative carries out the main direction that will be the LiFePO4 modification.
The bulk density of powder body material and the pattern of powder granule, particle diameter and distribution thereof are closely related.The LiFePO 4 powder material that random sheet or granular solid matter are formed, bulk density is low.The LiFePO 4 powder material of being made up of the spheric granules of rule will have high bulk density, and it also has excellent flowability, dispersiveness and processability, and this modulation and electrode slice that helps the anode material for lithium-ion batteries slurry applies.
At present, the preparation method of spherical doped iron lithium phosphate/charcoal composite granule mainly contains solid phase method, carbothermic method, sol-gal process, hydro thermal method and microwave method etc.Sol-gal process, hydro thermal method and microwave method are because therefore shortcoming such as cost height, technical difficulty be big realizes difficulty of industrialization.Solid phase method and carbothermic method are the more processes of present commercial application, and two kinds of methods all are earlier raw material to be mixed, then synthesizing iron lithium phosphate at high temperature.But, be difficult to obtain the high-purity positive electrode because the material granule of solid phase method and carbothermic method preparation is big and mix inhomogeneously.
Summary of the invention
Purpose of the present invention is exactly the deficiency that exists at above-mentioned prior art, providing a kind of can molecular level mix raw material, technological process is simple, and synthetic outward appearance is the class ball-type, has the preparation method of the spherical doped iron lithium phosphate/charcoal composite granule of good electrochemical.
The objective of the invention is to be achieved through the following technical solutions.
A kind of preparation method of spherical LiFePO 4, the molecular formula of its spherical doped iron lithium phosphate/charcoal composite granule is: Li
1-xM
xFe
1-yM '
yPO
4/ C, M, M ' represents dopant ion; It is characterized in that its preparation process adopts lithium dihydrogen phosphate and ferric nitrate to do raw material, take by weighing needed raw material and add doped metal ion salt and carbon source according to stoichiometric proportion, again above-mentioned raw materials is added in the deionized water, the spray-dried presoma that obtains of the mixed solution that is made into, presoma carries out the presoma calcining under inert atmosphere or weakly reducing atmosphere, calcine again after the grinding, obtain spherical doped iron lithium phosphate/charcoal composite granule.
The preparation method of a kind of spherical LiFePO 4 of the present invention is characterized in that the described process that takes by weighing raw material, according to Li
1-xM
xFe
1-yM '
yPO
4The stoichiometric proportion of/C is weighed, M, and M ' represents dopant ion, x=0-0.05 wherein, y=0-0.05; Carbon source takes by weighing according to raw material total mass ratio 5%-15%.
The preparation method of a kind of spherical LiFePO 4 of the present invention, its doped metal ion is to select among Mn, Mg, Ca, Ti, Ag, Ni, Nb, Al, Zn, the Zr one or more for use.
The preparation method of a kind of spherical LiFePO 4 of the present invention, its carbon source select in sucrose, soluble starch, glucose, fructose, polyethylene glycol, the polyvinyl alcohol one or more for use.
The preparation method of a kind of spherical LiFePO 4 of the present invention, the doped metal ion concentration that it is characterized in that the described mixed solution that is made into is 0.5mol/L-1mol/L.
The preparation method of a kind of spherical LiFePO 4 of the present invention, the inlet temperature that it is characterized in that described spray-drying process drier is 150-300 ℃, outlet temperature is 65-120 ℃, mixed solution flow velocity 5ml/min-20ml/min.
The preparation method of a kind of spherical LiFePO 4 of the present invention is characterized in that described presoma calcining is under inert atmosphere or weakly reducing atmosphere, under 300-500 ℃ of temperature, calcines 1-10 hour.
The preparation method of a kind of spherical LiFePO 4 of the present invention, it is characterized in that described calcining back presoma grinds after, be 500-1000 ℃ of temperature lower calcination 4-20 hour, obtain spherical doped iron lithium phosphate/charcoal composite granule.
Of the present invention under inert atmosphere or weakly reducing atmosphere a kind of preparation method of spherical LiFePO 4, it is characterized in that described inert atmosphere or weakly reducing atmosphere are high-purity N
2Gas or Ar-H
2(5%) mist.
The preparation method of a kind of spherical LiFePO 4 of the present invention is dissolved in all raw materials and is mixed with mixed solution in the deionized water, can guarantee that raw material mixes at molecular level, has effectively improved consistency of product; The doping that realizes metal cation and carbon source in the presoma mixed powder can guarantee to mix and cladding uniformity, improves the conductivity of LiFePO4.
Description of drawings
Fig. 1 is embodiment 2 gained presoma SEM figure;
Fig. 2 is embodiment 2 gained lithium iron phosphate/carbon composite granule SEM figure;
Fig. 3 is embodiment 2 gained lithium iron phosphate/carbon composite granule XRD figure;
Fig. 4 is embodiment 2 gained lithium iron phosphate/carbon positive electrode cycle performance figure.
Embodiment
A kind of preparation method of spherical LiFePO 4, the molecular formula of its spherical LiFePO 4 is: Li
1-xM
xFe
1-yM '
yPO
4/ C, M, M ' represents dopant ion; The measured step of its preparation process comprises suddenly:
(1) raw material is prepared: adopt lithium dihydrogen phosphate and ferric nitrate to do raw material, doped metal ion is according to Li
1-xM
xFe
1-yM '
yPO
4/ C, M, M ' represents dopant ion, x=0-0.05 wherein, y=0-0.05 takes by weighing; Carbon source takes by weighing according to raw material total mass ratio 5%-15%; Its doped metal ion is to select among Mn, Mg, Ca, Ti, Ag, Ni, Nb, Al, Zn, the Zr one or more for use; Carbon source is to select in sucrose, soluble starch, glucose, fructose, polyethylene glycol, the polyvinyl alcohol one or more for use.
(2) solution preparation: the raw material that step (1) is taken by weighing adds in the deionized water, and 0.5mol/L-1mol/L is made into mixed solution according to concentration of metal ions;
(3) spray drying: with the spray-dried presoma that obtains of the mixed solution for preparing, during spray drying the inlet temperature 150-300 of drier ℃, outlet temperature 65-120 ℃, mixed solution flow velocity 5ml/min-20ml/min obtains spherical presoma;
(4) presoma calcining: spherical presoma is calcined under inert atmosphere or weakly reducing atmosphere, first 300-500 ℃ pre-burning 1-10 hour, 500-1000 ℃ of calcining 4-20 hour again obtains spherical doped iron lithium phosphate/charcoal composite granule after the grinding.
Embodiment 1
With 103.93g lithium dihydrogen phosphate, 404.0g ferric nitrate, 56.45g glucose, add deionized water 2.5L, make mixed solution; Mixed solution is carried out spray drying treatment, 170 ℃ of inlet temperatures, 69 ℃ of outlet temperatures, mixed solution flow velocity 15ml/min obtains spherical granular precursor; Spherical presoma is in high-purity N
2300 ℃ of pre-burning 4h of elder generation under the gas atmosphere, cooling is naturally ground the back 650 ℃ of calcinings 20 hours, obtains spherical LiFePO
4/ C composite granule.
The battery performance test of gained material all adopts button cell, assembles in being full of the glove box of inert atmosphere.Negative pole adopts metal lithium sheet, and electrolyte adopts the LiPF of 1mol/L
6/ EC:DMC (1:1), wherein EC is an ethylene carbonate, DMC is a dimethyl carbonate.Positive plate preparation technology is as follows: with the positive electrode for preparing and conductive agent acetylene black, binding agent PVDF(polyvinylidene fluoride) mix by 85:8:7, add an amount of NMP(N-methyl pyrrolidone) in agate mortar, grind evenly, form the colloidal mixture of thickness, be uniformly coated on then on the thick aluminium foil of 0.02mm, place 120 ℃ of vacuumize 20h, the battery that assembles carries out charge-discharge performance and cycle performance test with blue electric battery test system.Charge-discharge magnification is under the 0.1C condition, and material initial discharge specific capacity is 116.7mAh/g, remains on 119.6 mAh/g through 50 recycle ratio capacity, and capability retention is 100%.
Embodiment 2
With 101.85g lithium dihydrogen phosphate, 404.0g ferric nitrate, 56.45g glucose, 5.13g magnesium nitrate (Mg (NO
3)
2.6H
2O), add deionized water 2.5L, make mixed solution; Mixed solution is carried out spray drying treatment, 175 ℃ of inlet temperatures, 85 ℃ of outlet temperatures, mixed solution flow velocity 15ml/min obtains spherical granular precursor (granule-morphology is seen accompanying drawing 1); Spherical presoma is in high-purity N
2300 ℃ of pre-burning 4h of elder generation under the gas atmosphere, cooling is naturally ground the back 650 ℃ of calcinings 20 hours, obtains sphere and mixes magnesium Li
0.98Mg
0.02FePO
4/ C composite granule (granule-morphology is seen accompanying drawing 2, and the XRD diffraction pattern is seen accompanying drawing 3).According to the method assembled battery of embodiment 1, to test, charge-discharge magnification is under the 0.1C condition, the material initial discharge capacity reaches 139.8mAh/g, remains on 139.6mAh/g through 50 circulation volumes, capability retention is that 99.9%(sees accompanying drawing 4).
Embodiment 3
With 103.93g lithium dihydrogen phosphate, 395.94g ferric nitrate, 56.45g glucose, 4.90g manganese acetate (C
4H
6MnO
4.4H
2O), add deionized water 2.5L, make mixed solution; Mixed solution is carried out spray drying treatment, 180 ℃ of inlet temperatures, 92 ℃ of outlet temperatures, mixed solution flow velocity 15ml/min obtains spherical granular precursor; Spherical presoma is in high-purity N
2350 ℃ of pre-burning 10h of elder generation under the gas atmosphere, cooling is naturally ground the back 650 ℃ of calcinings 20 hours, obtains sphere and mixes manganese LiFe
0.98Mn
0.02PO
4/ C composite granule.According to the method assembled battery of embodiment 1, to test, charge-discharge magnification is under the 0.1C condition, and the material initial discharge capacity is 136.1mAh/g, remains on 137.2mAh/g through 50 circulation volumes, and capability retention is 100%.
Embodiment 4
With 103.93g lithium dihydrogen phosphate, 395.94g ferric nitrate, 56.45g glucose, 5.82g nickel nitrate (Ni (NO
3)
2.6H
2O), add deionized water 2.5L, make mixed solution; Mixed solution is carried out spray drying treatment, 180 ℃ of inlet temperatures, 91 ℃ of outlet temperatures, mixed solution flow velocity 15ml/min obtains spherical granular precursor; Spherical presoma is in high-purity N
2350 ℃ of pre-burning 10h of elder generation under the gas atmosphere, cooling is naturally ground the back 650 ℃ of calcinings 0 hour, obtains sphere and mixes nickel LiFe
0.98Ni
0.02PO
4/ C composite granule.According to the method assembled battery of embodiment 1, to test, charge-discharge magnification is under the 0.1C condition, and the material initial discharge capacity is 126.1mAh/g, remains on 127.1mAh/g through 50 circulation volumes, and capability retention is 100%.
Embodiment 5
With 101.85g lithium dihydrogen phosphate, 404.0g ferric nitrate, 56.45g glucose, 5.44g zinc nitrate (Zn (NO
3)
2.6H
2O), add deionized water 2.5L, make mixed solution; Mixed solution is carried out spray drying treatment, 150 ℃ of inlet temperatures, 68 ℃ of outlet temperatures, mixed solution flow velocity 15ml/min obtains spherical granular precursor; Spherical presoma is in high-purity N
2350 ℃ of pre-burning 5h of elder generation under the gas atmosphere, cooling is naturally ground the back 650 ℃ of calcinings 15 hours, obtains sphere and mixes zinc Li
0.98Zn
0.02FePO
4/ C composite granule.According to the method assembled battery of embodiment 1, to test, charge-discharge magnification is under the 0.1C condition, and the material initial discharge capacity is 127.1mAh/g, remains on 127.3mAh/g through 50 circulation volumes, and capability retention is 100%.
Embodiment 6
With 101.85g lithium dihydrogen phosphate, 404.0g ferric nitrate, 56.45g glucose, 4.74g calcium nitrate (Ca (NO
3)
2.4H
2O), add deionized water 2.5L, make mixed solution; Mixed solution is carried out spray drying treatment, 160 ℃ of inlet temperatures, 78 ℃ of outlet temperatures, mixed solution flow velocity 15ml/min obtains spherical granular precursor; Spherical presoma is in high-purity N
2350 ℃ of pre-burning 5h of elder generation under the gas atmosphere, cooling is naturally ground the back 650 ℃ of calcinings 15 hours, obtains sphere and mixes calcium Li
0.98Ca
0.02FePO
4/ C composite granule.According to the method assembled battery of embodiment 1, to test, charge-discharge magnification is under the 0.1C condition, and the material initial discharge capacity is 131.1mAh/g, remains on 126.3mAh/g through 50 circulation volumes, and capability retention is 96.3%.
Embodiment 7
With 101.85g lithium dihydrogen phosphate, 395.94g ferric nitrate, 56.45g glucose, 2.57g magnesium nitrate, 2.91g nickel nitrate, add deionized water 2.5L, make mixed solution; Mixed solution is carried out spray drying treatment, 180 ℃ of inlet temperatures, 90 ℃ of outlet temperatures, mixed solution flow velocity 12ml/min obtains spherical granular precursor; Spherical presoma is at Ar-H
2(5%) 350 ℃ of pre-burning 5h of elder generation under the atmosphere, cooling is naturally ground the back 650 ℃ of calcinings 15 hours, obtains sphere and mixes magnesium nickel Li
0.98Mg
0.02Fe
0.98Ni
0.02PO
4/ C composite granule.According to the method assembled battery of embodiment 1, to test, charge-discharge magnification is under the 0.1C condition, and the material initial discharge capacity is 140.0mAh/g, remains on 139.7mAh/g through 50 circulation volumes, and capability retention is 99.8%.
With 101.85g lithium dihydrogen phosphate, 395.94g ferric nitrate, 56.45g glucose, 2.37g calcium nitrate (Ca (NO
3)
2.4H
2O), the 2.91g nickel nitrate, add deionized water 2.5L, make mixed solution; Mixed solution is carried out spray drying treatment, 180 ℃ of inlet temperatures, 90 ℃ of outlet temperatures, mixed solution flow velocity 12ml/min obtains spherical granular precursor; Spherical presoma is in high-purity N
2350 ℃ of pre-burning 5h of elder generation under the gas atmosphere, cooling is naturally ground the back 650 ℃ of calcinings 15 hours, obtains sphere and mixes calcium and nickel Li
0.98Ca
0.02Fe
0.98Ni
0.02PO
4/ C composite granule.According to the method assembled battery of embodiment 1, to test, charge-discharge magnification is under the 0.1C condition, and the material initial discharge capacity is 133.1mAh/g, remains on 130.7mAh/g through 50 circulation volumes, and capability retention is 98.2%.
Embodiment 9
With 101.85g lithium dihydrogen phosphate, 395.94g ferric nitrate, 56.45g glucose, 2.72g zinc nitrate (Zn (NO
3)
2.6H
2O), the 2.91g nickel nitrate, add deionized water 2.5L, make mixed solution; Mixed solution is carried out spray drying treatment, 170 ℃ of inlet temperatures, 82 ℃ of outlet temperatures, mixed solution flow velocity 15ml/min obtains spherical granular precursor; Spherical presoma is at Ar-H
2(5%) 300 ℃ of pre-burning 1h of elder generation under the atmosphere, cooling is naturally ground the back 700 ℃ of calcinings 5 hours, obtains sphere and mixes zinc and nickel Li
0.98Zn
0.02Fe
0.98Ni
0.02PO
4/ C composite granule.According to the method assembled battery of embodiment 1, to test, charge-discharge magnification is under the 0.1C condition, and the material initial discharge capacity is 137.3mAh/g, remains on 137.7mAh/g through 50 circulation volumes, and capability retention is 100%.
With 101.85g lithium dihydrogen phosphate, 404.0g ferric nitrate, 56.45g sucrose, 5.13g magnesium nitrate (Mg (NO
3)
2.6H
2O), add deionized water 2.5L, make mixed solution; Mixed solution is carried out spray drying treatment, 175 ℃ of inlet temperatures, 85 ℃ of outlet temperatures, mixed solution flow velocity 15ml/min obtains spherical granular precursor; Spherical presoma is in high-purity N
2350 ℃ of pre-burning 5h of elder generation under the gas atmosphere, cooling is naturally ground the back 750 ℃ of calcinings 5 hours, obtains sphere and mixes magnesium Li
0.98Mg
0.02FePO
4/ C composite granule.According to the method assembled battery of embodiment 1, to test, charge-discharge magnification is under the 0.1C condition, and the material initial discharge capacity reaches 137.8mAh/g, remains on 137.9mAh/g through 50 circulation volumes, and capability retention is 100%.
Embodiment 11
With 101.85g lithium dihydrogen phosphate, 404.0g ferric nitrate, 56.45g polyethylene glycol, 5.13g magnesium nitrate (Mg (NO
3)
2.6H
2O), add deionized water 2.5L, make mixed solution; Mixed solution is carried out spray drying treatment, 175 ℃ of inlet temperatures, 84 ℃ of outlet temperatures, mixed solution flow velocity 15ml/min obtains spherical granular precursor; Spherical presoma is in high-purity N
2350 ℃ of pre-burning 5h of elder generation under the gas atmosphere, cooling is naturally ground the back 750 ℃ of calcinings 5 hours, obtains sphere and mixes magnesium Li
0.98Mg
0.02FePO
4/ C composite granule.According to the method assembled battery of embodiment 1, to test, charge-discharge magnification is under the 0.1C condition, and the material initial discharge capacity reaches 135.3mAh/g, remains on 133.0mAh/g through 50 circulation volumes, and capability retention is 98.3%.
Embodiment 12
With 101.85g lithium dihydrogen phosphate, 404.0g ferric nitrate, 56.45g polyvinyl alcohol, 5.13g magnesium nitrate (Mg (NO
3)
2.6H
2O), add deionized water 2.5L, make mixed solution; Mixed solution is carried out spray drying treatment, 175 ℃ of inlet temperatures, 81 ℃ of outlet temperatures, mixed solution flow velocity 15ml/min obtains spherical granular precursor; Spherical presoma is in high-purity N
2350 ℃ of pre-burning 5h of elder generation under the gas atmosphere, cooling is naturally ground the back 750 ℃ of calcinings 5 hours, obtains sphere and mixes magnesium Li
0.98Mg
0.02FePO
4/ C composite granule.According to the method assembled battery of embodiment 1, to test, charge-discharge magnification is under the 0.1C condition, and the material initial discharge capacity reaches 136.3mAh/g, remains on 134.6mAh/g through 50 circulation volumes, and capability retention is 98.8%.
Embodiment 13
With 101.85g lithium dihydrogen phosphate, 404.0g ferric nitrate, 56.45g soluble starch, 5.13g magnesium nitrate (Mg (NO
3)
2.6H
2O), add deionized water 2.5L, make mixed solution; Mixed solution is carried out spray drying treatment, 175 ℃ of inlet temperatures, 87 ℃ of outlet temperatures, mixed solution flow velocity 15ml/min obtains spherical granular precursor; Spherical presoma is in high-purity N
2350 ℃ of pre-burning 5h of elder generation under the gas atmosphere, cooling is naturally ground the back 650 ℃ of calcinings 15 hours, obtains sphere and mixes magnesium Li
0.98Mg
0.02FePO
4/ C composite granule.According to the method assembled battery of embodiment 1, to test, charge-discharge magnification is under the 0.1C condition, and the material initial discharge capacity reaches 134.3mAh/g, remains on 132.7mAh/g through 50 circulation volumes, and capability retention is 98.8%.
Embodiment 14
With 101.85g lithium dihydrogen phosphate, 404.0g ferric nitrate, 28.23g sucrose, 28.23g glucose, 5.13g magnesium nitrate (Mg (NO
3)
2.6H
2O), add deionized water 2.5L, make mixed solution; Mixed solution is carried out spray drying treatment, 175 ℃ of inlet temperatures, 87 ℃ of outlet temperatures, mixed solution flow velocity 15ml/min obtains spherical granular precursor; Spherical presoma is in high-purity N
2350 ℃ of pre-burning 5h of elder generation under the gas atmosphere, cooling is naturally ground the back 650 ℃ of calcinings 15 hours, obtains sphere and mixes magnesium Li
0.98Mg
0.02FePO
4/ C composite granule.According to the method assembled battery of embodiment 1, to test, charge-discharge magnification is under the 0.1C condition, and the material initial discharge capacity reaches 138.8mAh/g, remains on 139mAh/g through 50 circulation volumes, and capability retention is 100%.
Embodiment 15
With 101.85g lithium dihydrogen phosphate, 404.0g ferric nitrate, 56.45g glucose, 5.13gMg (NO
3)
2.6H
2O places ball grinder, adds a certain amount of absolute ethyl alcohol wet-milling, obtains the presoma that mixes after the drying; This presoma is in high-purity N
2350 ℃ of pre-burning 5h of elder generation under the gas atmosphere, cooling is naturally ground the back 650 ℃ of calcinings 15 hours, obtains Li
0.98Mg
0.02FePO
4/ C composite granule.According to the method assembled battery of embodiment 1, to test, charge-discharge magnification is under the 0.1C condition, and the material initial discharge capacity is 108.8 mAh/g, remains on 115.1 mAh/g through 50 circulation volumes, and capability retention is 100%.
Claims (9)
1. the preparation method of a spherical LiFePO 4, the molecular formula of its spherical doped iron lithium phosphate/charcoal composite granule is: Li
1-xM
xFe
1-yM '
yPO
4/ C, M, M ' represents dopant ion; It is characterized in that its preparation process adopts lithium dihydrogen phosphate and ferric nitrate to do raw material, take by weighing needed raw material and add doped metal ion salt and carbon source according to stoichiometric proportion, again above-mentioned raw materials is added in the deionized water, the spray-dried presoma that obtains of the mixed solution that is made into, presoma carries out the presoma calcining under inert atmosphere or weakly reducing atmosphere, calcine again after the grinding, obtain spherical doped iron lithium phosphate/charcoal composite granule.
2. the preparation method of a kind of spherical LiFePO 4 according to claim 1 is characterized in that the described process that takes by weighing raw material, according to Li
1-xM
xFe
1-yM '
yPO
4The stoichiometric proportion of/C is weighed, M, and M ' represents dopant ion, x=0-0.05 wherein, y=0-0.05; Carbon source takes by weighing according to raw material total mass ratio 5%-15%.
3. the preparation method of a kind of spherical LiFePO 4 according to claim 1, its doped metal ion is to select among Mn, Mg, Ca, Ti, Ag, Ni, Nb, Al, Zn, the Zr one or more for use.
4. the preparation method of a kind of spherical LiFePO 4 according to claim 1, its carbon source select in sucrose, soluble starch, glucose, fructose, polyethylene glycol, the polyvinyl alcohol one or more for use.
5. the preparation method of a kind of spherical LiFePO 4 according to claim 1, the doped metal ion concentration that it is characterized in that the described mixed solution that is made into is 0.5mol/L-1mol/L.
6. the preparation method of a kind of spherical LiFePO 4 according to claim 1, the inlet temperature that it is characterized in that described spray-drying process drier is 150-300 ℃, outlet temperature is 65-120 ℃, mixed solution flow velocity 5ml/min-20ml/min.
7. the preparation method of a kind of spherical LiFePO 4 according to claim 1 is characterized in that described presoma calcining is under inert atmosphere or weakly reducing atmosphere, under 300-500 ℃ of temperature, calcines 1-10 hour.
8. the preparation method of a kind of spherical LiFePO 4 according to claim 1, it is characterized in that described calcining back presoma grinds after, be 500-1000 ℃ of temperature lower calcination 4-20 hour, obtain spherical doped iron lithium phosphate/charcoal composite granule.
9. according to claim 7 under inert atmosphere or weakly reducing atmosphere a kind of preparation method of spherical LiFePO 4, it is characterized in that described inert atmosphere or weakly reducing atmosphere are high-purity N
2Gas or Ar-H
2(5%) mist.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105608829A CN102013484A (en) | 2010-11-26 | 2010-11-26 | Preparation method of spherical lithium iron phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105608829A CN102013484A (en) | 2010-11-26 | 2010-11-26 | Preparation method of spherical lithium iron phosphate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102013484A true CN102013484A (en) | 2011-04-13 |
Family
ID=43843571
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105608829A Pending CN102013484A (en) | 2010-11-26 | 2010-11-26 | Preparation method of spherical lithium iron phosphate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102013484A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102651474A (en) * | 2012-05-24 | 2012-08-29 | 四川科能锂电有限公司 | Preparation method of anode active material lithium iron phosphate of lithium battery |
| CN102842714A (en) * | 2011-06-24 | 2012-12-26 | 河南科隆集团有限公司 | Multi-phosphate cathode material for lithium ion battery and method for producing multi-phosphate cathode material |
| CN108598383A (en) * | 2018-03-15 | 2018-09-28 | 桑顿新能源科技有限公司 | A kind of preparation method of the spherical composite ferric lithium phosphate material of Ti, N codope |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101209822A (en) * | 2006-12-31 | 2008-07-02 | 比亚迪股份有限公司 | Preparation method for lithium ion secondary battery positive pole active substance lithium iron phosphate |
| CN101746742A (en) * | 2008-12-11 | 2010-06-23 | 中国电子科技集团公司第十八研究所 | Method for preparing lithium ion battery anode material spherical LiFePO4 |
-
2010
- 2010-11-26 CN CN2010105608829A patent/CN102013484A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101209822A (en) * | 2006-12-31 | 2008-07-02 | 比亚迪股份有限公司 | Preparation method for lithium ion secondary battery positive pole active substance lithium iron phosphate |
| CN101746742A (en) * | 2008-12-11 | 2010-06-23 | 中国电子科技集团公司第十八研究所 | Method for preparing lithium ion battery anode material spherical LiFePO4 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102842714A (en) * | 2011-06-24 | 2012-12-26 | 河南科隆集团有限公司 | Multi-phosphate cathode material for lithium ion battery and method for producing multi-phosphate cathode material |
| CN102842714B (en) * | 2011-06-24 | 2016-08-03 | 河南科隆集团有限公司 | Lithium ion battery polynary phosphate cathode material and preparation method thereof |
| CN102651474A (en) * | 2012-05-24 | 2012-08-29 | 四川科能锂电有限公司 | Preparation method of anode active material lithium iron phosphate of lithium battery |
| CN108598383A (en) * | 2018-03-15 | 2018-09-28 | 桑顿新能源科技有限公司 | A kind of preparation method of the spherical composite ferric lithium phosphate material of Ti, N codope |
| 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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101237039B (en) | Method for synthesizing LiFePO4/C material based on chemical gas phase sediment auxiliary solid phase method | |
| CN1305148C (en) | Method for preparing high-density spherical lithium iron phosphate and lithium iron manganese phosphate | |
| CN102044667A (en) | Method for preparing spherical LFP (lithium iron phosphate)/carbon doped composite powder | |
| CN101955175B (en) | Industrial preparation method for lithium iron phosphate | |
| CN103956485B (en) | Lithium iron phosphate electrode material of a kind of three-dimensional hierarchical structure and preparation method thereof | |
| CN101752555B (en) | Method for preparing lithium ion battery anode material LiFePO4 | |
| CN101630739B (en) | Preparation method of modified doping lithium ferric phosphate | |
| CN102623708A (en) | Preparation method of lithium vanadium phosphate (Li3V2(PO4)3)/graphene composite material for positive electrode of lithium ion battery | |
| CN102437323A (en) | Anode material of lithium ion battery and preparation method thereof | |
| CN101752562B (en) | Compound doped modified lithium ion battery anode material and preparation method thereof | |
| CN101937987B (en) | Method for preparing composite anode material LiFePO4/C for lithium ion battery | |
| CN101504979A (en) | A novel preparation method for LiFePO4/C composite positive pole material | |
| CN102306772A (en) | Method for preparing fluorine sodium ferrous phosphate positive electrode material of mixed ion battery | |
| CN103594708B (en) | One is appraised at the current rate iron-based composite positive pole and preparation method thereof | |
| CN101582500B (en) | Method for preparing anode material of metal oxide nano-sheet lithium ion battery | |
| CN102709568A (en) | Preparation method for nickel cobalt lithium manganate LiNixConMn1-x-yO2 of anode material of lithium ion battery | |
| CN101478045A (en) | Preparation for high vibration high density lithium iron phosphate | |
| CN101973539B (en) | Method for synthesizing lithium iron phosphate anode material at low cost | |
| CN101673820A (en) | Method for preparing manganese lithium phosphate/carbon composite material by solid-liquid combination | |
| CN105024065A (en) | Lithium ion battery cathode material and preparation method thereof | |
| CN102420329A (en) | High-tap-density composite modified cathode material of lithium ion battery and preparation method thereof | |
| CN102832381A (en) | Preparation method of high-voltage cathode material Lil+xMn3/2-yNil/2-zMy+zO4 of lithium ion battery with long service life | |
| CN103746117A (en) | Preparation method of magnesium-ion-doped lithium ion battery positive pole lithium vanadium phosphate/carbon material | |
| CN105789621B (en) | A method of molten state lithium source surface tension is reduced so as to improve anode material for lithium-ion batteries high temperature solid-phase sintering process | |
| CN102267692B (en) | Self-sacrificing template method for preparing nanoscale lithium ferrous phosphate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110413 |