CN102881903A - Preparation method of porous lithium iron phosphate powder - Google Patents
Preparation method of porous lithium iron phosphate powder Download PDFInfo
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- CN102881903A CN102881903A CN2012104061880A CN201210406188A CN102881903A CN 102881903 A CN102881903 A CN 102881903A CN 2012104061880 A CN2012104061880 A CN 2012104061880A CN 201210406188 A CN201210406188 A CN 201210406188A CN 102881903 A CN102881903 A CN 102881903A
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Abstract
Disclosed is a preparation method of porous lithium iron phosphate powder. The preparation method includes dissolving trivalent iron salt into water and preparing solution; adding alkali liquor in the boiling state to obtain Fe(OH)3 nano particles, dispersing the Fe(OH)3 nano particles in the water after washing, forming iron sesquioxide colloid with stirring intensively; adding a water-soluble lithium source, a phosphorus source, a carbon source and doped ion compound into the iron sesquioxide colloid, intensively stirring to form colloid-shaped mixed pulp uniformly molecularly mixed; drying the pulp by mist and obtaining spherical lithium iron phosphate precursor with average grain diameter ranging from D50=2-3 micrometers; sintering the precursor in the inertia atmosphere at the temperature of 300-500 DEG C for 2-10 hours, and sintering the precursor again at the temperature of 500-800 DEG C for 2-12 hours and obtaining carbon-coated spherical porous lithium iron phosphate powder with average grain diameter of D50=2-3 micrometers.
Description
Technical field
[0001] the present invention relates to LiFePO 4 powder, a kind of preparation method of anode material for lithium-ion batteries.
Background technology
Ferric phosphate lithium cell has abundant raw material, environmentally friendly, current potential and theoretical specific capacity is higher, discharging voltage balance, good cycle, fail safe and thermal stability be than advantages of higher, the lithium-ion-power cell that is considered to the most probable extensive use has wide market prospects in fields such as electric motor car, hybrid electric vehicle, electric tool, energy-accumulating power stations.But the ionic conductance of LiFePO4 and electron conductivity are all lower, are only suitable for discharging and recharging under low current density, and the specific capacity reduction is the larger problem in this battery applications during high power charging-discharging, and this has limited the application of this material.
LiFePO4 is carried out the electric conductivity that a large amount of study on the modification improves LiFePO4 both at home and abroad, mainly comprised the modes such as synthesis of nano grade particles, carbon coating, metal ion mixing.The carbon cladding ratio material with carbon-coated surface of porous material is more thorough, more is conducive to improve the electronic conductivity of material, and electrolyte also can be deep into by hole the inside of material, and the lithium ion that shortens material internal enters electrolytical the evolving path, has improved simultaneously LiFePO
4The conduction of middle electronics and ion, therefore preparing porous calcium phosphate iron lithium also is a kind of up-and-coming technology.
At present, the preparation method of LiFePO 4 powder mainly contains solid phase method, carbothermic method, sol-gal process, hydro thermal method and microwave method etc.Therefore sol-gal process, hydro thermal method and microwave method realize difficulty of industrialization owing to shortcomings such as cost are high, technical difficulty is large.Solid phase method and carbothermic method are the more processes of present commercial application, and two kinds of methods all are first raw material to be mixed, then synthesizing iron lithium phosphate at high temperature.But since the material granule of solid phase method and carbothermic method preparation large and mix inhomogeneous, cause the carbon of final products to coat and ion doping inhomogeneous, and product purity is not high.Particularly the addition as the doping ion is few, and the employing accurately sol-gal process of control composition is an important technological means.Chinese patent (CN102005564A) discloses a kind of method that adopts ferric hydroxide colloid to prepare nanocrystalline LiFePO 4 powder, adopts Fe (OH)
3Colloid is raw material; in colloid, add lithium source, phosphorus source and organic carbon source; even and the low-temperature vacuum drying of strong stirring; form nanoscale presoma uniform, that contain lithium iron phosphorus carbon; put into crucible and be warmed up to 500-800 degree centigrade at the Muffle furnace of inert atmosphere protection; be incubated 2-24 hour; organic carbon source is cracked into carbon under inert atmosphere; ferric iron is reduced to ferrous iron by carbon; form the LiFePO4 that carbon coats, naturally cool to room temperature and obtain nanocrystalline LiFePO 4 powder by grinding or pulverizing.But, following deficiency is arranged in the described LiFePO4 preparation process of this patent: the first, do not remove preparation Fe (OH) in the preparation process
3The SO that introduces during colloid
4 2-, NO
3 -, Cl
-Deng anionic impurity, these anionic impurities enter behind the final products very big to its Electrochemical Performances; The second, the vacuumize mode of employing easily causes the presoma component segregation, finally cause carbon coat inhomogeneous, product purity is not high.
Summary of the invention
The objective of the invention is by a kind of
The preparation method of porous calcium phosphate iron powder for lithium.
The present invention isA kind of preparation method of porous calcium phosphate iron powder for lithium the steps include:
(1) raw material is prepared: according to stoichiometric proportion Li
xFe
yPO
4: M
z, M is the doping ion, x=0.8-1.2, and y=0.8-1.2, z=0.01-0.1 takes by weighing source of iron, lithium source, phosphorus source and doping metals compound, and the addition of carbon source accounts for the mass ratio 10-30% of presoma;
(2) colloid preparation: the source of iron that weighs up is dissolved in deionized water is mixed with Fe
3+The iron salt solutions of concentration 0.1～1mol/L; Iron salt solutions is heated to boiling, adds alkali lye and make pH=7～10, reaction generates Fe (OH)
3With Fe (OH)
3Separate, wash, again with Fe (OH)
3Be distributed in the deionized water, make Fe (OH)
3Concentration be 10～100g/L, then be heated to boiling, mixing speed is 200～600 rpm, the reaction time is 2-10h, obtains the di-iron trioxide colloid;
(3) slurry preparation: lithium source, phosphorus source, carbon source and doping metals compound are joined in the di-iron trioxide colloid, stir under 200～600 rpm and form homodisperse gluey mixed slurry;
(4) presoma preparation: adopt the spray drying mode that slurry is carried out drying, inlet temperature 110-130 ℃, obtain the spherical LiFePO 4 presoma of homogeneous chemical composition, even particle size distribution;
(5) calcining: spray drying gained presoma is put into crucible and again through two section 500-800 ℃ calcining 2-12 hour was formed spherical porous LiFePO 4 powder that carbon coat in 2-10 hour at the tube furnace of inert atmosphere protection through one section 300-500 ℃ calcining, need not fragmentation.
The present invention can make each composition reach molecular level evenly to mix take the di-iron trioxide colloid as dispersion, the even coating that the ion that is conducive to mix enters lattice and carbon.Preparation process is not introduced SO
4 2-, Cl
-, Na
+, K
+Deng foreign ion.The porous calcium phosphate iron lithium primary particle of preparation is nanoscale, and the spheric granules surface micropore is conducive to the embedding of taking off of the infiltration of electrolyte and lithium ion, therefore has good chemical property and high rate performance.Product need not fragmentation, and technique simply is fit to suitability for industrialized production.
Description of drawings
Fig. 1 is the process chart of the synthesizing porous LiFePO 4 powder of the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of the porous calcium phosphate iron lithium that synthesizes of the present invention.
Fig. 3 is the porous calcium phosphate iron lithium that synthesizes of the present invention in the specific discharge capacity of the 25 ℃ of lower 0.2C charge and discharge cycles situation of change with cycle-index.
Embodiment
The present invention isA kind of preparation method of porous calcium phosphate iron powder for lithium the steps include:
(1) raw material is prepared: according to stoichiometric proportion Li
xFe
yPO
4: M
z, M is the doping ion, x=0.8-1.2, and y=0.8-1.2, z=0.01-0.1 takes by weighing source of iron, lithium source, phosphorus source and doping metals compound, and the addition of carbon source accounts for the mass ratio 10-30% of presoma;
(2) colloid preparation: the source of iron that weighs up is dissolved in deionized water is mixed with Fe
3+The iron salt solutions of concentration 0.1～1mol/L; Iron salt solutions is heated to boiling, adds alkali lye and make pH=7～10, reaction generates Fe (OH)
3With Fe (OH)
3Separate, wash, again with Fe (OH)
3Be distributed in the deionized water, make Fe (OH)
3Concentration be 10～100g/L, then be heated to boiling, mixing speed is 200～600 rpm, the reaction time is 2-10h, obtains the di-iron trioxide colloid;
(3) slurry preparation: lithium source, phosphorus source, carbon source and doping metals compound are joined in the di-iron trioxide colloid, stir under 200～600 rpm and form homodisperse gluey mixed slurry;
(4) presoma preparation: adopt the spray drying mode that slurry is carried out drying, inlet temperature 110-130 ℃, obtain the spherical LiFePO 4 presoma of homogeneous chemical composition, even particle size distribution;
(5) calcining: spray drying gained presoma is put into crucible and again through two section 500-800 ℃ calcining 2-12 hour was formed spherical porous LiFePO 4 powder that carbon coat in 2-10 hour at the tube furnace of inert atmosphere protection through one section 300-500 ℃ calcining, need not fragmentation.
According to the preparation method of above-described porous calcium phosphate iron powder for lithium, described source of iron adopts iron chloride (FeCl
3.6H
2O), perhaps ferric nitrate [Fe (NO
3)
39H
2O], perhaps ferric sulfate [Fe
2(SO
4)
3], perhaps above-mentioned several.
According to the preparation method of above-described porous calcium phosphate iron powder for lithium, described lithium source is lithium carbonate (Li
2CO
3), perhaps lithium hydroxide (LiOH), perhaps lithium dihydrogen phosphate (LiH
2PO
4), perhaps described several.
According to the preparation method of above-described porous calcium phosphate iron powder for lithium, described phosphorus source is diammonium hydrogen phosphate [(NH
4)
2HPO
4], perhaps ammonium dihydrogen phosphate (NH
4H
2PO
4), perhaps lithium dihydrogen phosphate (LiH
2PO
4), perhaps phosphoric acid (H
3PO
4), perhaps described several.
According to the preparation method of above-described porous calcium phosphate iron powder for lithium, described carbon source is sucrose, perhaps soluble starch, and perhaps glucose, perhaps fructose, perhaps citric acid, perhaps polyethylene glycol, perhaps polyvinyl alcohol, perhaps phenolic resins is perhaps described several.
According to the preparation method of above-described porous calcium phosphate iron powder for lithium, described doping metals compound is magnesium nitrate, perhaps magnesium oxalate, perhaps nickel nitrate, perhaps cobalt nitrate, perhaps aluminum nitrate; Perhaps Rare-Earth Ce
3+Nitrate
,Perhaps rare earth Eu
3+Nitrate, perhaps rare earth Dy
3+Nitrate, perhaps rare earth La
3+Nitrate, perhaps rare earth Nd
3+Nitrate, perhaps Rare Earth Y
3+Nitrate, perhaps several in the described rare earth nitrades; Perhaps Rare-Earth Ce
3+Acetate, perhaps rare earth Eu
3+Acetate, perhaps rare earth Dy
3+Acetate, perhaps rare earth La
3+Acetate, perhaps rare earth Nd
3+Acetate, Rare Earth Y
3+Acetate, perhaps this several of described lanthanon acetate; Perhaps Rare-Earth Ce
3+Oxalates, perhaps rare earth Eu
3+Oxalates, perhaps rare earth Dy
3+Oxalates or rare earth La
3+Oxalates, perhaps rare earth Nd
3+Oxalates, perhaps Rare Earth Y
3+Oxalates, perhaps several in the described rare-earth oxalate.
The present invention is described further below in conjunction with the drawings and specific embodiments, but the present invention is not limited to following examples.
According to stoichiometric proportion LiMg
0.01FePO
4At first take by weighing 40.0g ferric sulfate [Fe
2(SO
4)
3], be dissolved in and be made into Fe in the deionized water
3+The solution of concentration 0.1mol/L, be heated to boiling and drip concentration be the NaOH solution of 0.1mol/L to pH=8.0, obtain Fe (OH)
3Suspension-turbid liquid is with Fe (OH)
3After carrying out centrifugation, washing, be distributed to again in the 1000g deionized water, be heated to boiling and under the 500rpm strong agitation, react 6h, obtain the di-iron trioxide colloid.Then take by weighing 2.4g lithium hydroxide (LiOH), 11.5g ammonium dihydrogen phosphate (NH
4H
2PO
4), 0.15g magnesium oxalate (MgC
2O
4.2H
2O), 2.6g glucose (calculating by 10% of gained presoma mass fraction after the spray drying), and these materials are all added in the di-iron trioxide colloid, continue to stir 2h with 500rpm speed and obtain uniform gluey mixed slurry; Slurry spray-dried (130 ℃ of inlet temperatures) forms the spherical LiFePO 4 presoma, and presoma is put into crucible and formed the spherical porous LiFePO 4 powder that carbon coats through two sections 700 ℃ calcining 10h at the tube furnace of inert atmosphere protection again through one section 350 ℃ calcining 2h.
The battery performance test of resulting materials all adopts button cell, assembles in being full of the glove box of inert atmosphere.Negative pole adopts metal lithium sheet, and electrolyte adopts 1mol.L
-LiPF6/EC:DMC (1:1), wherein EC is ethylene carbonate, DMC is 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, then be uniformly coated 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 0.2C condition, and material initial discharge specific capacity is 138mAh/g, and is unattenuated through 50 circulation volumes.
Embodiment 2
According to stoichiometric proportion LiMg
0.01FePO
4At first take by weighing 40.0g ferric sulfate [Fe
2(SO
4)
3], be dissolved in and be made into Fe in the deionized water
3+The solution of concentration 0.1mol/L, be heated to boiling and drip concentration be the ammonia spirit of 0.1mol/L to pH=8.0, obtain Fe (OH)
3Suspension-turbid liquid is with Fe (OH)
3After carrying out centrifugation, washing, be distributed to again in the 1000g deionized water, be heated to boiling and under the 500rpm strong agitation, react 6h, obtain the di-iron trioxide colloid.Then take by weighing 2.4g lithium hydroxide (LiOH), 11.5g ammonium dihydrogen phosphate (NH
4H
2PO
4), 0.15g magnesium oxalate (MgC
2O
4.2H
2O), 2.6g glucose (calculating by 10% of gained presoma mass fraction after the spray drying), and these materials are all added in the di-iron trioxide colloid, continue to stir 2h with 500rpm speed and obtain uniform gluey mixed slurry; Slurry spray-dried (130 ℃ of inlet temperatures) forms the spherical LiFePO 4 presoma, and presoma is put into crucible and formed the spherical porous LiFePO 4 powder that carbon coats through two sections 700 ℃ calcining 10h at the tube furnace of inert atmosphere protection again through one section 350 ℃ calcining 2h.
According to the method assembled battery of embodiment 1, to test, charge-discharge magnification is under the 0.2C condition, the material initial discharge capacity reaches 140.2mAh/g, and is unattenuated through 50 circulation volumes.
Embodiment 3
According to stoichiometric proportion LiMg
0.02FePO
4At first take by weighing 40.0g ferric sulfate [Fe
2(SO
4)
3], be dissolved in and be made into Fe in the deionized water
3+The solution of concentration 0.1mol/L, be heated to boiling and drip concentration be the ammonia spirit of 0.1mol/L to pH=8.0, obtain Fe (OH)
3Suspension-turbid liquid is with Fe (OH)
3After carrying out centrifugation, washing, be distributed to again in the 1000g deionized water, be heated to boiling and under the 500rpm strong agitation, react 6h, obtain the di-iron trioxide colloid.Then take by weighing 10.4g lithium dihydrogen phosphate (LiH
2PO
4), 0.3g magnesium oxalate (MgC
2O
4.2H
2O), 2.2g glucose (calculating by 10% of gained presoma mass fraction after the spray drying), and these materials are all added in the di-iron trioxide colloid, continue to stir 2h with 500rpm speed and obtain uniform gluey mixed slurry; Slurry spray-dried (130 ℃ of inlet temperatures) forms the spherical LiFePO 4 presoma, and presoma is put into crucible and formed the spherical porous LiFePO 4 powder (granule-morphology is seen accompanying drawing 2) that carbon coats through two sections 700 ℃ calcining 10h at the tube furnace of inert atmosphere protection again through one section 350 ℃ calcining 2h.
According to the method assembled battery of embodiment 1, to test, charge-discharge magnification is under the 0.2C condition, the material initial discharge capacity reaches 142.0mAh/g, through 50 circulation volumes unattenuated (seeing accompanying drawing 3).
Embodiment 4
According to stoichiometric proportion LiMg
0.01FePO
4At first take by weighing 40.0g ferric sulfate [Fe
2(SO
4)
3], be dissolved in and be made into Fe in the deionized water
3+The solution of concentration 0.1mol/L, be heated to boiling and drip concentration be the ammonia spirit of 0.1mol/L to pH=8.0, obtain Fe (OH)
3Suspension-turbid liquid is with Fe (OH)
3After carrying out centrifugation, washing, be distributed to again in the 1000g deionized water, be heated to boiling and under the 500rpm strong agitation, react 6h, obtain the di-iron trioxide colloid.Then take by weighing 10.4g lithium dihydrogen phosphate (LiH
2PO
4), 0.15g magnesium oxalate (MgC
2O
4.2H
2O), 2.2g glucose (calculating by 10% of gained presoma mass fraction after the spray drying), and these materials are all added in the di-iron trioxide colloid, continue to stir 2h with 500rpm speed and obtain uniform gluey mixed slurry; Slurry spray-dried (130 ℃ of inlet temperatures) forms the spherical LiFePO 4 presoma, and presoma is put into crucible and formed the spherical porous LiFePO 4 powder that carbon coats through two sections 700 ℃ calcining 10h at the tube furnace of inert atmosphere protection again through one section 350 ℃ calcining 2h.
According to the method assembled battery of embodiment 1, to test, charge-discharge magnification is under the 0.2C condition, the material initial discharge capacity reaches 140.4mAh/g, and is unattenuated through 50 circulation volumes.
Embodiment 5
According to stoichiometric proportion LiNd
0.01FePO
4At first take by weighing 40.0g ferric sulfate [Fe
2(SO
4)
3], be dissolved in and be made into Fe in the deionized water
3+The solution of concentration 0.1mol/L, be heated to boiling and drip concentration be the ammonia spirit of 0.1mol/L to pH=8.0, obtain Fe (OH)
3Suspension-turbid liquid is with Fe (OH)
3After carrying out centrifugation, washing, be distributed to again in the 1000g deionized water, be heated to boiling and under the 500rpm strong agitation, react 6h, obtain the di-iron trioxide colloid.Then take by weighing 10.4g lithium dihydrogen phosphate (LiH
2PO
4), 0.73g neodymium oxalate [Nd2 (C
2O
4)
3.10H
2O], 2.2g glucose (calculating by 10% of gained presoma mass fraction after the spray drying), and these materials are all added in the di-iron trioxide colloid, continue to stir 2h with 500rpm speed and obtain uniform gluey mixed slurry; Slurry spray-dried (130 ℃ of inlet temperatures) forms the spherical LiFePO 4 presoma, and presoma is put into crucible and formed the spherical porous LiFePO 4 powder that carbon coats through two sections 700 ℃ calcining 10h at the tube furnace of inert atmosphere protection again through one section 350 ℃ calcining 2h.
According to the method assembled battery of embodiment 1, to test, charge-discharge magnification is under the 0.2C condition, the material initial discharge capacity reaches 139.8mAh/g, and is unattenuated through 50 circulation volumes.
According to stoichiometric proportion LiMg
0.01FePO
4At first take by weighing 27.0g iron chloride (FeCl
3.6H
2O), be dissolved in and be made into Fe in the deionized water
3+The solution of concentration 0.1mol/L, be heated to boiling and drip concentration be the NaOH solution of 0.1mol/L to pH=8.0, obtain Fe (OH)
3Suspension-turbid liquid is with Fe (OH)
3After carrying out centrifugation, washing, be distributed to again in the 1000g deionized water, be heated to boiling and under the 500rpm strong agitation, react 6h, obtain the di-iron trioxide colloid.Then take by weighing 2.4g lithium hydroxide (LiOH), 11.5g ammonium dihydrogen phosphate (NH
4H
2PO
4), 0.15g magnesium oxalate (MgC
2O
4.2H
2O), 2.6g glucose (calculating by 10% of gained presoma mass fraction after the spray drying), and these materials are all added in the di-iron trioxide colloid, continue to stir 2h with 500rpm speed and obtain uniform gluey mixed slurry; Slurry spray-dried (130 ℃ of inlet temperatures) forms the spherical LiFePO 4 presoma, and presoma is put into crucible and formed the spherical porous LiFePO 4 powder that carbon coats through two sections 700 ℃ calcining 10h at the tube furnace of inert atmosphere protection again through one section 350 ℃ calcining 2h.
According to the method assembled battery of embodiment 1, to test, charge-discharge magnification is under the 0.2C condition, the material initial discharge capacity reaches 134.5mAh/g, and is unattenuated through 50 circulation volumes.
Embodiment 7
According to stoichiometric proportion LiMg
0.01FePO
4At first take by weighing 27.0g iron chloride (FeCl
3.6H
2O), be dissolved in and be made into Fe in the deionized water
3+The solution of concentration 0.1mol/L, be heated to boiling and drip concentration be the ammonia spirit of 0.1mol/L to pH=8.0, obtain Fe (OH)
3Suspension-turbid liquid is with Fe (OH)
3After carrying out centrifugation, washing, be distributed to again in the 1000g deionized water, be heated to boiling and under the 500rpm strong agitation, react 6h, obtain the di-iron trioxide colloid.Then take by weighing 2.4g lithium hydroxide (LiOH), 11.5g ammonium dihydrogen phosphate (NH
4H
2PO
4), 0.15g magnesium oxalate (MgC
2O
4.2H
2O), 2.6g glucose (calculating by 10% of gained presoma mass fraction after the spray drying), and these materials are all added in the di-iron trioxide colloid, continue to stir 2h with 500rpm speed and obtain uniform gluey mixed slurry; Slurry spray-dried (130 ℃ of inlet temperatures) forms the spherical LiFePO 4 presoma, and presoma is put into crucible and formed the spherical porous LiFePO 4 powder that carbon coats through two sections 700 ℃ calcining 10h at the tube furnace of inert atmosphere protection again through one section 350 ℃ calcining 2h.
According to the method assembled battery of embodiment 1, to test, charge-discharge magnification is under the 0.2C condition, the material initial discharge capacity reaches 137.7mAh/g, and is unattenuated through 50 circulation volumes.
Embodiment 8
According to stoichiometric proportion LiMg
0.01FePO
4At first take by weighing 27.0g iron chloride (FeCl
3.6H
2O), be dissolved in and be made into Fe in the deionized water
3+The solution of concentration 0.1mol/L, be heated to boiling and drip concentration be the ammonia spirit of 0.1mol/L to pH=8.0, obtain Fe (OH)
3Suspension-turbid liquid is with Fe (OH)
3After carrying out centrifugation, washing, be distributed to again in the 1000g deionized water, be heated to boiling and under the 500rpm strong agitation, react 6h, obtain the di-iron trioxide colloid.Then take by weighing 10.4g lithium dihydrogen phosphate (LiH
2PO
4), 0.15g magnesium oxalate (MgC
2O
4.2H
2O), 2.2g glucose (calculating by 10% of gained presoma mass fraction after the spray drying), and these materials are all added in the di-iron trioxide colloid, continue to stir 2h with 500rpm speed and obtain uniform gluey mixed slurry; Slurry spray-dried (130 ℃ of inlet temperatures) forms the spherical LiFePO 4 presoma, and presoma is put into crucible and formed the spherical porous LiFePO 4 powder that carbon coats through two sections 700 ℃ calcining 10h at the tube furnace of inert atmosphere protection again through one section 350 ℃ calcining 2h.
According to the method assembled battery of embodiment 1, to test, charge-discharge magnification is under the 0.2C condition, the material initial discharge capacity reaches 141.0mAh/g, and is unattenuated through 50 circulation volumes.
Embodiment 9
According to stoichiometric proportion LiMg
0.01FePO
4At first take by weighing 40.4g ferric nitrate [Fe (NO
3)
3.9H
2O], be dissolved in and be made into Fe in the deionized water
3+The solution of concentration 0.1mol/L, be heated to boiling and drip concentration be the ammonia spirit of 0.1mol/L to pH=8.0, obtain Fe (OH)
3Suspension-turbid liquid is with Fe (OH)
3After carrying out centrifugation, washing, be distributed to again in the 1000g deionized water, be heated to boiling and under the 500rpm strong agitation, react 6h, obtain the di-iron trioxide colloid.Then take by weighing 10.4g lithium dihydrogen phosphate (LiH
2PO
4), 0.15g magnesium oxalate (MgC
2O
4.2H
2O), 2.2g glucose (calculating by 10% of gained presoma mass fraction after the spray drying), and these materials are all added in the di-iron trioxide colloid, continue to stir 2h with 500rpm speed and obtain uniform gluey mixed slurry; Slurry spray-dried (130 ℃ of inlet temperatures) forms the spherical LiFePO 4 presoma, and presoma is put into crucible and formed the spherical porous LiFePO 4 powder that carbon coats through two sections 700 ℃ calcining 10h at the tube furnace of inert atmosphere protection again through one section 350 ℃ calcining 2h.
According to the method assembled battery of embodiment 1, to test, charge-discharge magnification is under the 0.2C condition, the material initial discharge capacity reaches 138.3mAh/g, and is unattenuated through 50 circulation volumes.
Embodiment 10
According to stoichiometric proportion LiMg
0.01FePO
4At first take by weighing 40.4g ferric nitrate [Fe (NO
3)
3.9H
2O], be dissolved in and be made into Fe in the deionized water
3+The solution of concentration 0.1mol/L, be heated to boiling and drip concentration be the NaOH solution of 0.1mol/L to pH=8.0, obtain Fe (OH)
3Suspension-turbid liquid is with Fe (OH)
3After carrying out centrifugation, washing, be distributed to again in the 1000g deionized water, be heated to boiling and under the 500rpm strong agitation, react 6h, obtain the di-iron trioxide colloid.Then take by weighing 10.4g lithium dihydrogen phosphate (LiH
2PO
4), 0.15g magnesium oxalate (MgC
2O
4.2H
2O), 2.2g glucose (calculating by 10% of gained presoma mass fraction after the spray drying), and these materials are all added in the di-iron trioxide colloid, continue to stir 2h with 500rpm speed and obtain uniform gluey mixed slurry; Slurry spray-dried (130 ℃ of inlet temperatures) forms the spherical LiFePO 4 presoma, and presoma is put into crucible and formed the spherical porous LiFePO 4 powder that carbon coats through two sections 700 ℃ calcining 10h at the tube furnace of inert atmosphere protection again through one section 350 ℃ calcining 2h.
According to the method assembled battery of embodiment 1, to test, charge-discharge magnification is under the 0.2C condition, the material initial discharge capacity reaches 136.6mAh/g, and is unattenuated through 50 circulation volumes.
Claims (6)
1. the preparation method of a porous calcium phosphate iron powder for lithium the steps include:
(1) raw material is prepared: according to stoichiometric proportion Li
xFe
yPO
4: M
z, M is the doping ion, x=0.8-1.2, and y=0.8-1.2, z=0.01-0.1 takes by weighing source of iron, lithium source, phosphorus source and doping metals compound, and the addition of carbon source accounts for the mass ratio 10-30% of presoma;
(2) colloid preparation: the source of iron that weighs up is dissolved in deionized water is mixed with Fe
3+The iron salt solutions of concentration 0.1～1mol/L; Iron salt solutions is heated to boiling, adds alkali lye and make pH=7～10, reaction generates Fe (OH)
3With Fe (OH)
3Separate, wash, again with Fe (OH)
3Be distributed in the deionized water, make Fe (OH)
3Concentration be 10～100g/L, then be heated to boiling, mixing speed is 200～600 rpm, the reaction time is 2-10h, obtains the di-iron trioxide colloid;
(3) slurry preparation: lithium source, phosphorus source, carbon source and doping metals compound are joined in the di-iron trioxide colloid, stir under 200～600 rpm and form homodisperse gluey mixed slurry;
(4) presoma preparation: adopt the spray drying mode that slurry is carried out drying, inlet temperature 110-130 ℃, obtain the spherical LiFePO 4 presoma of homogeneous chemical composition, even particle size distribution;
(5) calcining: spray drying gained presoma is put into crucible and again through two section 500-800 ℃ calcining 2-12 hour was formed spherical porous LiFePO 4 powder that carbon coat in 2-10 hour at the tube furnace of inert atmosphere protection through one section 300-500 ℃ calcining, need not fragmentation.
2. the preparation method of described porous calcium phosphate iron powder for lithium according to claim 1 is characterized in that described source of iron adopts iron chloride (FeCl
3.6H
2O), perhaps ferric nitrate [Fe (NO
3)
39H
2O], perhaps ferric sulfate [Fe
2(SO
4)
3], perhaps above-mentioned several.
3. the preparation method of described a kind of porous calcium phosphate iron powder for lithium according to claim 1 is characterized in that described lithium source is lithium carbonate (Li
2CO
3), perhaps lithium hydroxide (LiOH), perhaps lithium dihydrogen phosphate (LiH
2PO
4), perhaps described several.
4. the preparation method of described porous calcium phosphate iron powder for lithium according to claim 1 is characterized in that described phosphorus source is diammonium hydrogen phosphate [(NH
4)
2HPO
4], perhaps ammonium dihydrogen phosphate (NH
4H
2PO
4), perhaps lithium dihydrogen phosphate (LiH
2PO
4), perhaps phosphoric acid (H
3PO
4), perhaps described several.
5. the preparation method of described porous calcium phosphate iron powder for lithium according to claim 1 is characterized in that described carbon source is sucrose, perhaps soluble starch, perhaps glucose, perhaps fructose, perhaps citric acid, perhaps polyethylene glycol, perhaps polyvinyl alcohol, perhaps phenolic resins is perhaps described several.
6. the preparation method of described porous calcium phosphate iron powder for lithium according to claim 1 is characterized in that described doping metals compound is magnesium nitrate, perhaps magnesium oxalate, perhaps nickel nitrate, perhaps cobalt nitrate, perhaps aluminum nitrate;
Perhaps Rare-Earth Ce
3+Nitrate
,Perhaps rare earth Eu
3+Nitrate, perhaps rare earth Dy
3+Nitrate, perhaps rare earth La
3+Nitrate, perhaps rare earth Nd
3+Nitrate, perhaps Rare Earth Y
3+Nitrate, perhaps several in the described rare earth nitrades;
Perhaps Rare-Earth Ce
3+Acetate, perhaps rare earth Eu
3+Acetate, perhaps rare earth Dy
3+Acetate, perhaps rare earth La
3+Acetate, perhaps rare earth Nd
3+Acetate, Rare Earth Y
3+Acetate, perhaps this several of described lanthanon acetate;
Perhaps Rare-Earth Ce
3+Oxalates, perhaps rare earth Eu
3+Oxalates, perhaps rare earth Dy
3+Oxalates or rare earth La
3+Oxalates, perhaps rare earth Nd
3+Oxalates, perhaps Rare Earth Y
3+Oxalates, perhaps several in the described rare-earth oxalate.
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