CN100537419C - Process for preparing high density spherical lithium ferric phosphate - Google Patents
Process for preparing high density spherical lithium ferric phosphate Download PDFInfo
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- CN100537419C CN100537419C CNB2006100652123A CN200610065212A CN100537419C CN 100537419 C CN100537419 C CN 100537419C CN B2006100652123 A CNB2006100652123 A CN B2006100652123A CN 200610065212 A CN200610065212 A CN 200610065212A CN 100537419 C CN100537419 C CN 100537419C
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Abstract
The present invention is microwave synthesis process of high density spherical lithium ferric phosphate as the positive electrode material of lithium ion cell, and belongs to the field of energy source material preparing technology. Spherical lithium ferric phosphate is prepared through mixing ferrous sulfate and solid phosphorus in the required Fe/P ratio; adding in certain speed into deionized water; adding alkali matter to regulate pH value to form the precursor ammonium ferrous phosphate; drying the precursor, mixing with lithium acetate in the same ratio, adding proper amount of conducting agent, and high temperature treatment at 600-800 deg.c for 3-30 hr in the protecting atmosphere. Thus prepared spherical lithium ferric phosphate has average grain size of 5-10 microns, tap density 2.0-2.3 g/cu cm, and room temperature initial specific discharge capacity of 140-160 mA/g. The process is simple, low in cost, high in yield and suitable for industrial production.
Description
Technical field
The invention belongs to the energy and material preparing technical field, particularly the preparation method of a kind of high-density spherical ferric lithium phosphate of anode material for lithium-ion batteries.
Background technology
Along with the continuous development, particularly human society of social civilization entered the information age, cybertimes, just more thirst for high-quality electric energy.And battery, especially secondary cell must play very important effect in future in the society based on electric energy.From at the end of last century, portable electric appts such as notebook, mobile phone etc. are popularized in the world with a kind of surprising speed, and the consequent is to the high request of Miniature Power Unit and big demand; Because portable electric appts has dexterity, the portable characteristics, so they need volume little, capacity is big, lightweight Miniature Power Unit.In addition owing to the long-time frequent cause of using, the bigger secondary power supply that tends to use relatively economical of client.
Because the oil equal energy source is day by day exhausted, nuclear energy, sun power, water energy etc. will become main energy resource supply.Yet to use these energy easily, just need convert them to electric energy, so the storage of electric energy is not always avoided, secondary power supply not only can regulate because the power consumption fluctuation that factors such as weather, time cause can also be used to storing the electric energy that luminous energy, wind energy etc. produce.And the environmental pollution that fossil fuel caused is more and more paid attention to by people, and electromobile will progressively replace existing gasoline automobile, so secondary cell also will become minimizing air-polluting important means.
Positive electrode material is the important component part of lithium ion battery, also is the key of decision lithium ion battery performance.At present, main positive electrode material is LiCoO
2, LiNiO
2, LiMn
2O
4LiCoO
2Be unique industrialization on a large scale at present, commercial positive electrode material, 90% above lithium ion battery adopts this material.But this material price costliness, capacity is lower, and toxicity is bigger, has certain safety issue.LiNiO
2Cost is lower, and capacity is higher, but the preparation difficulty, and there is bigger potential safety hazard in poor heat stability.Spinel LiMn
2O
4Cost is low, and security is good, but capacity is low, and high temperature cyclic performance is poor.Therefore need develop novel positive electrode material satisfies the growing market requirement.
The LiFePO of olivine structural
4Stable operating voltage, platform identity is good, capacity is higher, Stability Analysis of Structures, high-temperature behavior and good cycle, safety non-toxic, with low cost, volume-diminished during charging, volume effect when cooperating with carbon negative pole material is good, good with most of electrolyte system compatibility, become new research focus both at home and abroad gradually.
But LiFePO
4Positive electrode material exists two problems, and the one, ionic diffusion coefficient and electronic conductivity are all very low, cause high-rate charge-discharge capability poor, and reversible specific capacity is low; The 2nd, tap density is low, causes volume and capacity ratio low.These two problems have seriously hindered the application of this material.People improve the specific conductivity of iron lithium phosphate by the whole bag of tricks, and have obtained major progress.Innovative approach mainly concentrates on doping and the surface modification:
(1) mixes conductive carbon material or conductive metal particle toward the iron lithium phosphate granule interior,, improve the electronic conductivity of material perhaps toward iron lithium phosphate particle surface coated with conductive carbon material or conducting metal.
(2) in LiFePO 4 material, mix high price foreign metal ion, as Mg
2+, Al
3+, Cr
3+, Ti
4+Deng, replace a part of Li
+Or Fe
2+The position, thereby make the iron lithium phosphate proper semiconductor change n type or p N-type semiconductorN into, conductivity of electrolyte materials can be improved 8 orders of magnitude.
(3) adopt novel procesies such as sol-gel method, liquid phase synthesizing method, reduce the size of iron lithium phosphate crystal grain, shorten Li as far as possible
+With the electron diffusion distance, improve conductivity of electrolyte materials.
But the iron lithium phosphate vibration density is spent low problem and is ignored and avoid by people always.The LiFePO of olivine structural
4Theoretical density has only 3.6g/cm
3, much smaller than other positive electrode material such as LiCoO
2(5.1g/cm
3), LiNiO
2(4.8g/cm
3) and LiMn
2O
4(4.2g/cm
3).And the iron lithium phosphate with good electrical chemical property improves conductivity of electrolyte materials by methods such as carbon dopes usually, so its tap density is lower, generally at 1.0g/cm
3About, be far smaller than commercial cobalt acid lithium 2.0-2.4g/cm
3Tap density, too small tap density makes that the volume and capacity ratio of iron lithium phosphate is more much lower than the sour lithium of cobalt, the battery volume of making will be very huge, be difficult to be applied to reality.Therefore, the tap density of raising iron lithium phosphate and volume and capacity ratio have the decision meaning to the practicability of iron lithium phosphate.
The tap density of powder body material and the pattern of powder granule, particle diameter and distribution thereof are closely related.The lithium iron phosphate positive material of having reported both at home and abroad all is made up of random sheet or granular particle at present, because supporting mutually, these particles cause between the particle slit excessive, reduced tap density, and since the random pattern of particulate make carbon can't close attachment at particle surface, also greatly reduce the tap density of material.According to the experience to positive electrode material researchs such as cobalt acid lithiums, the powder body material that the close spheroidal particle of regular matter is formed has higher tap density usually, therefore, is the important channel of improving the material tap density with closeization of LiFePO 4 material spheroidization matter.In addition, spherical product also has excellent flowability, dispersiveness and processability, very helps making the coating of positive electrode material slurry and electrode slice, improves the electrode slice quality.In addition, with respect to random particle, the spheroidal particle surface ratio of rule is easier to coat complete, even, firm decorative layer, such as to improving the vital carbon of electrochemical performances of lithium iron phosphate, firm carbon coating layer not only can improve the electroconductibility of material greatly, also can improve the tap density of material, so spherical LiFePO 4 is hopeful more further to improve over-all properties by finishing.
Material preparation speed and treatment capacity directly influence the cost and the output of the finished product, produce product as much as possible in the short period of time for reducing fund input, reducing cost, improve output and have great importance.With respect to traditional liquid phase synthesis process, rheology phase method can realize the synthetic fast of material, and has improved the processing power of unit reactor greatly; Can obtain the good spherical lithium iron phosphate anode material of granule-morphology by rheology phase method.
In application number is 200410103485.3 patent of invention " preparation method of high-density spherical ferric lithium phosphate as anode material of lithium-ion battery "; a kind of preparation method of high-density spherical ferric lithium phosphate is disclosed; this method is earlier with the trivalent iron salt aqueous solution, the phosphorus source aqueous solution, alkali aqueous solution reaction synthesizing spherical or class ball shape ferric phosphate presoma; the dry back of washing and lithium source, carbon source, doping metals compound uniform mixing; under inertia or protection of reducing atmosphere, obtained iron lithium phosphate in 8-48 hours through 600-900 ℃ of high-temperature heat treatment.The iron lithium phosphate median size that this method is prepared is 7-12 μ m, and tap density can reach 2.0-2.2g/cm
3, first discharge specific capacity can reach 140-155mAh/g under the room temperature.In application number is 200510000167.9 patent of invention " a kind of preparation method of high-density spherical ferric lithium phosphate ", a kind of preparation method of high-density spherical ferric lithium phosphate is disclosed, this method is to be raw material with trivalent iron salt iron nitrate, phosphoric acid, lithium acetate, obtains spherical LiFePO 4 by sol-gel method.The iron lithium phosphate median size that this method is prepared is 5-8 μ m, and tap density can reach 1.8-2.0g/cm
3First discharge specific capacity can reach 140-160mAh/g under the room temperature.In application number was 200510002012.9 patent of invention " preparation method of high-density spherical ferric lithium phosphate and iron manganese phosphate for lithium ", the preparation method of a kind of high-density spherical ferric lithium phosphate and iron manganese phosphate for lithium was disclosed.This method is with ferrous sulfate, phosphorus source, complexing agent or adds manganous sulfate therein again; be made into mixed aqueous solution after being mixed in proportion; again with ammonia soln reaction synthesizing spherical ferrous ammonium phosphate or manganous phosphate ferrous ammonium presoma; the dry back of washing mixes with mol ratio with Quilonum Retard at 1: 1; under the nitrogen atmosphere protection, obtained iron lithium phosphate or iron manganese phosphate for lithium in 8-48 hours through 600-900 ℃ of high-temperature heat treatment.The iron lithium phosphate median size that this method is prepared is 7-12 μ m, and tap density can reach 2.0-2.2g/cm
3, first discharge specific capacity can reach 145-160mAh/g under the room temperature.
The present invention propose with divalence ferrous salt and phosphorus source be raw material by rheology mutually legal system be equipped with the method for high-density spherical ferric lithium phosphate.
Summary of the invention
The purpose of this invention is to provide the preparation method of a kind of high-density spherical ferric lithium phosphate that is used for anode material for lithium-ion batteries, it is characterized in that: the preparation method of described high-density spherical ferric lithium phosphate comprises the steps:
(1) with ferrous sulfate, phosphorus source, reductive agent mixed grinding, wherein the mol ratio of iron phosphorus is (0.5-1): 1, and the reductive agent add-on is a reductive agent: deionized water=(0.001-0.05): 1 (mass ratio).
(2) with above-mentioned ferrous sulfate, Secondary ammonium phosphate, reductive agent blended solid powder, the alkaline matter powder is input to respectively in the reactor of band stirring continuously with spiral propeller, and the temperature of controlling reactor internal reaction liquid is 20-80 ℃; Ferrous sulfate, phosphorus source, reductive agent mix, and it is 0.0025g/min-0.25g/min that pressed powder adds the corresponding 1ml deionized water of speed, and the mass ratio of solid add-on and deionized water is 1:5-1:0.5; Add alkaline matter simultaneously, make the pH value of reactor internal reaction liquid be 4.0-8.0.Solid materials adds the back that finishes and continued stirring heating 0.1-5 hour.
(3) step (2) gained material is changed over to carry out solid-liquid separation in the solid separator, with the solid product of deionized water wash solid-liquid separation gained, until using BaCl
2Can not detect the SO in the washing water
4 2-Till; Product after the washing in 80-100 ℃ of dryings 2-6 hours, obtains spherical ferrous ammonium phosphate presoma in moisture eliminator.
(4) in the ratio of Li:Fe:P=1:1:1 (mol ratio), take by weighing the spherical ferrous ammonium phosphate of step (3) gained and add water with lithium acetate and mix, add the carbon source of 1～20wt% of iron lithium phosphate, heat evaporating water.
(5) step (4) products therefrom is placed tubular react furnace, under the nitrogen atmosphere protection, be warming up to 600-800 ℃, constant temperature 3-30 hours, naturally cooling in stove obtains spherical LiFePO 4.
Described reductive agent is one or more in hydrochloric acid hydroxylammonium, the xitix.
Described alkaline matter is one or more in volatile salt, bicarbonate of ammonia or the ammoniacal liquor; Wherein ammonia concn is 14 mol; Volatile salt and bicarbonate of ammonia all grind powdered.
The carbon source of using in the described preparation iron lithium phosphate process is in acetylene black, carbon black, sucrose, the starch one or more.
The invention has the beneficial effects as follows that a process for preparing median size is 5-10 μ m, tap density can reach 2.0-2.3g/cm
3, first discharge specific capacity can reach the high-bulk-density of 140-160mAh/g, the lithium ion battery anode material spherical LiFePO 4 of high-volume and capacity ratio under the room temperature.Compare with the trivalent iron salt route, the present invention utilizes divalent iron salt to be raw material, raw material sources are more extensive, price is cheaper, need not a large amount of carbon source reduction ferrous ions during thermal treatment, with respect to traditional liquid phase reaction method, presoma mean residence time in reactor shortens greatly, the unit reactor processing power greatly improves, and has very wide use value; Technology is simple, with low cost, the unit reactor high yield, be suitable for suitability for industrialized production.
Embodiment
The invention provides the preparation method of a kind of high-density spherical ferric lithium phosphate that is used for anode material for lithium-ion batteries.The method for preparing high-density spherical ferric lithium phosphate may further comprise the steps:
(1) with ferrous sulfate, phosphorus source, reductive agent mixed grinding, wherein the mol ratio of iron phosphorus is (0.5-1): 1, and the reductive agent add-on is a reductive agent: deionized water=(0.001-0.05): 1 (mass ratio).
(2) with above-mentioned ferrous sulfate, Secondary ammonium phosphate, reductive agent blended solid powder, the alkaline matter powder is input in the reactor of band stirring respectively continuously with spiral propeller, the temperature of controlling reactor internal reaction liquid is 20-80 ℃, ferrous sulfate, phosphorus source, reductive agent mix, and it is 0.0025g/min-0.25g/min that pressed powder adds the corresponding 1ml deionized water of speed; The mass ratio of solid add-on and deionized water is 1:5-1:0.5.Control the adding speed of volatile salt simultaneously, make the pH value of reactor internal reaction liquid be 4.0-8.0, solid materials adds the back that finishes and continued stirring heating 0.1-5 hour.
(3) step (2) gained material is changed over to carry out solid-liquid separation in the solid separator, with the solid product of deionized water washing solid-liquid separation gained, until using BaCl
2Can not detect the SO in the washing water
4 2-Till, the product after the washing in 80-100 ℃ of dryings 2-6 hours, obtains spherical ferrous ammonium phosphate presoma in moisture eliminator.
(4) in the ratio of Li:Fe:P=1:1:1 (mol ratio), take by weighing the spherical ferrous ammonium phosphate of step (3) gained and add water with lithium acetate and mix, add the carbon source of 1～20wt% of iron lithium phosphate, heat evaporating water.
(5) step (4) products therefrom is placed tubular react furnace, under the nitrogen atmosphere protection, be warming up to 600-800 ℃, constant temperature 3-30 hours, naturally cooling in stove obtains spherical LiFePO 4.
Described reductive agent is one or more in hydrochloric acid hydroxylammonium, the xitix.
Described alkaline matter is one or more in volatile salt, bicarbonate of ammonia or the ammoniacal liquor; Wherein ammonia concn is 14 mol; Volatile salt and bicarbonate of ammonia all grind powdered.
The carbon source of using in the described preparation iron lithium phosphate process is in acetylene black, carbon black, sucrose, the starch one or more.
Introduce embodiments of the invention below:
Embodiment 1
Iron vitriol FeSO with 700g
47H
2O, the Secondary ammonium phosphate (NH of 332g
4)
2HPO
4, the xitix of 10g mixes, and places the ball mill ball milling 2 hours; The 300g volatile salt was placed the ball mill ball milling 2 hours; With spiral propeller iron vitriol, Secondary ammonium phosphate, xitix are mixed, pressed powder is with 10g iron vitriol FeSO
47H
2O/ minute speed joins in the reactor that 1 liter of deionized water is housed reacts; Add the volatile salt powder with spiral propeller simultaneously, regulate the adding speed of volatile salt, with the pH value of controlling reactor internal reaction liquid is 4.5 to be as the criterion, temperature is 40 ℃ in the controlling reactor, material adds the back that finishes to be continued to stir 30 minutes, material in the reactor is discharged, carries out solid-liquid separation with whizzer, with 60 ℃ deionized water wash solid products to washing water BaCl
2Can not detect the SO in the washing water
4 2-Till, the product after the washing in 80 ℃ of dryings 3 hours, obtains spherical ferrous ammonium phosphate in moisture eliminator.The above-mentioned ferrous ammonium phosphate that makes of 60g, 32.8g lithium acetate, 12g sucrose are added the 50ml deionized water slowly stirred 10 minutes, obtain mixed slurry.With the mixed slurry heated and stirred, till slurry loses flowability; Material is put into alumina crucible, in tube furnace, get speed and be warming up to 800 ℃, constant temperature 15 hours by 200 ℃/hour, stop heating, in stove, naturally cool to room temperature, in this process, continue to feed nitrogen in the tube furnace, gas flow is 1 liter/minute, obtains spherical LiFePO 4 LiFePO
4Product.Recording this product median size is 7-10 μ m, and tap density is 2.3g/cm
3, be negative pole with the lithium sheet, recording this iron lithium phosphate first discharge specific capacity at room temperature is 155mAh/g.
Embodiment 2
With 700g iron vitriol FeSO
47H
2O, 289g primary ammonium phosphate (NH
4) H
2PO
4, the 3g xitix mixes, and places the ball mill ball milling 2 hours, and the 500g volatile salt was placed the ball mill ball milling 2 hours, with spiral propeller with iron vitriol, primary ammonium phosphate, xitix blended solid powder with 10g iron vitriol FeSO
47H
2O/ minute speed joins in the reactor that 1 liter of deionized water is housed reacts, and adds the volatile salt powder with spiral propeller simultaneously, regulates the adding speed of volatile salt, is 5.5 to be as the criterion with the pH value of controlling reactor internal reaction liquid; Temperature is 40 ℃ in the controlling reactor, and material adds the back that finishes to be continued to stir 30 minutes, and the material in the reactor is discharged, and carries out solid-liquid separation with whizzer; With 60 ℃ deionized water wash solid products to washing water BaCl
2Can not detect the SO in the washing water
4 2-Till.Product after the washing in 80 ℃ of dryings 3 hours, obtains spherical ferrous ammonium phosphate in moisture eliminator.The above-mentioned ferrous ammonium phosphate that makes of 60g, 32.8g lithium acetate, 12g sucrose are added the 50ml deionized water slowly stirred 10 minutes, obtain mixed slurry; With the mixed slurry heated and stirred, till slurry loses flowability, material is put into alumina crucible, get speed by 200 ℃/hour and be warming up to 800 ℃ in tube furnace, constant temperature 15 hours stops heating, in stove, naturally cool to room temperature, continue in the tube furnace to feed nitrogen in this process, gas flow is 1 liter/minute, obtains spherical LiFePO 4 LiFePO
4Product.Recording this product median size is 5～8 μ m, and tap density is 2.0g/cm
3With the lithium sheet is negative pole, and recording this iron lithium phosphate first discharge specific capacity at room temperature is 160mAh/g.
Embodiment 3
With 500g iron vitriol FeSO
47H
2O, 356g Secondary ammonium phosphate (NH
4)
2HPO
4, the 1g xitix mixes, and places the ball mill ball milling 2 hours; 500g bicarbonate of ammonia was placed the ball mill ball milling 2 hours; With spiral propeller with iron vitriol, Secondary ammonium phosphate, xitix blended solid powder with 10g iron vitriol FeSO
47H
2O/ minute speed joins in the reactor that 1 liter of deionized water is housed reacts.Add the volatile salt powder with spiral propeller simultaneously, regulate the adding speed of volatile salt, with the pH value of controlling reactor internal reaction liquid is 7.0 to be as the criterion, temperature is 40 ℃ in the controlling reactor, material adds the back that finishes to be continued to stir 30 minutes, material in the reactor is discharged, carries out solid-liquid separation with whizzer, with 60 ℃ deionized water wash solid products to washing water BaCl
2Can not detect the SO in the washing water
4 2-Till; Product after the washing in 80 ℃ of dryings 3 hours, obtains spherical ferrous ammonium phosphate in moisture eliminator.The above-mentioned ferrous ammonium phosphate that makes of 60g, 32.8g lithium acetate, 12g sucrose are added the 50ml deionized water slowly stirred 10 minutes, obtain mixed slurry.With the mixed slurry heated and stirred, till slurry loses flowability, material is put into alumina crucible, in tube furnace, get speed and be warming up to 800 ℃ by 200 ℃/hour, constant temperature 15 hours, stop heating, in stove, naturally cool to room temperature, in this process, continue to feed nitrogen in the tube furnace, gas flow is 1 liter/minute, obtain the spherical LiFePO 4 product, recording this product median size is 7-10 μ m, and tap density is 2.1g/cm
3With the lithium sheet is negative pole, and recording this iron lithium phosphate first discharge specific capacity at room temperature is 155mAh/g.
Embodiment 4
With 400g iron vitriol FeSO
47H
2O, 380g Secondary ammonium phosphate (NH
4)
2HPO
4, the 15g xitix mixes, placed the ball mill ball milling 2 hours, 500g bicarbonate of ammonia was placed the ball mill ball milling 2 hours, with spiral propeller with iron vitriol, Secondary ammonium phosphate, xitix blended solid powder with 10g iron vitriol FeSO
47H
2O/ minute speed joins in the reactor that 1 liter of deionized water is housed reacts; Join in the reactor with the ammoniacal liquor of volume pump simultaneously 14 mol, add speed with control ammoniacal liquor, the pH value of controlling reactor internal reaction liquid is 7.0 to be as the criterion, temperature is 40 ℃ in the controlling reactor, material adds the back that finishes to be continued to stir 30 minutes, material in the reactor is discharged, carry out solid-liquid separation with whizzer; With 60 ℃ deionized water wash solid products to washing water BaCl
2Can not detect the SO in the washing water
4 2 -Till; Product after the washing in 80 ℃ of dryings 3 hours, obtains spherical ferrous ammonium phosphate in moisture eliminator.The above-mentioned ferrous ammonium phosphate that makes of 60g, 32.8g lithium acetate, 12g sucrose are added the 50ml deionized water slowly stirred 10 minutes, obtain mixed slurry, with the mixed slurry heated and stirred, till slurry loses flowability; Material is put into alumina crucible, in tube furnace, get speed and be warming up to 800 ℃, constant temperature 15 hours by 200 ℃/hour, stop heating, in stove, naturally cool to room temperature, in this process, continue to feed nitrogen in the tube furnace, gas flow is 1 liter/minute, obtains spherical LiFePO 4 LiFePO
4Product.Recording this product median size is 8-10 μ m, and tap density is 2.0g/cm
3, be negative pole with the lithium sheet, recording this iron lithium phosphate first discharge specific capacity at room temperature is 150mAh/g.
Embodiment 5
Prepare spherical ferrous ammonium phosphate by embodiment 1 identical condition, with 2.53 gram carbon blacks and 6 gram cane sugar substitutions, 12 gram sucrose, other condition is with embodiment 1, obtain with carbon black and sucrose decomposition carbon is the spherical LiFePO 4 product of hybrid conductive agent, recording this product median size is 8-10 μ m, and tap density is 2.0g/cm
3With the lithium sheet is negative pole, and recording this iron lithium phosphate first discharge specific capacity at room temperature is 155mAh/g.
Embodiment 6
Prepare spherical ferrous ammonium phosphate by embodiment 1 identical condition, with 2.53 gram acetylene blacks and 6 gram cane sugar substitutions, 12 gram sucrose, other condition is with embodiment 1, and obtaining with acetylene black and sucrose decomposition carbon is the spherical LiFePO 4 product of hybrid conductive agent.Recording this product median size is 8-10 μ m, and tap density is 2.0g/cm
3With the lithium sheet is negative pole, and recording this iron lithium phosphate first discharge specific capacity at room temperature is 155mAh/g.
Embodiment 7
Prepare spherical ferrous ammonium phosphate by embodiment 1 identical condition, with 9.5 gram starch in replace, 12 gram sucrose, other condition is with embodiment 1, and obtaining with amylolysis carbon is the spherical LiFePO 4 product of conductive agent; Recording this product median size is 8-10 μ m, and tap density is 2.2g/cm
3, be negative pole with the lithium sheet, recording this iron lithium phosphate first discharge specific capacity at room temperature is 155mAh/g.
Claims (4)
1. the preparation method of a high-density spherical ferric lithium phosphate is characterized in that: with the iron vitriol FeSO of 700g
47H
2O, the Secondary ammonium phosphate (NH of 332g
4)
2HPO
4, the xitix of 10g mixes, and places the ball mill ball milling 2 hours; The 300g volatile salt was placed the ball mill ball milling 2 hours; Or with 700g iron vitriol FeSO
47H
2O, 289g primary ammonium phosphate (NH
4) H
2PO
4, the 3g xitix mixes, and places the ball mill ball milling 2 hours, and the 500g volatile salt was placed the ball mill ball milling 2 hours; Or with 500g iron vitriol FeSO
47H
2O, 356g Secondary ammonium phosphate (NH
4)
2HPO
4, the 1g xitix mixes, and places the ball mill ball milling 2 hours; 500g bicarbonate of ammonia was placed the ball mill ball milling 2 hours; Respectively with spiral propeller with iron vitriol, Secondary ammonium phosphate, xitix blended solid powder with 10g iron vitriol FeSO
47H
2O/ minute speed joins in the reactor that 1 liter of deionized water is housed reacts; Add the volatile salt powder with spiral propeller simultaneously, the adding speed of regulating volatile salt is 4.5,5.5 or 7 to be as the criterion with the pH value of controlling reactor internal reaction liquid; Temperature is 40 ℃ in the controlling reactor then, and material adds the back that finishes to be continued to stir 30 minutes, and the material in the reactor is discharged, and carries out solid-liquid separation with whizzer, with 60 ℃ deionized water wash solid products to washing water BaCl
2Can not detect the SO in the washing water
4 2-Till, the product after the washing in 80 ℃ of dryings 3 hours, obtains spherical ferrous ammonium phosphate in moisture eliminator; The above-mentioned ferrous ammonium phosphate that makes of 60g, 32.8g lithium acetate, 12g sucrose are added the 50ml deionized water slowly stirred 10 minutes, obtain mixed slurry; With the mixed slurry heated and stirred, till slurry loses flowability; Material is put into alumina crucible, in tube furnace, get speed and be warming up to 800 ℃, constant temperature 15 hours by 200 ℃/hour, stop heating, in stove, naturally cool to room temperature, in this process, continue to feed nitrogen in the tube furnace, gas flow is 1 liter/minute, obtains spherical LiFePO 4 LiFePO
4Product.
2. the preparation method of a high-density spherical ferric lithium phosphate is characterized in that: with 400g iron vitriol FeSO
47H
2O, 380g Secondary ammonium phosphate (NH
4)
2HPO
4, the 15g xitix mixes, placed the ball mill ball milling 2 hours, 500g bicarbonate of ammonia was placed the ball mill ball milling 2 hours, with spiral propeller with iron vitriol, Secondary ammonium phosphate, xitix blended solid powder with the 10g iron vitriol/minute speed join in the reactor that 1 liter of deionized water is housed and react; Join in the reactor with the ammoniacal liquor of volume pump with 14 mol simultaneously, add speed with control ammoniacal liquor, the pH value of controlling reactor internal reaction liquid is 7.0 to be as the criterion; Temperature is 40 ℃ in the controlling reactor, and material adds the back that finishes to be continued to stir 30 minutes, and the material in the reactor is discharged, and carries out solid-liquid separation with whizzer; With 60 ℃ deionized water wash solid products to washing water BaCl
2Can not detect the SO in the washing water
4 2-Till, the product after the washing in 80 ℃ of dryings 3 hours, obtains spherical ferrous ammonium phosphate in moisture eliminator; The above-mentioned ferrous ammonium phosphate that makes of 60g, 32.8g lithium acetate, 12g sucrose are added the 50ml deionized water slowly stirred 10 minutes, obtain mixed slurry; With the mixed slurry heated and stirred, till slurry loses flowability, material is put into alumina crucible, speed by 200 ℃/hour in tube furnace is warming up to 800 ℃, and constant temperature 15 hours stops heating, in stove, naturally cool to room temperature, continue in the tube furnace to feed nitrogen in this process, gas flow is 1 liter/minute, obtains spherical LiFePO 4 LiFePO
4Product.
3. according to the preparation method of the described high-density spherical ferric lithium phosphate of claim 1, it is characterized in that: at iron vitriol FeSO with 700g in the claim 1
47H
2O, the Secondary ammonium phosphate (NH of 332g
4)
2HPO
4, the xitix of 10g mixes, and places the ball mill ball milling 2 hours; The 60g ferrous ammonium phosphate that places 2 hours condition of ball mill ball milling to make the 300g volatile salt, with 2.53 gram carbon blacks or acetylene black and 6 gram cane sugar substitutions, 12 gram sucrose, adding the 50ml deionized water slowly stirred 10 minutes, obtain mixed slurry, with the mixed slurry heated and stirred, till slurry loses flowability; Material is put into alumina crucible, speed by 200 ℃/hour in tube furnace is warming up to 800 ℃, constant temperature 15 hours, stop heating, in stove, naturally cool to room temperature, continue to feed nitrogen in this process in the tube furnace, gas flow is 1 liter/minute, and obtaining with carbon black or acetylene black and sucrose decomposition carbon is the spherical LiFePO 4 product of hybrid conductive agent.
4. according to the preparation method of the described high-density spherical ferric lithium phosphate of claim 1, it is characterized in that: at iron vitriol FeSO with 700g in the claim 1
47H
2O, the Secondary ammonium phosphate (NH of 332g
4)
2HPO
4, the xitix of 10g mixes, and places the ball mill ball milling 2 hours; The 60g ferrous ammonium phosphate that places 2 hours condition of ball mill ball milling to make the 300g volatile salt, with 9.5 gram starch in replace, 12 gram sucrose, add the 50ml deionized water and slowly stirred 10 minutes, obtain mixed slurry, with the mixed slurry heated and stirred, till slurry loses flowability; Material is put into alumina crucible, speed by 200 ℃/hour in tube furnace is warming up to 800 ℃, constant temperature 15 hours, stop heating, in stove, naturally cool to room temperature, continue in the tube furnace to feed nitrogen in this process, gas flow is 1 liter/minute, and obtaining with amylolysis carbon is the spherical LiFePO 4 product of conductive agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN101373831B (en) * | 2007-08-24 | 2012-07-25 | 比克国际(天津)有限公司 | Method for preparing lithium ion battery anode material lithium iron phosphate |
| CN101859898B (en) * | 2010-06-03 | 2012-11-14 | 清华大学 | Preparation method of electrode materials for lithium batteries |
| CN103303893B (en) * | 2013-06-04 | 2014-12-10 | 清华大学深圳研究生院 | Preparation method of lithium iron phosphate |
| CN107857243A (en) * | 2017-11-15 | 2018-03-30 | 成都先进金属材料产业技术研究院有限公司 | The method that titanium white by product thing ferrous sulfate prepares LITHIUM BATTERY superfine iron phosphate |
| CN109088063A (en) * | 2018-08-15 | 2018-12-25 | 崔晓迪 | A kind of lithium ion battery material and preparation method thereof |
| CN110600705A (en) * | 2019-09-20 | 2019-12-20 | 程立勋 | Preparation method of battery positive electrode material |
| CN113387340A (en) * | 2021-07-02 | 2021-09-14 | 攀枝花学院 | Method for preparing ferrous phosphate hydrated salt crystal |
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| Title |
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| A novel concept for the synthesis of an improved LiFePO4lithium batteries cathode. F. Croce,A.D Epifanio, et al.Electrochemical and Solid-State Letters,Vol.5 No.3. 2002 |
| A novel concept for the synthesis of an improved LiFePO4lithium batteries cathode. F. Croce,A.D Epifanio, et al.Electrochemical and Solid-State Letters,Vol.5 No.3. 2002 * |
| LiFePO4/C 锂离子电池正极材料的电化学性能. 张宝，罗文斌，李新海，王志兴.中国有色金属学报，第2期. 2005 |
| LiFePO4/C 锂离子电池正极材料的电化学性能. 张宝，罗文斌，李新海，王志兴.中国有色金属学报，第2期. 2005 * |
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