CN101519199A - Method for preparing high-density spherical lithium iron phosphate for lithium ion power battery - Google Patents
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Abstract
The invention relates to a method for preparing high-density spherical lithium iron phosphate for lithium ion power batteries, which is characterized by comprising the preparing processes: acid, a ferric iron resource and phosphor resource are mixed into mixed water solution; alkali is prepared into water solution; the mixed water solution and the alkali water solution are respectively and continuously introduced into a reaction kettle to carry out coprecipitation reaction, and a spherical iron phosphate precursor is synthesized; the precursor is used as a raw material and is evenly mixed with a lithium resource, a carbon resource and a doping metal compound, and then, the mixture is heated in a stove to obtain a spherical lithium iron phosphate powder material under a protective atmosphere. The spherical lithium iron phosphate powder material prepared by the method has freely controllable average grain diameter being from 4 microns to 15 microns, narrow distribution of the grain diameter tap density as higher as 1.4 g/cm<3> to 2.2 g/cm<3>, and has the characteristics of high specific capacity, rate discharge and good safety performance. The method has simple technical processes and is suitable for industrial mass production.
Description
Technical field
The preparation method of high-density spherical lithium iron phosphate for lithium ion power battery relates to a kind of preparation of anode material for lithium-ion batteries, particularly a kind of preparation method of high-density spherical ferric lithium phosphate positive electrode material.
Background technology
Lithium ion battery has advantages such as specific energy is big, operating voltage is high, operating temperature range is wide, have extended cycle life, self-discharge is little, be widely used on the portable products such as mobile computer, mobile telephone, Video Camera, digital camera, mini CD-ROM drive and Handy Terminal, and along with to the improvement of current material and battery design technology and the appearance of novel material, lithium ion battery will have broad application prospects at aspects such as power truck, hybrid electric vehicle, uninterruptible power supply, large-scale communication power supplies.Anode material for lithium-ion batteries is the important component part of lithium ion battery, and it is the key factor of security, capacity and the price of decision battery.Iron lithium phosphate has advantages such as abundant raw material, cheap, environmentally friendly, discharging voltage balance, high security and thermostability, so it becomes the focus of current research as anode material for lithium-ion batteries of new generation.
But be subjected to the influence of crystalline structure, lithium iron phosphate positive material has low specific conductivity and tap density.In order to improve its use properties, adopt modes such as control granular size and pattern, carbon coating and metal ion mixing to improve its conductivity.Disclosed oxygen place doped as Chinese patent literature CN1772604, CN1785799 is disclosed transition element doped, and CN1785800 is disclosed rear-earth-doped, and CN1785823 is disclosed P site doped, the disclosed carbon of CN1280185 coats, and aforesaid method has improved the specific conductivity of iron lithium phosphate effectively.
The main at present high-temperature solid phase reaction method synthesizing iron lithium phosphate that adopts, as Chinese patent literature CN1581537, CN1753216, the disclosed method of CN1762798, CN1767238, promptly be with lithium source (Quilonum Retard or lithium hydroxide), phosphorus source (primary ammonium phosphate or ammonium hydrogen phosphate), source of iron (Ferrox or ferrous acetate) ground and mixed together, in the ground and mixed process, mix metallic compound and carbon source, improve the electroconductibility of material, then high-temperature roasting makes iron lithium phosphate under inert atmosphere.Preparation technology is simple for these methods, and condition is easy to control, is convenient to suitability for industrialized production, but the particle size distribution of product is wide, and crystalline size is bigger, and powder is by random granulometric composition, and tap density is low, and tap density generally has only 1.0g/cm
3, much smaller than the lithium of commercial cobalt acid 2.2-2.8g/cm
3Tap density.Low tap density makes that the volume and capacity ratio of iron lithium phosphate is more much lower than the sour lithium of cobalt, and this will limit its application on lithium-ion-power cell.Therefore, the tap density and the volume and capacity ratio of raising iron lithium phosphate are significant 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 LiFePO 4 powder material that random sheet or granular particle are formed, tap density is low.The LiFePO 4 powder material of being made up of the spheroidal particle of rule has high tap density, and it also has excellent flowability, dispersiveness and processability, and this helps the modulation of anode material for lithium-ion batteries slurry and the coating of electrode slice.In the patent of invention " preparation method of high-density spherical ferric lithium phosphate as anode material of lithium-ion battery " of Chinese patent literature CN1635648, a kind of preparation method of high-density spherical ferric lithium phosphate is disclosed, this method is mixed with solution respectively with trivalent iron salt, phosphorus source at first respectively, then according to the mole coefficient ratio of iron and phosphorus, control the liquid feeding speed of molysite and phosphorus source solution respectively, and by alkaline solution adjusting pH value, co-precipitation synthesizing spherical or class ball shape ferric phosphate presoma.The dry back of presoma washing and lithium source, carbon source, doping metals compound uniform mixing; under inertia or protection of reducing atmosphere; high-temperature roasting makes iron lithium phosphate, and the iron lithium phosphate median size that this patent is prepared is 7-12 μ m, and tap density can reach 2.0-2.2g/cm
3Though adopt Chinese patent literature CN1635648 disclosed method can improve the tap density of iron lithium phosphate, but realize that there is significant disadvantages in industrialized production: 1, in the suitability for industrialized production engineering, control the liquid feeding speed of molysite and phosphorus source solution respectively, the control condition harshness; 2, consider the production capacity factor, will use high density molysite and phosphorus source solution, and liquid feeding speed is fast, can there be fluctuation in the liquid feeding speed of molysite and phosphorus source solution in the actual production, and this will influence the ratio of component of iron and phosphorus in the product.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of high-density spherical ferric lithium phosphate of suitable suitability for industrialized production.
The objective of the invention is to be achieved through the following technical solutions.
The preparation method of high-density spherical lithium iron phosphate for lithium ion power battery is characterized in that its preparation process comprises: acid, ferric iron source, phosphorus source are made into mixed aqueous solution, alkali is mixed with the aqueous solution; The aqueous solution of mixed aqueous solution and alkali imported respectively continuously carry out coprecipitation reaction in the reactor, the tertiary iron phosphate presoma of synthesizing spherical; After being raw material and lithium source, carbon source, doping metals compound uniform mixing with the presoma, under the protective atmosphere, mixture is heat-treated in stove, obtains the spherical LiFePO 4 powder body material.
The preparation method of high-density spherical lithium iron phosphate for lithium ion power battery of the present invention, it is characterized in that the source of iron that adopts is one or more in iron nitrate, iron(ic) chloride, ferric oxide, tertiary iron phosphate, the ferric sulfate, the concentration of iron is 0.2-3mol/L in the mixed aqueous solution.
The preparation method of high-density spherical lithium iron phosphate for lithium ion power battery of the present invention, it is characterized in that the phosphorus source of adopting is one or more in phosphoric acid, ammonium hydrogen phosphate, primary ammonium phosphate, ammonium phosphate, disodium-hydrogen, SODIUM PHOSPHATE, MONOBASIC, sodium phosphate, potassium phosphate,monobasic, potassium primary phosphate, potassiumphosphate, Vanadium Pentoxide in FLAKES, the tertiary iron phosphate, the concentration of phosphorus is 0.2-3mol/L in the mixed aqueous solution.
The preparation method of high-density spherical lithium iron phosphate for lithium ion power battery of the present invention is characterized in that the acid of adopting is one or more in hydrochloric acid, nitric acid, the sulfuric acid, and consumption is the hydrogen in the acid: iron=(0.5-5): 1 mol ratio.
The preparation method of high-density spherical lithium iron phosphate for lithium ion power battery of the present invention is characterized in that the alkali that adopts is one or more in ammoniacal liquor, sodium hydroxide, the potassium hydroxide, and the concentration of alkali is 2-12mol/L in the aqueous solution of alkali.
The preparation method of high-density spherical lithium iron phosphate for lithium ion power battery of the present invention is characterized in that in the described prepared by co-precipitation presoma process, and the pH of control solution is 1-5, and temperature is 40-80 ℃.
The preparation method of high-density spherical lithium iron phosphate for lithium ion power battery of the present invention, it is characterized in that the lithium salts that adopts is one or more in Quilonum Retard, Lithium Acetate, lithium hydroxide, the lithium nitrate, consumption is a lithium: iron: phosphorus=(0.95-1.05): 1:1 (mol ratio).
The preparation method of high-density spherical lithium iron phosphate for lithium ion power battery of the present invention, it is characterized in that the carbon source that adopts is one or more in conductive carbon black, graphite, charcoal gel, carbon nanotube, carbon nano fiber, nano-sized carbon microballoon, glucose, sucrose, fructose, Mierocrystalline cellulose, starch, polyvinyl alcohol, polyoxyethylene glycol, styrene-butadiene rubber(SBR) breast, carboxymethyl cellulose, polystyrene, tetrafluoroethylene, polyvinylidene difluoride (PVDF), polyacrylonitrile, resol, the Resins, epoxy, the mass ratio that accounts for LiFePO 4 material is 2-20%.
The preparation method of high-density spherical lithium iron phosphate for lithium ion power battery of the present invention, it is characterized in that the doping metals compound that adopts is one or more in magnesium nitrate, magnesium oxalate, nickelous nitrate, Xiao Suangu, aluminum nitrate, titanium dioxide, zirconium dioxide, Niobium Pentxoxide, the Manganse Dioxide, consumption is to mix metal: phosphorus=(0.005-0.035): 1 (mol ratio).
The preparation method of high-density spherical lithium iron phosphate for lithium ion power battery of the present invention, it is characterized in that mixture first section high-temperature heat treatment process in kiln is that mixture is warmed up to 300-550 ℃ with 2-10 ℃/minute speed, constant temperature 1-10h carries out second section high-temperature heat treatment then.
The preparation method of high-density spherical lithium iron phosphate for lithium ion power battery of the present invention, it is characterized in that mixture second section high-temperature heat treatment process in kiln is that mixture is warmed up to 600-850 ℃ with the speed of 2-10 ℃/min, constant temperature 8-48h, naturally cooling in stove.
The preparation method of high-density spherical lithium iron phosphate for lithium ion power battery of the present invention is characterized in that shielding gas is one or more in hydrogen, nitrogen, argon gas or the ammonia.
The preparation method of high-density spherical lithium iron phosphate for lithium ion power battery of the present invention is characterized in that the kiln that adopts is push-plate type tunnel furnace, tube furnace, bell jar stove or rotary kiln.
Adopt the iron lithium phosphate outward appearance of the method preparation of patent of the present invention to be ball-type, advantages of good crystallization, structure is single, does not contain dephasign, and median size can arbitrarily be controlled between 4-15 μ m, narrow diameter distribution, tap density is up to 1.4-2.2g/cm
3, have the good characteristics of specific storage height, multiplying power discharging and safety performance.
Adopt the iron lithium phosphate of the method preparation of patent of the present invention, outward appearance is ball-type, has good chemical property, high tap density, satisfies the requirement of lithium ion power battery cathode material to iron lithium phosphate.The present invention is raw materials used abundant, and its preparation method is easy to suitability for industrialized production, has stronger economic benefit.
Description of drawings
Fig. 1 is synthetic presoma tertiary iron phosphate (FePO among the embodiment 1
42H
2O) stereoscan photograph, magnification are 1000 times;
Fig. 2 is the composite ferric lithium phosphate material (LiFePO among the embodiment 1
4/ C) charging and discharging curve, charge-discharge magnification is 0.1C, charging/discharging voltage is 2.5-4.2V;
Fig. 3 is the composite ferric lithium phosphate material (LiFePO among the embodiment 2
4/ C) stereoscan photograph, magnification is 1000 times;
Fig. 4 is the composite ferric lithium phosphate material (LiFePO among the embodiment 2
4/ C) cycle performance curve, charge-discharge magnification is 0.1C, charging/discharging voltage is 2.5-4.2V;
Embodiment
The preparation method of high-density spherical lithium iron phosphate for lithium ion power battery may further comprise the steps:
(1) acid, ferric iron source, phosphorus source are made into mixed aqueous solution, wherein the concentration of iron is 0.2-3mol/L, and the concentration of phosphorus is 0.2-3mol/L, and sour consumption is the hydrogen in the acid: iron=(0.5-5): 1 (mol ratio).
(2) alkali is mixed with the aqueous solution that concentration is 2-12mol/L.
(3) aqueous solution with above-mentioned mixed aqueous solution, alkali is input in the reactor of band stirring and thermometer respectively continuously with pump, the liquid feeding speed of control mixed aqueous solution, regulate the liquid feeding speed of alkali aqueous solution simultaneously, the pH value of control reactor internal reaction liquid is 1-5, and the temperature of reaction system is 40-80 ℃.
(4) with step (3) gained material filtering, with deionized water wash to the pH value of washing water greater than till 6, the product after the washing was contained in the moisture eliminator in 80-120 ℃ of dry 2-5 hour, obtain ball shape ferric phosphate.
(5) lithium source, carbon source, doping metals are mixed with alcohol, in ball mill ball milling 1-3 hour, added the tertiary iron phosphate ball milling then 10-40 minute, wherein to account for the mass ratio of LiFePO 4 material be 1-20wt% to carbon source, lithium: iron: phosphorus: doping metals=(0.95-1.05): 1:1:(0.005-0.035) (mol ratio).Then the slurry behind the mixing is contained in the loft drier in 80-120 ℃ of dry 1-3 hour, obtains the dry powder mixture.
(6) step (5) gained mixture is placed kiln, under protective atmosphere, be warmed up to 300-550 ℃ with the speed of 2-10 ℃/min; constant temperature 1-10h, and then be warmed up to 600-850 ℃, constant temperature 8-48h with the speed of 2-10 ℃/min; naturally cooling in stove obtains spherical LiFePO 4.
Embodiment 1
The mixed aqueous solution of preparation hydrochloric acid, iron trichloride, phosphoric acid, wherein the concentration of iron ion is 1.5mol/L, and concentration of phosphoric acid is 1.5mol/L, and the concentration of hydrochloric acid is 0.5mol/L.Compound concentration is the ammonia soln of 6mol/L.Respectively mixed aqueous solution, ammonia soln being input in advance oneself with volume pump fills in the reactor of 8 liters of deionized waters (reactor volume is 30 liters) and carries out coprecipitation reaction, regulate the liquid feeding speed of ammonia soln, the pH value of control reactor internal reaction liquid is 3.5 ± 0.05.The control reactor temperature is 65 ℃.After the continuously feeding 20 hours, stop charging, the material in the reactor is discharged, filter.With 70 ℃ deionized water wash solid products to the pH value of washing water greater than till 6.With the product after the washing in loft drier in 100 ℃ of dryings 3 hours, obtain ball shape ferric phosphate (FePO
42H
2O), (model: IRIS Intrepid II XSP) analyze, Fe in the product and the mass content of P are respectively 29.92%, 16.59%, and the atomic ratio of Fe and P closely is 1:1 tertiary iron phosphate have been carried out ICP-AES.With 13.9 gram Quilonum Retards, 9 gram glucose, 1 gram magnesium nitrate, adding fills in the ball grinder of alcohol ball milling 3 hours.Add 70 gram tertiary iron phosphates afterwards, continued ball milling 20 minutes.The mixing disposed slurry is contained in the loft drier in 80 ℃ of dryings 2 hours, obtains the dry powder mixture.The said mixture material is put into the atmosphere protection tube furnace, and feeding nitrogen is warmed up to 500 ℃ with 5 ℃/minute speed, and constant temperature 2h, and then is warmed up to 750 ℃ with 5 ℃/minute speed, and constant temperature 20h, and naturally cooling in stove obtains spherical LiFePO 4.The median size that records this material is 8-10 μ m, and tap density is 1.8g/cm
3With the lithium sheet is negative pole, the charging/discharging voltage of 2.5-4.2V, and the 0.1C rate charge-discharge, the first discharge specific capacity that at room temperature records iron lithium phosphate is 150mAh/g, and after 50 weeks of circulating, specific discharge capacity is 145mAh/g, and capability retention is 97%.
Embodiment 2
The mixed aqueous solution of preparation nitric acid, iron nitrate, primary ammonium phosphate, wherein the concentration of iron ion is 1.5mol/L, and the concentration of phosphate radical is 1.5mol/L, and the concentration of nitric acid is 2mol/L.Compound concentration is the ammonia soln of 6mol/L.Respectively mixed aqueous solution, ammonia soln being input in advance oneself with volume pump fills in the reactor of 8 liters of deionized waters (reactor volume is 30 liters) and carries out coprecipitation reaction, regulate the liquid feeding speed of ammonia soln, the pH value of control reactor internal reaction liquid is 3.8 ± 0.05.The control reactor temperature is 55 ℃.After the continuously feeding 20 hours, stop charging, the material in the reactor is discharged, filter.With 70 ℃ deionized water wash solid products to the pH value of washing water greater than till 6.With the product after the washing in loft drier in 100 ℃ of dryings 3 hours, obtain ball shape ferric phosphate (FePO
42H
2O), (model: IRIS Intrepid II XSP) analyze, Fe in the product and the mass content of P are respectively 29.84%, 16.53%, and the atomic ratio of Fe and P closely is 1:1 tertiary iron phosphate have been carried out ICP-AES.With 13.9 gram Quilonum Retards, 9 gram glucose, 0.3 gram titanium dioxide, adding fills in the ball grinder of alcohol ball milling 3 hours.Add 70 gram tertiary iron phosphates afterwards, continued ball milling 20 minutes.Slurry behind the mixing is contained in the loft drier in 80 ℃ of dryings 2 hours, obtains the dry powder mixture.The said mixture material is put into the atmosphere protection tube furnace, and feeding nitrogen is warmed up to 500 ℃ with 5 ℃/minute speed, and constant temperature 2h, and then is warmed up to 750 ℃ with 5 ℃/minute speed, and constant temperature 20h, and naturally cooling in stove obtains spherical LiFePO 4.The median size that records this material is 4-6 μ m, and tap density is 1.4g/cm
3With the lithium sheet is negative pole, the charging/discharging voltage of 2.5-4.2V, and the 0.1C rate charge-discharge, the first discharge specific capacity that at room temperature records iron lithium phosphate is 151mAh/g, and after 50 weeks of circulating, specific discharge capacity is 147mAh/g, and capability retention is 97%.
Embodiment 3
The mixed aqueous solution of preparation nitric acid, iron nitrate, sodium phosphate, wherein the concentration of iron ion is 1.5mol/L, and the concentration of phosphate radical is 1.5mol/L, and the concentration of nitric acid is 5mol/L.Compound concentration is the ammonia soln of 6mol/L.Respectively mixed aqueous solution, ammonia soln being input in advance oneself with volume pump fills in the reactor of 8 liters of deionized waters (reactor volume is 30 liters) and carries out coprecipitation reaction, regulate the liquid feeding speed of ammonia soln, the pH value of control reactor internal reaction liquid is 3.5 ± 0.05.The control reactor temperature is 65 ℃.After the continuously feeding 20 hours, stop charging, the material in the reactor is discharged, filter.With 70 ℃ deionized water wash solid products to the pH value of washing water greater than till 6.With the product after the washing in loft drier in 100 ℃ of dryings 3 hours, obtain ball shape ferric phosphate (FePO
42H
2O).With 13.9 gram Quilonum Retards, 9 gram glucose, 1.1 gram nickelous nitrates, adding fills in the ball grinder of alcohol ball milling 3 hours.Add 70 gram tertiary iron phosphates afterwards, continued ball milling 20 minutes.Slurry behind the mixing is contained in the loft drier in 80 ℃ of dryings 2 hours, obtains the dry powder mixture.The said mixture material is put into the atmosphere protection tube furnace, and feeding nitrogen is warmed up to 500 ℃ with 5 ℃/minute speed, and constant temperature 2h, and then is warmed up to 750 ℃ with 5 ℃/minute speed, and constant temperature 20h, and naturally cooling in stove obtains spherical LiFePO 4.The median size that records this material is 8-10 μ m, and tap density is 1.7g/cm
3With the lithium sheet is negative pole, the charging/discharging voltage of 2.5-4.2V, and the 0.1C rate charge-discharge, the first discharge specific capacity that at room temperature records iron lithium phosphate is 148mAh/g, and after 50 weeks of circulating, specific discharge capacity is 142mAh/g, and capability retention is 96%.
Embodiment 4
Tertiary iron phosphate is added stirring and dissolving in the hydrochloric acid, be mixed with mixed aqueous solution, wherein the concentration of iron ion is 1.5mol/L, and the concentration of phosphate radical is 1.5mol/L, and the concentration of hydrochloric acid is 5mol/L.Compound concentration is the sodium hydroxide solution of 2mol/L.Respectively mixed aqueous solution, sodium hydroxide solution being input in advance oneself with volume pump fills in the reactor of 8 liters of deionized waters (reactor volume is 30 liters) and carries out coprecipitation reaction, regulate the liquid feeding speed of sodium hydroxide solution, the pH value of control reactor internal reaction liquid is 3.3 ± 0.05.The control reactor temperature is 65 ℃.After the continuously feeding 20 hours, stop charging, the material in the reactor is discharged, filter.With 70 ℃ deionized water wash solid products to the pH value of washing water greater than till 6.With the product after the washing in loft drier in 100 ℃ of dryings 3 hours, obtain ball shape ferric phosphate (FePO
42H
2O).With 13.9 gram Quilonum Retards, 9 gram glucose, 0.4 gram Manganse Dioxide, adding fills in the ball grinder of alcohol ball milling 3 hours.Add 70 gram tertiary iron phosphates afterwards, continued ball milling 20 minutes.Slurry behind the mixing is contained in the loft drier in 80 ℃ of dryings 2 hours, obtains the dry powder mixture.The said mixture material is put into the atmosphere protection tube furnace, and feeding nitrogen is warmed up to 500 ℃ with 5 ℃/minute speed, and constant temperature 2h, and then is warmed up to 750 ℃ with 5 ℃/minute speed, and constant temperature 20h, and naturally cooling in stove obtains spherical LiFePO 4.The median size that records this material is 10-12 μ m, and tap density is 2.0g/cm
3With the lithium sheet is negative pole, the charging/discharging voltage of 2.5-4.2V, and the 0.1C rate charge-discharge, the first discharge specific capacity that at room temperature records iron lithium phosphate is 145mAh/g, and after 50 weeks of circulating, specific discharge capacity is 140mAh/g, and capability retention is 97%.
Claims (13)
1. the preparation method of high-density spherical lithium iron phosphate for lithium ion power battery is characterized in that its preparation process comprises: acid, ferric iron source, phosphorus source are made into mixed aqueous solution, alkali is mixed with the aqueous solution; The aqueous solution of mixed aqueous solution and alkali imported respectively continuously carry out coprecipitation reaction in the reactor, the tertiary iron phosphate presoma of synthesizing spherical; After being raw material and lithium source, carbon source, doping metals compound uniform mixing with the presoma, under the protective atmosphere, mixture is heat-treated in stove, obtains the spherical LiFePO 4 powder body material.
2. the preparation method of high-density spherical lithium iron phosphate for lithium ion power battery according to claim 1, it is characterized in that the source of iron that adopts is one or more in iron nitrate, iron(ic) chloride, ferric oxide, tertiary iron phosphate, the ferric sulfate, the concentration of iron is 0.2-3mol/L in the mixed aqueous solution.
3. the preparation method of high-density spherical lithium iron phosphate for lithium ion power battery according to claim 1, it is characterized in that the phosphorus source of adopting is one or more in phosphoric acid, ammonium hydrogen phosphate, primary ammonium phosphate, ammonium phosphate, disodium-hydrogen, SODIUM PHOSPHATE, MONOBASIC, sodium phosphate, potassium phosphate,monobasic, potassium primary phosphate, potassiumphosphate, Vanadium Pentoxide in FLAKES, the tertiary iron phosphate, the concentration of phosphorus is 0.2-3mol/L in the mixed aqueous solution.
4. the preparation method of high-density spherical lithium iron phosphate for lithium ion power battery according to claim 1 is characterized in that the acid of adopting is one or more in hydrochloric acid, nitric acid, the sulfuric acid, and consumption is the hydrogen in the acid: iron mol ratio=0.5-5: 1.
5. the preparation method of high-density spherical lithium iron phosphate for lithium ion power battery according to claim 1, it is characterized in that the alkali that adopts is one or more in ammoniacal liquor, sodium hydroxide, the potassium hydroxide, the concentration of alkali is 2-12mol/L in the aqueous solution of alkali.
6. the preparation method of high-density spherical lithium iron phosphate for lithium ion power battery according to claim 1 is characterized in that in the described prepared by co-precipitation presoma process, and the pH of control solution is 1-5, and temperature is 40-80 ℃.
7. the preparation method of high-density spherical lithium iron phosphate for lithium ion power battery according to claim 1, it is characterized in that the lithium salts that adopts is one or more in Quilonum Retard, Lithium Acetate, lithium hydroxide, the lithium nitrate, consumption is a lithium: iron: phosphorus mol ratio=0.95-1.05: 1: 1.
8. the preparation method of high-density spherical lithium iron phosphate for lithium ion power battery according to claim 1, it is characterized in that the carbon source that adopts is one or more in conductive carbon black, graphite, charcoal gel, carbon nanotube, carbon nano fiber, nano-sized carbon microballoon, glucose, sucrose, fructose, Mierocrystalline cellulose, starch, polyvinyl alcohol, polyoxyethylene glycol, styrene-butadiene rubber(SBR) breast, carboxymethyl cellulose, polystyrene, tetrafluoroethylene, polyvinylidene difluoride (PVDF), polyacrylonitrile, resol, the Resins, epoxy, the mass ratio that accounts for LiFePO 4 material is 2-20%.
9. the preparation method of high-density spherical lithium iron phosphate for lithium ion power battery according to claim 1, it is characterized in that the doping metals compound that adopts is one or more in magnesium nitrate, magnesium oxalate, nickelous nitrate, Xiao Suangu, aluminum nitrate, titanium dioxide, zirconium dioxide, Niobium Pentxoxide, the Manganse Dioxide, consumption is to mix metal: phosphorus mol ratio=0.005-0.035: 1.
10. the preparation method of high-density spherical lithium iron phosphate for lithium ion power battery according to claim 1, it is characterized in that mixture first section high-temperature heat treatment process in kiln is that mixture is warmed up to 300-550 ℃ with 2-10 ℃/minute speed, constant temperature 1-10h carries out second section high-temperature heat treatment then.
11. the preparation method of high-density spherical lithium iron phosphate for lithium ion power battery according to claim 10, it is characterized in that mixture second section high-temperature heat treatment process in kiln is that mixture is warmed up to 600-850 ℃ with the speed of 2-10 ℃/min, constant temperature 8-48h, naturally cooling in stove.
12. the preparation method of high-density spherical lithium iron phosphate for lithium ion power battery according to claim 1 is characterized in that shielding gas is one or more in hydrogen, nitrogen, argon gas or the ammonia.
13. the preparation method of high-density spherical lithium iron phosphate for lithium ion power battery according to claim 1 is characterized in that the kiln that adopts is push-plate type tunnel furnace, tube furnace, bell jar stove or rotary kiln.
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| CN115959644A (en) * | 2022-12-30 | 2023-04-14 | 河南佰利新能源材料有限公司 | Method for preparing high-performance lithium iron phosphate by sectional sintering |
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