CN102185136A - Preparation method of lithium ion battery cathode material nano lithium iron phosphate - Google Patents
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Abstract
The invention discloses a preparation method of a lithium ion battery cathode material nano lithium iron phosphate which belongs to the technical field of nano lithium iron phosphate preparation. The method comprises the following steps: preparing hydrous nano iron phosphate by a rotating packed bed method; roasting and dehydrating the hydrous nano iron phosphate to obtain anhydrous nano iron phosphate powder; weighing lithium source compound, carbon source compound and anhydrous nano iron phosphate according to a stoichiometric ratio, adding pure water and a dispersant, mixing and stirring the mixture uniformly, preparing a slurry, performing spray drying of the prepared slurry, performing heat treatment of the obtained powder with the protection of inert gas to obtain the nano lithium iron phosphate material. The nano lithium iron phosphate material prepared by the invention has uniform components and good batch stability, has specific discharge capacity at 1C rate of more than 130 mAh/g and specific discharge capacity at 5C rate of more than 110 mAh/g at room temperature, and has great application value in the power-type lithium ion battery field. The method is applicable to large-scale production, and has low cost.
Description
Technical field
The invention belongs to the nano-lithium iron phosphate preparing technical field, particularly a kind of preparation method of anode material for lithium-ion batteries nano-lithium iron phosphate.
Background technology
LiFePO 4 (LiFePO
4) be a kind of lithium ion battery novel anode material that grew up in recent years.It is abundant to have raw material sources, and preparation cost is low, specific capacity height, good cycle, advantage such as environmental pollution is little.At present, power type of new generation or accumulation energy type lithium ion battery have been widely used in.
But still there is weak point in it at aspects such as high rate during charging-discharging, cryogenic property, volumetric specific energys, these problems have had a strong impact on performances such as the energy density, power density of battery, have also influenced the operating characteristics and the scope of application of battery, the too high large-scale promotion application that also influences battery pack of the battery manufacturing cost that the material consistency problem causes.Therefore, must fundamentally solve the bottleneck problem that material exists, promptly promote the intrinsic performance of ferrousphosphate lithium material from aspects such as material synthesis techniques.
At present, most of LiFePO4 producer directly adopts high temperature solid-state method to prepare ferrousphosphate lithium material on the market.Though the high temperature solid-state method synthesis process is simple, but reactant is difficult for mixing, reaction time is long, and need repeatedly sintering, synthetic product granularity major part is a micron order, and skewness, often contains impurity, pattern is irregular, and the chemical property of different batches material differs greatly.This is because solid phase method is difficult to control accurately lithium, iron, phosphorus ratio, and product purity, crystallization shape, granularity control also have great difficulty, the less stable of product lot quantity, and whole process of production long flow path, and energy consumption is bigger.The existing high rate performance that studies have shown that nano-lithium iron phosphate is compared all with the micron order LiFePO 4 with cryogenic property and is improved; but how to prepare well behaved nanometer ferrousphosphate lithium material difficult problem really; find advanced technology, process stabilizing, practicality simple to operate and technology path that can large-scale production; simultaneously; also to consider manufacturing cost, the economy of aspects such as energy consumption and environmental protection and social influence.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of anode material for lithium-ion batteries nano-lithium iron phosphate is characterized in that this method carries out according to the following steps:
(1) utilize the RPB method to prepare nano hydrated ferric phosphate;
(2) the nano hydrated ferric phosphate with step (1) preparation dewatered 4～12 hours 400～600 ℃ of following roastings, obtained the waterless nano ferric phosphate powder body;
(3) according to mol ratio Li: C: Fe=(1～1.05): (1～1.2): 1 takes by weighing the waterless nano ferric phosphate of preparation in nanometer Li source compound, carbon-source cpd and the step (2), add pure water and dispersant, mix, obtain solid content and be 20～50% slurry, the granularity of SS is 20～60nm in the slurry;
(4) slurry that step (3) is made carries out spray drying, the presoma powder that obtains mixing;
(5) powder that step (4) is obtained 500～850 ℃ of heat treatments 2～14 hours, obtains nanometer ferrousphosphate lithium material under inert gas shielding.
Described nano hydrated ferric phosphate granularity is 20～60nm.
Described nanometer Li source compound granularity is 20～60nm.
Described nanometer Li source compound is a kind of in lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate and the lithium oxalate.
In the step (3), described carbon-source cpd is one or more in sucrose, glucose, citric acid, pentaerythrite, vitamin C, polyethylene glycol and the polyethers.
In the step (3), described dispersant is lauryl sodium sulfate, dodecyl sodium sulfate, dioctyl sodium sulfosuccinate (A Luosuo-OT), any one in sucrose fat, aliphatic acid sorb smooth (Span), polysorbate (Tween), polyoxyethylene, polyvinyl alcohol, triethyl group hexyl phosphoric acid, methyl anyl alcohol, cellulose derivative, polyacrylamide, the fatty acid polyethylene glycol ester.
Carbon content in the described nanometer ferrousphosphate lithium material is 0.5～5%.
Gained nanometer ferrousphosphate lithium material granularity is greatly between 40～160nm.
The invention provides the method that a kind of spray drying-carbothermic method prepares nanometer ferrousphosphate lithium material; at first start with from the presoma ferric phosphate of synthesizing lithium ferrous phosphate; select novel RPB to prepare nano ferric phosphate; and select nano-calcium carbonate lithium and other nanoscale lithium salts for use; subsequently; adopt ball milling mixing and spray drying technology to prepare mixed uniformly precursor material; under atmosphere protection, obtain narrower particle size distribution at last, the nanometer ferrous phosphate lithium material that free-running property is good with lower temperature heat treatment.
Beneficial effect of the present invention is:
(1) makes raw material with the ferric phosphate of cheapness, do not use expensive ferrous iron, not only reduced production cost, and avoided the easy oxidation of ferrous iron to generate the impurity that is difficult to remove and cause product impure;
(2) with ferric phosphate as source of iron and phosphorus source, the distributing very evenly and fixed ratio of iron, phosphorus atoms;
(3) adopt the high speed ball milling, add dispersant simultaneously nano ferric phosphate and nanometer lithium source material and carbon source material are fully mixed, the evolving path of lithium ion in the nano ferric phosphate particle is short, utilizes and improves material conductivity and high rate performance; Micron order material mixing before comparing, the ball milling time shortens greatly, and rotational speed of ball-mill reduces, and considers from the production angle, has saved energy consumption, has improved production efficiency.
(4) adopt RPB to prepare the method for lithium source materials such as nano ferric phosphate and nano-calcium carbonate lithium, technology is simple, is easy to control, and reaction is quick, the efficient height, and product quality consistency height, stable performance, preparation cost is low, is beneficial to large-scale production.
(5) adopt the high temperature solid-state method production technology of a step sintering simple, the cycle is short; Because various precursor material are nanometer scale, therefore, sintering temperature descends, and sintering time shortens, and has further reduced power consumption, emission-free pollution, the suitable large batch of suitability for industrialized production of waiting in the whole technical process;
(6) adopt spray-dired method, the wink-dry slurry is avoided segregation in the composition dry run, and the products obtained therefrom composition is even, in batches good stability;
(7) at nano ferric phosphate preparation and precursor material ball milling mix stages all than the even carbon dope that is easier to realize metal ion mixing and granule interior, to material modification and improve conductivity and be highly profitable;
(8) He Cheng nanometer ferrousphosphate lithium material has good electrochemical as anode material for lithium-ion batteries, at room temperature 1C multiplying power discharging specific capacity is greater than 130mAh/g, 5C multiplying power discharging specific capacity is greater than 110mAh/g, and cyclicity is good, is fit to the power anode material for lithium-ion batteries.
Description of drawings
Fig. 1 is the prepared cycle performance curve (1C six circulations, 5C ten circulations, 10C ten circulations, 15C two ten circulations, 5C five circulations) of nano-lithium iron phosphate under different multiplying of embodiment one;
Fig. 2 is the transmission electron microscope photo of the prepared nano-lithium iron phosphate of embodiment two.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is described further, following examples do not produce restriction to the present invention.
The used nanometer Li source compound of the present invention is a lithium carbonate, lithium hydroxide, lithium nitrate, a kind of in lithium acetate and the lithium oxalate, commercially available, wherein the nano-calcium carbonate lithium also can utilize the self-control of RPB method, utilize the RPB method to prepare the nano-calcium carbonate lithium, technology is as follows: earlier water-soluble lithium salts or lithium hydroxide are dissolved in the water lithium source solution, and the adding water soluble dispersing agent forms mixed solution in the solution of lithium source, start RPB, make its rotation, this mixed solution is sprayed by charging aperture and liquid distribution trough with measuring pump then, be distributed on the porous aggregate of RPB annular fill area, feed CO simultaneously
2Perhaps the water soluble carbonate saline solution makes water-soluble lithium salts or lithium hydroxide solution and CO under centrifugal action
2Gas or water soluble carbonate saline solution fully mix fast, the nano-calcium carbonate lithium particle that reactive crystallization generates is discharged by the discharging opening of RPB with mixed liquor, after filtration, washing, drying process obtain nano-scale lithium carbonate after handling, the nano-scale lithium carbonate granularity of preparation is greatly between 10～100nm.The used nanometer Li source compound granularity of the present invention is 20～60nm.
Utilize the RPB method to prepare nano hydrated ferric phosphate, with reference to the applicant's patent " a kind of preparation method of nano ferric phosphate " (application number: 200910235404.8), technology is as follows: with phosphoric acid or soluble phosphoric acid salting liquid both one of, one of water-soluble divalent iron salt and oxidant or water-soluble trivalent ferric salt solution, the mixed solution and the alkaline aqueous solution that form with water soluble dispersing agent are input in the RPB layer, regulate the rotating speed of RPB, control the pH value of reaction system between 1.6-6.0 with aqueous slkali, the nano ferric phosphate particle that reactive crystallization generates is discharged by the discharging opening of RPB with mixed liquor, after filtration, washing, drying process obtains nanoscale hypophosphite monohydrate iron after handling, and the nano hydrated ferric phosphate granularity of preparation is greatly between 10～100nm.The used nano hydrated ferric phosphate granularity of the present invention is 20～60nm.
Embodiment one:
Preparation anode material for lithium-ion batteries nano-lithium iron phosphate, carry out according to the following steps:
(1) be raw material with lithium hydroxide and sodium carbonate, utilize the RPB method to prepare the nano-calcium carbonate lithium, the particle mean size of gained lithium carbonate is 60nm;
(2) be raw material with ferric nitrate, phosphoric acid and ammoniacal liquor, utilize the RPB method to prepare nano hydrated ferric phosphate, specifically can (application number: 200910235404.8), the nano hydrated ferric phosphate particle mean size of gained be 40nm with reference to the applicant's patent " a kind of preparation method of nano ferric phosphate ";
(3) get the nano hydrated ferric phosphate FePO that 620g step (2) prepares
42H
2O, the heating rate with 4 ℃/min in air atmosphere is raised to 550 ℃ of roasting 6hr dehydrations, gets waterless nano ferric phosphate powder;
(4) take by weighing 110g sucrose, 500g waterless nano ferric phosphate and 125g nano-calcium carbonate lithium (mol ratio Li: C: Fe=1.02: 1.16: 1), add 3000ml water, the 20mg dodecyl sodium sulfate, ball milling mixing 2hr in basket ball mill, rotational speed of ball-mill 600rpm, form uniform solid content and be 20% slurry, the particle mean size of SS is 50nm in the slurry;
(5) slurry that step (4) is made pneumatic spray drying device drying, adopt and the fluidized drying mode, atomising device adopts the double-current method nozzle, control orifice gas flow and pressure and and the peristaltic pump charging rate, make inlet temperature remain on 200 ℃, outlet temperature is 120 ℃, and outlet air separates emptying through the one-level whirlpool, obtains the presoma powder that mixes after the spray drying;
(6) powder that step (5) is obtained at 600 ℃ of heat treatment 10hr, obtains nanometer ferrousphosphate lithium material under the high pure nitrogen protection.
Record that the weight content of carbon is about 4.0% in the ferrousphosphate lithium material.Gained nanometer ferrousphosphate lithium material particle mean size is 100nm.
Nanometer ferrousphosphate lithium material, Super-P conductive carbon black, PVDF binding agent are pressed mass ratio to be mixed at 8: 1: 1, with NMP is that solvent is made uniform slurry, then with its blade coating on the aluminium foil of 20 micron thickness, after 120 ℃ of vacuumize, obtain anode pole piece, with the lithium paper tinsel is to electrode, in being full of the glove box of argon gas, adorn Experimental cell, carry out charge-discharge test with constant current, charging/discharging voltage is 2.5-4.2V, it is 135mAh/g that room temperature records under the 1C multiplying power average specific discharge capacity, average specific discharge capacity 113mAh/g under the 5C multiplying power.The cycle performance curve of prepared nano-lithium iron phosphate under different multiplying be (six circulations of 1C, ten circulations of 5C, ten circulations of 10C, 20 circulations of 15C, five circulations of 5C) as shown in Figure 1.
Embodiment two:
Preparation anode material for lithium-ion batteries nano-lithium iron phosphate, carry out according to the following steps:
(1) be raw material with ferric acetate, phosphoric acid and potassium hydroxide, utilize the RPB method to prepare nano hydrated ferric phosphate, specifically can (application number: 200910235404.8), the nano hydrated ferric phosphate particle mean size of gained be 20nm with reference to the applicant's patent " a kind of preparation method of nano ferric phosphate ";
(2) get the nano hydrated ferric phosphate FePO that 620g step (1) prepares
42H
2O, 400 ℃ of roasting 12hr dehydrations get waterless nano ferric phosphate powder in air atmosphere;
(3) take by weighing the lithium hydroxide that 120g glucose, 500g waterless nano ferric phosphate and 145g particle mean size are 20nm (mol ratio Li: C: Fe=1.04: 1.2: 1), add 2000ml water, the 80mg polyvinyl alcohol, ball milling mixing 3hr in basket ball mill, rotational speed of ball-mill 800rpm, form uniform solid content and be 30% slurry, the particle mean size of SS is 20nm in the slurry;
(4) slurry that step (3) is made pneumatic spray drying device drying, adopt and the fluidized drying mode, atomising device adopts the double-current method nozzle, control orifice gas flow and pressure and and the peristaltic pump charging rate, make inlet temperature remain on 250 ℃, outlet temperature is 150 ℃, and outlet air separates emptying through the one-level whirlpool, obtains the presoma powder that mixes after the spray drying;
(5) powder that step (4) is obtained at 550 ℃ of heat treatment 12hr, obtains nanometer ferrousphosphate lithium material under the high pure nitrogen protection.
Record that the weight content of carbon is about 5.0% in the nanometer ferrousphosphate lithium material.Gained nanometer ferrousphosphate lithium material particle mean size is 60nm.The transmission electron microscope photo of prepared nano-lithium iron phosphate as shown in Figure 2.
Carry out charge-discharge performance test with embodiment one: carry out charge-discharge test with constant current, charging/discharging voltage is 2.5-4.2V, and room temperature records that average specific discharge capacity is 138mAh/g under the 1C multiplying power, average specific discharge capacity 128mAh/g under the 5C multiplying power.
Embodiment three:
Preparation anode material for lithium-ion batteries nano-lithium iron phosphate, carry out according to the following steps:
(1) be raw material with iron chloride, ammonium dihydrogen phosphate and ammoniacal liquor, utilize the RPB method to prepare nano hydrated ferric phosphate, specifically can (application number: 200910235404.8), the nano hydrated ferric phosphate particle mean size of gained be 50nm with reference to the applicant's patent " a kind of preparation method of nano ferric phosphate ";
(2) get the nano hydrated ferric phosphate FePO that 620g step (1) prepares
42H
2O, 450 ℃ of roasting 10hr dehydrations get waterless nano ferric phosphate powder in air atmosphere;
(3) take by weighing the nanometer lithium acetate that 100g pentaerythrite, 500g waterless nano ferric phosphate and 350g particle mean size are 60nm (Li: C: Fe=1.04: 1.11: 1), add 1000ml water, add the 40mg lauryl sodium sulfate, ball milling mixing 5hr in basket ball mill, rotational speed of ball-mill 1200rpm, form uniform solid content and be 50% slurry, the particle mean size of SS is 60nm in the slurry;
(4) slurry that step (3) is made pneumatic spray drying device drying, adopt and the fluidized drying mode, atomising device adopts the double-current method nozzle, control orifice gas flow and pressure and and the peristaltic pump charging rate, make inlet temperature remain on 300 ℃, outlet temperature is 110 ℃, and outlet air separates emptying through the one-level whirlpool, obtains the presoma powder that mixes after the spray drying;
(5) powder that step (4) is obtained at 650 ℃ of heat treatment 8hr, obtains nanometer ferrousphosphate lithium material under the high pure nitrogen protection.
The weight content that records carbon in the ferrousphosphate lithium material is 3.2%.Gained nanometer ferrousphosphate lithium material particle mean size is 80nm.
Carry out charge-discharge performance test with embodiment one: carry out charge-discharge test with constant current, charging/discharging voltage is 2.5-4.2V, and room temperature records that average specific discharge capacity is 145mAh/g under the 1C multiplying power, average specific discharge capacity 124mAh/g under the 5C multiplying power.
Embodiment four:
Preparation anode material for lithium-ion batteries nano-lithium iron phosphate, carry out according to the following steps:
(1) be raw material with ferric nitrate, ammonium dihydrogen phosphate and ammoniacal liquor, utilize the RPB method to prepare nano hydrated ferric phosphate, specifically can (application number: 200910235404.8), the nano hydrated ferric phosphate particle mean size of gained be 30nm with reference to the applicant's patent " a kind of preparation method of nano ferric phosphate ";
(2) get the nano hydrated ferric phosphate FePO that 620g step (1) prepares
42H
2O, 600 ℃ of roasting 4hr dehydrations get waterless nano ferric phosphate powder in air atmosphere;
(3) take by weighing the nanometer lithium oxalate that 100g vitamin C, 500g waterless nano ferric phosphate and 170g particle mean size are 30nm (Li: C: Fe=1.01: 1.03: 1), add 1200ml water, the 60mg polysorbate, ball milling mixing 4hr in basket ball mill, rotational speed of ball-mill 1000rpm, form uniform solid content and be 40% slurry, the particle mean size of SS is 30nm in the slurry;
(4) slurry that step (3) is made pneumatic spray drying device drying, adopt and the fluidized drying mode, atomising device adopts the double-current method nozzle, control orifice gas flow and pressure and and the peristaltic pump charging rate, make inlet temperature remain on 300 ℃, outlet temperature is 100 ℃, and outlet air separates emptying through the one-level whirlpool, obtains the presoma powder that mixes after the spray drying;
(5) powder that step (4) is obtained at 850 ℃ of heat treatment 2hr, obtains nanometer ferrousphosphate lithium material under the high pure nitrogen protection.
The weight content that records carbon in the ferrousphosphate lithium material is 0.5%.Gained nanometer ferrousphosphate lithium material particle mean size is 40nm.
Carry out charge-discharge performance test with embodiment one: carry out charge-discharge test with constant current, charging/discharging voltage is 2.5-4.2V, and room temperature records that average specific discharge capacity is 140mAh/g under the 0.1C multiplying power, average specific discharge capacity 115mAh/g under the 5C multiplying power.
Embodiment five:
Preparation anode material for lithium-ion batteries nano-lithium iron phosphate, carry out according to the following steps:
(1) be raw material with ferric nitrate, potassium dihydrogen phosphate and ammoniacal liquor, utilize the RPB method to prepare nano hydrated ferric phosphate, specifically can (application number: 200910235404.8), the nano hydrated ferric phosphate particle mean size of gained be 30nm with reference to the applicant's patent " a kind of preparation method of nano ferric phosphate ";
(2) get the nano hydrated ferric phosphate FePO that 620g step (2) prepares
42H
2O, the heating rate with 4 ℃/min in air atmosphere is raised to 500 ℃ of roasting 8hr dehydrations, gets waterless nano ferric phosphate powder;
(3) take by weighing the nano-calcium carbonate lithium that 120g glucose, 500g waterless nano ferric phosphate and 125g particle mean size are 40nm (Li: C: Fe=1.02: 1.21: 1), add 2500ml water, the 40mg lauryl sodium sulfate, ball milling mixing 1hr in basket ball mill, rotational speed of ball-mill 400rpm, form uniform solid content and be 25% slurry, the particle mean size of SS is 40nm in the slurry;
(4) slurry that step (3) is made pneumatic spray drying device drying, adopt and the fluidized drying mode, atomising device adopts the double-current method nozzle, control orifice gas flow and pressure and and the peristaltic pump charging rate, make inlet temperature remain on 250 ℃, outlet temperature is 100 ℃, and outlet air separates emptying through the one-level whirlpool, obtains the presoma powder that mixes after the spray drying;
(5) powder that step (4) is obtained at 500 ℃ of heat treatment 14hr, obtains nanometer ferrousphosphate lithium material under the high pure nitrogen protection.
The weight content that records carbon in the ferrousphosphate lithium material is 2.0%.Gained nanometer ferrousphosphate lithium material particle mean size is 70nm.
Nanometer ferrousphosphate lithium material, Super-P conductive carbon black, PVDF binding agent are pressed mass ratio to be mixed at 8: 1: 1, with NMP is that solvent is made uniform slurry, then with its blade coating on the aluminium foil of 20 micron thickness, after 120 ℃ of vacuumize, obtain anode pole piece, with the lithium paper tinsel is to electrode, in being full of the glove box of argon gas, adorn Experimental cell, carry out charge-discharge test with constant current, charging/discharging voltage is 2.5-4.2V, it is 136mAh/g that room temperature records under the 0.1C multiplying power average specific discharge capacity, average specific discharge capacity 110mAh/g under the 5C multiplying power.
Each embodiment is raw materials used, technology and product performance are as shown in table 1.
Claims (8)
1. the preparation method of an anode material for lithium-ion batteries nano-lithium iron phosphate is characterized in that this method carries out according to the following steps:
(1) utilize the RPB method to prepare nano hydrated ferric phosphate;
(2) the nano hydrated ferric phosphate with step (1) preparation dewatered 4～12 hours 400～600 ℃ of following roastings, obtained the waterless nano ferric phosphate powder body;
(3) according to mol ratio Li: C: Fe=(1～1.05): (1～1.2): 1 takes by weighing the waterless nano ferric phosphate of preparation in nanometer Li source compound, carbon-source cpd and the step (2), add pure water and dispersant, mix, obtain solid content and be 20～50% slurry, the granularity of SS is 20～60nm in the slurry;
(4) slurry that step (3) is made carries out spray drying, the presoma powder that obtains mixing;
(5) powder that step (4) is obtained 500～850 ℃ of heat treatments 2～14 hours, obtains nanometer ferrousphosphate lithium material under inert gas shielding.
2. the preparation method of a kind of anode material for lithium-ion batteries nano-lithium iron phosphate according to claim 1 is characterized in that described nano hydrated ferric phosphate granularity is 20～60nm.
3. the preparation method of a kind of anode material for lithium-ion batteries nano-lithium iron phosphate according to claim 1 is characterized in that described nanometer Li source compound granularity is 20～60nm.
4. according to the preparation method of claim 1 or 3 described a kind of anode material for lithium-ion batteries nano-lithium iron phosphates, it is characterized in that described nanometer Li source compound is a kind of in lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate and the lithium oxalate.
5. the preparation method of a kind of anode material for lithium-ion batteries nano-lithium iron phosphate according to claim 1, it is characterized in that in the step (3), described carbon-source cpd is one or more in sucrose, glucose, citric acid, pentaerythrite, vitamin C, polyethylene glycol and the polyethers.
6. the preparation method of a kind of anode material for lithium-ion batteries nano-lithium iron phosphate according to claim 1, it is characterized in that in the step (3), described dispersant is lauryl sodium sulfate, dodecyl sodium sulfate, dioctyl sodium sulfosuccinate (A Luosuo-OT), any one in sucrose fat, aliphatic acid sorb smooth (Span), polysorbate (Tween), polyoxyethylene, polyvinyl alcohol, triethyl group hexyl phosphoric acid, methyl anyl alcohol, cellulose derivative, polyacrylamide, the fatty acid polyethylene glycol ester.
7. the preparation method of a kind of anode material for lithium-ion batteries nano-lithium iron phosphate according to claim 1 is characterized in that the carbon content in the described nanometer ferrousphosphate lithium material is 0.5～5%.
8. the preparation method of a kind of anode material for lithium-ion batteries nanometer phosphoric acid industry iron lithium according to claim 1 is characterized in that gained nanometer ferrousphosphate lithium material granularity is between 40～160nm.
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| CN103022487A (en) * | 2012-12-20 | 2013-04-03 | 中国东方电气集团有限公司 | Preparation method for nanometer manganese lithium phosphate anode material of lithium battery |
| CN103258995A (en) * | 2013-06-06 | 2013-08-21 | 郑州瑞普生物工程有限公司 | Preparation method of lithium iron phosphate material |
| CN104300119A (en) * | 2013-07-17 | 2015-01-21 | 东莞市长安东阳光铝业研发有限公司 | Preparation method for lithium iron phosphate cathode material |
| CN108288698A (en) * | 2018-01-24 | 2018-07-17 | 杭州金马新能源科技有限公司 | A kind of preparation method of lithium iron phosphate positive material |
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| CN103022487B (en) * | 2012-12-20 | 2016-04-06 | 中国东方电气集团有限公司 | A kind of preparation method of nanometer manganese lithium phosphate anode material of lithium battery |
| CN103258995A (en) * | 2013-06-06 | 2013-08-21 | 郑州瑞普生物工程有限公司 | Preparation method of lithium iron phosphate material |
| CN104300119A (en) * | 2013-07-17 | 2015-01-21 | 东莞市长安东阳光铝业研发有限公司 | Preparation method for lithium iron phosphate cathode material |
| CN104300119B (en) * | 2013-07-17 | 2019-05-24 | 东莞东阳光科研发有限公司 | A kind of preparation method of lithium iron phosphate positive material |
| CN108336352A (en) * | 2017-12-29 | 2018-07-27 | 贵州唯特高新能源科技有限公司 | A kind of preparation method of high conductivity high vibration high density lithium iron phosphate |
| CN108288698A (en) * | 2018-01-24 | 2018-07-17 | 杭州金马新能源科技有限公司 | A kind of preparation method of lithium iron phosphate positive material |
| CN113769633A (en) * | 2021-08-27 | 2021-12-10 | 合肥国轩高科动力能源有限公司 | Lithium ion battery slurry mixing method |
| CN113769633B (en) * | 2021-08-27 | 2024-05-03 | 合肥国轩高科动力能源有限公司 | Slurry mixing method for lithium ion battery |
| CN115072693A (en) * | 2022-06-29 | 2022-09-20 | 蜂巢能源科技股份有限公司 | Lithium iron phosphate cathode material, preparation method thereof and lithium ion battery |
| CN115072693B (en) * | 2022-06-29 | 2023-11-24 | 蜂巢能源科技股份有限公司 | Lithium iron phosphate positive electrode material, preparation method thereof and lithium ion battery |
| CN115432689A (en) * | 2022-09-30 | 2022-12-06 | 福建紫金锂元材料科技有限公司 | Preparation method of high-performance long-life lithium iron phosphate cathode material |
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