CN101386404B - Method for preparing high-efficient fluorine-dopping lithium iron phosphate positive electrode material - Google Patents
Method for preparing high-efficient fluorine-dopping lithium iron phosphate positive electrode material Download PDFInfo
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- CN101386404B CN101386404B CN200810071643XA CN200810071643A CN101386404B CN 101386404 B CN101386404 B CN 101386404B CN 200810071643X A CN200810071643X A CN 200810071643XA CN 200810071643 A CN200810071643 A CN 200810071643A CN 101386404 B CN101386404 B CN 101386404B
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Abstract
The invention relates to a preparation method for an efficient fluorine-doped ferrous phosphate lithium anodal material, which is characterized in that the preparation process is as follows: according to the mole ratio of Li<+> to Fe<2+> to (PO4)<3-> to fluorine-doped agent of x : y : z : k, the components are weighted to form a reaction composite, wherein, x is equal to or more than 0.90 and equal to or less than 1.15, y is equal to or more than 0.95 and equal to or less than 1.10, z is equal to or more than 0.90 and equal to or less than 1.00, and k is equal to or more than 0.010 and equal to or less than 0.20. Lithium salt, phosphate salt, carbon-containing compound or carbon powder and wet grinding media are mixed, and are processed by ball milling mixing and vacuum drying; under the inert atmosphere or the weakly reducing atmosphere the dried powder is heated to 450-650 DGE C from room temperature, and sintering lasts 3-15 hours while holding the temperature to get reaction precursor. Ferrous salt, the fluorine-doped agent and the wet grinding media are added into the reaction precursor, the mixture thereof is processed by ball milling for 3-15 hours, and then is processed by vacuum drying at 70-110 DGE C. Under the inert atmosphere or the weakly reducing atmosphere the dried powder is heated to 650-900 DGE C from room temperature, sintering lasts 3-15 hours while holding the temperature, the dried powder is cooled to the room temperature to get the fluorine-doped ferrous phosphate lithium.
Description
Technical field
The invention belongs to the technical field of lithium ion battery electrode material, relate to a kind of preparation method who can be used for the ferrous phosphate doping lithium anode material of lithium ion battery, lithium cell, polymer Li-ion battery and ultracapacitor.
Technical background
LiFePO 4 has as the positive electrode material of lithium ion battery that security is good, stable cycle performance, cheap, and theoretical loading capacity can reach 170mAh/g.The important candidate material that is considered to anode material for lithium-ion batteries.But, LiFePO 4 is applied to lithium ion battery and also has many difficulties.As, the electronic conductivity of LiFePO 4 is low, ionic conductance is low, tap density and true density is little, low-temperature performance is relatively poor.In order to overcome the deficiency of LiFePO 4, carried out broad research both at home and abroad.
In order to improve the performance of LiFePO 4, with solid sintering technology LiFePO 4 is carried out doping vario-property and carried out many researchs.The doping agent that is used for doping vario-property comprises nickel fiber, copper fiber, iron fiber, zinc fiber, acetylene black, crystalline flake graphite, boride, carbide, transition metal oxide, carbon dust, sucrose, glucose, polyvinyl alcohol, dextrin, starch etc.The doped element that relates to comprises [CN1958441A such as alkalimetal ion, alkaline-earth metal ions, transition metal ion, halide-ions, rare earth metal; Choi D.et al., J.Power Sources2007,163:1064-1069; Croce F et al, Electrochem.SolidState Lett., 2002,5 (3): A47-A50; Park K S et al.Solid State Commun., 2004,129:311-314.].Preparation process adopts " method that mixed reactant of ball milling or the slurrying of ball-milling reaction thing combine with solid state sintering " mostly.Wherein the fluorine of mixing to LiFePO 4 has prepared attention.When the ferrous lithium of hexafluorophosphoric acid is mixed in preparation, can in diplobiont system, carry out, the sample of preparation shows different fluorine effect and the chemical properties mixed.
Mix in the fluorine system in the first kind, have F during preparation
-With NH
4 +Or H
+The technological process of coexistence heating.In preparation process, because the NH that the HF that reaction process discharges can volatilize and leave reaction system or come out with decomposition simultaneously
3Reaction generates NH
4F.And NH
4F can be because of being decomposed into HF and NH once more in high-temperature sintering process
3And reaction system is left in volatilization, therefore, can not detect fluorion [Wang Deyu, Inst. of Physics, CAS, doctorate paper, 2005.5. in the sample of their preparation; Wang D.Y.et al., J.Solid StateChem., 2004,177 (12): 4582-4587; Patent CN1753216, CN1785800A, CN1772604A, CN101162776A, CN1332878C, CN1332878C, CN1790782A, CN101081696A, CN1903707A, CN1834153].For example, patent CN1903707A makes solution with the soluble compounds of lithium fluoride, Fe and P, adds water-fast doping agent and makes suspension liquid, adopts double-sinter process to prepare carbon cladded ferrous lithium phosphate.The soluble compounds of the described P of containing of this patent comprises phosphoric acid, monometallic, ammonium phosphate, Secondary ammonium phosphate or primary ammonium phosphate.Wang Deyu [Wang Deyu, Inst. of Physics, CAS, doctor, 2005.5.; Dey Wang et al., Newsolid-state synthesis rout ine andmechanism for LiFeP04using LiF as lithium precursor, J.Solid State Chem., 2004,177 (12): 4582-4587] with FeC
2O
42H
2O, NH
4H
2PO
4Mix with LiF, prepared LiFePO 4 by twice sintering and twice ball milling.Wang Deyu thinks FeC
2O
42H
2O, NH
4H
2PO
4Reaction earlier forms FeHPO
4Intermediate phase, intermediate phase FeHPO
4Generate with the LiF reaction again and mix fluorine LiFePO
4They think the HF that emits in the reaction process can with decompose the NH of coming out
3Reaction generates NH
4F.When high temperature sintering, NH
4F is decomposed into HF and NH again
3And leave reaction system.Therefore, their sample of preparation can not detect fluorion.The efficient of mixing fluorine is not high.Because the price of fluorochemical is more expensive, poisonous.During as reaction raw materials, most expensive fluorions leave reaction system as the tail gas by product, obviously do not meet the requirement of energy-saving and emission-reduction with lithium fluoride.
Mix in the fluorine system in second class, do not have F during preparation
-With NH
4 +Or H
+The technological process [CN1333287C, CN100370644C, CN1834153, CN101162776A] of coexistence heating.
Patent CN1332878C mixes lithium salts, ferrous salt and phosphoric acid salt, adds lithium fluoride, blending agent again, attempts to prepare oxygen place doped iron lithium phosphate LiFeP (M by twice ball milling mixing and twice sintering
xO
4-x) powder.
Patent CN1790782A and patent CN101081696A are with lithium fluoride, ferrous salt or molysite, P
2O
5, conductive agent and additive ball milling be mixed, prepares LiFePO by twice sintering
4The positive electrode material of/C.LiaoX.-Z., etal[Liao X.-Z., et al, J Power Sources, 2007,174:720-725] by first ball milling FePO
4, Fe, Li
3PO
4, LiF, sucrose mixture, then mixture has been prepared the LiFe (PO that mixes fluorine at 600-650 ℃ of sintering
4)
1-xF
3x/ C (x=0,0.025,0.05,0.1).Sample shows good multiplying power discharging property.XRD analysis shows, is mixing the few LiFe (PO of fluorine amount
4)
1-xF
3xAmong/the C (x=0.025 or 0.05), fluorine element is gone into LiFePO with the solid solution of LiF form
4In the crystalline phase; Mixing the more LiFe (PO of fluorine amount
4)
0.90F
0.3Among/the C, fluorine element is then with Fe
2(PO
4) form of F and LiF exists in the crystalline phase.The fluorine element doping can make LiFePO
4Middle Li
+Travelling speed is accelerated, and makes that electrochemical polarization reduces when discharging and recharging.The low range loading capacity of mixing the more sample of fluorine amount decreases, but its high-rate discharge ability and high temperature circulation stability quite outstanding [Liao Xiaozhen, Shanghai Communications University, doctorate paper, 2005.9.].Kubo studies show that and mixes fluorine [[Kubo K., et al.J.Power Souce.1997,68:553-557; Kubo K., et al.J.Power Souce.1999,81-81:599-603] effect with mix cationic different.Stability of structure when mixing fluorine and can not improve material and discharge and recharge, but fluorion can present the characteristic that weak bond closes in lattice, help fluorion and on every side ion in the ion moving process, adjust the position.In addition, mix the fluorine sample and in charge and discharge process, generate a small amount of cenotype, can alleviate the internal stress that produces in the material structure in the charge and discharge process, restrain the lattice distortion and the collapse of the material structure that causes, prolonged cycle life greatly.Xing Caihong [Xing Caihong, Zhejiang University, master thesis, 2006.5.] is with LiF and FePO
44H
2O and LiOH H
2The O prepared in reaction Li
1-xFePO
4-xF
x/ C (x=0.01,0.03,0.05).Because the valency of iron is+2 in the product LiFePO 4, therefore, relates to Fe in the reaction process
3+To Fe
2+Transformation, need reduction process of experience.
In order to improve the improvement effect of fluorine to the LiFePO 4 performance of mixing, the present invention carries out the sintering of fs earlier with lithium salts and the carbonaceous organic material or the carbon dust mixing of Secondary ammonium phosphate (primary ammonium phosphate, ammonium phosphate), volatile acid.In the fs sintering process, volatile acid radical ion and ammonium radical ion or active H
+Can form the ammonium salt of volatile acid or volatile acid.At high temperature, the ammonium salt of volatile acid or volatile acid is decomposed into volatile acid and ammonia and leaves reaction system, carbonaceous organic material or carbon dust generate the nano carbon particle that is mixed in the phosphoric acid lithium salts in the mixed phase in oxygen-free environment simultaneously, stop the phosphoric acid lithium salts to grow into big crystal grain.In the subordinate phase sintering process, when adding LiF doping agent and conductive agent.Because and F
-The species that form volatile compound are few, the fluorion that adds can be retained in the product, also separated with the reacted product of fluorion with ferrous simultaneously by nano-sized carbon by the separated phosphoric acid lithium salts of nano-sized carbon, obviously improve the electronic conductivity of LiFePO 4 sample, improved the cyclical stability of mixing fluorine effect and heavy-current discharge.
Summary of the invention
The purpose of this invention is to provide a kind of preparation and mix the preparation method of the ferrous lithium anode material of hexafluorophosphoric acid.For achieving the above object, the technical solution adopted in the present invention is:
According to Li
+: Fe
2+: PO
4 3-: the mol ratio of mingling fluorine agent is x:y:z:k weighing response composite lithium salts, ferrous salt, phosphoric acid salt and mingling fluorine agent, adds carbon compound or carbon dust, wet grinding media when ball milling.Wherein, the scope of the numerical value of the x of reactant molar ratio, y, z, k is: 0.90≤x≤1.15,0.95≤y≤1.10,0.90≤z≤1.00,0.010≤k≤0.20; The add-on of carbon compound or carbon dust is according to 1%～20% of the LiFePO 4 quality of the Mass Calculation of reactant; The consumption of wet grinding media is intended to 1/10～10 times of volume of the reaction mixture of ball milling.
Lithium salts, phosphoric acid salt, carbon compound or carbon dust and wet grinding media are mixed, ball milling mixed 3 hours～15 hours under 100 rev/mins～1000 rev/mins rotating speed, carried out drying in arbitrary temperature of 70 ℃～110 ℃ of temperature ranges under the vacuum of 10Pa～10132Pa pressure.The exsiccant powder is under inert atmosphere or weakly reducing atmosphere, be heated to arbitrary temperature of 450 ℃～650 ℃ of temperature ranges by room temperature according to 1 ℃/min～30 ℃/heat-up rate of min, kept the temperature sintering 3 hours～15 hours, and be cooled to room temperature and make pre-reaction material.In pre-reaction material, add ferrous salt, mingling fluorine agent and wet grinding media, ball milling mixed 3 hours～15 hours under 100 rev/mins～1000 rev/mins rotating speed, carried out drying in arbitrary temperature of 70 ℃～110 ℃ of temperature ranges under the vacuum of 10Pa～10132Pa pressure.The exsiccant powder places under inert atmosphere or the weakly reducing atmosphere, be heated to arbitrary temperature of 650 ℃～900 ℃ of temperature ranges by room temperature according to 1 ℃/min～30 ℃/heat-up rate of min, kept the temperature sintering 3 hours～24 hours, and be cooled to room temperature and make and mix the ferrous lithium of hexafluorophosphoric acid.
Reactant composed as follows:
Mingling fluorine agent of the present invention is lithium fluoride, Sodium Fluoride, Potassium monofluoride or silver fluoride.
Phosphoric acid salt of the present invention is ammonium phosphate, Secondary ammonium phosphate or primary ammonium phosphate.
Lithium salts of the present invention is Quilonum Retard, lithium oxalate, lithium chloride, Lithium Acetate or lithium nitrate.
Ferrous salt of the present invention is Ferrox, Iron diacetate, iron protochloride, iron protocarbonate, ferrous hydroxide or iron protoxide.
Carbon compound of the present invention is polypropylene, polyacrylamide, polyvinyl alcohol, glucose, sucrose, starch, tapioca flour, pachyrhizus, potato powder, taro meal or bran powder.
Carbon dust of the present invention is acetylene black or Graphite Powder 99.
Inert atmosphere of the present invention or weakly reducing atmosphere are the anhydrous air of gas mixture, carbon monoxide or anaerobic of gas mixture, nitrogen and argon gas of gas mixture, argon gas and the hydrogen of nitrogen, argon gas, nitrogen and hydrogen.
Wet grinding media of the present invention is methyl alcohol, ethanol, propyl alcohol, acetone, formaldehyde or formic acid.
Compare with other inventive method, raw materials cost of the present invention is lower, mingling fluorine agent mix fluorine efficient height, raw material sources are extensive, preparation process is simple, does not discharge deleterious fluorochemical in the preparation process substantially.This electrode materials has outstanding discharge performance, and particularly cycle performance is good under the situation of heavy-current discharge, for industrialization is laid a good foundation.
Embodiment
Below in conjunction with embodiment the present invention is further detailed.Embodiment further replenishes and explanation of the present invention, rather than the restriction to inventing.
Embodiment 1
According to Li
+: Fe
2+: PO4
3-: the mol ratio of mingling fluorine agent is 0.90:0.95:0.90:0.20 weighing response composite Quilonum Retard, Ferrox, ammonium phosphate and lithium fluoride.The methanol mixed of 1% polypropylene of the LiFePO 4 quality of calculating with Quilonum Retard, ammonium phosphate, according to the reactant quality, 1/10 volume of above reaction mixture, ball milling mixed 3 hours under 100 rev/mins rotating speed, carried out vacuum-drying at 70 ℃ under the pressure of 10Pa.The exsiccant powder is heated to 450 ℃ according to the heat-up rate of 1 ℃/min by room temperature under nitrogen atmosphere, kept the temperature sintering 3 hours, is cooled to room temperature and makes pre-reaction material.The methyl alcohol that adds Ferrox, lithium fluoride, 10 times of volumes of above reaction mixture in pre-reaction material, ball milling mixed 15 hours under 200 rev/mins rotating speed, was carrying out vacuum-drying under 110 ℃ under 10132Pa pressure.The exsiccant powder is heated to 650 ℃ according to the heat-up rate of 30 ℃/min by room temperature under nitrogen atmosphere, kept the temperature sintering 24 hours, is cooled to room temperature and makes and mix the ferrous lithium of hexafluorophosphoric acid.
Embodiment 2
According to Li
+: Fe
2+: PO
4 3-: the mol ratio of mingling fluorine agent is 1.0:1.0:1.0:0.010 weighing response composite lithium oxalate, Iron diacetate, Secondary ammonium phosphate and lithium fluoride.10% polyacrylamide of the LiFePO 4 quality of calculating with lithium oxalate, Secondary ammonium phosphate, according to the reactant quality, above reaction mixture 10 times of volume of ethanol mix, ball milling mixed 15 hours under 1000 rev/mins rotating speed, carried out vacuum-drying at 110 ℃ under the pressure of 10132Pa.The exsiccant powder is heated to 650 ℃ according to the heat-up rate of 30 ℃/min by room temperature under argon gas atmosphere, kept the temperature sintering 15 hours, is cooled to room temperature and makes pre-reaction material.The propyl alcohol that adds 10 times of volumes of Iron diacetate, lithium fluoride, above reaction mixture in the pre-reaction material, ball milling mixed 15 hours under 300 rev/mins rotating speed, carried out vacuum-drying at 110 ℃ under the pressure of 1018Pa.The exsiccant powder is heated to 900 ℃ according to the heat-up rate of 1 ℃/min by room temperature under the atmosphere of 90% nitrogen and 10% hydrogen mixed gas, kept the temperature sintering 3 hours, is cooled to room temperature and makes and mix the ferrous lithium of hexafluorophosphoric acid.
Embodiment 3
According to Li
+: Fe
2+: PO
4 3-: the mol ratio of mingling fluorine agent is 0.90:1.10:1.0:0.05 weighing response composite lithium chloride, iron protochloride, primary ammonium phosphate and Sodium Fluoride.The acetone of 20% glucose of the LiFePO 4 quality of calculating with lithium chloride, primary ammonium phosphate, according to the reactant quality, 1 times of volume of above reaction mixture mixes, ball milling mixed 10 hours under 400 rev/mins of rotating speeds, carried out vacuum-drying at 85 ℃ under the pressure of 100Pa.Dried powder is heated to 650 ℃ according to the heat-up rate of 20 ℃/min by room temperature under nitrogen atmosphere, kept the temperature sintering 8 hours, is cooled to room temperature and makes pre-reaction material.The propyl alcohol that adds iron protochloride, Sodium Fluoride, 2 times of volumes of above reaction mixture in the pre-reaction material, ball milling mixed 12 hours under 500 rev/mins rotating speed, carried out vacuum-drying at 75 ℃ under 2000Pa pressure.The exsiccant powder is heated to 800 ℃ according to the heat-up rate of 10 ℃/min by room temperature under the atmosphere of 95% argon gas and 5% hydrogen mixed gas, kept the temperature sintering 12 hours, is cooled to room temperature and makes and mix the ferrous lithium of hexafluorophosphoric acid.
Embodiment 4
According to Li
+: Fe
2+: PO
4 3-: the mol ratio of mingling fluorine agent is 0.90:1.10:1.00:0.10 weighing response composite Lithium Acetate, iron protocarbonate, ammonium phosphate and Potassium monofluoride.The formaldehyde of 5% tapioca flour of the LiFePO 4 quality of calculating with Lithium Acetate, ammonium phosphate, according to the reactant quality, 3 times of volumes of above reaction mixture mixes, ball milling mixed 8 hours under 500 rev/mins of rotating speeds, carried out vacuum-drying at 80 ℃ under the pressure of 280Pa.The exsiccant powder is heated to 600 ℃ according to the heat-up rate of 5 ℃/min by room temperature in deoxygenation dewaters air atmosphere, kept the temperature sintering 5 hours, is cooled to room temperature and makes pre-reaction material.The formic acid that adds 3 times of volumes of iron protocarbonate, Potassium monofluoride, above reaction mixture in pre-reaction material, ball milling mixed 8 hours under 600 rev/mins rotating speed, carried out vacuum-drying at 95 ℃ under the pressure of 5000Pa.The exsiccant powder places under the argon gas atmosphere, is heated to 700 ℃ according to the heat-up rate of 15 ℃/min by room temperature, keeps the temperature sintering 18 hours, is cooled to room temperature and makes and mix the ferrous lithium of hexafluorophosphoric acid.
Embodiment 5
According to Li
+: Fe
2+: PO
4 3-: the mol ratio of mingling fluorine agent is 1.15:0.95:1.00:0.20 weighing response composite lithium nitrate, iron protoxide, Secondary ammonium phosphate and silver fluoride.The acetone of 5% acetylene black of the LiFePO 4 quality of calculating with lithium nitrate, Secondary ammonium phosphate, according to the reactant quality, 5 times of volumes of above reaction mixture mixes, ball milling mixed 3 hours under 600 rev/mins rotating speed, carried out vacuum-drying at 78 ℃ under the pressure of 10132Pa.The exsiccant powder places deoxygenation to dewater under the air, is heated to 500 ℃ according to the heat-up rate of 5 ℃/min by room temperature, keeps the temperature sintering 10 hours, is cooled to room temperature and makes pre-reaction material.The formaldehyde that adds iron protoxide, silver fluoride, 5 times of volumes of above reaction mixture in pre-reaction material, ball milling mixed 3 hours under 800 rev/mins rotating speed, carried out vacuum-drying at 85 ℃ under 3132Pa pressure.The exsiccant powder is heated to 680 ℃ according to the heat-up rate of 10 ℃/min by room temperature under argon gas atmosphere, kept the temperature sintering 24 hours, is cooled to room temperature and makes and mix the ferrous lithium of hexafluorophosphoric acid.
Claims (5)
1. the preparation method of the ferrous phosphate doping lithium anode material of an efficient fluorine-doped is characterized in that preparation process is made up of following steps:
(1) according to Li
+: Fe
2+: PO
4 3-: the mol ratio of mingling fluorine agent is x: y: z: k weighing response composite lithium salts, ferrous salt, phosphoric acid salt and mingling fluorine agent, wherein, the scope of the numerical value of the x of reactant molar ratio, y, z, k is: 0.90≤x≤1.15,0.95≤y≤1.10,0.90≤z≤1.00,0.010≤k≤0.20; 1%～20% weighing carbon compound or carbon dust of the LiFePO 4 quality of calculating according to the reactant quality; 1/10～10 times of volume according to reaction mixture is measured wet grinding media;
(2) lithium salts, phosphoric acid salt, carbon compound or carbon dust and wet grinding media are mixed, ball milling mixed 3 hours～15 hours under 100 rev/mins～1000 rev/mins rotating speed, carried out drying in arbitrary temperature of 70 ℃～110 ℃ of temperature ranges under the vacuum of 10Pa～10132Pa pressure; The exsiccant powder is under inert atmosphere or weakly reducing atmosphere, be heated to arbitrary temperature of 450 ℃～650 ℃ of temperature ranges by room temperature according to 1 ℃/min～30 ℃/heat-up rate of min, kept the temperature sintering 3 hours～15 hours, and be cooled to room temperature and make pre-reaction material; In pre-reaction material, add ferrous salt, mingling fluorine agent and wet grinding media, ball milling mixed 3 hours～15 hours under 100 rev/mins～1000 rev/mins rotating speed, carried out drying in arbitrary temperature of 70 ℃～110 ℃ of temperature ranges under the vacuum of 10Pa～10132Pa pressure; The exsiccant powder is under inert atmosphere or weakly reducing atmosphere, heat-up rate according to 1 ℃/min～30 ℃/min is heated under arbitrary temperature of 650 ℃～900 ℃ of temperature ranges by room temperature, kept the temperature sintering 3 hours～24 hours, and be cooled to room temperature and make and mix the ferrous lithium of hexafluorophosphoric acid;
Described lithium salts is Quilonum Retard, lithium oxalate, lithium chloride, Lithium Acetate or lithium nitrate;
Described phosphoric acid salt is ammonium phosphate, Secondary ammonium phosphate or primary ammonium phosphate;
Described carbon compound is polypropylene, polyacrylamide, polyvinyl alcohol, glucose, sucrose, starch, tapioca flour, pachyrhizus, potato powder, taro meal or bran powder; Described carbon dust is acetylene black or Graphite Powder 99.
2. the preparation method of the ferrous phosphate doping lithium anode material of efficient fluorine-doped according to claim 1 is characterized in that described mingling fluorine agent is lithium fluoride, Sodium Fluoride, Potassium monofluoride or silver fluoride.
3. the preparation method of the ferrous phosphate doping lithium anode material of efficient fluorine-doped according to claim 1 is characterized in that described ferrous salt is Ferrox, Iron diacetate, iron protochloride, iron protocarbonate, ferrous hydroxide or iron protoxide.
4. the preparation method of the ferrous phosphate doping lithium anode material of efficient fluorine-doped according to claim 1 is characterized in that described inert atmosphere or weakly reducing atmosphere are the anhydrous air of gas mixture, carbon monoxide or anaerobic of gas mixture, nitrogen and argon gas of gas mixture, argon gas and the hydrogen of nitrogen, argon gas, nitrogen and hydrogen.
5. the preparation method of the ferrous phosphate doping lithium anode material of efficient fluorine-doped according to claim 1 is characterized in that described wet grinding media is methyl alcohol, ethanol, propyl alcohol, acetone, formaldehyde or formic acid.
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| CN101640271B (en) * | 2008-07-31 | 2014-08-27 | 比克国际(天津)有限公司 | Titanium lithium ferrous phosphate cathode material and preparation method thereof |
| CN102569790A (en) * | 2010-12-30 | 2012-07-11 | 北京当升材料科技股份有限公司 | Lithium iron phosphate material |
| CN102569738A (en) * | 2010-12-30 | 2012-07-11 | 北京当升材料科技股份有限公司 | Preparation method of lithium iron phosphate material |
| CN103855391A (en) * | 2012-11-30 | 2014-06-11 | 海洋王照明科技股份有限公司 | Fluorine lithium iron phosphate/graphene composite and preparation method and application thereof |
| CN103000894B (en) * | 2012-12-20 | 2015-10-28 | 中国东方电气集团有限公司 | A kind of lithium battery polyanion lithium iron phosphate cathode material and preparation method thereof |
| CN103497761A (en) * | 2013-09-26 | 2014-01-08 | 苏州大学 | Eu<2+>-activated aluminum-barium fluoborate fluorescent powder as well as preparation method and application thereof |
| CN104617293B (en) * | 2013-11-04 | 2018-04-27 | 国联汽车动力电池研究院有限责任公司 | A kind of preparation method of the carbon coated lithium ferrous phosphate composite material of fluorine richness |
| CN104934600B (en) * | 2015-05-14 | 2017-05-24 | 厦门厦钨新能源材料有限公司 | Multi-element composite phosphate nanometer anode material and preparation method thereof |
| CN116081594A (en) * | 2023-02-23 | 2023-05-09 | 武汉工程大学 | Preparation method of sodium ion battery anode material |
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| CN1401559A (en) * | 2002-10-18 | 2003-03-12 | 北大先行科技产业有限公司 | Method for preparing ferrous lithium phosphate, and lithium ion cell therewith |
| CN1772604A (en) * | 2005-10-11 | 2006-05-17 | 清华大学 | Prepn process of oxygen place doped lithium ferric phosphate powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1401559A (en) * | 2002-10-18 | 2003-03-12 | 北大先行科技产业有限公司 | Method for preparing ferrous lithium phosphate, and lithium ion cell therewith |
| CN1772604A (en) * | 2005-10-11 | 2006-05-17 | 清华大学 | Prepn process of oxygen place doped lithium ferric phosphate powder |
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