CN104347854A - Method for preparing nano LiFePO4/C electrode material - Google Patents

Method for preparing nano LiFePO4/C electrode material Download PDF

Info

Publication number
CN104347854A
CN104347854A CN201410493196.2A CN201410493196A CN104347854A CN 104347854 A CN104347854 A CN 104347854A CN 201410493196 A CN201410493196 A CN 201410493196A CN 104347854 A CN104347854 A CN 104347854A
Authority
CN
China
Prior art keywords
electrode material
preparation
lifepo
lithium
nanoscale lifepo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201410493196.2A
Other languages
Chinese (zh)
Inventor
陈建
赵娜
王晓峰
贾铁昆
石冬梅
万琳
赵营刚
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Luoyang Institute of Science and Technology
Original Assignee
Luoyang Institute of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Luoyang Institute of Science and Technology filed Critical Luoyang Institute of Science and Technology
Priority to CN201410493196.2A priority Critical patent/CN104347854A/en
Publication of CN104347854A publication Critical patent/CN104347854A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a method for preparing a nano LiFePO4/C electrode material. The preparing method comprises the following steps: first, synthesizing a compound of iron phosphate and poly furfuryl alcohol by using an in-situ polymerization limit method, then grounding the compound with a lithium salt, uniformly mixing, and finally preparing the LiFePO4/C composite material by high temperature sintering in an inert atmosphere or reducing atmosphere. According to the method disclosed by the invention, the particle size of the electrode material can be effectively reduced, and the transmission efficiency of electrons can be remarkably improved due to the coated carbon layer. The composite material has high specific capacity, excellent rate performance and cycling performance, and is suitable for the high rate charging/discharging requirements.

Description

A kind of nanoscale LiFePO 4the preparation method of/C electrode material
Technical field
The invention belongs to the preparing technical field of anode material for lithium-ion batteries, be specifically related to a kind of nanoscale LiFePO 4the preparation method of/C electrode material.
Background technology
Along with the continuous destruction of people's living environment, a large amount of consumption of non-renewable energy resources, novel eco-friendly power source causes the attention of every country gradually, and wherein lithium ion battery is subject to the attention of vast researcher with plurality of advantages such as its high energy density, excellent cycle performances.Anode material for lithium-ion batteries mainly comprises cobalt acid lithium (LiCoO 2), LiMn2O4 (LiMn 2o 4) and LiFePO 4 (LiFePO 4) etc.Wherein there is the LiFePO of olivine structural 4due to its stable operating voltage, abundant raw material source, advantages such as structural stability is high, and security performance is good and become the anode material for lithium-ion batteries of most competitiveness.But LiFePO 4electronic conductivity and lithium ion diffusion coefficient low, cause it under high power charging-discharging condition, actual specific energy is low, and cycle performance is poor, which greatly limits LiFePO 4extensive use.
In order to can LiFePO be made 4reach application conditions, researcher takes number of ways to improve its chemical property, and these methods mainly comprise the doping etc. reducing the coated and metal ion of the particle diameter of active material, carbon.K.Amine etc. (I.Belharouak, C.Johnson, K.Amine, Electrochem.Commun.7 (2005) 983 – 988.) have prepared LiFePO by vapour deposition process 4/ C composite, this composite material is when discharge-rate is C/3, and discharge capacity can reach 140mAh g -1but this building-up process is loaded down with trivial details, yields poorly, and is difficult to large-scale production.J.S.Yang etc. (J.S.Yang, J.J.Xu, Electrochem.Solid State Lett.7 (2004) A515 – A518.) have synthesized LiFePO by sol-gel process 4/ C compound, this compound is under 2C multiplying power, and capacity can reach 150mAh g -1, demonstrate higher capacity.But author does not provide capacity under more high magnification and cycle performance.Li Deyu (200910073347.8) adopts Solid phase synthesis LiFePO 4/ C, need in building-up process through high speed shear dispersion to solid refinement, energy consumption is large, efficiency is low and be easily mixed into impurity.Gu great Ming (201110063208.4) has synthesized nano level LiFePO by spraying dry pyrolysismethod 4/ C electrode material, this material has higher discharge capacity, but synthetic method is equally comparatively loaded down with trivial details, is also unfavorable for suitability for industrialized production.
Summary of the invention
The object of this invention is to provide a kind of nanoscale LiFePO 4the preparation method of/C electrode material, it is simple that the method has preparation technology, and process is easy to the features such as control.
Experiment of the present invention be first with the trivalent iron salt of cheapness be source of iron, poly furfuryl alcohol for carbon source, by in-situ polymerization lambda limiting process synthesis poly furfuryl alcohol and the compound of ferric phosphate, then by by this compound and lithium salts grinding, mix, obtain LiFePO through high temperature sintering 4/ C composite.The carbon that its situ produces can suppress LiFePO 4contacting with each other and growth between particle, obtains the LiFePO with nano-scale 4active particle, thus add the contact area between active material and electrolyte.Coated carbon can improve the conduction of electronics between active material particles effectively simultaneously, is conducive to the charge transfer resistance reducing electrode.The acting in conjunction of both contributes to improving LiFePO 4the high rate performance of electrode material and cycle performance.
Lithium ion battery electrode material LiFePO of the present invention 4the preparation method of/C, its step is as follows:
A () takes appropriate solubility trivalent iron salt and furfuryl alcohol C respectively 5h 6o 2join in deionized water, wherein the mol ratio of trivalent iron salt and furfuryl alcohol is 1:(0.35 ~ 5.80), stirring makes it dissolve completely, mixes, and obtains solution 1;
B phosphorus that () takes appropriate solubility comes from three-neck flask, and adds appropriate deionized water, stirs and makes it dissolve completely, obtain solution 2, wherein the mol ratio in trivalent iron salt and phosphorus source is 1:1, then this three-neck flask is placed in oil bath or water-bath, and connects condenser pipe;
C solution 1 is added drop-wise in solution 2 by () at leisure, stir while drip, after dropwising, continuing stirring makes it react completely, and after reaction terminates, is taken out by flask from oil bath or water-bath, and in atmosphere leave standstill be cooled to room temperature, being carried out by product in flask filtering, washing to filtrate pH value is 6.8 ~ 7.2, then sediment is placed in baking oven dry, obtains the compound (PFA/FePO of poly furfuryl alcohol PFA and ferric phosphate 4);
D PFA/FePO that step (c) obtains by () 4compound and lithium salts grind, mix, wherein ferric phosphate FePO 4be 1:(1 ~ 1.05 with the mol ratio of Li), be placed in high temperature sintering under protective atmosphere, thus obtain described nanoscale LiFePO 4/ C electrode material.
In step (a), the trivalent iron salt of this solubility described is one or more in iron chloride, ferric sulfate.
In step (a), the concentration of this solubility trivalent iron salt described is 0.1 ~ 0.4moldm -3.
In step (a), the volume of described furfuryl alcohol is 0.3 ~ 1.2mL.
In step (b), described phosphorus source is one or more in phosphoric acid, ammonium dihydrogen phosphate.
In step (c), the temperature of this reaction is 70 ~ 120 DEG C, and the time of this reaction is 6 ~ 24 hours.
In step (c), the temperature of this drying is 80 ~ 150 DEG C, and the time of this drying is 3 ~ 24 hours.
In step (d), described lithium salts is one or more in lithium chloride, lithium nitrate, lithium acetate, lithium hydroxide, lithium carbonate.
In step (d), the temperature of this high temperature sintering is 550 ~ 850 DEG C, and the time of this high temperature sintering is 4 ~ 20 hours.
By technique scheme, the present invention at least has the following advantages:
By LiFePO prepared by the inventive method 4/ C composite has high specific capacity and excellent stable circulation performance, is applicable to high power charging-discharging demand.When charge-discharge magnification is 0.5C, initial specific capacity is 143.0 ~ 156.1mAh g -1.Circulate after 50 times, the retention of specific capacity is 85.0% ~ 94.3%.
Preparation technology of the present invention is simple, and process is easy to control, can the growth of inhibit activities material particle size effectively, obtains the electrode material with nano-scale, shortens the evolving path of lithium ion in electrode material.Meanwhile, the in-stiu coating of carbon can improve the electronic conductivity of material, and both actings in conjunction can significantly improve high rate performance and the cycle performance of electrode material.
Accompanying drawing explanation
Fig. 1 is that embodiment 1 prepares PFA/FePO 4the principle schematic of compound.
Fig. 2 is PFA/FePO prepared by embodiment 1 4and LiFePO 4the X-ray diffractogram of/C composite.
Fig. 3 is LiFePO prepared by embodiment 1 4liFePO in/C composite 4the charging and discharging curve figure of the 1st, 10,20,30,40,50 time under 0.5C charge-discharge magnification.
Fig. 4 is LiFePO prepared by embodiment 1 4liFePO in/C composite 4circulate respectively the cycle performance figure of 500 times under 5C, 10C, 20C, 50C multiplying power.
Embodiment
Introduce embodiments of the invention below, to increase further understanding of the present invention, but the present invention is limited to embodiment absolutely not.
Embodiment 1
1) ferric chloride hexahydrate (FeCl of 2.70g is accurately taken 36H 2and the furfuryl alcohol (C of 0.6mL O) 5h 6o 2), and join successively in the deionized water of 50mL, stir 30min and make it dissolve completely, mix, obtain solution 1;
2) 1.15g ammonium dihydrogen phosphate (NH is weighed 4h 2pO 4) be placed in the three-neck flask of 250mL, and add the deionized water of 50mL, stir and make it dissolve completely, obtain solution 2.Then this three-neck flask is placed in the oil bath of 85 DEG C, and connects condenser pipe;
3) solution 1 is added drop-wise in solution 2 at leisure, stirs and drip.After dropwising, at 85 DEG C, react 12h.Reaction terminate after, flask is taken out from oil bath, and in atmosphere leave standstill be cooled to room temperature.Product in flask is carried out filter, wash to filtrate in neutral (pH=6.8 ~ 7.2).The baking oven finally product of gained being put into 100 DEG C carries out drying process, obtains the compound (PFA/FePO of poly furfuryl alcohol (poly (furfuryl alcohol) is called for short PFA) and ferric phosphate 4);
4) a certain amount of PFA/FePO is weighed 4with two hydration lithium acetate (CH 3cOOLi2H 2o) put into mortar to carry out grinding and make it mix (FePO 4with CH 3cOOLi2H 2the mol ratio of O is 1:1), then by this mixture in high-purity N 2under atmosphere, 750 DEG C of calcining 6h obtain LiFePO 4/ C composite.The mass fraction recording carbon through thermogravimetric analysis (Thermogravimetry Analysis) is 10.2%.
Electrochemical property test:
By gained LiFePO 4the ratio of/C and conductive agent (acetylene black), binding agent (PVDF) 8:1:1 in mass ratio mixes, and with 1-METHYLPYRROLIDONE (NMP) for solvent, abundant mixing pulping is also spread evenly across on aluminium foil, then be placed in vacuum drying chamber 120 DEG C of dry 24h, after oven dry, be cut into the positive plate of electrode.Being assembled in the glove box being full of high-purity argon gas of simulated battery is carried out, and in case, oxygen content and moisture all control at below 1ppm.Take metal lithium sheet as negative pole, electrolyte is 1mol/L LiPF 6/ EC+DMC+EMC (mass ratio 1:1:1).On LAND CT2001A battery test system, carry out charge-discharge performance test with constant current, the voltage range of test is 2.0-4.2V.
Embodiment 2
Step is identical with the step in embodiment 1, and difference is step 1) in the concentration of trivalent iron salt be 0.1moldm -3.The mass fraction that thermogravimetric analysis records carbon is 18.0%.Carry out constant current charge-discharge performance test according to the method for testing described in embodiment 1, under 0.5C multiplying power, discharge capacity is 150.0mAh g first -1, the discharge capacity after 50 times that circulates is 135.5mAh g -1, specific capacity retention is 90.3%.
Embodiment 3
Step is identical with the step in embodiment 1, and difference is step 1) in the concentration of trivalent iron salt be 0.4moldm -3.The mass fraction that thermogravimetric analysis records carbon is 5.2%.Carry out constant current charge-discharge performance test according to the method for testing described in embodiment 1, under 0.5C multiplying power, discharge capacity is 143.0mAh g first -1, the discharge capacity after 50 times that circulates is 121.5mAh g -1, specific capacity retention is 85.0%.
Embodiment 4
Step is identical with the step in embodiment 1, and difference is step 1) in the volume of furfuryl alcohol be 0.3mL.The mass fraction that thermogravimetric analysis records carbon is 5.3%.Carry out constant current charge-discharge performance test according to the method for testing described in embodiment 1, under 0.5C multiplying power, discharge capacity is 146.1mAh g first -1, the discharge capacity after 50 times that circulates is 134.0mAhg -1, specific capacity retention is 91.7%.
Embodiment 5
Step is identical with the step in embodiment 1, and difference is step 1) in the volume of furfuryl alcohol be 1.2mL.The mass fraction that thermogravimetric analysis records carbon is 18.2%.Carry out constant current charge-discharge performance test according to the method for testing described in embodiment 1, under 0.5C multiplying power, discharge capacity is 152.0mAh g first -1, the discharge capacity after 50 times that circulates is 138.5mAhg -1, specific capacity retention is 91.1%.
Embodiment 6
Step is identical with the step in embodiment 1, and difference is step 3) in the heating-up temperature of oil bath or water-bath be 70 degrees Celsius, the time is 24 hours.The mass fraction that thermogravimetric analysis records carbon is 10.0%.Carry out constant current charge-discharge performance test according to the method for testing described in embodiment 1, under 0.5C multiplying power, discharge capacity is 151.5mAh g first -1, the discharge capacity after 50 times that circulates is 140.2mAh g -1, specific capacity retention is 92.5%.
Embodiment 7
Step is identical with the step in embodiment 1, and difference is step 3) in the heating-up temperature of oil bath or water-bath be 120 degrees Celsius, the time is 6 hours.The mass fraction that thermogravimetric analysis records carbon is 10.1%.Carry out constant current charge-discharge performance test according to the method for testing described in embodiment 1, under 0.5C multiplying power, discharge capacity is 150.8mAh g first -1, the discharge capacity after 50 times that circulates is 141.7mAh g -1, specific capacity retention is 94.0%.
Embodiment 8
Step is identical with the step in embodiment 1, difference be step 3) in bake out temperature be 80 degrees Celsius, the time is 24 hours.The mass fraction that thermogravimetric analysis records carbon is 10.1%.Carry out constant current charge-discharge performance test according to the method for testing described in embodiment 1, under 0.5C multiplying power, discharge capacity is 151.1mAh g first -1, the discharge capacity after 50 times that circulates is 140.9mAh g -1, specific capacity retention is 93.2%.
Embodiment 9
Step is identical with the step in embodiment 1, difference be step 3) in bake out temperature be 150 degrees Celsius, the time is 3 hours.The mass fraction that thermogravimetric analysis records carbon is 10.0%.Carry out constant current charge-discharge performance test according to the method for testing described in embodiment 1, under 0.5C multiplying power, discharge capacity is 150.4mAh g first -1, the discharge capacity after 50 times that circulates is 140.6mAh g -1, specific capacity retention is 93.5%.
Embodiment 10
Step is identical with the step in embodiment 1, difference be step 4) in sintering temperature be 850 degrees Celsius, sintering time is 4 hours.The mass fraction that thermogravimetric analysis records carbon is 10.0%.Carry out constant current charge-discharge performance test according to the method for testing described in embodiment 1, under 0.5C multiplying power, discharge capacity is 146.0mAh g first -1, the discharge capacity after 50 times that circulates is 135.7mAh g -1, specific capacity retention is 92.9%.
Embodiment 11
Step is identical with the step in embodiment 1, difference be step 4) in sintering temperature be 550 degrees Celsius, sintering time is 20 hours.The mass fraction that thermogravimetric analysis records carbon is 10.1%.Carry out constant current charge-discharge performance test according to the method for testing described in embodiment 1, under 0.5C multiplying power, discharge capacity is 147.0mAh g first -1, the discharge capacity after 50 times that circulates is 138.6mAh g -1, specific capacity retention is 94.3%.
We are to the LiFePO of gained 4/ C composite has carried out the sign (embodiment 1) of structures and characteristics.
Fig. 1 is PFA/FePO prepared by embodiment 1 4the principle schematic of compound.When handle is containing Fe 3+be added drop-wise at leisure with the solution 1 of furfuryl alcohol and be dissolved with NH 4h 2pO 4solution 2 in time, Fe 3+with PO 4 3-reaction generates FePO 4precipitation.H simultaneously in solution +with the heated condition of solution impels generation polymerization between furfuryl alcohol molecule to generate poly furfuryl alcohol.Due to FePO 4precipitation and poly furfuryl alcohol almost generate simultaneously, and the poly furfuryl alcohol of generation is easily adsorbed on FePO 4the surface of precipitation particles, thus intercepted FePO 4contacting with each other and growth between ion.
Fig. 2 is PFA/FePO prepared by embodiment 1 4and LiFePO 4the X-ray diffractogram of/C composite.PFA/FePO is not observed from figure 4the derivative peak of compound, this may be because this compound is amorphous state.In addition, after grinding with lithium salts, mixing, sinter the active material LiFePO obtained 4diffraction peak and LiFePO 4feature diffraction spectrogram consistent.
Fig. 3 is positive electrode active materials LiFePO 4the charging and discharging curve figure of the 1st, 10,20,30,40,50 time under 0.5C multiplying power.Can draw from figure, discharge capacity is 156.1mAh g first -1, the discharge capacity after 50 times that circulates still can reach 145.2mAh g -1, specific capacity retention is 93.0%.
Fig. 4 is positive electrode active materials LiFePO 4circulate the cycle performance figure of 500 times under 5C, 10C, 20C and 50C multiplying power.Electrochemical property test result shows, when discharge-rate is 5C, 10C, 20C and 50C respectively, initial discharge capacity is 126.3mAh g -1, 108.6mAh g -1, 82.5mAh g -1with 62.8mAh g -1.Electrode charge and discharge circulates after 500 times, and discharge capacity is 119.2mAh g -1, 98.4mAh g -1, 72.4mAh g -1with 57.1mAh g -1, the conservation rate of capacity is respectively 94.4%, 90.6%, 87.8% and 90.9%, shows that this active material still has excellent cyclical stability under high magnification.
In sum, the present invention with the trivalent iron salt of cheapness be source of iron, poly furfuryl alcohol for carbon source, by the synthesis of in-situ polymerization lambda limiting process, there is the LiFePO of nano-grade size 4/ C composite, adds the contact area between active material and electrolyte.Coated carbon can improve the conduction of electronics between active material particles effectively simultaneously, is conducive to the charge transfer resistance reducing electrode.This composite material has height ratio capacity, excellent high rate performance and cycle performance, is applicable to high power charging-discharging demand.
The above, it is only preferred embodiment of the present invention, not any pro forma restriction is done to the present invention, although the present invention discloses as above with preferred embodiment, but and be not used to limit the present invention, any those skilled in the art, do not departing within the scope of technical solution of the present invention, make a little change when the technology contents of above-mentioned announcement can be utilized or be modified to the Equivalent embodiments of equivalent variations, in every case be the content not departing from technical solution of the present invention, according to technical spirit of the present invention to any simple modification made for any of the above embodiments, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.

Claims (9)

1. a nanoscale LiFePO 4the preparation method of/C electrode material, is characterized in that it comprises the steps:
A () takes solubility trivalent iron salt and furfuryl alcohol C respectively 5h 6o 2join in deionized water, wherein the mol ratio of trivalent iron salt and furfuryl alcohol is 1:(0.35 ~ 5.80), stirring makes it dissolve completely, mixes, and obtains solution 1;
B phosphorus that () weighs solubility comes from three-neck flask, and adds deionized water, stirs and makes it dissolve completely, obtain solution 2, wherein the mol ratio in trivalent iron salt and phosphorus source is 1:1, then this three-neck flask is placed in oil bath or water-bath, and connects condenser pipe;
C solution 1 is added drop-wise in solution 2 by () at leisure, stir while drip, after dropwising, continuing stirring makes it react completely, and after reaction terminates, is taken out by flask from oil bath or water-bath, and in atmosphere leave standstill be cooled to room temperature, being carried out by product in flask filtering, washing to filtrate pH value is 6.8 ~ 7.2, then sediment is placed in baking oven dry, obtains the compound PFA/FePO of poly furfuryl alcohol PFA and ferric phosphate 4;
D PFA/FePO that step (c) obtains by () 4compound and lithium salts grinding, mix, wherein ferric phosphate FePO 4be 1:(1 ~ 1.05 with the mol ratio of Li), be placed in high temperature sintering under protective atmosphere, thus obtain described nanoscale LiFePO 4/ C electrode material.
2. a kind of nanoscale LiFePO as claimed in claim 1 4the preparation method of/C electrode material, is characterized in that: in step (a), and this solubility trivalent iron salt is one or both in iron chloride, ferric sulfate.
3. a kind of nanoscale LiFePO as claimed in claim 1 or 2 4the preparation method of/C electrode material, is characterized in that: in step (a), and the concentration of this solubility trivalent iron salt is 0.1 ~ 0.4moldm -3.
4. a kind of nanoscale LiFePO as claimed in claim 1 4the preparation method of/C electrode material, is characterized in that: in step (a), and the volume of this furfuryl alcohol is 0.3 ~ 1.2mL.
5. a kind of nanoscale LiFePO as claimed in claim 1 4the preparation method of/C electrode material, is characterized in that: in step (b), and this phosphorus source is one or both in phosphoric acid, ammonium dihydrogen phosphate.
6. a kind of nanoscale LiFePO as claimed in claim 1 4the preparation method of/C electrode material, is characterized in that: in step (c), and the temperature of this reaction is 70 ~ 120 DEG C, and the time of this reaction is 6 ~ 24 hours.
7. a kind of nanoscale LiFePO as claimed in claim 1 4the preparation method of/C electrode material, is characterized in that: in step (c), and the temperature of this drying is 80 ~ 150 DEG C, and the time of this drying is 3 ~ 24 hours.
8. a kind of nanoscale LiFePO as claimed in claim 1 4the preparation method of/C electrode material, is characterized in that: in step (d), this lithium salts be in lithium chloride, lithium nitrate, lithium acetate, lithium hydroxide, lithium carbonate one or more.
9. a kind of nanoscale LiFePO as claimed in claim 1 4the preparation method of/C electrode material, is characterized in that: in step (d), and the temperature of this high temperature sintering is 550 ~ 850 DEG C, and the time of this high temperature sintering is 4 ~ 20 hours.
CN201410493196.2A 2014-09-24 2014-09-24 Method for preparing nano LiFePO4/C electrode material Pending CN104347854A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410493196.2A CN104347854A (en) 2014-09-24 2014-09-24 Method for preparing nano LiFePO4/C electrode material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410493196.2A CN104347854A (en) 2014-09-24 2014-09-24 Method for preparing nano LiFePO4/C electrode material

Publications (1)

Publication Number Publication Date
CN104347854A true CN104347854A (en) 2015-02-11

Family

ID=52503004

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410493196.2A Pending CN104347854A (en) 2014-09-24 2014-09-24 Method for preparing nano LiFePO4/C electrode material

Country Status (1)

Country Link
CN (1) CN104347854A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106129337A (en) * 2016-06-27 2016-11-16 华中农业大学 A kind of preparation method of cathode of lithium iron phosphate lithium ion battery electrode
CN106684380A (en) * 2017-01-12 2017-05-17 吉林大学 In-situ polymerization limitation auxiliary preparation method of LiFePO4/C nano composite material
CN112271294A (en) * 2020-11-16 2021-01-26 华中科技大学 Nanoscale iron phosphate precursor and preparation method thereof, and lithium iron phosphate and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1478310A (en) * 2000-09-26 2004-02-25 �������繫˾ Method for synthesis of carbon-coated redox materials with controlled size
CN101689676A (en) * 2007-07-18 2010-03-31 第一工业制药株式会社 Lithium secondary battery
CN102683697A (en) * 2012-05-14 2012-09-19 中南大学 Preparation method of graphene-based LiFePO4/C composite material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1478310A (en) * 2000-09-26 2004-02-25 �������繫˾ Method for synthesis of carbon-coated redox materials with controlled size
CN101689676A (en) * 2007-07-18 2010-03-31 第一工业制药株式会社 Lithium secondary battery
CN102683697A (en) * 2012-05-14 2012-09-19 中南大学 Preparation method of graphene-based LiFePO4/C composite material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
陈建: ""聚阴离子型LiMPO4（M=Fe，Mn）和Li3V2（PO4）3锂离子电池正极材料的制备及性能研究"", 《中国博士学位论文全文数据库 工程科技Ⅱ辑》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106129337A (en) * 2016-06-27 2016-11-16 华中农业大学 A kind of preparation method of cathode of lithium iron phosphate lithium ion battery electrode
CN106129337B (en) * 2016-06-27 2018-10-12 华中农业大学 A kind of preparation method of cathode of lithium iron phosphate lithium ion battery electrode
CN106684380A (en) * 2017-01-12 2017-05-17 吉林大学 In-situ polymerization limitation auxiliary preparation method of LiFePO4/C nano composite material
CN112271294A (en) * 2020-11-16 2021-01-26 华中科技大学 Nanoscale iron phosphate precursor and preparation method thereof, and lithium iron phosphate and preparation method thereof

Similar Documents

Publication Publication Date Title
CN102201576B (en) Porous carbon in situ composite lithium iron phosphate cathode material and preparation method thereof
CN103435105B (en) A kind of ferriferous oxide/carbon composition lithium ion battery cathode material and its preparation method and application
US20200328406A1 (en) Layered lithium-rich manganese-based cathode material with olivine structured limpo4 surface modification and preparation method thereof
CN103928672B (en) A kind of positive electrode active material for lithium ion battery and preparation method thereof
CN105206809B (en) A kind of C3N4 carbon-covered iron lithium phosphate compound anode materials and preparation method thereof
CN105633369B (en) A kind of preparation method of carbon-coated LiFePO 4 for lithium ion batteries material
CN103956485B (en) Lithium iron phosphate electrode material of a kind of three-dimensional hierarchical structure and preparation method thereof
CN104638242A (en) Method for synthesizing lithium ion battery cathode material lithium iron phosphate through in situ polymerizing and cladding
CN103840157A (en) Preparation method for nano sheet-shaped lithium ion battery positive electrode material fluorine lithium vanadium phosphate
CN108039458A (en) A kind of sodium-ion battery positive material and its preparation method and application
CN109950487A (en) A kind of lithium sulfur battery anode material and preparation method thereof
CN108975297A (en) The method that the crystallization water by removing nanoscale iron phosphate prepares high performance lithium iron phosphate positive material
CN103413918B (en) A kind of synthetic method of anode material for lithium ion battery cobalt phosphate lithium
CN107069029B (en) A kind of lithium battery high-voltage anode material and preparation method thereof
CN102683698B (en) Preparation method of conductive modified lithium iron phosphate
CN104752722A (en) Doped modified lithium vanadium phosphate anode material as well as preparation method and application thereof
CN102267692B (en) Self-sacrificing template method for preparing nanoscale lithium ferrous phosphate
CN102769134B (en) Preparation method of lithium ion battery anode composite material LiFePO4/C
CN104347854A (en) Method for preparing nano LiFePO4/C electrode material
CN116154154B (en) Pure-phase polyanion type sulfate sodium ion battery positive electrode material and preparation method thereof
CN102897741B (en) Hydrothermal preparation method for nanometer lithium iron phosphate
CN102447099B (en) New method for preparing lithium ferrous phosphate double-salt anode material by using iron chippings, phosphoric acid and lithium hydroxide
CN104332612B (en) P Modification carbon-coated lithium ion battery anode composite material and Preparation method and use
CN103346313B (en) A kind of preparation method of cathode material lithium vanadium phosphate of lithium ion battery
CN104332628A (en) Preparation method and lithium ion battery of lithium ion battery positive material

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20150211