CN104157856A - Core-shell type LaFeO3@C lithium battery anode material and preparation method thereof - Google Patents

Core-shell type LaFeO3@C lithium battery anode material and preparation method thereof Download PDF

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CN104157856A
CN104157856A CN201410380212.7A CN201410380212A CN104157856A CN 104157856 A CN104157856 A CN 104157856A CN 201410380212 A CN201410380212 A CN 201410380212A CN 104157856 A CN104157856 A CN 104157856A
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lafeo
lafeo3
core
lanthanum
carbon
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CN104157856B (en
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牛和林
武小云
张胜义
毛昌杰
宋吉明
张君友
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Anhui University
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    • 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
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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 discloses a core-shell type LaFeO3@C lithium battery anode material and a preparation method thereof. The hydrothermal carbonization method is adopted for synthesizing a LaFeO3@C composite nanometer material with a core-shell structure for the first time. During the hydro-thermal synthesis process, carbonates and ammonia water are decomposed from urea, OH<-> is released from urea through hydrolysis, the solution is alkali, lanthanum ions and iron ions are precipitated, lanthanum and iron sediments are gathered for nucleation, a carbohydrate is subjected to the hydrothermal carbonization at 180 DEG C to form a shell carbon layer, so that the lanthanum and iron sediment cores can completely cover the inner part of the carbon layer to form the integral core-shell structure; the structure is further subjected to the high-temperature calcination under nitrogen, so that carbon-coated lanthanum ferrite, namely the LaFeO3@C is obtained for the first time. An electrochemical test proves that the lithium storage performance of the pure LaFeO3 nano-particles is quite small, the core-shell type LaFeO3@C nano-composite has excellent lithium storage performance and has great development potential and a scientific research value, and the application of the core-shell type LaFeO3@C nano-composite in the lithium battery anode material is a great discovery.

Description

A kind of hud typed LaFeO 3@C lithium cell cathode material and preparation method thereof
Technical field
The present invention relates to hydro thermal method and high-temperature heat treatment method in conjunction with obtaining having hud typed LaFeO 3the method of@C cathode of lithium battery composite material, belongs to hydro thermal method and high-temperature heat treatment synthesizing new composite material and lithium ion battery negative material technical field.
Background technology
Lithium ion battery has the advantages such as operating voltage is high, specific energy is high, self-discharge rate is low, asepsis environment-protecting and receives much concern because of it, become the main power source of current electronic product and electric equipment.Yet, along with renewal and the extensive concern of people to energy source and power of electronic product in recent years, lithium ion battery is had higher requirement, need it to there is higher energy density, higher power density and longer useful life.
After carbon back negative material occurs, due to it, to have cost low, higher cycle efficieny and good electrochemistry stable circulation performance, thus be widely used.But its lithium storage content is lower, and theoretical specific capacity is about 372mAh/g, and have potential safety hazard when high magnification charges, so development of new negative material becomes the key that improves performance of lithium ion battery.
P.Poizot etc. have proposed first transition metal oxide and can be used as lithium ion battery negative material, and have confirmed that by experiment its specific discharge capacity is 2～3 times of graphite cathode.Yet transition metal oxide negative material also exists following problem: irreversible capacity is high first; In cyclic process, the high cycle life that causes of cubical expansivity is low; Because it is semi-conducting material, the poor high rate performance that causes of its conductivity is poor.Research shows, reduce oxide particle size, coated with conductive agent, particle carried out to the methods such as surface modification and doping metals cation and all can improve the electric conductivity of oxide electrode, wherein material with carbon-coated surface modification is to improve the effective way that oxide electrode material electric conductivity was led and improved to apparent electricity between particle.Patent 201310100981.2 has been prepared the Fe of single diffuse nuclei shell structure 3o 4@C nano composite lithium ion negative material has very high specific capacity and higher cycle performance, in 0.01-0.3V voltage range, under 0.2C multiplying power, discharge and recharge, its first discharge capacity be 1031mAh/g, after 100 circulations, discharge capacity still has 544mAh/g. patent 201110131191.1 to prepare hud typed carbon coating cobalt based nanometer rod ion cathode material lithium, by electro-chemical test, find under 0.1C current density, reversible specific capacity is greater than 1000mAh/g first, after 100 circle circulations, more than reversible specific capacity still remains on 1000mAh/g, prove that this material has very strong cyclical stability when keeping height ratio capacity.And this material (1C, 2C, 5C) under large current condition also has good storage lithium performance.The people such as Chen reported on J.Mater.Chem22 (2012) 15056 that hydro thermal method prepared the coated Co of carbon of nucleocapsid structure 3o 4nano wire ion cathode material lithium, electro-chemical test shows, the Co that carbon is coated 3o 4the storage lithium performance of nano composite material is far away higher than not being coated the Co of carbon-coating 3o 4nano wire.Proved that material with carbon-coated surface modification can improve the storage lithium performance of nanometer anode material really greatly.
Ca-Ti ore type ABO 3oxide has low cost, easily-activated, high discharge capacity and the good features such as chemical stability and receives much concern.LaFeO 3be a kind of of ferrite series, belong to perovskite (ABO 3) type composite oxides.In recent years, due to LaFeO 3the crystal structure having had, magnetic, electrical conductance, piezoelectricity and electrooptical property, and be applied in solid electrolyte, solid fuel cell, engine, electrochemical device, sensor field.According to literature search, find no and close LaFeO 3application of micron, in the pertinent literature report of the aspects such as lithium ion battery negative, does not relate in actual industrial production yet.
The present invention is synthesized and has hud typed LaFeO first by hydro thermal method and high-temperature heat treatment method 3@C nano composite material.It is simple that hydro thermal method has equipment and process, is easy to control reaction condition, and product is reproducible, and productive rate is high, and synthetic method is green, be convenient to the advantages such as industrial mass production, so hydro thermal method is prepared hud typed LaFeO 3the method of@C composite nano materials has huge potential scientific research value and using value.Electrochemistry experiment shows hud typed LaFeO 3@C nano particle has excellent circulation storage lithium performance (be mainly reflected in specific capacity high, stable cycle performance, the adaptability of large electric current is good), and its storage lithium performance is far away higher than the LaFeO of coated carbon-coating not 3nano particle, for its application at lithium ion battery negative material provides possibility, has good development potentiality and application prospect.
Summary of the invention
The object of this invention is to provide a kind of LaFeO with nucleocapsid structure 3the preparation method of@C lithium cell cathode material.
The present invention is a kind of synthetic LaFeO with nucleocapsid structure 3the method of@C lithium cell cathode material, is characterized in that the method has following technical process and step:
Take respectively lanthanum nitrate, ferric nitrate, urea, carbohydrate is configured to the mixed aqueous solution of certain volume, after fully stirring, obtain water white mixed solution, wherein the consumption mol ratio of lanthanum nitrate, ferric nitrate and urea is between 1: 1: 100～1: 1: 20, and the concentration of carbohydrate is between 0.3-0.6M.
Mixed solution obtained above is transferred in hydrothermal reaction kettle, by hydrothermal reaction kettle sealing, puts at 180～220 ℃ of constant temperature blast drying ovens and react 12 hours, finish reaction, naturally cool to room temperature; Collect insoluble solid product, through washing the material obtaining after dry, be the coated lanthanum iron precipitate composite nano materials of carbon with nucleocapsid structure;
The coated lanthanum iron precipitate composite nano materials of carbon is carried out to calcination processing; Detailed process is: 600-1000 ℃ of calcining 2-12h in nitrogen atmosphere, the solid product of collecting is LaFeO 3@C.
The synthetic kernel shell structure LaFeO that the present invention sets forth 3the feature of the method for@C nano material is:
(1) take carbohydrate as carbon source, by hydro thermal method, prepare the coated lanthanum iron precipitate composite nano materials of carbon.In preparation process, first reaction forms lanthanum iron precipitate (core), and the reaction of carbohydrate hydrothermal carbonization generates carbon-coating (shell), obtains the composite nano materials of the completely coated lanthanum iron precipitate core of carbon-coating.
(2) by changing the hydro-thermal time, can change the thickness of composite material surface carbon-coating.
(3) by the coated lanthanum iron precipitate compound high-temperature calcination under air atmosphere and nitrogen atmosphere respectively of carbon, the former obtains pure LaFeO 3nano particle, the latter obtains LaFeO 3@C composite nanometer particle.
The present invention is the synthetic LaFeO with nucleocapsid structure first 3@C lithium cell cathode material, the discharge curve from different multiplying (Fig. 9) can find out, during 0.5C rate charge-discharge, LaFeO 3@C specific discharge capacity is approximately 533mAhg -1; During large multiplying power, LaFeO 3@C material demonstrates its specific discharge capacity under 2C multiplying power and still has 210mAhg -1, the surface passivated membrane producing during 4C has mainly played the effect that hinders lithium ion migration, thereby make the capacity of sample, is 174mAhg -1, while being still greater than 4C, do not wrap the pure LaFeO of carbon 3, while returning 0.5C rate charge-discharge after the large multiplying power discharging of 4C, LaFeO 3@C specific discharge capacity can be got back to the level of initial 0.5C substantially, illustrates that large current charge can not cause the damage of negative material, on the whole, and LaFeO 3@C material demonstrates better multiplying power conservation rate.
Accompanying drawing explanation
Fig. 1 is according to the LaFeO of embodiment 1 preparation 3and LaFeO 3the X ray diffracting spectrum (XRD) of@C composite nano materials;
Fig. 2 is according to the LaFeO of embodiment 1 preparation 3the transmission electron microscope photo (TEM) of nano material;
Fig. 3 is according to the LaFeO of embodiment 1 preparation 3the high-resolution-ration transmission electric-lens photo (HRTEM) of nano material;
Fig. 4 is according to the LaFeO of embodiment 1 preparation 3the transmission electron microscope photo (TEM) of@C composite nano materials;
Fig. 5 is according to the LaFeO of embodiment 1 preparation 3the high-resolution-ration transmission electric-lens photo (HRTEM) of@C composite nano materials;
Fig. 6 is according to the pure LaFeO of embodiment 1 preparation 3and LaFeO 3the constant current charge-discharge curve chart (current density 0.2C) that@C circulates first;
Fig. 7 is according to the LaFeO of embodiment 1 preparation 3and LaFeO 3@C material cycle performance curve (current density 1C);
Fig. 8 is according to the LaFeO of embodiment 1 preparation 3and LaFeO 3@C material electrochemical impedance spectrogram (EIS);
Fig. 9 is according to the LaFeO of embodiment 1 preparation 3and LaFeO 3the high rate performance of@C material.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1: weigh first respectively 0.22g La (NO 3) 36H 2o, 0.20g Fe (NO 3) 39H 2o, 0.3g urea, 1.773g mono-glucose monohydrate is dissolved in 35ml distilled water, obtains lurid mixed solution.Above-mentioned mixed solution is transferred in hydrothermal reaction kettle, and good seal, is warming up to 180 ℃, keeps 12h, and reaction finishes.Naturally after cooling, collect solid product, the sepia product of receiving after washing is dry is the coated lanthanum iron precipitate nano material of carbon.Above-mentioned sepia product, under air and nitrogen atmosphere, is warming up to 600 ℃ of calcining 4h respectively, and the bronzing solid that under air, calcining obtains is LaFeO 3, under nitrogen, calcining obtains tan product and is LaFeO 3@C composite nano materials.
Embodiment 2: weigh first respectively 0.22g La (NO 3) 36H 2o, 0.20g Fe (NO 3) 39H 2o, 0.45g urea, 1.773g mono-glucose monohydrate is dissolved in 35ml distilled water, obtains lurid mixed solution.Above-mentioned mixed solution is transferred in hydrothermal reaction kettle, and good seal, is warming up to 180 ℃, keeps 12h, and reaction finishes.Naturally after cooling, collect solid product, the sepia product of receiving after washing is dry is the coated lanthanum iron precipitate nano material of carbon.Above-mentioned sepia product, under air and nitrogen atmosphere, is warming up to 800 ℃ of calcining 3h respectively, and the bronzing solid that under air, calcining obtains is LaFeO 3, under nitrogen, calcining obtains tan product and is LaFeO 3@C composite nano materials.
Embodiment 3: weigh first respectively 0.22g La (NO 3) 36H 2o, 0.20g Fe (NO 3) 39H 2o, 0.6g urea, 1.773g mono-glucose monohydrate is dissolved in 35ml distilled water, obtains lurid mixed solution.Above-mentioned mixed solution is transferred in hydrothermal reaction kettle, and good seal, is warming up to 200 ℃, keeps 12h, and reaction finishes.Naturally after cooling, collect solid product, the sepia product of receiving after washing is dry is the coated lanthanum iron precipitate nano material of carbon.Above-mentioned sepia product, under air and nitrogen atmosphere, is warming up to 1000 ℃ of calcining 2h respectively, and the bronzing solid that under air, calcining obtains is LaFeO 3, under nitrogen, calcining obtains tan product and is LaFeO 3@C composite nano materials.
Embodiment 4: weigh first respectively 0.22g La (NO 3) 36H 2o, 0.20g Fe (NO 3) 39H 2o, 0.3g urea, 3.546g mono-glucose monohydrate is dissolved in 35ml distilled water, obtains lurid mixed solution.Above-mentioned mixed solution is transferred in hydrothermal reaction kettle, and good seal, is warming up to 200 ℃, keeps 12h, and reaction finishes.Naturally after cooling, collect solid product, the sepia product of receiving after washing is dry is the coated lanthanum iron precipitate nano material of carbon.Above-mentioned sepia product, under air and nitrogen atmosphere, is warming up to 600 ℃ of calcining 3h respectively, and the bronzing solid that under air, calcining obtains is LaFeO 3, under nitrogen, calcining obtains tan product and is LaFeO 3@C composite nano materials.
Embodiment 5: weigh first respectively 0.22g La (NO 3) 36H 2o, 0.20g Fe (NO 3) 39H 2o, 0.45g urea, 3.456g mono-glucose monohydrate is dissolved in 35ml distilled water, obtains lurid mixed solution.Above-mentioned mixed solution is transferred in hydrothermal reaction kettle, and good seal, is warming up to 220 ℃, keeps 12h, and reaction finishes.Naturally after cooling, collect solid product, the sepia product of receiving after washing is dry is the coated lanthanum iron precipitate nano material of carbon.Above-mentioned sepia product, under air and nitrogen atmosphere, is warming up to 800 ℃ of calcining 4h respectively, and the bronzing solid that under air, calcining obtains is LaFeO 3, under nitrogen, calcining obtains tan product and is LaFeO 3@C composite nano materials
Embodiment 6: weigh first respectively 0.22g La (NO 3) 36H 2o, 0.20g Fe (NO 3) 39H 2o, 0.6g urea, 3.456g mono-glucose monohydrate is dissolved in 35ml distilled water, obtains lurid mixed solution.Above-mentioned mixed solution is transferred in hydrothermal reaction kettle, and good seal, is warming up to 220 ℃, keeps 12h, and reaction finishes.Naturally after cooling, collect solid product, the sepia product of receiving after washing is dry is the coated lanthanum iron precipitate nano material of carbon.Above-mentioned sepia product, under air and nitrogen atmosphere, is warming up to 1000 ℃ of calcining 3h respectively, and the bronzing solid that under air, calcining obtains is LaFeO 3, under nitrogen, calcining obtains tan product and is LaFeO 3@C composite nano materials
Hydrothermal reaction process can be described as: in Hydrothermal Synthesis process, and urea decomposition carbonate and ammoniacal liquor, hydrolysis discharges OH -1, solution is alkalescence, makes lanthanum ion and precipitation of iron ions, generates lanthanum iron precipitate core, and carbohydrate forms shell carbon-coating at 180 ℃ of hydrothermal carbonizations, and the lanthanum iron precipitate of generation is coated on carbon-coating inside completely, forms complete nucleocapsid structure.
The LaFeO that Fig. 1 is used this method to make 3and LaFeO 3the XRD figure of@C composite nano materials, two kinds of products that make after high-temperature process in air and nitrogen as can be seen from Figure 1 go out peak and cubic system LaFeO 3diffraction maximum is corresponding one by one, and corresponding JCPDS card number is 75-0439, and without other obvious impurity peaks, ferrous acid lanthanum purity is high.
The LaFeO of Fig. 2 for using this method to make 3the TEM photo of nano material, as can be seen from Figure 2, the LaFeO that in air, calcination processing obtains flocking together 3nano particle, particle diameter is greatly about 30～40nm.
The LaFeO of Fig. 3 for using this method to make 3the HRTEM photo of nano material, as we can see from the figure LaFeO clearly 3lattice fringe, measure lattice fringe spacing and be respectively 0.389nm and 0.271nm, it respectively can be corresponding to LaFeO 3(100) face of (JCPDS cardNo.75-0439), (110) face.
The LaFeO of Fig. 4 for using this method to make 3the TEM figure of@C composite nano materials, finds out the LaFeO making after high-temperature process in nitrogen 3@C composite nano materials has kept the nucleocapsid structure pattern before calcining, LaFeO substantially 3nano particle is all wrapped in uniform carbon-coating.Inner LaFeO 3karyosome footpath is approximately 20～30nm, and carbon-coating thickness is approximately 25nm.
The LaFeO of Fig. 5 for using this method to make 3the HRTEM photo of@C composite nano materials, as we can see from the figure LaFeO clearly in carbon-coating 3lattice fringe, measures lattice fringe spacing and is respectively 0.390nm and 0.273nm, and it respectively can be corresponding to LaFeO 3(100) face of (JCPDS card No.75-0439), (110) face.
The cycle performance test of LaFeO3@C composite nano materials: by LaFeO3@C (or LaFeO3) negative material powder, conductive agent (acetylene black) and binding agent (polyvinylidene fluoride) (weight ratio is 80: 10: 10) mix, add appropriate organic solvent NMP (1-METHYLPYRROLIDONE), fully grind to form after even pasty state, be coated on Copper Foil, at 120 ℃, vacuumize 12h, makes electrode slice.The assembling of battery is to complete in being filled with the glove box of argon gas.The electrode slice, both positive and negative polarity battery case, lithium sheet, barrier film, the electrolyte that scribble active material are assembled into button cell (CR2032 type).Wherein scribble the electrode slice of active material as positive pole, lithium sheet is negative pole, and Celgard240 polypropylene porous film is made barrier film, and the EC+DMC of 1.0mol/L LiPF6 (volume ratio 1: 1) solution is done electrolyte.
The button cell assembling is at the upper test of new prestige battery charging and discharging tester (BTS-5V10) charge-discharge performance, adopts current constant mode to discharge and recharge battery, and voltage range is 0.0V-3.0V; First room temperature high rate performance test discharges and recharges 5 circulations with 0.5C, then 1C, 2C, 4C discharge and recharge and return 0.5C after 5 circulations and discharge and recharge 5 circulations successively; Electrochemical impedance spectroscopy test (AC signal amplitude is 5mV, and frequency range is 100kHz-0.01Hz) is tested at CHI604B type electrochemical workstation.
The LaFeO of Fig. 6 for using this method to make 3and LaFeO 3the constant current charge-discharge curve chart that@C composite nano materials circulates first under 0.2C current density.Under nitrogen, calcine 600 ℃ of gained LaFeO 3the initial discharge specific capacity of@C nucleocapsid structure material is 1167.0mAhg -1, be far longer than pure LaFeO 3the 728.0mAhg of material -1.Subsequently, in charging process, bi-material charge ratio capacity reaches 667.1mAhg -1and 312.0mAhg -1, from charging and discharging capacity, can find out, bi-material, all having larger irreversible capacity in circulation first, calculates LaFeO 3the irreversible capacity loss first of@C is 42.8%, is less than pure LaFeO 357.1%, experimental result explanation, this LaFeO 3the storage lithium performance of@C nucleocapsid structure material is better than pure LaFeO far away 3nano material.
The LaFeO of Fig. 7 for using this method to make 3and LaFeO 3the cycle performance curve chart (current density 1C) of@C composite nano materials.As seen from the figure under 1C current density, LaFeO 3the initial discharge specific capacity of@C nucleocapsid structure material is 733mAhg -1, be far longer than pure LaFeO 3the 450mAhg of material -1, specific discharge capacity still can keep 380mAhg for the second time -1and its cyclical stability is relatively good, after discharging and recharging completely for 50 times, its specific capacity remains on 300mAhg -1, and pure LaFeO 3after 50 circulations of nano material, specific discharge capacity only has 120.0mAhg -1.
The LaFeO of Fig. 8 for using this method to make 3and LaFeO 3@C composite nano materials electrochemical impedance spectrogram.As can be seen from the figure, the impedance spectrogram of bi-material is similar, all that curve by semicircle of high frequency region and an inclination of low frequency range forms, high frequency region is that electrode reaction dynamics (charge transfer process) is controlled, low frequency range is by the diffusion control of reactant or the product of electrode reaction, in figure, find out LaFeO 3high frequency region half diameter of a circle of@C is significantly less than LaFeO 3high frequency region half circular diameter, nucleocapsid structure LaFeO is described 3@C nano material charge transfer impedance is much smaller than LaFeO 3, lithium good electrical property.
The LaFeO of Fig. 9 for using this method to make 3and LaFeO 3the high rate performance of@C composite nano materials.Discharge curve from different multiplying can find out, during 0.5C rate charge-discharge, LaFeO3 C specific discharge capacity is approximately 533mAhg -1; During large multiplying power, LaFeO 3@C material demonstrates its specific discharge capacity under 2C multiplying power and still has 210mAhg -1, the surface passivated membrane producing during 4C has mainly played the effect that hinders lithium ion migration, thereby make the capacity of sample, is 174mAhg -1, while being still greater than 4C, do not wrap the pure LaFeO of carbon 3, while returning 0.5C rate charge-discharge after the large multiplying power discharging of 4C, LaFeO 3@C specific discharge capacity can be got back to the level of initial 0.5C substantially, illustrates that large current charge can not cause the damage of negative material, on the whole, and LaFeO 3@C material demonstrates better multiplying power conservation rate.
Should be understood that, for those of ordinary skills, can be improved according to the above description or convert, and all these improvement and conversion all should belong to the protection range of claims of the present invention.

Claims (2)

1. one kind synthetic has a hud typed LaFeO 3the method of@C lithium cell cathode material, is characterized in that, the method comprises the following steps:
(1) take respectively lanthanum nitrate, ferric nitrate, urea, carbohydrate is configured to the mixed aqueous solution of certain volume, after fully stirring, obtain lurid mixed solution, wherein the consumption mol ratio of lanthanum nitrate, ferric nitrate and urea is between 1: 1: 10～1: 1: 20, and the concentration of carbohydrate is between 0.3-0.6M;
(2) mixed solution obtained above is transferred in hydrothermal reaction kettle, by hydrothermal reaction kettle sealing, puts at 180～220 ℃ of constant temperature blast drying ovens and react 12 hours, finish reaction, naturally cool to room temperature; Collect insoluble solid product, through washing the material obtaining after dry, be the composite nano materials of the coated lanthanum iron precipitate of carbon with nucleocapsid structure;
(3) the coated lanthanum iron precipitate composite nano materials of carbon is carried out to calcination processing; Detailed process is: 600-1000 ℃ of calcining 2-12h in nitrogen atmosphere, the solid product of collecting is hud typed LaFeO 3@C.
2. the LaFeO with nucleocapsid structure that according to claim 1 prepared by method 3@C lithium cell cathode material.
CN201410380212.7A 2014-08-05 2014-08-05 Core-shell type LaFeO3@C lithium battery anode material and preparation method thereof Active CN104157856B (en)

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CN107987558A (en) * 2017-12-05 2018-05-04 华北水利水电大学 A kind of flowers shape LaFexEu1-xO3/TiO2The preparation method of compound superfine red ceramic paint
CN107987559A (en) * 2017-12-05 2018-05-04 华北水利水电大学 A kind of spherical compound superfine red ceramic paint and preparation method thereof
CN113735177A (en) * 2021-09-06 2021-12-03 派尔森环保科技有限公司 Shell-shaped LaFeO with high rate performance of hollow nanospheres3Preparation method of lithium ion battery cathode material

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CN106179369A (en) * 2016-07-25 2016-12-07 牛和林 Tool visible ray Fenton activity LaFeO3/ C carbon back perovskite semiconductor composite nano material and its preparation method and application
CN107987558A (en) * 2017-12-05 2018-05-04 华北水利水电大学 A kind of flowers shape LaFexEu1-xO3/TiO2The preparation method of compound superfine red ceramic paint
CN107987559A (en) * 2017-12-05 2018-05-04 华北水利水电大学 A kind of spherical compound superfine red ceramic paint and preparation method thereof
CN107987558B (en) * 2017-12-05 2020-03-31 华北水利水电大学 Flower cluster-shaped LaFexEu1-xO3/TiO2Preparation method of composite superfine red ceramic pigment
CN107987559B (en) * 2017-12-05 2020-04-07 华北水利水电大学 Spherical composite superfine red ceramic pigment and preparation method thereof
CN113735177A (en) * 2021-09-06 2021-12-03 派尔森环保科技有限公司 Shell-shaped LaFeO with high rate performance of hollow nanospheres3Preparation method of lithium ion battery cathode material

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