CN104157856B - 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 PDFInfo
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- CN104157856B CN104157856B CN201410380212.7A CN201410380212A CN104157856B CN 104157856 B CN104157856 B CN 104157856B CN 201410380212 A CN201410380212 A CN 201410380212A CN 104157856 B CN104157856 B CN 104157856B
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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
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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
- 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
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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
- H01M4/48—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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
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- 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
Technical field
The present invention relates to hydro-thermal method and high-temperature heat treatment method combine and obtain thering is hud typed lafeo3@c cathode of lithium battery
The method of composite, belongs to hydro-thermal method and high-temperature heat treatment synthesizing new composite and lithium ion battery negative material technology
Field.
Background technology
Lithium ion battery has the advantages that operating voltage is high, specific energy is high, self-discharge rate is low because of it, asepsis environment-protecting and enjoy
Concern, becomes the main power source of current electronic product and electrical equipment.However, the renewal with electronic product in recent years and people
Extensive concern to energy source and power, lithium ion battery is put forward higher requirement, need its have higher energy density,
Higher power density and longer service life.
After carbon based negative electrodes material occurs, because it has low cost, higher cycle efficieny and the circulation of good electrochemistry
Stability, thus be widely used.But its lithium storage content is relatively low, and theoretical specific capacity is about 372mah/g, and in high magnification
There is potential safety hazard, therefore exploitation novel anode material becomes the key improving performance of lithium ion battery during charging.
P.poizot etc. proposes transition metal oxide first and as lithium ion battery negative material, and can pass through experiment
Confirm that its specific discharge capacity is 2～3 times of graphite cathode.However, transition metal oxide negative material there is also as follows
Problem: irreversible capacity is high first；In cyclic process, cubical expansivity height leads to cycle life low；Because it is semiconductor material
Material, its electric conductivity is poor to lead to high rate performance poor.Research shows, reduces oxide particle size, coated with conductive agent, particle is entered
The method such as row surface modification and doping metals cation all can improve the electric conductivity of oxide electrode, and wherein material with carbon-coated surface changes
Property be to improve between particle apparent conductance and improve the effective way of oxide electrode material electric conductivity.Patent
201310100981.2 being prepared for the fe of single dispersing core shell structure3o4@c nano composite lithium ion negative material has very high ratio
Capacity and higher cycle performance, in 0.01-0.3v voltage range, discharge and recharge under 0.2c multiplying power, its discharge capacity first
For 1031mah/g, after 100 circulations, still to have 544mah/g. patent 201110131191.1 to be prepared for hud typed for discharge capacity
Carbon coating cobalt based nanometer rod ion cathode material lithium, finds under 0.1c current density by electro-chemical test, reversible ratio first
Capacity is more than 1000mah/g, and after 100 circle circulations, reversible specific capacity remains at more than 1000mah/g it was demonstrated that this material
While keeping height ratio capacity, there is very strong cyclical stability.And this material is under conditions of high current (1c, 2c, 5c)
There is good storage lithium performance.Chen et al. reported that hydro-thermal method prepared nucleocapsid on j.mater.chem22 (2012) 15056
Carbon coating co of structure3o4Nano wire ion cathode material lithium, electro-chemical test shows, the co of carbon coating3o4Nano composite material
Storage lithium performance be significantly larger than uncoated carbon-coating co3o4Nano wire.Demonstrate material with carbon-coated surface modification and really can greatly improve and receive
The storage lithium performance of rice negative material.
Ca-Ti ore type abo3Oxide has inexpensive, easily-activated, high discharge capacity and good chemical stability etc.
Feature receives much concern.lafeo3It is one kind of ferrite series, belong to perovskite (abo3) type composite oxides.In recent years, due to
lafeo3Crystal structure, magnetic, electrical conductance, piezoelectricity and the electrooptical property having had, and in solid electrolyte, solid fuel electricity
The fields such as pond, engine, electrochemical device, sensor are applied.According to literature search, find no pass lafeo3Nanometer material
Material is applied to the pertinent literature report of the aspects such as lithium ion battery negative, is also not directed in actual industrial production.
The present invention passes through hydro-thermal method and high-temperature heat treatment method and synthesizes first have hud typed lafeo3The nano combined material of@c
Material.Hydro-thermal method has equipment and process is simple it is easy to control reaction condition, and product is reproducible, and yield is high, and synthetic method is green
Color, the advantages of be easy to industrial mass production, therefore hydro-thermal method prepares hud typed lafeo3The method tool of@c composite nano materials
There are huge potential scientific research value and using value.Electrochemistry experiment shows hud typed lafeo3@c nano particle has excellent
Circulation storage lithium performance (it is mainly reflected in specific capacity high, stable cycle performance, the adaptability of high current is good), its storage lithium performance is much
Lafeo higher than uncoated carbon-coating3Nano particle, provides possibility for it in the application of lithium ion battery negative material, has
Development potentiality and application prospect well.
Content of the invention
It is an object of the invention to provide a kind of lafeo with core shell structure3The preparation method of@c lithium cell cathode material.
The present invention is the lafeo that a kind of synthesis has core shell structure3The method of@c lithium cell cathode material it is characterised in that
The method has following technical process and a step:
Weigh lanthanum nitrate, ferric nitrate, urea respectively, carbohydrate is configured to the mixed aqueous solution of certain volume, fully
After stirring, obtain water white mixed solution, the wherein consumption mol ratio of lanthanum nitrate, ferric nitrate and urea is 1: 1: 100～1
: between 1: 20, the concentration of carbohydrate is between 0.3-0.6m.
Mixed solution obtained above is transferred in hydrothermal reaction kettle, hydrothermal reaction kettle is sealed, put into constant temperature air blast
React 12 hours at 180～220 DEG C in drying box, terminate reaction, naturally cool to room temperature；Collect insoluble solid product, warp
Cross the carbon coating lanthanum iron precipitate composite nano materials that the material obtaining after washing is dried as has core shell structure；
Carbon coating lanthanum iron precipitate composite nano materials are carried out calcination processing；Detailed process is: in nitrogen atmosphere
600-1000 DEG C of calcining 2-12h, the solid product collected is lafeo3@c.
The synthesis core shell structure lafeo that the present invention illustrates3The feature of the method for@c nano material is:
(1) with carbohydrate as carbon source, carbon coating lanthanum iron precipitate composite nano materials are prepared by hydro-thermal method.Preparation process
In, first reaction forms lanthanum iron precipitate (core), and the reaction of carbohydrate hydrothermal carbonization generates carbon-coating (shell), obtains carbon-coating and wrap completely
Cover the composite nano materials of lanthanum iron precipitate core.
(2) pass through to change the hydro-thermal time, thus it is possible to vary the thickness of composite material surface carbon-coating.
(3) by carbon coating lanthanum iron precipitate compound high-temperature calcination under air atmosphere and nitrogen atmosphere respectively, the former obtains
To pure lafeo3Nano particle, the latter obtains lafeo3@c composite nanometer particle.
The present invention synthesizes the lafeo with core shell structure first3@c lithium cell cathode material, the electric discharge from different multiplying
When curve (Fig. 9) can be seen that 0.5c rate charge-discharge, lafeo3@c specific discharge capacity is about 533mahg-1；During big multiplying power,
lafeo3@c material shows that its specific discharge capacity under 2c multiplying power still has 210mahg-1, the surface passivated membrane producing during 4c is main
Serve the effect hindering lithium ion mobility, so that the capacity of sample is 174mahg-1, pure still above bag carbon non-during 4c
lafeo3, when returning 0.5c rate charge-discharge after the big multiplying power discharging of 4c, lafeo3@c specific discharge capacity can return to initially substantially
The level of 0.5c, illustrates that large current charge is not result in the damage of negative material, on the whole, lafeo3@c material shows ratio
More excellent multiplying power conservation rate.
Brief description
Fig. 1 is the lafeo according to embodiment 1 preparation3And lafeo3The x-ray diffraction collection of illustrative plates of@c composite nano materials
(xrd)；
Fig. 2 is the lafeo according to embodiment 1 preparation3The transmission electron microscope photo (tem) of nano material；
Fig. 3 is the lafeo according to embodiment 1 preparation3The high-resolution-ration transmission electric-lens photo (hrtem) of nano material；
Fig. 4 is the lafeo according to embodiment 1 preparation3The transmission electron microscope photo (tem) of@c composite nano materials；
Fig. 5 is the lafeo according to embodiment 1 preparation3The high-resolution-ration transmission electric-lens photo of@c composite nano materials
(hrtem)；
Fig. 6 is to prepare pure lafeo according to embodiment 13And lafeo3Constant current charge-discharge curve map (the electric current that@c circulates first
Density 0.2c)；
Fig. 7 is the lafeo according to embodiment 1 preparation3And lafeo3@c material circulation performance curve (current density 1c)；
Fig. 8 is the lafeo according to embodiment 1 preparation3And lafeo3@c material electrochemical impedance spectra (eis)；
Fig. 9 is the lafeo according to embodiment 1 preparation3And lafeo3The high rate performance of@c material.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1: weigh 0.22g la (no first respectively3)3·6h2O, 0.20g fe (no3)3·9h2O, 0.3g urea,
1.773g mono- glucose monohydrate is dissolved in 35ml distilled water, obtains lurid mixed solution.Above-mentioned mixed solution is shifted
To hydrothermal reaction kettle, good seal, it is warming up to 180 DEG C, keeps 12h, reaction terminates.After natural cooling, collect solid product, wash
Wash the sepia product receiving after being dried and be carbon coating lanthanum iron precipitate nano material.Above-mentioned sepia product, respectively in sky
Under gas and nitrogen atmosphere, it is warming up to 600 DEG C of calcining 4h, calcining the red brown solid obtaining under air is lafeo3, forge under nitrogen
Burning obtains tan product and is lafeo3@c composite nano materials.
Embodiment 2: weigh 0.22g la (no first respectively3)3·6h2O, 0.20g fe (no3)3·9h2O, 0.45g urinate
Element, 1.773g mono- glucose monohydrate is dissolved in 35ml distilled water, obtains lurid mixed solution.Above-mentioned mixed solution is turned
Move in hydrothermal reaction kettle, good seal, it is warming up to 180 DEG C, keeps 12h, reaction terminates.After natural cooling, collect solid product,
The sepia product that washing receives after being dried is carbon coating lanthanum iron precipitate nano material.Above-mentioned sepia product, exists respectively
Under air and nitrogen atmosphere, it is warming up to 800 DEG C of calcining 3h, calcining the red brown solid obtaining under air is lafeo3, under nitrogen
Calcining obtains tan product and is lafeo3@c composite nano materials.
Embodiment 3: weigh 0.22g la (no first respectively3)3·6h2O, 0.20g fe (no3)3·9h2O, 0.6g urea,
1.773g mono- glucose monohydrate is dissolved in 35ml distilled water, obtains lurid mixed solution.Above-mentioned mixed solution is shifted
To hydrothermal reaction kettle, good seal, it is warming up to 200 DEG C, keeps 12h, reaction terminates.After natural cooling, collect solid product, wash
Wash the sepia product receiving after being dried and be carbon coating lanthanum iron precipitate nano material.Above-mentioned sepia product, respectively in sky
Under gas and nitrogen atmosphere, it is warming up to 1000 DEG C of calcining 2h, calcining the red brown solid obtaining under air is lafeo3, forge under nitrogen
Burning obtains tan product and is lafeo3@c composite nano materials.
Embodiment 4: weigh 0.22g la (no first respectively3)3·6h2O, 0.20g fe (no3)3·9h2O, 0.3g urea,
3.546g mono- glucose monohydrate is dissolved in 35ml distilled water, obtains lurid mixed solution.Above-mentioned mixed solution is shifted
To hydrothermal reaction kettle, good seal, it is warming up to 200 DEG C, keeps 12h, reaction terminates.After natural cooling, collect solid product, wash
Wash the sepia product receiving after being dried and be carbon coating lanthanum iron precipitate nano material.Above-mentioned sepia product, respectively in sky
Under gas and nitrogen atmosphere, it is warming up to 600 DEG C of calcining 3h, calcining the red brown solid obtaining under air is lafeo3, forge under nitrogen
Burning obtains tan product and is lafeo3@c composite nano materials.
Embodiment 5: weigh 0.22g la (no first respectively3)3·6h2O, 0.20g fe (no3)3·9h2O, 0.45g urinate
Element, 3.456g mono- glucose monohydrate is dissolved in 35ml distilled water, obtains lurid mixed solution.Above-mentioned mixed solution is turned
Move in hydrothermal reaction kettle, good seal, it is warming up to 220 DEG C, keeps 12h, reaction terminates.After natural cooling, collect solid product,
The sepia product that washing receives after being dried is carbon coating lanthanum iron precipitate nano material.Above-mentioned sepia product, exists respectively
Under air and nitrogen atmosphere, it is warming up to 800 DEG C of calcining 4h, calcining the red brown solid obtaining under air is lafeo3, under nitrogen
Calcining obtains tan product and is lafeo3@c composite nano materials
Embodiment 6: weigh 0.22g la (no first respectively3)3·6h2O, 0.20g fe (no3)3·9h2O, 0.6g urea,
3.456g mono- glucose monohydrate is dissolved in 35ml distilled water, obtains lurid mixed solution.Above-mentioned mixed solution is shifted
To hydrothermal reaction kettle, good seal, it is warming up to 220 DEG C, keeps 12h, reaction terminates.After natural cooling, collect solid product, wash
Wash the sepia product receiving after being dried and be carbon coating lanthanum iron precipitate nano material.Above-mentioned sepia product, respectively in sky
Under gas and nitrogen atmosphere, it is warming up to 1000 DEG C of calcining 3h, calcining the red brown solid obtaining under air is lafeo3, forge under nitrogen
Burning obtains tan product and is lafeo3@c composite nano materials
Hydrothermal reaction process can be described as: during Hydrothermal Synthesiss, urea decomposes carbonate and ammoniacal liquor, hydrolysis release
oh-1, solution alkaline, make lanthanum ion and precipitation of iron ions, generate lanthanum iron precipitate core, carbohydrate is in 180 DEG C of hydro-thermal carbon
Change and form shell carbon-coating, the lanthanum iron precipitate of generation is coated on inside carbon-coating completely, form complete core shell structure.
Fig. 1 uses the lafeo that this method is obtained3And lafeo3The xrd figure of@c composite nano materials, as can be seen from Figure 1 in sky
The appearance of two kinds of products being obtained after gas and the process of nitrogen high temperature and cubic system lafeo3Diffraction maximum corresponds, corresponding
Jcpds card number is 75-0439, no other substantially impurity peaks, and cadmium ferrite purity is high.
Fig. 2 is the lafeo being obtained using this method3The tem photo of nano material, from figure 2, it is seen that in the air calcination processing
Obtain the lafeo flocking together3Nano particle, particle diameter is about in 30～40nm.
Fig. 3 is the lafeo being obtained using this method3The hrtem photo of nano material, as we can see from the figure clearly
lafeo3Lattice fringe, measure lattice fringe spacing be respectively 0.389nm and 0.271nm, it may correspond to lafeo3
(100) face of (jcpds cardno.75-0439), (110) face.
Fig. 4 is the lafeo being obtained using this method3@c composite nano materials tem figure it will be seen that nitrogen high temperature process after
Prepared lafeo3@c composite nano materials maintain the core shell structure pattern before calcining, lafeo substantially3Nano particle all wraps up
In uniform carbon-coating.Internal lafeo3Karyosome footpath is about 20～30nm, and carbon layers having thicknesses are about 25nm.
Fig. 5 is the lafeo being obtained using this method3The hrtem photo of@c composite nano materials, carbon as we can see from the figure
Clearly lafeo in layer3Lattice fringe, measures lattice fringe spacing and is respectively 0.390nm and 0.273nm, it can correspond to respectively
In lafeo3(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 than for 80: 10: 10) mixing, adds appropriate organic solvent
Nmp (n- methyl pyrrolidone), is fully ground uniformly after pasty state, is coated on Copper Foil, is vacuum dried 12h, makes electricity at 120 DEG C
Pole piece.The assembling of battery is to complete in the glove box be filled with argon gas.Electrode slice, the both positive and negative polarity battery of active material will be scribbled
Shell, lithium piece, barrier film, electrolyte are assembled into button cell (cr2032 type).The electrode slice wherein scribbling active material as positive pole,
Lithium piece is negative pole, and celgard240 polypropylene porous film does barrier film, ec+dmc (volume ratio 1: the 1) solution of 1.0mol/l lipf6
Do electrolyte.
The button cell assembling is in new prestige battery charging and discharging tester (bts-5v10) upper test charge-discharge performance, adopts
With current constant mode, discharge and recharge is carried out to battery, voltage range is 0.0v-3.0v；The test of room temperature high rate performance is filled with 0.5c first
5 circulations of electric discharge, then 1c, 2c, 4c discharge and recharge 5 returns 5 circulations of 0.5c discharge and recharge after circulating successively；Electrochemical impedance spectroscopy
Test (AC signal amplitude is 5mv, and frequency range is 100khz-0.01hz) is surveyed in chi604b type electrochemical workstation
Examination.
Fig. 6 is the lafeo being obtained using this method3And lafeo3@c composite nano materials under 0.2c current density first
The constant current charge-discharge curve map of circulation.600 DEG C of gained lafeo are calcined under nitrogen3The initial discharge specific volume of@c Core-shell structure material
Measure as 1167.0mahg-1, it is far longer than pure lafeo3The 728.0mahg of material-1.Subsequently, in charging process, bi-material fills
Electric specific capacity reaches 667.1mahg-1And 312.0mahg-1, from charging and discharging capacity as can be seen that bi-material circulates first
In be respectively provided with larger irreversible capacity, be calculated, lafeo3The irreversible capacity loss first of@c is 42.8%, less than pure
lafeo357.1%, experimental result illustrate, this lafeo3The storage lithium performance of@c Core-shell structure material is far better than pure lafeo3
Nano material.
Fig. 7 is the lafeo being obtained using this method3And lafeo3Cycle performance curve map (the electric current of@c composite nano materials
Density 1c).As seen from the figure under 1c current density, lafeo3The initial discharge specific capacity of@c Core-shell structure material is
733mahg-1, it is far longer than pure lafeo3The 450mahg of material-1, second specific discharge capacity remain to keep 380mahg-1And
Its cyclical stability is relatively good, and after 50 complete discharge and recharges, its specific capacity is maintained at 300mahg-1, and pure lafeo3Nano material
After 50 circulations, specific discharge capacity only has 120.0mahg-1.
Fig. 8 is the lafeo being obtained using this method3And lafeo3@c composite nano materials electrochemical impedance spectrogram.From in figure
As can be seen that the impedance spectra of bi-material is similar, it is all the song of an inclination by a semicircle of high frequency region and low frequency range
Line is constituted, and high frequency region is that electrode reaction dynamics (charge transfer process) controls, and low frequency range is by the reactant of electrode reaction or product
The diffusion of thing controls, and in figure is found out, lafeo3High frequency region half diameter of a circle of@c is significantly less than lafeo3High frequency region semicircle straight
Footpath, illustrates core shell structure lafeo3@c nano material charge transfer impedance is much smaller than lafeo3, lithium good electrical property.
Fig. 9 is the lafeo being obtained using this method3And lafeo3The high rate performance of@c composite nano materials.From different multiplying
Under discharge curve when can be seen that 0.5c rate charge-discharge, lafeo3@c specific discharge capacity is about 533mahg-1；Big multiplying power
When, lafeo3@c material shows that its specific discharge capacity under 2c multiplying power still has 210mahg-1, the surface passivated membrane that produces during 4c
Primarily serve the effect hindering lithium ion mobility, so that the capacity of sample is 174mahg-1, still above bag carbon non-during 4c
Pure lafeo3, when returning 0.5c rate charge-discharge after the big multiplying power discharging of 4c, lafeo3@c specific discharge capacity can return to substantially
The level of initial 0.5c, illustrates that large current charge is not result in the damage of negative material, on the whole, lafeo3@c material shows
Go out the excellent multiplying power conservation rate of comparison.
It should be appreciated that for those of ordinary skills, can be improved according to the above description or be converted,
And all these modifications and variations all should belong to the protection domain of claims of the present invention.
Claims (2)
1. a kind of synthesis has hud typed lafeo3The method of@c lithium cell cathode material it is characterised in that the method include following
Step:
(1) lanthanum nitrate, ferric nitrate, urea are weighed respectively, carbohydrate is configured to the mixed aqueous solution of certain volume, fully stirs
After mixing, obtain lurid mixed solution, wherein the consumption mol ratio of lanthanum nitrate, ferric nitrate and urea is 1: 1: 10～1: 1: 20
Between, the concentration of carbohydrate is between 0.3-0.6m；
(2) mixed solution obtained above is transferred in hydrothermal reaction kettle, hydrothermal reaction kettle is sealed, put into constant temperature air blast and do
React 12 hours at 180～220 DEG C in dry case, terminate reaction, naturally cool to room temperature；Collect insoluble solid product, pass through
The material that washing obtains after being dried as has the composite nano materials of the carbon coating lanthanum iron precipitate of core shell structure；
(3) carbon coating lanthanum iron precipitate composite nano materials are carried out calcination processing；Detailed process is: 600- in nitrogen atmosphere
1000 DEG C of calcining 2-12h, the solid product collected is hud typed lafeo3@c.
2. the lafeo with core shell structure of method preparation according to claim 13@c lithium cell cathode material.
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| 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 |
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