CN103811740B - A kind of nucleocapsid structure Li xv 2o 5/ LiV 3o 8intercalation materials of li ions and preparation method thereof - Google Patents

A kind of nucleocapsid structure Li xv 2o 5/ LiV 3o 8intercalation materials of li ions and preparation method thereof Download PDF

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CN103811740B
CN103811740B CN201410054280.4A CN201410054280A CN103811740B CN 103811740 B CN103811740 B CN 103811740B CN 201410054280 A CN201410054280 A CN 201410054280A CN 103811740 B CN103811740 B CN 103811740B
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CN103811740A (en
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王海燕
孙旦
蒋介草
陈红波
唐有根
刘平
刘洪涛
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Central South University
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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    • 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 kind of nucleocapsid structure Li xv 2o 5/ LiV 3o 8intercalation materials of li ions and preparation method thereof.By LiV 3o 8be placed in tube furnace and heat-treat reduction and can form Li xv 2o 5/ LiV 3o 8core-shell material, can effective Li in control objectives product by the flow controlling reducing gas xv 2o 5outer field thickness.Li xv 2o 5the introducing energy available protecting LiV of shell 3o 8, significantly can improve the interfacial electrochemistry character of electrode simultaneously, thus increase substantially the chemical property of material.The Li of preparation xv 2o 5/ LiV 3o 8compound intercalation materials of li ions has excellent stable circulation performance and high rate performance.The method technological process is short, simple to operate, with low cost, is easy to realize suitability for industrialized production.

Description

A kind of nucleocapsid structure Li xv 2o 5/ LiV 3o 8intercalation materials of li ions and preparation method thereof
Technical field
The invention belongs to high-energy battery field of material technology, be specifically related to a kind of high-performance compound lithium vanadate anode material with nucleocapsid structure and preparation method thereof.
Background technology
Oxyvanadium compound is owing to having relative inexpensiveness, and synthetic method is simple, and specific capacity high becomes the focus of Recent study.China's vanadium resource enriches, but the exploitation of navajoite mainly concentrates on primary product, and the comprehensive utilization degree of vanadium resource is not high, constrains the development of vanadium industry.Therefore the vanadium sub-group compound developing high power capacity, as new type lithium ion battery intercalation materials of li ions, utilizes optimization China vanadium resource and promotes economic development all significant.In vanadium system intercalation materials of li ions, most study is LiV 3o 8.This material has monocline, belongs to P2 1/ m point group.LiV 3o 8unit is two-layer V 3o 8 -in accompany the Layer cake structure of lithium ion.Special structure makes this material have good structural stability in lithium ion deintercalation process.
Research finds, LiV 3o 8discharge capacity and the synthetic method of cycle life and material and follow-up heat treatment process closely related.Traditional high temperature solid-state method is generally by Li 2cO 3with V 2o 5stoichiometrically mix, obtained in 650 DEG C of sintering, discharge capacity is about 180mAh g -1.Si etc. [Journal of Alloys and Compounds, 486 (2009) 400] are fuel with urea, adopt low-temperature combustion method to prepare the LiV of capacity up to 340mAh/g 3o 8, lower than 250mAh g after 30 circulations -1.Zhou etc. [Solid State Ionics, 179 (2008) 1763] have prepared LiV with the sol-gal process that EDTA is auxiliary in conjunction with solid-phase sintering process 3o 8.Discharge capacity is 251.7mAh/g first, and average each Capacity fading rate is 0.43%.Meanwhile, LiV 3o 8high rate performance not good.Liu etc. [J.Power Sources, 192 (2009) 668] have prepared monocrystalline LiV 3o 8nanometer rods, 20mA g -1under capacity is high to 348mAh g first -1, but at 100mA g -1drop to 200mAh g -1left and right.Pan etc. [J.Mater.Chem, 21 (2011) 10077] have synthesized LiV 3o 8nano flake, 100mA g -1under discharge capacity be about 260mAh g -1, 300 and 1000mA g -1under, be down to 194 and 166mAh g respectively -1, and capacity attenuation increases.How to improve LiV further 3o 8stable circulation performance and high rate performance be the emphasis of at present research.
Researcher has carried out the research of a large amount of doping and surface coating modification in succession, is intended to improve LiV further 3o 8chemical property.Research confirms, it is LiV that the dissolving of V causes material structure to change in charge and discharge process 3o 8the major reason of capacity attenuation.Therefore, on target material, the inactive material of coated one deck stops the dissolving of V, suppresses the volumetric expansion of material in charge and discharge process can improve its chemical property.In addition, coating layer will effectively reduce the reactivity of material and electrolyte interface, suppresses side reaction to occur, stabilized electrodes.Current carbon coating layer, polyaniline (PAn), AlPO 4, AlF 3and Al 2o 3successively be used for LiV 3o 8carry out finishing, effectively improve the cycle performance of material.But due to LiV 3o 8in V be+5 valencys, have stronger oxidability, in sintering link, coating layer is easy to induction basis material recurring structure and changes, and affects chemical property.Idris etc. [Compos.Sci.Technol., 71 (2011) 343] find the LiV that carbon is coated 3o 8nano flake reversible capacity is from coated front 335mAh g -1drop to 227mAh g -1.The LiV of polyaniline-coated 3o 8reversible capacity is from 283mAhg -1drop to 243mAhg -1[J.Power Sources, 64 (2012) 47].
The present invention devises a kind of method of converted in-situ, with LiV 3o 8for matrix, by the process of simple reducing atmosphere at LiV 3o 8surface directly generates Li xv 2o 5thin layer, thus a step defines the Li of nucleocapsid structure xv 2o 5/ LiV 3o 8composite material.Compared to original LiV 3o 8, the stable circulation performance of this composite material and high rate performance are obtained for and significantly improve.
Summary of the invention
The object of the invention is to propose a kind of high power capacity, long-life and the powerful anode material for lithium-ion batteries with nucleocapsid structure and preparation method thereof, this preparation method is a kind of converted in-situ method of novel simple, with LiV 3o 8for matrix, by heat treatment in reducing atmosphere at LiV 3o 8surface directly generates ultra-thin Li xv 2o 5layer, thus achieve nucleocapsid structure Li xv 2o 5/ LiV 3o 8the one-step method preparation of composite material; Solve the problem that this kind of material circulation life-span in prior art is short and high rate performance is not good.
A kind of nucleocapsid structure Li xv 2o 5/ LiV 3o 8intercalation materials of li ions is with LiV 3o 8for core, Li xv 2o 5, 0<x<1 is the composite nano materials of shell.
Described nanostructure is the one of nano particle, nanometer sheet, nano wire, nanometer rods, nanosphere.
A kind of nucleocapsid structure Li xv 2o 5/ LiV 3o 8the preparation method of intercalation materials of li ions, gets LiV 3o 8material is placed in protective gas, and then heat up heating, after protective gas being switched to reducibility gas process, naturally cools to room temperature, obtain Li xv 2o 5parcel LiV 3o 8core-shell structure material.
Described protective gas is the one of argon gas, nitrogen.Heating rate is 1 ~ 15 DEG C/min.Intensification is heated to 300 ~ 600 DEG C.Described reducibility gas is H 2with the mist of Ar, or CO and CO 2mist.H 2with H in the mist of Ar 2volume fraction is 3 ~ 20%; CO and CO 2mist in the volume fraction of CO be 5 ~ 20%.The reducing gas flow injected is 50 ~ 500cm 3/ min.Injecting the reducing gas after-baking time is 1 ~ 60min.
Principle of the present invention:
LiV 3o 8capacity attenuation and Lithium-ion embeding deviate from the vanadium occurred in process and dissolve closely related.The dissolving of vanadium can cause the change of material structure.Because of the restriction of crystal structure, LiV 3o 8lithium ion diffusion coefficient lower, cause high rate performance not good.The dissolving of vanadium in charge and discharge process can be suppressed by suitable finishing, the crystal structure of stabilizing material, thus extend cycle life.Research finds, Li xv 2o 5lithium ion diffusion coefficient than LiV 3o 8height about 2 orders of magnitude, the high rate performance of this material is better than LiV 3o 8.Based on this, the present invention utilizes LiV 3o 8middle pentavalent vanadium and reducibility gas reduction reaction at high temperature, at LiV 3o 8there is inverting reaction in surface, generates uniform Li xv 2o 5shell, forms core shell structure.Final Li can be controlled by the amount controlling the reducibility gas injected xv 2o 5the thickness of shell.Li xv 2o 5skin can not only effectively suppress basis material LiV 3o 8vanadium in charge and discharge process dissolves, guard electrode, and the interfacial electrochemistry character significantly improving combination electrode, thus improves high rate performance and the stable circulation performance of electrode.
Advantage of the present invention and good effect
The present invention has following distinguishing feature:
1): compared to other method for coating, the present invention does not introduce other impurity element, passes through LiV 3o 8inverting reaction can ensure product by the impact of other foreign ion, overcome that common cladding process is coated unevenly contacts untight deficiency with coating layer with basis material simultaneously, can Li be realized xv 2o 5the uniform close of layer is coated, thus significantly improves the stable circulation performance of material.
2): effectively can control core-shell composite material ectomesoderm Li by the injection of reducibility gas xv 2o 5thickness, due to Li xv 2o 5have good embedding lithium ability equally, therefore, this method obviously can not reduce the reversible capacity of composite material.
3): compared to LiV 3o 8, Li xv 2o 5there is higher lithium ion diffusion coefficient.Therefore, the Li of nucleocapsid structure xv 2o 5/ LiV 3o 8effectively can improve the interfacial electrochemistry character of electrode, thus obtain better high rate performance.
Good effect of the present invention:
The nucleocapsid structure Li of the present invention's synthesis xv 2o 5/ LiV 3o 8original LiV compared by composite material 3o 8, cycle performance and high rate performance are obtained for and significantly improve.The present invention supports for the further investigation of vanadate material and commercial application supplying method from now on.Meanwhile, heat treatment in reducing atmosphere one step that the present invention proposes generates nucleocapsid structure Li xv 2o 5/ LiV 3o 8coated research for other positive electrode is provided reference by the thinking of composite material.
Accompanying drawing explanation
Fig. 1 is respectively the XRD curve of the target material of embodiment 1, embodiment 2, embodiment 3, embodiment 4 and embodiment 5 preparation;
The high-resolution projection Electronic Speculum figure of the target material that Fig. 2 is respectively embodiment 3, prepared by embodiment 5;
The target material that Fig. 3 is respectively embodiment 1, prepared by embodiment 3 is at the cyclic voltammetry curve of 1.5 ~ 4.0V, and sweep speed is 0.1mV/s;
Fig. 4 is respectively the target material of embodiment 1, embodiment 2, embodiment 3 and embodiment 4 preparation at 1C multiplying power (300mA g -1) under circulation volume figure;
Fig. 5 is respectively the circulation volume figure of target material under different multiplying of embodiment 1, embodiment 2, embodiment 3 and embodiment 4 preparation;
Fig. 6 is that the target material of embodiment 5 preparation is at 1C multiplying power (300mA g -1) under circulation volume figure.
Embodiment
The invention will be further described by the following examples, and unrestricted the present invention.
Embodiment 1:
Take 2.5g sheet LiV 3o 8nano material is placed in tube furnace.With 120cm 3the flow of/min continues to inject argon shield gas, after half an hour, is heated to 450 DEG C of constant temperature 10min with 15 DEG C/min heating rate, closes tube furnace, naturally cools to room temperature, obtain the LiV without reducing gas process 3o 8, for comparative study.This material crystal structure is shown in the example 1 in Fig. 1.From XRD curve, the product of preparation belongs to monoclinic system, P2 1/ m point group.
The target material of preparation, conductive agent Super P and binding agent PVDF are pressed certain mass ratio (80:10:10) Homogeneous phase mixing, with oxolane (THF) for solvent, after fully stirring 6h, adopts coating device to be coated on aluminium foil by slurry Quick uniform.After solvent evaporates, the pole piece coated is placed in 110 DEG C of process 12h in vacuum drying chamber.Pole piece is made into the sequin of diameter 12mm.Take metal lithium sheet as negative pole, be bestowed by heaven the 1mol/L LiPF that company produces in Guangzhou 6eC:DMC(1:1, v/v) mixed solution is electrolyte, in inert atmosphere glove box (UNILAB MBRAUN Germany produces), assemble button half-cell (CR2016), glove box operating system is high-purity argon gas.Half-cell assembles rear standing 5h, at room temperature tests its electrochemical data with new prestige battery charging and discharging instrument.Adopt constant current charge and discharge pattern, voltage range is 1.5 ~ 4.0V.In Shanghai occasion China, electrochemical workstation carries out cyclic voltammetry, and sweep speed is 0.1mV/s.Fig. 3 have recorded the cyclic voltammetry curve of material, as can be known from Figure, and LiV 3o 8electrode has multipair obvious oxidation-reduction pair, respectively corresponding lithium ion embedding and deviate from process.Example 1 in Fig. 4 have recorded the cycle performance of material.As we know from the figure, LiV 3o 8nanometer sheet first discharge specific capacity under 1C multiplying power (300mA/g) is 178mAh g -1, after 100 circulations, drop to 120mAhg -1.Example 1 in Fig. 5 have recorded the high rate performance of material.The first discharge capacity of this material under 0.1C, 1C and 5C multiplying power is 278.7mAh g -1, 181.0mAh g -1and 50.2mAhg -1.It can thus be appreciated that, untreated LiV 3o 8nanometer sheet high rate performance is bad.
Embodiment 2
Take 2.52g sheet LiV 3o 8nano material is placed in tube furnace.With 120cm 3the flow of/min continues to inject argon shield gas, after half an hour, is heated to 450 DEG C of constant temperature 10min, argon stream is switched to H immediately with 15 DEG C/min heating rate 2/ Ar(H 2volume 5%) mist, H 2/ Ar mixed gas flow is 60cm 3/ min, stops gas inject after process 1min, closes tube furnace, naturally cool to room temperature, obtain target material.Its crystal structure is shown in the example 2 in Fig. 1.From XRD curve, the product of preparation belongs to monoclinic system, P2 1/ m point group, obvious impurity diffraction maximum, does not illustrate 1min H 2heat treatment in/Ar mist is at LiV 3o 8the Li generated on the surface xv 2o 5content is considerably less, below the detectability of XRD diffraction.
Half-cell manufacture craft and test are with embodiment 1.Example 2 in Fig. 4 have recorded the cycle performance of target material.As we know from the figure, this material first discharge specific capacity under 1C multiplying power is 165.1mAh g -1, after 100 and 200 circulations, remain on 154.7mAhg respectively -1and 155.1mAhg -1.H is not carried out compared in example 1 2the LiV of/Ar gas treatment 3o 8, in this example, the heat treatment of 1min significantly improves the cycle performance of target material.Example 2 in Fig. 5 have recorded the high rate performance of target material.The first discharge capacity of this material under 0.1C and 5C multiplying power is respectively 277.1mAh g -1and 80.3mAhg -1.The high rate performance of material is improved, and possible cause is the LiV on surface 3o 8with H 2there is reduction reaction, generate a small amount of Li xv 2o 5, form the Li of nucleocapsid structure xv 2o 5/ LiV 3o 8composite material.Li xv 2o 5shell obviously can improve the interfacial electrochemistry character of combination electrode.
Embodiment 3
Take 2.52g sheet LiV 3o 8nano material is placed in tube furnace.With 120cm 3the flow of/min continues to inject argon shield gas, after half an hour, is heated to 450 DEG C of constant temperature 10min, argon stream is switched to H immediately with 15 DEG C/min heating rate 2/ Ar(H 2volume 5%) mist, H 2/ Ar mixed gas flow is 60cm 3/ min, stops gas inject after process 5min, closes tube furnace, naturally cool to room temperature, obtain target material.Its crystal structure is shown in the example 3 in Fig. 1.From XRD curve, the product of preparation belongs to monoclinic system, P2 1/ m point group, obvious impurity diffraction maximum, does not illustrate 5min H 2the heat treatment of/Ar mist is at LiV 3o 8the Li generated on the surface xv 2o 5also little, its content is below the detectability of XRD diffraction.
Half-cell manufacture craft and test are with embodiment 1.The HRTEM that Fig. 2 (a) is target material schemes.Figure there is inside and outside two-layer dissimilar diffraction lattice district, main body diffraction lattice (d=0.38nm) corresponding LiV 3o 8{ 003} crystal face, skin thinner (~ 12nm), diffraction lattice (d=0.22nm) the corresponding Li of matrix xv 2o 5{ 601} crystal face, result confirms Li xv 2o 5/ LiV 3o 8the existence of nucleocapsid structure.The CV contrast of Fig. 3 finds, compared to the LiV do not processed in reducing atmosphere 3o 8, also there is obvious reduction peak at 3.25V place in target material prepared by this example, this is Li xv 2o 5the characteristic feature of electrode.Example 3 in Fig. 4 have recorded the cycle performance of target material.As we know from the figure, this material first discharge specific capacity under 1C multiplying power is 195.4mAh g -1, after 100 and 200 circulations, remain on 168.5mAhg respectively -1and 163.4mAhg -1.Compared to the material in example 1 and example 2, this example is after 5min thermal reduction process, and electrode electro Chemical performance obtains further raising.Example 3 in Fig. 5 have recorded the high rate performance of target material.The first discharge capacity of this material under 0.1C and 5C multiplying power is respectively 278.1mAh g -1and 152.1mAhg -1, high rate performance is significantly improved.Research confirms, the LiV on surface 3o 8with H 2there is reduction reaction, generate a small amount of Li xv 2o 5, form the Li of nucleocapsid structure xv 2o 5/ LiV 3o 8composite material.Li xv 2o 5the existence of coated thin layer can not only available protecting LiV 3o 8stablizing in charge and discharge process, can also significantly improve the interfacial electrochemistry character of electrode.
Embodiment 4
Take 2.52g sheet LiV 3o 8nano material is placed in tube furnace.With 120cm 3the flow of/min continues to inject argon shield gas, after half an hour, is heated to 450 DEG C of constant temperature 10min, argon stream is switched to H immediately with 15 DEG C/min heating rate 2/ Ar(H 2volume 5%) mist, H 2/ Ar mixed gas flow is 60cm 3/ min, stops gas inject after process 10min, closes tube furnace, naturally cool to room temperature, obtain target material.Its crystal structure is shown in the example 4 in Fig. 1.From XRD curve, the product of preparation belongs to monoclinic system, P2 1/ m point group, obvious impurity diffraction maximum, does not illustrate 10min H 2the heat treatment of/Ar mist is at LiV 3o 8the Li generated on the surface xv 2o 5amount still below the detectability of XRD diffraction.
Half-cell manufacture craft and test are with embodiment 1.Example 4 in Fig. 4 have recorded the cycle performance of target material.As we know from the figure, this material first discharge specific capacity under 1C multiplying power is 176.4mAh g -1, after 100 and 200 circulations, remain on 156.7mAhg respectively -1and 131.9mAhg -1.H is not carried out compared in example 1 2the LiV of/Ar gas treatment 3o 8, this example effectively improves the cycle performance of target material, but compared to example 2 and example 3, cycle performance reduces along with the prolongation in processing time.Example 4 in Fig. 5 have recorded the high rate performance of target material.The first discharge capacity of this material under 0.1C and 5C multiplying power is respectively 279.3mAh g -1and 115.2mAhg -1.Compared to example 1 and example 2, material high rate performance prepared by this example is improved, but than the difference in example 3.Illustrate at LiV 3o 8the Li generated on the surface xv 2o 5not The more the better.
Embodiment 5
Take 2.52g sheet LiV 3o 8nano material is placed in tube furnace.With 120cm 3the flow of/min continues to inject argon shield gas, after half an hour, is heated to 450 DEG C of constant temperature 10min simultaneously, argon stream is switched to H immediately with 15 DEG C/min heating rate 2/ Ar(H 2volume 5%) mist, H 2/ Ar mixed gas flow is 60cm 3/ min, stops gas inject after process 30min, closes tube furnace, naturally cool to room temperature, obtain target material.Its crystal structure is shown in the example 5 in Fig. 1.From XRD curve, the product of preparation belongs to monoclinic system, P2 1, there is new diffraction maximum, with Li in/m point group simultaneously 0.7v 2o 5standard spectrum coincide, and result confirms to have occurred Li in target material xv 2o 5phase, this example also can further illustrate the Li that can obtain having nucleocapsid structure by the heat treatment of reducibility gas xv 2o 5/ LiV 3o 8.Example 2, example 3, in example 4, XRD fails to detect Li xv 2o 5the diffraction maximum of phase is because the Li generated xv 2o 5amount is few, does not reach the detectability (ordinary circumstance, ratio is all difficult to detect lower than 5% instrument) of instrument.
Half-cell manufacture craft and test are with embodiment 1.The HRTEM that Fig. 2 (b) is target material schemes.Figure also there is inside and outside two-layer dissimilar diffraction lattice district, main body diffraction lattice (d=0.38nm) corresponding LiV 3o 8{ 003} crystal face, outer layer zone diffraction lattice (d=0.22nm) the corresponding Li of matrix xv 2o 5601} crystal face, compares example 3, and along with the prolongation of heat treatment time, outer Li xv 2o 5thickness obviously increase (~ 28nm), result also demonstrate that Li xv 2o 5/ LiV 3o 8the existence of nucleocapsid structure.Fig. 6 have recorded the cycle performance of target material under 1C multiplying power.The discharge capacity first of this material is 152.4mAh g -1, after 100 and 200 circulations, remain on 138.2mAhg respectively -1and 116.2mAhg -1.To compare in example 1 not heat treated material in reducing atmosphere, cycle performance and reversible capacity are obtained for raising, but compare the heat treatment of 5min in example 3, and performance obviously declines, further illustrate, heat treatment excessively of a specified duration is unfavorable for the chemical property of target material.
Embodiment 6
Take the bar-shaped LiV of 2.52g 3o 8nano material is placed in tube furnace.With 300cm 3the flow of/min continues to inject argon shield gas, after half an hour, is heated to 550 DEG C of constant temperature 10min, argon stream is switched to H immediately with 10 DEG C/min heating rate 2/ Ar(H 2volume ratio 10%) mist, H 2/ Ar mixed gas flow is 60cm 3/ min, stops gas inject after process 5min, closes tube furnace, naturally cool to room temperature, obtain target material.
Half-cell manufacture craft and test are with embodiment 1, and material type prepared by performance and embodiment 3 seemingly.
Embodiment 7
Take the bar-shaped LiV of 2.52g 3o 8nano material is placed in tube furnace.With 150cm 3the flow of/min continues to inject argon shield gas, after half an hour, is heated to 550 DEG C of constant temperature 10min, argon stream is switched to CO/CO immediately with 10 DEG C/min heating rate 2(CO volume 10%) mist, gas flow is 100cm 3/ min, stops gas inject after process 5min, closes tube furnace, naturally cool to room temperature, obtain target material.
Half-cell manufacture craft and test are with embodiment 1, and material type prepared by performance and embodiment 3 seemingly.

Claims (10)

1. a nucleocapsid structure Li xv 2o 5/ LiV 3o 8intercalation materials of li ions, is characterized in that, is with LiV 3o 8for core, Li xv 2o 5, 0<x<1 is the composite nano materials of shell.
2. material according to claim 1, is characterized in that, described composite nano materials is the one of nanometer sheet, nano wire, nanometer rods, nanosphere.
3. a nucleocapsid structure Li xv 2o 5/ LiV 3o 8the preparation method of intercalation materials of li ions, is characterized in that, gets LiV 3o 8material is placed in protective gas, and then heat up heating, protective gas is switched to reducibility gas and after further heat treatment, naturally cools to room temperature, obtain Li xv 2o 5, 0<x<1, parcel LiV 3o 8core-shell structure material.
4. preparation method according to claim 3, is characterized in that, described protective gas is the one of argon gas, nitrogen.
5. preparation method according to claim 3, is characterized in that, heating rate is 1 ~ 15 DEG C/min.
6. the preparation method according to claim 3 or 5, is characterized in that, heats up and is heated to 300 ~ 600 DEG C.
7. preparation method according to claim 3, is characterized in that, described reducibility gas is H 2with the mist of Ar, or CO and CO 2mist.
8. preparation method according to claim 7, is characterized in that, H 2with H in the mist of Ar 2volume fraction is 3 ~ 20%; CO and CO 2mist in the volume fraction of CO be 5 ~ 20%.
9. the preparation method according to claim 3 or 7 or 8, is characterized in that, the reducibility gas flow of injection is 50 ~ 500cm 3/ min.
10. preparation method according to claim 3, is characterized in that, injecting the reducibility gas after-baking time is 1 ~ 60min.
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Citations (2)

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Publication number Priority date Publication date Assignee Title
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CN102299312A (en) * 2011-08-08 2011-12-28 浙江大学 Three-dimensional porous lithium vanadate anode material and preparation method thereof

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Publication number Priority date Publication date Assignee Title
US6413676B1 (en) * 1999-06-28 2002-07-02 Lithium Power Technologies, Inc. Lithium ion polymer electrolytes

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101065866A (en) * 2004-10-22 2007-10-31 巴茨卡普公司 Nanostructure material, method for the preparation thereof
CN102299312A (en) * 2011-08-08 2011-12-28 浙江大学 Three-dimensional porous lithium vanadate anode material and preparation method thereof

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