CN105070910A - Preparation method and application of carbon-coated lithium nickel vanadium oxide nano material - Google Patents

Preparation method and application of carbon-coated lithium nickel vanadium oxide nano material Download PDF

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CN105070910A
CN105070910A CN201510426435.7A CN201510426435A CN105070910A CN 105070910 A CN105070910 A CN 105070910A CN 201510426435 A CN201510426435 A CN 201510426435A CN 105070910 A CN105070910 A CN 105070910A
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lithium nickel
nano material
nickel vanadium
preparation
lithium
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崔朝军
张修太
孙兴川
李现常
李成波
戴玉强
高倩倩
牛永生
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Anyang Institute of Technology
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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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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 preparation method of a carbon-coated lithium nickel vanadium oxide nano material. The preparation method comprises the following steps of: 1) uniformly mixing vanadium pentoxide powder and a hydrogen peroxide solution, adding a lithium salt and uniformly mixing the materials, and adding nickel acetate and uniformly mixing the materials to form lithium nickel vanadium oxide sol; 2) adding a carbon source into the lithium nickel vanadium oxide sol prepared in the step 1), uniformly mixing the materials to prepare a green mixture, allowing the mixture to stand for 3-7 days at a constant temperature of 150-180 DEG C, cooling the product, repeatedly washing the product with deionized water and absolute ethyl alcohol, and drying the product to obtain a gray product, namely the lithium nickel vanadium nano material; and 3) heating the lithium nickel vanadium nano material obtained in the step 2) in a condition of inert atmosphere and at a constant temperature of 400-800 DEG C for 4-8 hours, and cooling the material to obtain a black product, wherein the black product is the carbon-coated lithium nickel vanadium nano material. The preparation method has the advantages of simplicity in device, convenience in operation and control, moderate reaction condition, cheap raw material and the like, and particularly, the electrochemical performance test shows that a new material synthesized according to the method has excellent electrochemical performance.

Description

The preparation method of carbon coated lithium nickel vanadium oxygen nano material and application thereof
Technical field
The invention belongs to field of lithium ion battery, particularly relate to preparation method and the application thereof of carbon coated lithium nickel vanadium oxygen nano material.
Background technology
Since 21 century, the energy and shortage of resources, environmental pollution and climate warming have badly influenced the sustainable development of human society, and for this reason, clean, safety, regenerative resource and new forms of energy development and utilization is extremely urgent.As automobile production and marketing state maximum in the world, China is using the most important thing of new-energy automobile as future development.The development and apply of hybrid power and pure electric automobile can not only reduce the degree of dependence to oil, and can reduce CO 2discharge capacity, mitigation of global climate warms, significant to world's sustainable development.The birth of high specific energy, high magnification, long-life, high safety, low cost power lithium-ion battery is the breach of hybrid power and pure electric automobile fast development and practical application, and in " 12 " national science and technology development plan is listed the research and development of power lithium-ion battery by China.
How the pattern of electrode material and structure to the Electrochemical Performances of lithium ion battery comparatively greatly, therefore, improve focus and difficult point that the capacity density of lithium ion battery, energy density, cycle life, high rate performance and fail safe are current researches further.Research up-to-date in the world shows, the Strange properties of nano structural material significantly can promote the performance of lithium ion battery, compared with traditional structural materials, material structure nanometer significantly can promote the specific area of material, and contributing to increases specific capacity and reduce polarization; Significantly can shorten Li +the diffusion length of ion, contributes to improving multiplying power property; Li can be adapted to better +ion embeds/deviates from the change in volume in process, thus improves cyclical stability.Graphite is the earliest for the negative material of commercial Li-ion battery, the specific capacity low due to it and and high rate performance, make it be difficult to be applied to power lithium-ion battery.Nearest research shows, carbon nano-tube and Graphene have high specific capacity and good high rate performance, blemish in an otherwise perfect thing be that preparation process is complicated and expensive.The high specific capacity that silica-based and tin base cathode material has, low voltage platform, environmental friendliness and rich reserves, enjoy the favor of vast investigation of materials worker.Regrettably, because change in volume in its charge and discharge process is comparatively large, causes its structure to be destroyed, badly influence the cycle performance of electrode material.Spinel structure Li 4ti 5o 12because in charge and discharge process, volume changes hardly, make it have excellent cyclical stability, secondly, fail safe, cheap price and environmental friendliness are also the advantages that it receives much concern.But higher voltage platform, low conductivity and ionic diffusion coefficient make it well can not be applied to power lithium-ion battery.
Vanadium oxide base negative material has abundant valence state and special layer structure, easily synthesizes, the highest theoretical specific capacity is 1471mAh/g, and China's vanadium resource enriches, relative low price, this makes vanadium oxide base complex have broad application prospects as lithium ion battery negative material, be hopeful to meet the requirement to high-energy-density, high-power, low cost power lithium-ion battery of hybrid power and pure electric automobile, one of negative material of new generation becoming current primary study.But its traditional structure is due to problems such as specific area are little, conductivity is low, lithium ion diffusion rate is slow, be difficult to the performance improving lithium ion battery breakthroughly.Research up-to-date in the world shows, adulterated by Graphene or carbon coated, not only can the structure of stabilized nanoscale electrode material, and the electric conductivity of electrode material can also be improved, thus improve its chemical property significantly.
Both at home and abroad make the patent of lithium ion battery negative material about vanadium oxide based composites few in number.It is Li that Chinese patent (publication number is CN101222043) prepares chemical formula xm yv zo 2+dlithium vanadium oxides composite, wherein 0.1≤x≤2.5,0≤y≤0.5,0.5≤z≤.5,0≤d≤0.5, and M is selected from the group be made up of Al, Cr, Mo, Ti, W, Zr and combination thereof, has good energy per volume density and high power capacity as lithium ion battery negative material.Chinese patent (CN101262076) makes positive pole with spinel lithium manganese oxide compound or its metal or nonmetallic material, and adopt lithium-barium oxide or its metal or nonmetallic dopant material to make negative pole, its composition is expressed as Li 1+am bv 3-bo 8-cn c, 0≤a≤1,0≤b≤1,0≤c≤1, a kind of metallic element of wherein M representative doping or Determination of multiple metal elements, a kind of nonmetalloid of N representative doping or multiple nonmetalloid.Chinese patent (CN101728525) has prepared lithium ion battery negative material lithium-barium oxide and carbon, and wherein lithium-barium oxide is LiVO 2and Li 2v 2o 4.Chinese patent (CN104681784) has prepared the coated lithium vanadate negative material of carbon, and it is nucleocapsid structure, and its core portion is lithium vanadate, and its shell portion is carbon coating layer.Japan Patent (JP2012208116) has been reported for work a kind of novel lithium vanadate negative material, and this negative material has suitable embedding/deviate from current potential, effectively can eliminate the Li dendrite problem that electronegative potential causes.
But existing vanadium oxide based composites has following defect: shortcomings such as specific area are little, conductivity is low, lithium ion diffusion rate is slow.
Also not find at present with vanadium pentoxide powder, hydrogen peroxide, lithium salts and nickel acetate, for raw material, to utilize glucose or citric acid to be carbon source, prepare the patent report that carbon coated lithium nickel vanadium oxygen nano material is used as lithium ion battery negative material.
Summary of the invention
Technical problem to be solved by this invention to overcome when existing vanadium oxide based nano-material makes lithium ion battery negative material the shortcomings such as specific area is little, conductivity is low, lithium ion diffusion rate is slow, provides the preparation method of a kind of lithium ion battery negative material carbon coated lithium nickel vanadium oxygen nano material.The present invention by with the vanadium pentoxide powder of cheapness, hydrogen peroxide, lithium salts and nickel acetate for raw material, with glucose or citric acid for carbon source, carbon coated lithium nickel vanadium oxygen nano material is prepared in conjunction with sol-gel process, hydro thermal method and high temperature cabonization, this method device therefor is simple, be easy to that operation controls, reaction condition is gentle and the prices of raw and semifnished materials are cheap, especially electrochemical property test shows that the new material that this method is synthesized has excellent chemical property, be expected to the chemical property promoting lithium ion battery further, there is potential development space and application prospect.
The technical scheme that the present invention solves the problems of the technologies described above is as follows:
The preparation method of carbon coated lithium nickel vanadium oxygen nano material, comprises the following steps:
1) by vanadium pentoxide powder and hydrogenperoxide steam generator mixing, stir and evenly mix, release after the gentle body of large calorimetric until vigorous reaction, then add lithium salts, mixing, then add nickel acetate, mixing, form lithium nickel vanadium oxygen colloidal sol;
2) carbon source is joined step 1) in the lithium nickel vanadium oxygen colloidal sol prepared, stir and evenly mix, obtained green mixture, 3-7 days is placed under green mixture being placed in 150-180 DEG C of constant temperature, cooling, products therefrom is through deionized water, absolute ethyl alcohol cyclic washing, drying, and obtained gray product, is lithium nickel vanadium oxygen nano material;
3) by step 2) the lithium nickel vanadium oxygen nano material 400-800 DEG C of heated at constant temperature 4-8 hour under inert atmosphere conditions that obtain, cooling, gained black product is carbon coated lithium nickel vanadium oxygen nano material.
The invention has the beneficial effects as follows: the present invention is by with the vanadium pentoxide powder of cheapness, hydrogen peroxide, lithium salts, nickel acetate and carbon source (such as glucose or citric acid) are raw material, in conjunction with sol-gel process, hydro thermal method and high temperature cabonization prepare carbon coated lithium nickel vanadium oxygen nano material, this preparation method's device therefor is simple, be easy to operation control, reaction condition is gentle, the prices of raw and semifnished materials are cheap and be convenient to large-scale production, especially the coated conductivity not only increasing electrode material of carbon, and improve the structural stability of electrode material, the chemical property of lithium ion battery is had obvious improvement.Electrochemical property test also shows that the new material that the method is synthesized has excellent chemical property, is expected to the chemical property promoting lithium ion battery further, has potential development space and application prospect.The present invention, when preparing lithium nickel vanadium oxygen nano material, places 3-7 days under selecting 150-180 DEG C of constant temperature, is easy to generate lithium nickel vanadium oxygen nano material, and the difficulty obtaining lithium nickel vanadium oxygen nano material is under other conditions larger.The present invention adopts 400-800 DEG C of heated at constant temperature 4-8 hour when carbon wraps up, and can be easy to generate uniform carbon coated lithium nickel vanadium oxygen nano material.
On the basis of technique scheme, the present invention can also do following improvement.
Further, step 1) in, in described hydrogenperoxide steam generator, the mass percent concentration of hydrogen peroxide is 30%.
The beneficial effect of above-mentioned further scheme is adopted to be: to be conducive to fully dissolving vanadic oxide.
Further, step 1) in, described vanadium pentoxide powder and hydrogen peroxide are with mol ratio 1: (60-200) mixes.
The beneficial effect of above-mentioned further scheme is adopted to be: to be conducive to dissolving vanadic oxide; If lower than this ratio, can not fully dissolve; If higher than this ratio, it is excessive to cause, and is unfavorable for that ensuing reaction is carried out, cannot obtains target product.
Further, step 1) in, described lithium salts is any one in lithium hydroxide, lithium carbonate and lithium oxalate.
The beneficial effect of above-mentioned further scheme is adopted to be: to be conducive to generating lithium vanadium oxygen.
Further, step 1) in, the mol ratio of described lithium hydroxide addition and vanadium pentoxide powder addition is 2: 1; The mol ratio of described lithium carbonate addition and vanadium pentoxide powder addition is 1: 1; The mol ratio of described lithium oxalate addition and vanadium pentoxide powder addition is 1: 1.
The beneficial effect of above-mentioned further scheme is adopted to be: the productive rate being conducive to improving lithium vanadium oxygen; If lower than this ratio, productive rate will be caused low; If higher than this ratio, lithium will be caused excessive, the carrying out of impact reaction.
Further, step 1) in, the mol ratio of described nickel acetate addition and vanadium pentoxide powder addition is 2: 1.
The beneficial effect of above-mentioned further scheme is adopted to be: to be conducive to generating lithium nickel vanadium oxygen.
Further, step 2) in, described carbon source is glucose or citric acid, and the mass percent of the lithium nickel vanadium oxygen that the addition of described carbon source accounts in the lithium nickel vanadium oxygen colloidal sol obtained in theory is 10%-30%.
The beneficial effect of above-mentioned further scheme is adopted to be: to be conducive to provide carbon source, to be convenient to Formed coated lithium nickel vanadium oxygen; If lower than this ratio, enough carbon can not be provided coated; If higher than this ratio, the performance of lithium nickel vanadium oxygen can not be embodied.
Further, step 3) in, described inert atmosphere is nitrogen or argon gas.
The beneficial effect of above-mentioned further scheme is adopted to be: to be easy to Formed coated lithium nickel vanadium oxygen, to avoid carbon oxidized.
The present invention also provides the preparation method of above-mentioned carbon coated lithium nickel vanadium oxygen nano material the carbon coated lithium nickel vanadium oxygen nano material prepared.
Above-mentioned carbon coated lithium nickel vanadium oxygen nano material may be used for preparing lithium ion battery especially as lithium ion battery negative material.
Accompanying drawing explanation
Fig. 1 is scanning electron microscopy (the be called for short SEM) figure (be the glucose of 10% containing mass fraction) of carbon coated lithium nickel vanadium oxygen nano material prepared by the present invention;
Fig. 2 is transmission electron microscope (the be called for short TEM) figure (be the glucose of 10% containing mass fraction) of carbon coated lithium nickel vanadium oxygen nano material prepared by the present invention;
The charge-discharge performance of carbon prepared by Fig. 3 the present invention coated lithium nickel vanadium oxygen nano material (be the glucose of 10% containing mass fraction).
Embodiment
Be described principle of the present invention and feature below in conjunction with accompanying drawing, example, only for explaining the present invention, is not intended to limit scope of the present invention.
A preparation method for lithium ion battery negative material carbon coated lithium nickel vanadium oxygen nano material, comprises the following steps:
1) vanadium pentoxide powder and hydrogenperoxide steam generator (wherein the mass percent concentration of hydrogen peroxide is 30%) are mixed under 0-5 DEG C of water bath condition, described vanadium pentoxide powder and hydrogen peroxide are with mol ratio 1: (60-200) mixes, magnetic agitation 2-3 hour, after vigorous reaction releases the gentle body of large calorimetric, (described lithium salts is lithium hydroxide to add lithium salts again, in lithium carbonate and lithium oxalate any one), magnetic agitation 30-60 minute, add nickel acetate (mol ratio of described nickel acetate addition and vanadium pentoxide powder addition is 2: 1) again, magnetic agitation 30-60 minute, form lithium nickel vanadium oxygen colloidal sol,
2) glucose or citric acid are joined step 1 as carbon source) in the lithium nickel vanadium oxygen colloidal sol prepared, the mass percent of the lithium nickel vanadium oxygen that the addition of described carbon source accounts in the lithium nickel vanadium oxygen colloidal sol obtained in theory is 10-30%, after magnetic agitation 4-8 hour, obtain green mixture, green mixture is moved in water heating kettle, 150-180 DEG C of constant temperature places 3-7 days, naturally cool to 20-25 DEG C, products therefrom through deionized water, absolute ethyl alcohol cyclic washing to pH=7, vacuum 60-100 DEG C after dry 8-16 hour gray product, be lithium nickel vanadium oxygen nano material;
3) by 2) the lithium nickel vanadium oxygen nano material that obtains is moved in tube furnace, 400-800 DEG C of heated at constant temperature 4-8 hour under inert atmosphere (such as nitrogen or argon gas) condition, naturally cool to 20-25 DEG C, gained black product is carbon coated lithium nickel vanadium oxygen nano material.
Embodiment 1
A preparation method for lithium ion battery negative material carbon coated lithium nickel vanadium oxygen, comprising:
1) by 0.91gV 2o 5powder (analyzing pure) and H 2o 2solution (mass percent concentration is 30%, analyzes pure) mixes with mol ratio 1: 60, mixes, magnetic agitation 2 hours, after vigorous reaction releases the gentle body of large calorimetric, then add 0.42gLiOHH under 4 DEG C of water bath condition 2o (analyzing pure), magnetic agitation 30 minutes, then add 2.49gC 4h 6niO 44H 2o (analyzing pure), magnetic agitation 30 minutes, forms lithium nickel vanadium oxygen colloidal sol.
2) by 0.18g glucose, (molecular formula is C 6h 12o 6) join step 1) in the lithium nickel vanadium oxygen colloidal sol prepared, magnetic agitation is after 4 hours, mixture is moved in water heating kettle, 150 DEG C of constant temperature place 5 days, naturally cool to 20 DEG C, products therefrom is through deionized water, absolute ethyl alcohol cyclic washing to pH=7, and vacuum 80 DEG C of dryings obtained gray product after 12 hours, were lithium nickel vanadium oxygen nano material.
3) by step 2) the lithium nickel vanadium oxygen nano material that obtains is moved in tube furnace, and 600 DEG C of heated at constant temperature 4 hours under argon gas atmosphere condition, naturally cool to 20 DEG C, products therefrom is carbon coated lithium nickel vanadium oxygen nano material 1.33g.
Embodiment 2
A preparation method for lithium ion battery negative material carbon coated lithium nickel vanadium oxygen, comprising:
1) by 0.91gV 2o 5powder (analyzing pure) and H 2o 2(mass percent concentration is 30%, analyzes pure) mixes with mol ratio 1: 100, mixes, magnetic agitation 3 hours, after vigorous reaction releases the gentle body of large calorimetric, then add 0.37gLi under 0 DEG C of water bath condition 2cO 3(analyzing pure), magnetic agitation 45 minutes, then add 2.49gC 4h 6niO 44H 2o (analyzing pure), magnetic agitation 45 minutes, forms lithium nickel vanadium oxygen colloidal sol.
2) by 0.36g glucose, (molecular formula is C 6h 12o 6) join step 1) in the lithium nickel vanadium oxygen colloidal sol prepared, magnetic agitation is after 4 hours, mixture is moved in water heating kettle, 180 DEG C of constant temperature place 3 days, naturally cool to 22 DEG C, products therefrom is through deionized water, absolute ethyl alcohol cyclic washing to pH=7, and vacuum 100 DEG C of dryings obtained gray product after 10 hours, were lithium nickel vanadium oxygen nano material;
3) by step 2) the lithium nickel vanadium oxygen nano material that obtains is moved in tube furnace, and 400 DEG C of heated at constant temperature 6 hours under blanket of nitrogen condition, naturally cool to 22 DEG C, products therefrom is carbon coated lithium nickel vanadium oxygen nano material 1.45g.
Embodiment 3
A preparation method for lithium ion battery negative material carbon coated lithium nickel vanadium oxygen, comprising:
1) by 0.91gV 2o 5powder (analyzing pure) and H 2o 2(mass percent concentration is 30%, analyzes pure) mixes with mol ratio 1: 200, and mix under 5 DEG C of water bath condition, magnetic agitation 2.5 hours, after vigorous reaction releases the gentle body of large calorimetric, then (molecular formula is Li to add 0.51g lithium oxalate 2c 2o 4, analyze pure), magnetic agitation 60 minutes, then add 2.49gC 4h 6niO 44H 2o (analyzing pure), magnetic agitation 45 minutes, forms lithium nickel vanadium oxygen colloidal sol.
2) by 0.54g citric acid, (molecular formula is C 6h 8o 7) join step 1) in the lithium nickel vanadium oxygen colloidal sol prepared, magnetic agitation is after 6 hours, mixture is moved in water heating kettle, 150 DEG C of constant temperature place 7 days, naturally cool to 25 DEG C, products therefrom is through deionized water, absolute ethyl alcohol cyclic washing to pH=7, and vacuum 80 DEG C of dryings obtained gray product after 10 hours, were lithium nickel vanadium oxygen nano material;
3) by step 2) the lithium nickel vanadium oxygen nano material that obtains is moved in tube furnace, and 800 DEG C of heated at constant temperature 8 hours under argon atmospher condition, naturally cool to 25 DEG C, products therefrom is carbon coated lithium nickel vanadium oxygen nano material 1.52g.
Experimental example 4 utilizes carbon coated lithium nickel vanadium oxygen nano material to prepare lithium ion battery negative
1, the pattern of carbon coated lithium nickel vanadium oxygen nano material, structure and electrochemical property test
The microscopic appearance of sample is observed by scanning electron microscopy (SEM, HitachiS-4800) and transmission electron microscope (TEM, FEITecnaiF20); Using lithium metal as auxiliary electrode and reference electrode, the LiPF containing 1mol/L 6(Shenzhen Xin Zhoubang Co., Ltd provides (m (EC): m (EMC): m (DEC)=1: 1: the 1) solution of (Chinese is lithium hexafluoro phosphate), LBC305) be electrolyte, wherein EC is ethylene carbonate, EMC is methyl ethyl carbonate, DEC is dimethyl carbonate, in the glove box being full of argon gas, assemble lithium ion battery; Adopt battery test system LANDCT2001A to carry out charge-discharge test, charge-discharge test voltage range is 0.01-3.0V, and constant current charge-discharge rate of current is 100mA/g.
2, being prepared as follows of work electrode:
The sample (prepared by embodiment 1) of mass percent 70%, the carbon black of 20% are mixed with 10%PVDF (Kynoar), slowly add 1-Methyl-2-Pyrrolidone and carry out uniform stirring, until stir into pasty state, then by its even application on Copper Foil.The Copper Foil applied is placed in vacuum drying chamber, first 80 DEG C of process 2 hours, then 120 DEG C of dryings 12 hours, then naturally cool to room temperature.Copper Foil is chosen raw material and is coated with to obtain more uniform region, be cut into the disk that diameter is about 12mm, weigh with electronic balance (precision: 0.1mg), and calculate the quality of active material according to original proportioning 7: 2: 1.
As depicted in figs. 1 and 2, the lithium nickel vanadium oxygen nano particle that shape appearance figure shows carbon coated is evenly distributed the microscopic appearance of carbon coated lithium nickel vanadium oxygen nano material prepared by the inventive method embodiment 1, and particle size is about about 80nm; The charge-discharge performance of carbon coated lithium nickel vanadium oxygen nano material as shown in Figure 3, first charge-discharge specific capacity is 477.5mAh/g and 737.5mAh/g respectively, coulombic efficiency is 65% first, second time coulombic efficiency is just elevated to 92%, then in ensuing cyclic process, coulombic efficiency is close to 100%, and the reversible specific capacity after 100 circulations is 435mAh/g.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (10)

1. the preparation method of carbon coated lithium nickel vanadium oxygen nano material, is characterized in that, comprise the following steps:
1) by vanadium pentoxide powder and hydrogenperoxide steam generator mixing, stir and evenly mix, release after the gentle body of large calorimetric until vigorous reaction, then add lithium salts, mixing, then add nickel acetate, mixing, form lithium nickel vanadium oxygen colloidal sol;
2) carbon source is joined step 1) in the lithium nickel vanadium oxygen colloidal sol prepared, stir and evenly mix, obtained green mixture, green mixture is placed 3-7 days under 150-180 DEG C of constant temperature, cooling, products therefrom is through deionized water, absolute ethyl alcohol cyclic washing, drying, and obtained gray product, is lithium nickel vanadium oxygen nano material;
3) by step 2) the lithium nickel vanadium oxygen nano material 400-800 DEG C of heated at constant temperature 4-8 hour under inert atmosphere conditions that obtain, cooling, gained black product is carbon coated lithium nickel vanadium oxygen nano material.
2. the preparation method of carbon coated lithium nickel vanadium oxygen nano material according to claim 1, is characterized in that, step 1) in, in described hydrogenperoxide steam generator, the mass percent concentration of hydrogen peroxide is 30%.
3. the preparation method of carbon coated lithium nickel vanadium oxygen nano material according to claim 1, is characterized in that, step 1) in, described vanadium pentoxide powder and hydrogen peroxide are with mol ratio 1: (60-200) mixes.
4. the preparation method of carbon coated lithium nickel vanadium oxygen nano material according to claim 1, is characterized in that, step 1) in, described lithium salts is any one in lithium hydroxide, lithium carbonate and lithium oxalate.
5. the preparation method of carbon coated lithium nickel vanadium oxygen nano material according to claim 4, is characterized in that, step 1) in, the mol ratio of described lithium hydroxide addition and vanadium pentoxide powder addition is 2: 1; The mol ratio of described lithium carbonate addition and vanadium pentoxide powder addition is 1: 1; The mol ratio of described lithium oxalate addition and vanadium pentoxide powder addition is 1: 1.
6. the preparation method of carbon coated lithium nickel vanadium oxygen nano material according to any one of claim 1-5, is characterized in that, step 1) in, the mol ratio of described nickel acetate addition and vanadium pentoxide powder addition is 2: 1.
7. the preparation method of carbon coated lithium nickel vanadium oxygen nano material according to claim 6, it is characterized in that, step 2) in, described carbon source is glucose or citric acid, and the mass percent of the lithium nickel vanadium oxygen that the addition of described carbon source accounts in the lithium nickel vanadium oxygen colloidal sol obtained in theory is 10%-30%.
8. the preparation method of carbon coated lithium nickel vanadium oxygen nano material according to claim 7, is characterized in that, step 3) in, described inert atmosphere is nitrogen or argon gas.
9. the carbon coated lithium nickel vanadium oxygen nano material that described in any one of claim 1 to 8 prepared by the preparation method of carbon coated lithium nickel vanadium oxygen nano material.
10. carbon according to claim 9 coated lithium nickel vanadium oxygen nano material is for the preparation of lithium ion battery negative material.
CN201510426435.7A 2015-07-20 2015-07-20 Preparation method and application of carbon-coated lithium nickel vanadium oxide nano material Pending CN105070910A (en)

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