CN105280898A - Vanadium-doped lithium nickel cobalt manganese oxide nanometer material and preparation method and application thereof - Google Patents

Vanadium-doped lithium nickel cobalt manganese oxide nanometer material and preparation method and application thereof Download PDF

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CN105280898A
CN105280898A CN201510598739.1A CN201510598739A CN105280898A CN 105280898 A CN105280898 A CN 105280898A CN 201510598739 A CN201510598739 A CN 201510598739A CN 105280898 A CN105280898 A CN 105280898A
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nickel cobalt
manganese oxide
cobalt manganese
lithium nickel
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CN105280898B (en
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麦立强
胡正耀
王洛洛
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Anhui Guoxin New Material Co.,Ltd.
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Wuhan University of Technology WUT
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection 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
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention relates to a preparation method of a vanadium-doped lithium nickel cobalt manganese oxide nanometer material. The material which can be taken as an active cathode material for lithium ion batteries is of an alpha-NaFeO2 laminated structure, and belongs to an R3m space group; the particle size of the material is 100-300 nm; and particles are stuck together. The vanadium-doped lithium nickel cobalt manganese oxide LiNi1/3Co1/3Mn1/3O2 nanometer material is prepared through the combination with a simple and practicable coprecipitation method and a solid phase sintering method; when the material is taken as the active cathode material for lithium ion batteries, the material has the characteristics of high power and good cycling stability; and secondly, the preparation method is simple in technology, a precursor slurry can be obtained through simple and practicable parallel flow feeding, and the vanadium-doped lithium nickel cobalt manganese oxide nanometer material can be obtained by carrying out centrifugal washing and drying and solid phase sintering in air atmosphere on the slurry. The method is high in practicability and easy for magnification, accords with the characteristic of green chemistry, and is beneficial for market popularization.

Description

Vanadium doping lithium nickel cobalt manganese oxide nano material and its preparation method and application
Technical field
The invention belongs to nano material and technical field of electrochemistry, be specifically related to vanadium doping lithium nickel cobalt manganese oxide (LiNi 1/3co 1/3mn 1/3o 2) preparation method of nano material, this material can be used as anode active material of lithium ion battery.
Background technology
Nowadays, in order to promote the fast development in electric automobile field further, study one of forward position and focus that and low cost lithium ion battery good based on the high power capacity of novel nano structure, high power, high stability, thermal adaptability is current low-carbon economy epoch Study on Li-ion batteries.LiNi 1/3co 1/3mn 1/3o 2combine LiNiO 2, LiCoO 2and LiMnO 2the advantage of this 3 class material, defines LiNiO 2/ LiCoO 2/ LiMnO 2common solution system, there is obvious trielement synergistic effect.Have that cheap, easy synthesis, theoretical capacity are high, stable electrochemical property and fail safe is good etc. that advantage is considered to one of anode material for lithium-ion batteries of most potentiality.
LiNi 1/3co 1/3mn 1/3o 2there is α-NaFeO 2layer structure, belongs to space group.Wherein Ni/Co/Mn is main is respectively present in lattice with 2+/3+/4+, in charge and discharge process, and Ni 2+, Co 3+for active material participates in electrochemical reaction, Mn 4+for inert matter does not participate in electrochemical reaction, but the stability of crystal structure can be improved, reduce the cost of positive electrode simultaneously.By analyzing influence material electrochemical performance mechanism, carry out modification to it, product electrochemistry can improve constantly, current LiNi 1/3co 1/3mn 1/3o 2move towards practical, but the practicality for this material, also have problem to solve: (1) is due to Ni 2+radius and Li +close, Ni during synthesis 2+easily enter lithium position, cause dislocation, cause discharging efficiency first not high, first time discharge capacity loss is larger; (2) lithium ion diffusion coefficient is little, and under high potential, capacity attenuation is very fast, and the compound thermodynamic stability after the poor and de-lithium of high rate during charging-discharging is desirable not enough, easily causes oxygen to lack and phase transformation.For these problems, by means of existing achievement in research, relevant scholar is to LiNi 1/3co 1/3mn 1/3o 2positive electrode has carried out extensive and careful bulk phase-doped and surface coating modification research.
Doping vario-property is carried out to positive electrode and can improve material structural stability before and after discharge and recharge, suppress phase transformation to produce, improve de-lithium degree, increase material capacity, improve materials conductive rate.Theoretical according to crystal chemistry, micro-external constituent element doping sometimes causes crystal defect, can improve ion in bulk diffusion speed; According to band theory, adopt high price or low price ion doping can form p-type or n-type semiconductor for semiconducting compound, thus improve crystal conduction rate.In recent years, researchers explore different metal element (Mg, Al, Zr, Ti, Na, Fe, Ru etc.) doping to LiNi 1/3co 1/3mn 1/3o 2the impact of positive electrode chemical property.But, the LiNi that trace vanadium replaces 1/3co 1/3mn 1/3o 2nano material also rarely has report.
Summary of the invention
Technical problem to be solved by this invention provides a kind of vanadium doping lithium nickel cobalt manganese oxide LiNi for above-mentioned prior art 1/3co 1/3mn 1/3o 2and preparation method thereof, its technique is simple, the requirement that meets Green Chemistry and be convenient to amplificationization, on this basis, and vanadium doping lithium nickel cobalt manganese oxide LiNi 1/3co 1/3mn 1/3o 2also there is excellent chemical property.
The present invention solves the problems of the technologies described above adopted technical scheme: vanadium doping lithium nickel cobalt manganese oxide nano material, has α-NaFeO 2layer structure, belongs to space group, its granular size is 100-300nm, and reunites together between particle, and it is following method products therefrom, includes following steps:
1) join in distilled water by nickelous sulfate, cobaltous sulfate, manganese sulfate, stirring and dissolving, obtains metal salt solution;
2) taking with slaine mol ratio is the carbonate deposition agent of 1:1, is joined in distilled water and obtains clear solution, stir;
3) measure a small amount of concentrated ammonia liquor dilution after as end liquid; Under continuing magnetic force stirring condition, by step 1) and 2) gained solution is added drop-wise to step 3 simultaneously) in ammonia spirit in, control pH value in reaction 8.0;
4) obtain earth mill base body after normal temperature or 65 DEG C of stirring in water bath 24 ~ 72h, centrifuge washing post-drying obtains precursor powder;
5) by precursor powder in Muffle furnace after pre-burning, disperse to mix in alcohol with vanadic oxide and lithium source, stirring and drying obtains powder;
6) by step 5) powder that obtains calcines after grinding a little again, finally obtains the vanadium doping lithium nickel cobalt manganese oxide nano material of black.
By such scheme, step 2) described in carbonate deposition agent be Na 2cO 3and NH 4hCO 3in the mixing of any one or they.
By such scheme, step 3) described in lithium source be LiAc, Li 2cO 3, LiNO 3, any one or they in LiOH mixing.
By such scheme, step 5) described in calcined temperature be 500 DEG C, the time is 5 hours, step 6) described in calcining heat be 800-900 DEG C, the time is 12 ~ 20 hours.
The preparation method of described vanadium doping lithium nickel cobalt manganese oxide nano material, includes following steps:
1) join in distilled water by nickelous sulfate, cobaltous sulfate, manganese sulfate, stirring and dissolving, obtains metal salt solution;
2) taking with slaine mol ratio is the carbonate deposition agent of 1:1, is joined in distilled water and obtains clear solution, stir;
3) measure a small amount of concentrated ammonia liquor dilution after as end liquid; Under continuing magnetic force stirring condition, by step 1) and 2) gained solution is added drop-wise to step 3 simultaneously) in ammonia spirit in, control pH value in reaction 8.0;
4) obtain earth mill base body after normal temperature or 65 DEG C of stirring in water bath 24 ~ 72h, centrifuge washing post-drying obtains precursor powder;
5) by precursor powder in Muffle furnace after pre-burning, disperse to mix in alcohol with vanadic oxide and lithium source, stirring and drying obtains powder;
6) by step 5) powder that obtains calcines after grinding a little again, finally obtains the vanadium doping lithium nickel cobalt manganese oxide nano material of black.
Described vanadium doping lithium nickel cobalt manganese oxide nano material is as the application of anode active material of lithium ion battery.
Vanadium doping lithium nickel cobalt manganese oxide electrode material of the present invention has short ion transfer path, high ion diffusion rates and electron conduction.Vanadium replaces and causes the trivalent Mn content in lattice to increase, and in charge and discharge process, Manganic ion improves lattice stability and electron conduction by the change of valence state, reduces the polarization that electrode material produces in fast charging and discharging process and finally realizes LiNi 1/3co 1/3mn 1/3o 2electrode material, in the application of high power, long-life electrode Material Field, becomes the potential application material of lithium ion battery used for electric vehicle.
The invention has the beneficial effects as follows: the present invention has mainly prepared vanadium doping lithium nickel cobalt manganese oxide LiNi by simple coprecipitation in conjunction with solid sintering technology 1/3co 1/3mn 1/3o 2nano material, when it is as anode active material of lithium ion battery, shows that power is high, the feature of good cycling stability; Secondly, present invention process is simple, can obtain presoma slurry by simple cocurrent adding material, and under carrying out centrifuge washing drying and air atmosphere to slurry, solid-phase sintering can obtain vanadium doping lithium nickel cobalt manganese oxide nano material.The method feasibility is strong, is easy to amplificationization, meets the feature of Green Chemistry, is beneficial to the marketization and promotes.
Accompanying drawing explanation
Fig. 1 is the vanadium doping lithium nickel cobalt manganese oxide LiNi of the embodiment of the present invention 1 1/3co 1/3mn 1/3o 2the XRD figure of nano material;
Fig. 2 is the vanadium doping lithium nickel cobalt manganese oxide LiNi of the embodiment of the present invention 1 1/3co 1/3mn 1/3o 2the SEM figure of nano material;
Fig. 3 is the vanadium doping lithium nickel cobalt manganese oxide LiNi of the embodiment of the present invention 1 1/3co 1/3mn 1/3o 2the TEM figure of nano material;
Fig. 4 is the vanadium doping lithium nickel cobalt manganese oxide LiNi of the embodiment of the present invention 1 1/3co 1/3mn 1/3o 2the normal temperature cycle performance of battery figure of nano material.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1:
Vanadium doping lithium nickel cobalt manganese oxide LiNi 1/3co 1/3mn 1/3o 2the preparation method of nano material, it comprises the steps:
1) by 2.6284g nickelous sulfate (NiSO 4), 2.8115g cobaltous sulfate (CoSO 4), 1.6395g manganese sulfate (MnSO 4) (Ni:Co:Mn=1:1:0.99) join in 15mL deionized water, stirring at normal temperature is dissolved, and obtains the metal salt solution of claret;
2) 3.1797g sodium carbonate (Na is taken 2cO 3) (sodium carbonate and slaine mol ratio are 1:1) join in 15mL deionized water, stirring at normal temperature is dissolved, and obtains transparent precipitant solution;
3) 0.42ml concentrated ammonia liquor (NH is measured 3h 2o) join 20ml deionization dilution with water, ammonia spirit as end liquid, by step 1) and 2) in metal salt solution and precipitant solution add simultaneously, control reaction system pH about 8.0, sample drip terminate after obtain pink colour slurry;
4) obtain earth mill base body after 65 DEG C of stirring in water bath 48h, centrifuge washing post-drying, obtains precursor powder;
5) by precursor powder 500 DEG C of pre-burning 5h in Muffle furnace, the black powder obtained and 0.0273g vanadic oxide (V 2o 5) and 1.2588g lithium hydroxide (LiOH) mix in alcohol and be uniformly dispersed, 80 DEG C of stirring and dryings;
6) under 800 DEG C of air atmospheres, calcine 16h after being ground a little by the black precursor powder mixing vanadium source and lithium source, finally obtain the vanadium doping lithium nickel cobalt manganese oxide LiNi of black 1/3co 1/3mn 1/3o 2nano material.
With product vanadium doping lithium nickel cobalt manganese oxide LiNi of the present invention 1/3co 1/3mn 1/3o 2nano material is example, and its structure is determined by x-ray diffractometer.As shown in Figure 1, X-ray diffracting spectrum (XRD) shows, vanadium doping lithium nickel cobalt manganese oxide LiNi 1/3co 1/3mn 1/3o 2thing has α-NaFeO mutually 2layer structure, belongs to space group, because doped chemical amount is little, does not observe dephasign peak in XRD collection of illustrative plates.
SEM image (Fig. 2) and TEM image (Fig. 3) show the LiNi prepared by us 1/3co 1/3mn 1/3o 2for nano-scale particle.Independent vanadium doping LiNi 1/3co 1/3mn 1/3o 2granular size is 0.1-0.3 μm, and granule reunites with piling up to assemble together becomes the bulky grain being of a size of tens microns.
Vanadium doping lithium nickel cobalt manganese oxide LiNi prepared by the present invention 1/3co 1/3mn 1/3o 2as anode active material of lithium ion battery, all the other steps of the preparation method of lithium ion battery are identical with common preparation method.The preparation method of positive plate is as follows, adopts vanadium doping lithium nickel cobalt manganese oxide LiNi 1/3co 1/3mn 1/3o 2as active material, Super carbon is as conductive agent, and PVDF is as binding agent; First 0.27gPVDF is dissolved in 14.73gN-methyl pyrrolidone (NMP) and obtains binder solution; After taking 210mg active material and the grinding evenly of 60mgSuper carbon, add 1.6667g binder solution, be more evenly coated on aluminium foil after grinding 5 minutes, the oven drying being then placed in 80 DEG C is for subsequent use after 24 hours.With the LiPF of 1M 6be dissolved in as electrolyte in vinyl carbonate (EC) and dimethyl carbonate (DMC), lithium sheet is negative pole, and Celgard2325 is barrier film, and CR2025 type stainless steel is that battery case is assembled into fastening lithium ionic cell.
With the vanadium doping lithium nickel cobalt manganese oxide LiNi of the present embodiment gained 1/3co 1/3mn 1/3o 2for example, as shown in fig. 4 a, under the current density of 0.5C, 1C, 2C, 5C, 10C and 20C, vanadium doping LiNi 1/3co 1/3mn 1/3o 2first discharge specific capacity can reach 169.4,161.1,160.4,149.9,142.9 and 137.7mAh/g respectively.The high rate performance excellence (Fig. 4 b) of material, after the discharge and recharge under the different current density of experience 0.5C ~ 20C, the discharge capacity of material under 20C current density still can reach 136.6mAh/g.After the above-mentioned fast charging and discharging of experience, the capacity of material under 0.5C current density can return to 165.1mAh/g, and the structural stability of illustrative material is good.In addition, the cyclical stability of material is very outstanding (Fig. 4 c) also, and under the current density of 1C, the specific capacity after material circulation 1000 times is still 114mAh/g, and capability retention is 70.8%, and secondary capacity attenuation rate is 0.036%.In whole battery testing process, most of coulombic efficiency all can reach 99%, shows the cyclic reversibility that material is good.Above-mentioned performance shows, vanadium doping lithium nickel cobalt manganese oxide LiNi 1/3co 1/3mn 1/3o 2nano material has very excellent chemical property, is a kind of potential anode material for lithium-ion batteries.
Embodiment 2:
Vanadium doping lithium nickel cobalt manganese oxide LiNi 1/3co 1/3mn 1/3o 2the preparation method of nano material, it comprises the steps:
1) by 2.6284g nickelous sulfate (NiSO 4), 2.8115g cobaltous sulfate (CoSO 4), 1.6395g manganese sulfate (MnSO 4) (Ni:Co:Mn=1:1:0.99) join in 15mL deionized water, stirring at normal temperature is dissolved, and obtains the metal salt solution of claret;
2) 1.5899g sodium carbonate (Na is taken 2cO 3) and 1.1859g carbonic hydroammonium (NH 4hCO 3) (Na 2cO 3: NH 4hCO 3: slaine=1:1:2) join in 15mL deionized water, stirring at normal temperature is dissolved, and obtains transparent precipitant solution;
3) 0.42ml concentrated ammonia liquor (NH is measured 3h 2o) join 20ml deionization dilution with water, ammonia spirit as end liquid, by step 1) and 2) in metal salt solution and precipitant solution add simultaneously, control reaction system pH about 8.0, sample drip terminate after obtain pink colour slurry;
4) obtain earth mill base body after 65 DEG C of stirring in water bath 48h, centrifuge washing post-drying, obtains precursor powder;
5) by precursor powder 500 DEG C of pre-burning 5h in Muffle furnace, the black powder obtained and 0.0273g vanadic oxide (V 2o 5) and 1.2588g lithium hydroxide (LiOH) mix in alcohol and be uniformly dispersed, 80 DEG C of stirring and dryings;
6) under 800 DEG C of air atmospheres, calcine 16h again after being ground a little by the black precursor powder mixing vanadium source and lithium source, finally obtain black lithium nickel cobalt manganese oxide LiNi 1/3co 1/3mn 1/3o 2nano material.
With the vanadium doping LiNi of the present embodiment gained 1/3co 1/3mn 1/3o 2for example, the first discharge specific capacity under 1C current density can reach 129mAh/g respectively, and after 500 circulations, specific discharge capacity is 90.4mAh/g.
Embodiment 3:
Vanadium doping lithium nickel cobalt manganese oxide LiNi 1/3co 1/3mn 1/3o 2the preparation method of nano material, it comprises the steps:
1) by 2.6284g nickelous sulfate (NiSO 4), 2.8115g cobaltous sulfate (CoSO 4), 1.6395g manganese sulfate (MnSO 4) (Ni:Co:Mn=1:1:0.99) join in 15mL deionized water, stirring at normal temperature is dissolved, and obtains the metal salt solution of claret;
2) 3.1797g sodium carbonate (Na is taken 2cO 3) (sodium carbonate and slaine mol ratio are 1:1) join in 15mL deionized water, stirring at normal temperature is dissolved, and obtains transparent precipitant solution;
3) 0.42ml concentrated ammonia liquor (NH is measured 3h 2o) join 20ml deionization dilution with water, ammonia spirit as end liquid, by step 1) and 2) in metal salt solution and precipitant solution add simultaneously, control reaction system pH about 8.0, sample drip terminate after obtain pink colour slurry;
4) obtain earth mill base body after stirred at ambient temperature 48h, centrifuge washing post-drying, obtains precursor powder;
5) by precursor powder 500 DEG C of pre-burning 5h in Muffle furnace, the black powder obtained and 0.0273g vanadic oxide (V 2o 5) and 1.2588g lithium hydroxide (LiOH) mix in alcohol and be uniformly dispersed, 80 DEG C of stirring and dryings;
6) under 800 DEG C of air atmospheres, calcine 16h again after being ground a little by the black precursor powder mixing vanadium source and lithium source, finally obtain black lithium nickel cobalt manganese oxide LiNi 1/3co 1/3mn 1/3o 2nano material.
With the vanadium doping LiNi of the present embodiment gained 1/3co 1/3mn 1/3o 2for example, the first discharge specific capacity under 1C current density can reach 145.8mAh/g respectively, and after 500 circulations, specific discharge capacity is 94.3mAh/g.
Embodiment 4:
Vanadium doping lithium nickel cobalt manganese oxide LiNi 1/3co 1/3mn 1/3o 2the preparation method of nano material, it comprises the steps:
1) by 2.6284g nickelous sulfate (NiSO 4), 2.8115g cobaltous sulfate (CoSO 4), 1.6395g manganese sulfate (MnSO 4) (Ni:Co:Mn=1:1:0.99) join in 15mL deionized water, stirring at normal temperature is dissolved, and obtains the metal salt solution of claret;
2) 3.1797g sodium carbonate (Na is taken 2cO 3) (sodium carbonate and slaine mol ratio are 1:1) join in 15mL deionized water, stirring at normal temperature is dissolved, and obtains transparent precipitant solution;
3) measure 0.42ml concentrated ammonia liquor and join 20ml deionization dilution with water, ammonia spirit is as end liquid, by step 1) and 2) in metal salt solution and precipitant solution add simultaneously, control reaction system pH about 8.0, sample drip terminate after obtain pink colour slurry;
4) obtain earth mill base body after 65 DEG C of stirring in water bath 48h, centrifuge washing post-drying, obtains precursor powder;
5) by precursor powder 500 DEG C of pre-burning 5h in Muffle furnace, the black powder obtained and 0.0273g vanadic oxide (V 2o 5) and 1.2588g lithium hydroxide (LiOH) mix in alcohol and be uniformly dispersed, 80 DEG C of stirring and dryings;
6) under 850 DEG C of air atmospheres, calcine 16h again after being ground a little by the black precursor powder mixing vanadium source and lithium source, finally obtain black lithium nickel cobalt manganese oxide LiNi 1/3co 1/3mn 1/3o 2nano material.
With the vanadium doping LiNi of the present embodiment gained 1/3co 1/3mn 1/3o 2for example, the first discharge specific capacity under 0.5C current density can reach 153.5mAh/g respectively, and after 300 circulations, specific discharge capacity is 116.2mAh/g.
Embodiment 5:
Vanadium doping lithium nickel cobalt manganese oxide LiNi 1/3co 1/3mn 1/3o 2the preparation method of nano material, it comprises the steps:
1) by 2.6284g nickelous sulfate (NiSO 4), 2.8115g cobaltous sulfate (CoSO 4), 1.6395g manganese sulfate (MnSO 4) (Ni:Co:Mn=1:1:0.99) join in 15mL deionized water, stirring at normal temperature is dissolved, and obtains the metal salt solution of claret;
2) 3.1797g sodium carbonate (Na is taken 2cO 3) (sodium carbonate and slaine mol ratio are 1:1) join in 15mL deionized water, stirring at normal temperature is dissolved, and obtains transparent precipitant solution;
3) 0.42ml concentrated ammonia liquor (NH is measured 3h 2o) join 20ml deionization dilution with water, ammonia spirit as end liquid, by step 1) and 2) in metal salt solution and precipitant solution add simultaneously, control reaction system pH about 8.0, sample drip terminate after obtain pink colour slurry;
4) obtain earth mill base body after 65 DEG C of stirring in water bath 48h, centrifuge washing post-drying, obtains precursor powder;
5) by precursor powder 500 DEG C of pre-burning 5h in Muffle furnace, the black powder obtained and 0.0273g vanadic oxide (V 2o 5) and 1.2588g lithium hydroxide (LiOH) mix in alcohol and be uniformly dispersed, 80 DEG C of stirring and dryings;
6) under 900 DEG C of air atmospheres, calcine 16h again after being ground a little by the black precursor powder mixing vanadium source and lithium source, finally obtain black lithium nickel cobalt manganese oxide LiNi 1/3co 1/3mn 1/3o 2nano material.
With the vanadium doping LiNi of the present embodiment gained 1/3co 1/3mn 1/3o 2for example, the first discharge specific capacity under 0.5C current density can reach 162.2mAh/g respectively, and after 300 circulations, specific discharge capacity is 119.5mAh/g.
Embodiment 6:
2% vanadium doping lithium nickel cobalt manganese oxide LiNi 1/3co 1/3mn 1/3o 2the preparation method of nano material, it comprises the steps:
1) by 2.6284g nickelous sulfate (NiSO 4), 2.8115g cobaltous sulfate (CoSO 4), 1.5889g manganese sulfate (MnSO 4) (Ni:Co:Mn=1:1:0.98) join in 15mL deionized water, stirring at normal temperature is dissolved, and obtains the metal salt solution of claret;
2) 3.1797g sodium carbonate (Na is taken 2cO 3) (sodium carbonate and slaine mol ratio are 1:1) join in 15mL deionized water, stirring at normal temperature is dissolved, and obtains transparent precipitant solution;
3) 0.42ml concentrated ammonia liquor (NH is measured 3h 2o) join 20ml deionization dilution with water, ammonia spirit as end liquid, by step 1) and 2) in metal salt solution and precipitant solution add simultaneously, control reaction system pH about 8.0, sample drip terminate after obtain pink colour slurry;
4) obtain earth mill base body after 65 DEG C of stirring in water bath 48h, centrifuge washing post-drying, obtains precursor powder;
5) by precursor powder 500 DEG C of pre-burning 5h in Muffle furnace, the black powder obtained and 0.0546g vanadic oxide (V 2o 5) and 1.2588g lithium hydroxide (LiOH) mix in alcohol and be uniformly dispersed, 80 DEG C of stirring and dryings;
6) under 800 DEG C of air atmospheres, calcine 16h again after being ground a little by the black precursor powder mixing vanadium source and lithium source, finally obtain the lithium nickel cobalt manganese oxide LiNi that black vanadium doping amount is 2% 1/3co 1/3mn 1/3o 2nano material.
With the vanadium doping LiNi of the present embodiment gained 1/3co 1/3mn 1/3o 2for example, the first discharge specific capacity under 1C current density can reach 163.4mAh/g respectively, and after 300 circulations, specific discharge capacity is 120.2mAh/g.
Embodiment 7:
3% vanadium doping lithium nickel cobalt manganese oxide LiNi 1/3co 1/3mn 1/3o 2the preparation method of nano material, it comprises the steps:
1) by 2.6284g nickelous sulfate (NiSO 4), 2.8115g cobaltous sulfate (CoSO 4), 1.5381g manganese sulfate (MnSO 4) (Ni:Co:Mn=1:1:0.97) join in 15mL deionized water, stirring at normal temperature is dissolved, and obtains the metal salt solution of claret;
2) 3.1797g sodium carbonate (Na is taken 2cO 3) (sodium carbonate and slaine mol ratio are 1:1) join in 15mL deionized water, stirring at normal temperature is dissolved, and obtains transparent precipitant solution;
3) 0.42ml concentrated ammonia liquor (NH is measured 3h 2o) join 20ml deionization dilution with water, ammonia spirit as end liquid, by step 1) and 2) in metal salt solution and precipitant solution add simultaneously, control reaction system pH about 8.0, sample drip terminate after obtain pink colour slurry;
4) obtain earth mill base body after 65 DEG C of stirring in water bath 48h, centrifuge washing post-drying, obtains precursor powder;
5) by precursor powder 500 DEG C of pre-burning 5h in Muffle furnace, the black powder obtained and 0.0819g vanadic oxide (V 2o 5) and 1.2588g lithium hydroxide (LiOH) mix in alcohol and be uniformly dispersed, 80 DEG C of stirring and dryings;
6) under 800 DEG C of air atmospheres, calcine 16h again after being ground a little by the black precursor powder mixing vanadium source and lithium source, finally obtain the lithium nickel cobalt manganese oxide LiNi that black vanadium doping amount is 3% 1/3co 1/3mn 1/3o 2nano material.
With the vanadium doping LiNi of the present embodiment gained 1/3co 1/3mn 1/3o 2for example, the first discharge specific capacity under 1C current density can reach 148.2mAh/g respectively, and after 300 circulations, specific discharge capacity is 117.4mAh/g.

Claims (9)

1. vanadium doping lithium nickel cobalt manganese oxide nano material, has α-NaFeO 2layer structure, belongs to R3 _m space group, its granular size is 100-300nm, and reunites together between particle, and it is following method products therefrom, includes following steps:
1) join in distilled water by nickelous sulfate, cobaltous sulfate, manganese sulfate, stirring and dissolving, obtains metal salt solution;
2) taking with slaine mol ratio is the carbonate deposition agent of 1:1, is joined in distilled water and obtains clear solution, stir;
3) measure a small amount of concentrated ammonia liquor dilution after as end liquid; Under continuing magnetic force stirring condition, by step 1) and 2) gained solution is added drop-wise to step 3 simultaneously) in ammonia spirit in, control pH value in reaction 8.0;
4) obtain earth mill base body after normal temperature or 65 DEG C of stirring in water bath 24 ~ 72h, centrifuge washing post-drying obtains precursor powder;
5) by precursor powder in Muffle furnace after pre-burning, disperse to mix in alcohol with vanadic oxide and lithium source, stirring and drying obtains powder;
6) by step 5) powder that obtains calcines after grinding a little again, finally obtains the vanadium doping lithium nickel cobalt manganese oxide nano material of black.
2. vanadium doping lithium nickel cobalt manganese oxide nano material according to claim 1, is characterized in that, step 2) described in carbonate deposition agent be Na 2cO 3and NH 4hCO 3in the mixing of any one or they.
3. vanadium doping lithium nickel cobalt manganese oxide nano material according to claim 1, is characterized in that, step 3) described in lithium source be LiAc, Li 2cO 3, LiNO 3, any one or they in LiOH mixing.
4. vanadium doping lithium nickel cobalt manganese oxide nano material according to claim 1, is characterized in that, step 5) described in calcined temperature be 500 DEG C, the time is 5 hours, step 6) described in calcining heat be 800-900 DEG C, the time is 12 ~ 20 hours.
5. the preparation method of vanadium doping lithium nickel cobalt manganese oxide nano material according to claim 1, includes following steps:
1) join in distilled water by nickelous sulfate, cobaltous sulfate, manganese sulfate, stirring and dissolving, obtains metal salt solution;
2) taking with slaine mol ratio is the carbonate deposition agent of 1:1, is joined in distilled water and obtains clear solution, stir;
3) measure a small amount of concentrated ammonia liquor dilution after as end liquid; Under continuing magnetic force stirring condition, by step 1) and 2) gained solution is added drop-wise to step 3 simultaneously) in ammonia spirit in, control pH value in reaction 8.0;
4) obtain earth mill base body after normal temperature or 65 DEG C of stirring in water bath 24 ~ 72h, centrifuge washing post-drying obtains precursor powder;
5) by precursor powder in Muffle furnace after pre-burning, disperse to mix in alcohol with vanadic oxide and lithium source, stirring and drying obtains powder;
6) by step 5) powder that obtains calcines after grinding a little again, finally obtains the vanadium doping lithium nickel cobalt manganese oxide nano material of black.
6. the preparation method of vanadium doping lithium nickel cobalt manganese oxide nano material according to claim 5, is characterized in that, step 2) described in carbonate deposition agent be Na 2cO 3and NH 4hCO 3in the mixing of any one or they.
7. the preparation method of vanadium doping lithium nickel cobalt manganese oxide nano material according to claim 5, is characterized in that, step 3) described in lithium source be LiAc, Li 2cO 3, LiNO 3, any one or they in LiOH mixing.
8. the preparation method of vanadium doping lithium nickel cobalt manganese oxide nano material according to claim 5, it is characterized in that, step 5) described in calcined temperature be 500 DEG C, the time is 5 hours, step 6) described in calcining heat be 800-900 DEG C, the time is 12 ~ 20 hours.
9. vanadium doping lithium nickel cobalt manganese oxide nano material according to claim 1 is as the application of anode active material of lithium ion battery.
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