CN105280898B - Vanadium doping lithium nickel cobalt manganese oxide nano material and its preparation method and application - Google Patents

Vanadium doping lithium nickel cobalt manganese oxide nano material and its preparation method and application Download PDF

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CN105280898B
CN105280898B CN201510598739.1A CN201510598739A CN105280898B CN 105280898 B CN105280898 B CN 105280898B CN 201510598739 A CN201510598739 A CN 201510598739A CN 105280898 B CN105280898 B CN 105280898B
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nickel cobalt
cobalt manganese
nano material
manganese oxide
lithium nickel
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CN105280898A (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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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection 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
    • 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
    • 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 present invention relates to the preparation method of vanadium doping lithium nickel cobalt manganese oxide nano material, can be used as anode active material of lithium ion battery, has α NaFeO2Layer structure, belongs toSpace group, its granular size is 100 300nm, and is reunited between particle together, and the present invention is mainly prepared for vanadium doping lithium nickel cobalt manganese oxide LiNi by simple and practicable coprecipitation combination solid sintering technology1/ 3Co1/3Mn1/3O2Nano material, when it is as anode active material of lithium ion battery, the characteristics of showing power high, good cycling stability；Secondly, present invention process is simple, and presoma slurry is can obtain by simple and practicable cocurrent adding material, and solid-phase sintering under centrifuge washing drying and air atmosphere is carried out to slurry and can obtain vanadium doping lithium nickel cobalt manganese oxide nano material.This method feasibility is strong, the characteristics of being easy to amplificationization, meet Green Chemistry, is promoted beneficial to the marketization.

Description

Vanadium doping lithium nickel cobalt manganese oxide nano material and its preparation method and application
Technical field
The invention belongs to nanometer material and electrochemical technology field, and in particular to vanadium doping lithium nickel cobalt manganese oxide (LiNi1/3Co1/3Mn1/3O2) nano material preparation method, which can be used as anode active material of lithium ion battery.
Background technology
Nowadays, in order to further promote the fast development in electric automobile field, the Gao Rong based on novel nano structure is studied Amount, high power, high stability, thermal adaptability are good and inexpensive lithium ion battery is current low-carbon economy epoch lithium ion battery One of the forward position of research and hot spot.LiNi1/3Co1/3Mn1/3O2Combine LiNiO2, LiCoO2And LiMnO2This 3 class material it is excellent Point, forms LiNiO2/LiCoO2/LiMnO2Common solution system, there are the effect of obvious trielement synergistic.With cheap, easy Synthesis, the advantages that theoretical capacity is high, stable electrochemical property and security are good be considered as most potential lithium ion battery just One of pole material.
LiNi1/3Co1/3Mn1/3O2With α-NaFeO2Layer structure, belongs toSpace group.Wherein Ni/Co/Mn is led respectively To be present in 2+/3+/4+ in lattice, in charge and discharge process, Ni2+、Co3+Electrochemical reaction, Mn are participated in for active material4+ Be not involved in electrochemical reaction for inert matter, but the stability of crystal structure can be improved, at the same reduce positive electrode into This.By analyzing influence material electrochemical performance mechanism, it is modified, product chemical property is continuously improved, mesh Preceding LiNi1/3Co1/3Mn1/3O2Move towards practical, but for the practicality of the material, it is also problematic to solve：(1) by In Ni2+Radius and Li+It is close, Ni during synthesis2+Easily enter lithium position, cause dislocation, cause first discharging efficiency it is not high, put for the first time Loss of capacitance is larger；(2) lithium ion diffusion coefficient is small, and capacity attenuation is very fast under high potential, and high rate during charging-discharging is poor And the compound thermodynamic stability after de- lithium is preferable not enough, easily cause oxygen missing and phase transformation.For these problems, by means of existing Achievement in research, related scholar is to LiNi1/3Co1/3Mn1/3O2Positive electrode has carried out extensive and careful bulk phase-doped and surface Coating modification is studied.
Modification is doped to positive electrode can improve material in discharge and recharge front-end geometry stability, suppress phase transformation and produce, De- lithium degree is improved, increases material capacity, improves materials conductive rate.It is theoretical according to crystal chemistry, sometimes micro external constituent element doping Cause crystal defect, ion can be improved in bulk diffusion speed；According to band theory, for semiconducting compound using high price Or low price ion doping can form p-type or n-type semiconductor, so as to improve crystal conduction rate.In recent years, researchers explore not Same metallic element (Mg, Al, Zr, Ti, Na, Fe, Ru etc.) doping is to LiNi1/3Co1/3Mn1/3O2Positive electrode chemical property Influence.But the LiNi of trace vanadium substitution1/3Co1/3Mn1/3O2Nano material is also rarely reported.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of vanadium doping lithium nickel cobalt manganese oxygen for the above-mentioned prior art Compound LiNi1/3Co1/3Mn1/3O2And preparation method thereof, its technique is simple, meets the requirement of Green Chemistry and is easy to amplificationization, On the basis of this, vanadium doping lithium nickel cobalt manganese oxide LiNi1/3Co1/3Mn1/3O2Also there is excellent chemical property.
Technical solution is used by the present invention solves above-mentioned technical problem：Vanadium doping lithium nickel cobalt manganese oxide nanometer material Material, has α-NaFeO2Layer structure, belongs toSpace group, its granular size are 100-300nm, and are reunited between particle one Rise, it is following methods products therefrom, includes following steps：
1) nickel sulfate, cobaltous sulfate, manganese sulfate are added in distilled water, stirring and dissolving, obtains metal salt solution；
2) it is 1 to weigh with metal salt molar ratio:1 carbonate deposition agent, add it in distilled water obtain it is transparent molten Liquid, stirs evenly；
3) bottom liquid is used as after measuring a small amount of concentrated ammonia liquor dilution；Under continuing magnetic force stirring condition, by step 1) and 2) gained Solution is added drop-wise in the ammonia spirit in step 3) at the same time, and control pH value in reaction is 8.0；
4) soil mill base body is obtained after room temperature or 65 DEG C of 24~72h of stirring in water bath, is dried after centrifuge washing and obtain presoma Powder；
5) by precursor powder in Muffle furnace after pre-burning, dispersion mixing is equal in alcohol with vanadic anhydride and lithium source Even, stirring and drying obtains powder；
6) calcined again after the powder for obtaining step 5) is somewhat ground, finally obtain the vanadium doping lithium nickel cobalt manganese of black Oxide-based nanomaterial.
By such scheme, the carbonate deposition agent described in step 2) is Na2CO3And NH4HCO3In any one or they Mixing.
By such scheme, the lithium source described in step 3) is LiAc, Li2CO3、LiNO3, any one or they in LiOH Mixing.
By such scheme, the calcined temperature described in step 5) is 500 DEG C, when the time is 5 small, the calcining temperature described in step 6) Spend for 800-900 DEG C, when the time is 12~20 small.
The preparation method of the vanadium doping lithium nickel cobalt manganese oxide nano material, includes following steps：
1) nickel sulfate, cobaltous sulfate, manganese sulfate are added in distilled water, stirring and dissolving, obtains metal salt solution；
2) it is 1 to weigh with metal salt molar ratio:1 carbonate deposition agent, add it in distilled water obtain it is transparent molten Liquid, stirs evenly；
3) bottom liquid is used as after measuring a small amount of concentrated ammonia liquor dilution；Under continuing magnetic force stirring condition, by step 1) and 2) gained Solution is added drop-wise in the ammonia spirit in step 3) at the same time, and control pH value in reaction is 8.0；
4) soil mill base body is obtained after room temperature or 65 DEG C of 24~72h of stirring in water bath, is dried after centrifuge washing and obtain presoma Powder；
5) by precursor powder in Muffle furnace after pre-burning, dispersion mixing is equal in alcohol with vanadic anhydride and lithium source Even, stirring and drying obtains powder；
6) calcined again after the powder for obtaining step 5) is somewhat ground, finally obtain the vanadium doping lithium nickel cobalt manganese of black Oxide-based nanomaterial.
Application of the vanadium doping lithium nickel cobalt manganese oxide nano material as anode active material of lithium ion battery.
Vanadium doping lithium nickel cobalt manganese oxide electrode material of the present invention has short ion transmission path, high ion diffusion speed Rate and electron conduction.Vanadium substitution causes the trivalent Mn contents in lattice to increase, and Manganic ion passes through valency in charge and discharge process The change of state improves lattice stability and electron conduction, reduces the pole that electrode material produces during fast charging and discharging Change finally realizes LiNi1/3Co1/3Mn1/3O2Electrode material is become in the application of high power, long-life electrode Material Field The potential application material of lithium ion battery used for electric vehicle.
The beneficial effects of the invention are as follows：The present invention mainly passes through simple and practicable coprecipitation combination solid-phase sintering legal system For vanadium doping lithium nickel cobalt manganese oxide LiNi1/3Co1/3Mn1/3O2Nano material, it is as anode active material of lithium ion battery When, the characteristics of showing power high, good cycling stability；Secondly, present invention process is simple, passes through simple and practicable cocurrent adding material Presoma slurry is can obtain, solid-phase sintering under centrifuge washing drying and air atmosphere is carried out to slurry and can obtain vanadium doping lithium Nickel, cobalt and manganese oxide nano material.This method feasibility is strong, the characteristics of being easy to amplificationization, meet Green Chemistry, beneficial to the marketization Promote.
Brief description of the drawings
Fig. 1 is the vanadium doping lithium nickel cobalt manganese oxide LiNi of the embodiment of the present invention 11/3Co1/3Mn1/3O2The XRD of nano material Figure；
Fig. 2 is the vanadium doping lithium nickel cobalt manganese oxide LiNi of the embodiment of the present invention 11/3Co1/3Mn1/3O2The SEM of nano material Figure；
Fig. 3 is the vanadium doping lithium nickel cobalt manganese oxide LiNi of the embodiment of the present invention 11/3Co1/3Mn1/3O2The TEM of nano material Figure；
Fig. 4 is the vanadium doping lithium nickel cobalt manganese oxide LiNi of the embodiment of the present invention 11/3Co1/3Mn1/3O2Nano material it is normal Warm cycle performance of battery figure.
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention Content is not limited solely to the following examples.
Embodiment 1：
Vanadium doping lithium nickel cobalt manganese oxide LiNi1/3Co1/3Mn1/3O2The preparation method of nano material, it includes following step Suddenly：
1) by 2.6284g nickel sulfates (NiSO4), 2.8115g cobaltous sulfates (CoSO4), 1.6395g manganese sulfates (MnSO4)(Ni: Co:Mn=1:1:0.99) it is added in 15mL deionized waters, stirring at normal temperature dissolving, obtains the metal salt solution of claret；
2) 3.1797g sodium carbonate (Na is weighed2CO3) (sodium carbonate and metal salt molar ratio are 1:1) 15mL deionizations are added to In water, stirring at normal temperature dissolving, obtains transparent precipitant solution；
3) 0.42ml concentrated ammonia liquors (NH is measured3·H2O) be added in 20ml deionized waters and dilute, ammonia spirit as bottom liquid, By step 1) and 2) metal salt solution and precipitant solution in add at the same time, and reaction system pH is 8.0 or so for control, sample drop Pink colour slurry is obtained after adding；
4) soil mill base body is obtained after 65 DEG C of stirring in water bath 48h, is dried after centrifuge washing, obtains precursor powder；
5) by precursor powder in Muffle furnace 500 DEG C of pre-burning 5h, obtained black powder and 0.0273g vanadic anhydrides (V2O5) and 1.2588g lithium hydroxides (LiOH) mix and be uniformly dispersed in alcohol, 80 DEG C of stirring and dryings；
6) 16h is calcined under 800 DEG C of air atmospheres after the black precursor powder for mixing vanadium source and lithium source is somewhat ground, Finally obtain the vanadium doping lithium nickel cobalt manganese oxide LiNi of black1/3Co1/3Mn1/3O2Nano material.
With the product vanadium doping lithium nickel cobalt manganese oxide LiNi of the present invention1/3Co1/3Mn1/3O2Exemplified by nano material, its structure Determined by x-ray diffractometer.As shown in Figure 1, X-ray diffracting spectrum (XRD) shows, vanadium doping lithium nickel cobalt manganese oxide LiNi1/3Co1/3Mn1/3O2Thing mutually has α-NaFeO2Layer structure, belongs toSpace group, since doped chemical amount is seldom, Dephasign peak is not observed in XRD spectrum.
SEM image (Fig. 2) and TEM image (Fig. 3) show the LiNi prepared by us1/3Co1/3Mn1/3O2For nanoscale Grain.Single vanadium doping LiNi1/3Co1/3Mn1/3O2Granular size is 0.1-0.3 μm, and little particle, which reunites with accumulating together, to be gathered into For the bulky grain that size is tens microns.
Vanadium doping lithium nickel cobalt manganese oxide LiNi prepared by the present invention1/3Co1/3Mn1/3O2Live as lithium ion cell positive Property material, remaining step of the preparation method of lithium ion battery are identical with common preparation method.The preparation method of positive plate is as follows, Using vanadium doping lithium nickel cobalt manganese oxide LiNi1/3Co1/3Mn1/3O2As active material, Super carbon is made as conductive agent, PVDF For binding agent；0.27g PVDF are dissolved in 14.73g 1-methyl-2-pyrrolidinones (NMP) first and obtain binder solution；Weigh After 210mg active materials and the grinding uniformly of 60mg Super carbon, 1.6667g binder solutions are added, then grind uniform after five minutes Coated in the oven drying 24 on aluminium foil, being subsequently placed in 80 DEG C it is small when standby use.With the LiPF of 1M6It is dissolved in vinyl carbonate (EC) and in dimethyl carbonate (DMC) it is used as electrolyte, lithium piece is anode, and Celgard2325 is membrane, CR2025 type stainless steels Fastening lithium ionic cell is assembled into for battery case.
With the vanadium doping lithium nickel cobalt manganese oxide LiNi obtained by the present embodiment1/3Co1/3Mn1/3O2Exemplified by, as shown in fig. 4 a, Under the current density of 0.5C, 1C, 2C, 5C, 10C and 20C, vanadium doping LiNi1/3Co1/3Mn1/3O2First discharge specific capacity can To respectively reach 169.4,161.1,160.4,149.9,142.9 and 137.7mAh/g.The high rate performance of material is excellent (Fig. 4 b), After the discharge and recharge under undergoing 0.5C~20C difference current densities, discharge capacity of the material under 20C current densities still can be with Reach 136.6mAh/g.After above-mentioned fast charging and discharging is undergone, capacity of the material under 0.5C current densities can return to 165.1mAh/g, illustrates that the structural stability of material is good.In addition, the cyclical stability of material is also very prominent (Fig. 4 c), in 1C Current density under, the specific capacity after material circulation 1000 times is still 114mAh/g, capacity retention ratio 70.8%, and secondary capacity declines Lapse rate is 0.036%.During whole battery testing, most of coulombic efficiencies up to 99%, show that material is good and follow Ring invertibity.Above-mentioned performance shows, vanadium doping lithium nickel cobalt manganese oxide LiNi1/3Co1/3Mn1/3O2Nano material has very excellent Different chemical property, is a kind of potential anode material for lithium-ion batteries.
Embodiment 2：
Vanadium doping lithium nickel cobalt manganese oxide LiNi1/3Co1/3Mn1/3O2The preparation method of nano material, it includes following step Suddenly：
1) by 2.6284g nickel sulfates (NiSO4), 2.8115g cobaltous sulfates (CoSO4), 1.6395g manganese sulfates (MnSO4)(Ni: Co:Mn=1:1:0.99) it is added in 15mL deionized waters, stirring at normal temperature dissolving, obtains the metal salt solution of claret；
2) 1.5899g sodium carbonate (Na is weighed2CO3) and 1.1859g ammonium hydrogen carbonate (NH4HCO3)(Na2CO3:NH4HCO3:Gold Belong to salt=1:1:2) it is added in 15mL deionized waters, stirring at normal temperature dissolving, obtains transparent precipitant solution；
3) 0.42ml concentrated ammonia liquors (NH is measured3·H2O) be added in 20ml deionized waters and dilute, ammonia spirit as bottom liquid, By step 1) and 2) metal salt solution and precipitant solution in add at the same time, and reaction system pH is 8.0 or so for control, sample drop Pink colour slurry is obtained after adding；
4) soil mill base body is obtained after 65 DEG C of stirring in water bath 48h, is dried after centrifuge washing, obtains precursor powder；
5) by precursor powder in Muffle furnace 500 DEG C of pre-burning 5h, obtained black powder and 0.0273g vanadic anhydrides (V2O5) and 1.2588g lithium hydroxides (LiOH) mix and be uniformly dispersed in alcohol, 80 DEG C of stirring and dryings；
6) calcined again under 800 DEG C of air atmospheres after the black precursor powder for mixing vanadium source and lithium source is somewhat ground 16h, finally obtains black lithium nickel cobalt manganese oxide LiNi1/3Co1/3Mn1/3O2Nano material.
With the vanadium doping LiNi obtained by the present embodiment1/3Co1/3Mn1/3O2Exemplified by, the ratio of electric discharge first under 1C current densities Capacity can respectively reach 129mAh/g, and specific discharge capacity is 90.4mAh/g after 500 circulations.
Embodiment 3：
Vanadium doping lithium nickel cobalt manganese oxide LiNi1/3Co1/3Mn1/3O2The preparation method of nano material, it includes following step Suddenly：
1) by 2.6284g nickel sulfates (NiSO4), 2.8115g cobaltous sulfates (CoSO4), 1.6395g manganese sulfates (MnSO4)(Ni: Co:Mn=1:1:0.99) it is added in 15mL deionized waters, stirring at normal temperature dissolving, obtains the metal salt solution of claret；
2) 3.1797g sodium carbonate (Na is weighed2CO3) (sodium carbonate and metal salt molar ratio are 1:1) 15mL deionizations are added to In water, stirring at normal temperature dissolving, obtains transparent precipitant solution；
3) 0.42ml concentrated ammonia liquors (NH is measured3·H2O) be added in 20ml deionized waters and dilute, ammonia spirit as bottom liquid, By step 1) and 2) metal salt solution and precipitant solution in add at the same time, and reaction system pH is 8.0 or so for control, sample drop Pink colour slurry is obtained after adding；
4) soil mill base body is obtained after stirring 48h at room temperature, is dried after centrifuge washing, obtains precursor powder；
5) by precursor powder in Muffle furnace 500 DEG C of pre-burning 5h, obtained black powder and 0.0273g vanadic anhydrides (V2O5) and 1.2588g lithium hydroxides (LiOH) mix and be uniformly dispersed in alcohol, 80 DEG C of stirring and dryings；
6) calcined again under 800 DEG C of air atmospheres after the black precursor powder for mixing vanadium source and lithium source is somewhat ground 16h, finally obtains black lithium nickel cobalt manganese oxide LiNi1/3Co1/3Mn1/3O2Nano material.
With the vanadium doping LiNi obtained by the present embodiment1/3Co1/3Mn1/3O2Exemplified by, the ratio of electric discharge first under 1C current densities Capacity can respectively reach 145.8mAh/g, and specific discharge capacity is 94.3mAh/g after 500 circulations.
Embodiment 4：
Vanadium doping lithium nickel cobalt manganese oxide LiNi1/3Co1/3Mn1/3O2The preparation method of nano material, it includes following step Suddenly：
1) by 2.6284g nickel sulfates (NiSO4), 2.8115g cobaltous sulfates (CoSO4), 1.6395g manganese sulfates (MnSO4)(Ni: Co:Mn=1:1:0.99) it is added in 15mL deionized waters, stirring at normal temperature dissolving, obtains the metal salt solution of claret；
2) 3.1797g sodium carbonate (Na is weighed2CO3) (sodium carbonate and metal salt molar ratio are 1:1) 15mL deionizations are added to In water, stirring at normal temperature dissolving, obtains transparent precipitant solution；
3) 0.42ml concentrated ammonia liquors are measured and are added in 20ml deionized waters and diluted, ammonia spirit is as bottom liquid, by step 1) Added at the same time with the metal salt solution and precipitant solution in 2), control reaction system pH is after 8.0 or so, sample dropwise addition Obtain pink colour slurry；
4) soil mill base body is obtained after 65 DEG C of stirring in water bath 48h, is dried after centrifuge washing, obtains precursor powder；
5) by precursor powder in Muffle furnace 500 DEG C of pre-burning 5h, obtained black powder and 0.0273g vanadic anhydrides (V2O5) and 1.2588g lithium hydroxides (LiOH) mix and be uniformly dispersed in alcohol, 80 DEG C of stirring and dryings；
6) calcined again under 850 DEG C of air atmospheres after the black precursor powder for mixing vanadium source and lithium source is somewhat ground 16h, finally obtains black lithium nickel cobalt manganese oxide LiNi1/3Co1/3Mn1/3O2Nano material.
With the vanadium doping LiNi obtained by the present embodiment1/3Co1/3Mn1/3O2Exemplified by, the electric discharge first under 0.5C current densities Specific capacity can respectively reach 153.5mAh/g, and specific discharge capacity is 116.2mAh/g after 300 circulations.
Embodiment 5：
Vanadium doping lithium nickel cobalt manganese oxide LiNi1/3Co1/3Mn1/3O2The preparation method of nano material, it includes following step Suddenly：
1) by 2.6284g nickel sulfates (NiSO4), 2.8115g cobaltous sulfates (CoSO4), 1.6395g manganese sulfates (MnSO4)(Ni: Co:Mn=1:1:0.99) it is added in 15mL deionized waters, stirring at normal temperature dissolving, obtains the metal salt solution of claret；
2) 3.1797g sodium carbonate (Na is weighed2CO3) (sodium carbonate and metal salt molar ratio are 1:1) 15mL deionizations are added to In water, stirring at normal temperature dissolving, obtains transparent precipitant solution；
3) 0.42ml concentrated ammonia liquors (NH is measured3·H2O) be added in 20ml deionized waters and dilute, ammonia spirit as bottom liquid, By step 1) and 2) metal salt solution and precipitant solution in add at the same time, and reaction system pH is 8.0 or so for control, sample drop Pink colour slurry is obtained after adding；
4) soil mill base body is obtained after 65 DEG C of stirring in water bath 48h, is dried after centrifuge washing, obtains precursor powder；
5) by precursor powder in Muffle furnace 500 DEG C of pre-burning 5h, obtained black powder and 0.0273g vanadic anhydrides (V2O5) and 1.2588g lithium hydroxides (LiOH) mix and be uniformly dispersed in alcohol, 80 DEG C of stirring and dryings；
6) calcined again under 900 DEG C of air atmospheres after the black precursor powder for mixing vanadium source and lithium source is somewhat ground 16h, finally obtains black lithium nickel cobalt manganese oxide LiNi1/3Co1/3Mn1/3O2Nano material.
With the vanadium doping LiNi obtained by the present embodiment1/3Co1/3Mn1/3O2Exemplified by, the electric discharge first under 0.5C current densities Specific capacity can respectively reach 162.2mAh/g, and specific discharge capacity is 119.5mAh/g after 300 circulations.
Embodiment 6：
2% vanadium doping lithium nickel cobalt manganese oxide LiNi1/3Co1/3Mn1/3O2The preparation method of nano material, it includes as follows Step：
1) by 2.6284g nickel sulfates (NiSO4), 2.8115g cobaltous sulfates (CoSO4), 1.5889g manganese sulfates (MnSO4)(Ni: Co:Mn=1:1:0.98) it is added in 15mL deionized waters, stirring at normal temperature dissolving, obtains the metal salt solution of claret；
2) 3.1797g sodium carbonate (Na is weighed2CO3) (sodium carbonate and metal salt molar ratio are 1:1) 15mL deionizations are added to In water, stirring at normal temperature dissolving, obtains transparent precipitant solution；
3) 0.42ml concentrated ammonia liquors (NH is measured3·H2O) be added in 20ml deionized waters and dilute, ammonia spirit as bottom liquid, By step 1) and 2) metal salt solution and precipitant solution in add at the same time, and reaction system pH is 8.0 or so for control, sample drop Pink colour slurry is obtained after adding；
4) soil mill base body is obtained after 65 DEG C of stirring in water bath 48h, is dried after centrifuge washing, obtains precursor powder；
5) by precursor powder in Muffle furnace 500 DEG C of pre-burning 5h, obtained black powder and 0.0546g vanadic anhydrides (V2O5) and 1.2588g lithium hydroxides (LiOH) mix and be uniformly dispersed in alcohol, 80 DEG C of stirring and dryings；
6) calcined again under 800 DEG C of air atmospheres after the black precursor powder for mixing vanadium source and lithium source is somewhat ground 16h, finally obtains the lithium nickel cobalt manganese oxide LiNi that black vanadium doping amount is 2%1/3Co1/3Mn1/3O2Nano material.
With the vanadium doping LiNi obtained by the present embodiment1/3Co1/3Mn1/3O2Exemplified by, the ratio of electric discharge first under 1C current densities Capacity can respectively reach 163.4mAh/g, and specific discharge capacity is 120.2mAh/g after 300 circulations.
Embodiment 7：
3% vanadium doping lithium nickel cobalt manganese oxide LiNi1/3Co1/3Mn1/3O2The preparation method of nano material, it includes as follows Step：
1) by 2.6284g nickel sulfates (NiSO4), 2.8115g cobaltous sulfates (CoSO4), 1.5381g manganese sulfates (MnSO4)(Ni: Co:Mn=1:1:0.97) it is added in 15mL deionized waters, stirring at normal temperature dissolving, obtains the metal salt solution of claret；
2) 3.1797g sodium carbonate (Na is weighed2CO3) (sodium carbonate and metal salt molar ratio are 1:1) 15mL deionizations are added to In water, stirring at normal temperature dissolving, obtains transparent precipitant solution；
3) 0.42ml concentrated ammonia liquors (NH is measured3·H2O) be added in 20ml deionized waters and dilute, ammonia spirit as bottom liquid, By step 1) and 2) metal salt solution and precipitant solution in add at the same time, and reaction system pH is 8.0 or so for control, sample drop Pink colour slurry is obtained after adding；
4) soil mill base body is obtained after 65 DEG C of stirring in water bath 48h, is dried after centrifuge washing, obtains precursor powder；
5) by precursor powder in Muffle furnace 500 DEG C of pre-burning 5h, obtained black powder and 0.0819g vanadic anhydrides (V2O5) and 1.2588g lithium hydroxides (LiOH) mix and be uniformly dispersed in alcohol, 80 DEG C of stirring and dryings；
6) calcined again under 800 DEG C of air atmospheres after the black precursor powder for mixing vanadium source and lithium source is somewhat ground 16h, finally obtains the lithium nickel cobalt manganese oxide LiNi that black vanadium doping amount is 3%1/3Co1/3Mn1/3O2Nano material.
With the vanadium doping LiNi obtained by the present embodiment1/3Co1/3Mn1/3O2Exemplified by, the ratio of electric discharge first under 1C current densities Capacity can respectively reach 148.2mAh/g, and specific discharge capacity is 117.4mAh/g after 300 circulations.

Claims (9)

1. vanadium doping lithium nickel cobalt manganese oxide nano material, has α-NaFeO2Layer structure, belongs toSpace group, its particle are big Small is 100-300nm, and is reunited between particle together, it is following methods products therefrom, includes following steps：
1) nickel sulfate, cobaltous sulfate, manganese sulfate are added in distilled water, stirring and dissolving, obtains metal salt solution；
2) it is 1 to weigh with metal salt molar ratio:1 carbonate deposition agent, adds it to and clear solution is obtained in distilled water, stir Mix uniformly；
3) bottom liquid is used as after measuring a small amount of concentrated ammonia liquor dilution；Under continuing magnetic force stirring condition, by step 1) and 2) resulting solution It is added drop-wise at the same time in the ammonia spirit in step 3), control pH value in reaction is 8.0；
4) soil mill base body is obtained after room temperature or 65 DEG C of 24~72h of stirring in water bath, is dried after centrifuge washing and obtain precursor powder；
5) by precursor powder in Muffle furnace after pre-burning, dispersion mixing is uniform in alcohol with vanadic anhydride and lithium source, stirs Mix drying and obtain powder；
6) calcined again after the powder for obtaining step 5) is somewhat ground, finally obtain the vanadium doping lithium nickel cobalt manganese of black Thing nano material.
2. vanadium doping lithium nickel cobalt manganese oxide nano material according to claim 1, it is characterised in that described in step 2) Carbonate deposition agent is Na2CO3And NH4HCO3In any one or their mixing.
3. vanadium doping lithium nickel cobalt manganese oxide nano material according to claim 1, it is characterised in that described in step 5) Lithium source is LiAc, Li2CO3、LiNO3, any one or their mixing in LiOH.
4. vanadium doping lithium nickel cobalt manganese oxide nano material according to claim 1, it is characterised in that described in step 5) Calcined temperature is 500 DEG C, and when the time is 5 small, the calcining heat described in step 6) is 800-900 DEG C, when the time is 12~20 small.
5. a kind of preparation method of the vanadium doping lithium nickel cobalt manganese oxide nano material described in claim 1, includes following step Suddenly：
1) nickel sulfate, cobaltous sulfate, manganese sulfate are added in distilled water, stirring and dissolving, obtains metal salt solution；
2) it is 1 to weigh with metal salt molar ratio:1 carbonate deposition agent, adds it to and clear solution is obtained in distilled water, stir Mix uniformly；
3) bottom liquid is used as after measuring a small amount of concentrated ammonia liquor dilution；Under continuing magnetic force stirring condition, by step 1) and 2) resulting solution It is added drop-wise at the same time in the ammonia spirit in step 3), control pH value in reaction is 8.0；
4) soil mill base body is obtained after room temperature or 65 DEG C of 24~72h of stirring in water bath, is dried after centrifuge washing and obtain precursor powder；
5) by precursor powder in Muffle furnace after pre-burning, dispersion mixing is uniform in alcohol with vanadic anhydride and lithium source, stirs Mix drying and obtain powder；
6) calcined again after the powder for obtaining step 5) is somewhat ground, finally obtain the vanadium doping lithium nickel cobalt manganese of black Thing nano material.
6. the preparation method of vanadium doping lithium nickel cobalt manganese oxide nano material according to claim 5, it is characterised in that step It is rapid 2) described in carbonate deposition agent be Na2CO3And NH4HCO3In any one or their mixing.
7. the preparation method of vanadium doping lithium nickel cobalt manganese oxide nano material according to claim 5, it is characterised in that step It is rapid 5) described in lithium source be LiAc, Li2CO3、LiNO3, any one or their mixing in LiOH.
8. the preparation method of vanadium doping lithium nickel cobalt manganese oxide nano material according to claim 5, it is characterised in that step It is rapid 5) described in calcined temperature be 500 DEG C, the time for 5 it is small when, calcining heat described in step 6) is 800-900 DEG C, and the time is 12~20 it is small when.
9. the vanadium doping lithium nickel cobalt manganese oxide nano material described in claim 1 is as anode active material of lithium ion battery Using.
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