CN107742717A - A kind of nickel cobalt aluminium anode material for lithium-ion batteries of niobium doping - Google Patents

A kind of nickel cobalt aluminium anode material for lithium-ion batteries of niobium doping Download PDF

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CN107742717A
CN107742717A CN201710892815.9A CN201710892815A CN107742717A CN 107742717 A CN107742717 A CN 107742717A CN 201710892815 A CN201710892815 A CN 201710892815A CN 107742717 A CN107742717 A CN 107742717A
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nickel cobalt
cobalt aluminium
lithium
niobium
nickel
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许开华
王家良
张云河
乐绪清
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Jingmen GEM New Material Co Ltd
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Jingmen GEM New Material Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/46—Alloys based on magnesium or aluminium
    • H01M4/463—Aluminium based
    • 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 invention discloses nickel cobalt aluminium anode material for lithium-ion batteries of a kind of niobium doping and preparation method thereof, the chemical expression of the nickel cobalt aluminium anode material for lithium-ion batteries of niobium doping is LiaNixCoyAlzNbbO2, wherein 1≤a≤1.2；0.3≤x≤0.98；0.01≤y≤0.6；0.001≤z≤0.1；B=4/5 a/5 3x/5 3y/5 3z/5,0.00001≤b≤0.2.The present invention by the compound of monocrystalline nickel cobalt aluminium composite precursor and niobium by carrying out ultrahigh speed premixing, again by the compound of monocrystalline nickel cobalt aluminium presoma and niobium compound and common polycrystalline nickel cobalt aluminium presoma mixed at high speed, improve mixed effect, because monocrystalline composite precursor high mechanical strength, ultra-high-speed mixing can be used, and is unlikely to broken, while monocrystalline composite precursor can play a part of collision medium, the compound of niobium is fully broken up, is sufficiently mixed doped chemical and host element.

Description

A kind of nickel cobalt aluminium anode material for lithium-ion batteries of niobium doping
Technical field
The invention belongs to battery material technical field, and in particular to a kind of nickel cobalt aluminium lithium ion cell positive material of niobium doping Material and preparation method thereof.
Background technology
Nickel cobalt aluminium lithium (LNCA) ion battery positive electrode is due to very high energy density and relatively low valency Lattice are widely used in IT product and new-energy automobile field, but simple nickel cobalt lithium aluminate belongs to semi-conducting material, electronics Electrical conductivity is very low；And the conduction of lithium ion is also very big by the resistance of transmission channel, its electrical conductivity is caused there was only 10-9-10-7S/cm；And the electrical conductivity of positive electrode directly affects the charging interval of IT product battery and the big multiplying power discharging of electrokinetic cell Performance, as to the higher and higher requirement of lithium ion battery fast charging and discharging, the electrical conductivity for improving positive electrode is very necessary 's.
The content of the invention
In view of this, it is a primary object of the present invention to provide a kind of nickel cobalt aluminium lithium ion cell positive material of niobium doping Material, solves the problems, such as that existing positive electrode electrical conductivity is low, specific discharge capacity is low；The present invention also aims to provide the positive pole The preparation method of material, it this method solve doped chemical skewness in the prior art, guiding discharge specific capacity and conductance The problem of rate is unbalance.
To reach above-mentioned purpose, the technical proposal of the invention is realized in this way：A kind of nickel cobalt aluminium lithium ion of niobium doping Cell positive material, its chemical expression are：LiaNixCoyAlzNbbO2, wherein 1≤a≤1.2；0.3≤x≤0.98；0.01≤ y≤0.6；0.001≤z≤0.1；B=4/5-a/5-3x/5-3y/5-3z/5,0.00001≤b≤0.2.
What another technical scheme of the present invention was realized in：A kind of nickel cobalt aluminium lithium ion cell positive material of niobium doping The preparation method of material, this method are achieved by the steps of：
Step 1, polycrystalline nickel cobalt aluminium composite precursor, monocrystalline nickel cobalt aluminium composite precursor, nanoscale five is weighed respectively to aoxidize Two niobiums and lithium source；
Step 2, the compound of the monocrystalline nickel cobalt aluminium composite precursor described in step 1 and nanoscale niobium is added into ultrahigh speed Mixed in blender, obtain the first mixture；
Step 3, the first mixture step 2 obtained and the polycrystalline nickel cobalt aluminium composite precursor described in step 1 And lithium source is added in high speed blender and mixed, and obtains the nickel cobalt aluminium presoma of niobium doping；
Step 4, the nickel cobalt aluminium presoma that the niobium that the step 3 obtains adulterates is fitted into porcelain boat and be calcined, obtain niobium The nickel cobalt aluminium anode material for lithium-ion batteries of doping.
Preferably, in the step 1, the polycrystalline nickel cobalt aluminium composite precursor and the monocrystalline nickel cobalt aluminium composite precursor Mass ratio be (2-20)：1.
Preferably, in the step 1, in polycrystalline nickel cobalt aluminium composite precursor and monocrystalline the nickel cobalt aluminium composite precursor Nickel, cobalt, aluminium mole the ratio between be (0.3-0.98)：(0.01-0.6)：(0.001-0.1).
Preferably, in the step 1, the amount of weighing of the nanoscale niobium pentaoxide is nickel, cobalt, aluminium integral molar quantity 0.0001-2%.
Preferably, in the step 1, the amount of weighing of lithium source lithium in molar ratio：Me=(1.2-0.9):1 calculates, its In, Me is nickel, cobalt, the mole sum of aluminium.
Preferably, in the step 1, the polycrystalline nickel cobalt aluminium composite precursor and the monocrystalline nickel cobalt aluminium composite precursor It is the one or more in nickel, cobalt, the complex hydroxide of aluminium, composite oxides, compound oxyhydroxide.
Preferably, in the step 1, the lithium source be lithium nitrate, lithium acetate, lithium carbonate and lithium hydroxide in one kind or It is a variety of.
Preferably, in the step 2, the rotating speed of the ultrahigh speed blender is 5500-20000r/min.
Preferably, in the step 3, the rotating speed of the high speed blender is 500-10000r/min.
Preferably, in the step 4, the sintering temperature is 600-1200 DEG C, roasting time 6-36h.
Positive electrode of the present invention effectively provides its electrical conductivity and electric discharge specific volume by mixing the compound of nanoscale niobium Amount；The inventive method first passes through carries out ultrahigh speed premixing by the compound of monocrystalline nickel cobalt aluminium composite precursor and niobium, then will be single The compound of brilliant nickel cobalt aluminium presoma and niobium compound and common polycrystalline nickel cobalt aluminium presoma mixed at high speed, improve niobium element Effect is uniformly distributed, because monocrystalline composite precursor high mechanical strength, can use ultra-high-speed mixing, and is unlikely to broken, together Shi Danjing composite precursors can play a part of collision medium, and the compound of niobium is fully broken up, and make doped chemical and pivot Element is sufficiently mixed.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to Limit the present invention.
The embodiments of the invention provide a kind of nickel cobalt aluminium anode material for lithium-ion batteries of niobium doping, its chemical expression For：LiaNixCoyAlzNbbO2, wherein 1≤a≤1.2；0.3≤x≤0.98；0.01≤y≤0.6；0.001≤z≤0.1；B= 4/5-a/5-3x/5-3y/5-3z/5,0.00001≤b≤0.2.
The embodiment of the present invention additionally provides the preparation method of the anode material for lithium-ion batteries, and this method is as follows Realize：
Step 1, it is (2-20) according to mass ratio：1 to weigh nickel cobalt al mole ratio respectively be (0.3-0.98)：(0.01- 0.6)：The polycrystalline nickel cobalt aluminium composite precursor and monocrystalline nickel cobalt aluminium composite precursor and a certain amount of nanometer of (0.001-0.1) Niobium pentaoxide (Nb2O5) and lithium source；Wherein, polycrystalline nickel cobalt aluminium composite precursor and the monocrystalline nickel cobalt aluminium composite precursor are equal For the one or more in nickel, cobalt, the complex hydroxide of aluminium, composite oxides, compound oxyhydroxide；Nanoscale five aoxidizes The amount of weighing of two niobiums is nickel, cobalt, the 0.0001-2% of aluminium integral molar quantity；The amount of weighing of lithium source lithium in molar ratio：Me=(1.2- 0.9):1 calculates, and Me is nickel, cobalt, the mole sum of aluminium；Lithium source is in lithium nitrate, lithium acetate, lithium carbonate and lithium hydroxide It is one or more；
Step 2, it is by the compound of the monocrystalline nickel cobalt aluminium composite precursor described in step 1 and nanoscale niobium addition rotating speed Mixed in 5500-20000r/min ultrahigh speed blender, obtain the first mixture；
Step 3, the first mixture step 2 obtained and the polycrystalline nickel cobalt aluminium composite precursor described in step 1 And lithium source is added in the high speed blender that rotating speed is 500-10000r/min and mixed, and obtains the nickel cobalt aluminium forerunner of niobium doping Body；
Step 4, the nickel cobalt aluminium presoma that the niobium that the step 3 obtains adulterates is fitted into porcelain boat, at 600-1200 DEG C 6-36h is calcined, obtains the nickel cobalt aluminium anode material for lithium-ion batteries of niobium doping.
Positive electrode of the present invention effectively provides its electrical conductivity and electric discharge specific volume by mixing the compound of nanoscale niobium Amount；The inventive method first passes through carries out ultrahigh speed premixing by the compound of monocrystalline nickel cobalt aluminium composite precursor and niobium, then will be single The compound of brilliant nickel cobalt aluminium presoma and niobium compound and common polycrystalline nickel cobalt aluminium presoma mixed at high speed, improve niobium element Effect is uniformly distributed, because monocrystalline composite precursor high mechanical strength, can use ultra-high-speed mixing, and is unlikely to broken, together Shi Danjing composite precursors can play a part of collision medium, and the compound of niobium is fully broken up, and make doped chemical and pivot Element is sufficiently mixed.
Embodiment 1
Prepare LiNi0.98Co0.01Al1/150Nb0.002O2Positive electrode；
Step 1, it is 10 according to mass ratio：1 weighs nickel, cobalt, al mole ratio 0.98 respectively:0.01:0.006 polycrystalline nickel Cobalt aluminium composite precursor, monocrystalline nickel cobalt aluminium composite precursor and a certain amount of nanoscale niobium pentaoxide (Nb2O5) and lithium nitrate (LiNO3)；Wherein, lithium nitrate (LiNO3) with nickel, cobalt, aluminium mole sum ratio be 1:0.997；Nanoscale niobium pentaoxide The amount of weighing for nickel, cobalt, the 0.002% of aluminium mole sum；
Step 2, by the monocrystalline nickel cobalt aluminium composite precursor and nanoscale Nb in step 12O5Addition rotating speed is 10000r/min Ultrahigh speed blender in mixed, obtain the first mixture；
Step 3, the first mixture step 2 obtained and the polycrystalline nickel cobalt aluminium composite precursor and nitric acid in step 1 Lithium (LiNO3) rotating speed is added to be mixed in 3000r/min high speed blender, obtain the nickel cobalt aluminium presoma of niobium doping；
Step 4, the nickel cobalt aluminium presoma that the niobium that step 3 obtains adulterates is fitted into porcelain boat, is calcined 20h at 900 DEG C, obtains Obtain the nickel cobalt aluminium anode material for lithium-ion batteries (LiNi of niobium doping0.98Co0.01Al1/150Nb0.002O2), it is designated as positive electrode -1.
Embodiment 2
Prepare LiNi0.98Co0.01Al1/150Nb0.002O2Positive electrode；
Step 1, it is 2 according to mass ratio：1 weighs nickel, cobalt, al mole ratio 0.98 respectively:0.01:0.006 polycrystalline nickel Cobalt aluminium composite precursor, monocrystalline nickel cobalt aluminium composite precursor and a certain amount of nanoscale niobium pentaoxide (Nb2O5) and lithium carbonate (Li2CO3)；Wherein, lithium carbonate (Li2CO3) with nickel, cobalt, aluminium mole sum ratio be 1:0.92；The oxidation of nanoscale five two The amount of weighing of niobium is nickel, cobalt, the 0.002% of aluminium mole sum；
Step 2, by the monocrystalline nickel cobalt aluminium composite precursor and nanoscale Nb in step 12O5Addition rotating speed is 20000r/min Ultrahigh speed blender in mixed, obtain the first mixture；
Step 3, the first mixture step 2 obtained and the polycrystalline nickel cobalt aluminium composite precursor and carbonic acid in step 1 Lithium (Li2CO3) rotating speed is added to be mixed in 500r/min high speed blender, obtain the nickel cobalt aluminium presoma of niobium doping；
Step 4, the nickel cobalt aluminium presoma that the niobium that step 3 obtains adulterates is fitted into porcelain boat, is calcined 36h at 600 DEG C, obtains Obtain the nickel cobalt aluminium anode material for lithium-ion batteries (LiNi of niobium doping0.98Co0.01Al1/150Nb0.002O2), it is designated as positive electrode -2.
Embodiment 3
Prepare LiNi0.98Co0.01Al1/150Nb0.002O2Positive electrode；
Step 1, it is 20 according to mass ratio：1 weighs nickel, cobalt, al mole ratio 0.98 respectively:0.01:0.006 polycrystalline nickel Cobalt aluminium composite precursor, monocrystalline nickel cobalt aluminium composite precursor and a certain amount of nanoscale niobium pentaoxide (Nb2O5) and hydroxide Lithium (LiOH)；Wherein, lithium hydroxide (LiOH) and the ratio of nickel, cobalt, aluminium mole sum are 1:0.997；Nanoscale five aoxidizes The amount of weighing of two niobiums is nickel, cobalt, the 0.002% of aluminium mole sum；
Step 2, by the monocrystalline nickel cobalt aluminium composite precursor and nanoscale Nb in step 12O5Addition rotating speed is 15000r/min Ultrahigh speed blender in mixed, obtain the first mixture；
Step 3, the first mixture step 2 obtained and the polycrystalline nickel cobalt aluminium composite precursor and hydrogen-oxygen in step 1 Change lithium (LiOH) and add rotating speed to be mixed in 5000r/min high speed blender, obtain the nickel cobalt aluminium presoma of niobium doping；
Step 4, the nickel cobalt aluminium presoma that the niobium that step 3 obtains adulterates is fitted into porcelain boat, is calcined 6h at 1200 DEG C, obtains Obtain the nickel cobalt aluminium anode material for lithium-ion batteries (LiNi of niobium doping0.98Co0.01Al1/150Nb0.002O2), it is designated as positive electrode -3.
Embodiment 4
Prepare LiNi0.9Co1/75Al1/300Nb0.05O2Positive electrode；
Step 1, it is 10 according to mass ratio：1 weighs nickel, cobalt, al mole ratio 0.9 respectively:0.013:0.003 polycrystalline nickel Cobalt aluminium composite precursor, monocrystalline nickel cobalt aluminium composite precursor and a certain amount of nanoscale niobium pentaoxide (Nb2O5) and lithium nitrate (LiNO3)；Wherein, lithium nitrate (LiNO3) with nickel, cobalt, aluminium mole sum ratio be 1:0.997；Nanoscale niobium pentaoxide The amount of weighing for nickel, cobalt, the 0.05% of aluminium mole sum；
Step 2, by the monocrystalline nickel cobalt aluminium composite precursor and nanoscale Nb in step 12O5Addition rotating speed is 10000r/min Ultrahigh speed blender in mixed, obtain the first mixture；
Step 3, the first mixture step 2 obtained and the polycrystalline nickel cobalt aluminium composite precursor and nitric acid in step 1 Lithium (LiNO3) rotating speed is added to be mixed in 3000r/min high speed blender, obtain the nickel cobalt aluminium presoma of niobium doping；
Step 4, the nickel cobalt aluminium presoma that the niobium that step 3 obtains adulterates is fitted into porcelain boat, is calcined 20h at 900 DEG C, obtains Obtain the nickel cobalt aluminium anode material for lithium-ion batteries (LiNi of niobium doping0.9Co1/75Al1/300Nb0.05O2), it is designated as positive electrode -4.
Embodiment 5
Prepare LiNi0.9Co1/75Al1/300Nb0.05O2Positive electrode；
Step 1, it is 2 according to mass ratio：1 weighs nickel, cobalt, al mole ratio 0.9 respectively:0.013:0.003 polycrystalline nickel Cobalt aluminium composite precursor, monocrystalline nickel cobalt aluminium composite precursor and a certain amount of nanoscale niobium pentaoxide (Nb2O5) and lithium carbonate (Li2CO3)；Wherein, lithium carbonate (Li2CO3) with nickel, cobalt, aluminium mole sum ratio be 1:0.997；The oxidation of nanoscale five two The amount of weighing of niobium is nickel, cobalt, the 0.05% of aluminium mole sum；
Step 2, by the monocrystalline nickel cobalt aluminium composite precursor and nanoscale Nb in step 12O5Addition rotating speed is 20000r/min Ultrahigh speed blender in mixed, obtain the first mixture；
Step 3, the first mixture step 2 obtained and the polycrystalline nickel cobalt aluminium composite precursor and carbonic acid in step 1 Lithium (Li2CO3) rotating speed is added to be mixed in 500r/min high speed blender, obtain the nickel cobalt aluminium presoma of niobium doping；
Step 4, the nickel cobalt aluminium presoma that the niobium that step 3 obtains adulterates is fitted into porcelain boat, is calcined 36h at 600 DEG C, obtains Obtain the nickel cobalt aluminium anode material for lithium-ion batteries (LiNi of niobium doping0.9Co1/75Al1/300Nb0.05O2), it is designated as positive electrode -5.
Embodiment 6
Prepare LiNi0.9Co1/75Al1/300Nb0.05O2Positive electrode；
Step 1, it is 20 according to mass ratio：1 weighs nickel, cobalt, al mole ratio 0.9 respectively:0.013:0.003 polycrystalline nickel Cobalt aluminium composite precursor, monocrystalline nickel cobalt aluminium composite precursor and a certain amount of nanoscale niobium pentaoxide (Nb2O5) and hydroxide Lithium (LiOH)；Wherein, lithium hydroxide (LiOH) and the ratio of nickel, cobalt, aluminium mole sum are 1:0.997；Nanoscale five aoxidizes The amount of weighing of two niobiums is nickel, cobalt, the 0.05% of aluminium mole sum；
Step 2, by the monocrystalline nickel cobalt aluminium composite precursor and nanoscale Nb in step 12O5Addition rotating speed is 10000r/min Ultrahigh speed blender in mixed, obtain the first mixture；
Step 3, the first mixture step 2 obtained and the polycrystalline nickel cobalt aluminium composite precursor and hydrogen-oxygen in step 1 Change lithium (LiOH) and add rotating speed to be mixed in 3000r/min high speed blender, obtain the nickel cobalt aluminium presoma of niobium doping；
Step 4, the nickel cobalt aluminium presoma that the niobium that step 3 obtains adulterates is fitted into porcelain boat, is calcined 6h at 1200 DEG C, obtains Obtain the nickel cobalt aluminium anode material for lithium-ion batteries (LiNi of niobium doping0.9Co1/75Al1/300Nb0.05O2), it is designated as positive electrode -6.
Embodiment 7
Prepare LiNi0.96Co1/75Al0.01NB0.01O2Positive electrode；
Step 1, it is 10 according to mass ratio：1 weighs nickel, cobalt, al mole ratio 0.96 respectively:0.013:0.01 polycrystalline nickel Cobalt aluminium composite precursor, monocrystalline nickel cobalt aluminium composite precursor and a certain amount of nanoscale niobium pentaoxide (Nb2O5) and lithium nitrate (LiNO3)；Wherein, lithium nitrate (LiNO3) with nickel, cobalt, aluminium mole sum ratio be 1:0.98；Nanoscale niobium pentaoxide The amount of weighing for nickel, cobalt, the 0.01% of aluminium mole sum；
Step 2, by the monocrystalline nickel cobalt aluminium composite precursor and nanoscale Nb in step 12O5Addition rotating speed is 10000r/min Ultrahigh speed blender in mixed, obtain the first mixture；
Step 3, the first mixture step 2 obtained and the polycrystalline nickel cobalt aluminium composite precursor and nitric acid in step 1 Lithium (LiNO3) rotating speed is added to be mixed in 3000r/min high speed blender, obtain the nickel cobalt aluminium presoma of niobium doping；
Step 4, the nickel cobalt aluminium presoma that the niobium that step 3 obtains adulterates is fitted into porcelain boat, is calcined 20h at 900 DEG C, obtains Obtain the nickel cobalt aluminium anode material for lithium-ion batteries (LiNi of niobium doping0.96Co1/75Al0.01Nb0.01O2), it is designated as positive electrode -7.
Embodiment 8
Prepare LiNi0.96Co1/75Al0.01Nb0.01O2Positive electrode；
Step 1, it is 2 according to mass ratio：1 weighs nickel, cobalt, al mole ratio 0.96 respectively:0.013:0.01 polycrystalline nickel Cobalt aluminium composite precursor, monocrystalline nickel cobalt aluminium composite precursor and a certain amount of nanoscale niobium pentaoxide (Nb2O5) and lithium carbonate (Li2CO3)；Wherein, lithium carbonate (Li2CO3) with nickel, cobalt, aluminium mole sum ratio be 1:0.98；The oxidation of nanoscale five two The amount of weighing of niobium is nickel, cobalt, the 0.01% of aluminium mole sum；
Step 2, by the monocrystalline nickel cobalt aluminium composite precursor and nanoscale Nb in step 12O5Addition rotating speed is 20000r/min Ultrahigh speed blender in mixed, obtain the first mixture；
Step 3, the first mixture step 2 obtained and the polycrystalline nickel cobalt aluminium composite precursor and carbonic acid in step 1 Lithium (Li2CO3) rotating speed is added to be mixed in 500r/min high speed blender, obtain the nickel cobalt aluminium presoma of niobium doping；
Step 4, the nickel cobalt aluminium presoma that the niobium that step 3 obtains adulterates is fitted into porcelain boat, is calcined 36h at 600 DEG C, obtains Obtain the nickel cobalt aluminium anode material for lithium-ion batteries (LiNi of niobium doping0.96Co1/75Al0.01Nb0.01O2), it is designated as positive electrode -8.
Embodiment 9
Prepare LiNi0.96Co1/75Al0.01Nb0.01O2Positive electrode；
Step 1, it is 20 according to mass ratio：1 weighs nickel, cobalt, al mole ratio 0.96 respectively:0.013:0.01 polycrystalline nickel Cobalt aluminium composite precursor, monocrystalline nickel cobalt aluminium composite precursor and a certain amount of nanoscale niobium pentaoxide (Nb2O5) and hydroxide Lithium (LiOH)；Wherein, lithium hydroxide (LiOH) and the ratio of nickel, cobalt, aluminium mole sum are 1:0.98；The oxidation of nanoscale five two The amount of weighing of niobium is nickel, cobalt, the 0.01% of aluminium mole sum；
Step 2, by the monocrystalline nickel cobalt aluminium composite precursor and nanoscale Nb in step 12O5Addition rotating speed is 10000r/min Ultrahigh speed blender in mixed, obtain the first mixture；
Step 3, the first mixture step 2 obtained and the polycrystalline nickel cobalt aluminium composite precursor and hydrogen-oxygen in step 1 Change lithium (LiOH) and add rotating speed to be mixed in 3000r/min high speed blender, obtain the nickel cobalt aluminium presoma of niobium doping；
Step 4, the nickel cobalt aluminium presoma that the niobium that step 3 obtains adulterates is fitted into porcelain boat, is calcined 6h at 1200 DEG C, obtains Obtain the nickel cobalt aluminium anode material for lithium-ion batteries (LiNi of niobium doping0.96Co1/75Al0.01Nb0.01O2), it is designated as positive electrode -9.
Assemble button cell and detection：
Embodiment 1-9 is obtained niobium doping nickel cobalt aluminium anode material for lithium-ion batteries be as positive pole, metal lithium sheet Negative pole, 9 button cells are assembled into respectively and carry out discharge and recharge contrast test, testing result such as following table：
Table 1 is the specific discharge capacity detection of the cell positive material that embodiment 1-9 is obtained and conventional batteries positive electrode Data
Specific discharge capacity (mAh/g) under 3C multiplying powers
Positive electrode -1 186
Positive electrode -2 184
Positive electrode -3 182
Positive electrode -4 181
Positive electrode -5 182
Positive electrode -6 183
Positive electrode -7 186
Positive electrode -8 187
Positive electrode -9 183
Conventional material 177
As can be drawn from Table 1：The nickel cobalt aluminium lithium ion cell positive that the niobium obtained using 1-9 of the embodiment of the present invention is adulterated The specific discharge capacity of battery made from material is better than the specific discharge capacity of the battery of conventional batteries positive electrode acquisition.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the scope of the present invention.

Claims (10)

1. the nickel cobalt aluminium anode material for lithium-ion batteries of a kind of niobium doping, it is characterised in that its chemical expression is： LiaNixCoyAlzNbbO2, wherein 1≤a≤1.2；0.3≤x≤0.98；0.01≤y≤0.6；0.001≤z≤0.1；B=4/5- A/5-3x/5-3y/5-3z/5,0.00001≤b≤0.2.
2. a kind of preparation method of the nickel cobalt aluminium anode material for lithium-ion batteries of niobium doping, it is characterised in that this method passes through such as Lower step is realized：
Step 1, polycrystalline nickel cobalt aluminium composite precursor, monocrystalline nickel cobalt aluminium composite precursor, nanoscale niobium pentaoxide are weighed respectively And lithium source；
Step 2, the compound of the monocrystalline nickel cobalt aluminium composite precursor described in step 1 and nanoscale niobium is added into ultrahigh speed batch mixing Mixed in device, obtain the first mixture；
Step 3, the first mixture for the step 2 being obtained and the polycrystalline nickel cobalt aluminium composite precursor described in step 1 and Lithium source is added in high speed blender and mixed, and obtains the nickel cobalt aluminium presoma of niobium doping；
Step 4, the nickel cobalt aluminium presoma that the niobium that the step 3 obtains adulterates is fitted into porcelain boat and be calcined, obtain niobium doping Nickel cobalt aluminium anode material for lithium-ion batteries.
3. a kind of preparation method of the nickel cobalt aluminium anode material for lithium-ion batteries of niobium doping according to claim 2, it is special Sign is, in the step 1, the mass ratio of the polycrystalline nickel cobalt aluminium composite precursor and the monocrystalline nickel cobalt aluminium composite precursor For (2-20)：1.
4. a kind of preparation method of the nickel cobalt aluminium anode material for lithium-ion batteries of niobium doping according to claim 3, it is special Sign is, in the step 1, nickel in polycrystalline nickel cobalt aluminium composite precursor and monocrystalline the nickel cobalt aluminium composite precursor, cobalt, aluminium Mole the ratio between be (0.3-0.98)：(0.01-0.6)：(0.001-0.1).
5. a kind of preparation method of the nickel cobalt aluminium anode material for lithium-ion batteries of niobium doping according to claim 4, it is special Sign is, in the step 1, the amount of weighing of the nanoscale niobium pentaoxide is nickel, cobalt, the 0.0001- of aluminium integral molar quantity 2%.
6. a kind of preparation method of the nickel cobalt aluminium anode material for lithium-ion batteries of niobium doping according to claim 5, it is special Sign is, in the step 1, the amount of weighing of lithium source lithium in molar ratio：Me=(1.2-0.9):1 calculates, wherein, Me is Nickel, cobalt, the mole sum of aluminium.
7. a kind of preparation method of the nickel cobalt aluminium anode material for lithium-ion batteries of niobium doping according to claim 6, it is special Sign is, in the step 1, the polycrystalline nickel cobalt aluminium composite precursor and the monocrystalline nickel cobalt aluminium composite precursor be nickel, One or more in cobalt, the complex hydroxide of aluminium, composite oxides, compound oxyhydroxide.
8. a kind of preparation method of the nickel cobalt aluminium anode material for lithium-ion batteries of niobium doping according to claim 7, it is special Sign is, in the step 2, the rotating speed of the ultrahigh speed blender is 5500-20000r/min.
9. a kind of preparation method of the nickel cobalt aluminium anode material for lithium-ion batteries of niobium doping according to claim 8, it is special Sign is, in the step 3, the rotating speed of the high speed blender is 500-10000r/min.
A kind of 10. system of the nickel cobalt aluminium anode material for lithium-ion batteries of niobium doping according to claim 2-9 any one Preparation Method, it is characterised in that in the step 4, the sintering temperature is 600-1200 DEG C, roasting time 6-36h.
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