CN105118967B - A kind of doping tertiary cathode material of metal oxide coating modification and preparation method thereof - Google Patents

A kind of doping tertiary cathode material of metal oxide coating modification and preparation method thereof Download PDF

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CN105118967B
CN105118967B CN201510612137.7A CN201510612137A CN105118967B CN 105118967 B CN105118967 B CN 105118967B CN 201510612137 A CN201510612137 A CN 201510612137A CN 105118967 B CN105118967 B CN 105118967B
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matrix
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cathode material
lithium
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CN105118967A (en
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罗海峰
朱晓沛
江卫军
吴剑文
蔡硕
文博
戴丽琴
苏迎春
张溪
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Beijing mengguli New Material Technology Co.,Ltd.
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Zhongxinguoan Mengguli Power Supply Technology 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
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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 a kind of doping tertiary cathode material of metal oxide coating modification and preparation method thereof, the positive electrode is by Li (Ni0.5Mn0.3Co0.2)1‑xSrxO2·mAl2O3Represent, including matrix and the clad for being coated on matrix outer, wherein, matrix is by Li (Ni0.5Mn0.3Co0.2)1‑xSrxO2Represent, clad is Al2O3, the positive electrode using solid phase method coordinate multiphase nucleation process be prepared from；The doping tertiary cathode material for the metal oxide coating modification that the present invention is provided has higher an electron conduction and cyclical stability, and its Surface coating is uniform, completely, and the simple controllable, cost of preparation method it is low, suitable for large-scale industrial production.

Description

A kind of doping tertiary cathode material of metal oxide coating modification and preparation method thereof
Technical field
The invention belongs to cell positive material field, and in particular to a kind of doping ternary of metal oxide coating modification is just Pole material and preparation method thereof.
Background technology
In lithium ion anode material field, rich nickel system positive electrode (LiNixM1-xO2, M=Mn, Co, Al, x>0.5) have There are high-energy-density, long circulation life and good security performance, it is wide always concerned, wherein, LiNixMnyCo1-x-yO2Stratiform Tertiary cathode material has the cooperative effect of tri- kinds of ions of Ni, Mn, Co, thus with preferably electrical property, but its stable circulation Property, high rate performance need to be improved, in addition, in material the ratio of tri- kinds of elements of Ni, Mn, Co to its chemical property by important shadow Ring, material is by LiNi0.5Mn0.3Co0.2O2It is transformed into LiNi0.6Mn0.2Co0.2O2When, its chemical property drastically deteriorates, therefore, choosing Select suitably match it is most important.
Its chemical property can be improved by carrying out surface modification to positive electrode with the oxide without electro-chemical activity, such as Patent CN201310020961 uses Al2O3Coating modification LiNi1/3Co1/3Mn1/3O2, precipitating reagent and shape are added in preparation process Looks control machine is to control grain forming, and the discharge capacity and cyclical stability that positive electrode is made increase, but improve journey Degree is limited, and 6 later capability retentions of constant current charge and discharge cycle decline to a great extent.
Above-mentioned situation based on prior art, it is an object of the invention to LiNixMnyCo1-x-yO2Tertiary cathode material enters One step is modified, to obtain the lithium ion anode material with excellent electrochemical performance and cyclical stability.
The content of the invention
In order to overcome above mentioned problem, the present inventor is ground with keen determination to the anode material for lithium-ion batteries of coating modification Study carefully, as a result find：A certain amount of Sr elements are adulterated in nickle cobalt lithium manganate as matrix, Al is coated in matrix outer2O3Cladding Layer, and the covering amount of clad and the morphosis of obtained positive electrode are adjusted, it can obtain cyclical stability and electric conductivity The positive electrode of the coating modification significantly improved.
It is an object of the invention to provide following aspect：
(1) a kind of doping tertiary cathode material of metal oxide coating modification, by Li (Ni0.5Mn0.3Co0.2)1- xSrxO2·mAl2O3Represent, wherein 0 ﹤ x≤0.1, preferably 0 ﹤ x≤0.05, more preferably 0 ﹤ x≤0.003,0.005%≤m≤5%, It is preferred that 0.01%≤m≤0.25%.
The tertiary cathode material includes matrix and is coated on the clad of matrix outer, wherein,
Described matrix is by Li (Ni0.5Mn0.3Co0.2)1-xSrxO2Represent,
The clad is Al2O3。
Al2O3Account for the 0.005~5% of the positive electrode weight, preferably 0.01~0.25%.
The clad is coated on the surface of matrix, and preferably discontinuous phase is coated.
Described matrix is nano-scale particle, the positive electrode be nanometer or micron particles, preferably its particle diameter be 0.5~ 8 μm, more preferably preferably 1~6 μm, 3~5 μm.
Under 0.2C multiplying powers, the initial discharge capacity of the positive electrode is 145~160mAhg-1, discharging efficiency first For 79~85%；
Under 1C multiplying powers, the initial discharge capacity of the positive electrode is 135~150mAhg-1, constant current charge and discharge follow After ring 20 is enclosed, capability retention is more than 99.5%, after constant current charge and discharge cycle 50 is enclosed, and capability retention is more than 98%.
(2) a kind of preparation method according to above-mentioned (1) positive electrode, this method comprises the following steps：
Step 1), the preparation of matrix
Nickel-cobalt-manganese ternary presoma, lithium source and barium source are mixed, crushes, sieve after high-temperature calcination, obtain described matrix；
Step 2), the preparation of the doping tertiary cathode material of coating modification
By step 1) made from matrix add in solvent, stirring is lower to heat, and adds lithium source, mixed liquor A is obtained, by silicon source Add in solvent, stirring is to dissolving, and constant speed is added in the mixed liquor A, heats and stirring reaction, and filtering reacting liquid is filtered out Sieved after insoluble matter drying, calcining, obtain the doping tertiary cathode material of the metal oxide coating modification.
Wherein, in step 1) in, nickel-cobalt-manganese ternary presoma, lithium source and barium source are crossed after 100~300 mesh sieves respectively and massaged You compare 1:(1~1.06):(0~0.005) be well mixed, in air atmosphere calcine 3~40 hours, during which calcining heat by 200 DEG C of programs are increased to 1000 DEG C, and heating rate is 5 DEG C/min, are then down to room temperature, and size-reduced, 100~300 mesh sieves excessively are obtained To described matrix.
By step 1) made from matrix add in solvent, stirring is lower to heat, and temperature rises to after 30~70 DEG C and adds lithium source, after It is continuous to be warming up to 60~100 DEG C, it is uniformly mixing to obtain mixed liquor A；
Silicon source is added in solvent, stirring adds to the mixed liquor by constant flow pump to dissolving with 1~20mL/min constant speed In A, solution is warming up to 60~100 DEG C of simultaneously stirring reaction 1~2 hours after adding, then filtering reacting liquid, the insoluble matter filtered out It is placed in 120~170 DEG C of baking ovens and dries, crosses 100~500 mesh sieves and calcined 2~10 hours after 400~900 DEG C, be preferable over 500 ~750 DEG C are calcined 3~5 hours, are down to room temperature, cross the doping that the metal oxide coating modification is obtained after 100~500 mesh sieves Tertiary cathode material.
In step 1) and step 2) in, the nickel-cobalt-manganese ternary presoma is nickel cobalt manganese hydroxide, is preferably Ni0.5Co0.2Mn0.3(OH)2, the lithium source is lithium carbonate, lithium nitrate or lithium hydroxide, preferably lithium carbonate, and the barium source is carbon Sour strontium or strontium nitrate, source of aluminium is aluminum nitrate,
Step 2) in, the lithium source and silicon source press elemental mole ratios Li:Al=(0.1~3):(2~10) add, preferably Li:Al=(0.5~2):(2~5), more preferably Li:Al=1:3, the solvent is ultra-pure water.
The present invention have the advantage that including：
(1) the doping tertiary cathode material for the metal oxide coating modification that the present invention is provided is using doping specified quantitative Sr members The nickle cobalt lithium manganate of element is as matrix, with higher capacitance, and is conducive to improving Li in material+Diffusivity, reduction Cation mixing phenomenon, so as to improve the electrochemical stability of material；
(2) matrix is prepared into specific big by the doping tertiary cathode material for the metal oxide coating modification that the present invention is provided Small nano-scale particle, and in the Al of its Surface coating specified quantitative2O3Clad, reduces decomposition of the electrolyte to positive electrode, And Li-Al-O phases are formed in charge and discharge process, increase the Li of material+Ionic conductivity, further increases positive electrode Cyclical stability；
(3) the doping tertiary cathode material for the metal oxide coating modification that the present invention is provided has excellent high rate performance And cyclical stability, the initial discharge capacity under 0.2C multiplying powers is 145~160mAhg-1, first discharging efficiency be 79~ 85%, the initial discharge capacity under 1C multiplying powers is 135~150mAhg-1, after constant current charge and discharge cycle 20 is enclosed, capacity is kept Rate is more than 99.5%, after constant current charge and discharge cycle 50 is enclosed, and capability retention is more than 98%；
(4) present invention uses solid phase method, and Sr ions are mixed into LiNi0.5Mn0.3Co0.2O2In, then using multiphase nucleation process Carry out Al2O3Cladding, obtains the doping tertiary cathode material of the metal oxide coating modification, by controlling preparation condition, makes Must be evenly coated, completely, and the simple controllable, cost of preparation method it is low, suitable for large-scale industrial production.
Brief description of the drawings
Fig. 1 shows that the scanning electron microscope test figure of matrix is made in embodiment 1；
Fig. 2 shows that the scanning electron microscope test figure of positive electrode is made in embodiment 3；
Fig. 3 shows that the cycle performance test result comparison diagram of positive electrode is made in the embodiment of the present invention 1~5.
Embodiment
Below by drawings and examples, the present invention is described in more detail.Illustrated by these, the features of the present invention It will be become more apparent from clearly with advantage.
According to the first aspect of the invention there is provided a kind of doping tertiary cathode material of metal oxide coating modification, by Li(Ni0.5Mn0.3Co0.2)1-xSrxO2·mAl2O3Represent.
The tertiary cathode material includes matrix and is coated on the clad of matrix outer, wherein,
Described matrix is by Li (Ni0.5Mn0.3Co0.2)1-xSrxO2Represent, as adulterate a certain amount of Sr elements LiNi0.5Mn0.3Co0.2O2, wherein LiNi0.5Mn0.3Co0.2O2With preferable heat endurance and higher capacitance, mix wherein The Sr of miscellaneous specified quantitative2+Be conducive to improving Li in material+Diffusivity, suppress John Teller effects, reduce cation mixing Phenomenon, so as to improve the electrochemical stability of material, as a result of repeated studies by the present inventors, find when 0 ﹤ x≤0.1, preferably 0 ﹤ x≤ When 0.05, more preferably 0 ﹤ x≤0.003, matrix Li (Ni0.5Mn0.3Co0.2)1-xSrxO2Show preferably chemical property and Cyclical stability, under 0.2C multiplying powers, its initial discharge capacity is 155.6mAhg-1, discharging efficiency is 76.8% first； Under 1C multiplying powers, its initial discharge capacity is 144.4mAhg-1, after constant current charge and discharge cycle 20 is enclosed, capability retention is 98.61%, after constant current charge and discharge cycle 50 is enclosed, capability retention is 97.16%.
The clad is Al2O3, it is uniformly wrapped on the outer surface of above-mentioned matrix, can effectively suppress electrolyte to matrix The erosion of material, forms Li-Al-O phases in charge and discharge process, increases the Li of material+Ionic conductivity, significantly improves positive pole material The cyclical stability of material, and Al2O3Covering amount not the higher the better, itself and Sr2+Electricity of the proportioning of doping to positive electrode Chemical property and cyclical stability have a major impact, and work as Al2O3The 0.005~5% of the positive electrode weight is accounted for, is preferably When 0.01~0.25%, i.e. 0.005%≤m≤5%, preferably 0.01%≤m≤0.25%, the coating modification positive electrode Chemical property and cyclical stability are best.
In a preferred embodiment in accordance with the present invention, described matrix and positive electrode are nanometer or micron particles, Its particle diameter is 0.5~8 μm, and preferably 1~6 μm, more preferably 3~5 μm, coating modification more abundant, performance boost effect is more aobvious Write；The clad is coated on the surface of matrix, can be continuous phase cladding or discontinuous phase cladding, preferably discontinuous phase bag Cover, Al2O3The weight of clad directly affects the thickness of clad and the performance of positive electrode, if Al2O3Covering amount is very few, resistance The effect that only matrix decomposed and improved positive electrode electric conductivity by electrolyte oxidation is poor, if Al2O3Covering amount is excessive, Li+In matrix Transmission between electrolyte receives obstruction, and the cycle performance of positive electrode declines on the contrary, therefore, and the present invention by visiting repeatedly Rope, preferably described Al2O3Covering amount accounts for the 0.005~5% of the positive electrode weight, preferably 0.01~0.25%.
The positive electrode for the coating modification as described above that the present invention is provided has excellent high rate performance and cyclical stability, Under 0.2C multiplying powers, the initial discharge capacity of the positive electrode is 145~160mAhg-1, first discharging efficiency be 79~ 85%；
Under 1C multiplying powers, the initial discharge capacity of the positive electrode is 135~150mAhg-1, constant current charge and discharge follow After ring 20 is enclosed, capability retention is more than 99.5%, after constant current charge and discharge cycle 50 is enclosed, and capability retention is more than 98%.
According to the second aspect of the invention there is provided a kind of preparation method of positive electrode as described above, specifically include following Step：
Step 1), the preparation of matrix
Nickel-cobalt-manganese ternary presoma, lithium source and barium source are mixed, crushes, sieve after high-temperature calcination, obtain described matrix.
In a preferred embodiment in accordance with the present invention, by nickel-cobalt-manganese ternary presoma, lithium source and barium source respectively cross 100~ In molar ratio 1 after 300 mesh sieves:(1~1.06):(0~0.005) it is well mixed, calcines 3~40 hours in air atmosphere, it is excellent Select 5~36 hours, during which calcining heat is increased to 1000 DEG C by 200 DEG C of programs, and heating rate is 5 DEG C/min, is then down to room Temperature, size-reduced, 100~300 mesh sieves excessively, obtains described matrix.
Above-mentioned steps 1) in, the mode to crushing has no particular limits, and can be grinding commonly used in the art, ball Mill, Ultrasonic Pulverization etc., it is preferred to use ball mill is handled 2~4 hours, cross 100~300 mesh sieves after crushing, it is 0.5 to obtain particle diameter ~8 μm of blapharoplast.Above-mentioned matrix has more suitably specific surface area, can carry out sufficient coating modification so that clad Proportion and thickness are suitable, so as to obtain high rate performance and the more excellent positive electrode of cyclical stability.
In a preferred embodiment in accordance with the present invention, the nickel-cobalt-manganese ternary presoma is nickel cobalt manganese hydroxide, excellent Elect Ni as0.5Co0.2Mn0.3(OH)2, the lithium source is lithium carbonate, lithium nitrate or lithium hydroxide, preferably lithium carbonate, the barium source For strontium carbonate or strontium nitrate.
Step 2), the preparation of the doping tertiary cathode material of coating modification
By step 1) made from matrix add in solvent, stirring is lower to heat, and adds lithium source, adjusts the pH of solution, promotes The hydrolysis of aluminum nitrate, obtains mixed liquor A, and silicon source is added in solvent, and stirring is to dissolving, and constant speed is added in the mixed liquor A, plus Heat and stirring reaction, filtering reacting liquid sieve after the insoluble matter drying filtered out, calcining, obtain the metal oxide cladding Modified doping tertiary cathode material.
Step 2) in the lithium source that adds can adjust mixed liquor A pH to alkalescent, promote the silicon source being subsequently added to be hydrolyzed to Aluminium hydroxide, and then be coated on the surface of matrix, therefore, step 2) in the lithium source that adds can play quickening reaction rate, reduction The effect of production cycle, wherein, the lithium source and silicon source press elemental mole ratios Li:Al=(0.1~3):(2~10) add, it is excellent Select Li:Al=(0.5~2):(2~5), more preferably Li:Al=1:3.
In a preferred embodiment in accordance with the present invention, by step 1) made from matrix add in solvent, stirring is lower to heat, Temperature is risen to after 30~70 DEG C by elemental mole ratios Li:Al=(0.1~3)：(2~10) lithium source is added, it is continuously heating to 60~ 100 DEG C, it is uniformly mixing to obtain mixed liquor A；
Silicon source is added in solvent, stirring adds to the mixed liquor by constant flow pump to dissolving with 1~20mL/min constant speed In A, solution is warming up to 60~100 DEG C of simultaneously stirring reaction 1~2 hours after adding, then filtering reacting liquid, the insoluble matter filtered out It is placed in 120~170 DEG C of baking ovens and dries, crosses 100~500 mesh sieves and calcined 2~10 hours after 400~900 DEG C, be down to room temperature, Cross the doping tertiary cathode material that the metal oxide coating modification is obtained after 100~500 mesh sieves.
It is highly preferred that by step 1) made from matrix add in solvent, stirring is lower to heat, temperature rise to after 40~60 DEG C by Elemental mole ratios Li:Al=(0.5~2)：(2~5) lithium source is added, 70~90 DEG C is continuously heating to, is uniformly mixing to obtain mixing Liquid A；
Silicon source is added in solvent, stirring adds to the mixed liquor by constant flow pump to dissolving with 5~15mL/min constant speed In A, solution is warming up to 70~90 DEG C of simultaneously stirring reaction 1~2 hours after adding, then filtering reacting liquid, the insoluble matter filtered out It is placed in 130~160 DEG C of baking ovens and dries, crosses 200~400 mesh sieves and calcined 3~5 hours after 500~750 DEG C, be down to room temperature, mistake The doping tertiary cathode material of the metal oxide coating modification is obtained after 200~400 mesh sieves.
It is further preferred that by step 1) made from matrix add in solvent, stirring is lower to heat, temperature rise to after 50 DEG C by Elemental mole ratios Li:Al=1:3 add lithium source, are continuously heating to 80 DEG C, are uniformly mixing to obtain mixed liquor A；
Silicon source is added in solvent, stirring adds to the mixed liquor A by constant flow pump to dissolving with 10mL/min constant speed In, solution is warming up to 80 DEG C of simultaneously stirring reaction 1~2 hours after adding, then filtering reacting liquid, the insoluble matter filtered out is placed in Dried in 150 DEG C of baking ovens, cross 300 mesh sieves and calcined 4~5 hours after 550~700 DEG C, be down to room temperature, obtained after crossing 300 mesh sieves The doping tertiary cathode material of the metal oxide coating modification.
In a preferred embodiment in accordance with the present invention, the lithium source is lithium carbonate, lithium nitrate or lithium hydroxide, is preferably Lithium carbonate, source of aluminium is aluminium carbonate, aluminum acetate or aluminum nitrate, preferably aluminum nitrate, and the solvent is ultra-pure water.
In above-mentioned steps 2) in the silicon source and matrix of special ratios are sufficiently mixed uniformly so that silicon source uniform deposition is in base The surface of body, positive electrode performance after coating modification is homogeneous, stably；
Surface deposited the matrix of silicon source after calcining, and silicon source is converted into Al2O3And matrix surface is coated on, obtain described The positive electrode of coating modification.
Using above-mentioned preparation method, by Al2O3Metal oxide is made in the nickle cobalt lithium manganate matrix surface for being coated on doping Sr The doping tertiary cathode material of coating modification, its electron conduction and cyclical stability are significantly improved, and preparation process Simple controllable, cost is low, suitable for large-scale industrial production.
Embodiment
The preparation of the nickle cobalt lithium manganate matrix of the doping Sr elements of embodiment 1
Lithium carbonate 84.4g, nickel cobalt manganese hydroxide 200g, strontium carbonate 1.08g are weighed, is added sequentially in 200 mesh sieves, mistake It is well mixed after sieve；
Above-mentioned substance after sieving is fitted into crucible, calcines 36 hours, is during which calcined under air atmosphere in Muffle furnace Temperature is increased to 1000 DEG C by 200 DEG C of programs, and heating rate is 5 DEG C/min, and room temperature, ball mill grinding 3 hours are then down to naturally 200 mesh sieves are crossed afterwards, obtain described matrix Li (Ni0.5Mn0.3Co0.2)1-xSrxO2, wherein x=0.003.
The 0.01%Al of embodiment 22O3The preparation of the doping tertiary cathode material of coating modification
Lithium carbonate 0.06g is weighed, is added into the beaker equipped with 120mL ultra-pure waters, heating is lower to stir, and treats that temperature is increased to More than 50 DEG C, weigh 120g steps 1) made from matrix add in above-mentioned solution, solution is simultaneously heated to 80 DEG C by lasting stir, and is obtained To mixed liquor A；
Weigh ANN aluminium nitrate nonahydrate 0.167g to add into the beaker equipped with 30mL ultra-pure waters, stirring and dissolving passes through constant current Pump is added into the mixed liquor A with 10mL/min flow velocity, and solution is warming up into 80 DEG C after the entry to be completely, and lasting stirring is anti- Answer 1~2 hour；
By the solution filtering after the completion of above-mentioned reaction, the insoluble matter filtered out is placed in 150 DEG C of baking ovens and dried, and crosses 300 mesh sieves, It is then charged into porcelain boat, in being calcined 5 hours at 550 DEG C in Muffle furnace, is naturally cooling to room temperature, institute is obtained after crossing 300 mesh sieves State 0.01%Al2O3The doping tertiary cathode material of coating modification.
The 0.03%Al of embodiment 32O3The preparation of the doping tertiary cathode material of coating modification
Using preparation method similar to Example 2, differ only in：Add lithium carbonate 0.1g, ANN aluminium nitrate nonahydrate 0.5g, obtains the 0.03%Al2O3The doping tertiary cathode material of coating modification.
The 0.06%Al of embodiment 42O3The preparation of the doping tertiary cathode material of coating modification
Using preparation method similar to Example 2, differ only in：Add lithium carbonate 0.23g, ANN aluminium nitrate nonahydrate 1.0g, obtains the 0.06%Al2O3The doping tertiary cathode material of coating modification.
The 0.12%Al of embodiment 52O3The preparation of the doping tertiary cathode material of coating modification
Using preparation method similar to Example 2, differ only in：Add lithium carbonate 0.715g, ANN aluminium nitrate nonahydrate 2.0g, obtains the 0.12%Al2O3The doping tertiary cathode material of coating modification.
Comparative example
Comparative example 1
Using the preparation method similar with embodiment 2 to embodiment 1, differ only in：During matrix is prepared not The Sr elements that undoped in strontium carbonate, i.e. matrix are added, 0.01%Al is obtained2O3The tertiary cathode material of coating modification.
Comparative example 2
Using the preparation method similar with embodiment 2 to embodiment 1, differ only in：Increase the use of ANN aluminium nitrate nonahydrate Amount so that Al2O3The 10% of the positive electrode weight is accounted for, 10%Al is obtained2O3The doping tertiary cathode material of coating modification.
Experimental example
The elementary analysis of experimental example 1
Elementary analysis is carried out to positive electrode made from embodiment 1~5,1 is the results are shown in Table.
Positive electrode elementary analysis result made from the embodiment 1~5 of table 1.
Thus calculate and obtain,
Matrix made from embodiment 1 is Li (Ni0.5Mn0.3Co0.2)1-xSrxO2, wherein x=0.0033；
Positive electrode made from embodiment 2 is Li (Ni0.5Mn0.3Co0.2)1-xSrxO2·mAl2O3, wherein x=0.0032, m =0.024%；
Positive electrode made from embodiment 3 is Li (Ni0.5Mn0.3Co0.2)1-xSrxO2·mAl2O3, wherein x=0.0029, m =0.058%；
Positive electrode made from embodiment 4 is Li (Ni0.5Mn0.3Co0.2)1-xSrxO2·mAl2O3, wherein x=0.0033, m =0.097%；
Positive electrode made from embodiment 5 is Li (Ni0.5Mn0.3Co0.2)1-xSrxO2·mAl2O3, wherein x=0.0034, m =0.20%.
It these results suggest that, the matrix and cladding being pre-designed using the preparation method of the embodiment of the present invention 1~5 Modified anode material, the preparation method that the present invention is provided is reliable, practical.
The scanning electron microscope test of experimental example 2
The microstructure of positive electrode made from embodiment 1 and embodiment 3 is observed using SEM, is as a result seen Fig. 1 and Fig. 2.
As shown in figure 1, matrix made from embodiment 1 is surface substantially smooth particle, particle diameter is 3~6 μm；
As shown in Fig. 2 positive electrode particle diameter made from embodiment 3 is 4~6 μm, there is discontinuous clad on its surface.
The electrical performance testing of experimental example 3
Button cell is made in positive electrode made from embodiment 1~5 and comparative example 1~2, respectively in 0.2C and 1C multiplying powers Lower electric discharge capacity and cycle performance, are as a result shown in Fig. 3 and table 2.
Initial discharge of the positive electrode made from the embodiment 1~5 of table 2. and comparative example 1~2 under 0.2C and 1C multiplying powers is held Amount and cycle performance test result
As shown in table 2, with the matrix phase ratio in embodiment 1, the doping ternary of coating modification made from embodiment 2~5 is just The discharge capacity and capability retention of pole material are improved；The Al in embodiment 2~52O3Covering amount be incremented by, but it puts Capacitance and capability retention are in the variation tendency for first increasing and subtracting afterwards, 0.03%Al2O3The doping tertiary cathode material of coating modification Can be optimal, it follows that Al2O3Covering amount not the higher the better, too high levels reduce some performances of positive electrode on the contrary.
The present invention is described in detail above in association with preferred embodiment and exemplary example.But need what is stated It is that these embodiments are only the illustrative explanations to the present invention, do not constitute any limit to protection scope of the present invention System.In the case of without departing from spirit and scope of the present invention, the technology of the present invention content and embodiments thereof can be carried out Various improvement, equivalencing or modification, these are each fallen within protection scope of the present invention.Protection scope of the present invention is with appended power Profit requires to be defined.

Claims (9)

1. a kind of preparation method of the doping tertiary cathode material of metal oxide coating modification, the tertiary cathode material is by Li (Ni0.5Mn0.3Co0.2)1-xSrxO2·mAl2O3Represent, wherein 0 ﹤ x≤0.1,0.005%≤m≤5%, and, the tertiary cathode Material includes matrix and is coated on the clad of matrix outer, wherein, described matrix is by Li (Ni0.5Mn0.3Co0.2)1-xSrxO2Table Show, the clad is Al2O3, it is characterised in that
This method comprises the following steps：
Step 1), the preparation of matrix
Nickel-cobalt-manganese ternary presoma, lithium source and barium source are mixed, crushes, sieve after high-temperature calcination, obtain described matrix；
Step 2), the preparation of the doping tertiary cathode material of coating modification
By step 1) made from matrix add in solvent, stirring is lower to heat, and adds lithium source, obtains mixed liquor A, silicon source is added In solvent, stirring is to dissolving, and constant speed is added in the mixed liquor A, heats and stirring reaction, filtering reacting liquid, what is filtered out is insoluble Sieved after thing drying, calcining, obtain the doping tertiary cathode material of the metal oxide coating modification.
2. preparation method according to claim 1, it is characterised in that step 1) in,
Nickel-cobalt-manganese ternary presoma, lithium source and barium source are crossed in molar ratio 1 after 100~300 mesh sieves respectively:(1~1.06):(0~ 0.005) it is well mixed, in air atmosphere calcining 3~40 hours, during which calcining heat is increased to 1000 DEG C by 200 DEG C of programs, Heating rate is 5 DEG C/min, is then down to room temperature, and size-reduced, 100~300 mesh sieves excessively obtain described matrix.
3. preparation method according to claim 1, it is characterised in that step 2) in,
By step 1) made from matrix add in solvent, stirring is lower to heat, and temperature, which is risen to after 30~70 DEG C, adds lithium source, continues to rise Temperature is uniformly mixing to obtain mixed liquor A to 60~100 DEG C；
Silicon source is added in solvent, stirring is added in the mixed liquor A to dissolving by constant flow pump with 1~20mL/min constant speed, Solution is warming up to 60~100 DEG C of simultaneously stirring reaction 1~2 hours after adding, then filtering reacting liquid, the insoluble matter filtered out is placed in Dried in 120~170 DEG C of baking ovens, cross 100~500 mesh sieves and calcined 2~10 hours after 400~900 DEG C, be down to room temperature, cross 100 The doping tertiary cathode material of the metal oxide coating modification is obtained after~500 mesh sieves.
4. preparation method according to claim 3, it is characterised in that cross 100~500 mesh sieves after 500~750 DEG C of calcinings 3~5 hours.
5. the preparation method according to one of claims 1 to 3, it is characterised in that step 1) and step 2) in, the nickel cobalt Manganese ternary precursor is nickel cobalt manganese hydroxide, and the lithium source is lithium carbonate, lithium nitrate or lithium hydroxide, and the barium source is carbonic acid Strontium or strontium nitrate, source of aluminium are aluminum nitrate,
Step 2) in, the lithium source and silicon source press elemental mole ratios Li:Al=(0.1~3):(2~10) add, the solvent is Ultra-pure water.
6. preparation method according to claim 5, it is characterised in that step 1) and step 2) in, the nickel-cobalt-manganese ternary Presoma is Ni0.5Co0.2Mn0.3(OH)2。
7. preparation method according to claim 6, it is characterised in that step 1) and step 2) in, the lithium source is carbonic acid Lithium.
8. preparation method according to claim 5, it is characterised in that step 2) in, the lithium source and silicon source are rubbed by element You compare Li:Al=(0.5~2):(2~5) add.
9. preparation method according to claim 8, it is characterised in that step 2) in, the lithium source and silicon source are rubbed by element You compare Li:Al=1:3 add.
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