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CN107403913A - A kind of nickel cobalt lithium aluminate cathode material of surface modification and preparation method thereof - Google Patents

A kind of nickel cobalt lithium aluminate cathode material of surface modification and preparation method thereof Download PDF

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CN107403913A
CN107403913A CN201710561502.5A CN201710561502A CN107403913A CN 107403913 A CN107403913 A CN 107403913A CN 201710561502 A CN201710561502 A CN 201710561502A CN 107403913 A CN107403913 A CN 107403913A
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nickel cobalt
cathode material
cobalt lithium
lithium aluminate
surface modification
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CN107403913B (en
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瞿美臻
陈滔
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University of Chinese Academy of Sciences
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Chengdu Organic Chemicals Co Ltd of CAS
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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
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/485—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
    • 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
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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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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Abstract

The present invention discloses nickel cobalt lithium aluminate cathode material of a kind of surface modification and preparation method thereof, the positive electrode is made up of stratified material nickel cobalt lithium aluminate positive active material and the modification layer on its surface, and the surface modified layer includes surface doping modified layer and boracic oxide fusion clad；Its preparation method is：Boron-containing compound and ternary precursor are obtained into the ternary anode material precursor of surface pre-coated by wet-mixing, the ternary anode material precursor of surface pre-coated is mixed with lithium salts, cools to obtain the nickel cobalt lithium aluminate cathode material of surface modification again by high-temperature calcination.The nickel cobalt lithium aluminate cathode material of surface modification described herein, its crystal structure is stable, has good chemical property, technique is simple, and energy consumption and cost are low, beneficial to the large-scale production of positive electrode.

Description

A kind of nickel cobalt lithium aluminate cathode material of surface modification and preparation method thereof
Technical field
The present invention relates to anode material of lithium battery technical field, and in particular to a kind of nickel cobalt lithium aluminate positive pole of surface modification Material and preparation method thereof.
Background technology
The lithium ion battery advantage such as have energy density height, energy efficiency height, memory-less effect, self-discharge rate low, by It is widely used in consumption electronic product, electric vehicle, the association area such as large-scale energy-accumulating power station and Aero-Space.But with mesh Preceding electric automobile is greatly developed, and the energy density and power density to lithium ion battery propose higher requirement, therefore, is compeled The positive electrode of the higher energy density to be found that is essential replaces current material.
The tertiary cathode material of nickelic system such as nickel cobalt lithium aluminate cathode material has energy density high, and cost is low, to environment The advantages of friendly, therefore receive the extensive concern of people, it is considered to be lithium ion battery used for electric vehicle has prospect very much Positive electrode.But as the NCA tertiary cathode materials of nickelic system, it there is problems：First, positive electrode is in discharge and recharge During Volume Changes repeatedly, easily cause the generation of active particle micro-crack, polarization increase；2nd, material surface easily with Moisture and carbon dioxide in air, which react, generates LiOH and Li2CO3Deng accessory substance, cause the enhancing of material surface alkalescence with And the change of surface crystal structure；3rd, the Ni under charged state4+Oxidation electrolyte produces thicker SEI films and oxygen evolution； 4th, the HF attack material surfaces in electrolyte dissolve metal ion.Problem above can cause tertiary cathode material electric The decline of chemical property, and limit its further application.
Research shows that it is a kind of effective means to solve the above problems that Surface coating processing is carried out to material.Common surface Cladding material includes：Metal oxide, metal phosphate, fluoride or other positive electrodes etc..But currently used surface Method for coating is two-step method.I.e.：To calcine the tertiary cathode material prepared as matrix, to ensure the uniformity of material cladding And good chemical property also needs to carry out in addition, it is necessary to carry out wet-chemical cladding under conditions of organic solvent such as ethanol Secondary clacining could finally obtain the tertiary cathode material of coating modification.Although this method for coating can obtain in laboratory conditions Preferable chemical property, but technological process increase and preparation condition harshness are obtained, production cost can be caused to increase, operating process is multiple The miscellaneous large-scale production being also unfavorable in industry.
The content of the invention
In view of this, the application provides a kind of nickel cobalt lithium aluminate cathode material of surface modification and preparation method thereof, gained The crystal structure of positive electrode is stable, and surface side reaction is inhibited, is obviously improved chemical property, can realize pre-coated side Prepared by method, its technique is simple, secondary surface modified without carrying out, and energy consumption and production cost is reduced, so as to be advantageous to it Large-scale production and application.
To solve above technical problem, technical scheme provided by the invention is a kind of nickel cobalt lithium aluminate positive pole of surface modification Material, the positive electrode are made up of stratified material nickel cobalt lithium aluminate positive active material and the modification layer on its surface, institute Stating surface modified layer includes surface doping modified layer and boracic oxide fusion clad.
Preferably, the chemical formula of the positive electrode is LiNixCoyAlzO2, wherein, x+y+z=1,0.5≤x<0.9,0< Y≤0.3,0<z≤0.1.
Preferably, the positive electrode is spherical or spherical particle, and the particle size range of the particle is 0.5~20um.
Preferably, in the boracic oxide fusion clad, the mol ratio of boron element and the positive electrode is (0.1 ~5):100.
Technical scheme also provides a kind of preparation method of the nickel cobalt lithium aluminate cathode material of above-mentioned surface modification, bag Include following steps：
(1) it is Ni by boron-containing compound and chemical formulaxCoyAlz(OH)2Ternary precursor table is obtained by wet-mixing The ternary anode material precursor of face pre-coated；
(2) ternary anode material precursor of the surface pre-coated is mixed with lithium salts, cooled again by high-temperature calcination Obtain the nickel cobalt lithium aluminate cathode material of surface modification.
Wherein, boron-containing compound and chemical formula are NixCoyAlz(OH)2Ternary precursor mol ratio be 1：(49~ 99)。
Preferably, step (1) described boron-containing compound be ammonium borate, boric acid, diboron trioxide, in lithium metaborate at least It is a kind of.
Preferably, step (1) described chemical formula is NixCoyAlz(OH)2Ternary precursor in, nickel content is not less than 60%, 0.5≤x<0.9,0<Y≤0.3,0<z≤0.1.
Preferably, step (2) described lithium salts is at least one of lithium hydroxide or lithium carbonate.
Preferably, step (1) described wet-mixing is specially：The ternary precursor of weighing is mixed with boron-containing compound Afterwards, deionized water is added, obtains mixed aqueous solution, 0.5~2h is dissolved under 30~60 DEG C of stirring conditions, is warming up to 70~100 DEG C Continue 3~8h of stirring, until moisture evaporating completely, 3~12h is dried in vacuo at 80~120 DEG C, obtains the three of surface pre-coated First positive electrode material precursor.
It is more highly preferred to, the gross mass of the ternary precursor and boron-containing compound is the 20 of the mixed aqueous solution quality ~50%.
Preferably, step (2) described high-temperature calcination includes the first constant temperature stage and the second constant temperature stage, first constant temperature Stage is 300~500 DEG C, and the second constant temperature stage is 720~800 DEG C, the first constant temperature stage and second constant temperature The time in stage is 0.5~15h.
Preferably, again in temperature-fall period, it is 2~20 DEG C/min to control heating rate for step (2) described high-temperature calcination, cooling Speed is 0.1 DEG C/min furnace coolings.
By above technical scheme, described nickel cobalt lithium aluminate cathode material is in presoma preparation and high-temperature calcination Carry out what surface modification obtained in journey, wherein in high-temperature calcination, boron element under the high temperature conditions, is doped in boron-containing compound In the lattice body phase of positive electrode, carry out coordination with the oxygen atom in lattice and form boric acid polyanion, and form one layer of transition Phase so that surface modification part and main material part combine even closer, improve lattice stability and heat endurance, hinder simultaneously The release of the oxygen in positive electrode is hindered, has improved security performance, the chemical property of positive electrode can be obviously improved.
In addition, technical scheme employs the method that presoma is carried out to pre-coated, then carry out follow-up high temperature and forge The nickel cobalt lithium aluminate cathode material that can obtain high-quality surface modification is burnt, technological process is simplified, compared to two traditional steps Method coats, and its process conditions and operating procedure are simpler, and working condition milder is easy to control, and need not be used in preparation process Organic solvent, it is pollution-free, production cost has been saved, has been advantageous to large-scale production application.
Based on above-mentioned elaboration, technical scheme is relative to prior art, its advantage：
(1) boron-containing compound of selection uniformly can be deposited on ternary precursor, obtaining the ternary of surface pre-coated just Pole material precursor, the nickel cobalt lithium aluminate cathode material of boric acid polyanion surface modification is prepared through high-temperature calcination, surface is repaiied The part boron atom of layer is adornd under the conditions of high-temperature process, is doped in the lattice body phase of positive electrode, coordination formation is carried out with oxygen Boric acid polyanion, stable crystal structure, surface side reaction are inhibited, and form one layer of transitional face so that finishing coat What is combined with material of main part is even closer, significantly improves chemical property, while hinders the release of the oxygen in positive electrode, carries High security performance.
(2) coated using pre-coated method compared to traditional two-step method, process conditions and operating procedure are simpler, nothing It need to carry out secondary surface modified, working condition is gently easy to control, and organic solvent, nothing need not be used during preparation Pollution, has saved production cost, has been advantageous to large-scale production application.
(3) the nickel cobalt lithium aluminate cathode material for the surface modification that method provided by the invention is prepared, there is good heat Stability and excellent cycle performance.
Brief description of the drawings
Fig. 1 is the SEM figures of the ternary anode material precursor of non-surface modification in the embodiment of the present application 1；
Fig. 2 is the SEM figures of the ternary anode material precursor of surface modification in the embodiment of the present application 1；
Fig. 3 is the SEM figures of the nickel cobalt lithium aluminate cathode material of surface modification in the embodiment of the present application 1；
Fig. 4 is the SEM figures of the nickel cobalt lithium aluminate cathode material of surface modification in the embodiment of the present application 2；
Fig. 5 is the XRD of the nickel cobalt lithium aluminate cathode material of surface modification in the embodiment of the present application 2.
Embodiment
In order that those skilled in the art more fully understands technical scheme, it is below in conjunction with the accompanying drawings and specific real Applying example, the present invention is described in further detail.
The nickel cobalt lithium aluminate cathode material of a kind of surface modification described in technical scheme, by stratified material nickel cobalt aluminium Sour lithium positive active material and the modification layer on its surface form, and the surface modified layer includes surface doping modified layer With boracic oxide fusion clad.It is to be mixed by the ternary anode material precursor of boron-containing compound surface pre-coated with lithium salts Close, be prepared by high-temperature calcination.In the nickel cobalt lithium aluminate cathode material of the surface modification, boron element and the positive pole material The mol ratio of material is (0.1~5):100.The positive electrode is spherical or spherical particle, and particle diameter is 0.5~20um, specifically , refer to that the nickel cobalt lithium aluminate particle of surface modification is spherical or spherical, particle diameter is 0.5~20um.The positive electrode Chemical formula is LiNixCoyAlzO2, wherein, x+y+z=1,0.5≤x<0.9,0<Y≤0.3,0<z≤0.1.
It is Ni that its preparation method, which comprises the following steps boron-containing compound and chemical formula,xCoyAlz(OH)2Ternary precursor The ternary anode material precursor of surface pre-coated is obtained by wet-mixing；By the tertiary cathode material of the surface pre-coated Presoma mixes with lithium salts, cools to obtain the nickel cobalt lithium aluminate cathode material of surface modification again by high-temperature calcination.
Wherein, boron-containing compound is at least one of ammonium borate, boric acid, diboron trioxide, lithium metaborate.
Wherein, the wet-mixing is specially：After the ternary precursor of weighing is mixed with boron-containing compound, addition go from Sub- water, obtains mixed aqueous solution, under 30~60 DEG C of stirring conditions dissolve 0.5~2h, be warming up to 70~100 DEG C continue stirring 3~ 8h, until moisture evaporating completely, 3~12h is dried in vacuo at 80~120 DEG C, obtains the tertiary cathode material of surface pre-coated Presoma.
Wherein, the high-temperature calcination includes the first constant temperature stage and the second constant temperature stage, and the first constant temperature stage is 300 ~500 DEG C, the second constant temperature stage is 720~800 DEG C, the time in the first constant temperature stage and the second constant temperature stage It is 0.5~15h；High-temperature calcination is again in temperature-fall period, and it is 2~20 DEG C/min to control heating rate, and rate of temperature fall is 0.1 DEG C/ Min furnace coolings.
Mixed with lithium salts using the ternary anode material precursor of above-mentioned surface pre-coated and pass through high-temperature calcination and prepared The nickel cobalt lithium aluminate cathode material of boric acid polyanion surface modification there is good heat endurance and excellent cycle performance.
With reference to parameter setting in specific embodiment and experimental result, the technology of present techniques is imitated with reference to accompanying drawing Fruit is verified.
Embodiment 1
A kind of using boric acid is boron-containing compound to ternary precursor mixed type metal hydroxides Ni0.8Co0.15Al0.05 (OH)2After (its SEM figures are as shown in Figure 1) carries out surface pre-coated, the nickel cobalt aluminic acid of the surface modification prepared by high-temperature calcination Lithium anode material, its preparation method comprise the following steps：
(1) preparation of the ternary anode material precursor of surface pre-coated
By ternary precursor mixed type metal hydroxides and boric acid in molar ratio 98:2 add in beaker, then add inward A certain amount of deionized water, wherein mixed type metal hydroxides and boric acid total content are 30%, the stirring and dissolving 2h at 40 DEG C, It is warming up to 80 DEG C again to continue to stir, until moisture evaporating completely.Gained mixture is transferred in baking oven, vacuum is done at 120 DEG C Dry 5h, obtain by the ternary anode material precursor of boric acid surface pre-coated.Its SEM figures are as shown in Figure 2.
(2) preparation of the nickel cobalt lithium aluminate cathode material of surface modification
By the ternary anode material precursor of surface pre-coated obtained above and LiOH in molar ratio 1：1.05 weigh, and Be sufficiently mixed grinding, it is to be ground uniformly after, mixed-powder is transferred in corundum boat, and be pushed into tube furnace center and calcined, It is passed through oxygen simultaneously.Heating rate is 5 DEG C/min, the first insulation reaction 5h at 450 DEG C, then be warming up at 720 DEG C and sinter 15h, The nickel cobalt lithium aluminate cathode material of surface modification is obtained, it is 185.9mAh to obtain first circle specific discharge capacity through electrochemical property test g-1.The circle of circulation 200 under 2C multiplying powers, capacity retention are 97.2%.
Embodiment 2
A kind of using ammonium borate is boron-containing compound to ternary precursor mixed type metal hydroxides Ni0.8Co0.15Al0.05 (OH)2After carrying out surface pre-coated, the nickel cobalt lithium aluminate cathode material of the surface modification prepared by high-temperature calcination, its preparation side Method comprises the following steps：
(1) preparation of the ternary anode material precursor of surface pre-coated
By ternary precursor mixed type metal hydroxides and ammonium borate in molar ratio 99:1 adds in beaker, then adds inward Enter a certain amount of deionized water, wherein mixed type metal hydroxides and ammonium borate total content are 20%, are stirred at 30 DEG C molten 1h is solved, then is warming up to 90 DEG C and continues to stir, until moisture evaporating completely.Gained mixture is transferred in baking oven, it is true at 100 DEG C Sky dries 12h, obtains by the ternary anode material precursor of ammonium borate surface pre-coated.
(2) preparation of the nickel cobalt lithium aluminate cathode material of surface modification
By the ternary anode material precursor of surface pre-coated obtained above and lithium carbonate in molar ratio 1：1.05 weigh, And be sufficiently mixed grinding, it is to be ground uniformly after, mixed-powder is transferred in corundum boat, and be pushed into tube furnace center and forged Burn, while be passed through oxygen.Heating rate is 2 DEG C/min, the first insulation reaction 5h at 450 DEG C, then be warming up at 800 DEG C and sinter 15h, the nickel cobalt lithium aluminate cathode material (SEM is schemed as shown in figure 4, XRD is as shown in Figure 5) of surface modification is obtained, through electrochemistry It is 189.6mAh g that performance test, which obtains first circle specific discharge capacity,-1.The circle of circulation 200 under 2C multiplying powers, capacity retention are 88.7%.
Embodiment 3
A kind of using diboron trioxide is boron-containing compound to ternary precursor mixed type metal hydroxides Ni0.8Co0.15Al0.05(OH)2After carrying out surface pre-coated, the nickel cobalt lithium aluminate positive pole of the surface modification prepared by high-temperature calcination Material, its preparation method comprise the following steps：
(1) preparation of the ternary anode material precursor of surface pre-coated
By ternary precursor mixed type metal hydroxides and diboron trioxide in molar ratio 98:2 add in beaker, then past In add a certain amount of deionized water, wherein mixed type metal hydroxides and diboron trioxide total content are 40%, at 50 DEG C Lower stirring and dissolving 0.5h, then be warming up to 70 DEG C and continue to stir, until moisture evaporating completely.Gained mixture is transferred to baking oven In, 10h is dried in vacuo at 80 DEG C, is obtained by the ternary anode material precursor of diboron trioxide surface pre-coated.
(2) preparation of the nickel cobalt lithium aluminate cathode material of surface modification
By the ternary anode material precursor of surface pre-coated obtained above and lithium carbonate in molar ratio 1：1.05 weigh, And be sufficiently mixed grinding, it is to be ground uniformly after, mixed-powder is transferred in corundum boat, and be pushed into tube furnace center and forged Burn, while be passed through oxygen.Heating rate is 10 DEG C/min, the first insulation reaction 5h at 300 DEG C, then be warming up at 780 DEG C and sinter 15h, obtain the nickel cobalt lithium aluminate cathode material of surface modification.Obtaining first circle specific discharge capacity through electrochemical property test is 186.7mAh g-1.The circle of circulation 200 under 2C multiplying powers, capacity retention are 94.9%.
Embodiment 4
A kind of using lithium metaborate is boron-containing compound to ternary precursor mixed type metal hydroxides Ni0.8Co0.15Al0.05 (OH)2After carrying out surface pre-coated, the nickel cobalt lithium aluminate cathode material of the surface modification prepared by high-temperature calcination, its preparation side Method comprises the following steps：
(1) preparation of the ternary anode material precursor of surface pre-coated
By ternary precursor mixed type metal hydroxides and lithium metaborate in molar ratio 99:1 adds in beaker, then inward A certain amount of deionized water is added, wherein mixed type metal hydroxides and lithium metaborate total content are 50%, are stirred at 60 DEG C Dissolving 1.5h is mixed, then is warming up to 100 DEG C and continues to stir, until moisture evaporating completely.Gained mixture is transferred in baking oven, 90 3h is dried in vacuo at DEG C, is obtained by the ternary anode material precursor of lithium metaborate surface pre-coated.
(2) preparation of the nickel cobalt lithium aluminate cathode material of surface modification
By the ternary anode material precursor of surface pre-coated obtained above and lithium carbonate in molar ratio 1：1.05 weigh, And be sufficiently mixed grinding, it is to be ground uniformly after, mixed-powder is transferred in corundum boat, and be pushed into tube furnace center and forged Burn, while be passed through oxygen.Heating rate is 20 DEG C/min, the first insulation reaction 5h at 500 DEG C, then be warming up at 800 DEG C and sinter 15h, obtain the nickel cobalt lithium aluminate cathode material of surface modification.Obtaining first circle specific discharge capacity through electrochemical property test is 188.9mAh g-1.The circle of circulation 200 under 2C multiplying powers, capacity retention are 90.1%.
Comparative example 1
By original ternary precursor mixed type metal hydroxides Ni0.8Co0.15Al0.05(OH)2With LiOH in molar ratio 1：1.05 weigh, and are sufficiently mixed grinding, it is to be ground it is uniform after, mixed-powder is transferred in corundum boat, and be pushed into tube furnace Center is calcined, while is passed through oxygen.Heating rate is 5 DEG C/min, the first insulation reaction 5h at 480 DEG C, then be warming up to 750 15h is sintered at DEG C, obtains the nickel cobalt lithium aluminate cathode material of non-surface modification.First circle electric discharge ratio is obtained through electrochemical property test Capacity is 190.7mAh g-1.The circle of circulation 200 under 2C multiplying powers, capacity retention are 74.5%.
In above example 1~3 and comparative example, the preparation of electrode and its electrochemical property test method are as follows：
With 1-METHYLPYRROLIDONE (NMP) for solvent, Kynoar (PVDF) is binding agent, and Super P are conductive agent, Wherein PVDF is using being preceding previously dissolved in NMP.In mass ratio 80：10：10 weigh nickel cobalt lithium aluminate cathode material, PVDF respectively With conductive agent Super P, and batch mixing grinding is carried out；The slurry that above-mentioned grinding is obtained be coated in 9 microns thick as collector On bright aluminium foil, after NMP volatilizations completely, electrode slice is rolled with roll squeezer, then be punched into a diameter of 13mm electrode slice；Then Electrode slice is placed in vacuum drying oven the drying overnight at 105 DEG C；After weighing pole piece, it is transferred quickly in glove box；With metal Lithium is to electrode, and Celgard 2400 is barrier film, and electrolyte is that 1mol/L LiPF6 are dissolved in EC/DMC/EMC (volume ratios 1:1: 1) in the mixed solvent.Electrochemical property test is carried out to the battery assembled, test equipment is blue electric CT2001A constant currents test Cabinet, test voltage scope are 2.8-4.3V.
It the above is only the preferred embodiment of the present invention, it is noted that above-mentioned preferred embodiment is not construed as pair The limitation of the present invention, protection scope of the present invention should be defined by claim limited range.For the art For those of ordinary skill, without departing from the spirit and scope of the present invention, some improvements and modifications can also be made, these change Enter and retouch and also should be regarded as protection scope of the present invention.

Claims (10)

  1. A kind of 1. nickel cobalt lithium aluminate cathode material of surface modification, it is characterised in that：The positive electrode is by stratified material nickel cobalt Lithium aluminate positive active material and the modification layer on its surface are formed, and the surface modified layer is modified including surface doping Layer and boracic oxide fusion clad.
  2. A kind of 2. nickel cobalt lithium aluminate cathode material of surface modification according to claim 1, it is characterised in that：The positive pole The chemical formula of material is LiNixCoyAlzO2, wherein, x+y+z=1,0.5≤x<0.9,0<Y≤0.3,0<z≤0.1.
  3. A kind of 3. nickel cobalt lithium aluminate cathode material of surface modification according to claim 1, it is characterised in that：The positive pole Material is spherical or spherical particle, and the particle size range of the particle is 0.5~20um.
  4. A kind of 4. nickel cobalt lithium aluminate cathode material of surface modification according to claim 1, it is characterised in that：The boracic In oxide fusion clad, the mol ratio of boron element and the positive electrode is (0.1~5):100.
  5. 5. a kind of preparation method of the nickel cobalt lithium aluminate cathode material of the surface modification described in any one of Claims 1 to 4, it is special Sign is：Comprise the following steps：
    (1) it is Ni by boron-containing compound and chemical formulaxCoyAlz(OH)2Ternary precursor surface obtained by wet-mixing wrapped in advance The ternary anode material precursor covered；
    (2) ternary anode material precursor of the surface pre-coated is mixed with lithium salts, cools to obtain again by high-temperature calcination The nickel cobalt lithium aluminate cathode material of surface modification.
  6. 6. a kind of preparation method of the nickel cobalt lithium aluminate cathode material of surface modification according to claim 5, its feature exist In：Step (1) described boron-containing compound is at least one of ammonium borate, boric acid, diboron trioxide, lithium metaborate.
  7. 7. a kind of preparation method of the nickel cobalt lithium aluminate cathode material of surface modification according to claim 5, its feature exist In：Step (1) described wet-mixing is specially：After the ternary precursor of weighing is mixed with boron-containing compound, deionization is added Water, mixed aqueous solution is obtained, 0.5~2h is dissolved under 30~60 DEG C of stirring conditions, 70~100 DEG C is warming up to and continues 3~8h of stirring, Until moisture evaporating completely, 3~12h is dried in vacuo at 80~120 DEG C, obtains the tertiary cathode material forerunner of surface pre-coated Body.
  8. 8. a kind of preparation method of the nickel cobalt lithium aluminate cathode material of surface modification according to claim 7, its feature exist In：The gross mass of the ternary precursor and boron-containing compound is the 20~50% of the mixed aqueous solution quality.
  9. 9. a kind of preparation method of the nickel cobalt lithium aluminate cathode material of surface modification according to claim 5, its feature exist In：Step (2) described high-temperature calcination includes the first constant temperature stage and the second constant temperature stage, and the first constant temperature stage is 300~ 500 DEG C, the second constant temperature stage is 720~800 DEG C, and the time in the first constant temperature stage and the second constant temperature stage is equal For 0.5~15h.
  10. 10. a kind of preparation method of the nickel cobalt lithium aluminate cathode material of surface modification according to claim 5, its feature exist In：Step (2) described high-temperature calcination is again in temperature-fall period, and it is 2~20 DEG C/min to control heating rate, and rate of temperature fall is 0.1 DEG C/ Min furnace coolings.
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