CN105958062A - Polycrystal high-nickel positive electrode material used for lithium ion battery and preparation method for polycrystal high-nickel positive electrode material - Google Patents
Polycrystal high-nickel positive electrode material used for lithium ion battery and preparation method for polycrystal high-nickel positive electrode material Download PDFInfo
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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
- H01M4/52—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
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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
- 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
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- 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
Disclosed is a polycrystal high-nickel positive electrode material used for a lithium ion battery. The polycrystal high-nickel positive electrode material comprises a base material with a layered structure and a coating layer which is arranged outside the base material and has a spinel structure; the general formula of the base material is Li<a>Ni<1-x-y>Co<x>M<y>O<2>, wherein M is at least one kind of Mn and Al; the coating layer is lithium manganese oxide; the mass percentage of the total impurity lithium on the surface of the base material is less than 0.085% based on the total mass percentage of the base material; the preparation method for the positive electrode material comprises the following steps of weighing Ni<1-x-y>Co<x>M<y>(OH)<2>, and mixing with a lithium source, then carrying out thermal treatment, cooling, crushing and sieving to obtain the base material; measuring the content of the residual impurity Li<2>CO<3> and LiOH on the surface of the base material, adding into the metal Mn compound according to the measurement result, and carrying out low-temperature thermal treatment in an oxygen atmosphere to obtain the polycrystal high-nickel positive electrode material used for the lithium ion battery. The polycrystal high-nickel positive electrode material provided by the invention has the advantages of low material alkalinity, low inflatable degree, excellent processing property and cycling performance, and the like.
Description
Technical field
The present invention relates to a kind of anode for lithium battery material and preparation method thereof, especially relate to a kind of secondary lithium batteries nickelic just
Pole material and preparation method thereof.
Background technology
Nickelic positive electrode has theoretical discharge specific capacity height, good rate capability, with low cost, safety advantages of higher, is suitable for
In as electric motor car (EV), hybrid electric vehicle (HEV) and the high-energy positive electrode of plug-in hybrid automobile.But along with nickel
The accounting of content is the highest, and the impurity lithium salt content of material surface residual is the highest, and the mixing degree of material cationic is the biggest, thus
Cause slurry in cell fabrication processes that " fruit jelly " phenomenon, storge quality difference and the problem such as battery flatulence, cycle performance difference easily occur,
Have a strong impact on the commercialization of high-nickel material.
CN201110162133 Chinese patent discloses a kind of employing liquid-phase precipitation method and prepares kernel, and middle and top layer is combined heterogeneous
Mn-based material xLi2MnO3·LiNi0.3Mn0.7O2Y (MO), its content is highly controllable, and kernel composition uniformity is good, has Gao An
Full property and the characteristic of long circulation life, but oxide is inert substance, is unfavorable for the migration of lithium ion and electronics, easily causes first
Discharge capacity declines.
CN200910109331 Chinese patent and CN201210359842 Chinese patent disclose lithium ion conductor compound bag
Cover lithium battery tertiary material matrix, by dropping miscellaneous lithium, improve processing characteristics and chemical property, but lithium ion conductor compound is not
Play capacity, discharge capacity and first charge-discharge efficiency first can be reduced.
Summary of the invention
The technical problem to be solved is, overcomes the deficiency and defect mentioned in background above technology, it is provided that a kind of material
Basicity is low, flatulence degree is little, have excellent machinability, higher first charge-discharge efficiency and the lithium-ion electric of excellent cycling performance
The nickelic positive electrode of pond polycrystalline, correspondingly provides that a kind of step is simple, it is easy to operate, the aforementioned lithium ion battery of low cost is used
The preparation method of the nickelic positive electrode of polycrystalline.
For solving above-mentioned technical problem, the technical scheme that the present invention proposes is a kind of nickelic positive electrode of lithium ion battery polycrystalline,
The nickelic positive electrode of described polycrystalline includes base material and the clad of the outer spinel structure of base material, the formula of described base material of layer structure
For LiaNi1-x-yCoxMyO2, wherein, M is at least one in Mn and Al, and a, x, y represent Li, Co in base material respectively
With the molar ratio of M, the value of described a, x, y meets claimed below:
1≤a≤1.2,0.6≤1-x-y ＜ 1,0 ＜ x≤0.4,0≤y ＜ 0.4；
Described clad is lithium manganese oxide, and substrate surface total impurities lithium (LiOH and Li2CO3Middle lithium content) to account for base material total
The mass percent of weight is below 0.085%.
Technique scheme of the present invention utilizes the difference of lithium concentration, removes to absorb the material of high lithium concentration with low lithium concentration containing manganese compound
Elemental lithium in the miscellaneous lithium in material surface, forms corresponding lithium manganese oxide；The formation of recycling lithium manganese oxide, reduces surface
Residual lithium, improve the purpose of drawing abillity and electrical property.
The above-mentioned nickelic positive electrode of lithium ion battery polycrystalline, it is preferred that the second particle of the nickelic positive electrode of described polycrystalline is big
Little for 11-15 μm, 11.50≤pH≤11.70.The nickelic positive electrode of polycrystalline under this particle diameter and pH value store in atmosphere time
Between be obviously prolonged, this also improves the nickelic positive electrode of polycrystalline " fruit jelly " phenomenon in coating process.
The above-mentioned nickelic positive electrode of lithium ion battery polycrystalline, it is preferred that the primary particle of the nickelic positive electrode of described polycrystalline is big
Little for 300-500nm.2032 button cells that this nickelic positive electrode of preferred polycrystalline assembles are at voltage range 3.0-4.3V, 1C
Circulate capability retention >=95% of 50 weeks.Our research indicate that, the particle diameter of primary particle and the size of second particle in
Conspiracy relation, the second particle that product is made up of multiple primary particles, control size and the second particle of primary particle simultaneously
Size, can take into account processing characteristics and the electrical property of product.
The above-mentioned nickelic positive electrode of lithium ion battery polycrystalline, it is preferred that described lithium manganese oxide is Li4Mn5O12And/or
Li2MnO3Mixture.
As total technology design, the present invention also provides for the system of a kind of above-mentioned nickelic positive electrode of lithium ion battery polycrystalline
Preparation Method, comprises the following steps:
(1) Weigh Compound Ni1-x-yCoxMy(OH)2With lithium source (the preferred lithium carbonate in described lithium source, lithium oxide or Lithium hydrate,
More preferably Lithium hydrate) mixing, make the stoichiometric proportion of Li, Ni, Co, M in mixing raw material meet a:(1-x-y): x:y, so
By heat treatment, cooling, broken, screening, obtaining chemical formula is LiaNi1-x-yCoxMyO2The base material represented；Wherein a, x, y
It is respectively 1≤a≤1.2,0.6≤1-x-y ＜ 1,0 ＜ x≤0.4,0≤y ＜ 0.4；
(2) the impurity Li of the substrate surface remaining of above-mentioned steps (1) gained is measured2CO3With LiOH content, according to measurement result
Add in corresponding metal Mn compound, in having oxygen atmosphere, sieve after Low Temperature Heat Treatment, cooling, obtain lithium ion battery
With the nickelic positive electrode of polycrystalline.
Above-mentioned preparation method, it is preferred that described compound N i1-x-yCoxMy(OH)2Mean diameter D50 be 8～11 μm, and
The preferred near-spherical of shape of powder particle, primary particle is fine and close class Folium Pini shape.Use the presoma of class Folium Pini shape, product
The particle diameter of primary particle just can better control at 300-500nm, and the regulation and control to mean diameter D50, then can effectively reduce burning
Junction temperature, cost-effective.
Above-mentioned preparation method, it is preferred that described heat treatment refers to sinter at a temperature of 600 DEG C～800 DEG C 8～20h.By excellent
The sintering temperature of selected control single firing reaches to control granular size, and cladding can reduce the miscellaneous lithium of substrate surface, thus reduce pH.
Above-mentioned preparation method, it is preferred that the temperature of described Low Temperature Heat Treatment at 400 DEG C～600 DEG C, the time of Low Temperature Heat Treatment
Control 2～12h.
Above-mentioned preparation method, it is preferred that in described step (2), the addition of metal Mn compound is the miscellaneous of described mensuration
Matter Li2CO3With in LiOH 0.5～1.25 times of total elemental lithium mole.
Above-mentioned preparation method, we pass through preferably to control covering amount in preparation technology and heat treatment temperature can better control over
The molecular composition of lithium manganese oxide and ratio.
Above-mentioned preparation method, it is preferred that described metal Mn compound is manganese dioxide, manganese carbonate or manganese oxalate.
Compared with prior art, it is an advantage of the current invention that:
1. the product surface of the present invention uses the compound containing element M n to process, and reduces the miscellaneous lithium of material surface residual,
Extend slurry and store the time, and reduce the high temperature flatulence of product；
2. in the scheme being more highly preferred to, the Li of Surface Creation4Mn5O12Capacity can be provided self, and first charge-discharge efficiency is high,
Can effectively promote the first charge-discharge efficiency of material；
3. in the scheme being more highly preferred to, at the Li of positive electrode Surface Creation of the present invention2MnO3Self can play the work of rock-steady structure
With, this composite can provide higher capacity, and reflects higher cyclical stability in charge and discharge process；
4. the product formation of present invention nickel, cobalt and manganese oxide and lithium manganese oxide compound coating layer, owing to not being simple by lithium
Mn oxide and nickel, cobalt and manganese oxide carry out the high temperature solid solution body of routine, saving while energy consumption, it is ensured that the structure of product
Stability and chemical property.
On the whole, the nickelic positive electrode of lithium ion battery polycrystalline that the inventive method prepares, not only storge quality and adding are used
Work better performances, and the lithium secondary battery made with it have excellence room temperature chemical property, high temperature flatulence is low.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or prior art
In description, the required accompanying drawing used is briefly described, it should be apparent that, the accompanying drawing in describing below is some realities of the present invention
Execute example, for those of ordinary skill in the art, on the premise of not paying creative work, it is also possible to according to these accompanying drawings
Obtain other accompanying drawing.
Fig. 1 is the XRD figure spectrum of impurity lithium salts biphasic reaction afterproduct remaining with substrate surface in the embodiment of the present invention 1.
Fig. 2 is the embodiment of the present invention 1 and the XRD figure spectrum of the prepared nickelic tertiary cathode material of comparative example 1,2,3.
Fig. 3 is presoma used by the embodiment of the present invention and the SEM figure of the prepared nickelic tertiary cathode material of embodiment 1, Zuo Tuwei
Presoma, right figure is nickelic tertiary cathode material.
Fig. 4 is the embodiment of the present invention 1 and the contrast of the prepared nickelic tertiary cathode material cycle performance curve of comparative example 1,2,3
Figure (0.1C, 3.0V-4.3V).
Detailed description of the invention
For the ease of understanding the present invention, below in conjunction with Figure of description and preferred embodiment, the present invention is made more comprehensively, careful
Ground describes, but protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical term used hereinafter is generally understood that with those skilled in the art is identical.
Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to limit the protection model of the present invention
Enclose.
Unless otherwise specified, the various raw materials used in the present invention, reagent, instrument and equipment etc. all can be purchased by market
Can buy or can be prepared by existing method.
Embodiment 1:
The nickelic positive electrode of secondary lithium batteries polycrystalline of a kind of present invention, including base material and the base material outer spinelle knot of layer structure
The clad of structure, base material is positive electrode Li1.05Ni0.8Co0.1Mn0.1O2；The clad that substrate outer surface is uniformly coated with is Li2MnO3
And Li4Mn5O12Mixture.
Polycrystalline nickelic positive electrode pH after the surface modification of the present embodiment is 11.65, and second particle size is 12.8 μm, once
Granular size is 450nm.
The preparation method of the nickelic positive electrode of secondary lithium batteries polycrystalline of above-mentioned the present embodiment, specifically includes following steps:
(1) prepared by base material: Weigh Compound Ni0.8Co0.1Mn0.1(OH)2The nickel cobalt manganese compound 375g represented and lithium source
177.88g, wherein the tap density of nickel cobalt manganese compound is 2.15g/cm3, the test of laser diffraction (Laser diffraction) method
Mean diameter D50=10.8 μm, powder particle be shaped as near-spherical, primary particle is class Folium Pini shape (seeing Fig. 3)；Lithium source
Select monohydrate lithium hydroxide；Dry ball milling mixes, and then through 750 DEG C of heat treatment 15h in oxygen atmosphere stove, then cools down, broken,
Screening, obtaining chemical formula is Li1.05Ni0.8Co0.1Mn0.1O2The base material represented；
(2) surface modification treatment: use the total impurities of the substrate surface remaining of determination of acid-basetitration above-mentioned steps (1) gained
Lithium content is 0.347%；Weigh the Li of the above-mentioned synthesis of 200g1.05Ni0.8Co0.1Mn0.1O2Base material, adds the manganese dioxide of 5.22g,
Dry ball milling mixes, and is placed in oxygen atmosphere stove, and 550 DEG C of heat preservation hot process 10h, after furnace cooling, crush and screen,
Obtain the surface coated nickelic positive electrode of secondary lithium batteries polycrystalline.
Comparative example 1:
A kind of nickelic positive electrode of secondary lithium batteries, chemical formula is Li1.05Ni0.8Co0.1Mn0.1O2。
Polycrystalline nickelic positive electrode pH after the surface modification of the present embodiment is 12.03, and second particle size is 14.9 μm, once
Granular size is 420nm.
The preparation method of the nickelic positive electrode of secondary lithium batteries polycrystalline of above-mentioned comparative example 1 is:
Weigh Compound Ni0.8Co0.1Mn0.1(OH)2The nickel cobalt manganese compound 375g represented and lithium source 177.88g, wherein nickel cobalt manganese
The tap density of compound is 2.15g/cm3, the mean diameter D50=10.8 μm of laser diffraction (Laser diffraction) method test,
Powder particle be shaped as near-spherical, primary particle is class Folium Pini shape；Monohydrate lithium hydroxide is selected in lithium source；Dry ball milling mixes,
Then through 750 DEG C of heat treatment 15h in oxygen atmosphere stove, then cooling down, broken, screening, obtaining chemical formula is
Li1.05Ni0.8Co0.1Mn0.1O2The nickelic positive electrode represented.
Comparative example 2:
A kind of nickelic positive electrode of secondary lithium batteries polycrystalline, including stratiform base material and base material outside spinel-type clad, base material
For positive electrode Li1.05Ni0.8Co0.1Mn0.1O2；The clad that substrate outer surface is uniformly coated with is Li2MnO3And Li4Mn5O12's
Mixture.
Polycrystalline nickelic positive electrode pH after the surface modification of the present embodiment is 11.70, and second particle size is 16.1 μm, once
Granular size is 750nm.
The preparation method of the nickelic positive electrode of secondary lithium batteries polycrystalline of above-mentioned comparative example 2, specifically includes following steps:
(1) prepared by base material: Weigh Compound Ni0.8Co0.1Mn0.1(OH)2The nickel cobalt manganese compound 375g represented and lithium source
177.88g, wherein the tap density of nickel cobalt manganese compound is 2.15g/cm3, the test of laser diffraction (Laser diffraction) method
Mean diameter D50=10.8 μm, powder particle be shaped as near-spherical, primary particle is class Folium Pini shape；Single water hydrogen-oxygen is selected in lithium source
Change lithium；Dry ball milling mixes, and then through 830 DEG C of heat treatment 15h in oxygen atmosphere stove, then cools down, broken, and screening obtains
Chemical formula is Li1.05Ni0.8Co0.1Mn0.1O2The base material represented；
(2) surface modification treatment: use the total impurities of the substrate surface remaining of determination of acid-basetitration above-mentioned steps (1) gained
Lithium content is 0.237%；Weigh the Li of the above-mentioned synthesis of 200g1.05Ni0.8Co0.1Mn0.1O2Base material, adds the manganese dioxide of 3.56g,
Dry ball milling mixes, and is placed in oxygen atmosphere stove, and 550 DEG C of heat preservation hot process 10h, after furnace cooling, crush and screen,
Obtain the surface coated nickelic positive electrode of secondary lithium batteries polycrystalline.
From the embodiment of the present invention, this comparative example differs primarily in that sintering temperature is different, when being sintered higher than 800 DEG C, obtain
Product primary particle can be more than 500nm, this causes covered effect to be deteriorated, and processing characteristics and cycle performance reduce.
Comparative example 3:
A kind of nickelic positive electrode of secondary lithium batteries, chemical formula is Li1.05Ni0.8Co0.1Mn0.1O2。
Polycrystalline nickelic positive electrode pH after the surface modification of the present embodiment is 12.01, and second particle size is 15.7 μm, once
Granular size is 790nm.
The preparation method of the nickelic positive electrode of secondary lithium batteries polycrystalline of above-mentioned comparative example 3 is:
Weigh Compound Ni0.8Co0.1Mn0.1(OH)2The nickel cobalt manganese compound 375g represented and lithium source 177.88g, wherein nickel cobalt manganese
The tap density of compound is 2.15g/cm3, the mean diameter D50=10.8 μm of laser diffraction (Laser diffraction) method test,
Powder particle be shaped as near-spherical, primary particle is class Folium Pini shape；Monohydrate lithium hydroxide is selected in lithium source；Dry ball milling mixes,
Then through 830 DEG C of heat treatment 15h in oxygen atmosphere stove, then cooling down, broken, screening, obtaining chemical formula is
Li1.05Ni0.8Co0.1Mn0.1O2The base material represented.
Nano-manganese dioxide, lithium carbonate and Lithium hydrate are mixed by we, according to ratio described in embodiment 1, method and sintering
System is reacted, and shows through XRD test, and products therefrom is Li2MnO3And Li4Mn5O12(seeing Fig. 1)；As can be seen here,
Nano-manganese dioxide can react with the impurity lithium salts of substrate surface remaining, obtains the lithium manganese oxide of correspondence.
Fig. 2 is the invention described above embodiment 1 and the XRD figure spectrum of the prepared positive electrode of comparative example 1,2,3.From the point of view of Fig. 2,
All there are not other dephasign peaks in collection of illustrative plates, and this shows that Surface coating does not changes the structure of material.The ratio of I (003)/I (104) is more than 1.2,
And ratio is the biggest, the mixing degree of material cationic is the lowest.The positive electrode I (003) that embodiment 1 and comparative example 1,2,3 prepare
The ratio of/I (104) is respectively 1.284,1.181,1.276 and 1.199.This shows the MnO added2Lithium in absorbable structure, shape
Become corresponding lithium manganese oxide, reduce the lithium ion in structure, reduce lithium nickel mixing.Additionally, due to substrate material surface is miscellaneous
The content of the content of matter lithium and the coating of surface modification rear substrate material surface is less, and XRD all examines and do not measures.
Fig. 3 is presoma used by the embodiment of the present invention 1 and the SEM figure of the prepared positive electrode of embodiment 1.Can from Fig. 3
Go out, presoma (compound N i0.8Co0.1Mn0.1(OH)2) primary particle is class Folium Pini shape, reunite closely.Embodiment 1 prepares
The primary particle of the nickelic positive electrode of lithium ion battery polycrystalline be 450nm, there is small particle powder in primary particle surface, should
For Li2MnO3And Li4Mn5O12Mixture, there is uniform clad in illustrative material surface.
Slurry is tested:
By embodiments of the invention 1 and the prepared positive electrode of comparative example 1,2,3, PVDF (Kynoar), acetylene black
With NMP (N-Methyl pyrrolidone) by weight the ratio mixing of 100: 2.3: 2.3: 45, stirring, making solid content is
The slurry of 60%～70%.Use viscosity tester tested viscosity change, test environment, humidity 45%-55%, temperature 25 DEG C～
30 DEG C, the testing time is 0h, 1h, 2h, 4h, 7h, 10h, 12h, 21h, and the result obtained is as shown in table 1 below.
Table 1: impurity lithium content, pH and the slurry test result of the surface remaining of embodiment 1 and comparative example 1～3
| Impurity lithium (%) | pH | Time/the h of slurry " fruit jelly " | |
| Embodiment 1 | 0.083 | 11.65 | 12 |
| Comparative example 1 | 0.347 | 12.03 | 1 |
| Comparative example 2 | 0.087 | 11.70 | 7 |
| Comparative example 3 | 0.237 | 12.01 | 2 |
As it can be seen from table 1 use the surface remaining of the nickelic positive electrode of lithium ion battery polycrystalline prepared of way of the present invention
Impurity lithium content is minimum, is 0.083%, and the time of slurry generation " fruit jelly " phenomenon is the longest.The method of modifying of the visible present invention is to miscellaneous
The impurity-eliminating effect of matter lithium salts clearly, has been obviously improved drawing abillity simultaneously.
Electric performance test:
The positive electrode that embodiments of the invention 1 and comparative example 1,2,3 are prepared respectively with conductive black, binding agent PVDF
It is the ratio of 90: 5: 5 in mass ratio, is applied to after making solvent mix homogeneously with NMP on Al paper tinsel, after 120 DEG C of dry 12h,
Roll and be die-cut into 12mm disk, at MNIKROUNA Super (1220/750) glove box (O of argon shield2＜ 1ppm,
H2O ＜ 1ppm) in, it is assembled into CR2032 type button cell with lithium sheet as negative pole, at 25 DEG C, under 3.0-4.3V, carries out electrification
Learning performance test, the result obtained as shown in table 2 (can be found in Fig. 3 and Fig. 4) simultaneously.
Table 2: embodiment 1 and the battery performance test of comparative example 1～3 and high-temperature storage test result
High-temperature storage is tested:
By embodiments of the invention 1 and the prepared positive electrode of comparative example 1,2,3, PVDF (Kynoar), acetylene black
With NMP (N-Methyl pyrrolidone) by weight the ratio mixing of 100: 2.3: 2.3: 45, stirring, making solid content is
The slurry of 60%～70%, coats on the aluminium foil of 16 μ m-thick by slurry, dries at 150 DEG C, and cut-parts, at 7MPa pressure
Lower roll is pressed into positive plate；Graphite, acetylene black, CMC (sodium carboxymethyl cellulose), SBR (butadiene-styrene rubber breast) and water are pressed
The ratio mixing of weight ratio 100: 1: 1.7: 2: 130, stirring is made the slurry that solid content is 40%-50%, is coated with by slurry
It is distributed on the Copper Foil of 10 μ m-thick, dries at 120 DEG C, cut-parts, be pressed into negative plate at 3MPa pressure lower roll；Barrier film is
The microporous polypropylene membrane (Celgard 2400) of import；Electrolyte is 1mol/L LiPF6/ ethylene carbonate (EC)+carbonic acid diformazan
Ester (DMC) (volume ratio 1: 1)；Make the cylindrical lithium ion secondary battery of diameter 18mm, length 65mm.Take 5
Individual battery, at room temperature 25 DEG C, with the constant current charge of 1C to 4.2V, then the constant-voltage charge with 4.2V, cut-off current is
0.01C；It is then placed at lower 150 DEG C of air atmosphere high-temperature cabinet stores 5h, with or without the deformation of battery or ruptures with eyes range estimation,
Or with or without with the ignition ruptured, the result obtained is as above shown in table 2.
From upper table 2 and Fig. 3, Fig. 4 it can be seen that use lithium ion battery polycrystalline nickelic positive pole material prepared by the inventive method
The initial discharge capacity of material is 199.9mAh/g, and first charge-discharge efficiency is 90.5%, and the capability retention of 51 circulations is 98%.
Comparative example 1 and comparative example 1, comparative example 2, comparative example 3, lithium ion battery polycrystalline nickelic positive pole material prepared by the present invention
The first charge-discharge efficiency of material improves 1.2%-2.5%, and the capability retention of 51 circulations improves 3.9%～5.7%, high-temperature storage
Performance have also been obtained certain lifting.The weight of primary particle size is additionally can be seen that from the comparison with comparative example 2, comparative example 3
The property wanted, when primary particle is more than 500nm, cycle performance will reduce, and the capability retention of 50 weeks is less than 95%.
Above example and comparative example experimental data fully show: the nickelic positive pole of lithium ion battery polycrystalline that the inventive method prepares
Spinel-type clad in material reduces the impurity Li of remained on surface the most to a certain extent2CO3And LiOH, improve material
The processing characteristics of material, the Simultaneous Stabilization structure of material, improve the chemical property of material.Spinel-type clad has certainly
Body provides capacity, the effect of stabilizing material structure, it is to avoid the capacitance loss that cladding is brought, and improves the first charge-discharge of material
Efficiency and cycle performance.All in all, the nickelic positive electrode of lithium ion battery polycrystalline that the inventive method prepares is ensureing first
While charge/discharge capacity, processing characteristics, flatulence degree, first charge-discharge efficiency and cycle performance are all obviously improved.
Embodiment 2:
The nickelic positive electrode of secondary lithium batteries polycrystalline of a kind of present invention, including base material and the base material outer spinelle knot of layer structure
The clad of structure, base material is tertiary cathode material Li1.05(Ni0.8Co0.1Mn0.1)0.98Al0.02O2；The point that substrate outer surface is uniformly coated with
The mixture Li that spar type clad is2MnO3And Li4Mn5O12。
Polycrystalline nickelic positive electrode pH after the surface modification of the present embodiment is 11.68, and second particle size is 13.5 μm, once
Granular size is 480nm.
The preparation method of the nickelic positive electrode of secondary lithium batteries polycrystalline of above-mentioned the present embodiment, specifically includes following steps:
(1) prepared by base material: Weigh Compound Ni0.8Co0.1Mn0.1(OH)2Nickel cobalt manganese compound 375g, the lithium source 176.95g represented
With aluminium oxide 1.05g, wherein the tap density of nickel cobalt manganese compound is 2.15g/cm3, laser diffraction (Laser diffraction) method
Test mean diameter D50=10.8 μm, powder particle be shaped as near-spherical, primary particle is Folium Pini shape；Single water is selected in lithium source
Lithium hydrate；Dry ball milling mixes, and then through 780 DEG C of heat treatment 15h in oxygen atmosphere stove, then cools down, broken, screening,
Obtaining chemical formula is Li1.05(Ni0.8Co0.1Mn0.1)0.98Al0.02O2The base material represented；
(2) surface modification treatment: use the total impurities of the substrate surface remaining of determination of acid-basetitration above-mentioned steps (1) gained
Lithium content is 0.366%；Weigh the Li of the above-mentioned synthesis of 200g1.05(Ni0.8Co0.1Mn0.1)0.98Al0.02O2Base material, adds 5.50g's
Manganese dioxide, dry ball milling mixes, is placed in oxygen atmosphere stove, and 600 DEG C of heat preservation hot process 12h, after furnace cooling, carry out
Crush and screen, obtain the surface coated nickelic positive electrode of secondary lithium batteries polycrystalline.
After testing, the present embodiment prepare surface modification the nickelic positive electrode of secondary lithium batteries polycrystalline total impurities lithium content by
0.366% originally reduces to 0.085%, and pH is 11.68, and initial discharge capacity is 199.1mAh/g, and first charge-discharge efficiency is
89.8%, the capability retention of 51 circulations is 96.8%.
Embodiment 3:
The nickelic positive electrode of secondary lithium batteries polycrystalline of a kind of present invention, including base material and the base material outer spinelle knot of layer structure
The clad of structure, base material is tertiary cathode material Li1.04Ni0.8Co0.2O2；The spinel-type clad that substrate outer surface is uniformly coated with
For mixture Li2MnO3And Li4Mn5O12。
Polycrystalline nickelic positive electrode pH after the surface modification of the present embodiment is 11.64, and second particle size is 14.2 μm, once
Granular size is 450nm.
The preparation method of the nickelic positive electrode of secondary lithium batteries polycrystalline of above-mentioned the present embodiment, specifically includes following steps:
(1) prepared by base material: Weigh Compound Ni0.8Co0.2(OH)2The nickel cobalt compound 375g represented and lithium source 174.99g, its
The tap density of middle nickel cobalt compound is 2.3g/cm3, the mean diameter of laser diffraction (Laser diffraction) method test
D50=11.0 μm, powder particle be shaped as near-spherical, primary particle is class Folium Pini shape；Monohydrate lithium hydroxide is selected in lithium source；Dry
Method ball milling mixes, and then through 760 DEG C of heat treatment 12h in oxygen atmosphere stove, then cools down, broken, and screening, obtaining chemical formula is
Li1.04Ni0.8Co0.2O2The base material represented；
(2) surface modification treatment: use the total impurities of the substrate surface remaining of determination of acid-basetitration above-mentioned steps (1) gained
Lithium content is 0.351%；Weigh the Li of the above-mentioned synthesis of 200g1.04Ni0.8Co0.2O2Base material, adds the manganese carbonate of 6.98g, dry method
Ball milling mixes, and is placed in oxygen atmosphere stove, and 600 DEG C of heat preservation hot process 12h, after furnace cooling, crush and screen, obtain
The surface coated nickelic positive electrode of secondary lithium batteries polycrystalline.
After testing, the present embodiment prepare surface modification the nickelic positive electrode of secondary lithium batteries polycrystalline total impurities lithium content by
0.366% originally reduces to 0.073%, and pH is 11.64, and initial discharge capacity is 198mAh/g, and first charge-discharge efficiency is
88.9%, the capability retention of 51 circulations is 95.4%.
Claims (10)
1. the nickelic positive electrode of lithium ion battery polycrystalline, the nickelic positive electrode of described polycrystalline include layer structure base material and
The clad of the outer spinel structure of base material, the formula of described base material is LiaNi1-x-yCoxMyO2, wherein, M is in Mn and Al
At least one, a, x, y represent the molar ratio of Li, Co and M in base material respectively, it is characterised in that: described a, x, y
Value meet claimed below:
1≤a≤1.2,0.6≤1-x-y ＜ 1,0 ＜ x≤0.4,0≤y ＜ 0.4；
Described clad is lithium manganese oxide, and substrate surface total impurities lithium accounts for the mass fraction of base material gross weight below 0.085%.
The nickelic positive electrode of lithium ion battery polycrystalline the most according to claim 1, it is characterised in that described polycrystalline is nickelic
The second particle size of positive electrode is 11-15 μm, 11.50≤pH≤11.70.
The nickelic positive electrode of lithium ion battery polycrystalline the most according to claim 1, it is characterised in that described polycrystalline is nickelic
The primary particle size of positive electrode is 300-500nm；The nickelic positive electrode of described polycrystalline follows at voltage range 3.0-4.3V, 1C
Ring capability retention >=95% of 50 weeks.
4. according to the nickelic positive electrode of lithium ion battery polycrystalline according to any one of claims 1 to 3, it is characterised in that institute
Stating lithium manganese oxide is Li4Mn5O12And/or Li2MnO3Mixture.
5. a preparation method for the nickelic positive electrode of lithium ion battery polycrystalline as according to any one of Claims 1 to 4, bag
Include following steps:
(1) Weigh Compound Ni1-x-yCoxMy(OH)2Mix with lithium source, make the chemistry of Li, Ni, Co, M in mixing raw material
Metering ratio meets a:(1-x-y): x:y, the most thermally treated, cooling, broken, screening, obtaining chemical formula is LiaNi1-x-yCoxMyO2
The base material represented；Wherein a, x, y are respectively 1≤a≤1.2,0.6≤1-x-y ＜ 1,0 ＜ x≤0.4,0≤y ＜ 0.4；
(2) the impurity Li of the substrate surface remaining of above-mentioned steps (1) gained is measured2CO3With LiOH content, according to measurement result
Add corresponding metal Mn compound, in having oxygen atmosphere, sieve after Low Temperature Heat Treatment, cooling, obtain lithium ion battery and use
The nickelic positive electrode of polycrystalline.
Preparation method the most according to claim 5, it is characterised in that described compound N i1-x-yCoxMy(OH)2Average particle
Footpath D50 is 8～11 μm, described compound N i1-x-yCoxMy(OH)2Primary particle be class Folium Pini shape.
Preparation method the most according to claim 5, it is characterised in that described heat treatment refers in oxygen atmosphere stove
8～20h are sintered at a temperature of 600 DEG C～800 DEG C.
Preparation method the most according to claim 5, it is characterised in that the temperature of described Low Temperature Heat Treatment at 400 DEG C～
600 DEG C, the time of Low Temperature Heat Treatment controls 2～12h.
Preparation method the most according to claim 5, it is characterised in that in described step (2), adding of metal Mn compound
Dosage is the impurity Li of described mensuration2CO3With in LiOH 0.5～1.25 times of total elemental lithium mole.
Preparation method the most according to claim 5, it is characterised in that described metal Mn compound is manganese dioxide, carbonic acid
Manganese or manganese oxalate；Described lithium source includes lithium carbonate, lithium oxide or Lithium hydrate.
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Inventor after: Zhou Hui Inventor after: Dong Hong Inventor after: Li Juan Inventor after: Li Xu Inventor after: Tan Xinxin Inventor before: Dong Hong Inventor before: Li Juan Inventor before: Li Xu Inventor before: Tan Xinxin |
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Application publication date: 20160921 |