CN106299320B - A kind of cobalt nickel lithium manganate ternary material of modification and preparation method thereof - Google Patents
A kind of cobalt nickel lithium manganate ternary material of modification and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of cobalt nickel lithium manganate ternary materials of modification, including nickel-cobalt lithium manganate material and are compounded in the titanium dioxide layer on the nickel-cobalt lithium manganate material surface.The invention in cobalt nickel lithium manganate ternary material surface recombination layer of titanium dioxide, be effectively reduced the variation of NCM ternary material surface micro-structure during initial charge, increase first all efficiency；And due to using titanium dioxide as shell, core-shell structure is formed with NCM material, only lithium ion can cannot pass through by titanium dioxide layer, nickel ion and manganese ion, the dissolution for reducing the Ni and Mn in cyclic process in NCM ternary material, optimizes the cycle performance of ternary material.
Description
Technical field
The present invention relates to technical field of lithium ion battery electrode, are related to a kind of cobalt nickel lithium manganate ternary material of modification
And preparation method thereof, and in particular to a kind of nickelic cobalt nickel lithium manganate ternary material of modification and preparation method thereof.
Background technique
Lithium ion battery have operating voltage is high, specific energy is high, have extended cycle life, is light-weight, white electric discharge less, memoryless effect
Should be with cost performance ratio, oneself becomes the fields rechargeable type power supplys such as high power electric vehicle, artificial satellite, aerospace
Main selecting object.Therefore lithium ion battery and its associated materials become the research hotspot of scientific research personnel.Positive electrode is lithium
One of ion battery critical material decides the performance of lithium ion battery.And current limiting lithium ion power battery energy density,
Power density, cycle life and the maximum bottleneck of safety are positive electrode technology.
In current power lithium-ion battery positive electrode, cobalt nickel lithium manganate ternary material (NCM), i.e. nickle cobalt lithium manganate
Ternary layered positive electrode, chemical formula LiNi1-x-yCoxMnyO2, due to the synergistic effect of tri- kinds of elements of Ni, Co and Mn, tool
Have that specific discharge capacity is high, energy density is high, cost is relatively low and advantages of environment protection, becomes world market power lithium in recent years
The great positive electrode of ion battery application field increment.Ni-based ternary material or nickelic ternary material among these
(LiNi1-x-yCoxMnyO2(1-x-y >=0.5)) combine LiCoO2, LiNiO2And LiMnO2Three kinds of anode material for lithium-ion batteries
The advantages of, performance is better than any of the above one-component positive electrode, and there are apparent synergistic effects.In the system, material
Chemical property and physical property are different with the change of these three transition metal element ratios.Ni is introduced, is helped to improve
The capacity of material, but Ni2+When too high levels, with Li+Mixing cause cycle performance to deteriorate.By introducing Co, can reduce
Cation mixing occupy-place, the layer structure of effective stabilizing material reduce impedance value, improve conductivity, but work as the increasing of Co ratio
It will lead to that a and c reduces and c/a increase, capacity are lower when greatly to a certain range.Mn is introduced, material cost can be not only reduced, and
And the safety and stability of material can also be improved.
Just because of NCM ternary material cycle performance is excellent, specific energy is high, low toxicity, good rate capability relatively are considered
It is most potential pure electric vehicle and energy storage lithium ion battery battery positive electrode.But nickel-cobalt lithium manganate cathode material, especially
It is nickelic tertiary cathode material, and there is also defects to be made due to variation of material surface micro-structure during initial charge
Not high at the battery first charge-discharge efficiency that ternary material is positive electrode, head effect is generally less than 90%.In cyclic process
Side reaction can occur with the HF in organic bath, cause the dissolution of Ni and Mn, to affect its electrical property, become NCM tri-
The yoke that first material further develops.
Therefore, a kind of cobalt nickel lithium manganate ternary material with better electrical property how is obtained, it has also become each in field
Production firm's urgent problem to be solved.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that provide a kind of modification cobalt nickel lithium manganate ternary material and
Preparation method, composite modified cobalt nickel lithium manganate ternary material provided by the invention, especially composite modified nickelic nickel cobalt
LiMn2O4 ternary material, cycle performance with higher and stability.Meanwhile preparation method simple process provided by the invention,
Mild condition is suitable for large-scale production and application.
The present invention provides a kind of cobalt nickel lithium manganate ternary material of modification, including nickel-cobalt lithium manganate material and it is compounded in
The titanium dioxide layer on the nickel-cobalt lithium manganate material surface；
Shown in the chemical formula of the nickel-cobalt lithium manganate material such as formula (I),
LiNi1-x-yCoxMnyO2(I)；Wherein, 0,1 > 1-x-y > 0 of x > 0, y >.
Preferably, the nickel-cobalt lithium manganate material is nickelic tertiary cathode material；
Shown in the chemical formula such as formula (II) of the nickelic tertiary cathode material,
LiNi1-x-yCoxMnyO2(II)；Wherein, (1-x-y) >=0.5, x > 0, y > 0.
Preferably, 0.1≤x≤0.2 and/or 0.1≤y≤0.3.
Preferably, the mass ratio of the titanium dioxide and the nickel-cobalt lithium manganate material is (0.1~2)：1；
The partial size D of the nickel-cobalt lithium manganate material50It is 12~14 μm.
The present invention also provides a kind of preparation methods of the cobalt nickel lithium manganate ternary material of modification, include the following steps：
1) after dispersing nickel-cobalt lithium manganate material into the water, processing obtains the aqueous nickel-cobalt lithium manganate material in surface；
Shown in the chemical formula of the nickel-cobalt lithium manganate material such as formula (I),
LiNi1-x-yCoxMnyO2(I)；Wherein, 0,1 > 1-x-y > 0 of x > 0, y >；
2) after the aqueous nickel-cobalt lithium manganate material in the surface obtained above-mentioned steps, titanium source and organic solvent mixing, hydrolysis
Reaction, obtains nickle cobalt lithium manganate composite material；
3) after the nickle cobalt lithium manganate composite material calcining obtained above-mentioned steps, modified nickle cobalt lithium manganate ternary material is obtained
Material.
Preferably, the titanium source includes tetraethyl titanate and/or butyl titanate；
The organic solvent includes one of ethyl alcohol, n-butanol, ethylene glycol, isopropanol and acetone or a variety of.
Preferably, the mass ratio of the nickel-cobalt lithium manganate material and the water is (20~40)：(15~25)；
The mass ratio of the titanium source and the nickel-cobalt lithium manganate material is 1：(200~400)；
The mass ratio 1 of the titanium source and the organic solvent：(1000~2000).
Preferably, the time of the dispersion is 30~60min；
The processing includes filtration and or drying；
The mixing the specific steps are：After first titanium source and organic solvent dispersion are mixed, then the nickel cobalt aqueous with surface
Lithium manganate material mixing.
Preferably, the time of the hydrolysis is 3~5h；
It further include filtering and drying steps again after the completion of the hydrolysis；
The temperature of the drying is 100~130 DEG C, and the time of the drying is 2~4h.
Preferably, the calcining is to calcine under vacuum conditions；
The temperature of the calcining is 400~700 DEG C, and the time of the calcining is 1~5h.
The present invention provides a kind of cobalt nickel lithium manganate ternary material of modification, including nickel-cobalt lithium manganate material and it is compounded in
The titanium dioxide layer on the nickel-cobalt lithium manganate material surface；Shown in the chemical formula of the nickel-cobalt lithium manganate material such as formula (I),
LiNi1-x-yCoxMnyO2(I)；Wherein, 0,1 > 1-x-y > 0 of x > 0, y >.Compared with prior art, the present invention be directed to due to
NCM material surface microstructure change causes the battery first charge-discharge efficiency that ternary material is positive electrode not high, and is following
Side reaction can occur with the HF in organic bath during ring, cause the defect of the dissolution of Ni and Mn.The invention
In cobalt nickel lithium manganate ternary material surface recombination layer of titanium dioxide, NCM ternary material is effectively reduced in initial charge
The variation of surface micro-structure in the process increases first all efficiency；And due to using titanium dioxide as shell, with NCM material
Material forms core-shell structure, and only lithium ion can cannot be passed through by titanium dioxide layer, nickel ion and manganese ion, reduced and be circulated throughout
The dissolution of Ni and Mn in journey in NCM ternary material, optimize the cycle performance of ternary material.The experimental results showed that this is sent out
The battery that the cobalt nickel lithium manganate ternary material of the modification of bright preparation is prepared as positive electrode, first week efficiency is about 0.83~
0.86；After circulation 50 times, within gram specific capacity loss only 13%, 22% or more is improved compared to uncoated NCM material.
Detailed description of the invention
Fig. 1 is the nickelic ternary material of coated by titanium dioxide and uncoated nickelic ternary material prepared by the embodiment of the present invention 1
Li[Ni0.6Co0.2Mn0.2]O2Gram specific capacity cycle performance comparison diagram.
Specific embodiment
In order to further appreciate that the present invention, the preferred embodiments of the invention are described below with reference to embodiment, but
It is it should be appreciated that these descriptions only require the invention patent to further illustrate the features and advantages of the present invention
Limitation.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to those skilled in the art
The preparation of conventional method known to member.
All raw materials of the present invention, are not particularly limited its purity, and present invention preferably employs analyze pure or lithium ion battery
The purity of field routine.
The present invention provides a kind of cobalt nickel lithium manganate ternary material of modification, including nickel-cobalt lithium manganate material and it is compounded in
The titanium dioxide layer on the nickel-cobalt lithium manganate material surface；
Shown in the chemical formula of the nickel-cobalt lithium manganate material such as formula (I),
LiNi1-x-yCoxMnyO2(I)；Wherein, 0,1 > 1-x-y > 0 of x > 0, y >.
The nickel-cobalt lithium manganate material is not particularly limited in the present invention, with well known to those skilled in the art for making
The NCM ternary material of lithium ion cell positive, the present invention are preferably cobalt nickel lithium manganate ternary material, the nickle cobalt lithium manganate
The chemical formula of ternary material preferably as shown in formula (I),
LiNi1-x-yCoxMnyO2(I)；Wherein, 0,1 > 1-x-y > 0 of x > 0, y >；
The present invention is the performance for improving ternary material as positive electrode, and the nickel-cobalt lithium manganate material is more preferably nickelic
Nickle cobalt lithium manganate tertiary cathode material (or rich nickel cobalt nickel lithium manganate ternary material, Ni-based ternary material), the nickelic ternary
Shown in the chemical formula of positive electrode such as formula (II),
LiNi1-x-yCoxMnyO2(II)；Wherein, (1-x-y) >=0.5, x > 0, y > 0.
Further, the value range of the x is preferably 0.1≤x≤0.2, more preferable 0.12≤x≤0.18, more preferably
For 0.14≤x≤0.16；The value range of the y is preferably 0.1≤y≤0.3, more preferable 0.13≤y≤0.27, more preferably
0.16≤y≤0.24, most preferably 0.19≤y≤0.21；The value range of the 1-x-y is preferably 0.5≤1-x-y≤0.9, more
It is preferred that 0.6≤1-x-y≤0.9, most preferably 0.7≤1-x-y≤0.8.
The nickel-cobalt lithium manganate material other conditions are not particularly limited in the present invention, with well known to those skilled in the art
The normal condition of NCM ternary material, those skilled in the art can be according to practical condition, combining case and products
Performance is selected, and the present invention is to be further ensured that the performance of trielement composite material, the partial size D of the nickel-cobalt lithium manganate material50
Preferably 12~14 μm, more preferably 12.3~13.7 μm, most preferably 12.5~13.5 μm.The present invention is to the titanium dioxide
It is not particularly limited, with titanic oxide material well known to those skilled in the art, the present invention is to its concrete property without spy
It does not limit, those skilled in the art can select according to practical condition, combining case and properties of product.
The present invention to it is described it is compound be not particularly limited, with composite definitions well known to those skilled in the art, this hair
Bright preferably cladding, half coat, are laminated or generate, more preferably cladding or half cladding, most preferably coat.The present invention is to described
Cladding is not particularly limited, with cladding well known to those skilled in the art definition, the preferably full cladding of the present invention.The present invention
The mass ratio of the titanium dioxide and the nickel-cobalt lithium manganate material is not particularly limited, those skilled in the art can basis
Practical condition, cladding situation and properties of product are selected, titanium dioxide of the present invention and the nickle cobalt lithium manganate
The mass ratio of material is preferably (0.1%~2%):1, more preferably (0.4%~1.7%):1, more preferably (0.7%~
1.4%):1, most preferably (0.9%~1.2%):1.
The present invention is in cobalt nickel lithium manganate ternary material surface recombination layer of titanium dioxide, in particular for nickelic nickel cobalt manganese
Sour lithium ternary material, is effectively reduced the variation of NCM ternary material surface micro-structure during initial charge, increases head
All efficiency；And due to using titanium dioxide as shell, core-shell structure is formed with NCM material, only lithium ion can pass through
Titanium dioxide layer, nickel ion and manganese ion cannot pass through, and reduce the molten of Ni in cyclic process in NCM ternary material and Mn
Solution, optimizes the cycle performance of ternary material.
The present invention provides a kind of preparation methods of the cobalt nickel lithium manganate ternary material of modification, include the following steps：
1) after dispersing nickel-cobalt lithium manganate material into the water, processing obtains the aqueous nickel-cobalt lithium manganate material in surface；
Shown in the chemical formula of the nickel-cobalt lithium manganate material such as formula (I),
LiNi1-x-yCoxMnyO2(I)；Wherein, 0,1 > 1-x-y > 0 of x > 0, y >；
2) after the aqueous nickel-cobalt lithium manganate material in the surface obtained above-mentioned steps, titanium source and organic solvent mixing, hydrolysis
Reaction, obtains nickle cobalt lithium manganate composite material；
3) after the nickle cobalt lithium manganate composite material calcining obtained above-mentioned steps, modified nickle cobalt lithium manganate ternary material is obtained
Material.
The present invention is to optimum principles such as the selection of the raw material and ratios, such as without especially indicating, with aforementioned modified nickel cobalt
Consistent in LiMn2O4 ternary material, this is no longer going to repeat them.
After the present invention first disperses nickel-cobalt lithium manganate material into the water, processing obtains the aqueous nickle cobalt lithium manganate in surface
Material；Shown in the chemical formula of the nickel-cobalt lithium manganate material such as formula (I).
The source of the nickel-cobalt lithium manganate material is not particularly limited in the present invention, and those skilled in the art can be according to normal
Rule method carry out preparation or commercially；The present invention is to the specific element ratio of the nickel-cobalt lithium manganate material without spy
It does not limit, with the element ratio of nickel-cobalt lithium manganate material well known to those skilled in the art.The present invention is preferred processing condition,
Properties of product are further increased, the nickel-cobalt lithium manganate material is preferably nickelic nickel-cobalt lithium manganate material；The nickle cobalt lithium manganate
The particle diameter distribution of material, D50 are preferably 12~14 μm, more preferably 12.5~13.5 μm, most preferably 12.8~13.2 μm.
The dispersion is not particularly limited in the present invention, is with dispersing mode well known to those skilled in the art and condition
Can, those skilled in the art can be adjusted according to practical condition, product situation and performance requirement, of the present invention
Dispersion is preferably evenly dispersed, and the time of the dispersion is preferably 30~60min, more preferably 35~55min, and most preferably 40
~50min.The dosage of the water is not particularly limited in the present invention, those skilled in the art can according to practical condition,
Product situation and performance requirement are adjusted, and the present invention is preferably so that nickel-cobalt lithium manganate material surface sufficiently soaks, more
The mass ratio of the preferably described nickel-cobalt lithium manganate material and the water is (20~40)：(15~25), more preferably (25~35)：
(15~25), more preferably (25~35)：(17~23), most preferably (28~32)：(19~21).The present invention is to the processing
It is not particularly limited, to remove extra water, facilitates later processing operation, can choose by processing, it can also be without
Processing is crossed, those skilled in the art can be adjusted according to practical condition, product situation and performance requirement, the present invention
The processing is preferably filtered or drying.The filtering or dry mode and condition is not particularly limited in the present invention, with this
Filtering or dry mode and condition known to the technical staff of field, those skilled in the art can be according to actual production feelings
Condition, product situation and performance requirement are adjusted, and preferably 1~5 μm of the filter diameter of filtering of the present invention, more preferably 2~4 μ
M, most preferably 3 μm；The filter type is preferably filter paper filtering, and more preferably double-layer filter paper filters.
The aqueous nickel-cobalt lithium manganate material in then surface that the present invention obtains above-mentioned steps, titanium source and organic solvent mixing
Afterwards, hydrolysis obtains nickle cobalt lithium manganate composite material.
The titanium source is not particularly limited in the present invention, with the titanium source well known to those skilled in the art for such reaction
, those skilled in the art can be adjusted according to practical condition, product situation and performance requirement, institute of the present invention
Stating titanium source is preferably tetraethyl titanate and/or butyl titanate, more preferably tetraethyl titanate or butyl titanate, most preferably
Tetraethyl titanate.The organic solvent is not particularly limited in the present invention, with well known to those skilled in the art for such anti-
The organic solvent answered, those skilled in the art can carry out according to practical condition, product situation and performance requirement
Adjustment, organic solvent of the present invention preferably include one of ethyl alcohol, n-butanol, ethylene glycol, isopropanol and acetone or a variety of,
More preferably ethyl alcohol, n-butanol, isopropanol or acetone, most preferably ethyl alcohol.The present invention is not special to the dosage of the titanium source
Limitation, those skilled in the art can be adjusted according to practical condition, product situation and performance requirement, institute of the present invention
The mass ratio for stating titanium source and the nickel-cobalt lithium manganate material is preferably 1：(200~400), more preferably 1：(250~350), most
Preferably 1：(270~330).The dosage of the organic solvent is not particularly limited in the present invention, and those skilled in the art can be with
It is adjusted according to practical condition, product situation and performance requirement, titanium source of the present invention and the organic solvent
Mass ratio is preferably 1：(1000~2000), more preferably 1：(1200~1800), most preferably 1：(1400~1600).
The mixed mode and parameter is not particularly limited in the present invention, with mixing well known to those skilled in the art
Mode and parameter, those skilled in the art can adjust according to practical condition, product situation and performance requirement
Whole, the present invention is to improve the effect of late phase reaction, and guarantee is fully dispersed, and the mixed specific steps are preferably：First by titanium source
After organic solvent dispersion mixing, then the nickel-cobalt lithium manganate material aqueous with surface mixes；It is initially formed organic dispersion of titanium source
Liquid, then the nickel-cobalt lithium manganate material aqueous with surface mix.The condition of the hydrolysis is not particularly limited in the present invention, with
The condition of hydrolysis well known to those skilled in the art, those skilled in the art can be according to practical conditions, production
Product situation and performance requirement are adjusted, and the time of hydrolysis of the present invention is preferably 3~5h, more preferably 3.5~
4.5h, most preferably 3.7~4.3h.
The present invention is to remove extra solvent, facilitates later processing operation, after the completion of hydrolysis, can choose through
Later it handles, it can also can be according to practical condition, product situation and property without post-processing, those skilled in the art
It can require to be adjusted, it is also preferable to include filtering and drying steps again after the completion of hydrolysis of the present invention.The present invention couple
The filtering again and dry concrete technology and condition are not particularly limited, and with filtering well known to those skilled in the art and do
Dry concrete technology and condition, those skilled in the art can want according to practical condition, product situation and performance
It asks and is adjusted, the temperature of drying of the present invention is preferably 100~130 DEG C, and more preferably 105~125 DEG C, most preferably
110~120 DEG C；The time of the drying is preferably 2~4h, more preferably 2.5~3.5h, most preferably 2.7~3.3h.
Above-mentioned steps of the present invention provide one kind in NCM ternary material, especially nickelic ternary material in-stiu coating dioxy
Nickelic ternary material, is first dispersed in water, its surface is made sufficiently to absorb water, then by treated sample by the method for changing titanium
It is put into the organic solution dissolved with titanium source, allows titanium source to carry out in-situ hydrolysis reaction on NCM ternary material surface, in nickelic ternary
The uniformly reaction of material generates metatitanic acid, the NCM ternary material uniformly coated to after the reaction was completed, obtain metatitanic acid
Material.
The NCM ternary material of the nickle cobalt lithium manganate composite material that the present invention finally obtains above-mentioned steps, i.e. metatitanic acid cladding
After material calcining, modified cobalt nickel lithium manganate ternary material is obtained.
The condition of the calcining is not particularly limited in the present invention, multiple with nickle cobalt lithium manganate well known to those skilled in the art
Condensation material calcining concrete technology and condition, those skilled in the art can according to practical condition, product situation with
And performance requirement is adjusted, and the temperature of calcining of the present invention is preferably 400~700 DEG C, and more preferably 450~650 DEG C, most
Preferably 500~600 DEG C；The time of the calcining is preferably 1~5h, more preferably 2~4h, most preferably 2.5~3.5h；Institute
The heating rate for stating calcining is preferably 5~10 DEG C/min, more preferably 6~9 DEG C/min, most preferably 7~8 DEG C/min；It is described
Calcining is more preferably calcined in the condition of vacuum.The specific pressure value of the vacuum is not particularly limited in the present invention, with ability
The normal pressures value of nickle cobalt lithium manganate composite material vacuum calcining known to field technique personnel, those skilled in the art can be with
It is adjusted according to practical condition, product situation and performance requirement.
Modified cobalt nickel lithium manganate ternary material has been prepared in above-mentioned steps of the present invention, and the present invention utilizes NCM ternary material
Material, the hygroscopic feature in especially nickelic ternary material surface are hydrolyzed using titanium source in nickelic ternary material surface in situ, due to
Titanium source is reacted in nickelic ternary material surface in situ, generates metatitanic acid, and then be sintered and form titanium dioxide (TiO2) clad,
So that coated by titanium dioxide layer is densely incorporated in nickelic ternary material surface, covered effect is good, in material after finally drying sintering
Material surface forms fine and close coated by titanium dioxide layer, and the existing cladding scheme of effective solution causes shell in positive electrode table
Not fine and close enough the defect in face.The above-mentioned preparation method of the present invention also has many advantages, such as that process is simple, is convenient for industrial applications, and directly
It reacts and carries out in nickelic ternary material surface in situ, be coated on ternary material surface, shape to resulting titanium dioxide even compact
At a protective layer, when reducing ternary material as anode material for lithium-ion batteries during initial charge surface micro-structure
Variation, increase first all efficiency, and can be reduced being dissolved in electrolyte of Ni and Mn in cyclic process in ternary material.
The present invention is effectively reduced NCM ternary in cobalt nickel lithium manganate ternary material surface recombination layer of titanium dioxide
The variation of material surface micro-structure during initial charge increases first all efficiency；And make due to using titanium dioxide
For shell, core-shell structure is formed with NCM material, only lithium ion can cannot lead to by titanium dioxide layer, nickel ion and manganese ion
It crosses, reduces the dissolution of the Ni and Mn in cyclic process in NCM ternary material, optimize the cycle performance of ternary material；And
It due to using titanium source is reacted in nickelic ternary material surface in situ, sintering forms coated by titanium dioxide layer, so that clad
It is densely incorporated in nickelic ternary material surface, covered effect is good, and simple process, mild condition, is suitable for extensive raw
Produce application.The experimental results showed that the cobalt nickel lithium manganate ternary material of modification prepared by the present invention is prepared as positive electrode
Battery, first week efficiency value is about 0.83~0.86；After circulation 50 times, within gram specific capacity loss only 13%, compared to uncoated
NCM material improve 22% or more.
In order to further illustrate the present invention, with reference to embodiments to a kind of nickle cobalt lithium manganate of modification provided by the invention
Ternary material and preparation method thereof is described in detail, but it is to be understood that these embodiments are with technical solution of the present invention
Premised under implemented, the detailed implementation method and specific operation process are given, only be further illustrate the present invention
Feature and advantage, rather than limiting to the claimed invention, protection scope of the present invention are also not necessarily limited to following implementation
Example.
Embodiment 1
First by 4g D50=12~14 μm of nickelic ternary material Li [Ni0.6Co0.2Mn0.2] O2 is dispersed in 2ml water
In, it after magnetic agitation 30 minutes, soaks nickelic ternary material surface sufficiently, is filtered with the filter paper in two layers of 3 μm of aperture
The nickelic ternary material aqueous to surface.
Then 0.114g tetraethyl titanate is dispersed in 250mL ethanol solution, it is aqueous that above-mentioned surface is added
Nickelic ternary material, stir 4h, allow tetraethyl titanate nickelic ternary material surface occur in-situ hydrolysis reaction, nickelic three
The uniformly reaction of first material generates metatitanic acid, will to after the reaction was completed, be filtered with the filter paper in two layers of 3 μm of aperture
Product is put into 120 DEG C of baking 2h in baking oven, obtains the nickelic ternary material that metatitanic acid uniformly coats.
Substance used in above-mentioned steps is counted in mass ratio, tetraethyl titanate：Nickelic ternary material：Water：Ethyl alcohol=1：35:
18：1750.
The nickelic ternary material that above-mentioned metatitanic acid uniformly coats finally is warming up to 450 with 5 DEG C of heating rates per minute
DEG C, and calcining at constant temperature 5 hours, it is pyrolyzed metatitanic acid sufficiently and forms titanium dioxide, the coated by titanium dioxide obtained after furnace cooling
Modified nickelic ternary material, i.e. Li [Ni0.6Co0.2Mn0.2]O2/TiO2.Wherein, the quality of titanium dioxide is about nickelic ternary material
Expect the 1% of quality.
By conventional Li [Ni0.6Co0.2Mn0.2]O2And the Li of coated by titanium dioxide prepared by the embodiment of the present invention 1
[Ni0.6Co0.2Mn0.2]O2Respectively with conductive black and binder PVDF with mass ratio 90：10：10 are uniformly mixed, and are coated in aluminium foil
On, anode pole piece, 100 DEG C of vacuum drying 20h are cut into after dry.Lithium metal is cathode, and electrolyte is that LiPF6 is dissolved in mass ratio
It is 1：1：In 1 ethylene carbonate (EC)/dimethyl carbonate (DMC)/methyl ethyl carbonate (EMC) organic solvent, concentration is
1mol/L is assembled into button cell.
To the button cell of above-mentioned steps preparation at 25 DEG C, within the scope of 3~4.3V, with 0.2C charge and discharge, test material
Cycle performance, first week efficiency is 0.86.
Referring to Fig. 1, Fig. 1 be the embodiment of the present invention 1 prepare the nickelic ternary material of coated by titanium dioxide with it is uncoated nickelic
Ternary material Li [Ni0.6Co0.2Mn0.2]O2Gram specific capacity cycle performance comparison diagram.As shown in Figure 1, it recycles 50 times, it is uncoated
Li [Ni0.6Co0.2Mn0.2]O2Gram specific capacity drops to 114mAh/g from 160mAh/g；And packet prepared by the embodiment of the present invention 1
Cover modified Li [Ni0.6Co0.2Mn0.2]O2Then under 160mAh/g to 139mAh/g, cycle performance has significantly for gram specific capacity
It improves.
Embodiment 2
By 4g D50The nickelic ternary material Li [Ni of=12~14um0.6Co0.2Mn0.2]O2It is dispersed in 2ml water, magnetic force stirs
After mixing 30 minutes, it is filtered to obtain the aqueous nickelic ternary material in surface with the filter paper in two layers of 3 μm of aperture.
0.0114g tetraethyl titanate is dispersed in 25ml ethanol solution, the aqueous height in above-mentioned surface is added
Nickel ternary material stirs 5h, is filtered with the filter paper in two layers of 3 μm of aperture, product is put into 120 DEG C of baking 2h in baking oven, is obtained
The nickelic ternary material that metatitanic acid uniformly coats.
The tetraethyl titanate in mass ratio of substance used in above-mentioned steps：Nickelic ternary material：Water：Ethyl alcohol=1：350:
175：1750.
Gains are warming up to 500 DEG C, and calcining at constant temperature 5 hours with 10 DEG C of heating rates per minute, fill metatitanic acid
Divide pyrolysis to form titanium dioxide, the nickelic ternary material of coated by titanium dioxide is obtained after furnace cooling.Wherein, the matter of titanium dioxide
Amount is about the 0.1% of nickelic ternary material quality.
To the nickelic ternary material of coated by titanium dioxide prepared by embodiment 2, button cell is prepared according to above-mentioned steps, so
Afterwards at 25 DEG C, within the scope of 3~4.3V, with 0.2C charge and discharge, the cycle performance of test material, first week efficiency is 0.83.
Embodiment 3
By 4g D50The nickelic ternary material Li [Ni of=12~14um0.6Co0.2Mn0.2]O2It is dispersed in 2ml water, magnetic force stirs
After mixing 30 minutes, it is filtered to obtain the aqueous nickelic ternary material in surface with the filter paper in two layers of 3 μm of aperture.
0.344g butyl titanate is dispersed in 650ml ethanol solution, the aqueous height in above-mentioned surface is added
Nickel ternary material stirs 3h, is filtered with the filter paper in two layers of 3 μm of aperture, product is put into 120 DEG C of baking 2h in baking oven, is obtained
The nickelic ternary material that metatitanic acid uniformly coats.
The butyl titanate in mass ratio of substance used in above-mentioned steps：Nickelic ternary material：Water：Ethyl alcohol=1：12：6：1500.
Gains are warming up to 450 DEG C, and calcining at constant temperature 6 hours with 5 DEG C of heating rates per minute, keep metatitanic acid abundant
Pyrolysis forms titanium dioxide, and the nickelic ternary material of required coated by titanium dioxide is obtained after furnace cooling.Wherein, titanium dioxide
Quality be about the 2% of nickelic ternary material quality.
To the nickelic ternary material of coated by titanium dioxide prepared by embodiment 3, button cell is prepared according to above-mentioned steps, so
Afterwards at 25 DEG C, within the scope of 3~4.3V, with 0.2C charge and discharge, the cycle performance of test material, first week efficiency is 0.85.
A kind of cobalt nickel lithium manganate ternary material of modification provided by the invention and preparation method thereof has been carried out in detail above
Introduction, used herein a specific example illustrates the principle and implementation of the invention, and above embodiments are said
It is bright to be merely used to help understand method and its core concept of the invention, including best mode, and but also this field is appointed
What technical staff can practice the present invention, including any device or system of manufacture and use, and implement the method for any combination.
It should be pointed out that for those skilled in the art, it without departing from the principle of the present invention, can also be right
Some improvement and modification can also be carried out by the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.This hair
The range of bright patent protection is defined by the claims, and may include those skilled in the art it is conceivable that other implementations
Example.If these other embodiments have the structural element for being not different from claim character express, or if they are wrapped
The equivalent structural elements with the character express of claim without essence difference are included, then these other embodiments should also be included in power
In the range of benefit requires.
Claims (10)
1. a kind of preparation method of the cobalt nickel lithium manganate ternary material of modification, which is characterized in that include the following steps：
1) after dispersing nickel-cobalt lithium manganate material into the water, processing obtains the aqueous nickel-cobalt lithium manganate material in surface；
The nickel-cobalt lithium manganate material is nickelic tertiary cathode material；
2) after the aqueous nickel-cobalt lithium manganate material in the surface obtained above-mentioned steps, titanium source and organic solvent mixing, hydrolysis,
Obtain nickle cobalt lithium manganate composite material；
3) after the nickle cobalt lithium manganate composite material calcining obtained above-mentioned steps, modified cobalt nickel lithium manganate ternary material is obtained.
2. preparation method according to claim 1, which is characterized in that the cobalt nickel lithium manganate ternary material of the modification includes
Nickel-cobalt lithium manganate material and the titanium dioxide layer for being compounded in the nickel-cobalt lithium manganate material surface.
3. preparation method according to claim 1, which is characterized in that the chemical formula such as formula of the nickelic tertiary cathode material
(II) shown in,
LiNi1-x-yCoxMnyO2(II)；Wherein, (1-x-y) >=0.5, x > 0, y > 0.
4. preparation method according to claim 3, which is characterized in that
0.1≤x≤0.2 and/or 0.1≤y≤0.3.
5. preparation method according to claim 2, which is characterized in that the titanium dioxide and the nickel-cobalt lithium manganate material
Mass ratio be (0.1%~2%)：1；
The partial size D of the nickel-cobalt lithium manganate material50It is 12~14 μm.
6. preparation method according to claim 1, which is characterized in that the titanium source includes tetraethyl titanate and/or metatitanic acid
Four butyl esters；
The organic solvent includes one of ethyl alcohol, n-butanol, ethylene glycol, isopropanol and acetone or a variety of.
7. preparation method according to claim 1, which is characterized in that the quality of the nickel-cobalt lithium manganate material and the water
Than for (20~40)：(15~25)；
The mass ratio of the titanium source and the nickel-cobalt lithium manganate material is 1：(200~400)；
The mass ratio 1 of the titanium source and the organic solvent：(1000~2000).
8. preparation method according to claim 1, which is characterized in that the time of the dispersion is 30~60min；
The processing includes filtration and or drying；
The mixing the specific steps are：After first titanium source and organic solvent dispersion are mixed, then the nickel cobalt mangaic acid aqueous with surface
Lithium material mixing.
9. preparation method according to claim 1, which is characterized in that the time of the hydrolysis is 3~5h；
It further include filtering and drying steps again after the completion of the hydrolysis；
The temperature of the drying is 100~130 DEG C, and the time of the drying is 2~4h.
10. preparation method according to claim 1, which is characterized in that the calcining is to calcine under vacuum conditions；
The temperature of the calcining is 400~700 DEG C, and the time of the calcining is 1~5h.
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