CN107591519A - Modified lithium nickel cobalt manganese positive electrode material and preparation method thereof - Google Patents
Modified lithium nickel cobalt manganese positive electrode material and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of modified lithium nickel cobalt manganese positive electrode material and preparation method thereof.The formula of the modified lithium nickel cobalt manganese positive electrode material is LiaNixCoyMnzMγO2‑δRδ.Wherein, 1.03≤a≤1.23,0<X≤0.9,0<Y≤1,0<Z≤1, x+y+z=1,0<γ≤0.075,0<δ≤0.05, one or more of the doped chemical M in Ni, Co, Mn, Sn, Mg, Ca, Ti, Zr, V, Nb, Mo, W, Al, B, one or more of the doped chemical R in N, P, S, Si, Se, doped chemical M and doped chemical R are respectively positioned on grain boundaries.In the present invention, crystal boundary doping is carried out to conventional lithium nickel cobalt manganese positive electrode material, obtained modification lithium nickel cobalt manganese positive electrode material still has sufficiently stable structure during the repeated charge of heavy current.
Description
Technical field
The present invention relates to technical field of lithium ion, more particularly to a kind of modified lithium nickel cobalt manganese positive electrode material and its preparation
Method.
Background technology
Compared with other traditional secondary batteries, lithium ion battery has small volume, voltage height, energy density height etc. many excellent
Point, achieve a series of rapid progresses in consumer electronics fields such as mobile phone, notebooks.With the flourishing hair of new energy cause
Exhibition, the just positive exploitation high power density of increasing researcher, high circulation stability, the lithium-ion electric of high security
Pond, to its electrokinetic cell as electric car.
In numerous positive electrodes that lithium ion battery uses, lithium nickel cobalt manganese (NCM) positive electrode of layer structure due to
With discharge capacity it is high, have a safety feature, Stability Analysis of Structures, low cost the characteristics of be considered as following power lithium-ion battery
One of optimal selection of positive electrode.However, for lithium cobalt oxide, lithium manganese oxygen positive electrode, lithium nickel cobalt manganese positive electrode material
High rate performance it is bad.
In order to improve its high rate performance, at this stage it is most research concentrate on reduce particle size, carry out it is bulk phase-doped
Or in surface modification.It was discovered by researchers that lithium ion in lithium nickel cobalt manganese positive electrode material can be improved by appropriate Zr doping
Diffusion coefficient, and then improve it and circulate conservation rate and high rate performance (referring to document Improvement of
electrochemical properties of layered LiNi1/3Co1/3Mn1/3O2positive electrode
material by zirconium doping,Solid State Ionics,Volume 189,Issue 1,6May 2011,
Pages 69-73).Chinese patent CN200710035746 filed in September in 2007 14 days discloses one kind in LiNi1/3Co1/ 3Mn1/3O2One layer of porous Al F of Surface coating3The method of film, this layer of porous membrane can suppress electrolyte between positive electrode
Side reaction, and then improve its chemical property under high magnification.Gao Po et al. have synthesized crystallization using sol-gel process
Well, the LiNi of nanometer-sized monodisperse1/3Co1/3Mn1/3O2Particle, higher capacity can be played in heavy-current discharge and circulation is protected
Holdup is (referring to document Po Gao, Gang Yang, Haidong Liu, Lu Wang, Haishan Zhou, Lithium
diffusion behavior and improved high rate capacity of LiNi1/3Co1/3Mn1/3O2as
cathode material for lithium batteries,Solid State Ionics 207(2012),50-56)。
But in actual applications, the NCM material specific surface areas of small particle are big, big with electrolyte contacts area therefore dynamic
Excellent in mechanical performance, but side reaction simultaneously is fast, storage performance is poor, according to above-mentioned bulk phase-doped or surface coating method, can damage
Lose discharge capacity or power-performance.Therefore, how to take into account power-performance and storage performance is always that lithium nickel cobalt manganese positive electrode material exists
The problem applied in big multiplying power or high power lithium ion cell.
The content of the invention
In view of problem present in background technology, it is an object of the invention to provide a kind of modified lithium nickel cobalt manganese positive electrode material
And preparation method thereof, it can take into account the power-performance of lithium ion battery, cycle performance and high-temperature storage performance.
In order to achieve the above object, in the first aspect of the present invention, the invention provides a kind of modified lithium nickel cobalt manganese positive pole
Material, its formula are LiaNixCoyMnzMγO2-δRδ.Wherein, 1.03≤a≤1.23,0<X≤0.9,0<Y≤1,0<Z≤1, x+y+
Z=1,0<γ≤0.075,0<δ≤0.05, doped chemical M be selected from Ni, Co, Mn, Sn, Mg, Ca, Ti, Zr, V, Nb, Mo, W, Al,
One or more in B, one or more of the doped chemical R in N, P, S, Si, Se, doped chemical M and doped chemical R are equal
Positioned at grain boundaries.
In the second aspect of the present invention, the invention provides a kind of preparation method of modified lithium nickel cobalt manganese positive electrode material, uses
In the modification lithium nickel cobalt manganese positive electrode material described in preparation first aspect present invention, including step：(1) nickel salt, cobalt salt, manganese salt are pressed
Atomic ratio Ni:Co:Mn=x:y:Z is made into mixed solution, and reaction is then added drop-wise to together with the solution of the first doped compound and is held
Reacted, reacted after terminating through being dried to obtain presoma (Ni in devicexCoyMnz)(OH)2/MγRδ, the first doped compound is selected from
MR、MR2、MR3、MR4、M3R2、M4R3、M2R、M2R3In one or more；(2) by presoma (NixCoyMnz)(OH)2/MγRδWith
Lithium salts presses atomic ratio Li:(Ni+Co+Mn)=a:1 uniformly mixing, Li is obtained through calciningaNixCoyMnzMγO2-δRδ, complete modified lithium
The preparation of nickel cobalt manganese anode material.Wherein, 1.03≤a≤1.23,0<X≤0.9,0<Y≤1,0<Z≤1, x+y+z=1,0<γ
≤ 0.075,0<δ≤0.05, the one kind of doped chemical M in Ni, Co, Mn, Sn, Mg, Ca, Ti, Zr, V, Nb, Mo, W, Al, B
Or several, one or more of the doped chemical R in N, P, S, Si, Se.
In the third aspect of the present invention, the invention provides the modified lithium nickel cobalt manganese positive electrode material of another kind, it includes：It is interior
Core；And clad, it is coated on the surface of kernel.Wherein, the kernel is according to first aspect present invention
LiaNixCoyMnzMγO2-δRδ.The formula of the clad is LiM 'cObOr M 'cOb, M ' be selected from Ni, Co, Mn, Sn, Mg, Ti, Zr,
V, the one or more in Nb, Mo, W, Al, B, Si, Zn, Bi, 0<C≤2,0<b/c≤3.
In the fourth aspect of the present invention, the invention provides the preparation method of another modified lithium nickel cobalt manganese positive electrode material,
For preparing the modification lithium nickel cobalt manganese positive electrode material described in third aspect present invention, including step：(1) by nickel salt, cobalt salt, manganese salt
By atomic ratio Ni:Co:Mn=x:y:Z is made into mixed solution, and reaction is then added drop-wise to together with the solution of the first doped compound
Reacted, reacted after terminating through being dried to obtain presoma (Ni in containerxCoyMnz)(OH)2/MγRδ, the choosing of the first doped compound
From MR, MR2、MR3、MR4、M3R2、M4R3、M2R、M2R3In one or more；(2) by presoma (NixCoyMnz)(OH)2/MγRδ
Atomic ratio Li is pressed with lithium salts:(Ni+Co+Mn)=a:1 uniformly mixing, Li is obtained through calciningaNixCoyMnzMγO2-δRδ；(3) by
One cladding compound L iM 'cObOr M 'cObWith LiaNixCoyMnzMγO2-δRδUniformly mixing, calcining, complete modified lithium nickel cobalt manganese just
The preparation of pole material.Wherein, 1.03≤a≤1.23,0<X≤0.9,0<Y≤1,0<Z≤1, x+y+z=1,0<γ≤0.075,0
<δ≤0.05,0<C≤2,0<B/c≤3, doped chemical M are selected from Ni, Co, Mn, Sn, Mg, Ca, Ti, Zr, V, Nb, Mo, W, Al, B
In one or more, one or more of the doped chemical R in N, P, S, Si, Se, M ' be selected from Ni, Co, Mn, Sn, Mg,
One or more in Ti, Zr, V, Nb, Mo, W, Al, B, Si, Zn, Bi.
Relative to prior art, beneficial effects of the present invention are：
In the present invention, crystal boundary doping, obtained modification lithium nickel cobalt manganese positive pole are carried out to conventional lithium nickel cobalt manganese positive electrode material
Material still has sufficiently stable structure during the repeated charge of heavy current.
Using the lithium ion battery of the modified lithium nickel cobalt manganese positive electrode material of the present invention, in HEV (hybrid vehicle), UPS electricity
When the fields such as source, electrokinetic cell (power-cell), start-stop power supply are applied, there is higher power out-put characteristic and good follow
Ring performance and high temperature storing stabilization, it can effectively meet lithium ion battery high power density, long life and high safety
The requirement of property.
Brief description of the drawings
Fig. 1 is the schematic diagram of modified lithium nickel cobalt manganese positive electrode material.
Embodiment
The following detailed description of modification lithium nickel cobalt manganese positive electrode material according to the present invention and preparation method thereof.
Illustrate modification lithium nickel cobalt manganese positive electrode material according to a first aspect of the present invention first.
The formula of modification lithium nickel cobalt manganese positive electrode material according to a first aspect of the present invention is LiaNixCoyMnzMγO2-δRδ.Its
In, 1.03≤a≤1.23,0<X≤0.9,0<Y≤1,0<Z≤1, x+y+z=1,0<γ≤0.075,0<δ≤0.05, doping member
One or more of the plain M in Ni, Co, Mn, Sn, Mg, Ca, Ti, Zr, V, Nb, Mo, W, Al, B, doped chemical R be selected from N, P,
S, the one or more in Si, Se, doped chemical M and doped chemical R are respectively positioned on grain boundaries.
In modification lithium nickel cobalt manganese positive electrode material described according to a first aspect of the present invention, crystal boundary refers to that structure is identical and takes
Interface between different crystal grain.Crystal boundary can be located inside primary particle, may be alternatively located at the inside of second particle.Reference picture 1,
1 represents crystal grain, and 2 represent crystal boundary.Doped chemical M and doped chemical R position can be confirmed by spherical aberration correction TEM Electronic Speculum.
In modification lithium nickel cobalt manganese positive electrode material described according to a first aspect of the present invention, doped chemical M and doped chemical R
Due to the reason such as ionic radius and electronic shell distribution, it is easy to be gathered in grain boundaries.So, doped chemical M and doped chemical R exist
Grain boundaries can play the interface impedance for reducing lithium ion in transmitting procedure, reduce the interface energy during the quick deintercalation of lithium ion
The effect at base, be advantageous to improve the power-performance of lithium ion battery, while obtained positive electrode is in the charge and discharge repeatedly of heavy current
Still there is sufficiently stable structure in electric process, finally improve cycle performance under the big multiplying power of lithium ion battery and high gentle
Store up performance.Routine it is bulk phase-doped in, doped chemical positioned at substitution transition metal ions position or lithium ion position, meeting
Gram volume performance and the voltage platform of lithium nickel cobalt manganese positive electrode material are influenceed, causes power density to be lost.In the Surface coating of routine
In, cladding element is only located at the surface of lithium nickel cobalt manganese positive electrode material, can not improve between internal grain the structural stability at interface and
Lithium ion transport properties, power-performance is caused to deteriorate.
In modification lithium nickel cobalt manganese positive electrode material described according to a first aspect of the present invention, the average grain diameter of primary particle
(D50) it is 0.1 μm~2 μm, the average grain diameter (D50) of second particle is 2 μm~7 μm.By further controlling being averaged for particle
Particle diameter, be advantageous to obtain the higher lithium ion battery of power density.
In modification lithium nickel cobalt manganese positive electrode material described according to a first aspect of the present invention, the modified lithium nickel cobalt manganese positive pole
The specific surface area of material is 0.3m2/ g~2m2/ g, preferably 0.8m2/ g~1.5m2/g.The modified lithium nickel cobalt manganese positive electrode material
Specific surface area within this range, be advantageous to further improve lithium ion battery power-performance.Specific surface area is excessive, described to change
The stability of property lithium nickel cobalt manganese positive electrode material decreases.
In modification lithium nickel cobalt manganese positive electrode material described according to a first aspect of the present invention, doped chemical M doping mistake
Height, it is unfavorable for the power of lithium ion battery and the lifting of energy density.Preferably, 0.0001≤γ≤0.02.
In modification lithium nickel cobalt manganese positive electrode material described according to a first aspect of the present invention, doped chemical R doping mistake
Height, it is unfavorable for the power of lithium ion battery and the lifting of energy density.Preferably, 0.0003≤δ≤0.015.
In modification lithium nickel cobalt manganese positive electrode material described according to a first aspect of the present invention, x, y, z is in following combinations
One kind：X=1/3, y=1/3, z=1/3；X=0.35, y=0.35, z=0.30；X=0.4, y=0.2, z=0.4；X=
0.5th, y=0.25, z=0.25；X=0.5, y=0.2, z=0.3；X=0.8, y=0.1, z=0.1；X=0.85, y=
0.075th, z=0.0075.
Secondly the preparation method of the modification lithium nickel cobalt manganese positive electrode material of explanation according to a second aspect of the present invention, for preparing this
Modification lithium nickel cobalt manganese positive electrode material described in invention first aspect, including step：(1) nickel salt, cobalt salt, manganese salt are pressed into atomic ratio
Ni:Co:Mn=x:y:Z is made into mixed solution, then is added drop-wise in reaction vessel with together with the solution of the first doped compound
Row reaction, reacts after terminating through being dried to obtain presoma (NixCoyMnz)(OH)2/MγRδ, the first doped compound be selected from MR,
MR2、MR3、MR4、M3R2、M4R3、M2R、M2R3In one or more；(2) by presoma (NixCoyMnz)(OH)2/MγRδWith lithium
Salt presses atomic ratio Li:(Ni+Co+Mn)=a:1 uniformly mixing, Li is obtained through calciningaNixCoyMnzMγO2-δRδ, complete modified lithium nickel
The preparation of cobalt manganese anode material.Wherein, 1.03≤a≤1.23,0<X≤0.9,0<Y≤1,0<Z≤1, x+y+z=1,0<γ≤
0.075,0<δ≤0.05, one kind in Ni, Co, Mn, Sn, Mg, Ca, Ti, Zr, V, Nb, Mo, W, Al, B of doped chemical M or
It is several, one or more of the doped chemical R in N, P, S, Si, Se.
In the preparation method of modification lithium nickel cobalt manganese positive electrode material described according to a second aspect of the present invention, the first dopingization
Compound adds during driving body before the synthesis, and the first doped compound shifts to an earlier date the grain edge aggregation in presoma, finally
While presoma is formed, due to the effect of surface energy, the first doped compound is easily adsorbed onto crystal edge, calcining when
It is diffused, reacts herein, the path of nucleation greatly shortens, and can reduce the temperature and time of calcining, forms crystal boundary doping.
In the preparation method of modification lithium nickel cobalt manganese positive electrode material described according to a second aspect of the present invention, in step (1)
First doped compound is selected from Mg3N2、WS2、MoS2、VP2、CoP3、MnP4、NiP2、NbP、Sn4P3、TiP2、ZrP2、WSe2、WP2、
One or more in TiP.
In the preparation method of modification lithium nickel cobalt manganese positive electrode material described according to a second aspect of the present invention, in step (1)
The pH value of reaction system is 10.8~12.0.Control the pH value of reaction system, be advantageous to obtain grain diameter is smaller and distribution more
The modification lithium nickel cobalt manganese positive electrode material of concentration.
In the preparation method of modification lithium nickel cobalt manganese positive electrode material described according to a second aspect of the present invention, in step (1)
Reaction temperature is 50 DEG C~80 DEG C.Controlling reaction temperature, be advantageous to obtain the modification lithium that grain diameter is smaller and distribution is more concentrated
Nickel cobalt manganese anode material.
In the preparation method of modification lithium nickel cobalt manganese positive electrode material described according to a second aspect of the present invention, in step (2)
Calcining heat is 400 DEG C~950 DEG C.
Illustrate modification lithium nickel cobalt manganese positive electrode material according to a third aspect of the present invention again, it is according to first party of the present invention
The alternate embodiment of modification lithium nickel cobalt manganese positive electrode material described in face.
Described modification lithium nickel cobalt manganese positive electrode material includes according to a third aspect of the present invention：Kernel；And clad, cladding
On the surface of kernel.Wherein, the kernel is the Li according to first aspect present inventionaNixCoyMnzMγO2-δRδ.The bag
The formula of coating is LiM 'cObOr M 'cOb, M ' is selected from Ni, Co, Mn, Sn, Mg, Ti, Zr, V, Nb, Mo, W, Al, B, Si, Zn, Bi
In one or more, 0<C≤2,0<b/c≤3.
In modification lithium nickel cobalt manganese positive electrode material described according to a third aspect of the present invention, while to the lithium nickel cobalt manganese of routine
Material carries out crystal boundary doping vario-property and surface coating modification.Doped chemical M and doped chemical R play reduction lithium ion in grain boundaries
Interface impedance in transmitting procedure, the effect of the interface energy barrier during the reduction quick deintercalation of lithium ion, while clad is also
Stable crystal interfacial structure can be played a part of, suppress positive electrode because the quick deintercalation of lithium ion causes surface lithium ion
Concentration is too low and generation situations such as causing phase transformation.Finally improve the circulation under the power-performance of lithium ion battery, big multiplying power
Performance and high-temperature storage performance.
In modification lithium nickel cobalt manganese positive electrode material described according to a third aspect of the present invention, M ' in clad with
LiaNixCoyMnzMγO2-δRδMol ratio be β:1, it is preferable that 0<β≤0.015.Within this range, be advantageous to obtain power
Can, the cycle performance under big multiplying power and high-temperature storage performance preferably lithium ion battery.β is excessive, the work(of lithium ion battery
Rate performance can be deteriorated.
Next the preparation method of the modification lithium nickel cobalt manganese positive electrode material of explanation according to a fourth aspect of the present invention, for preparing
Modification lithium nickel cobalt manganese positive electrode material described in third aspect present invention, including step：(1) nickel salt, cobalt salt, manganese salt are pressed into atomic ratio
Ni:Co:Mn=x:y:Z is made into mixed solution, then is added drop-wise in reaction vessel with together with the solution of the first doped compound
Row reaction, reacts after terminating through being dried to obtain presoma (NixCoyMnz)(OH)2/MγRδ, the first doped compound be selected from MR,
MR2、MR3、MR4、M3R2、M4R3、M2R、M2R3In one or more；(2) by presoma (NixCoyMnz)(OH)2/MγRδWith lithium
Salt presses atomic ratio Li:(Ni+Co+Mn)=a:1 uniformly mixing, Li is obtained through calciningaNixCoyMnzMγO2-δRδ；(3) by the first bag
Cover compound L iM 'cObOr M 'cObWith LiaNixCoyMnzMγO2-δRδUniformly mixing, calcining, complete modified lithium nickel cobalt manganese positive pole material
The preparation of material.Wherein, 1.03≤a≤1.23,0<X≤0.9,0<Y≤1,0<Z≤1, x+y+z=1,0<γ≤0.075,0<δ≤
0.05,0<C≤2,0<B/c≤3, doped chemical M is in Ni, Co, Mn, Sn, Mg, Ca, Ti, Zr, V, Nb, Mo, W, Al, B
One or more, one or more of the doped chemical R in N, P, S, Si, Se, M ' be selected from Ni, Co, Mn, Sn, Mg, Ti, Zr,
V, the one or more in Nb, Mo, W, Al, B, Si, Zn, Bi.
In the preparation method of modification lithium nickel cobalt manganese positive electrode material described according to a fourth aspect of the present invention, in step (3)
First cladding compound L iM 'cObOr M 'cObIn M ' and LiaNixCoyMnzMγO2-δRδMol ratio be β:1,0<β≤0.015.
In the preparation method of modification lithium nickel cobalt manganese positive electrode material described according to a fourth aspect of the present invention, in step (1)
First doped compound is selected from Mg3N2、WS2、MoS2、VP2、CoP3、MnP4、NiP2、NbP、Sn4P3、TiP2、ZrP2、WSe2、WP2、
One or more in TiP.
In the preparation method of modification lithium nickel cobalt manganese positive electrode material described according to a fourth aspect of the present invention, in step (3)
First cladding compound is selected from MgO, Al2O3、SiO2、ZrO2、ZnO、TiO2、B2O3、Bi2O3、Nb2O5、MoO2、MoO3、NiO、
MnO2、V2O5、WO2、WO3、SnO2、LiNbO3、Li2TiO3、Li2ZrO3、LiMn2O4、Li2MoO4In one or more.
In the preparation method of modification lithium nickel cobalt manganese positive electrode material described according to a fourth aspect of the present invention, in step (1)
The pH value of reaction system is 10.8~12.0.
In the preparation method of modification lithium nickel cobalt manganese positive electrode material described according to a fourth aspect of the present invention, in step (1)
Reaction temperature is 50 DEG C~80 DEG C.
In the preparation method of modification lithium nickel cobalt manganese positive electrode material described according to a fourth aspect of the present invention, in step (2)
Calcining heat is 400 DEG C~950 DEG C.
In the preparation method of modification lithium nickel cobalt manganese positive electrode material described according to a fourth aspect of the present invention, in step (3)
Calcining heat is 400 DEG C~950 DEG C.
With reference to embodiment, the application is expanded on further.It should be understood that these embodiments be merely to illustrate the application without
For limiting scope of the present application.
Comparative example 1
By NiSO4、CoSO4、MnSO4By atomic ratio Ni:Co:Mn=0.35:0.35:0.30 is made into mixed aqueous solution, its
In, the concentration of the summation of cation is 2mo1/L.
Mixed aqueous solution and 2mol/L NaOH solution, 3mol/L ammonia spirit are added drop-wise in reaction vessel jointly,
11.0 ± 0.2, heating water bath is reacted to 50 DEG C control system pH value.After the D50 of control sediment reaches 3 μm~4 μm
Stop charging, be aged 2h, precursor powder is obtained after press filtration, washing, forced air drying 8h.
By obtained precursor powder and lithium salts Li2CO3By atomic ratio Li:(Ni+Co+Mn)=1.1:1 ball milling mixing is equal
It is even, it is placed in the sintering furnace of air atmosphere, 18h is sintered at 910 DEG C, by grinding sub-sieve, that is, obtains layered crystal structure
The Li of pure phase1.1(Ni0.35Co0.35Mn0.30)O2Positive electrode.
Comparative example 2
By NiSO4、CoSO4、MnSO4By atomic ratio Ni:Co:Mn=0.35:0.35:0.30 is made into mixed aqueous solution, its
In, the concentration of the summation of cation is 2mo1/L.
Mixed aqueous solution and 2mol/L NaOH solution, 3mol/L ammonia spirit are added drop-wise in reaction vessel jointly,
11.0 ± 0.2, heating water bath is reacted to 50 DEG C control system pH value.After the D50 of control sediment reaches 3 μm~4 μm
Stop charging, be aged 2h, precursor powder is obtained after press filtration, washing, forced air drying 8h.
By obtained precursor powder and lithium salts Li2CO3, the first cladding compound ZrO2Ball milling mixing is uniform, wherein, it is former
Son compares Li:(Ni+Co+Mn)=1.1:1, atomic ratio Zr:(Ni+Co+Mn)=0.0005:1 (β=0.0005 in corresponding table 1),
It is placed in the sintering furnace of air atmosphere, 18h is sintered at 910 DEG C, by grinding sub-sieve, that is, obtaining Surface coating has ZrO2's
Li1.1(Ni0.35Co0.35Mn0.30)O2Positive electrode.
Comparative example 3
By ZrSO4、NiSO4、CoSO4、MnSO4By atomic ratio Ni:Co:Mn=0.35:0.35:0.30, atomic ratio Zr:(Ni
+ Co+Mn)=0.0005:1 (γ=0.0005 in corresponding table 1) is made into mixed aqueous solution, wherein, the summation of cation it is dense
Spend for 2mo1/L.
Mixed aqueous solution and 2mol/L NaOH solution, 3mol/L ammonia spirit are added drop-wise in reaction vessel jointly,
11.0 ± 0.2, heating water bath is reacted to 50 DEG C control system pH value.After the D50 of control sediment reaches 3 μm~4 μm
Stop charging, be aged 2h, the precursor powder of Zr doping is obtained after press filtration, washing, forced air drying 8h.
By obtained precursor powder and lithium salts Li2CO3By atomic ratio Li:(Ni+Co+Mn+Zr)=1.1:1 ball milling mixing
Uniformly, it is placed in the sintering furnace of air atmosphere, 18h is sintered at 910 DEG C, by grinding sub-sieve, that is, obtains layered crystal structure
Zr doping positive electrode.
Embodiment 1
By NiSO4、CoSO4、MnSO4By atomic ratio Ni:Co:Mn=0.35:0.35:0.30 is made into mixed aqueous solution, its
In, the concentration of the summation of cation is 2mo1/L.
By mixed aqueous solution, 2mol/L NaOH solution, 3mol/L ammonia spirit and the first doped compound ZrP2
Aqueous dispersions are added drop-wise in reaction vessel jointly, and 11.0 ± 0.2, heating water bath is reacted to 50 DEG C control system pH value.
Wherein, the first doped compound ZrP2Addition ensure press atomic ratio P:(Ni+Co+Mn)=0.0005:1 (i.e. δ=
0.0005, γ=0.00025).The D50 of control sediment stops charging after reaching 3 μm~4 μm, is aged 2h, by press filtration, washes
Wash, obtain precursor powder after forced air drying 8h.
By obtained precursor powder and lithium salts Li2CO3By atomic ratio Li:(Ni+Co+Mn)=1.1:1 ball milling mixing is equal
It is even, it is placed in the sintering furnace of air atmosphere, 18h is sintered at 910 DEG C, by grinding sub-sieve, that is, obtains adulterating in grain boundary sites
There are Zr and the positive electrode of P element, complete the preparation of final modified lithium nickel cobalt manganese positive electrode material.
Embodiment 2
By NiSO4、CoSO4、MnSO4By atomic ratio Ni:Co:Mn=0.35:0.35:0.30 is made into mixed aqueous solution, its
In, the concentration of the summation of cation is 2mo1/L.
By mixed aqueous solution, 2mol/L NaOH solution, 3mol/L ammonia spirit and the first doped compound ZrP2
Aqueous dispersions are added drop-wise in reaction vessel jointly, and 11.0 ± 0.2, heating water bath is reacted to 50 DEG C control system pH value.
Wherein, the first doped compound ZrP2Addition ensure press atomic ratio P:(Ni+Co+Mn)=0.0005:1 (i.e. δ=
0.0005, γ=0.00025).The D50 of control sediment stops charging after reaching 3 μm~4 μm, is aged 2h, by press filtration, washes
Wash, obtain precursor powder after forced air drying 8h.
By obtained precursor powder and lithium salts Li2CO3By atomic ratio Li:(Ni+Co+Mn)=1.1:1 ball milling mixing is equal
It is even, it is placed in the sintering furnace of air atmosphere, 18h is sintered at 910 DEG C, by grinding sub-sieve, that is, obtains adulterating in grain boundary sites
There are Zr and the positive electrode of P element.
By above-mentioned positive electrode powder and the first cladding compound ZrO2Ball milling mixing is uniform, wherein the first cladding compound
ZrO2Addition ensure press atomic ratio Zr:(Ni+Co+Mn)=0.0005:1 (i.e. β=0.0005), is placed in air atmosphere
In sintering furnace, 8h is sintered at 700 DEG C, by grinding sub-sieve, i.e., is carried out interface doping vario-property and surface coating modification simultaneously
Modification lithium nickel cobalt manganese positive electrode material.
Embodiment 3-14 preparation process is same as Example 2, and difference is the species of the first doped compound and its contained
Amount, the species of the first cladding compound and its content are different, for details, reference can be made to table 1 and draw.
Using the positive electrode prepared by than Surface Tester (Tristar302) test comparison example 1-3 and embodiment 1-14
Specific surface area BET, as a result referring to table 1.
By the positive electrode being prepared in comparative example 1-3 and embodiment 1-14 respectively with conductive agent super-P and CNT
Mixture, binding agent Kynoar (PVDF) press 94:2:1:3 mass ratio, mixed in 1-METHYLPYRROLIDONE (NMP) solvent
Close, 12h is stirred under normal temperature, transfer coated is on the Al paper tinsel collectors that thickness is 16 μm, through 120 DEG C of vacuum drying, cold pressing, cut-parts
Model 426080 is wound into graphite cathode piece, the lithium ion battery that capacity is 2Ah, electrolyte is using 1mol/L's after slitting
LiPF6As lithium salts, organic solvent uses EC/EMC=3:7 (V/V), barrier film use polypropylene (PP) perforated membrane.
Next the performance test of explanation lithium ion battery.
(1) the power-performance test of lithium ion battery
At 25 DEG C, constant-current charge, charge cutoff voltage 4.2V, with 4.2V constant-voltage charges are carried out with 0.4A current density
It is 0.1A to current density, then with 0.4A current density constant-current discharge to 2.8V, obtained discharge capacity is as lithium-ion electric
The rated capacity Cn (i.e. 100%SOC) in pond.
At 25 DEG C, with 0.2C current density, lithium ion battery is charged to the 50% (i.e. 50% of above-mentioned rated capacity
SOC), afterwards respectively at 25 DEG C and -20 DEG C, using 10C as pulse current, using HPPC method, at 25 DEG C and -20 DEG C of test
Lithium ion battery 50%SOC electric discharges 10s discharge energy density.
(2) the cycle performance test of lithium ion battery
At 25 DEG C, charge and discharge cycles test is carried out to lithium ion battery with 3C current density, voltage range is arranged to
2.8V~4.2V.
(3) the high-temperature storage performance test of lithium ion battery
At 25 DEG C, 4.2V is completely charged to 0.5C current density, is placed in 60 DEG C of insulating box after storing 30 days and takes afterwards
Go out, the volume of lithium ion battery is tested using drainage, and 2.8V is discharged to using 0.5C current density, test 100%SOC
Under recover capacity, and compared with volume and discharge capacity with testing to obtain at 25 DEG C, calculate lithium ion battery
Volume change and residual capacity conservation rate.
It can be seen that in comparative example 1 from the data of table 2 and lithium nickel cobalt manganese positive electrode material be not modified, lithium ion battery
Performance it is poor, especially power-performance is very poor.In comparative example 2 to lithium nickel cobalt manganese positive electrode material carry out Surface coating, lithium from
The cycle performance and high-temperature storage performance of sub- battery make moderate progress, but power-performance deteriorates.Comparative example 3 to lithium nickel cobalt manganese just
Pole material carries out the bulk phase-doped of routine, can play the effect for improving cycle performance to a certain extent, but can not take into account
Power-performance and high-temperature storage performance.
Interface doping vario-property, the power-performance of lithium ion battery, circulation are carried out in embodiment 1 to lithium nickel cobalt manganese positive electrode material
Performance and high-temperature storage performance are improved.Embodiment 2-14 carries out interface doping to lithium nickel cobalt manganese positive electrode material and changed simultaneously
Property and surface coating modification, on the one hand improve the power-performance under room temperature and low temperature, on the other hand take into account improve cycle performance and
High-temperature storage performance.
The announcement of book according to the above description, those skilled in the art in the invention can also be carried out to above-mentioned embodiment
Appropriate change and modification.Therefore, the invention is not limited in embodiment disclosed and described above, to the present invention's
Some modifications and changes should also be as falling into the scope of the claims of the present invention.In addition, although used in this specification
Some specific terms, but these terms are merely for convenience of description, do not form any restrictions to the present invention.
Claims (13)
- A kind of 1. modified lithium nickel cobalt manganese positive electrode material, it is characterised in thatThe formula of the modified lithium nickel cobalt manganese positive electrode material is LiaNixCoyMnzMγO2-δRδ；Wherein, 1.03≤a≤1.23,0<X≤0.9,0<Y≤1,0<Z≤1, x+y+z=1,0<γ≤0.075,0<δ≤0.05, One or more of the doped chemical M in Ni, Co, Mn, Sn, Mg, Ca, Ti, Zr, V, Nb, Mo, W, Al, B, doped chemical R choosings From the one or more in N, P, S, Si, Se, doped chemical M and doped chemical R are located at grain boundaries.
- 2. modified lithium nickel cobalt manganese positive electrode material according to claim 1, it is characterised in that 0.0001≤γ≤0.02, 0.0003≤δ≤0.015。
- 3. modified lithium nickel cobalt manganese positive electrode material according to claim 1, it is characterised in that the modified lithium nickel cobalt manganese positive pole The specific surface area of material is 0.3m2/ g~2m2/ g, preferably 0.8m2/ g~1.5m2/g。
- A kind of 4. preparation method of modified lithium nickel cobalt manganese positive electrode material, for preparing changing any one of claim 1-3 Property lithium nickel cobalt manganese positive electrode material, it is characterised in that including step：(1) nickel salt, cobalt salt, manganese salt are pressed into atomic ratio Ni:Co:Mn=x:y:Z is made into mixed solution, then adulterates chemical combination with first The solution of thing is added drop-wise in reaction vessel together to be reacted, and is reacted after terminating through being dried to obtain presoma (NixCoyMnz) (OH)2/MγRδ, the first doped compound is selected from MR, MR2、MR3、MR4、M3R2、M4R3、M2R、M2R3In one or more；(2) by presoma (NixCoyMnz)(OH)2/MγRδAtomic ratio Li is pressed with lithium salts:(Ni+Co+Mn)=a:1 uniformly mixing, warp Calcining obtains LiaNixCoyMnzMγO2-δRδ, complete the preparation of modified lithium nickel cobalt manganese positive electrode material；Wherein, 1.03≤a≤1.23,0<X≤0.9,0<Y≤1,0<Z≤1, x+y+z=1,0<γ≤0.075,0<δ≤0.05, One or more of the doped chemical M in Ni, Co, Mn, Sn, Mg, Ca, Ti, Zr, V, Nb, Mo, W, Al, B, doped chemical R choosings From the one or more in N, P, S, Si, Se.
- 5. the preparation method of modified lithium nickel cobalt manganese positive electrode material according to claim 4, it is characterised in that in step (1) First doped compound is selected from Mg3N2、WS2、MoS2、VP2、CoP3、MnP4、NiP2、NbP、Sn4P3、TiP2、ZrP2、WSe2、WP2、 One or more in TiP.
- 6. the preparation method of modified lithium nickel cobalt manganese positive electrode material according to claim 4, it is characterised in that in step (1) The pH value of reaction system is 10.8~12.0, and reaction temperature is 50 DEG C~80 DEG C in step (1).
- 7. a kind of modified lithium nickel cobalt manganese positive electrode material, including：Kernel；AndClad, it is coated on the surface of kernel；Characterized in that,The kernel is the Li according to any one of claim 1-3aNixCoyMnzMγO2-δRδ；The formula of the clad is LiM 'cObOr M 'cOb, M ' be selected from Ni, Co, Mn, Sn, Mg, Ti, Zr, V, Nb, Mo, W, Al, B, One or more in Si, Zn, Bi, 0<C≤2,0<b/c≤3.
- 8. modified lithium nickel cobalt manganese positive electrode material according to claim 7, it is characterised in that M ' in clad with LiaNixCoyMnzMγO2-δRδMol ratio be β:1,0<β≤0.015.
- A kind of 9. preparation method of modified lithium nickel cobalt manganese positive electrode material, for preparing changing any one of claim 7-8 Property lithium nickel cobalt manganese positive electrode material, it is characterised in that including step：(1) nickel salt, cobalt salt, manganese salt are pressed into atomic ratio Ni:Co:Mn=x:y:Z is made into mixed solution, then adulterates chemical combination with first The solution of thing is added drop-wise in reaction vessel together to be reacted, and is reacted after terminating through being dried to obtain presoma (NixCoyMnz) (OH)2/MγRδ, the first doped compound is selected from MR, MR2、MR3、MR4、M3R2、M4R3、M2R、M2R3In one or more；(2) by presoma (NixCoyMnz)(OH)2/MγRδAtomic ratio Li is pressed with lithium salts:(Ni+Co+Mn)=a:1 uniformly mixing, warp Calcining obtains LiaNixCoyMnzMγO2-δRδ；(3) by the first cladding compound L iM 'cObOr M 'cObWith LiaNixCoyMnzMγO2-δRδUniformly mixing, calcining, complete to be modified The preparation of lithium nickel cobalt manganese positive electrode material；Wherein, 1.03≤a≤1.23,0<X≤0.9,0<Y≤1,0<Z≤1, x+y+z=1,0<γ≤0.075,0<δ≤0.05, 0<C≤2,0<B/c≤3, one kind in Ni, Co, Mn, Sn, Mg, Ca, Ti, Zr, V, Nb, Mo, W, Al, B of doped chemical M or It is several, one or more of the doped chemical R in N, P, S, Si, Se, M ' be selected from Ni, Co, Mn, Sn, Mg, Ti, Zr, V, Nb, One or more in Mo, W, Al, B, Si, Zn, Bi.
- 10. the preparation method of modified lithium nickel cobalt manganese positive electrode material according to claim 9, it is characterised in that in step (3) First cladding compound L iM 'cObOr M 'cObIn M ' and LiaNixCoyMnzMγO2-δRδMol ratio be β:1,0<β≤0.015.
- 11. the preparation method of modified lithium nickel cobalt manganese positive electrode material according to claim 9, it is characterised in that in step (1) First doped compound is selected from Mg3N2、WS2、MoS2、VP2、CoP3、MnP4、NiP2、NbP、Sn4P3、TiP2、ZrP2、WSe2、WP2、 One or more in TiP.
- 12. the preparation method of modified lithium nickel cobalt manganese positive electrode material according to claim 9, it is characterised in that in step (3) First cladding compound is selected from MgO, Al2O3、SiO2、ZrO2、ZnO、TiO2、B2O3、Bi2O3、Nb2O5、MoO2、MoO3、NiO、 MnO2、V2O5、WO2、WO3、SnO2、LiNbO3、Li2TiO3、Li2ZrO3、LiMn2O4、Li2MoO4In one or more.
- 13. the preparation method of modified lithium nickel cobalt manganese positive electrode material according to claim 9, it is characterised in that in step (1) The pH value of reaction system is 10.8~12.0, and reaction temperature is 50 DEG C~80 DEG C in step (1).
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101300696A (en) * | 2006-05-10 | 2008-11-05 | 株式会社Lg化学 | Material for lithium secondary battery of high performance |
| CN103098272A (en) * | 2010-07-23 | 2013-05-08 | 住友金属矿山株式会社 | Positive electrode active material for nonaqueous electrolyte secondary battery, method for producing same, and nonaqueous electrolyte secondary battery |
| CN104218243A (en) * | 2014-07-01 | 2014-12-17 | 宁波金和锂电材料有限公司 | Highly stable lithium nickel cobalt aluminate positive electrode material and its preparation method |
| CN105406056A (en) * | 2015-12-31 | 2016-03-16 | 湖南桑顿新能源有限公司 | Long-cycle and high-safety power lithium ion battery positive electrode material and preparation method thereof |
| CN105609755A (en) * | 2016-02-29 | 2016-05-25 | 深圳市贝特瑞新能源材料股份有限公司 | Preparation method for positive electrode active material, and positive electrode active material |
-
2016
- 2016-07-06 CN CN201610527060.8A patent/CN107591519B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101300696A (en) * | 2006-05-10 | 2008-11-05 | 株式会社Lg化学 | Material for lithium secondary battery of high performance |
| CN103098272A (en) * | 2010-07-23 | 2013-05-08 | 住友金属矿山株式会社 | Positive electrode active material for nonaqueous electrolyte secondary battery, method for producing same, and nonaqueous electrolyte secondary battery |
| CN104218243A (en) * | 2014-07-01 | 2014-12-17 | 宁波金和锂电材料有限公司 | Highly stable lithium nickel cobalt aluminate positive electrode material and its preparation method |
| CN105406056A (en) * | 2015-12-31 | 2016-03-16 | 湖南桑顿新能源有限公司 | Long-cycle and high-safety power lithium ion battery positive electrode material and preparation method thereof |
| CN105609755A (en) * | 2016-02-29 | 2016-05-25 | 深圳市贝特瑞新能源材料股份有限公司 | Preparation method for positive electrode active material, and positive electrode active material |
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