CN109742336A - A kind of surface layer coats the tertiary cathode material and preparation method of tungstate lithium and doping W - Google Patents
A kind of surface layer coats the tertiary cathode material and preparation method of tungstate lithium and doping W Download PDFInfo
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- CN109742336A CN109742336A CN201811492423.4A CN201811492423A CN109742336A CN 109742336 A CN109742336 A CN 109742336A CN 201811492423 A CN201811492423 A CN 201811492423A CN 109742336 A CN109742336 A CN 109742336A
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Abstract
The present invention provides a kind of surface layer cladding tungstate lithium and adulterates the tertiary cathode material and preparation method of W.The preparation of presoma is using current industrialized hydroxide coprecipitation in the method for the invention, and method is easy, production cost is low, process conditions are mild.Using one-step method realization tungsten source is added, then increase temperature calcining and obtain, preparation method is simple in heretofore described preparation surface layer cladding tungstate lithium and the tertiary cathode material for adulterating W during presoma is mixed with lithium salts.The surface layer cladding tungstate lithium and the tertiary cathode material for adulterating W, which can improve nickelic tertiary cathode material, leads to material entirety poor circulation because surface structure is unstable in cyclic process, the chemical property and structural stability for improving tertiary cathode material in the present invention using both cladding and doping synergistic effect, to obtain high performance nickelic tertiary cathode material.
Description
Technical field
The present invention relates to a kind of surface layer cladding tungstate lithium and the tertiary cathode materials and preparation method of doping W, belong to chemistry
Energy-storage battery field.
Background technique
Lithium ion battery has many advantages, such as that energy force density is high, power density height, stable operating voltage, has extended cycle life, this
It determines its great development prospect in terms of new-energy automobile, has become electric car at present and hybrid vehicle is main
Power source.But the continuous promotion with people to electric car course continuation mileage demand, develop the lithium-ion electric of high-energy density
Pond is most important.Current commercialized power lithium-ion battery mainly has cobalt acid lithium, LiMn2O4, LiFePO4 and nickel-cobalt-manganese ternary
Battery, wherein nickel-cobalt-manganese ternary battery is shown one's talent due to its higher energy density, becomes next-generation high-performance power lithium battery
Main product.
Current commercialized ternary cell positive material is mainly nickelic anode (LiNixCoyMn1-x-yO2, x > 0.6), with
The raising of nickel content, circulation volume are gradually promoted, but its cyclical stability and safety gradually decrease.This is mainly due to
Ni2+With Li+Ionic radius is very close, during charge discharge, Ni2+It is easy to be migrated from the position 3b to the position 3a shape
At a cube rock salt phase, the scarce lithium degree in surface layer is more serious relative to ontology in addition, is more advantageous to Ni2+Migration, promote material table
Layer is constantly undergone phase transition, to destroy the electrochemical cycle stability of material.In addition during circulation, in active material table
Layer can increasingly generate one layer of solid electrolyte interface film (SEI), consume a large amount of Li+, simultaneously because the SEI film generated is uneven
Even, and electrolyte cannot be inhibited to contact with the direct of material surface, when height takes off lithium state, surface layer has a large amount of unstable
Fixed Ni4+, the decomposition of electrolyte is accelerated, while also promoting the transformation of material surface structure.As it can be seen that improving material surface knot
The stability of structure is most important for the performance for promoting material overall performance.
Currently, that is, ion doping and surface wrap there are mainly two types of the method for modifying of common nickelic tertiary cathode material surface layer
It covers.Ion doping can be improved the stability of layer structure, widen Li+Diffusion admittance.Surface cladding be able to suppress material with
Direct contact between electrolyte, the side reaction for reducing electrolyte and positive electrode occur, meanwhile, if clad is conductive is situated between
Matter can also promote the Li on positive electrode surface+Transmission, promotes the high rate performance of material.By rationally design by ion doping with
Surface cladding combines, and making the nickelic positive electrode of both modified synergic is the developing direction of the following study on the modification.
Summary of the invention
Lead to material entirety cyclicity because surface structure is unstable in cyclic process for nickelic tertiary cathode material
Can be poor the problems such as, the purpose of the present invention is to provide the tertiary cathode materials and preparation of a kind of surface layer cladding tungstate lithium and doping W
Method.
The invention provides the following technical scheme:
A kind of surface layer coats the tertiary cathode material of tungstate lithium and doping W, and the surface layer coats the three of tungstate lithium and doping W
First positive electrode includes nickel-cobalt-manganternary ternary anode material and the wolframic acid lithium layer being attached to except the nickel-cobalt-manganternary ternary anode material；
The nickel-cobalt-manganternary ternary anode material is LiNixCoyMn1-x-yO2, wherein x > 0.6, y > 0,1-x-y > 0；The nickel-cobalt-manganese ternary is just
Pole material extend internally 5-10nm region in adulterate W ion, formed W ion doped layer.
According to the present invention, the wolframic acid lithium layer being attached to except the nickel-cobalt-manganternary ternary anode material is completely coated with institute
It states nickel-cobalt-manganternary ternary anode material or the wolframic acid lithium layer being attached to except the nickel-cobalt-manganternary ternary anode material is incomplete
Ground coats the nickel-cobalt-manganternary ternary anode material；Preferably, the incompletely cladding includes point cladding or island cladding.
According to the present invention, the partial size of the surface layer cladding tungstate lithium and the tertiary cathode material for adulterating W is 8-12 microns.
According to the present invention, the doping of W ion described in the tertiary cathode material of the surface layer cladding tungstate lithium and doping W
It is the 0.5-2mol% of the nickel-cobalt-manganternary ternary anode material with the sum of the covering amount of the tungstate lithium.
The present invention also provides above-mentioned surface layer cladding tungstate lithium and the preparation methods for the tertiary cathode material for adulterating W comprising
Following step:
1) the presoma Ni of the nickel-cobalt-manganternary ternary anode material is preparedxCoyMn1-x-y(OH)2, wherein x > 0.6, y > 0,1-
x-y>0；
2) presoma of lithium hydroxide, the nickel-cobalt-manganternary ternary anode material of step 1) is mixed with ammonium metatungstate, then
Mixture is subjected to precalcining under oxygen atmosphere, then heats up and is calcined again, obtain the surface layer cladding tungstate lithium and is mixed
The tertiary cathode material of miscellaneous W.
According to the present invention, the presoma of the nickel-cobalt-manganternary ternary anode material of the step 1) is to make by the following method
For what is obtained:
The soluble inorganic salt of the soluble inorganic salt of nickel, the soluble inorganic salt of cobalt and manganese 1-1) is configured to salt-mixture
Solution；
1-2) under nitrogen protection, the mixing salt solution, sodium hydroxide solution, ammonium hydroxide of the step 1-1) are mixed,
Reaction, is prepared the presoma of the nickel-cobalt-manganternary ternary anode material.
Embodiment according to the present invention, step 1-1) in, the soluble inorganic salt of the soluble-salt of the nickel, the cobalt
And the soluble inorganic salt of the manganese is each independently sulfate, nitrate, chlorate or acetate, preferably sulfate；
Embodiment according to the present invention, the step 1-1) in, nickel in the mixing salt solution of the preparation, cobalt, manganese from
Sub- total concentration is 1.0~4.0mol/L；
Embodiment according to the present invention, the step 1-2) in, the solubility of the sodium hydroxide solution and the ammonium hydroxide
It is identical as salt-mixture solubility；
Embodiment according to the present invention, the step 1-2) in, reaction system is controlled using the sodium hydroxide solution
PH stablize in 11 ± 0.2 ranges；
Embodiment according to the present invention, the step 1-2) in, the temperature for controlling reaction is stablized in 50~55 DEG C of ranges
It is interior；The time of reaction is controlled within the scope of 2~8h；
Embodiment according to the present invention, the step 1-2) in, it is described mixing be at the uniform velocity be added dropwise the mixing salt solution,
The sodium hydroxide solution, the ammonium hydroxide, and the rate of addition for controlling the mixing salt solution and the ammonium hydroxide is consistent, pH passes through
The charging rate of regulation sodium hydroxide solution stablizes it in 11 ± 0.2 ranges, and control feed time is 4-8h；
Embodiment according to the present invention, the step 1-2) it is carried out in the reactor with agitating function, Xiang Suoshu
Deionized water is added in reactor as reactive group bottom liquid (dosage such as 50-100ml/ reaction system 500ml), and instills the ammonia
Water, adjustment pH are 11 ± 0.2, are passed through inert gas shielding, are stirred with the speed of 600r/min, at the uniform velocity into reaction vessel
The mixing salt solution, the sodium hydroxide solution, the ammonium hydroxide is added dropwise, controls the dropwise addition speed of the mixing salt solution and ammonium hydroxide
Degree is consistent, and pH stablizes it in 11 ± 0.2 ranges by regulating and controlling the charging rate of sodium hydroxide solution, and control feed time is
4-8h, while the temperature stabilization for controlling reaction continues to be passed through 2~8h of stirring of inert gas at 50~55 DEG C, after charging, it will
Obtained product utilization deionized water filtration washing, drying, obtain the presoma of nickel-cobalt-manganternary ternary anode material.
Embodiment according to the present invention, the step 1-2) in, the inert gas is one of nitrogen or argon gas；
Embodiment according to the present invention, the step 1-2) in, the dropwise addition speed of the mixing salt solution and the ammonium hydroxide
Degree is 0.2~0.5ml/min；
Embodiment according to the present invention, the step 1-2) in, the filtration washing at least carries out three times；
Embodiment according to the present invention, the step 1-2) in, the drying is 80 DEG C of dryings 24 under vacuum conditions
~48h.
Embodiment according to the present invention, in the step 2), the nickel cobalt of the mole of lithium hydroxide and the step 1)
The mole ratio of the presoma of manganese tertiary cathode material is 1.05:1, the nickel cobalt manganese of the mole of ammonium metatungstate and the step 1)
The mole ratio of the presoma of tertiary cathode material is 1:(600~2400).
Embodiment according to the present invention, in the step 2), the temperature range of the precalcining is 450-600 DEG C, excellent
It is selected as 500 DEG C；The time of the precalcining is 3~8h, preferably 5h；The temperature range of the calcining is 700-800 DEG C, preferably
It is 750 DEG C；The calcination time is 12~36h, preferably 15h.
Embodiment according to the present invention, in step 2), the calcining is carried out in tube furnace；The gas stream of oxygen
Speed is 100-500ml/min；The heating rate of two calcination stages is 1~3 DEG C/min.
Embodiment according to the present invention, in step 2), the ammonium metatungstate be preferably formulated to after aqueous solution again with hydrogen-oxygen
Change the presoma mixing of the nickel-cobalt-manganternary ternary anode material of lithium and step 1), the purpose is to ammonium metatungstates to be more conducive to it in the liquid phase
Dispersion, mixes it adequately with material；The mixing is preferably ground.
Embodiment according to the present invention, the preparation method include the following steps:
(1) by the soluble inorganic salt of the soluble inorganic salt of nickel, the soluble inorganic salt of cobalt and manganese by nickel, cobalt and manganese
The ratio that molar ratio is 8:1:1 is configured to mixing salt solution with deionized water, prepares sodium hydroxide solution and ammonium hydroxide；
(2) deionized water is added in reactor as reactive group bottom liquid, and instills ammonium hydroxide, adjustment pH is 11 ± 0.2, is passed through
Inert gas shielding is stirred with the speed of 600r/min, and mixing salt solution, sodium hydroxide are at the uniform velocity added dropwise into reaction vessel
Solution, ammonium hydroxide, the rate of addition for controlling mixing salt solution and ammonium hydroxide is consistent, the charging rate that pH passes through regulation sodium hydroxide solution
Stablize it in 11 ± 0.2 ranges, control feed time is 4-8h, while the temperature for controlling reaction is stablized at 50~55 DEG C,
Continue to be passed through 2~8h of stirring of inert gas after charging, by obtained product utilization deionized water filtration washing, be dried to obtain
A kind of presoma (Ni of nickel-cobalt-manganternary ternary anode material0.8Co0.1Mn0.1(OH)2)；
(3) by lithium hydroxide powder, ternary member positive electrode hydroxide precursor powder obtained above and metatungstic acid
Ammonium salt solution is uniformly mixed in mortar, then mixture is carried out precalcining under oxygen atmosphere under certain temperature, is then risen again
Temperature to certain temperature is calcined, and is obtained a kind of surface layer cladding tungstate lithium and is adulterated the tertiary cathode material of W.
Beneficial effects of the present invention:
The preparation of presoma is using current industrialized hydroxide coprecipitation, method letter in the method for the invention
Just, production cost is low, process conditions are mild.
Heretofore described preparation surface layer coats tungstate lithium and the tertiary cathode material of doping W is realized using one-step method,
Tungsten source is added during presoma is mixed with lithium salts, then increases temperature calcining and obtains, preparation method is simple.
Improve the chemical property and structure of tertiary cathode material in the present invention using both cladding and doping synergistic effect
Stability, to obtain high performance nickelic tertiary cathode material.
Detailed description of the invention
Fig. 1 is the X-ray diffraction of tertiary cathode material prepared by embodiment 1 and tertiary cathode material prepared by comparative example 1
(XRD) comparison diagram of spectrogram.
Fig. 2 is electron-microscope scanning (SEM) figure of tertiary cathode material prepared by embodiment 2.
Fig. 3 is electron-microscope scanning (SEM) figure of tertiary cathode material prepared by comparative example 1
Fig. 4 is energy spectrum analysis (EDS) figure of tertiary cathode material prepared by embodiment 2.
Fig. 5 is the X-ray photoelectricity of tertiary cathode material prepared by embodiment 2 and tertiary cathode material prepared by comparative example 1
Sub- energy spectrum analysis (XPS) figure.
Fig. 6 is that the charge and discharge of the tertiary cathode material of embodiment 1-3 preparation and the tertiary cathode material of the preparation of comparative example 1 follow
Ring performance map.
Specific embodiment
To be best understood from the present invention, the invention will be described in further detail combined with specific embodiments below.It should be understood that
, the specific embodiments described herein are merely illustrative of the invention, the protection being not intended to restrict the invention
Range.Furthermore, it is to be understood that those skilled in the art can make the present invention after having read documented content of the invention
Various changes or modification, such equivalent forms equally fall into protection scope of the present invention.
In following embodiment:
X-ray diffractometer: instrument model: Rigaku Ultima IV, Japan；
Scanning electron microscope (SEM): instrument model: FEI Quanta, Holland；
EDS power spectrum test: instrument model: Oxford INCA, Oxford Instruments (Shanghai) Co., Ltd.；
X-ray photoelectron spectroscopy: instrument model: EscaLab 250Xi, the U.S.；
Charge-discharge performance test: instrument model: LAND CT2001A, China.
Comparative example 1
The ratio of Ni:Co:Mn=8:1:1 weighs NiSO in molar ratio4·6H2O、CoSO4·7H2O and MnSO4·H2O is used
Deionized water is made into the mixing salt solution that Ni, Co, Mn total ion concentration are 2mol/L, then prepares same concentrations with deionized water
NaOH and ammonium hydroxide.
50mL deionized water is added into reaction kettle as reactive group bottom liquid, it is 11 ± 0.2 that ammonium hydroxide, which is added, and adjusts pH.It will stir
Mixing speed control is 600r/min, and reaction temperature control is 55 DEG C.Mixing salt solution and ammonium hydroxide are pumped with the speed of 0.4ml/min
Enter in reaction kettle, while adjusting sodium hydroxide solution charging rate stablizes pH in 11 ± 0.2, feed time 4h, charging knot
Continue to be passed through argon gas stirring 4h after beam.After the reaction was completed, sediment is utilized into deionized water filtration washing, drying, nickel cobalt is made
Presoma (the Ni of manganese tertiary cathode material0.8Co0.1Mn0.1(OH)2)。
By lithium hydroxide powder, above-mentioned Ni0.8Co0.1Mn0.1(OH)2Powder is uniformly mixed in mortar, then by mixture
It is placed in tube furnace under oxygen atmosphere in 500 DEG C of precalcining 5h, then heats up again 750 DEG C and calcine 15h, obtain corresponding ternary
Positive electrode.The wherein mole and Ni of lithium hydroxide0.8Co0.1Mn0.1(OH)2Mole ratio be 1.05:1, two calcination stages
Heating rate be 2 DEG C/min.
Embodiment 1
The ratio of Ni:Co:Mn=8:1:1 weighs NiSO in molar ratio4·6H2O、CoSO4·7H2O and MnSO4·H2O is used
Deionized water is made into the mixing salt solution that Ni, Co, Mn total ion concentration are 2mol/L, then prepares same concentrations with deionized water
NaOH and ammonium hydroxide.
50mL deionized water is added into reaction kettle as reactive group bottom liquid, it is 11 ± 0.2 that ammonium hydroxide, which is added, and adjusts pH.It will stir
Mixing speed control is 600r/min, and reaction temperature control is 55 DEG C.Mixing salt solution and ammonium hydroxide are pumped with the speed of 0.4ml/min
Enter in reaction kettle, while adjusting sodium hydroxide solution charging rate stablizes pH in 11 ± 0.2, feed time 4h, charging knot
Continue to be passed through argon gas stirring 4h after beam.After the reaction was completed, sediment is utilized into deionized water filtration washing, drying, be prepared
The presoma Ni of nickel-cobalt-manganternary ternary anode material0.8Co0.1Mn0.1(OH)2。
By lithium hydroxide powder, above-mentioned Ni0.8Co0.1Mn0.1(OH)2Powder and ammonium metatungstate solution mix in mortar
Uniformly, then by mixture it is placed in tube furnace under oxygen atmosphere in 500 DEG C of precalcining 5h, then heats up 750 DEG C and calcine again
15h obtains surface layer cladding tungstate lithium and adulterates the tertiary cathode material of W.Wherein the mole of lithium hydroxide with
Ni0.8Co0.1Mn0.1(OH)2Mole ratio be 1.05:1, the mole and Ni of ammonium metatungstate0.8Co0.1Mn0.1(OH)2Mole
For amount than being 1:600, the heating rate of two calcination stages is 2 DEG C/min.
Fig. 1 be the ternary of the tertiary cathode material using X-ray diffractometer prepare by embodiment 1 and the preparation of comparative example 1 just
The test analysis for the crystal structure that pole material carries out.It can be seen that there is no change for tertiary cathode material prepared by embodiment 1
The main crystal structure of original nickelic positive electrode, both typical α-NaFeO2Structure belongs to R-3m space group.But
It is found that the tertiary cathode material prepared in embodiment 1 shows the diffraction of tungstate lithium from 15 ° -30 ° of partial enlargement XRD diagram
Peak, this illustrates that material surface is successfully wrapped by.From Fig. 6 cycle performance, although material prepared by embodiment 1 holds in electric discharge
There is certain loss in amount, but whole stable circulation performance gets a promotion.
Embodiment 2
The ratio of Ni:Co:Mn=8:1:1 weighs NiSO in molar ratio4·6H2O、CoSO4·7H2O and MnSO4·H2O is used
Deionized water is made into the mixing salt solution that Ni, Co, Mn total ion concentration are 2mol/L, then prepares same concentrations with deionized water
NaOH and ammonium hydroxide.
50mL deionized water is added into reaction kettle as reactive group bottom liquid, it is 11 ± 0.2 that ammonium hydroxide, which is added, and adjusts pH.It will stir
Mixing speed control is 600r/min, and reaction temperature control is 55 DEG C.Mixing salt solution and ammonium hydroxide are pumped with the speed of 0.4ml/min
Enter in reaction kettle, while adjusting sodium hydroxide solution charging rate stablizes pH in 11 ± 0.2, feed time 4h, charging knot
Continue to be passed through argon gas stirring 4h after beam.After the reaction was completed, sediment is utilized into deionized water filtration washing, drying, be prepared
The presoma Ni of nickel-cobalt-manganternary ternary anode material0.8Co0.1Mn0.1(OH)2。
By lithium hydroxide powder, above-mentioned Ni0.8Co0.1Mn0.1(OH)2Powder and ammonium metatungstate solution mix in mortar
Uniformly, then by mixture it is placed in tube furnace under oxygen atmosphere in 500 DEG C of precalcining 5h, then heats up 750 DEG C and calcine again
15h obtains surface layer cladding tungstate lithium and adulterates the tertiary cathode material of W.Wherein the mole of lithium hydroxide with
Ni0.8Co0.1Mn0.1(OH)2Mole ratio be 1.05:1, the mole and Ni of ammonium metatungstate0.8Co0.1Mn0.1(OH)2Mole
For amount than being 1:1200, the heating rate of two calcination stages is 2 DEG C/min.
Fig. 2 and Fig. 3 is the tungstate lithium tertiary cathode material prepared using scanning electron microscope to embodiment 2 and comparison
The morphology analysis that tertiary cathode material prepared by example 1 carries out.It can be seen that tertiary cathode prepared by embodiment 2 from Fig. 2 and Fig. 3
Tertiary cathode material prepared by material and comparative example 1 is that the spherical second particle formed is assembled by primary particle, outside
It sees pattern to be consistent, particle diameter is 8-12 microns.Fig. 4 is ternary prepared by the embodiment 2 obtained using EDS energy spectrum analysis
The distribution diagram of element of positive electrode, as can be seen from Figure 4 Ni, Co, Mn, O and W Elemental redistribution are uniform.Fig. 5 is to utilize X-ray
The XPS of tertiary cathode material prepared by tertiary cathode material and comparative example 1 prepared by the embodiment 2 that XPS Analysis obtains
Spectrogram.From in left figure it can be seen that comparative example 1 in material surface Ni element mainly with Ni3+Form exists, wherein Ni2+/Ni3+
The ratio between be 0.43, and in example 2 since there are W in the surface layer of nickel-cobalt-manganternary ternary anode material6+Doping, according to charge
Balance theory, Ni in material surface2+Content rises, Ni2+/Ni3+The ratio between increase to 1.14.35.81eV and 37.97eV in right figure
Two peaks further demonstrate the presence of tungstate lithium clad and W doped layer in surface layer.It is real from Fig. 6 cycle performance
The stable circulation performance for applying the material of the preparation of example 2 is greatly improved.
Embodiment 3
The ratio of Ni:Co:Mn=8:1:1 weighs NiSO in molar ratio4·6H2O、CoSO4·7H2O and MnSO4·H2O is used
It is 2mol L that deionized water, which is made into Ni, Co, Mn total ion concentration,-1Mixing salt solution, then with deionized water prepare same concentrations
NaOH and ammonium hydroxide.
50mL deionized water is added into reaction kettle as reactive group bottom liquid, it is 11 ± 0.2 that ammonium hydroxide, which is added, and adjusts pH.It will stir
Mixing speed control is 600r/min, and reaction temperature control is 55 DEG C.Mixing salt solution and ammonium hydroxide are pumped with the speed of 0.4ml/min
Enter in reaction kettle, while adjusting sodium hydroxide solution charging rate stablizes pH in 11 ± 0.2, feed time 4h, charging knot
Continue to be passed through argon gas stirring 4h after beam.After the reaction was completed, sediment is utilized into deionized water filtration washing, drying, nickel cobalt is made
Presoma (the Ni of manganese tertiary cathode material0.8Co0.1Mn0.1(OH)2)。
By lithium hydroxide powder, above-mentioned cobalt-manganese ternary positive electrode material precursor (Ni0.8Co0.1Mn0.1(OH)2) powder and
Ammonium metatungstate solution is uniformly mixed in mortar, then mixture is placed in tube furnace under oxygen atmosphere in 500 DEG C of precalcinings
Then 5h heats up 750 DEG C again and calcines 15h, obtain a kind of surface layer cladding tungstate lithium and adulterate the tertiary cathode material of W.Wherein hydrogen
The mole and Ni of lithia0.8Co0.1Mn0.1(OH)2Mole ratio be 1.05:1, the mole of ammonium metatungstate with
Ni0.8Co0.1Mn0.1(OH)2Mole ratio be 1:2400, the heating rate of two calcination stages is 2 DEG C/min.
Fig. 6 is the charge and discharge cycles of tertiary cathode material prepared by embodiment 3 and tertiary cathode material prepared by comparative example 1
Performance map.In 2.8-4.35V voltage range, constant current charge-discharge test, the head week of the two are carried out under the current density of 190mA/g
Discharge capacity is respectively 168.2 and 169mAh/g, and after 50 weeks charge-discharge tests, the discharge capacity of embodiment 3 is still bright
The aobvious discharge capacity higher than comparative example 1, the surface layer cladding and doped scheme for showing the application are in the whole life cycle of battery
Front side technology effect is brought for a long time.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of surface layer cladding tungstate lithium and the tertiary cathode material for adulterating W, the surface layer cladding tungstate lithium and the ternary for adulterating W
Positive electrode includes nickel-cobalt-manganternary ternary anode material and the wolframic acid lithium layer being attached to except the nickel-cobalt-manganternary ternary anode material；Institute
Stating nickel-cobalt-manganternary ternary anode material is LiNixCoyMn1-x-yO2, wherein x > 0.6, y > 0,1-x-y > 0；The nickel-cobalt-manganese ternary anode
Material extend internally 5-10nm region in adulterate W ion, formed W ion doped layer.
2. surface layer cladding tungstate lithium according to claim 1 and the tertiary cathode material for adulterating W, wherein the surface layer packet
The partial size for covering tungstate lithium and adulterating the tertiary cathode material of W is 8-12 microns；Preferably, described to be attached to the nickel-cobalt-manganese ternary
Wolframic acid lithium layer except positive electrode is completely coated with the nickel-cobalt-manganternary ternary anode material or described is attached to the nickel cobalt
Wolframic acid lithium layer except manganese tertiary cathode material incompletely coats the nickel-cobalt-manganternary ternary anode material；Preferably, it is described not
It is completely coated with including coating or leading shape cladding.
3. surface layer cladding tungstate lithium according to claim 1 or 2 and the tertiary cathode material for adulterating W, wherein the surface layer
The sum of cladding tungstate lithium and the doping and the covering amount of the tungstate lithium that adulterate W ion described in the tertiary cathode material of W are
The 0.5-2mol% of the nickel-cobalt-manganternary ternary anode material.
4. the preparation method of the described in any item surface layer cladding tungstate lithiums of claim 1-3 and the tertiary cathode material for adulterating W,
Include the following steps:
1) the presoma Ni of the nickel-cobalt-manganternary ternary anode material is preparedxCoyMn1-x-y(OH)2, wherein x > 0.6, y > 0,1-x-y >
0；
2) presoma of lithium hydroxide, the nickel-cobalt-manganternary ternary anode material of step 1) is mixed with ammonium metatungstate, then will mixed
It closes object and carries out precalcining under oxygen atmosphere, then heat up and calcined again, obtain the surface layer cladding tungstate lithium and adulterate W's
Tertiary cathode material.
5. the preparation method according to claim 4, wherein before the nickel-cobalt-manganternary ternary anode material of the step 1)
Body is driven to be prepared via a method which to obtain:
1-1) that the soluble inorganic salt of the soluble inorganic salt of nickel, the soluble inorganic salt of cobalt and manganese is configured to salt-mixture is molten
Liquid；
1-2) under nitrogen protection, the mixing salt solution, sodium hydroxide solution, ammonium hydroxide of the step 1-1) are mixed, reaction,
The presoma of the nickel-cobalt-manganternary ternary anode material is prepared.
6. preparation method according to claim 5, wherein step 1-1) in, the soluble-salt of the nickel, the cobalt
The soluble inorganic salt of soluble inorganic salt and the manganese is each independently sulfate, nitrate, chlorate or acetate, preferably
For sulfate；
Preferably, the step 1-1) in, nickel in the mixing salt solution of the preparation, cobalt, manganese ion total concentration be 1.0~
4.0mol/L。
7. preparation method according to claim 5 or 6, wherein the step 1-2) in, the sodium hydroxide solution and institute
The solubility for stating ammonium hydroxide is identical as salt-mixture solubility；
Preferably, the step 1-2) in, the pH using sodium hydroxide solution control reaction system stablizes in 11 ± 0.2 models
In enclosing；
Preferably, the step 1-2) in, the temperature for controlling reaction is stablized within the scope of 50~55 DEG C；The time of control reaction exists
Within the scope of 2~8h；
Preferably, the step 1-2) in, it is described mixing be at the uniform velocity be added dropwise the mixing salt solution, the sodium hydroxide solution,
The ammonium hydroxide, and the rate of addition for controlling the mixing salt solution and the ammonium hydroxide is consistent, pH passes through regulation sodium hydroxide solution
Charging rate make its stablize in 11 ± 0.2 ranges, control feed time be 4-8h.
8. according to the described in any item preparation methods of claim 5-7, wherein the step 1-2) anti-with agitating function
It answers in device and carries out, deionized water is added in Xiang Suoshu reactor as reactive group bottom liquid (dosage such as 50-100ml/ reaction system
500ml), and the ammonium hydroxide is instilled, adjustment pH is 11 ± 0.2, is passed through inert gas shielding, is stirred with the speed of 600r/min
It mixes, the mixing salt solution, the sodium hydroxide solution, the ammonium hydroxide is at the uniform velocity added dropwise into reaction vessel, controls the mixing
The rate of addition of salting liquid and ammonium hydroxide is consistent, and pH stablizes it 11 ± 0.2 by regulating and controlling the charging rate of sodium hydroxide solution
In range, control feed time is 4-8h, while the temperature for controlling reaction is stablized at 50~55 DEG C, continues to be passed through after charging
Obtained product utilization deionized water filtration washing, drying are obtained nickel-cobalt-manganese ternary anode material by 2~8h of stirring of inert gas
The presoma of material；
Preferably, the step 1-2) in, the inert gas is one of nitrogen or argon gas；
Preferably, the step 1-2) in, the rate of addition of the mixing salt solution and the ammonium hydroxide is 0.2~0.5ml/min；
Preferably, in the step 2), before the nickel-cobalt-manganternary ternary anode material of the mole of lithium hydroxide and the step 1)
The mole ratio for driving body is 1.05:1, the forerunner of the mole of ammonium metatungstate and the nickel-cobalt-manganternary ternary anode material of the step 1)
The mole ratio of body is 1:(600~2400).
9. according to the described in any item preparation methods of claim 5-8, wherein in the step 2), the temperature of the precalcining
Section is 450-600 DEG C, preferably 500 DEG C；The time of the precalcining is 3~8h, preferably 5h；The humidity province of the calcining
Between be 700-800 DEG C, preferably 750 DEG C；The calcination time is 12~36h, preferably 15h.
Preferably, in step 2), the calcining is carried out in tube furnace；The gas flow rate of oxygen is 100-500ml/min；
The heating rate of two calcination stages is 1~3 DEG C/min.
10. according to the described in any item preparation methods of claim 5-9, wherein the preparation method includes the following steps:
(1) by the soluble inorganic salt of the soluble inorganic salt of nickel, the soluble inorganic salt of cobalt and manganese by nickel, mole of cobalt and manganese
It is configured to mixing salt solution with deionized water than the ratio for 8:1:1, prepares sodium hydroxide solution and ammonium hydroxide；
(2) deionized water is added in reactor as reactive group bottom liquid, and instills ammonium hydroxide, adjustment pH is 11 ± 0.2, is passed through inertia
Gas shield is stirred with the speed of 600r/min, and it is molten that mixing salt solution, sodium hydroxide are at the uniform velocity added dropwise into reaction vessel
Liquid, ammonium hydroxide, the rate of addition for controlling mixing salt solution and ammonium hydroxide is consistent, and pH is made by regulating and controlling the charging rate of sodium hydroxide solution
It is stablized in 11 ± 0.2 ranges, and control feed time is 4-8h, while the temperature for controlling reaction is stable at 50~55 DEG C, into
Continue to be passed through 2~8h of stirring of inert gas after material, by obtained product utilization deionized water filtration washing, is dried to obtain one
The presoma of kind nickel-cobalt-manganternary ternary anode material；
(3) lithium hydroxide powder, ternary member positive electrode hydroxide precursor powder obtained above and ammonium metatungstate is molten
Liquid is uniformly mixed in mortar, then mixture is carried out precalcining under oxygen atmosphere under certain temperature, is then warming up to again
Certain temperature is calcined, and is obtained surface layer cladding tungstate lithium and is adulterated the tertiary cathode material of W.
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