CN107293703A - A kind of modified tertiary cathode material and preparation method thereof - Google Patents
A kind of modified tertiary cathode material and preparation method thereof Download PDFInfo
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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Abstract
The present invention relates to a kind of modified tertiary cathode material and preparation method thereof, the positive electrode is the Li/Ni composite oxides that presoma coats M in concentration gradient distribution and material surface, and M is one or more of Al, Ti, Mg, Zn, Zr.The formula of this material is LiNixCoyMn1‑x‑yO2, wherein, the ＜ y ＜ 0.5 of 0.2 ＜ x ＜ 0.8,0.1, and x+y<1.The preparation of the material includes：NixCoyMn1‑x‑y(OH)2Preparation, material sintering and the cladding process of presoma.The presoma of the modification tertiary cathode material includes core and is coated on the outer layer shell parts of core, compared with the homogeneous tertiary cathode material of internal structure, the modification tertiary cathode material had both played higher specific discharge capacity, cyclical stability, processing characteristics and the security performance of material also have obvious improvement simultaneously, with higher superiority of effectiveness.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries technical field, more particularly to a kind of lithium ion
Battery modified tertiary cathode material and preparation method thereof.
Background technology
Lithium ion battery have voltage height, specific energy height, service life length, memory-less effect,
Environmental pollution is small, the low advantage of self-discharge rate, makes it in digital product, electric tool, electricity
It is used widely in the fields such as dynamic bicycle.Anode material for lithium-ion batteries is lithium ion battery
One of core material, the development of anode material of lithium battery and the close phase of the application of lithium ion battery
Close.Therefore, safe, inexpensive, high performance positive electrode is always lithium ion cell positive material
Expect the core of industry research.
The positive electrode of current industrialization mainly has LiCoO2, LiFePO4, Li2MnO4
And tertiary cathode material.Wherein LiCoO2It is still the most positive electrode of current consumption.But by
In LiCoO2Cost it is higher, battery production business actively finds new alternative materials.Lithium
Ion battery ternary material LiNixCoyMn1-x-yO2Due to possessing specific discharge capacity height, security
The advantages of good, cheap, non-environmental-pollution, has obtained the extensive concern of researcher.
However, lithium nickel-cobalt-manganese ternary positive electrode material is compared with lithium cobaltate cathode material, the former due to
Nickle atom with high level and the position for occupying lithium atom, cause surface exist it is more from
By lithium impurity, under the high temperature conditions, lithium impurity easily reacts with electrolyte and produces gas,
Cause lithium ion battery flatulence and deformation, there is great potential safety hazard.Simultaneously as high price
The presence of nickel, causes lithium nickel-cobalt-manganese ternary positive electrode material surface texture unstable, in discharge and recharge
Easily corroded in journey by hydrofluoric acid in electrolyte so that capacity of lithium ion battery decay compared with
It hurry up, limit the use of lithium ion battery.
For current lithium nickel-cobalt-manganese ternary positive electrode material present in lithium ion battery applications this
A little problems, can be modified in terms of presoma, while surface bag can also be carried out to material
Cover modification.By preparing the concentration gradient presoma with core shell structure, material can be improved and existed
Structural stability in cyclic process；By the way that electrolyte can be reduced to work in material surface cladding
The corrosion of property material, so as to effectively improve the cycle performance and security performance of lithium ion battery.
The content of the invention
The invention aims to overcome above-mentioned problem, there is provided a kind of modified lithium nickel cobalt
Manganese tertiary cathode material and preparation method thereof, on the basis of raw materials for production cost is not improved, leads to
Cross the regulation to component and the lifting of production Technology, synthesize a kind of with concentration gradient
Presoma, then carries out Surface coating processing, so as to reach improvement after oversintering to material again
The cycle performance of lithium nickel-cobalt-manganese ternary positive electrode material and the purpose of security performance.
In order to achieve the above object, the present invention has following technical scheme：
A kind of modified lithium nickel-cobalt-manganese ternary positive electrode material of the present invention, molecular formula is
LiNixCoyMn1-x-yO2, wherein the ＜ y ＜ 0.5 of 0.2 ＜ x ＜ 0.8,0.1, and x+y<1, it is used
Presoma includes core and is coated on the outer layer shell parts of core, point of the core
Minor is NimConMn1-m-n(OH)2, wherein, the ＜ n ＜ 0.5 of 0.5 ＜ m ＜ 1,0.05, and
m+n<1；The molecular formula of the outer layer shell parts is NikColMn1-k-l(OH)2, wherein, 0.2
The ＜ l ＜ 0.5 of ＜ k ＜ 0.8,0.1, and k+l<1；The positive electrode is coated with M, M be Al,
One or more of Ti, Mg, Zn, Zr.
The preparation method of described modification tertiary cathode material comprises the following steps：
(1) by soluble nickel salt, cobalt salt, manganese salt according to Ni:Co:Mn:=m:n:(1-m-n's) rubs
You are than being made into mixed solution A, and the total concentration of mixed solution A is 0.1-4mol/L；By solubility
Nickel salt, cobalt salt, manganese salt are according to Ni:Co:Mn:=k:l:The mol ratio of (1-k-l) is made into mixed solution B,
Mixed solution B total concentration is 0.1-4mol/L；Compound concentration is 1-10mol/L NaOH
Solution C；Compound concentration is 2-12mol/L ammonia spirit D；By measuring pump to reactor
In with certain flow simultaneously add tetra- kinds of solution of A, B, C, D, be sufficiently stirred for, control
Solution temperature is maintained at 40-70 DEG C in reactor, and the flow velocity of solution C is adjusted at any time, to keep
The pH value of solution is between 10-12 in reactor；Into reactor add A, B this two
When planting solution, it should be noted that adjust the flow velocity of both solution, make the presoma of preparation that concentration is presented
Gradient is distributed；Reaction uses deionized water after obtained precipitation is separated by centrifugal filtration after terminating
Washing is to neutrality, and drying 4-12h is obtained used in the modified ternary material at 80-200 DEG C
Presoma；
(2) presoma for obtaining lithium source and step (1) is according to mol ratio Li：(Ni+Co+Mn) etc.
Mixed, well mixed material is calcined in high temperature furnace, calcining heat in 1.0-1.2
For 800~1000 DEG C, calcination time is 8h~20h, then cool down, it is broken, crush, except iron,
Screening, obtains LiNixCoyMn1-x-yO2Material；
(3) by step (2) resulting materials LiNixCoyMn1-x-yO2Dry or wet cladding is carried out,
Dry method coats process：By LiNixCoyMn1-x-yO2Powder is with the compound containing M by melting
5-10h is calcined at 400-700 DEG C after conjunction machine is well mixed, obtains coating M's
LiNixCoyMn1-x-yO2Material；Wet method cladding will be prepared under aqueous systems or organic system
The compound solution containing M be added to LiNi obtained by step (2)xCoyMn1-x-yO2The slurry of preparation
In material, 0.5-4h is stirred, then vacuum drying is calcined 5-10h at 400-700 DEG C, wrapped
Cover M LiNixCoyMn1-x-yO2Material.
Nickel salt, cobalt salt and manganese salt described in step (1) be sulfate, acetate, nitrate,
One or more of chlorate.
Lithium source is one or more of lithium carbonate, lithium hydroxide, lithium nitrate described in step (2).
Compound containing M described in step (3) be aluminum oxide, aluminium isopropoxide, aluminum oxyhydroxide,
One or more of aluminum nitrate, isopropyl titanate, titanium oxide, zinc oxide, magnesia, zirconium oxide.
M covering amount described in step (3) is 0.03-3wt%.
The solid content of slurry described in step (3) is 10-50%, mixing speed 100-1000r/min.
Vacuum drying purpose described in step (3) is in order that coating process of the element in drying
The being evenly coated property kept, can also avoid Li in positive electrode+Excessive abjection, influence material
The chemical property such as the capacity of material and circulation.
Due to taking above technical scheme, the advantage of the invention is that：Pass through the side of the present invention
The lithium nickel-cobalt-manganese ternary positive electrode material of modification prepared by method, is by changing in the presoma stage first
Property, it is molten according to nickel, cobalt, manganese ternary salt on the premise of no raising presoma prepares cost
Liquid A and nickel, cobalt, manganese ternary salting liquid two kinds of salting liquids of B composition and ratio it is different and make
With the different combination of volume, the inhomogenous modified presoma of presoma internal structure is prepared, so
Afterwards again through oversintering and follow-up coating modification, a kind of modified tertiary cathode material is obtained.This changes
Property ternary material kernel portion there is higher specific capacity, the material of casing part has more
Stable chemical property, the composition of cladding can improve the cycle performance and security of material
Energy.Compared with the homogeneous ternary material of internal structure, the modification ternary material has higher put
Electric specific capacity, preferable cycle performance and security performance.
Brief description of the drawings
Fig. 1 is the XRD of embodiment 1 and comparative example 1；
Fig. 2 is the first charge-discharge curve map of embodiment 1 and comparative example 1；
Fig. 3 is the 1C cyclic curve figures for the positive electrode that embodiment 1 is prepared with comparative example 1.
Embodiment
By the following examples and Fig. 1-Fig. 3 to the present invention detailed process be described further,
These embodiments are provided only for the explanation present invention, be should not be understood to limit the present
Scope and spirit.
Comparative example 1：LiNi0.6Co0.2Mn0.2O2The preparation of positive electrode
Nickel sulfate, cobaltous sulfate and manganese sulfate are pressed into Ni：Co：Mn mol ratios are 0.6:0.2:0.2
It is configured to the salting liquid that concentration is 2mol/L.The salting liquid configured is noted with certain flow velocity
Enter in reactor, temperature of reaction kettle is constant at 60 DEG C.4mol/L is injected into reactor simultaneously
Ammoniacal liquor and 4mol/L NaOH solutions, adjust alkali soluble flow velocity, keep pH stable in 10-12
Between, it is fully injected into salting liquid in reactor, presoma prepares reaction and completed.Will reaction
After the completion of solidliquid mixture by centrifuging, washing at 120 DEG C to drying after neutrality
12h.By the presoma after drying and lithium carbonate according to mol ratio Li：(Ni+Co+Mn) it is equal to
1.10 are mixed, and are well mixed in batch mixer, 900 DEG C of calcining 12h in high temperature furnace,
Atmosphere is 3L/min oxygen.Material furnace cooling, crosses 325 mesh sieves, obtains pair after crushing
The LiNi of ratio 10.6Co0.2Mn0.2O2Positive electrode.Test the XRD of the ternary material, put
Electric specific capacity, circulation volume conservation rate.
Embodiment 1
Nickel sulfate, cobaltous sulfate and manganese sulfate are pressed into Ni：Co：Mn mol ratios are
0.65:0.175:0.175 is configured to the salting liquid A that concentration is 2mol/L, by nickel sulfate, sulfuric acid
Cobalt and manganese sulfate press Ni：Co：Mn mol ratios are 0.333:0.333:0.333, which is configured to concentration, is
2mol/L salting liquid B.By the salting liquid A configured and salting liquid B by measuring pump with
Certain flow velocity is injected in reactor simultaneously, and temperature of reaction kettle is constant at 60 DEG C.Simultaneously to anti-
The NaOH solution of ammoniacal liquor and 4mol/L that 4mol/L is injected in kettle is answered, alkali soluble flow velocity is adjusted,
PH stable is kept between 10-12.In whole course of reaction, by adjusting measuring pump
Accurate control salting liquid A and B flow velocity, make the precursor concentration distribution gradient of preparation.
By the solidliquid mixture after the completion of reaction by centrifuging, after washing to neutrality at 120 DEG C
12h is dried, Ni is made0.6Co0.2Mn0.2(OH)2Presoma.By the presoma and carbon after drying
Sour lithium is according to mol ratio Li：(Ni+Co+Mn) mixed equal to 1.10, in batch mixer
It is well mixed, 900 DEG C of calcining 12h in high temperature furnace, atmosphere is 3L/min oxygen.Material
Furnace cooling, crosses 325 mesh sieves after crushing, obtain presoma by modified
LiNi0.6Co0.2Mn0.2O2Positive electrode.
Embodiment 1 and the XRD of the gained sample of comparative example 1 are linearly sharp keen as seen from Figure 1,
Two curve comparisons, which have no other miscellaneous peaks, to be present, and shows that the gained sample of embodiment 1 has preferable layer
Shape structure, no dephasign is present.Sample is made after 2016 button cells, as shown in Fig. 2 real
Example 1 and the gained sample of comparative example 1 0.1C under 2.75-4.25V voltages is applied to discharge first specific volume
Amount is respectively 177mAh/g and 171.7mAh/g.Cycle performance is existed by 18650 batteries
2.8-4.2V carries out discharge and recharge assessment, as shown in figure 3, material shows good cycle performance,
Capability retention is respectively 95.4% and 91.7% after the circulation in 1C160 weeks of full electricity.
Comparative example 2：The inhomogenous LiNi of internal structure0.6Co0.2Mn0.2O2The preparation of positive electrode
Nickel sulfate, cobaltous sulfate and manganese sulfate are pressed into Ni：Co：Mn mol ratios are
0.65:0.175:0.175 is configured to the salting liquid A that concentration is 2mol/L, by nickel sulfate, sulfuric acid
Cobalt and manganese sulfate press Ni：Co：Mn mol ratios are 0.333:0.333:0.333, which is configured to concentration, is
2mol/L salting liquid B.Other steps are with comparative example 1.
Embodiment 2
The inhomogenous LiNi of internal structure obtained with comparative example 20.6Co0.2Mn0.2O2For matrix,
With HAlO2For silicon source, wet method cladding is carried out to it.2kg is added into stirring container
LiNi0.6Co0.2Mn0.2O2Added while stirring after material and 1kg deionized waters, stirring 0.5h
12.74g HAlO2Solution, continues to stir 1h after adding, and slurry then is transferred into rotation steams
Send out in container, be evaporated slurry using Rotary Evaporators, be put into high temperature furnace and calcine, 550 DEG C
Sinter and 325 mesh sieves are crossed after 8h, obtain coating 0.03%Al modification LiNi0.6Co0.2Mn0.2O2
Material.
Embodiment 2 is made after 2016 button cells with the gained sample of comparative example 2,
2.75-4.25V under voltage 0.1C first discharge specific capacities be respectively 178.5mAh/g and
177mAh/g, capability retention is respectively 99.8% and 95.4% after the circulation in 1C160 weeks of full electricity.
Embodiment 3-4
The inhomogenous LiNi of internal structure obtained with comparative example 20.6Co0.2Mn0.2O2For matrix,
Add the HAlO of different quality2Solution, the covering amount for making final aluminium is respectively 1%, 3%, its
His step be the same as Example 2.
Embodiment 5
The inhomogenous LiNi of internal structure obtained with comparative example 20.6Co0.2Mn0.2O2For matrix,
With Al2O3And TiO2For silicon source and titanium source, wet method cladding is carried out to it.Add into stirring container
Enter 2kg LiNi0.6Co0.2Mn0.2O2Material and 667g deionized waters, the stirring of stirring 0.5h back
Side addition disperses Al with deionized water2O3And TiO2The mixed solution of formation so that Al：
(Al+Ti) %=0.5, continues to stir 2h after adding, slurry then is transferred into rotary evaporation container
In, slurry is evaporated using Rotary Evaporators, is put into high temperature furnace and calcines, 500 DEG C of sintering 5h
325 mesh sieves are crossed afterwards, obtain the modification LiNi of cladding 0.03% (Al+Ti)0.6Co0.2Mn0.2O2Material
Material.
Embodiment 6-7
The inhomogenous LiNi of internal structure obtained with comparative example 20.6Co0.2Mn0.2O2For matrix,
Add the Al of different quality2O3And TiO2Dispersion mixing solution, makes final Al and Ti cladding
Total amount is respectively 1%, 3%, other step be the same as Examples 5.
Comparative example 3：LiNi0.7Co0.15Mn0.15O2The preparation of positive electrode
Nickel sulfate, cobaltous sulfate and manganese sulfate are pressed into Ni：Co：Mn mol ratios are 0.7:0.15:0.15
It is configured to the salting liquid that concentration is 2.5mol/L.By the salting liquid configured with certain flow velocity
Inject in reactor, temperature of reaction kettle is constant at 60 DEG C.5mol/L is injected into reactor simultaneously
Ammoniacal liquor and 5mol/L NaOH solution, adjust alkali soluble flow velocity, keep pH stable
Between 10-12, it is fully injected into salting liquid in reactor, presoma prepares reaction and completed.
By the solidliquid mixture after the completion of reaction by centrifuging, after washing to neutrality at 120 DEG C
Dry 12h.By the presoma after drying and lithium hydroxide according to mol ratio Li/ (Ni+Co+Mn)
Equal to 1.10 mixing, it is well mixed in batch mixer, 850 DEG C of calcining 12h in high temperature furnace,
Atmosphere is 5L/min oxygen.Material furnace cooling, crosses 325 mesh sieves, obtains pair after crushing
The LiNi of ratio 30.7Co0.15Mn0.15O2Positive electrode.
Embodiment 8
Nickel sulfate, cobaltous sulfate and manganese sulfate are pressed into Ni：Co：Mn mol ratios are 0.8:0.15:0.05
The salting liquid A that concentration is 2.5mol/L is configured to, nickel sulfate, cobaltous sulfate and manganese sulfate are pressed
Ni：Co：Mn mol ratios are 0.4:0.15:0.45 is configured to the salting liquid that concentration is 2.5mol/L
B.The salting liquid A configured and salting liquid B are noted simultaneously by measuring pump with certain flow velocity
Enter in reactor, temperature of reaction kettle is constant at 60 DEG C.5mol/L is injected into reactor simultaneously
Ammoniacal liquor and 5mol/L NaOH solution, adjust alkali soluble flow velocity, keep pH stable
Between 10-12.In whole course of reaction, salting liquid is accurately controlled by adjusting measuring pump
A and B flow velocity, makes the precursor concentration distribution gradient of preparation.By consolidating after the completion of reaction
Liquid mixture dries 12h after washing to neutrality by centrifuging at 120 DEG C, is made and divides
Minor is Ni0.7Co0.15Mn0.15(OH)2Presoma.By the presoma and lithium hydroxide after drying
It is equal to 1.10 mixing according to mol ratio Li/ (Ni+Co+Mn), is well mixed in batch mixer,
850 DEG C of calcining 12h in high temperature furnace, atmosphere is 5L/min oxygen.Material furnace cooling,
325 mesh sieves are crossed after crushing, presoma are obtained by modified LiNi0.7Co0.15Mn0.15O2
Positive electrode.
Embodiment 8 is made after 2016 button cells with the gained sample of comparative example 3,
2.75-4.25V under voltage 0.1C first discharge specific capacities be respectively 181.5mAh/g and
180.5mAh/g, capability retention is respectively 93.6% and 89.8% after the circulation in 1C160 weeks of full electricity.
Comparative example 4：The inhomogenous LiNi of internal structure0.7Co0.15Mn0.15O2The system of positive electrode
It is standby
Nickel sulfate, cobaltous sulfate and manganese sulfate are pressed into Ni：Co：Mn mol ratios are 0.8:0.15:0.05
The salting liquid A that concentration is 2.5mol/L is configured to, nickel sulfate, cobaltous sulfate and manganese sulfate are pressed
Ni：Co：Mn mol ratios are 0.4:0.15:0.45 is configured to the salting liquid that concentration is 2.5mol/L
B.Other steps are with comparative example 3.
Embodiment 9
The inhomogenous LiNi of internal structure obtained with comparative example 40.7Co0.15Mn0.15O2Positive pole material
Expect for matrix, with ZrO2For zirconium source, dry method cladding is carried out to it.2kg is weighed first
LiNi0.7Co0.15Mn0.15O2Material and 0.08g ZrO2First premix, then mixed with fusion machine,
Material after will be well mixed, which is put into high temperature furnace, to be calcined, and 325 mesh sieves are crossed after 650 DEG C of sintering 5h,
Obtain coating 0.03%Zr modification LiNi0.7Co0.15Mn0.15O2Material.
Embodiment 9 is made after 2016 button cells with the gained sample of comparative example 4,
2.75-4.25V under voltage 0.1C first discharge specific capacities be respectively 182.6mAh/g and
181.5mAh/g, capability retention is respectively 98.2% and 93.6% after the circulation in 1C160 weeks of full electricity.
Embodiment 10-11
The inhomogenous LiNi of internal structure obtained with comparative example 40.7Co0.15Mn0.15O2Positive pole material
Expect for matrix, the ZrO of addition different quality2, the covering amount for making final zirconium is respectively 1%, 3%,
Other step be the same as Examples 14.
Table 1：The manufacturing condition and electric performance test result of modified tertiary cathode material
Obviously, the above embodiment of the present invention is only intended to clearly illustrate the act that the present invention is made
Example, and it is not the restriction to embodiments of the present invention.For the ordinary skill of art
For personnel, other various forms of changes or change can also be made on the basis of the above description
It is dynamic.Here all embodiments can not be exhaustive.Every technical side for belonging to the present invention
Row of the obvious changes or variations that case is extended out still in protection scope of the present invention.
Claims (7)
1. a kind of modified tertiary cathode material, it is characterised in that：Molecular formula is
LiNixCoyMn1-x-yO2, wherein the ＜ y ＜ 0.5 of 0.2 ＜ x ＜ 0.8,0.1, and x+y<1, it is used
Presoma includes core and is coated on the outer layer shell parts of core, point of the core
Minor is NimConMn1-m-n(OH)2, wherein, the ＜ n ＜ 0.5 of 0.5 ＜ m ＜ 1,0.05, and
m+n<1；The molecular formula of the outer layer shell parts is NikColMn1-k-l(OH)2, wherein, 0.2
The ＜ l ＜ 0.5 of ＜ k ＜ 0.8,0.1, and k+l<1；The positive electrode is coated with M, M be Al,
One or more of Ti, Mg, Zn, Zr.
2. the preparation method of modified tertiary cathode material according to claim 1, it is special
Levy and be, comprise the following steps：
(1) by soluble nickel salt, cobalt salt, manganese salt according to Ni:Co:Mn:=m:n:(1-m-n's) rubs
You are than being made into mixed solution A, and the total concentration of mixed solution A is 0.1-4mol/L；By solubility
Nickel salt, cobalt salt, manganese salt are according to Ni:Co:Mn:=k:l:The mol ratio of (1-k-l) is made into mixed solution B,
Mixed solution B total concentration is 0.1-4mol/L；Compound concentration is 1-10mol/L NaOH
Solution C；Compound concentration is 2-12mol/L ammonia spirit D；By measuring pump to reactor
In with certain flow simultaneously add tetra- kinds of solution of A, B, C, D, be sufficiently stirred for, control
Solution temperature is maintained at 40-70 DEG C in reactor, and the flow velocity of solution C is adjusted at any time, to keep
The pH value of solution is between 10-12 in reactor；Into reactor add A, B this two
When planting solution, it should be noted that adjust the flow velocity of both solution, make the presoma of preparation that concentration is presented
Gradient is distributed；Reaction uses deionized water after obtained precipitation is separated by centrifugal filtration after terminating
Washing is to neutrality, and drying 4-12h is obtained used in the modified ternary material at 80-200 DEG C
Presoma；
(2) presoma for obtaining lithium source and step (1) is according to mol ratio Li：(Ni+Co+Mn) etc.
Mixed, well mixed material is calcined in high temperature furnace, calcining heat in 1.0-1.2
For 800~1000 DEG C, calcination time is 8h~20h, then cool down, it is broken, crush, except iron,
Screening, obtains LiNixCoyMn1-x-yO2Material；
(3) by step (2) resulting materials LiNixCoyMn1-x-yO2Dry or wet cladding is carried out,
Dry method coats process：By LiNixCoyMn1-x-yO2Powder is with the compound containing M by melting
5-10h is calcined at 400-700 DEG C after conjunction machine is well mixed, obtains coating M's
LiNixCoyMn1-x-yO2Material；Wet method cladding will be prepared under aqueous systems or organic system
The compound solution containing M be added to LiNi obtained by step (2)xCoyMn1-x-yO2The slurry of preparation
In material, 0.5-4h is stirred, then vacuum drying is calcined 5-10h at 400-700 DEG C, wrapped
Cover M LiNixCoyMn1-x-yO2Material.
3. preparation method according to claim 2, it is characterised in that institute in step (1)
State nickel salt, cobalt salt and manganese salt be in sulfate, acetate, nitrate, chlorate it is a kind of with
On.
4. preparation method according to claim 2, it is characterised in that institute in step (2)
It is one or more of lithium carbonate, lithium hydroxide, lithium nitrate to state lithium source.
5. preparation method according to claim 2, it is characterised in that institute in step (3)
It is aluminum oxide, aluminium isopropoxide, aluminum oxyhydroxide, aluminum nitrate, isopropyl to state the compound containing M
One or more of alcohol titanium, titanium oxide, zinc oxide, magnesia, zirconium oxide.
6. preparation method according to claim 2, it is characterised in that institute in step (3)
The covering amount for stating M is 0.03-3wt%.
7. preparation method according to claim 2, it is characterised in that institute in step (3)
The solid content for stating slurry is 10-50%, mixing speed 100-1000r/min.
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Cited By (13)
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| CN107785561A (en) * | 2017-11-22 | 2018-03-09 | 江门市科恒实业股份有限公司 | A kind of preparation method of high voltage monocrystalline lithium ion tertiary cathode material |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102306752A (en) * | 2011-08-11 | 2012-01-04 | 宁波金和新材料股份有限公司 | Surface coating technology of lithium ion battery cathode material |
| CN102347483A (en) * | 2011-10-11 | 2012-02-08 | 上海中兴派能能源科技有限公司 | Multilayer composite ternary material and precursor thereof as well as preparation method of multilayer composite ternary material and precursor |
| CN103367736A (en) * | 2012-04-06 | 2013-10-23 | 协鑫动力新材料（盐城）有限公司 | Surface clad lithium ion battery positive material precursor, and preparation method and application thereof |
| CN103367704A (en) * | 2012-04-06 | 2013-10-23 | 协鑫动力新材料（盐城）有限公司 | Gradient distribution multivariate composite material precursor as well as preparation method and application thereof |
| CN103840147A (en) * | 2012-11-22 | 2014-06-04 | 广饶格林新能源有限公司 | Preparation method for lithium ion battery anode material lithium manganese spinel oxide |
| CN104282880A (en) * | 2014-10-24 | 2015-01-14 | 湖南杉杉新材料有限公司 | Lithium-cobalt composite oxide lithium ion positive material and preparation method thereof |
-
2016
- 2016-04-12 CN CN201610223350.3A patent/CN107293703A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102306752A (en) * | 2011-08-11 | 2012-01-04 | 宁波金和新材料股份有限公司 | Surface coating technology of lithium ion battery cathode material |
| CN102347483A (en) * | 2011-10-11 | 2012-02-08 | 上海中兴派能能源科技有限公司 | Multilayer composite ternary material and precursor thereof as well as preparation method of multilayer composite ternary material and precursor |
| CN103367736A (en) * | 2012-04-06 | 2013-10-23 | 协鑫动力新材料（盐城）有限公司 | Surface clad lithium ion battery positive material precursor, and preparation method and application thereof |
| CN103367704A (en) * | 2012-04-06 | 2013-10-23 | 协鑫动力新材料（盐城）有限公司 | Gradient distribution multivariate composite material precursor as well as preparation method and application thereof |
| CN103840147A (en) * | 2012-11-22 | 2014-06-04 | 广饶格林新能源有限公司 | Preparation method for lithium ion battery anode material lithium manganese spinel oxide |
| CN104282880A (en) * | 2014-10-24 | 2015-01-14 | 湖南杉杉新材料有限公司 | Lithium-cobalt composite oxide lithium ion positive material and preparation method thereof |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107785561A (en) * | 2017-11-22 | 2018-03-09 | 江门市科恒实业股份有限公司 | A kind of preparation method of high voltage monocrystalline lithium ion tertiary cathode material |
| CN108134073A (en) * | 2017-12-25 | 2018-06-08 | 桑德集团有限公司 | A kind of tertiary cathode material and preparation method thereof |
| CN108134073B (en) * | 2017-12-25 | 2020-02-18 | 桑德新能源技术开发有限公司 | Ternary cathode material and preparation method thereof |
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| CN109461893B (en) * | 2017-12-29 | 2020-05-26 | 北京当升材料科技股份有限公司 | Novel lithium ion battery anode material and preparation method thereof |
| CN110034274A (en) * | 2018-01-11 | 2019-07-19 | 宁波纳微新能源科技有限公司 | Modified tertiary cathode material, preparation method and lithium ion battery |
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| CN114094085B (en) * | 2021-11-24 | 2023-07-21 | 蜂巢能源科技有限公司 | Positive electrode material and preparation method and application thereof |
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