CN107302087A - A kind of lithium battery nickle cobalt lithium manganate tertiary cathode material and preparation method thereof - Google Patents
A kind of lithium battery nickle cobalt lithium manganate tertiary cathode material and preparation method thereof Download PDFInfo
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- CN107302087A CN107302087A CN201710624969.XA CN201710624969A CN107302087A CN 107302087 A CN107302087 A CN 107302087A CN 201710624969 A CN201710624969 A CN 201710624969A CN 107302087 A CN107302087 A CN 107302087A
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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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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The present invention is applied to anode material of lithium battery field there is provided a kind of lithium battery nickle cobalt lithium manganate tertiary cathode material and preparation method thereof, and methods described includes：Prepare two groups of different nickel-cobalt lithium manganate materials of nickel content；Colloidal sol by aluminium salt and containing cladding element prepares covering material；Two groups of nickel-cobalt lithium manganate materials of preparation are mixed according to certain mass than uniform, then mixed with the covering material, is then sintered in batch-type furnace, obtains the nickle cobalt lithium manganate tertiary cathode material.The present invention is by the way that the nickel-cobalt lithium manganate material of different Ni contents is mixed, material specific capacity can be improved, and the covering material containing at least one of Zr, Mg, Ti, Ce, La, Nb, Ba, V, Ni, Co, Mn, Al element is uniformly wrapped on material surface to improve cycle performance.Manufacture craft of the present invention is simple, it is ensured that excellent product performance and stably.
Description
Technical field
The invention belongs to anode material of lithium battery technical field, more particularly to a kind of lithium battery nickle cobalt lithium manganate tertiary cathode
Material and preparation method thereof.
Background technology
At present, serondary lithium battery is widely used in 3C numbers and electric automobile field, but for being by energy density
For the battery pack of 150-200Wh/Kg serondary lithium battery composition, it is growing that its energy discharged can not still meet people
Demand, lithium battery of the exploitation with more high-energy-density turns into focus of concern.Nickle cobalt lithium manganate three compared with cobalt acid lithium
The advantages of first positive electrode has higher theoretical specific capacity, long-life, high security and low stain, therefore, nickle cobalt lithium manganate
Tertiary cathode material turns into one of lithium rechargeable battery instantly most with prospects.The most important spy of tertiary cathode material
It is specific capacity and cycle performance (service life) to levy, and improves nickel content and surface in material and is modified as the main of tertiary cathode material
Developing direction.
In general, nickel content is higher in tertiary cathode material, the specific capacity of material is higher, but cyclical stability can be with
Decline.
Improving the cyclical stability of tertiary cathode material generally has three kinds of modes：(1) sintering temperature is reduced.Temperature is lower,
Lithium nickel mixing effect in tertiary cathode material is lower, and material structure is more stable, and cycle efficieny can then be raised.But, temperature
It is too low, it is easily caused and sinters insufficient, the excessive lithium salts of material surface residual, influence material property performance.Secondly, temperature mistake
Low to cause lithium ion activity reduction, there is excessive lithium room in material internal, and the capacity first of influence material is played.(2) mix
Miscellaneous inert element.There are some researches show：Inert element is (such as：Mg, Al etc.) participate in build tertiary cathode material overall structure it is favourable
In stabilizing material stratiform structure.In tertiary cathode material charge and discharge process, inert element is not involved in redox reaction, plays
Rock-steady structure, suppresses the generation of irreversible transition.However, the incorporation of inert element can cause tertiary cathode material to discharge first appearance
The reduction of amount, the generation of the negative effect may hinder it largely to apply in tertiary cathode material.(3) surface reconditioning.By
It is to cause cycle performance to decline topmost two in the generation of tertiary cathode material surface irreversible transition and particle microfissure
Individual factor.Therefore, it is thin in tertiary cathode material particle surface one layer of uniform metal oxide of cladding using surface restoration technique
Film, the film can suppress the irreversible transition of material surface, increase lithium ion transport passage, and suppress material and electrolyte it
Between side reaction.Importantly, rational surface restoration technique can't reduce tertiary cathode material discharge capacity first, because
And the technology is widely used in lithium battery industry.
Therefore lack in the market a kind of while having the lithium battery tertiary cathode of height ratio capacity and preferable cycle performance
Material.
The content of the invention
In view of the above problems, it is an object of the invention to provide a kind of lithium battery nickle cobalt lithium manganate tertiary cathode material and its
Preparation method, it is intended to which the lithium battery tertiary cathode material for solving existing method preparation can not be while ensureing height ratio capacity and preferably following
The technical problem of ring performance.
On the one hand, the preparation method of the lithium battery nickle cobalt lithium manganate tertiary cathode material, comprises the steps：
Prepare two groups of different nickel-cobalt lithium manganate materials of nickel content；
Colloidal sol by aluminium salt and containing cladding element prepares covering material；
By two groups of nickel-cobalt lithium manganate materials of preparation according to certain mass than uniform mixing, then it is mixed with the covering material
Close, then sintered in batch-type furnace, obtain the nickle cobalt lithium manganate tertiary cathode material.
Further, the step of preparing nickel-cobalt lithium manganate material is specific as follows：
By ternary precursor and lithium source containing nickel cobalt manganese according to 1.00≤Li of mol ratio:(Ni+Co+Mn) it is≤1.10 uniform
Mixing, then 5~20h of high temperature sintering in 700~950 DEG C of temperature ranges, and make the oxygen content in environment be more than 20%, then
Pulverize and sieve and prepare nickel-cobalt lithium manganate material；Assuming that the two groups of nickel-cobalt lithium manganate materials prepared are expressed as LiNi(1-x-y)
CoxMnyO2And LiNi(1-m-n)ComMnnO2, 0.4≤x+y≤0.5, x≤y, 0.4≤m+n≤0.5, m here>N, and m+n ≠ x+
Y, x, y, m, n are not 0.
Further, the colloidal sol by aluminium salt and containing cladding element prepares covering material step, specifically includes：
Aluminium salt is mixed with the colloidal sol containing cladding element 5~10h is dried after 0.5~3h, gained is produced after then drying
Thing is calcined 1~10h in 150~750 DEG C of temperature ranges, prepares covering material.
Further, two groups of nickel-cobalt lithium manganate materials by preparation according to certain mass than uniform mixing, then with institute
Covering material mixing is stated, is then sintered in batch-type furnace, obtains the nickle cobalt lithium manganate tertiary cathode material step, specific bag
Include：
By two groups of nickel-cobalt lithium manganate material mass ratioes 1 of preparation:1 to 9:After 1 0.5~2h of uniform mixing, according still further to 0.1~
1% mass ratio adds the covering material and uniformly mixes 0.5~3h, and 3~10h is then sintered in batch-type furnace, is prepared
The nickle cobalt lithium manganate tertiary cathode material.
Further, the lithium source is at least one of lithium carbonate, lithium hydroxide and lithium oxalate.
Further, the mean particle size D 50 of every group of nickel-cobalt lithium manganate material of preparation is 4~20 μm.
Further, the aluminium salt is at least one of aluminum oxide, aluminium hydroxide, aluminum nitrate, aluminium carbonate.
Further, the cladding element is at least one in Zr, Mg, Ti, Ce, La, Y, Si, Nb, Ba, V, Ni, Co, Mn
Kind.
Further, the drying temperature during preparation covering material is the sintering temperature of sintering in 50~300 DEG C, batch-type furnace
Spend for 200~700 DEG C.
On the other hand, present invention also offers the lithium battery nickle cobalt lithium manganate ternary that a kind of use above method is prepared
Positive electrode.
The beneficial effects of the invention are as follows：The method comprises the steps of firstly, preparing two groups of nickel-cobalt lithium manganate material products, then, by above-mentioned two
Plant nickel-cobalt lithium manganate material uniformly to mix according to a certain percentage, and mix, calcine with the aluminium salt containing cladding element, prepare height
Capacity and high circulation type nickle cobalt lithium manganate tertiary cathode material.The present invention is fine and close using material structure made from solid-phase synthesis,
Primary particle is uniform in size, by the way that the nickel-cobalt lithium manganate material of different Ni contents is mixed, can improve material specific capacity；And
In covering material containing cladding element, be conducive to increase lithium ion transport passage, reduce cyclic process in irreversible transition and
Grain efflorescence, so as to improve the discharge capacity first and cycle performance of material.
Brief description of the drawings
Fig. 1 is the flow of the preparation method of lithium battery nickle cobalt lithium manganate tertiary cathode material provided in an embodiment of the present invention
Figure；
Fig. 2 is the nickle cobalt lithium manganate tertiary cathode material stereoscan photograph finally given in embodiment one；
Fig. 3 be embodiment two and the finished product material of comparative example one under the conditions of 2.75V~4.3V and 25 DEG C, 45 DEG C, follow
Graph of a relation between ring number of times and specific capacity.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
In order to illustrate technical solutions according to the invention, illustrated below by specific embodiment.
Fig. 1 shows the flow of the preparation method for the lithium battery nickle cobalt lithium manganate tertiary cathode material that the present invention is provided, and is
It is easy to illustrate to illustrate only the part related to the embodiment of the present invention.
As shown in figure 1, the preparation method of the lithium battery nickle cobalt lithium manganate tertiary cathode material of this offer comprises the steps：
The different nickel-cobalt lithium manganate material of step S101, two groups of nickel contents of preparation.
During nickel-cobalt lithium manganate material is prepared, first by ternary precursor and lithium source containing nickel cobalt manganese according to mole
Than 1.00≤Li:(Ni+Co+Mn) it is≤1.10 uniform to mix, i.e., the nickel in the elemental lithium in lithium source and nickel-cobalt-manganese ternary presoma
The mol ratio of cobalt manganese element sum is between 1.00 to 1.10, in this step, and the lithium is that the lithium source is lithium carbonate, hydroxide
At least one of lithium and lithium oxalate；Then 5~20h of high temperature sintering in 700~950 DEG C of temperature ranges, and making in environment
Oxygen content is more than 20%, then pulverizes and sieves and prepares nickel-cobalt lithium manganate material.This step needs to prepare two groups of different Ni contents
Nickel-cobalt lithium manganate material A1 and A2, prepare two groups of nickel-cobalt lithium manganate materials used in nickel-cobalt-manganese ternary presoma in nickel content
It is different, it is assumed that the two groups of nickel-cobalt lithium manganate materials prepared are expressed as LiNi(1-x-y)CoxMnyO2And LiNi (A1)(1-m-n)
ComMnnO2(A2), 0.4≤x+y≤0.5, x≤y, 0.4≤m+n≤0.5, m here>N, x, y, m, n are not 0, such 1-x-y
≠ 1-m-n, i.e. m+n ≠ x+y.
The mean particle size D of the two groups of nickel-cobalt lithium manganate materials finally prepared50Between 4~20 μm.
Step S102, the colloidal sol by aluminium salt and containing cladding element prepare covering material.
In this step, the aluminium salt is at least one of aluminum oxide, aluminium hydroxide, aluminum nitrate, aluminium carbonate, miserable miscellaneous bag
It is at least one of Zr, Mg, Ti, Ce, La, Y, Si, Nb, Ba, V, Ni, Co, Mn to cover element.Specifically, by aluminium salt with it is described
The colloidal sol for coating element mixes dry 5~10h after 0.5~3h, and drying temperature is 50~300 DEG C, gained production after then drying
Thing is calcined 1~10h in 150~750 DEG C of temperature ranges, prepares covering material.
Step S103, by two groups of nickel-cobalt lithium manganate materials of preparation according to certain mass than uniform mixing, then with the bag
Material mixing is covered, is then sintered in batch-type furnace, obtains the nickle cobalt lithium manganate tertiary cathode material.
In this step, two groups of nickel-cobalt lithium manganate material A1 and A2 of preparation are according to mass ratio 1:1 to 9:1, then by two groups
Material is uniformly mixed after 0.5~2h, and the mass ratio addition covering material according still further to 0.1~1% and uniformly mixing 0.5~
3h, that is, the covering material added accounts for the 0.1% to 1% of A1, A2 gross mass, and 3~10h, sintering temperature are then sintered in batch-type furnace
Spend for 200~700 DEG C, can finally prepare the nickle cobalt lithium manganate tertiary cathode material.
The present invention mixes the nickel-cobalt-manganese ternary presoma that two kinds have different Ni contents with lithium source respectively, then calcine,
The steps such as crushing, sieving, prepare mean particle size D50Two kinds of nickel-cobalt lithium manganate material products between 4~20 μm；Then,
By above-mentioned two groups of materials according to 1:1~9:1 uniformly mixes, and mixes, calcines with the aluminium salt of the element containing cladding, prepares high power capacity
With high circulation type nickle cobalt lithium manganate tertiary cathode material.The present invention by the way that the nickel-cobalt lithium manganate materials of different Ni contents is mixed,
Material specific capacity can be improved, and at least one of Zr, Mg, Ti, Ce, La, Nb, Ba, V, Ni, Co, Mn, Al element will be contained
Covering material material surface is uniformly wrapped on to improve cycle performance.Manufacture craft of the present invention is simple, it is ensured that product
Can be excellent and stably.
Lower mask body enumerates embodiment and comparative example is also further illustrated.
Embodiment one：
Select Ni:Co:Mn=50:20:30 and mean particle size D50=10 μm of nickel-cobalt-manganese ternary presoma, according to mol ratio
Li:(Ni+Co+Mn) appropriate lithium hydroxide=1.03 is weighed.Nickel cobalt manganese presoma and lithium hydroxide are placed in high-speed mixer
Mix after 3h, be positioned over sintering 15h in 900 DEG C of batch-type furnaces, then take out sample comminution sieving and obtain nickel-cobalt lithium manganate material A1.
According to above step, by Ni:Co:Mn=55:25:20 and 50=10 μm of mean particle size D nickel cobalt manganese presoma carry out 900 DEG C burning
Knot, pulverizes and sieves and obtains nickel-cobalt lithium manganate material A2.Then, by above-mentioned two groups of nickel-cobalt lithium manganate materials according to mass ratio A1：A2
=1:1 mixing 1.5h.
According to mol ratio Al:Zr=1:2, by nanoscale Al2O3150 DEG C are put into powder input zirconium colloidal sol after stirring 1h to do
Dried in dry case and roasting 10h in 700 DEG C of batch-type furnaces is put into after 10h, prepare required covering material.
The covering material (Al content is 3000ppm) obtained by preparation is added in nickel-cobalt lithium manganate material upon mixing, and
Roasting 8h in 450 DEG C of batch-type furnaces is put into after mixing 2h.Gained sintered product is crossed and screens out iron, nickle cobalt lithium manganate ternary is being prepared just
Pole finished material, its stereoscan photograph is as shown in Figure 2.
Chemical property is carried out to gained finished-product material by the following method to test：The nickel cobalt synthesized with embodiment one
Lithium manganate material is positive active material, and lithium piece is negative pole, is assembled into experimental button cell.The composition of positive plate is m (active matters
Matter):M (acetylene black):M (PVDF)=80:12:8, tested using Siken test systems, charging/discharging voltage be 2.75~
4.3V, charge-discharge magnification is 1.0C, cycle performance test is carried out under normal temperature (25 DEG C) environment, at 25 DEG C, discharge specific volume first
Amount can reach 173.3mAh/g, and first charge-discharge efficiency reaches that 89.1%, 50th circle circulation conservation rates are 97.1%.
Embodiment two：
Select Ni:Co:Mn=60:20:20 and mean particle size D50=15 μm of nickel-cobalt-manganese ternary presoma, according to mol ratio
Li:(Ni+Co+Mn) appropriate lithium hydroxide=1.07 is weighed.Nickel cobalt manganese presoma and lithium hydroxide are placed in high-speed mixer
Mix after 3h, be positioned over sintering 13h in 850 DEG C of batch-type furnaces, then take out sample comminution sieving and obtain nickel-cobalt lithium manganate material A1.
According to above step, by Ni:Co:Mn=55:25:20 and mean particle size D50=5 μm of nickel cobalt manganese presoma carries out 900 DEG C of burnings
Knot, pulverizes and sieves and obtains nickel-cobalt lithium manganate material A2.Then, by nickle cobalt lithium manganate product in above-mentioned two according to mass ratio A1：A2
=4:1 mixing 1.5h.
According to mol ratio Al:Ce=3:1, by nanoscale Al2O3In input zirconium colloidal sol 150 DEG C of drying boxes are put into after stirring 1h
Roasting 7h in 600 DEG C of batch-type furnaces is put into after interior dry 10h, required covering material is prepared.
The covering material (Al content is 2000ppm) obtained by preparation is added in mixed nickel-cobalt lithium manganate material, and is mixed
Close and roasting 8h in 450 DEG C of batch-type furnaces is put into after 2h.Gained sintered product is crossed and screens out iron, nickle cobalt lithium manganate tertiary cathode is prepared
Finished material.
Detain making and the performance test be the same as Example one of electricity, under the conditions of 25 DEG C, above-mentioned finished-product material first discharge specific capacity
178.7mAh/g is can reach, first charge-discharge efficiency reaches 89.7%, 50thCircle circulation conservation rate is 96.8%；Under the conditions of 45 DEG C,
First discharge specific capacity reaches 185.4mAh/g, and first charge-discharge efficiency reaches 91.3%.
Comparative example one：
Select Ni:Co:Mn=60:20:20 and mean particle size D50Respectively 15 μm and 5 μm of nickel-cobalt-manganese ternary presoma,
According to mol ratio Li:(Ni+Co+Mn) appropriate lithium hydroxide=1.07 is weighed.Nickel cobalt manganese presoma is put with lithium hydroxide respectively
Mixed in high-speed mixer after 3h, be positioned over sintering 13h in 850 DEG C of batch-type furnaces, then taken out sample comminution and sieve, and according to
Mass ratio 4:1 mixing 1h.Thereafter, Al is added in above-mentioned mixed nickel-cobalt lithium manganate material2O3And CeO2(Al is powder
2000ppm, Ce are 1000ppm) roasting 8h in 600 DEG C of batch-type furnaces is put into after mixing 1h, obtain final nickle cobalt lithium manganate ternary material
Expect finished product.
Detain making and the performance test be the same as Example one of electricity, under the conditions of 25 DEG C, above-mentioned finished-product material first discharge specific capacity
176.7mAh/g is can reach, first charge-discharge efficiency reaches 84.6%, 50thCircle circulation conservation rate is 92.8%；Under the conditions of 45 DEG C,
First discharge specific capacity reaches 184.3mAh/g, and first charge-discharge efficiency reaches 89.7%.
Embodiment two and the finished product material of comparative example one are under the conditions of 2.75V~4.3V and 25 DEG C, 45 DEG C, cycle-index
Relation between specific capacity is as shown in Figure 3.As can be known from Fig. 3, under the conditions of 25 DEG C, 45 DEG C, by same loop number of times
After use, the remaining specific capacity of the battery of embodiment two is much larger than comparative example one；On the other hand, in remaining battery specific capacity identical
In the case of, the cycle-index that the battery of embodiment two can be used is much larger than comparative example one.Thus, it can be known that using the present embodiment method
The lithium battery that the lithium battery tertiary cathode material of preparation is obtained, while having height ratio capacity and preferable cycle performance.
To sum up, the present invention is fine and close using material structure made from solid-phase synthesis, and primary particle is uniform in size, is conducive to increasing
Plus lithium ion transport passage, irreversible transition and granule atomization in cyclic process are reduced, so that the electric discharge first for improving material is held
Amount and cycle performance.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
Any modifications, equivalent substitutions and improvements made within refreshing and principle etc., should be included in the scope of the protection.
Claims (10)
1. a kind of preparation method of lithium battery nickle cobalt lithium manganate tertiary cathode material, it is characterised in that methods described includes following
Step：
Prepare two groups of different nickel-cobalt lithium manganate materials of nickel content；
Colloidal sol by aluminium salt and containing cladding element prepares covering material；
Two groups of nickel-cobalt lithium manganate materials of preparation are mixed according to certain mass than uniform, then mixed with the covering material, so
Sintered afterwards in batch-type furnace, obtain the nickle cobalt lithium manganate tertiary cathode material.
2. the preparation method of lithium battery nickle cobalt lithium manganate tertiary cathode material as claimed in claim 1, it is characterised in that prepare nickel
The step of cobalt lithium manganate material, is specific as follows：
By ternary precursor and lithium source containing nickel cobalt manganese according to 1.00≤Li of mol ratio:(Ni+Co+Mn) it is≤1.10 uniform mixed
Close, then 5~20h of high temperature sintering in 700~950 DEG C of temperature ranges, and the oxygen content in environment is more than 20%, then powder
Nickel-cobalt lithium manganate material is prepared in broken sieving；Assuming that the two groups of nickel-cobalt lithium manganate materials prepared are expressed as LiNi(1-x-y)
CoxMnyO2And LiNi(1-m-n)ComMnnO2, 0.4≤x+y≤0.5, x≤y, 0.4≤m+n≤0.5, m here>N, and m+n ≠ x+
Y, x, y, m, n are not 0.
3. the preparation method of lithium battery nickle cobalt lithium manganate tertiary cathode material as claimed in claim 1, it is characterised in that described logical
Cross aluminium salt and the colloidal sol containing cladding element prepares covering material step, specifically include：
Aluminium salt is mixed with the colloidal sol containing cladding element 5~10h is dried after 0.5~3h, products therefrom exists after then drying
1~10h of roasting, prepares covering material in 150~750 DEG C of temperature ranges.
4. the preparation method of lithium battery nickle cobalt lithium manganate tertiary cathode material as claimed in claim 3, it is characterised in that described to incite somebody to action
The two groups of nickel-cobalt lithium manganate materials prepared are mixed according to certain mass than uniform mixing, then with the covering material, then in case
Sintered in formula stove, obtain the nickle cobalt lithium manganate tertiary cathode material step, specifically include：
By two groups of nickel-cobalt lithium manganate material mass ratioes 1 of preparation:1 to 9:After 1 0.5~2h of uniform mixing, according still further to 0.1~1%
Mass ratio add the covering material and uniformly mix 0.5~3h, 3~10h is then sintered in batch-type furnace, prepare described in
Nickle cobalt lithium manganate tertiary cathode material.
5. the preparation method of lithium battery nickle cobalt lithium manganate tertiary cathode material as described in any one of Claims 1 to 4, its feature exists
In the lithium source is at least one of lithium carbonate, lithium hydroxide and lithium oxalate.
6. the preparation method of lithium battery nickle cobalt lithium manganate tertiary cathode material as claimed in claim 5, it is characterised in that preparation
The mean particle size D of every group of nickel-cobalt lithium manganate material50It is 4~20 μm.
7. the preparation method of lithium battery nickle cobalt lithium manganate tertiary cathode material as claimed in claim 6, it is characterised in that the aluminium
Salt is at least one of aluminum oxide, aluminium hydroxide, aluminum nitrate, aluminium carbonate.
8. the preparation method of lithium battery nickle cobalt lithium manganate tertiary cathode material as claimed in claim 7, it is characterised in that the bag
It is at least one of Zr, Mg, Ti, Ce, La, Y, Si, Nb, Ba, V, Ni, Co, Mn to cover element.
9. the preparation method of lithium battery nickle cobalt lithium manganate tertiary cathode material as claimed in claim 8, it is characterised in that prepare bag
It is 200~700 DEG C to cover the sintering temperature that the drying temperature in materials process is sintering in 50~300 DEG C, batch-type furnace.
10. a kind of lithium battery nickle cobalt lithium manganate tertiary cathode material, it is characterised in that using such as any one of claim 1-9 institutes
Method is stated to be made.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108417797A (en) * | 2018-02-09 | 2018-08-17 | 山东丰元化学股份有限公司 | Nickelic tertiary cathode composite material and preparation method |
| CN108598388A (en) * | 2018-03-23 | 2018-09-28 | 格林美（无锡）能源材料有限公司 | A kind of C/SiO2Coat lithium electricity tertiary cathode material and preparation method thereof |
| CN108767221A (en) * | 2018-05-24 | 2018-11-06 | 北方奥钛纳米技术有限公司 | modified anode material of lithium battery, preparation method and lithium ion battery |
| CN109216665A (en) * | 2017-10-31 | 2019-01-15 | 格林美（无锡）能源材料有限公司 | Sb doped lead oxide coats nickel-cobalt lithium manganate cathode material and preparation method |
| CN109599540A (en) * | 2018-11-15 | 2019-04-09 | 北方奥钛纳米技术有限公司 | Active material and preparation method thereof, lithium ion battery |
| CN109616613A (en) * | 2018-10-17 | 2019-04-12 | 深圳市卓能新能源股份有限公司 | Battery anode slice and its manufacturing method and lithium ion battery and its manufacturing method |
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| CN112820861A (en) * | 2019-11-15 | 2021-05-18 | 深圳市贝特瑞纳米科技有限公司 | Cathode material, preparation method thereof and lithium ion battery |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101820063A (en) * | 2009-02-27 | 2010-09-01 | 株式会社日立制作所 | Positive electrode material for lithium ion secondary battery and lithium ion secondary battery using the same |
| CN103107337A (en) * | 2012-04-01 | 2013-05-15 | 湖南大学 | Method for improving cycling stability of lithium ion battery anode material |
| CN103326018A (en) * | 2013-07-04 | 2013-09-25 | 北大先行科技产业有限公司 | Uniform modified multihole anode material with controllable surface structures and preparation method of uniform modified multihole anode material |
| CN105355911A (en) * | 2015-11-28 | 2016-02-24 | 中信大锰矿业有限责任公司大新锰矿分公司 | Preparation method of aluminum oxide coated lithium nickel manganese cobalt cathode material |
-
2017
- 2017-07-27 CN CN201710624969.XA patent/CN107302087B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101820063A (en) * | 2009-02-27 | 2010-09-01 | 株式会社日立制作所 | Positive electrode material for lithium ion secondary battery and lithium ion secondary battery using the same |
| CN103107337A (en) * | 2012-04-01 | 2013-05-15 | 湖南大学 | Method for improving cycling stability of lithium ion battery anode material |
| CN103326018A (en) * | 2013-07-04 | 2013-09-25 | 北大先行科技产业有限公司 | Uniform modified multihole anode material with controllable surface structures and preparation method of uniform modified multihole anode material |
| CN105355911A (en) * | 2015-11-28 | 2016-02-24 | 中信大锰矿业有限责任公司大新锰矿分公司 | Preparation method of aluminum oxide coated lithium nickel manganese cobalt cathode material |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109216665A (en) * | 2017-10-31 | 2019-01-15 | 格林美（无锡）能源材料有限公司 | Sb doped lead oxide coats nickel-cobalt lithium manganate cathode material and preparation method |
| CN109962217A (en) * | 2017-12-25 | 2019-07-02 | 格林美（无锡）能源材料有限公司 | Lithium manganese silicate coated nickel-cobalt-manganese ternary material and preparation method thereof |
| CN108417797A (en) * | 2018-02-09 | 2018-08-17 | 山东丰元化学股份有限公司 | Nickelic tertiary cathode composite material and preparation method |
| CN108417797B (en) * | 2018-02-09 | 2020-08-28 | 山东丰元化学股份有限公司 | High-nickel ternary positive electrode composite material and preparation method thereof |
| CN108598388A (en) * | 2018-03-23 | 2018-09-28 | 格林美（无锡）能源材料有限公司 | A kind of C/SiO2Coat lithium electricity tertiary cathode material and preparation method thereof |
| CN108767221A (en) * | 2018-05-24 | 2018-11-06 | 北方奥钛纳米技术有限公司 | modified anode material of lithium battery, preparation method and lithium ion battery |
| CN109616613A (en) * | 2018-10-17 | 2019-04-12 | 深圳市卓能新能源股份有限公司 | Battery anode slice and its manufacturing method and lithium ion battery and its manufacturing method |
| CN109599540A (en) * | 2018-11-15 | 2019-04-09 | 北方奥钛纳米技术有限公司 | Active material and preparation method thereof, lithium ion battery |
| CN109830645A (en) * | 2018-12-18 | 2019-05-31 | 深圳市卓能新能源股份有限公司 | Battery anode slice and its manufacturing method and lithium battery and its manufacturing method |
| CN112820861A (en) * | 2019-11-15 | 2021-05-18 | 深圳市贝特瑞纳米科技有限公司 | Cathode material, preparation method thereof and lithium ion battery |
| CN112820861B (en) * | 2019-11-15 | 2024-06-07 | 深圳市贝特瑞纳米科技有限公司 | Positive electrode material, preparation method thereof and lithium ion battery |
| CN112174221A (en) * | 2020-08-27 | 2021-01-05 | 浙江美都海创锂电科技有限公司 | Reagent for wet coating of high-nickel ternary cathode material and preparation method and application thereof |
| US11973179B2 (en) | 2020-09-24 | 2024-04-30 | Sk On Co., Ltd. | Cathode active material for lithium secondary battery and method of manufacturing the same |
| CN114094059A (en) * | 2021-09-28 | 2022-02-25 | 格林美(湖北)新能源材料有限公司 | Composite nano-layer coated cobalt-free single crystal positive electrode material and preparation method thereof |
| CN113937267A (en) * | 2021-09-30 | 2022-01-14 | 蜂巢能源科技有限公司 | Cathode material, preparation method thereof, cathode comprising cathode material and lithium ion battery |
| CN113937267B (en) * | 2021-09-30 | 2023-03-10 | 蜂巢能源科技有限公司 | Cathode material, preparation method thereof, cathode comprising cathode material and lithium ion battery |
| CN117133919A (en) * | 2023-10-23 | 2023-11-28 | 宜宾锂宝新材料有限公司 | Modified lithium ion battery positive electrode material, preparation method thereof and lithium battery |
| CN117133919B (en) * | 2023-10-23 | 2024-01-19 | 宜宾锂宝新材料有限公司 | Modified lithium ion battery positive electrode material, preparation method thereof and lithium battery |
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