CN107302087B - 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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- 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 is suitable for anode material of lithium battery field, provides a kind of lithium battery nickle cobalt lithium manganate tertiary cathode material and preparation method thereof, which comprises the different nickel-cobalt lithium manganate material of two groups of nickel contents of preparation；Covering material is prepared by aluminium salt and the colloidal sol containing cladding element；Two groups of nickel-cobalt lithium manganate materials of preparation are mixed according to certain mass than uniform, then are 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 mixing the nickel-cobalt lithium manganate material of different Ni contents, 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 stabilization.
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 cathodes
Material and preparation method thereof.
Background technique
Currently, serondary lithium battery is widely used in 3C number and electric car field, however for being by energy density
For the battery pack of the serondary lithium battery composition of 150-200Wh/Kg, it is growing that the energy of release is not able to satisfy people still
Demand, developing, there is the lithium battery of more high-energy-density to have become focus concerned by people.Nickle cobalt lithium manganate three compared with cobalt acid lithium
First positive electrode has many advantages, such as higher theoretical specific capacity, long-life, high security and low pollution, therefore, nickle cobalt lithium manganate
Tertiary cathode material has become one of lithium ion secondary battery instantly most with prospects.The most important spy of tertiary cathode material
Sign is specific capacity and cycle performance (service life), 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.
Usually there are three types of modes for the cyclical stability of raising tertiary cathode material: (1) reducing sintering temperature.Temperature is lower,
Lithium nickel mixing effect in tertiary cathode material is lower, and material structure is more stable, and cycle efficieny can then increase.But temperature
It is too low, it is easy to cause sintering insufficient, material surface remains excessive lithium salts, influences material property performance.Secondly, temperature mistake
Low to will lead to the reduction of lithium ion activity, there is excessive lithium vacancy in material internal, and the capacity for the first time for influencing material plays.(2) it mixes
Miscellaneous inert element.Existing research shows: it is advantageous that inert element (such as: Mg, Al) participates in building tertiary cathode material overall structure
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 inhibits the generation of irreversible transition.However, the incorporation of inert element can cause tertiary cathode material to discharge for the first time appearance
The generation of the reduction of amount, the negative effect may hinder it largely to apply in tertiary cathode material.(3) surface reconditioning.By
It is that cycle performance is caused to decline most important two in the generation of tertiary cathode material surface irreversible transition and particle microfissure
A factor.Therefore, thin in tertiary cathode material particle surface one layer of uniform metal oxide of cladding using surface restoration technique
Film, the film are able to suppress the irreversible transition of material surface, increase lithium ion transport channel, and inhibit material and electrolyte it
Between side reaction.Importantly, reasonable surface restoration technique can't reduce tertiary cathode material discharge capacity for the first time, because
And the technology is widely used in lithium battery industry.
Therefore lack lithium battery tertiary cathode a kind of while that there is height ratio capacity and preferable cycle performance currently on the market
Material.
Summary of the invention
In view of the above problems, the purpose of the present invention is 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 guarantee height ratio capacity simultaneously and preferably follow
The technical issues of ring performance.
On the one hand, the preparation method of the lithium battery nickle cobalt lithium manganate tertiary cathode material, includes the following steps:
Prepare two groups of different nickel-cobalt lithium manganate materials of nickel content；
Covering material is prepared by aluminium salt and the colloidal sol containing cladding element；
By two groups of nickel-cobalt lithium manganate materials of preparation according to certain mass than uniformly mixing, then it is mixed with the covering material
It closes, is then sintered in batch-type furnace, obtains the nickle cobalt lithium manganate tertiary cathode material.
Further, the step of preparing nickel-cobalt lithium manganate material is specific as follows:
By the ternary precursor containing nickel cobalt manganese and lithium source according to 1.00≤Li:(Ni+Co+Mn of molar ratio)≤1.10 uniformly
It mixes, then 5~20h of high temperature sintering in 700~950 DEG C of temperature ranges, and the oxygen content in environment is made to be greater than 20%, then
It pulverizes and sieves and prepares nickel-cobalt lithium manganate material；Assuming that two groups of nickel-cobalt lithium manganate materials of preparation 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 > n, and m+n ≠ x+ here
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:
Dry 5~10h after aluminium salt is mixed 0.5~3h with the colloidal sol containing cladding element, then produces gained after drying
Object roasts 1~10h in 150~750 DEG C of temperature ranges, and covering material is prepared.
Further, two groups of nickel-cobalt lithium manganate materials by preparation according to certain mass than uniformly 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, it is specific to wrap
It includes:
After two groups of nickel-cobalt lithium manganate material mass ratio 1:1 of preparation are uniformly mixed 0.5~2h to 9:1, 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 aluminium 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 50~300 DEG C, the sintering temperature being sintered in batch-type furnace
Degree is 200~700 DEG C.
On the other hand, the present invention also provides a kind of lithium battery nickle cobalt lithium manganate ternarys being prepared using the above method
Positive electrode.
The beneficial effects of the present invention are: the method comprises the steps of firstly, preparing two groups of nickel-cobalt lithium manganate material products, then, by above-mentioned two
Kind nickel-cobalt lithium manganate material uniformly mixes according to a certain percentage, and mixes, calcines with the aluminium salt containing cladding element, prepares 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, and by mixing the nickel-cobalt lithium manganate material of different Ni contents, material specific capacity can be improved；And
In covering material containing cladding element, be conducive to increase lithium ion transport channel, reduce cyclic process in irreversible transition and
Grain dusting, to improve the discharge capacity for the first time and cycle performance of material.
Detailed description of the invention
Fig. 1 is the process 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 finally obtained nickle cobalt lithium manganate tertiary cathode material stereoscan photograph in embodiment one；
Fig. 3 is embodiment two and one finished product material of comparative example under the conditions of 2.75V~4.3V and 25 DEG C, 45 DEG C, is followed
Relational graph between ring number and specific capacity.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
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, the following is a description of specific embodiments.
Fig. 1 shows the process of the preparation method of lithium battery nickle cobalt lithium manganate tertiary cathode material provided by the invention, is
Convenient for explanation, only parts related to embodiments of the present invention are shown.
As shown in Figure 1, the preparation method of the lithium battery nickle cobalt lithium manganate tertiary cathode material of this offer includes the following steps:
Step S101, the different nickel-cobalt lithium manganate material of two groups of nickel contents is prepared.
During preparing nickel-cobalt lithium manganate material, first by the ternary precursor containing nickel cobalt manganese and lithium source according to mole
Than 1.00≤Li:(Ni+Co+Mn)≤1.10 uniformly mixing, i.e. nickel in elemental lithium in lithium source and nickel-cobalt-manganese ternary presoma
The molar ratio of the sum of cobalt manganese element is between 1.00 to 1.10, and in this step, 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 make in environment
Oxygen content is greater 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 the nickel content used in two groups of nickel-cobalt lithium manganate materials in nickel-cobalt-manganese ternary presoma
It is different, it is assumed that two groups of nickel-cobalt lithium manganate materials being prepared are expressed as LiNi(1-x-y)CoxMnyO2(A1) and LiNi(1-m-n)
ComMnnO2(A2), 0.4≤x+y≤0.5, x≤y, 0.4≤m+n≤0.5, m > n, x, y, m, n are not 0 here, such 1-x-y
≠ 1-m-n, i.e. m+n ≠ x+y.
The mean particle size D for two groups of nickel-cobalt lithium manganate materials being finally prepared50Between 4~20 μm.
Step S102, the colloidal sol by aluminium salt and containing cladding element prepares covering material.
In this step, the aluminium salt is at least one of aluminium oxide, aluminium hydroxide, aluminum nitrate, aluminium carbonate, miserable miscellaneous packet
Covering element is at least one of Zr, Mg, Ti, Ce, La, Y, Si, Nb, Ba, V, Ni, Co, Mn.Specifically, by aluminium salt with it is described
The colloidal sol of cladding element mixes dry 5~10h after 0.5~3h, and drying temperature is 50~300 DEG C, then produces gained after drying
Object roasts 1~10h in 150~750 DEG C of temperature ranges, and covering material is prepared.
Step S103, by two groups of nickel-cobalt lithium manganate materials of preparation according to certain mass than uniformly mixing, then with the packet
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
After material uniformly mixes 0.5~2h, add the covering material according still further to 0.1~1% mass ratio and 0.5 is uniformly mixed~
3h, that is, the covering material added account for the 0.1% to 1% of A1, A2 gross mass, and 3~10h, sintering temperature are then sintered in batch-type furnace
Degree is 200~700 DEG C, can finally prepare the nickle cobalt lithium manganate tertiary cathode material.
The present invention mixes two kinds of nickel-cobalt-manganese ternary presomas with different Ni contents with lithium source respectively, then calcine,
Crush, sieving and etc., mean particle size D is prepared50Two kinds of nickel-cobalt lithium manganate material products between 4~20 μm；Then,
Above-mentioned two groups of materials are uniformly mixed according to 1:1~9:1, and mixes, calcine with the aluminium salt of the element containing cladding, prepare high 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 be uniformly wrapped on material surface to improve cycle performance.Manufacture craft of the present invention is simple, it is ensured that product
It can be excellent and stable.
Lower mask body is enumerated embodiment and comparative example and 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 molar 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
It after mixing 3h, is placed in 900 DEG C of batch-type furnaces and is sintered 15h, then take out sample comminution sieving and obtain nickel-cobalt lithium manganate material A1.
According to above step, Ni:Co:Mn=55:25:20 and 50=10 μm of mean particle size D of nickel cobalt manganese presoma are subjected to 900 DEG C of burnings
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 molar ratio Al:Zr=1:2, by nanoscale Al2O3150 DEG C are put into after stirring 1h in powder investment zirconium colloidal sol to do
It is put into 700 DEG C of batch-type furnaces after dry 10h in dry case and roasts 10h, prepare required covering material.
It is added in nickel-cobalt lithium manganate material upon mixing and prepares resulting covering material (Al content 3000ppm), and
It is put into 450 DEG C of batch-type furnaces after mixing 2h and roasts 8h.Gained sintered product is crossed and screens out iron, is preparing nickle cobalt lithium manganate ternary just
Pole finished material, stereoscan photograph are as shown in Figure 2.
Carrying out electrochemistry to gained finished-product material by the following method can be carried out test: the nickel cobalt synthesized with embodiment one
Lithium manganate material is positive active material, and lithium piece is cathode, is assembled into experimental button cell.The group of positive plate becomes m (active matter
Matter): m (acetylene black): m (PVDF)=80:12:8 is tested using Siken test macro, charging/discharging voltage be 2.75~
4.3V, charge-discharge magnification 1.0C carry out cycle performance test under room temperature (25 DEG C) environment, and at 25 DEG C, discharge specific volume for the first time
Amount can reach 173.3mAh/g, and it is 97.1% that first charge-discharge efficiency, which reaches 89.1%, 50th circle circulation conservation rate,.
Embodiment two:
Select Ni:Co:Mn=60:20:20 and mean particle size D50=15 μm of nickel-cobalt-manganese ternary presoma, according to molar 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
It after mixing 3h, is placed in 850 DEG C of batch-type furnaces and is sintered 13h, 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 molar ratio Al:Ce=3:1, by nanoscale Al2O3150 DEG C of drying boxes are put into after stirring 1h in investment zirconium colloidal sol
It is put into after interior dry 10h in 600 DEG C of batch-type furnaces and roasts 7h, prepare required covering material.
It is added in mixed nickel-cobalt lithium manganate material and prepares resulting covering material (Al content 2000ppm), and mixed
Roasting 8h in 450 DEG C of batch-type furnaces is put into after closing 2h.Gained sintered product is crossed and screens out iron, prepares nickle cobalt lithium manganate tertiary cathode
Finished material.
The production and performance test for detaining electricity are as in the first embodiment, under the conditions of 25 DEG C, above-mentioned finished-product material first discharge specific capacity
It can reach 178.7mAh/g, 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,
Appropriate lithium hydroxide is weighed according to molar ratio Li:(Ni+Co+Mn)=1.07.Nickel cobalt manganese presoma is set with lithium hydroxide respectively
It after mixing 3h in high-speed mixer, is placed in 850 DEG C of batch-type furnaces and is sintered 13h, then take out sample comminution and be sieved, 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 1000ppm) it is put into 600 DEG C of batch-type furnaces after mixing 1h and roasts 8h, obtain final nickle cobalt lithium manganate ternary material
Expect finished product.
The production and performance test for detaining electricity are as in the first embodiment, under the conditions of 25 DEG C, above-mentioned finished-product material first discharge specific capacity
It can reach 176.7mAh/g, 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 one finished product material of comparative example are under the conditions of 2.75V~4.3V and 25 DEG C, 45 DEG C, cycle-index
Relationship 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
After use, the remaining specific capacity of two battery of embodiment is much larger than comparative example one；On the other hand, identical in remaining battery specific capacity
In the case of, the cycle-index that two battery of embodiment 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 obtains, while there is 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 increase
Add lithium ion transport channel, reduce irreversible transition and granule atomization in cyclic process, so that the electric discharge for the first time 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 in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (7)
1. a kind of preparation method of lithium battery nickle cobalt lithium manganate tertiary cathode material, which is characterized in that the method includes following
Step:
Prepare two groups of different nickel-cobalt lithium manganate materials of nickel content；
Covering material is prepared by aluminium salt and the colloidal sol containing cladding element；
Two groups of nickel-cobalt lithium manganate materials of preparation are mixed according to certain mass than uniform, then are mixed with the covering material, so
It is sintered in batch-type furnace afterwards, obtains the nickle cobalt lithium manganate tertiary cathode material；
Wherein, the colloidal sol by aluminium salt and containing cladding element prepares covering material step, specifically includes:
Dry 5~10h after aluminium salt is mixed 0.5~3h with the colloidal sol containing cladding element, then exists products therefrom after drying
1~10h is roasted in 150~750 DEG C of temperature ranges, and covering material is prepared；
Wherein, two groups of nickel-cobalt lithium manganate materials by preparation according to certain mass than uniformly mixing, then with the cladding material
Material mixing, is then sintered in batch-type furnace, obtains the nickle cobalt lithium manganate tertiary cathode material step, specifically include:
After two groups of nickel-cobalt lithium manganate material mass ratio 1:1 of preparation are uniformly mixed 0.5~2h to 9:1, 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, prepares the nickel
Cobalt manganic acid lithium tertiary cathode material.
2. the preparation method of lithium battery nickle cobalt lithium manganate tertiary cathode material as described in claim 1, which is characterized in that prepare nickel
The step of cobalt lithium manganate material, is specific as follows:
By the ternary precursor containing nickel cobalt manganese and lithium source according to 1.00≤Li:(Ni+Co+Mn of molar ratio)≤1.10 uniformly mixed
It closes, then 5~20h of high temperature sintering in 700~950 DEG C of temperature ranges, and the oxygen content in environment is made to be greater than 20%, then powder
Nickel-cobalt lithium manganate material is prepared in broken sieving；Two groups of nickel-cobalt lithium manganate materials of preparation are expressed as LiNi(1-x-y)CoxMnyO2
And LiNi(1-m-n)ComMnnO2, 0.4≤x+y≤0.5, x≤y, 0.4≤m+n≤0.5, m > n, and m+n ≠ x+y here, x, y, m,
N is not 0.
3. the preparation method of lithium battery nickle cobalt lithium manganate tertiary cathode material as claimed in claim 2, which is characterized in that the lithium
Source is at least one of lithium carbonate, lithium hydroxide and lithium oxalate.
4. the preparation method of lithium battery nickle cobalt lithium manganate tertiary cathode material as described in claim 1, which is characterized in that preparation
The mean particle size D of every group of nickel-cobalt lithium manganate material50It is 4~20 μm.
5. the preparation method of lithium battery nickle cobalt lithium manganate tertiary cathode material as described in claim 1, which is characterized in that the packet
Covering element is at least one of Zr, Mg, Ti, Ce, La, Y, Si, Nb, Ba, V, Ni, Co, Mn.
6. the preparation method of lithium battery nickle cobalt lithium manganate tertiary cathode material as described in claim 1, which is characterized in that preparation packet
Covering the drying temperature in materials process is 50~300 DEG C, and the sintering temperature being sintered in batch-type furnace is 200~700 DEG C.
7. a kind of lithium battery nickle cobalt lithium manganate tertiary cathode material, which is characterized in that using as described in claim any one of 1-6
Method is made.
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| EP3974391A1 (en) * | 2020-09-24 | 2022-03-30 | SK Innovation Co., Ltd. | Cathode active material for lithium secondary battery and method of manufacturing the same |
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