CN102173465A - Method for preparing lithium nickel cobalt aluminum oxides serving as lithium ion battery positive electrode material - Google Patents
Method for preparing lithium nickel cobalt aluminum oxides serving as lithium ion battery positive electrode material Download PDFInfo
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Abstract
The invention relates to a method for preparing lithium nickel cobalt aluminum oxides serving as a high-capacity lithium ion battery positive electrode material, which comprises the following steps of: performing preoxidation roasting on nickel cobalt composite hydroxides or nickel cobalt composite carbonates by taking spherical nickel cobalt aluminum composite hydroxides or spherical nickel cobalt aluminum composite carbonates prepared by a coprecipitation method as a raw material to obtain uniform solid solution of high-valence state spherical nickel cobalt oxides in advance, so that all element are mixed in a molecular level; and mixing the preoxidized high-valence state nickel cobalt oxides and lithium salt uniformly, roasting at a high temperature under the atmosphere of oxygen, and cooling and crushing to obtain the lithium nickel cobalt aluminum oxide positive electrode material with a spherical structure. The prepared lithium nickel cobalt aluminum oxide positive electrode material has uniform granular distribution, discharging specific capacity of more than 185 mAh/g(4.3V vs Li), high circulating performance, a simple preparation process and low cost.
Description
Technical field
The present invention relates to belong to energy storage material and electrochemical field, especially a kind of preparation method of lithium ion battery anode material lithium nickel cobalt alumina.
Background technology
As the battery of the green high-capacity of a new generation, lithium ion battery has high energy density, and high advantages such as discharge platform have been widely used in the digital products such as mobile phone, digital camera, notebook computer.Development along with the technology of lithium ion battery requires lithium ion battery to have characteristics such as superpower, high-energy-density, low cost.Anode material for lithium-ion batteries is the important component part of lithium ion battery, is the major influence factors of lithium ion battery performance.At present, the positive electrode material of commercial applications mainly contains LiCoO2, LiMn2O4 and LiFePO4, and LiCoO2 is in occupation of most of market.Li
mNi
1-x-yCo
xAl
yO
2As a kind of heavy body (〉=190mAh/g) and the relatively low anode material for lithium-ion batteries of cost, be with the important materials of lithium ion battery applications to heavy body such as electromobile, storage station, military weapon, powerful industrial macrocell field.
The method of synthetic lithium nickel cobalt alumina positive electrode material comprises solid phase method, coprecipitation method, low fever solid phase reaction, complexometry, sol-gel method.Solid phase method technology is simple, and cost is low, but this method synthetic materials exists stable electrochemical property poor, and size distribution is inhomogeneous, shortcomings such as crystal morphology irregularity; Coprecipitation technology is simple relatively, the capacity height of synthetic materials, and good cycle is the synthetic at present the most promising method of lithium nickel cobalt alumina positive electrode material; The additive method complicated operation, the cost height.
During prior art for preparing lithium ion battery anode material lithium nickel cobalt alumina, general earlier nickel salt, cobalt salt and aluminium salt are prepared into co-precipitation nickelous cobalt precursor, should precipitate then and lithium salts carries out high-temperature calcination after mixing.Because nickelous at high temperature is difficult to be oxidized to nickelic, it is nickelic that people's oxidizer oxidation nickelous when liquid phase coprecipitation is also arranged, and for example, the Chinese Academy of Sciences's Chengdu organic chemistry Liu Xing of institute spring discloses a kind of anode material for lithium-ion batteries LiNi
1-xCo
xO
2Preparation method (CN1843930), this method comprises the mixing salt solution of preparation nickelous, cobalt, adds the mixing solutions and the violent stirring of alkaline precipitating agent and oxygenant, makes the Co in the solution
2+, Ni
2+Be oxidized to+3 valencys are with Ni
1-xCo
xThe form of OOH precipitates, after washing, the drying; With aforementioned presoma that obtains and lithium salts thorough mixing, under air atmosphere,, placed again 650-900 ℃ of calcination 4-48 hour in 300-500 ℃ of preheating 2-12 hour, naturally cool to room temperature.But adopt this kind liquid phase oxidation also to have some drawbacks, easily form flocks when precipitating and be difficult to filter, also be difficult to form spherical macrobead precipitation, need a large amount of oxygenants in addition, increase cost as trivalent ion.When adopting existing method to prepare lithium nickel cobalt alumina positive electrode material, shortcomings such as the reversible capacity that exists positive electrode material is low, stable circulation performance difference.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of lithium ion battery anode material lithium nickel cobalt alumina, the lithium nickel cobalt alumina crystal size that this method is prepared is evenly distributed, crystal morphology is regular, 2.80-4.3V between reversible capacity greater than 185mAh/g, and have good stable circulation performance.
For solving the problems of the technologies described above, technical scheme of the present invention is: a kind of preparation method of lithium ion battery anode material lithium nickel cobalt alumina may further comprise the steps:
(1) prepares spherical nickel-cobalt aluminum complex hydroxide presoma or spherical nickel-cobalt aluminium compound carbonate presoma with coprecipitation method;
(2), described presoma is carried out the preoxidation calcination processing separately, obtain the spherical nickel-cobalt aluminum oxide homogenous solid solution of high valence state;
(3) with the spherical nickel-cobalt aluminum oxide and the lithium salts uniform mixing of high valence state, high-temperature calcination in oxygen atmosphere is cooled off the back fragmentation and is obtained lithium nickel cobalt alumina positive electrode material.
The present invention adopts the pre-oxidation treatment technology, and presoma with before lithium salts mixes, is carried out oxidation pre-treatment to oxyhydroxide or carbonate precursor with certain temperature earlier, makes in advance that precursor decomposes, oxidation, forms the high valence state oxide compound homogenous solid solution of nickel cobalt; Again pretreated presoma is mixed with lithium salts, when carrying out high-temperature calcination, because in the presoma preprocessing process, the nickel cobalt has become high valence state oxide compound, and nickel cobalt and doped element have been diffuseed to form with respect to the more uniform sosoloid of presoma mutually by pre-burning, so when mixing the lithium salts high-temperature calcination, the reaction of lithium ion and nickel cobalt is easier to be carried out, material property can be more excellent.
As improvement, described spherical nickel-cobalt aluminum oxide chemical formula is Li
mNi
1-x-yCo
xAl
yO
2, 0.05＜x＜0.3,0＜y＜0.1,0.96＜m＜1.3 wherein.
As improvement, in the described step (1), with single nickel salt, rose vitriol and Tai-Ace S 150 is raw material, according to Ni: Co: Al mol ratio (0.7～0.8): (0.15～0.25): (0.02～0.06) prepares spherical nickel-cobalt aluminum complex hydroxide presoma or spherical nickel-cobalt aluminium compound carbonate presoma with coprecipitation method again.
As improvement, in the described step (2), described preoxidation incinerating atmosphere is oxygen.
As improvement, in the described step (2), described preoxidation calcination processing temperature is 300-850 ℃, and the treatment time is 1-9h.
As improvement, nickel cobalt aluminum complex hydroxide presoma or nickel cobalt aluminium compound carbonate presoma are placed resistance furnace, heat up ℃ with the speed of 8～12 ℃/min, preoxidation obtains the nickel cobalt aluminum composite oxide in oxygen atmosphere.
As improvement, in the described step (3), nickel cobalt aluminum composite oxide and lithium salts are pressed atomic ratio n
Li: (n
Ni+ n
Co+ n
Al)=(1.10～1.20): the mixed of (0.80～1.20) is a ball-milling medium with ethanol, and ball milling 3～5 hours evenly, after oven dry is placed on and slowly is warmed up to 650～850 ℃ in the resistance furnace in oxygen atmosphere, constant temperature 6～30 hours, naturally cooling, fragmentation obtains product after the classification.
As improvement, described lithium salts is a kind of in lithium hydroxide, Quilonum Retard, lithium nitrate, lithium chloride, lithium oxalate, the Lithium Acetate or several.
The beneficial effect that the present invention is compared with prior art brought is:
(1) significantly reduce the cost of anode material for lithium-ion batteries, adopt nickel content height in the synthetic material of the present invention and the content of cobalt only is 0.05-0.3 (atomic ratio), raw materials cost reduces greatly, has protected rare cobalt resource;
(2) the reversible specific capacity height of synthetic materials, good cycling stability, between the 2.8-4.3V scope, reversible specific capacity is greater than 185mAh/g;
(3) adopt method of the present invention, can obtain spherical presoma of high density type and spherical lithium nickel cobalt alumina positive electrode material, help improving the volume energy density of lithium ion battery.
Description of drawings
Fig. 1 is the SEM collection of illustrative plates of nickel cobalt aluminum complex hydroxide;
Fig. 2 is the SEM collection of illustrative plates of the product of embodiment 1;
Fig. 3 is the XRD figure spectrum of embodiment 1 product;
Fig. 4 is the first charge-discharge curve of embodiment 1 product;
Fig. 5 is the cycle performance figure of embodiment 1 product;
Fig. 6 is the XRD figure spectrum of embodiment 2 products;
Fig. 7 is the first charge-discharge curve of embodiment 2 products;
Fig. 8 is the cycle performance figure of embodiment 2 products;
Fig. 9 is the XRD figure spectrum of embodiment 3 products;
Figure 10 is the first charge-discharge curve of embodiment 3 products;
Figure 11 is the cycle performance figure of embodiment 3 products;
Figure 12 is the XRD figure spectrum of embodiment 4 products;
Figure 13 is the first charge-discharge curve of embodiment 4 products;
Figure 14 is the cycle performance figure of embodiment 4 products;
Figure 15 is the XRD figure spectrum of embodiment 5 products;
Figure 16 is the first charge-discharge curve of embodiment 5 products;
Figure 17 is the cycle performance figure of embodiment 5 products;
Figure 18 is the XRD figure spectrum of embodiment 6 products;
Figure 19 is the first charge-discharge curve of embodiment 6 products;
Figure 20 is the cycle performance figure of embodiment 6.
Embodiment
The invention will be further described below in conjunction with Figure of description.
Embodiment 1
(1) be raw material with single nickel salt, rose vitriol and Tai-Ace S 150, according to Ni: Co: Al mol ratio 0.70: 0.25: 0.05 prepares the complex hydroxide presoma of spherical nickel-cobalt aluminium by coprecipitation method;
(2) the complex hydroxide presoma with nickel cobalt aluminium places resistance furnace, is warming up to 300 ℃ with the speed of 8 ℃/min, is incubated 1 hour, and preoxidation obtains the composite oxides Li of nickel cobalt aluminium in oxygen atmosphere
mNi
1-x-yCo
xAl
yO
2, x=0.25, y=0.05, m=1.0;
(3) composite oxides and the lithium hydroxide of nickel cobalt aluminium are pressed atomic ratio n
Li: (n
Ni+ n
Co+ n
AlThe mixed of)=1.10: 0.80 is a ball-milling medium with ethanol, and ball milling 3 hours evenly, after oven dry is placed on and slowly is warmed up to 600 ℃ in the resistance furnace in oxygen atmosphere, constant temperature 10 hours, naturally cooling, fragmentation, classification promptly obtains nickelic lithium nickel cobalt alumina positive electrode material.
Embodiment 2
(1) be raw material with single nickel salt, rose vitriol and Tai-Ace S 150, according to Ni: Co: Al mol ratio 0.73: 0.25: 0.02 prepares the complex hydroxide presoma of spherical nickel-cobalt aluminium by coprecipitation method;
(2) the complex hydroxide presoma with nickel cobalt aluminium places resistance furnace, is warming up to 350 ℃ with the speed of 8.5 ℃/min, is incubated 2 hours, and preoxidation obtains the composite oxides Li of nickel cobalt aluminium in oxygen atmosphere
mNi
1-x-yCo
xAl
yO
2, x=0.25, y=0.02, m=1.0;
(3) composite oxides and the lithium hydroxide of nickel cobalt aluminium are pressed atomic ratio n
Li: (n
Ni+ n
Co+ n
AlThe mixed of)=1.10: 0.90 is a ball-milling medium with ethanol, and ball milling 3.5 hours evenly, after oven dry is placed on and slowly is warmed up to 620 ℃ in the resistance furnace in oxygen atmosphere, constant temperature 11 hours, naturally cooling, fragmentation, classification promptly obtains nickelic lithium nickel cobalt alumina positive electrode material.
Embodiment 3
(1) be raw material with single nickel salt, rose vitriol and Tai-Ace S 150, according to Ni: Co: Al mol ratio 0.75: 0.20: 0.05 prepares the complex hydroxide presoma of spherical nickel-cobalt aluminium by coprecipitation method;
(2) the complex hydroxide presoma with nickel cobalt aluminium places resistance furnace, is warming up to 400 ℃ with the speed of 9 ℃/min, is incubated 3 hours, and preoxidation obtains the composite oxides Li of nickel cobalt aluminium in oxygen atmosphere
mNi
1-x-yCo
xAl
yO
2, x=0.20, y=0.05, m=0.98;
(3) composite oxides and the lithium hydroxide of nickel cobalt aluminium are pressed atomic ratio n
Li: (n
Ni+ n
Co+ n
AlThe mixed of)=1.15: 0.95 is a ball-milling medium with ethanol, and ball milling 3.5 hours evenly, after oven dry is placed on and slowly is warmed up to 650 ℃ in the resistance furnace in oxygen atmosphere, constant temperature 15 hours, naturally cooling, fragmentation, classification promptly obtains nickelic lithium nickel cobalt alumina positive electrode material.
Embodiment 4
(1) be raw material with single nickel salt, rose vitriol and Tai-Ace S 150, according to Ni: Co: Al mol ratio 0.76: 0.20: 0.04 prepares the complex hydroxide presoma of spherical nickel-cobalt aluminium by coprecipitation method;
(2) the complex hydroxide presoma with nickel cobalt aluminium places resistance furnace, is warming up to 500 ℃ with the speed of 10 ℃/min, is incubated 7 hours, and preoxidation obtains the composite oxides Li of nickel cobalt aluminium in oxygen atmosphere
mNi
1-x-yCo
xAl
yO
2, x=0.20, y=0.04, m=1.10;
(3) composite oxides and the lithium hydroxide of nickel cobalt aluminium are pressed atomic ratio n
Li: (n
Ni+ n
Co+ n
AlThe mixed of)=1.10: 1.00 is a ball-milling medium with ethanol, and ball milling 4 hours evenly, after oven dry is placed on and slowly is warmed up to 700 ℃ in the resistance furnace in oxygen atmosphere, constant temperature 20 hours, naturally cooling, fragmentation, classification promptly obtains nickelic lithium nickel cobalt alumina positive electrode material.
(1) be raw material with single nickel salt, rose vitriol and Tai-Ace S 150, according to Ni: Co: Al mol ratio 0.80: 0.15: 0.05 prepares the compound carbonate presoma of spherical nickel-cobalt aluminium by coprecipitation method;
(2) the compound carbonate presoma with nickel cobalt aluminium places resistance furnace, is warming up to 750 ℃ with the speed of 10 ℃/min, is incubated 8 hours, and preoxidation obtains the composite oxides Li of nickel cobalt aluminium in oxygen atmosphere
mNi
1-x-yCo
xAl
yO
2, x=0.15, y=0.05, m=1.12;
(3) composite oxides and the lithium hydroxide of nickel cobalt aluminium are pressed atomic ratio n
Li: (n
Ni+ n
Co+ n
AlThe mixed of)=1.15: 0.95 is a ball-milling medium with ethanol, and ball milling 4 hours evenly, after oven dry is placed on and slowly is warmed up to 750 ℃ in the resistance furnace in oxygen atmosphere, constant temperature 17 hours, naturally cooling, fragmentation, classification promptly obtains nickelic lithium nickel cobalt alumina positive electrode material.
(1) be raw material with single nickel salt, rose vitriol and Tai-Ace S 150, according to Ni: Co: Al mol ratio 0.80: 0.14: 0.06 prepares the compound carbonate presoma of spherical nickel-cobalt aluminium by coprecipitation method;
(2) the compound carbonate presoma with nickel cobalt aluminium places resistance furnace, is warming up to 850 ℃ with the speed of 12 ℃/min, is incubated 9 hours, and preoxidation obtains the composite oxides Li of nickel cobalt aluminium in oxygen atmosphere
mNi
1-x-yCo
xAl
yO
2, x=0.14, y=0.06, m=1.25;
(3) composite oxides and the lithium hydroxide of nickel cobalt aluminium are pressed atomic ratio n
Li: (n
Ni+ n
Co+ n
AlThe mixed of)=1.20: 1.20 is a ball-milling medium with ethanol, and ball milling 4 hours evenly, after oven dry is placed on and slowly is warmed up to 800 ℃ in the resistance furnace in oxygen atmosphere, constant temperature 19 hours, naturally cooling, fragmentation, classification promptly obtains nickelic lithium nickel cobalt alumina positive electrode material.
Claims (8)
1. the preparation method of a lithium ion battery anode material lithium nickel cobalt alumina is characterized in that: may further comprise the steps:
(1) prepares spherical nickel-cobalt aluminum complex hydroxide presoma or spherical nickel-cobalt aluminium compound carbonate presoma with coprecipitation method;
(2), described presoma is carried out the preoxidation calcination processing separately, obtain the spherical nickel-cobalt aluminum oxide homogenous solid solution of high valence state;
(3) with the spherical nickel-cobalt aluminum oxide and the lithium salts uniform mixing of high valence state, high-temperature calcination in oxygen atmosphere is cooled off the back fragmentation and is obtained lithium nickel cobalt alumina positive electrode material.
2. the preparation method of a kind of lithium ion battery anode material lithium nickel cobalt alumina according to claim 1 is characterized in that: described spherical nickel-cobalt aluminum oxide chemical formula is Li
mNi
1-x-yCo
xAl
yO
2, 0.05＜x＜0.3,0＜y＜0.1,0.96＜m＜1.3 wherein.
3. the preparation method of a kind of lithium ion battery anode material lithium nickel cobalt alumina according to claim 1, it is characterized in that: in the described step (1), with single nickel salt, rose vitriol and Tai-Ace S 150 is raw material, according to Ni: Co: Al mol ratio (0.7～0.8): (0.15～0.25): (0.02～0.06) prepares nickel cobalt aluminum complex hydroxide presoma with coprecipitation method.
4. the preparation method of a kind of lithium ion battery anode material lithium nickel cobalt alumina according to claim 1 is characterized in that: in the described step (2), described preoxidation incinerating atmosphere is oxygen.
5. the preparation method of a kind of lithium ion battery anode material lithium nickel cobalt alumina according to claim 1 is characterized in that: in the described step (2), described preoxidation calcination processing temperature is 300-850 ℃, and the treatment time is 1-9h.
6. the preparation method of a kind of lithium ion battery anode material lithium nickel cobalt alumina according to claim 5, it is characterized in that: nickel cobalt aluminum complex hydroxide presoma is placed resistance furnace, heat up ℃ with the speed of 8～12 ℃/min, preoxidation obtains the nickel cobalt aluminum composite oxide in oxygen atmosphere.
7. the preparation method of a kind of lithium ion battery anode material lithium nickel cobalt alumina according to claim 1 is characterized in that: in the described step (3), nickel cobalt aluminum composite oxide and lithium salts are pressed atomic ratio n
Li: (n
Ni+ n
Co+ n
Al)=(1.10～1.20): the mixed of (0.80～1.20) is a ball-milling medium with ethanol, and ball milling 3～5 hours evenly, after oven dry is placed on and slowly is warmed up to 650～850 ℃ in the resistance furnace in oxygen atmosphere, constant temperature 6～30 hours, naturally cooling, fragmentation obtains product after the classification.
8. the preparation method of a kind of lithium ion battery anode material lithium nickel cobalt alumina according to claim 1 is characterized in that: described lithium salts is a kind of in lithium hydroxide, Quilonum Retard, lithium nitrate, lithium chloride, lithium oxalate, the Lithium Acetate or several.
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Cited By (18)
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|---|---|---|---|---|
| CN102875130A (en) * | 2012-10-15 | 2013-01-16 | 福建师范大学 | Method for preparing doped lithium-enriched solid solution cathode material by using carbon-added compound |
| CN103066257A (en) * | 2012-12-03 | 2013-04-24 | 国光电器股份有限公司 | Preparation method of lithium-nickel-cobalt-aluminum oxide for anode materials of lithium ion batteries |
| CN103094546A (en) * | 2013-01-25 | 2013-05-08 | 湖南邦普循环科技有限公司 | Method for preparing nickel-cobalt lithium aluminate as anode material of lithium ion battery |
| CN103633308A (en) * | 2013-11-28 | 2014-03-12 | 宁波金和新材料股份有限公司 | Lithium, nickel, cobalt, aluminum and oxygen-rich cathode material and preparation method thereof |
| CN103700844A (en) * | 2013-12-18 | 2014-04-02 | 江苏科捷锂电池有限公司 | Preparation method of lithium ion battery nickel, cobalt and aluminum composite ternary cathode material |
| CN105720242A (en) * | 2014-12-02 | 2016-06-29 | 中国电子科技集团公司第十八研究所 | Method for modifying lithium ion battery cathode material |
| CN105810937A (en) * | 2014-12-30 | 2016-07-27 | 河南科隆新能源有限公司 | Preparation method of lithium ion battery cathode material NCA with high specific energy |
| CN105932323A (en) * | 2016-06-22 | 2016-09-07 | 电子科技大学 | Preparation methods of nickel-cobalt-aluminum hydroxide precursor and nickel-cobalt-aluminum ternary lithium-ion positive electrode material |
| CN105958061A (en) * | 2016-06-04 | 2016-09-21 | 苏州思创源博电子科技有限公司 | Preparation method for nickel-cobalt-aluminum ternary positive electrode material |
| CN105958053A (en) * | 2016-06-04 | 2016-09-21 | 苏州思创源博电子科技有限公司 | Preparation method for lithium ion battery from ternary positive electrode material |
| CN106025208A (en) * | 2016-06-04 | 2016-10-12 | 苏州思创源博电子科技有限公司 | Preparation method for carbon-coated ternary positive electrode material |
| CN106207154A (en) * | 2015-05-26 | 2016-12-07 | 苏州艾美得新能源材料有限公司 | Method for preparing anode material, positive electrode and battery |
| CN108511746A (en) * | 2018-03-02 | 2018-09-07 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of the modified nickelic tertiary cathode material of pre-oxidation |
| CN109449400A (en) * | 2018-10-25 | 2019-03-08 | 中伟新材料有限公司 | A kind of oxide precursor of anode material of lithium battery and preparation method thereof |
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| CN112186171A (en) * | 2019-07-05 | 2021-01-05 | 西北工业大学 | Pre-oxidation method and application of lithium nickelate positive electrode material precursor for lithium ion battery |
| CN114956206A (en) * | 2022-05-31 | 2022-08-30 | 宜宾锂宝新材料有限公司 | Pre-oxidation method of high-nickel ternary material precursor and obtained precursor material |
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| CN105720242A (en) * | 2014-12-02 | 2016-06-29 | 中国电子科技集团公司第十八研究所 | Method for modifying lithium ion battery cathode material |
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| CN106207154A (en) * | 2015-05-26 | 2016-12-07 | 苏州艾美得新能源材料有限公司 | Method for preparing anode material, positive electrode and battery |
| CN105958061A (en) * | 2016-06-04 | 2016-09-21 | 苏州思创源博电子科技有限公司 | Preparation method for nickel-cobalt-aluminum ternary positive electrode material |
| CN105958053A (en) * | 2016-06-04 | 2016-09-21 | 苏州思创源博电子科技有限公司 | Preparation method for lithium ion battery from ternary positive electrode material |
| CN106025208A (en) * | 2016-06-04 | 2016-10-12 | 苏州思创源博电子科技有限公司 | Preparation method for carbon-coated ternary positive electrode material |
| CN105932323A (en) * | 2016-06-22 | 2016-09-07 | 电子科技大学 | Preparation methods of nickel-cobalt-aluminum hydroxide precursor and nickel-cobalt-aluminum ternary lithium-ion positive electrode material |
| CN108511746A (en) * | 2018-03-02 | 2018-09-07 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of the modified nickelic tertiary cathode material of pre-oxidation |
| CN109449400A (en) * | 2018-10-25 | 2019-03-08 | 中伟新材料有限公司 | A kind of oxide precursor of anode material of lithium battery and preparation method thereof |
| CN112186171A (en) * | 2019-07-05 | 2021-01-05 | 西北工业大学 | Pre-oxidation method and application of lithium nickelate positive electrode material precursor for lithium ion battery |
| CN111446445A (en) * | 2020-04-21 | 2020-07-24 | 西北工业大学 | Plasma treatment method for nickel-based lithium ion positive electrode material precursor |
| CN111446445B (en) * | 2020-04-21 | 2022-03-22 | 西北工业大学 | Plasma treatment method for nickel-based lithium ion positive electrode material precursor |
| CN111834631A (en) * | 2020-07-13 | 2020-10-27 | 万华化学集团股份有限公司 | Preparation method of high-nickel cathode material of lithium ion battery |
| CN111834631B (en) * | 2020-07-13 | 2021-07-23 | 万华化学集团股份有限公司 | Preparation method of high-nickel cathode material of lithium ion battery |
| CN114956206A (en) * | 2022-05-31 | 2022-08-30 | 宜宾锂宝新材料有限公司 | Pre-oxidation method of high-nickel ternary material precursor and obtained precursor material |
| CN114956206B (en) * | 2022-05-31 | 2023-12-08 | 宜宾锂宝新材料有限公司 | Pre-oxidation method of high-nickel ternary material precursor and precursor material obtained by pre-oxidation method |
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Application publication date: 20110907 |