CN103708567A - Lithium nickel cobalt oxide positive electrode material of lithium ion battery and preparation method thereof - Google Patents
Lithium nickel cobalt oxide positive electrode material of lithium ion battery and preparation method thereof Download PDFInfo
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- CN103708567A CN103708567A CN201310717858.5A CN201310717858A CN103708567A CN 103708567 A CN103708567 A CN 103708567A CN 201310717858 A CN201310717858 A CN 201310717858A CN 103708567 A CN103708567 A CN 103708567A
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- lithium
- positive electrode
- electrode material
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- ionic cell
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a lithium nickel cobalt oxide positive electrode material of a lithium ion battery and a preparation method thereof. The lithium nickel cobalt oxide positive electrode material comprises the following materials: Ni(NO3)2.6H2O, Co(NO3)2.6H2O, LiOH.H2O and ammonia water. The preparation method comprises the following preparation steps: under a stirring state, dropping mixed liquor of lithium hydroxide and ammonia water into mixed liquor of cobalt nitrate and nickel nitrate, and reacting to obtain a mixed hydroxide; after drying, adding lithium hydroxide for mixing, and placing into a muffle furnace after grinding, pre-sintering for 6 hours at 600 DEG C; and sintering for 12 hours at 900 DEG C, grinding the product and passing through a 300-mesh sample-separating sieve to obtain the lithium nickel cobalt positive electrode material of the lithium ion battery. The product is good in morphological structure, stable in structure, less in impurity content, high in discharge capacity and good in cycle performance.
Description
Technical field
The present invention relates to battery manufacture field, particularly a kind of lithium ionic cell nickel lithium cobaltate cathode material and preparation method.
Background technology
Lithium ion battery has unique advantages such as specific energy is high, operating voltage is high, temperature limit is wide, self-discharge rate is low, have extended cycle life, pollution-free, safety performance is good, now be widely used as pocket valuable household electrical appliance as the power supply of mobile telephone, portable computer, pick up camera, photographic camera etc., and in Aeronautics and Astronautics, navigation, man-made satellite, small medical and military domain of communication equipment, progressively substituted traditional power supply.For lithium ion battery, no matter positive electrode material aspect cost or at aspect of performance, all occupies very important status.Business-like anode material for lithium-ion batteries mainly only has LiCoO at present
2, but cobalt natural resources is limited, and expensive, cause its cost higher, and LiCoO
2self also has many shortcomings, for example structural stability is poor, and between 3.50～4.35 V, circulation time subjects to destroy, although its cycle performance is better than other positive electrode material, but still can decay, cycle performance needs further to improve for the space exploration of long lifetime demand.Therefore how to LiCoO
2carry out modification, to reduce its cost, improve the study hotspot that other the anode material for lithium-ion batteries of better performances of its chemical property and R and D becomes current relevant Study on Li-ion batteries using field.
Summary of the invention
The object of the present invention is to provide a kind of at LiCoO
2the lithium nickel cobalt dioxide positive electrode material of middle Ni doped, to improve specific storage and the cycle performance of lithium ion battery.
For achieving the above object, this lithium ionic cell nickel lithium cobaltate cathode material, is characterized in that, comprises following starting material: Ni (NO
3)
26H
2o, Co (NO
3)
26H
2o, LiOHH
2o, wherein mol ratio n (Ni): n (Co)=0.1:0.9 ~ 0.5:0.5(n (Ni)+n (Co)=1 wherein), n (Li): n (Ni+Co)=6:1; Starting material also comprise sequestrant.
The making step of described positive electrode material is as follows:
(1) n (Ni): n (Co)=0.1:0.9 ~ 0.5:0.5(n (Ni)+n (Co)=1 wherein in molar ratio) take Ni (NO
3)
26H
2o, Co (NO
3)
26H
2o is dissolved in deionized water after mixing, and obtains mixed solution A;
(2) n (Li): n (Ni+Co)=5:1 takes LiOHH in molar ratio
2o is dissolved in a certain amount of deionized water, adds a little sequestrant, obtains mixing solutions B;
(3) under the state constantly stirring, mixed solution A is dropwise joined in mixing solutions B, make it coprecipitation reaction occur until the pH value of solution reaches 10 ~ 12, continue to filter and dry after stirring for some time;
(4) n (Li): n (Ni+Co)=1:1 takes LiOHH in molar ratio
2o adds in the oven dry product of step (3) gained, obtains solid mixture;
(5) solid mixture step (4) being obtained is put into retort furnace after grinding, at 600 ℃ of pre-burning 6 h, obtain presoma, by presoma sintering 12 h at 900 ℃, after product is ground, cross 300 order sub-sieves, obtain lithium ionic cell nickel lithium cobaltate cathode material.
Described sequestrant is ammoniacal liquor.
Described material N i (NO
3)
26H
2o, Co (NO
3)
26H
2the mol ratio n of O (Ni): n (Co)=0.3:0.7.
Substantive distinguishing features of the present invention and progress are: the method synthesis of anode material of lithium-ion battery lithium nickel cobalt dioxide that adopts coprecipitation method and high temperature solid-state method to combine, this product makes nickel estimate element to reach atom level and mix, and product pattern is good, Stability Analysis of Structures, foreign matter content is few, loading capacity is high, good cycle.
Accompanying drawing explanation
Fig. 1 is LiNi
xco
1-xo
2x-ray diffractogram.
Fig. 2 is LiNi
xco
1-xo
2cycle performance graphic representation.
Embodiment
Below in conjunction with accompanying drawing and the present invention will be further described:
Embodiment 1
N (Ni): n (Co)=0.1:0.9 takes Ni (NO in molar ratio
3)
26H
2o, Co (NO
3)
26H
2o is dissolved in deionized water after mixing, and obtains mixed solution A; N (Li): n (Ni+Co)=5:1 takes LiOHH in molar ratio
2o is dissolved in a certain amount of deionized water, adds a little sequestrant ammoniacal liquor, obtains mixing solutions B; Under the state constantly stirring, mixing solutions B is dropwise joined in mixed solution A, make it coprecipitation reaction occur until the pH value of solution reaches 10 ~ 12, continue to filter and dry after stirring for some time.N (Li): n (Ni+Co)=1:1 takes LiOHH in molar ratio
2o adds in the oven dry product of front step gained, obtains solid mixture; After this solid mixture is ground, put into retort furnace, at 600 ℃ of pre-burning 6 h, obtain presoma, by presoma sintering 12 h at 900 ℃, after product is ground, cross 300 order sub-sieves, obtain lithium ion battery LiNi
0.1co
0.9o
2positive electrode material.
N (Ni): n (Co)=0.2:0.8 takes Ni (NO in molar ratio
3)
26H
2o, Co (NO
3)
26H
2o is dissolved in deionized water after mixing, and remaining making step is identical with embodiment 1, obtains LiNi
0.2co
0.8o
2positive electrode material.
Embodiment 3
N (Ni): n (Co)=0.3:0.7 takes Ni (NO in molar ratio
3)
26H
2o, Co (NO
3)
26H
2o is dissolved in deionized water after mixing, and remaining step is identical with embodiment 1, obtains LiNi
0.3co
0.7o
2positive electrode material.
Embodiment 4
N (Ni): n (Co)=0.4:0.6 takes Ni (NO in molar ratio
3)
26H
2o, Co (NO
3)
26H
2o is dissolved in deionized water after mixing, and remaining step is identical with embodiment 1, obtains LiNi
0.4co
0.6o
2positive electrode material.
N (Ni): n (Co)=0.5:0.5 takes Ni (NO in molar ratio
3)
26H
2o, Co (NO
3)
26H
2o is dissolved in deionized water after mixing, and remaining step is identical with embodiment 1, obtains LiN
i0.5co
0.5o
2.
To implementing lithium nickel cobalt dioxide LiNi synthetic in 1 ~ embodiment 5
xco
1-xo
2cobalt acid lithium LiCoO with Ni doped not
2structure is carried out XRD analysis, as shown in Figure 1, and the LiNi after Ni doped element
xco
1-xo
2the diffraction peak of product and parent LiCoO
2diffraction peak basically identical, the diffraction angle of each diffraction peak is substantially identical, in spectrogram, do not find obvious dephasign peak, proved that the Ni element of doping has entered into the matrix lattice of laminate structure, in every set product, the peak type of each diffraction peak is more sharp-pointed, and the division of diffraction peak is all obvious, these features have all shown prepared LiNi
xco
1-xo
2product all has good crystalline structure.
To implementing lithium nickel cobalt dioxide LiNi synthetic in 1 ~ embodiment 5
xco
1-xo
2with cobalt acid lithium LiCoO
2carry out Performance Analysis, these positive electrode materials are made to battery and carry out constant current charge-discharge performance test, Fig. 2 is LiNi
xco
1-xo
2cycle performance curve, following table is LiNi
xco
1-xo
2specific discharge capacity and cycle efficiency.
Table 1 LiNi
xco
1-xo
2specific discharge capacity and cycle efficiency
By Fig. 2 and table 1, can be obtained LiCoO
2through the doping of Ni element, the specific storage of material is significantly improved, the LiCoO preparing in experiment
2first discharge specific capacity be 61.93 mAhg
-1, and LiNi
0.3co
0.7o
2, LiNi
0.4co
0.6o
2first discharge specific capacity all approach 100.00 mAhg
-1, but Ni constituent content is when higher, and the cycle performance of product is poor, circulates after 30 times, LiNi
0.4co
0.6o
2capability retention be only 66.17%, LiNi
0.5co
0.5o
2lower.When doping x is 0.3, chemical constitution is LiNi
0.3co
0.7o
2product first discharge specific capacity be 99.06 mAhg
-1, the specific discharge capacity after 30 times that circulates is 76.72 mAhg
-1, capability retention is 76.72%, and reversibility is good, and the over-all properties showing in synthetic product is best.
Claims (4)
1. a lithium ionic cell nickel lithium cobaltate cathode material, is characterized in that, comprises following starting material: Ni (NO
3)
26H
2o, Co (NO
3)
26H
2o, LiOHH
2o, wherein mol ratio n (Ni): n (Co)=0.1:0.9 ~ 0.5:0.5(n (Ni)+n (Co)=1 wherein), n (Li): n (Ni+Co)=6:1; Starting material also comprise sequestrant.
2. the preparation method of lithium ionic cell nickel lithium cobaltate cathode material according to claim 1, is characterized in that, the making step of described positive electrode material is as follows:
(1) n (Ni): n (Co)=0.1:0.9 ~ 0.5:0.5(n (Ni)+n (Co)=1 wherein in molar ratio) take Ni (NO
3)
26H
2o, Co (NO
3)
26H
2o is dissolved in deionized water after mixing, and obtains mixed solution A;
(2) n (Li): n (Ni+Co)=5:1 takes LiOHH in molar ratio
2o is dissolved in a certain amount of deionized water, adds a little sequestrant, obtains mixing solutions B;
(3) under the state constantly stirring, mixing solutions B is dropwise joined in mixed solution A, make it coprecipitation reaction occur until the pH value of solution reaches 10 ~ 12, continue to filter and dry after stirring for some time;
(4) n (Li): n (Ni+Co)=1:1 takes LiOHH in molar ratio
2o adds in the oven dry product of step (3) gained, obtains solid mixture;
(5) solid mixture step (4) being obtained is put into retort furnace after grinding, at 600 ℃ of pre-burning 6 h, obtain presoma, by presoma sintering 12 h at 900 ℃, after product is ground, cross 300 order sub-sieves, obtain lithium ionic cell nickel lithium cobaltate cathode material.
3. lithium ionic cell nickel lithium cobaltate cathode material according to claim 1 and 2, is characterized in that: described sequestrant is ammoniacal liquor.
4. lithium ionic cell nickel lithium cobaltate cathode material according to claim 1 and 2, is characterized in that: described material N i (NO
3)
26H
2o, Co (NO
3)
26H
2the mol ratio n of O (Ni): n (Co)=0.3:0.7.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019068454A1 (en) | 2017-10-06 | 2019-04-11 | Basf Se | Electrode active material, its manufacture and use |
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| CN103296274A (en) * | 2013-05-15 | 2013-09-11 | 中信国安盟固利电源技术有限公司 | Coated nickel lithium cobalt oxide positive material with high capacity, low residual alkali and low pH value, and preparation method thereof |
-
2013
- 2013-12-24 CN CN201310717858.5A patent/CN103708567A/en active Pending
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| CN101083321A (en) * | 2006-05-31 | 2007-12-05 | 湖南美特新材料有限公司 | Lithium manganese cobalt nickle oxygen of manganese cobalt nickle triple lithium ionic cell positive material and its synthesizing method |
| CN103296274A (en) * | 2013-05-15 | 2013-09-11 | 中信国安盟固利电源技术有限公司 | Coated nickel lithium cobalt oxide positive material with high capacity, low residual alkali and low pH value, and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 肖启振: "锂离子电池正极材料锂镍钴氧化物(LiNi0.8Co0.2O2)的制备及改性研究", 《中国优秀博硕士学位论文全文数据库（硕士） 工程科技Ⅱ辑》 * |
| 黄元乔: "电极材料LiaNi0.7Co0.3O2的合成及电化学性质", 《湖北第二师范学院学报》 * |
| 黄元乔等: "LiaNi0.75Co0.25O2的共沉淀法合成及其电化学性质研究", 《功能材料》 * |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019068454A1 (en) | 2017-10-06 | 2019-04-11 | Basf Se | Electrode active material, its manufacture and use |
| CN111132935A (en) * | 2017-10-06 | 2020-05-08 | 巴斯夫欧洲公司 | Electrode active material, its preparation and use |
| JP2020536367A (en) * | 2017-10-06 | 2020-12-10 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Electrode active material, its manufacture and usage |
| US11283074B2 (en) * | 2017-10-06 | 2022-03-22 | Basf Se | Electrode active material, its manufacture and use |
| CN111132935B (en) * | 2017-10-06 | 2022-07-15 | 巴斯夫欧洲公司 | Electrode active material, its preparation and use |
| JP7189521B2 (en) | 2017-10-06 | 2022-12-14 | ビーエーエスエフ ソシエタス・ヨーロピア | ELECTRODE ACTIVE MATERIAL, PRODUCTION AND USAGE THEREOF |
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Application publication date: 20140409 |