CN108199027A - A kind of niobium doping is without cobalt nickel-base anode material and preparation method thereof - Google Patents
A kind of niobium doping is without cobalt nickel-base anode material and preparation method thereof Download PDFInfo
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- CN108199027A CN108199027A CN201810017505.7A CN201810017505A CN108199027A CN 108199027 A CN108199027 A CN 108199027A CN 201810017505 A CN201810017505 A CN 201810017505A CN 108199027 A CN108199027 A CN 108199027A
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Abstract
The invention discloses a kind of doping of niobium without cobalt nickel-base anode material and preparation method thereof, belong to technical field of lithium ion, the molecular formula of the positive electrode is Li [NixMn1‑x]1‑yNbyO2, wherein 0.5≤x≤0.9,0 ＜ y ＜ 0.1；The preparation method is：Nickel, the mixed solution of manganese salt and the mixed solution of alkali and ammonium hydroxide are first made respectively, then prepares presoma NixMn1‑x(OH)2, then presoma with the compound of lithium, the compound of niobium is uniformly mixed, is sintered at high temperature, obtains mixing niobium nickel-base anode material.Niobium provided by the present invention mixes no cobalt nickel-base anode material using nickel-base anode material, niobium-doped to be modified, and stablizes cathode material structure, Ionic diffusion can be improved, and then improve the cyclical stability and high rate performance of positive electrode；Production cost can also be saved.
Description
Technical field
The present invention relates to technical field of lithium ion, be specifically related to a kind of niobium doping without cobalt nickel-base anode material and its
Preparation method.
Background technology
Lithium ion battery is with operating voltage height, energy density height, light weight, small, self discharge is few, cycle life
The features such as length, charge and discharge memory-less effect, be 21 century " environmentally protective power supply ".The lithium ion battery of early stage is mainly used for pen
Remember on the 3C electronic products such as this computer, mobile phone, digital camera.In recent years, as prepared by positive electrode and battery process skill
The promotion of art level, the energy density and power density of lithium ion battery are significantly improved, the stable circulation performance of battery and
Big high rate performance is improved, and lithium ion battery is just applied to pure electric automobile (EV), plug-in hybrid-power automobile (PHEV)
It waits on the vehicles.
At present, the energy density for being limited to Li-ion batteries piles is relatively low, and the course continuation mileage of new-energy automobile is generally at 300 kilometers
Hereinafter, and consumer demand cannot be met.Therefore, lithium ion battery of the exploitation with higher energy density is extremely urgent.Just
Pole material is the important component of lithium ion battery, performance quality and development and application of the cost height to lithium ion battery
Play key effect.It is famous with height ratio capacity, low cost, environmental-friendly advantage without cobalt nickel-base anode material, it is that development is high
One of alternative positive electrode of energy density lithium ion battery.But also there are some problem, packets for the nickel-base material of nickel manganese solid solution
It is poor etc. to include structural instability in cyclic process, thermal stability.It needs further to research and solve.
In order to further enhance the chemical property of nickel-base anode material, the modification of no cobalt nickel-base anode material becomes extensive
The research hotspot of concern.Doping vario-property is the effective way for improving no cobalt nickel-base anode material electrochemical performance.
Invention content
1. technical problems to be solved
The technical problem to be solved in the present invention is that providing a kind of niobium adulterates without cobalt nickel-base anode material and preparation method thereof,
It uses nickel-base anode material, niobium-doped to be modified, and stablizes cathode material structure, Ionic diffusion can be carried
Height, and then improve the cyclical stability and high rate performance of positive electrode.
2. technical solution
To solve the above problems, the present invention adopts the following technical scheme that：
Without cobalt nickel-base anode material, molecular formula is Li [Ni for a kind of niobium dopingxMn1-x]1-yNbyO2, wherein 0.5≤x≤
0.9,0 ＜ y ＜ 0.1.
The present invention also provides a kind of above-mentioned preparation method of the niobium doping without cobalt nickel-base anode material, include the following steps：
(1) by soluble nickel salt, manganese salt according to molar ratio x：(1-x) is dissolved in deionized water, it is made into a concentration of 0.5~
The transition-metal ion solution of 4mol/L, wherein 0.5≤x≤0.9；
(2) mixed solution with alkaline and ammonium hydroxide, a concentration of 1~6mol/L；
(3) a certain amount of deionized water and heat temperature raising are added in a kettle, and nickel for preparing in (1), manganese salt are mixed
The mixed solution for closing the alkali prepared in solution and (2) and ammonium hydroxide is added dropwise in reaction kettle respectively by peristaltic pump, and simultaneously to anti-
Solution in kettle is answered to carry out heating stirring, while be passed through N into reaction kettle2, control the temperature of reaction system, pH in reaction kettle permanent
It is fixed, carry out coprecipitation reaction；Precipitated product, suction filtration, drying are washed with deionized after having reacted, obtains presoma NixMn1-x
(OH)2；
(4) it is (1-y) in molar ratio by the presoma and the compound of lithium that are prepared in (3), the compound of niobium：1：Y ball millings
It is uniformly mixed, wherein 0 ＜ y ＜ 0.1, the powder high temperature sintering that will be mixed, obtain mixing niobium nickel-base anode material.
Further, soluble nickel salt described in step (1) is one in nickel sulfate, nickel chloride, nickel nitrate, nickel acetate
Kind；Soluble manganese salt is one kind in manganese sulfate, manganese chloride, manganese nitrate, manganese acetate.
Further, aqueous slkali described in step (2) is one kind in sodium hydroxide, sodium carbonate, potassium hydroxide.
Further, the temperature of reaction system is 30~70 DEG C in reaction kettle described in step (3), and pH is 9~12.
Further, high temperature sintering described in step (4) is to be warming up to 400~600 with the heating rate of 1~6 DEG C/min
DEG C, 3~8h is kept the temperature, is then warming up to 750~960 DEG C again with the heating rate of 1~6 DEG C/min, keeps the temperature 6~20h.
3. advantageous effect
(1) present invention is doped with niobium element in no cobalt nickel-base anode material.The fusing point of niobium reaches 2468 DEG C, and boiling point reaches
4742 DEG C, other refractory metals of density ratio are low, are 8.57 grams/cc.The architectural characteristic of niobium is relatively stable, and niobium is in low temperature
Superconductor property is presented under state.At normal atmospheric pressure, its critical-temperature is 9.2K, is highest in all simple substance superconductors
's.Its magnetic penetration depth is also highest in all elements.After the material doped niobium element of cobalt nickel-base anode, cathode material structure
Remain unchanged, unit cell volume increase, can effectively expand the transmission channel of lithium ion, cathode material structure can be stablized, improve its from
Sub- diffusion, solving the nickel-base material of nickel manganese solid solution, structural instability, thermal stability are poor in cyclic process asks
Topic makes nickel-base anode material have higher specific capacity and good cyclical stability and high rate performance.In addition, niobium can also be resisted
Various erosions, and dielectric oxide layer can be formed, can preferably protect no cobalt nickel-base anode material and ensure its normal operation.
(2) niobium is relatively conventional, and price is relatively low.Modification is doped using niobium, is conducive to save production cost.
(3) preparation method of positive electrode provided by the present invention is easy to operate, and environmental demand condition is relatively low, is conducive to
It is promoted to be applied to actual production.
Niobium provided by the present invention mixes no cobalt nickel-base anode material using nickel-base anode material, niobium-doped to be modified,
Stablize cathode material structure, Ionic diffusion can be improved, and then improve the cyclical stability and again of positive electrode
Rate performance；Production cost can also be saved；Preparation method is easy to operate, may advantageously facilitate it applied to actual production.
Description of the drawings
Fig. 1 is the XRD diagram of product in embodiment 2；
Fig. 2 is the XRD diagram of product in comparative example；
Fig. 3 is the SEM figures of product in embodiment 2；
Fig. 4 is the SEM figures of product in comparative example；
Fig. 5 is embodiment 2 and the cyclic curve figure of product in comparative example；
Fig. 6 is embodiment 2 and the multiplying power line chart of product in comparative example.
Specific embodiment
The present invention is described in further detail with reference to the accompanying drawings and examples.
Embodiment 1
Without cobalt nickel-base anode material, molecular formula is Li [Ni for a kind of niobium doping0.5Mn0.5]0.99Nb0.01O2。
Above-mentioned niobium adulterates the preparation method without cobalt nickel-base anode material, includes the following steps：
(1) it is 0.5 by nickel, manganese Metal ion molar ratio：0.5, chloric acid nickel, chloric acid manganese are dissolved in deionized water, with
Nickel, manganese ion total concentration be 2mol/L, volume be 1L mixing salt solution；
(2) compound concentration is 4mol/L, and volume is the sodium hydroxide of 1L and the mixed ammonium/alkali solutions of ammonium hydroxide；
(3) a certain amount of deionized water and heat temperature raising are added in a kettle, and nickel for preparing in (1), manganese salt are mixed
The mixed ammonium/alkali solutions prepared in solution and (2) are closed to be added dropwise in reaction kettle by peristaltic pump simultaneously, and to solution in reaction kettle into
Row heating stirring, while N is passed through into reaction kettle2Make protection gas, the temperature for controlling reaction system in reaction kettle is 30 DEG C, pH is permanent
It is set to 9, carries out coprecipitation reaction；After having reacted, precipitated product is washed with deionized, suction filtration, is dried in 90 DEG C of temperature environments
It does for 24 hours, obtains presoma Ni0.5Mn0.5(OH)2；
(4) by the presoma prepared in (3) and lithium hydroxide, niobium pentaoxide in molar ratio 0.99：1：0.005 ratio
Ball milling mixing is uniform, and the powder mixed is placed in the sintering of batch-type furnace high temperature.Sintering process is：Using heating rate as 1 DEG C/
Min is warming up to 400 DEG C, keeps the temperature 8h, then with the heating rate of 1 DEG C/min, is warming up to 750 DEG C, 20h is to get Li for heat preservation
[Ni0.5Mn0.5]0.99Nb0.01O2Positive electrode.It is ground up, sieved to obtain and mixes niobium nickel-base anode material.
By Li [Ni0.5Mn0.5]0.99Nb0.01O2Positive electrode is assembled into button cell, makees relevant parameter performance detection：
Voltage be 2.75V, discharge rate 0.1C, temperature be 25 DEG C under conditions of be melted into；
It is 2.75V in voltage, discharge rate recycles 50 times under conditions of being 0.2C；
It is each successively under conditions of discharge rate is respectively 0.2C, 0.5C, 1C, 2C, 5C, 0.2C to recycle 4 times.
Embodiment 2
Without cobalt nickel-base anode material, molecular formula is Li [Ni for a kind of niobium doping0.7Mn0.3]0.96Nb0.04O2。
Above-mentioned niobium adulterates the preparation method without cobalt nickel-base anode material, includes the following steps：
(1) it is 0.7 by nickel, manganese Metal ion molar ratio：0.3, nickel sulfate, manganese sulfate are dissolved in deionized water, with
Nickel, manganese ion total concentration be 2mol/L, volume be 1L mixing salt solution；
(2) compound concentration is 4mol/L, and volume is the sodium hydroxide of 1L and the mixed ammonium/alkali solutions of ammonium hydroxide；
(3) a certain amount of deionized water and heat temperature raising are added in a kettle, and nickel for preparing in (1), manganese salt are mixed
The mixed ammonium/alkali solutions prepared in solution and (2) are closed to be added dropwise in reaction kettle by peristaltic pump simultaneously, and to solution in reaction kettle into
Row heating stirring, while N is passed through into reaction kettle2Make protection gas, the temperature for controlling reaction system in reaction kettle is 55 DEG C, pH is permanent
It is set to 11.2, carries out coprecipitation reaction；After having reacted, precipitated product, suction filtration is washed with deionized, in 90 DEG C of temperature environments
Drying for 24 hours, obtains presoma Ni0.7Mn0.3(OH)2；
(4) by the presoma prepared in (3) and lithium hydroxide, niobium pentaoxide in molar ratio 0.96：1：0.02 ratio
Ball milling mixing is uniform, and the powder mixed is placed in the sintering of batch-type furnace high temperature.Sintering process is：Using heating rate as 3 DEG C/
Min, is warming up to 550 DEG C, keeps the temperature 6h, then with 1.5 DEG C/min, heating rate, be warming up to 820 DEG C, 15h is to get Li for heat preservation
[Ni0.7Mn0.3]0.96Nb0.04O2Positive electrode.It is ground up, sieved to obtain and mixes niobium nickel-base anode material.
By Li [Ni0.7Mn0.3]0.96Nb0.04O2Positive electrode is assembled into button cell, makees relevant parameter performance detection：
Voltage be 3.25V, discharge rate 0.1C, temperature be 25 DEG C under conditions of be melted into；
It is 3.25V in voltage, discharge rate recycles 50 times under conditions of being 0.2C；
It is each successively under conditions of discharge rate is respectively 0.2C, 0.5C, 1C, 2C, 5C, 0.2C to recycle 4 times.
Embodiment 3
Without cobalt nickel-base anode material, molecular formula is Li [Ni for a kind of niobium doping0.8Mn0.2]0.94Nb0.06O2。
Above-mentioned niobium adulterates the preparation method without cobalt nickel-base anode material, includes the following steps：
(1) it is 0.8 by nickel, manganese Metal ion molar ratio：0.2, nickel nitrate, manganese nitrate are dissolved in deionized water, with
Nickel, manganese ion total concentration be 2mol/L, volume be 1L mixing salt solution；
(2) compound concentration is 4mol/L, and volume is the sodium carbonate of 1L and the mixed ammonium/alkali solutions of ammonium hydroxide；
(3) a certain amount of deionized water and heat temperature raising are added in a kettle, and nickel for preparing in (1), manganese salt are mixed
The mixed ammonium/alkali solutions prepared in solution and (2) are closed to be added dropwise in reaction kettle by peristaltic pump simultaneously, and to solution in reaction kettle into
Row heating stirring, while N is passed through into reaction kettle2Make protection gas, the temperature for controlling reaction system in reaction kettle is 45 DEG C, pH is permanent
It is set to 10, carries out coprecipitation reaction；After having reacted, precipitated product is washed with deionized, suction filtration, is dried in 90 DEG C of temperature environments
It does for 24 hours, obtains presoma Ni0.8Mn0.2(OH)2；
(4) by the presoma prepared in (3) and lithium hydroxide, niobium pentaoxide in molar ratio 0.94：1：0.03 ratio
Ball milling mixing is uniform, and the powder mixed is placed in the sintering of batch-type furnace high temperature.Sintering process is：Using heating rate as 5 DEG C/
Min, is warming up to 500 DEG C, keeps the temperature 5h, then with 5 DEG C/min, heating rate, be warming up to 850 DEG C, 10h is to get Li for heat preservation
[Ni0.8Mn0.2]0.94Nb0.06O2Positive electrode.It is ground up, sieved to obtain and mixes niobium nickel-base anode material.
By Li [Ni0.8Mn0.2]0.94Nb0.06O2Positive electrode is assembled into button cell, makees relevant parameter performance detection：
Voltage be 3.85V, discharge rate 0.1C, temperature be 25 DEG C under conditions of be melted into；
It is 3.85V in voltage, discharge rate recycles 50 times under conditions of being 0.2C；
It is each successively under conditions of discharge rate is respectively 0.2C, 0.5C, 1C, 2C, 5C, 0.2C to recycle 4 times.
Embodiment 4
Without cobalt nickel-base anode material, molecular formula is Li [Ni for a kind of niobium doping0.9Mn0.1]0.91Nb0.09O2。
Above-mentioned niobium adulterates the preparation method without cobalt nickel-base anode material, includes the following steps：
(1) it is 0.9 by nickel, manganese Metal ion molar ratio：0.1, nickel acetate, manganese acetate are dissolved in deionized water, with
Nickel, manganese ion total concentration be 2mol/L, volume be 1L mixing salt solution；
(2) compound concentration is 4mol/L, and volume is the potassium hydroxide of 1L and the mixed ammonium/alkali solutions of ammonium hydroxide；
(3) a certain amount of deionized water and heat temperature raising are added in a kettle, and nickel for preparing in (1), manganese salt are mixed
The mixed ammonium/alkali solutions prepared in solution and (2) are closed to be added dropwise in reaction kettle by peristaltic pump simultaneously, and to solution in reaction kettle into
Row heating stirring, while N is passed through into reaction kettle2Make protection gas, the temperature for controlling reaction system in reaction kettle is 70 DEG C, pH is permanent
It is set to 12, carries out coprecipitation reaction；After having reacted, precipitated product is washed with deionized, suction filtration, is dried in 90 DEG C of temperature environments
It does for 24 hours, obtains presoma Ni0.9Mn0.1(OH)2；
(4) by the presoma prepared in (3) and lithium hydroxide, niobium pentaoxide in molar ratio 0.91：1：0.045 ratio
Ball milling mixing is uniform, and the powder mixed is placed in the sintering of batch-type furnace high temperature.Sintering process is：Using heating rate as 6 DEG C/
Min, is warming up to 600 DEG C, keeps the temperature 3h, then with 6 DEG C/min, heating rate, be warming up to 960 DEG C, 6h is to get Li for heat preservation
[Ni0.9Mn0.1]0.91Nb0.09O2Positive electrode.It is ground up, sieved to obtain and mixes niobium nickel-base anode material.
By Li [Ni0.9Mn0.1]0.91Nb0.09O2Positive electrode is assembled into button cell, makees relevant parameter performance detection：
Voltage be 4.35V, discharge rate 0.1C, temperature be 25 DEG C under conditions of be melted into；
It is 4.35V in voltage, discharge rate recycles 50 times under conditions of being 0.2C；
It is each successively under conditions of discharge rate is respectively 0.2C, 0.5C, 1C, 2C, 5C, 0.2C to recycle 4 times.
Comparative example
A kind of no cobalt nickel-base anode material, molecular formula LiNi0.7Mn0.3O2, be free of niobium (Nb) element.
The preparation method of above-mentioned no cobalt nickel-base anode material, includes the following steps：
(1) it is 0.7 by nickel, manganese Metal ion molar ratio：0.3, nickel sulfate, manganese sulfate are dissolved in deionized water, with
Nickel, manganese ion total concentration be 2mol/L, volume be 1L mixing salt solution；
(2) compound concentration is 4mol/L, and volume is the sodium hydroxide of 1L and the mixed ammonium/alkali solutions of ammonium hydroxide；
(3) a certain amount of deionized water and heat temperature raising are added in a kettle, and nickel for preparing in (1), manganese salt are mixed
The mixed ammonium/alkali solutions prepared in solution and (2) are closed to be added dropwise in reaction kettle by peristaltic pump simultaneously, and to solution in reaction kettle into
Row heating stirring, while N is passed through into reaction kettle2Make protection gas, the temperature for controlling reaction system in reaction kettle is 55 DEG C, pH is permanent
It is set to 11.2, carries out coprecipitation reaction；After having reacted, precipitated product, suction filtration is washed with deionized, in 90 DEG C of temperature environments
Drying for 24 hours, obtains presoma Ni0.7Mn0.3(OH)2；
(4) by the presoma prepared in (3) and lithium hydroxide in molar ratio 1：1 ratio ball milling mixing is uniform；It will mixing
Good powder is placed in the sintering of batch-type furnace high temperature.Sintering process is：Using heating rate as 3 DEG C/min, 550 DEG C are warming up to, heat preservation
6h, then with 1.5 DEG C/min, heating rate, be warming up to 820 DEG C, 15h is to get LiNi for heat preservation0.7Mn0.3O2Positive electrode.It grinds
Honed sieve obtains mixing niobium nickel-base anode material.
By LiNi0.7Mn0.3O2Positive electrode is assembled into button cell, makees relevant parameter performance detection：
Voltage be 3.25V, discharge rate 0.1C, temperature be 25 DEG C under conditions of be melted into；
It is 3.25V in voltage, discharge rate recycles 50 times under conditions of being 0.2C；
It is each successively under conditions of discharge rate is respectively 0.2C, 0.5C, 1C, 2C, 5C, 0.2C to recycle 4 times.
Relevant parameter performance is carried out to the product in embodiment (being representative with embodiment 2) and comparative example below to compare.
1.XRD (X-ray diffraction)
X-ray diffraction is carried out to product in embodiment 2 and comparative example respectively.
Fig. 1 and Fig. 2 represents the XRD of product in embodiment 2 and comparative example as a result, as seen from the figure respectively, product in embodiment 2
Diffraction maximum peak up to more than 17000, and the diffraction maximum peak of product is 16000 or so in comparative example, embodiment 2 and right
Other numerical value of product and its fluctuation situation are similar in ratio.
2.SEM (scanning electron microscope)
Electron micrographs are carried out to product in embodiment 2 and comparative example respectively.
Fig. 3 and Fig. 4 represents the SEM of product in embodiment 2 and comparative example as a result, as seen from the figure respectively, product in embodiment 2
Structure more clear and definite.
3. specific discharge capacity in cyclic process
By product in embodiment 2 and comparative example voltage be 3.25V, discharge rate be 0.2C under conditions of recycle 50 times.
Two curves in Fig. 5 represent that specific discharge capacity is examined in the cyclic process of product in embodiment 2 and comparative example respectively
It surveys as a result, as seen from the figure, specific discharge capacity fluctuation range is smaller during product circulation in embodiment 2, then its cyclical stability
It is higher.
4. high rate performance
By product in embodiment 2 and comparative example under conditions of discharge rate is respectively 0.2C, 0.5C, 1C, 2C, 5C, 0.2C
It is each successively to recycle 4 times.
Two broken lines represent the testing result of product in embodiment 2 and comparative example respectively in Fig. 6, as seen from the figure, initial
In the state of 0.2C and 0.5C, embodiment 2 is close with the specific discharge capacity of product in comparative example；Later, product in embodiment 2
Specific discharge capacity of the specific discharge capacity than product in comparative example is more, and gap is increasing between the two.Then produced in embodiment 2
The high rate performance of object is better than comparative example.
To sum up, niobium is adulterated in no cobalt nickel-base anode material, cathode material structure can be stablized, promote the cycle of positive electrode
Stability and high rate performance.
Those of ordinary skill in the art it should be appreciated that more than embodiment be intended merely to illustrate the present invention,
And be not used as limitation of the invention, as long as in the spirit of the present invention, the change to embodiment described above
Change, modification will be all fallen in scope of the presently claimed invention.
Claims (6)
1. a kind of niobium doping is without cobalt nickel-base anode material, which is characterized in that its molecular formula is Li [NixMn1-x]1-yNbyO2, wherein
0.5≤x≤0.9,0 ＜ y ＜ 0.1.
2. a kind of niobium according to claim 1 adulterates the preparation method without cobalt nickel-base anode material, which is characterized in that including such as
Lower step：
(1) by soluble nickel salt, manganese salt according to molar ratio x：(1-x) is dissolved in deionized water, is made into a concentration of 0.5~4mol/L
Transition-metal ion solution, wherein 0.5≤x≤0.9；
(2) mixed solution with alkaline and ammonium hydroxide, a concentration of 1~6mol/L；
(3) a certain amount of deionized water and heat temperature raising are added in a kettle, the nickel prepared in (1), the mixing of manganese salt is molten
The alkali and the mixed solution of ammonium hydroxide prepared in liquid and (2) are added dropwise in reaction kettle respectively by peristaltic pump, and simultaneously to reaction kettle
Interior solution carries out heating stirring, while N is passed through into reaction kettle2, control the temperature of reaction system, pH in reaction kettle constant, into
Row coprecipitation reaction；Precipitated product, suction filtration, drying are washed with deionized after having reacted, obtains presoma NixMn1-x(OH)2；
(4) it is (1-y) in molar ratio by the presoma and the compound of lithium that are prepared in (3), the compound of niobium：1：Y ball milling mixings
Uniformly, wherein 0 ＜ y ＜ 0.1, the powder high temperature sintering that will be mixed, obtain mixing niobium nickel-base anode material.
3. preparation method according to claim 2, which is characterized in that soluble nickel salt described in step (1) be nickel sulfate,
One kind in nickel chloride, nickel nitrate, nickel acetate；Soluble manganese salt is one kind in manganese sulfate, manganese chloride, manganese nitrate, manganese acetate.
4. preparation method according to claim 2, which is characterized in that aqueous slkali described in step (2) is sodium hydroxide, carbon
One kind in sour sodium, potassium hydroxide.
5. preparation method according to claim 2, which is characterized in that reaction system in reaction kettle described in step (3)
Temperature is 30~70 DEG C, and pH is 9~12.
6. preparation method according to claim 2, which is characterized in that high temperature sintering described in step (4) be with 1~6 DEG C/
The heating rate of min is warming up to 400~600 DEG C, keeps the temperature 3~8h, is then warming up to 750 again with the heating rate of 1~6 DEG C/min
~960 DEG C, keep the temperature 6~20h.
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| CN109970106A (en) * | 2019-03-28 | 2019-07-05 | 广东迈纳科技有限公司 | A kind of large-scale producing method of nickelic no cobalt precursor and positive electrode |
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| CN111584872A (en) * | 2020-05-20 | 2020-08-25 | 哈尔滨工业大学（威海） | Niobium-doped lithium ion battery positive electrode material and preparation method thereof |
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| CN110190276A (en) * | 2019-07-10 | 2019-08-30 | 河南电池研究院有限公司 | A kind of preparation method of niobium, aluminium codope anode material for lithium-ion batteries |
| WO2021195524A1 (en) | 2020-03-27 | 2021-09-30 | Board Of Regents, The University Of Texas System | Low-cobalt and cobalt-free, high-energy cathode materials for lithium batteries |
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| CN112382734A (en) * | 2020-08-25 | 2021-02-19 | 万向一二三股份公司 | Lithium ion battery positive plate using cobalt-free high-nickel positive electrode material |
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| CN113060776A (en) * | 2021-03-31 | 2021-07-02 | 蜂巢能源科技有限公司 | Layered cobalt-free cathode material, preparation method thereof and lithium ion battery |
| CN113060776B (en) * | 2021-03-31 | 2023-07-25 | 蜂巢能源科技有限公司 | Layered cobalt-free positive electrode material, preparation method thereof and lithium ion battery |
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| CN115231624A (en) * | 2022-05-12 | 2022-10-25 | 多氟多新能源科技有限公司 | High-cost-performance cobalt-nickel-manganese-free binary material and preparation method thereof |
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| CN115275184A (en) * | 2022-07-26 | 2022-11-01 | 合肥综合性国家科学中心能源研究院(安徽省能源实验室) | High-nickel cobalt-free cathode material of lithium ion battery and preparation method thereof |
| CN115810745A (en) * | 2022-12-23 | 2023-03-17 | 成都理工大学 | High-performance cobalt-free high-nickel lithium ion battery cathode material and preparation method thereof |
| CN115676919A (en) * | 2022-12-28 | 2023-02-03 | 河南科隆电源材料有限公司 | Modified cobalt-free precursor material and preparation method thereof |
| CN115663198A (en) * | 2022-12-29 | 2023-01-31 | 宜宾锂宝新材料有限公司 | Cobalt-free cathode material, preparation method thereof, cathode and lithium ion battery |
| CN115663198B (en) * | 2022-12-29 | 2023-04-14 | 宜宾锂宝新材料有限公司 | Cobalt-free cathode material, preparation method thereof, cathode and lithium ion battery |
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