CN108258201A - Doping type small particle nickel-cobalt lithium manganate cathode material and its presoma and the preparation method of the two - Google Patents
Doping type small particle nickel-cobalt lithium manganate cathode material and its presoma and the preparation method of the two Download PDFInfo
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Abstract
The present invention relates to doping type small particle nickel-cobalt lithium manganate cathode material and its presoma and the preparation method of the two, the present invention produces small particle hydroxide precursor using core coprecipitation is made, and the chemical general formula of the presoma is mA/NixCoyMn1‑x‑y(OH)2, wherein 0.3≤x≤0.5,0.1≤y ＜ 0.5, A are zirconium, magnesium, titanium, aluminium one or more therein, m represents that element A accounts for the mass fraction of nickel cobalt manganese hydroxide precursor gross mass as m%, 0.05≤m≤0.5；4.0 >=D10 of grain size >=1.5um, 2.0um≤D50≤5.0um, D90≤8um, specific surface area≤30m2/ g, 2.0 >=TD of tap density >=1.3g/cm3.The features such as presoma has Elemental redistribution uniform, and granule-morphology is spherical or spherical, and specific surface area is controllable, and tap density is higher, and the sintering Posterior circle service life is high and capacity is high.
Description
Technical field
The present invention relates to the preparation sides of a kind of doping type small particle power type nickel-cobalt lithium manganate cathode material and its presoma
Method.
Background technology
Lithium-ion-power cell is with its operating voltage is high, energy density is big, the advantages such as environmental-friendly are widely used to electricity
The fields such as motor-car, electric tool and power grid energy storage.Wherein as the critical material for influencing lithium-ion-power cell performance, anode material
The development ＆ production of material is most important.High-energy-density, long-life and high security positive electrode have become countries in the world research and development and have closed
The hot spot of note.
Lithium ion power battery cathode material of greatest concern at present includes LiFePO4 (LiFePO4), LiMn2O4
(LiMn2O4), nickel-cobalt-manganese ternary material (LiNi1-x-yCoxMnyO2) 3 kinds.The cycle life of nickel-cobalt-manganese ternary material is much better than
LiCoO2, energy density is higher than LiFePO4, specific capacity is better than LiMn2O4, be lithium ion power battery cathode material important choosing
It selects, while is also the main direction of development of following power battery anode material.
Lithium-ion-power cell generally requires that positive electrode energy density is big, power density is high, has extended cycle life, price
It is low.However with promotion of the electronic equipment to lithium ion battery with high energy density demand, traditional positive electrode has been unable to meet will
It asks.Research shows that improving charging voltage, the capacity of battery can be improved, and then improve its energy density.But positive electrode is in high electricity
Screw-down structure becomes unstable, declines the cycle performance of battery.At present, most domestic positive electrode manufacturer is with upstream
The presoma of enterprise prepares positive electrode for raw material, shows that positive electrode performance 90% depends on ternary precursor according to the study,
So the presoma haveing excellent performance is most important for ternary material.Therefore some metallic elements are added in presoma from root
Improve lattice structure on this, improve structural stability, can fundamentally improve material circulation performance.
Invention content
The object of the present invention is to provide a kind of doping type small particle power type nickel-cobalt lithium manganate cathode material presoma and its
Preparation method, to obtain the small particle that Elemental redistribution is uniform, good sphericity, even particle size distribution, cycle life are high and capacity is high
Positive electrode；
In order to achieve the above object, the present invention has following technical solution：
The present invention's
A kind of doping type small particle nickel cobalt manganese hydroxide precursor, it is characterised in that：Chemical general formula is mA/
NixCoyMn1-x-y(OH)2, wherein 0.3≤x≤0.5,0.1≤y ＜ 0.5, A are zirconium, magnesium, titanium, aluminium one or more therein, m
Represent that element A accounts for the mass fraction of nickel cobalt manganese hydroxide precursor gross mass as m%, 0.05≤m≤0.5；Wherein nickel cobalt manganese
4.0 >=D10 of grain size >=1.5um of hydroxide, 2.0um≤D50≤5.0um, D90≤8um, specific surface area≤30m2/ g, shakes
2.0 >=TD of real density >=1.3g/cm3；Shape is spherical or spherical.
A kind of preparation method of doping type small particle nickel cobalt manganese hydroxide, includes the following steps：
(1) according to chemical general formula mA/NixCoyMn1-x-y(OH)2Middle nickel, cobalt, manganese molar ratio total ion concentration are 1.0-
Nickel, cobalt, the manganese mixing salt solution of 2.5mol/L, then mixes element A, and element A is made to account for the total matter of nickel cobalt manganese hydroxide precursor
The mass fraction of amount be m%, 0.05≤m≤0.5；Compound concentration is the sodium hydroxide solution of 4-8mol/L；Prepare 5-10mol/L
Ammonia solution；
(2) it is 0.5-4.5g/L that ammonia density is added in into the reaction kettle of sealing, and pH value is the mother liquor of 10.0-12.5, is added in
The volume of mother liquor is the 30-80% of reaction kettle total volume；The mother liquor is ammonia and the mixed solution of sodium hydroxide；
(3) nitrogen is passed through into the reaction kettle, opens stirring, rotating speed 100-800r/min；By 4-8mol/L hydrogen-oxygens
The ammonia spirit for changing sodium solution and 5-10mol/L is continuously pumped by alkali pump and ammonia pump in reaction kettle respectively, continues 5-15min；
Ammonia pump and alkali pump are then shut off, passes through metal mixed liquid pump doped with the nickel of element A, cobalt, manganese mixing salt solution by prepared
It is pumped into reaction kettle, continues 5-15min；Then alkali pump, ammonia pump are also opened, control reaction system ammonia density is 0.5-4.5g/
L, pH value 10.0-12.5, reaction temperature are 25-65 DEG C, are pumped into instead with doped with the nickel of element A, cobalt, manganese mixing salt solution
It answers in kettle, material particular diameter is gradually grown up in reaction system, material particular diameter numerical value in every test reaction kettle every other hour；Work as reaction kettle
Overflow valve is opened after full, reaction kettle material particular diameter size and overflow material when material being made to flow into surge tank, and recording underflow stream
Particle size；When in reaction kettle material with overflow material average grain diameter in 2.0um-5.0um when stop react；Ammonia pump, alkali pump and
Metal salt solution pump is precision metering pump.
(4) after reaction, solid material is obtained after sloughing mother liquor and washing with centrifuge.
(5) solid material washed is put into baking oven, controlled at 80-130 DEG C, is dried to moisture≤1.5% i.e.
It can；
(6) material dried is crossed into the screening of 400 mesh screens and can obtain the hydroxide precursor.
A kind of doping type nickel-cobalt lithium manganate cathode material of the present invention has above-mentioned hydroxide precursor, presoma
Chemical general formula is mA/NixCoyMn1-x-y(OH)2, wherein 0.3≤x≤0.5,0.1≤y ＜ 0.5, A are zirconium, magnesium, titanium, aluminium are therein
One or more, m represent that element A accounts for the mass fraction of nickel cobalt manganese hydroxide precursor gross mass as m%, 0.05≤m≤
0.5。
A kind of preparation method of doping type nickel-cobalt lithium manganate cathode material of the present invention is by will be before above-mentioned hydroxide
It drives after body crushes with the baking mixed preparation of lithium source, i.e., the powder of the presoma and lithium source is blended in 700-950 DEG C of roasting 6-
24h。
It is further：First, chemistry is obtained according to the preparation method of the doping type small particle nickel cobalt manganese hydroxide
General formula is mA/NixCoyMn1-x-y(OH)2Modification ternary material precursor；Then by above-mentioned presoma and lithium source in molar ratio 1:
1-1: the 1.2 multistage roastings in Muffle furnace after mixing, 700-950 DEG C of calcination temperature, roasting time 6-24h, multistage roasting
After burning through cooling down, crushing, being sieved obtains doping type nickel-cobalt lithium manganate cathode material.
The preparation method of the nickel-cobalt lithium manganate cathode material introduces metallic element during nickel cobalt manganese presoma is prepared
To stablize its structure, in forerunner's production procedure, the mixing of atom level between doped chemical and main element is realized, relatively
It is adulterated in solid phase surface, this method of modifying can be such that Doped ions enter in the lattice of presoma, fundamentally stablize its knot
Structure.
Due to taking above technical scheme, the advantage of the invention is that：Compared with prior art, using the doping vario-property
Nickel cobalt manganese lithium anode material preparation method prepare cobalt nickel oxide manganses lithium anode material have following characteristics：
(1) it is adulterated relative to traditional solid phase surface, this method stabilizes material structure on the whole so that sintering obtains
Positive electrode under high voltages there is higher stability can realize and work at higher voltages, greatly improve battery appearance
Amount, while its cycle performance has also obtained larger improvement；
(2) production presoma process and later stage doping process are combined into one by the present invention, not only simplify preparation flow, but also can
Cost-effective, used raw material is large chemical products, easily realizes industrialization.
Description of the drawings
Fig. 1 is the SEM figures under modification nickel cobalt manganese hydroxide precursor difference enlargement ratio prepared by embodiment 1；
Fig. 2 is the SEM figures under modification nickel-cobalt lithium manganate cathode material difference enlargement ratio prepared by embodiment 1；
Fig. 3 is the cycle performance figure of modification nickel-cobalt lithium manganate cathode material prepared by embodiment 1；
Fig. 4 is the first charge-discharge curve graph of cobalt nickel oxide manganses lithium anode material prepared by embodiment 1.
Specific embodiment
It is carried out specifically with reference to the preparation method of the nickel-cobalt lithium manganate cathode material of Fig. 1-4 pairs of doping zirconiums of the invention
It is bright
Embodiment 1
0.1Zr/Ni1/3Co1/3Mn1/3(OH)2Preparation：
(1) by Ni：Co：The molar ratio 1 of Mn:1:1, the zirconates for accounting for nickel-cobalt-manganese ternary presoma gross mass 0.1% is added in,
Compound concentration is the nickel cobalt manganese zirconium sulfate mixed aqueous solution of 1.5mol/L, and compound concentration is that the sodium hydroxide of 8mol/L is water-soluble
Liquid, compound concentration are the ammonia spirit of 8mol/L；
(2) it is 1.0-2g/L that ammonia density is added in into reaction kettle, and pH value is the mother liquor of 11.0-11.5, and mother liquor is made to be
The 60% of reaction kettle volume；
(3) nitrogen 1L/min is passed through into the reaction kettle of sealing, opens stirring, rotating speed 140r is configured with step (1)
Sodium hydrate aqueous solution and ammonia spirit be continuously pumped into 15min in reaction kettle, during which metal mixed liquid pump is closed, and closes ammonia alkali
Pump；Metal mixed liquid pump is opened, the prepared metal salt solution of step is pumped into reaction kettle, and pH value in test reaction kettle,
System pH is about 15min in 11.0-11.5, this process；
(4) three pumps are opened simultaneously, the hydrogen that the metal salt solution prepared in step (1) and step (1) have been configured respectively
Aqueous solution of sodium oxide is added to ammonia spirit cocurrent in reaction kettle, and controlling reaction temperature is 35 DEG C, rotating speed 140r/min,
NH3Concentration 1.0-2.0g/L, and sodium hydrate aqueous solution flow is adjusted, control the pH=11.0-11.5 of reaction solution；
(5) as metal salt solution is continued into reaction kettle, grain size is gradually grown up in system, anti-per test every other hour
Grain diameter value in kettle is answered, opens overflow valve after reaction kettle is full, reaction kettle when material being made to flow into surge tank, and recording underflow stream
Middle grain size number.When in reaction kettle material with overflow material average particle size in 3.10um when stop react.
(6) after reaction, mother liquor is sloughed with centrifuge, obtains nickel cobalt manganese hydroxide solids material.
(7) dewatered solid material is dried at 90 DEG C, until moisture≤1.5%.
(8) material dried crosses the screening of 400 mesh screens, before material is doping vario-property nickel cobalt manganese hydroxide after screening
Drive body.
Gained presoma grain size be D10=1.80um, D50=3.10um, D90=5.0um, tap density=1.3g/
cm3, surface area=20m2/ g, for spherical or spherical presoma；Fig. 1 is the SEM under the presoma difference enlargement ratio
Figure.
By step (8) presoma and lithium source, 1: 1.1 multistage roasts in Muffle furnace after mixing in molar ratio, with 3 DEG C/
The heating rate of min makes its calcination temperature rise to 720 DEG C, roasting time 18h, through cooling down, crushing, being sieved after multistage roasting
To modified nickel-cobalt lithium manganate cathode material.Fig. 2 is the SEM that gained is modified under nickel-cobalt lithium manganate cathode material difference enlargement ratio
Figure.
Embodiment 2：
0.08Mg/Ni0.5Co0.2Mn0.3(OH)2Preparation：
(1) by Ni：Co：The molar ratio 5 of Mn:2:3, the magnesium for accounting for nickel-cobalt-manganese ternary presoma gross mass 0.08% is added in,
Compound concentration is the nickel cobalt manganese magnesium sulfate mixed aqueous solution of 1.8mol/L, and compound concentration is that the sodium hydroxide of 6mol/L is water-soluble
Liquid, compound concentration are the ammonia spirit of 10mol/L；
(2) it is 2.5-3.0g/L that ammonia density is added in into reaction kettle, and pH value is the mother liquor of 11.5-12.0, and makes mother liquor
It is the 80% of reaction kettle volume；
(3) nitrogen 0.7L/min is passed through into the reaction kettle of sealing, opens stirring, rotating speed 380r/min, with step (1)
The sodium hydrate aqueous solution being configured is continuously pumped into 10min in reaction kettle with ammonia spirit, and during which metal mixed liquid pump is closed, and closes
Close ammonia alkali pump；Metal mixed liquid pump is opened, step (1) prepared metal salt solution is pumped into 10min in reaction kettle.
(4) three pumps are opened simultaneously, the hydrogen that the metal salt solution prepared in step (1) and step (1) have been configured respectively
Aqueous solution of sodium oxide is added to ammonia spirit cocurrent in reaction kettle, and controlling reaction temperature is 50 DEG C, rotating speed 380r/min,
NH3Concentration 2.5-3.0g/L, and sodium hydrate aqueous solution flow is adjusted, control the pH=11.5-12.0 of reaction solution；
(5) as metal salt solution is continued into reaction kettle, grain size is gradually grown up in system, anti-per test every other hour
Grain diameter value in kettle is answered, opens overflow valve after reaction kettle is full, reaction kettle when material being made to flow into surge tank, and recording underflow stream
Middle grain size number.When in reaction kettle material with overflow material average particle size in 2.88um when stop react.
(6) after reaction, mother liquor is sloughed with centrifuge, obtains nickel cobalt manganese hydroxide solids material.
(7) dewatered solid material is dried at 80 DEG C, until moisture≤1.5%.
(8) material dried crosses the screening of 400 mesh screens, before material is doping vario-property nickel cobalt manganese hydroxide after screening
Drive body；Gained presoma D10=1.60um, D50=2.88um, D90=4.6um, tap density=1.3g/cm3, surface area
=18.2m2/ g, for spherical or spherical presoma.
By step (8) presoma and lithium source, 1: 1.1 multistage roasts in Muffle furnace after mixing in molar ratio, with 5 DEG C/
The heating rate of min makes its calcination temperature rise to 900 DEG C, roasting time 10h, after multistage roasting through cooling down, crushing, being sieved obtains
Modified nickel-cobalt lithium manganate cathode material.
Embodiment 3：
0.42Al/Ni0.4Co0.2Mn0.4(OH)2Preparation：
(1) by Ni：Co：The molar ratio 4 of Mn:2:4, add in the aluminium member for accounting for nickel-cobalt-manganese ternary presoma gross mass 0.42%
Element, compound concentration are the nickel cobalt manganese aluminium sulfate mixed aqueous solution of 2.0mol/L, and compound concentration is the sodium hydroxide water of 8mol/L
Solution, compound concentration are the ammonia spirit of 8mol/L；
(2) it is 0.5-1.0g/L that ammonia density is added in into reaction kettle, and pH value is the mother liquor of 10.5-11.0, and makes mother liquor
It is the 40% of reaction kettle volume；
(3) nitrogen 1.5L/min is passed through into the reaction kettle of sealing, opens stirring, rotating speed 200r/min, with step (1)
The sodium hydrate aqueous solution being configured is continuously pumped into 5min in reaction kettle with ammonia spirit, and during which metal mixed liquid pump is closed, and closes
Close ammonia alkali pump；Metal mixed liquid pump is opened, the prepared metal salt solution of step, which is pumped into reaction kettle, makes pH value in reaction kettle
For 10.5-11.0, this process is about 5min.
(4) three pumps are opened simultaneously, the hydrogen that the metal salt solution prepared in step (1) and step (1) have been configured respectively
Aqueous solution of sodium oxide is added to ammonia spirit cocurrent in reaction kettle, and controlling reaction temperature is 45 DEG C, rotating speed 200r/min,
NH3Concentration=0.5-1.0g/L, and sodium hydrate aqueous solution flow is adjusted, control the pH=10.5-11.0 of reaction solution；
(5) as metal salt solution is continued into reaction kettle, grain size is gradually grown up in system, anti-per test every other hour
Grain diameter value in kettle is answered, opens overflow valve after reaction kettle is full, reaction kettle when material being made to flow into surge tank, and recording underflow stream
Middle grain size number.When in reaction kettle material with overflow material average particle size in 3.21um when stop react.
(6) after reaction, mother liquor is sloughed with centrifuge, obtains nickel cobalt manganese hydroxide solids material.
(7) dewatered solid material is dried at 100 DEG C, until moisture≤1.5%；
(8) material dried crosses the screening of 400 mesh screens, before material is doping vario-property nickel cobalt manganese hydroxide after screening
Drive body.Gained presoma D10=2.01um, D50=3.21um, D90=5.42um, tap density=1.53g/cm3, surface face
Product=18.72m2/ g, for spherical or spherical presoma.
By step (8) presoma and lithium source, 1: 1.1 multistage roasts in Muffle furnace after mixing in molar ratio, with 2 DEG C/
The heating rate of min makes its calcination temperature rise to 850 DEG C, roasting time 15h, after multistage roasting through cooling down, crushing, being sieved obtains
Modified nickel-cobalt lithium manganate cathode material.
In addition, also by carrying out X-ray diffraction (XRD) and scanning electron microscope to Examples 1 to 3 products therefrom
(SEM) it tests, the centre obtained in the cobalt nickel oxide manganses lithium anode material preparation method being modified to use doping zirconium, magnesium, titanium, aluminium
Body and final positive electrode obtained are analyzed, and are led to the same conclusion.Fig. 2 is positive electrode prepared by embodiment 1
SEM schemes, it can be seen from the figure that product sphericity is preferable, even particle distribution.Fig. 3 is modification nickel cobalt manganese prepared by embodiment 1
The cycle performance figure of sour lithium anode material；Fig. 4 is that the first charge-discharge of cobalt nickel oxide manganses lithium anode material prepared by embodiment 1 is bent
Line chart.It can be seen that positive electrode prepared by this method has higher stability, Ke Yishi under high voltages from Fig. 3 and Fig. 4
Now higher operating at voltages, its cycle performance has also obtained larger improvement while battery capacity is greatly improved.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description
To make other variations or changes in different ways.Here all embodiments can not be exhaustive.It is every to belong to this hair
The obvious changes or variations that bright technical solution is extended out are still in the row of protection scope of the present invention.
Claims (5)
1. a kind of doping type small particle nickel cobalt manganese hydroxide precursor, it is characterised in that：Chemical general formula is mA/NixCoyMn1-x-y
(OH)2, wherein 0.3≤x≤0.5,0.1≤y ＜ 0.5, A are zirconium, magnesium, titanium, aluminium one or more therein, m represents that element A accounts for
The mass fraction of nickel cobalt manganese hydroxide precursor gross mass be m%, 0.05≤m≤0.5；4.0 >=D10 of grain size >=1.5um,
2.0um≤D50≤5.0um, D90≤8um, specific surface area≤30m2/ g, 2.0 >=TD of tap density >=1.3g/cm3。
2. a kind of preparation method of doping type small particle nickel cobalt manganese hydroxide precursor, which is characterized in that include the following steps：
(1) according to chemical general formula mA/NixCoyMn1-x-y(OH)2Middle nickel, cobalt, manganese molar ratio total ion concentration are 1.0-
Nickel, cobalt, the manganese mixing salt solution of 2.5mol/L, then mixes element A, and element A is made to account for the total matter of nickel cobalt manganese hydroxide precursor
The mass fraction of amount be m%, 0.05≤m≤0.5；Compound concentration is the sodium hydroxide solution of 4-8mol/L；Prepare 5-10mol/L
Ammonia solution；
(2) it is 0.5-4.5g/L that ammonia density is added in into the reaction kettle of sealing, and pH value is the mother liquor of 10.0-12.5, adds in mother liquor
Volume be reaction kettle total volume 30-80%；The mother liquor is ammonia and the mixed solution of sodium hydroxide；
(3) nitrogen is passed through into the reaction kettle, opens stirring, rotating speed 100-800r/min；By 4-8mol/L sodium hydroxides
The ammonia spirit of solution and 5-10mol/L are continuously pumped by alkali pump and ammonia pump in reaction kettle respectively, continue 5-15min；Then
Ammonia pump and alkali pump are closed, is pumped into prepared doped with the nickel of element A, cobalt, manganese mixing salt solution by metal mixed liquid pump
In reaction kettle, continue 5-15min；Then alkali pump, ammonia pump are also opened, control reaction system ammonia density is 0.5-4.5g/L, pH
It is worth for 10.0-12.5, reaction temperature is 25-65 DEG C, and reaction kettle is pumped into doped with the nickel of element A, cobalt, manganese mixing salt solution
In, material particular diameter is gradually grown up in reaction system, material particular diameter numerical value in every test reaction kettle every other hour；After reaction kettle is full
Overflow valve is opened, reaction kettle material particular diameter size and overflow material grain size when material being made to flow into surge tank, and recording underflow stream
Size；When in reaction kettle material with overflow material average grain diameter in 2.0um-5.0um when stop react；
(4) after reaction, solid material is obtained after sloughing mother liquor and washing with centrifuge；
(5) solid material washed is put into baking oven, controlled at 80-130 DEG C, is dried to moisture≤1.5%；
(6) material dried is crossed into the screening of 400 mesh screens and can obtain the hydroxide precursor.
3. the preparation method of doping type small particle nickel cobalt manganese hydroxide precursor according to claim 2, feature exist
In：Ammonia pump, alkali pump and metal salt solution pump are precision metering pump.
4. a kind of nickel-cobalt lithium manganate cathode material prepared by hydroxide precursor, it is characterised in that：Its presoma chemical general formula
For mA/NixCoyMn1-x-y(OH)2, wherein 0.3≤x≤0.5,0.1≤y ＜ 0.5, A are zirconium, magnesium, titanium, aluminium one kind or several therein
Kind, m represents that element A accounts for the mass fraction of nickel cobalt manganese hydroxide precursor gross mass as m%, 0.05≤m≤0.5.
5. a kind of method that hydroxide precursor prepares nickel-cobalt lithium manganate cathode material, it is characterised in that：By the hydroxide
Object presoma and lithium carbonate or lithium hydroxide in high-speed mixer are uniformly mixed at 1: 1-1: 1.2 in molar ratio；It is subsequently placed in stove
In, with the heating rate of 2-6 DEG C/min under air or oxygen atmosphere, 700-950 DEG C is risen to, calcining 6-24 hours is kept, forges
After burning, the nickel-cobalt lithium manganate cathode material is can obtain after supercooling, broken, screening.
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| CN109336193A (en) * | 2018-10-21 | 2019-02-15 | 圣戈莱（北京）科技有限公司 | Multielement original position codope ternary material precursor and its preparation method and application |
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| CN109336193A (en) * | 2018-10-21 | 2019-02-15 | 圣戈莱（北京）科技有限公司 | Multielement original position codope ternary material precursor and its preparation method and application |
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| CN109713274A (en) * | 2018-12-28 | 2019-05-03 | 天能电池(芜湖)有限公司 | A kind of high-capacity lithium ion power battery and preparation method thereof |
| CN110540253A (en) * | 2019-07-23 | 2019-12-06 | 河南科隆新能源股份有限公司 | Doped nickel-cobalt-manganese hydroxide precursor and preparation method thereof |
| CN112850807A (en) * | 2019-11-28 | 2021-05-28 | 惠州比亚迪电池有限公司 | Ternary precursor, preparation method, ternary material and lithium ion battery |
| CN112850807B (en) * | 2019-11-28 | 2024-01-09 | 惠州比亚迪电池有限公司 | Ternary precursor, preparation method, ternary material and lithium ion battery |
| CN112591805A (en) * | 2020-12-14 | 2021-04-02 | 荆门市格林美新材料有限公司 | Method for improving particle size distribution width of nickel-cobalt-manganese ternary precursor |
| CN112591805B (en) * | 2020-12-14 | 2023-09-26 | 荆门市格林美新材料有限公司 | Method for improving particle size distribution width of nickel-cobalt-manganese ternary precursor |
| CN112725628A (en) * | 2020-12-23 | 2021-04-30 | 贵州大龙汇成新材料有限公司 | Method for recovering valuable elements from manganese sulfide slag |
| CN112678880A (en) * | 2020-12-23 | 2021-04-20 | 贵州大龙汇成新材料有限公司 | Method for recycling manganese slag |
| CN113292114A (en) * | 2021-05-24 | 2021-08-24 | 厦门大学 | Preparation method of Ti-Mg-containing co-doped NCM811 type precursor |
| CN113809321A (en) * | 2021-09-15 | 2021-12-17 | 深圳石墨烯创新中心有限公司 | Preparation method and application of precursor of aluminum and zirconium doped lithium nickelate cathode material |
| CN113651374A (en) * | 2021-10-20 | 2021-11-16 | 浙江帕瓦新能源股份有限公司 | Preparation method of ferrozirconium-doped nickel-cobalt-manganese ternary precursor |
| CN113651374B (en) * | 2021-10-20 | 2021-12-21 | 浙江帕瓦新能源股份有限公司 | Preparation method of ferrozirconium-doped nickel-cobalt-manganese ternary precursor |
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