CN110504447A - A kind of nickel cobalt manganese presoma of Fluorin doped and the preparation method and application thereof - Google Patents
A kind of nickel cobalt manganese presoma of Fluorin doped and the preparation method and application thereof Download PDFInfo
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- CN110504447A CN110504447A CN201910816115.0A CN201910816115A CN110504447A CN 110504447 A CN110504447 A CN 110504447A CN 201910816115 A CN201910816115 A CN 201910816115A CN 110504447 A CN110504447 A CN 110504447A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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 present invention provides nickel cobalt manganese presoma of a kind of Fluorin doped and the preparation method and application thereof, method includes: that the soluble-salt of nickel, cobalt is configured to the first mixed liquor containing nickel salt and cobalt salt；The soluble salt solutions of manganese and soluble fluoride salt dissolving complexing agent are configured to the second mixed liquor under conditions of being passed through protective gas；First mixed liquor, the second mixed liquor and sodium hydroxide solution and ammonia spirit cocurrent are added in the reaction kettle with Vltrasonic device, keeping temperature is 50~60 DEG C, and it is stirred with the speed of 500~800r/min to reaction and is terminated, sediment is obtained after aged and separation of solid and liquid, gained sediment is washed and dry, obtains fluorine-ion-doped nickel cobalt manganese presoma.Gained persursor material has spherical structure, and specific surface area is 5.6~6.3m2/ g, tap density are 2.2~2.7g/cm3, gained positive electrode chemical property is good.
Description
Technical field
The present invention relates to battery material preparation technical field, in particular to the nickel cobalt manganese presoma and its system of a kind of Fluorin doped
Preparation Method and application.
Background technique
Lithium ion battery has many advantages, such as high-energy, long-life, memory-less effect and low pollution, is widely used in hand
Each field such as machine, computer, electric car.Currently, the positive electrode that lithium ion battery uses mainly has cobalt acid lithium, ferric phosphate
Lithium, LiMn2O4 and nickle cobalt lithium manganate etc..Wherein, the maximum positive electrode of occupation rate of market is cobalt acid lithium, but cobalt is as strategy
Property resource reserve is seldom, expensive, and the security performance of cobalt acid lithium is poor, limits the further development of the material.And
Nickle cobalt lithium manganate has many advantages, such as that specific capacity is high, thermal stability is good and cheap, be in anode material for lithium-ion batteries most
Potential one kind has a good application prospect in dynamic fields such as electric vehicle, electric tools.
Currently, the common method for preparing nickle cobalt lithium manganate has high temperature solid-state method and co-precipitation-high temperature solid-state method.High temperature solid-state
Method is that nickel source, cobalt source, manganese source, lithium source ball milling then are carried out high-temperature calcination.The disadvantages of the method are as follows being difficult to nickel cobalt manganese three
The pattern for the material that kind element is uniformly mixed, therefore cannot give full play to the synergistic effect of three, and prepare is difficult to control,
The powder body material usually synthesized is made of random particle, the tap density of this material, and poor fluidity is unfavorable for positive material
The production of material.Another method is co-precipitation-high temperature solid-state method, that is, is first passed through before coprecipitation prepares nickel cobalt manganese hydroxide
Body is driven, lithium source sintering is added, obtains nickle cobalt lithium manganate.This method does not change substantially in the sintering process being added after lithium source
The pattern and granularity of presoma, and the pattern of nickel-cobalt lithium manganate material, granularity play pass in many performances of lithium ion battery
The effect of key.Therefore, synthesize to become with the nickel cobalt manganese hydroxide precursor for being suitable for pattern and granularity and influence nickel cobalt mangaic acid
The key factor of lithium performance.
But had difficulties using traditional Co deposited synthesis nickel cobalt manganese hydroxide precursor, mainly due to manganese
The precipitating concentration of ion is long-pending to differ several orders of magnitude with the precipitating concentration of nickel, cobalt element product, in coprecipitation reaction manganese ion and
Settling velocity hydroxy is very fast, and flocculent deposit easy to form, causes presoma particle size growth difficult, forerunner obtained
Body tap density is low, sphericity is poor, granularity is small, is difficult to clean.
It is therefore desirable to the deposition velocities to manganous hydroxide during closing presoma with coprecipitation to regulate and control, and realize manganese
Element and cobalt, nickel element homogeneous deposition, improve the tap density and specific surface area of presoma, improve the electrochemistry of positive electrode
Energy.
Summary of the invention
The present invention provides nickel cobalt manganese presomas of a kind of Fluorin doped and the preparation method and application thereof, and its purpose is to mention
The tap density and specific surface area of high presoma, improve the chemical property of positive electrode.
In order to achieve the above object, the invention provides the following technical scheme:
A kind of preparation method of the nickel cobalt manganese presoma of Fluorin doped, includes the following steps:
(1) soluble-salt of nickel, cobalt is configured to the first mixed liquor containing nickel salt and cobalt salt；By the soluble salt solutions of manganese
The second mixed liquor is configured to soluble fluoride salt dissolving complexing agent；Wherein, the molar ratio of fluorine ion and manganese ion is 1~5:1；
(2) by the first mixed liquor obtained by step (1), the second mixed liquor and sodium hydroxide under conditions of being passed through protective gas
Solution and ammonia spirit cocurrent are added in the reaction kettle with Vltrasonic device, and keeping temperature is 50~60 DEG C, and with 500~
The speed of 800r/min, which is stirred to reaction, to be terminated, aged and obtain sediment after being separated by solid-liquid separation, gained sediment it is washed and
It is dry, obtain fluorine-ion-doped nickel cobalt manganese presoma；
Wherein, the additional amount of the sodium hydroxide solution is that pH value of solution is made to be maintained at 9~12；The molal quantity of the ammonium hydroxide with
Nickel, cobalt, three metal ion species total moles of manganese ratio be 1~10:1；The power of the Vltrasonic device is set as 520~560W.
Preferably, nickel salt described in step (1) is nickel sulfate, nickel chloride, nickel acetate or nickel nitrate；The cobalt salt is sulfuric acid
Cobalt, cobalt acetate or cobalt nitrate；The manganese salt is manganese sulfate, manganese chloride, manganese acetate or manganese nitrate.
Preferably, soluble fluoride salt dissolving described in step (1) is sodium fluoride, ammonium fluoride or potassium fluoride.
Preferably, protective gas described in step (2) is nitrogen or argon gas.
Preferably, the concentration of sodium hydroxide solution described in step (2) is 2~8mol/L.
Preferably, the concentration of ammonia spirit described in step (2) is 5~10mol/L.
Preferably, digestion time is 24~72h in step (2).
Preferably, dry for vacuum drying described in step (2), drying temperature is 90~105 DEG C, drying time is 20~
24h。
The present invention also provides a kind of nickel cobalt manganese presoma of Fluorin doped, the presoma is prepared by the above method.
The present invention also provides a kind of nickel-cobalt lithium manganate cathode material of Fluorin doped, the positive electrode is by above-mentioned Fluorin doped
Nickel cobalt manganese presoma mixed with lithium source, be sintered after be made.
The preparation method of the nickel cobalt manganese presoma of Fluorin doped provided by the invention by by the soluble salt solutions of manganese with it is solvable
Property fluoride salt complexing agent is configured to the second mixed liquor, it is molten with nickel, cobalt mixing salt solution, sodium hydroxide solution and ammonium hydroxide
Liquid cocurrent is added in the reaction kettle with Vltrasonic device, and fluorine-ion-doped nickel cobalt manganese presoma precipitating is generated after being stirred to react.
Wherein, [the MnF to occupy the majority is initially formed after manganese ion is mixed with fluorine ion6]4-With [the MnF that occupies the minority4]2-Cooperation ion, these
Cooperate ion can be with slow release Mn2+And F—Ion reaches effectively control Mn2+With (OH)—It generates Mn (OH)3The speed of precipitating,
Make Mn2+With Ni2+、CO2+Homogeneous deposition together forms more uniform spherical structure, improve presoma tap density and
Specific surface area.
Above scheme of the invention have it is following the utility model has the advantages that
Fluorine in the preparation method of the nickel cobalt manganese presoma of Fluorin doped provided by the invention in soluble fluoride salt dissolving complexing agent
Ion and manganese ion form cooperation ion, these cooperation ions can slow release manganese ion and fluorine ion, reach effectively control manganese
Ion and deposition velocity hydroxy, are allowed to the homogeneous deposition together with nickel ion, cobalt ions, improve the tap density of presoma
And specific surface area.The nickel cobalt manganese precursor powder material of Fluorin doped obtained is in more uniform spherical structure in embodiment, than
Surface area is 5.6~6.3m2/ g, tap density are 2.2~2.7g/cm3。
The present invention is provided the first mixed liquor, the second mixed liquor and hydrogen in the preparation method step (2) of nickel cobalt manganese presoma
Sodium hydroxide solution and ammonia spirit cocurrent are added in the reaction kettle with Vltrasonic device, the acting body of ultrasonic wave in the present invention
It is present: on the one hand making each stock dispersion of reaction process more evenly, can significantly to inhibit the group of nano material in reaction process
It is poly-；On the other hand, localized hyperthermia, high-energy brought by ultrasonic cavitation facilitate the formation of nucleus, effectively shorten the reaction time,
And the size and shape of particle can be controlled by adjusting ultrasonic frequency.The power of Vltrasonic device is set as by the present invention
520~560W forms the precursor powder of spherical structure, effectively increases the chemical property of material.By embodiment system
The presoma obtained is assembled into button cell, test result 179.5mAhg after positive electrode is made-1(0.2C), 170mAhg-1
(0.5C), 162.5mAhg-1(1C), 151mAhg-1(2C), 139mAhg-1(5C), 124.5mAhg-1(10C).2C is recycled 300 weeks
90.2% or more capacity retention ratio afterwards.
Specific embodiment
To keep the technical problem to be solved in the present invention, technical solution and advantage clearer, below in conjunction with specific implementation
Example is described in detail.
Embodiment 1
A kind of preparation method of the nickel cobalt manganese presoma of Fluorin doped provided in this embodiment, includes the following steps:
(1) nickel nitrate and cobalt nitrate are configured to the first mixed liquor containing nickel salt and cobalt salt, the concentration of the first mixed liquor is
1mol/L；Manganese nitrate and sodium fluoride are configured to the second mixed liquor；Wherein, nickel, cobalt, manganese ion molar ratio be 5:2:3；Fluorine from
The molar ratio of son and manganese ion is 2:1；
(2) using pH value be 10 ammonia spirit as bottom liquid, by step under conditions of being passed through argon gas as protective gas
(1) ammonia that the sodium hydroxide solution and concentration that the first mixed liquor of gained, the second mixed liquor and concentration are 2mol/L are 5mol/L
Aqueous solution cocurrent be added with Vltrasonic device reaction kettle in, keep temperature be 60 DEG C, and with the speed of 500r/min stir to
Reaction terminates, and is separated by solid-liquid separation after being aged 36h, obtains sediment, be dried in vacuo at 90 DEG C after gained sediment is washed
For 24 hours, fluorine-ion-doped nickel cobalt manganese presoma is obtained；
Wherein, the additional amount of the sodium hydroxide solution is that pH value of solution is made to be maintained at 9；The molal quantity and nickel of the ammonium hydroxide,
Cobalt, three metal ion species total moles of manganese ratio be 1:1；The power of the Vltrasonic device is set as 540W.
The nickel cobalt manganese presoma for the Fluorin doped that the above process is prepared is spherical structure, and particle is relatively uniform, compares table
Size is 5.6m2/ g, tap density 2.5g/cm3。
(3) by Li2CO3It is mixed with the ratio that Fluorin doped nickel cobalt manganese presoma obtained by step (2) is 1.03 in molar ratio
It is even, obtain with lithium presoma, gained be sintered 12h with lithium presoma at 850 DEG C, carry out crushing after cooled to room temperature and
Sieving, obtains Fluorin doped nickel-cobalt lithium manganate cathode material；
Positive electrode obtained by the present embodiment is assembled into button cell to test, specially the following steps are included:
A. according to positive electrode: carbon black: suitable N- methyl pyrrole network is added in the mixing of segregation vinyl fluoride=90:2:8 ratio
Alkanone stirs to form uniform sizing material, and then gained slurry is coated uniformly on aluminium foil, drying, roll-in, cutting, forms anode
Piece；
B. positive plate, cathode (lithium piece), electrolyte, diaphragm and battery case are assembled into and are buckled in the glove box of argon gas protection
Formula battery carries out electrochemical property test, test result 179.5mAhg-1(0.2C), 170mAhg-1(0.5C),
162.5mAhg-1(1C), 151mAhg-1(2C), 139mAhg-1(5C), 124.5mAhg-1(10C).Capacity is protected after 2C is recycled 300 weeks
90.2% or more holdup.
Embodiment 2
A kind of preparation method of the nickel cobalt manganese presoma of Fluorin doped provided in this embodiment, includes the following steps:
(1) nickel chloride and cobalt chloride are configured to the first mixed liquor containing nickel salt and cobalt salt, the concentration of the first mixed liquor is
1.5mol/L；Manganese chloride and potassium fluoride are configured to the second mixed liquor；Wherein, nickel, cobalt, manganese ion molar ratio be 1:1:1；Fluorine
The molar ratio of ion and manganese ion is 1:1；
(2) using pH value be 11 ammonia spirit as bottom liquid, by step under conditions of being passed through nitrogen as protective gas
(1) ammonia that the sodium hydroxide solution and concentration that the first mixed liquor of gained, the second mixed liquor and concentration are 6mol/L are 8mol/L
Aqueous solution cocurrent be added with Vltrasonic device reaction kettle in, keep temperature be 50 DEG C, and with the speed of 700r/min stir to
Reaction terminates, and is separated by solid-liquid separation after being aged 72h, obtains sediment, be dried in vacuo at 105 DEG C after gained sediment is washed
20h obtains fluorine-ion-doped nickel cobalt manganese presoma；
Wherein, the additional amount of the sodium hydroxide solution is that pH value of solution is made to be maintained at 11；The molal quantity and nickel of the ammonium hydroxide,
Cobalt, three metal ion species total moles of manganese ratio be 8:1；The power of the Vltrasonic device is set as 520W.
The nickel cobalt manganese presoma for the Fluorin doped that the above process is prepared is spherical structure, and particle is relatively uniform, compares table
Size is 6.1m2/ g, tap density 2.7g/cm3。
(3) by Li2CO3It is mixed with the ratio that Fluorin doped nickel cobalt manganese presoma obtained by step (2) is 1.03 in molar ratio
It is even, obtain with lithium presoma, gained be sintered 12h with lithium presoma at 850 DEG C, carry out crushing after cooled to room temperature and
Sieving, obtains Fluorin doped nickel-cobalt lithium manganate cathode material；
Positive electrode obtained by the present embodiment is assembled into button cell by 1 the method for embodiment to test, test knot
Fruit is 173.5mAhg-1(0.2C), 164mAhg-1(0.5C), 155.5mAhg-1(1C), 146mAhg-1(2C), 134mAhg-1
(5C), 121.5mAhg-1(10C).90.4% or more capacity retention ratio after 2C is recycled 300 weeks.
Embodiment 3
A kind of preparation method of the nickel cobalt manganese presoma of Fluorin doped provided in this embodiment, includes the following steps:
(1) nickel chloride and cobalt chloride are configured to the first mixed liquor containing nickel salt and cobalt salt, the concentration of the first mixed liquor is
1.5mol/L；Manganese chloride and potassium fluoride are configured to the second mixed liquor；Wherein, nickel, cobalt, manganese ion molar ratio be 5:2:3；Fluorine
The molar ratio of ion and manganese ion is 5:1；
(2) using pH value be 11 ammonia spirit as bottom liquid, by step under conditions of being passed through nitrogen as protective gas
(1) ammonia that the sodium hydroxide solution and concentration that the first mixed liquor of gained, the second mixed liquor and concentration are 8mol/L are 10mol/L
Aqueous solution cocurrent be added with Vltrasonic device reaction kettle in, keep temperature be 55 DEG C, and with the speed of 800r/min stir to
Reaction terminates, and ageing is separated by solid-liquid separation afterwards for 24 hours, obtains sediment, is dried in vacuo at 100 DEG C after gained sediment is washed
22h obtains fluorine-ion-doped nickel cobalt manganese presoma；
Wherein, the additional amount of the sodium hydroxide solution is that pH value of solution is made to be maintained at 12；The molal quantity and nickel of the ammonium hydroxide,
Cobalt, three metal ion species total moles of manganese ratio be 10:1；The power of the Vltrasonic device is set as 560W.
The nickel cobalt manganese presoma for the Fluorin doped that the above process is prepared is spherical structure, and particle is relatively uniform, compares table
Size is 6.3m2/ g, tap density 2.6g/cm3。
(3) by Li2CO3It is mixed with the ratio that Fluorin doped nickel cobalt manganese presoma obtained by step (2) is 1.03 in molar ratio
It is even, obtain with lithium presoma, gained be sintered 12h with lithium presoma at 850 DEG C, carry out crushing after cooled to room temperature and
Sieving, obtains Fluorin doped nickel-cobalt lithium manganate cathode material；
Positive electrode obtained by the present embodiment is assembled into button cell by 1 the method for embodiment to test, test knot
Fruit is 176.5mAhg-1(0.2C), 165mAhg-1(0.5C), 154.5mAhg-1(1C), 142mAhg-1(2C), 130mAhg-1
(5C), 117.5mAhg-1(10C).89.5% or more capacity retention ratio after 2C is recycled 300 weeks.
The above is a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, without departing from the principles of the present invention, it can also make several improvements and retouch, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the nickel cobalt manganese presoma of Fluorin doped, which comprises the steps of:
(1) soluble-salt of nickel, cobalt is configured to the first mixed liquor containing nickel salt and cobalt salt；By the soluble salt solutions of manganese with can
Dissolubility fluoride salt complexing agent is configured to the second mixed liquor；Wherein, the molar ratio of fluorine ion and manganese ion is 1~5:1；
(2) by the first mixed liquor obtained by step (1), the second mixed liquor and sodium hydroxide solution under conditions of being passed through protective gas
And ammonia spirit cocurrent is added in the reaction kettle with Vltrasonic device, keeping temperature is 50~60 DEG C, and with 500~800r/
The speed of min, which is stirred to reaction, to be terminated, and sediment is obtained after aged and separation of solid and liquid, and gained sediment is washed and dry,
Obtain fluorine-ion-doped nickel cobalt manganese presoma；
Wherein, the additional amount of the sodium hydroxide solution is that pH value of solution is made to be maintained at 9~12；The molal quantity and nickel of the ammonium hydroxide,
Cobalt, three metal ion species total moles of manganese ratio be 1~10:1；The power of the Vltrasonic device is set as 480~560W.
2. preparation method according to claim 1, which is characterized in that nickel salt described in step (1) be nickel sulfate, nickel chloride,
Nickel acetate or nickel nitrate；The cobalt salt is cobaltous sulfate, cobalt acetate or cobalt nitrate；The manganese salt is manganese sulfate, manganese chloride, manganese acetate
Or manganese nitrate.
3. preparation method according to claim 1, which is characterized in that soluble fluoride salt dissolving described in step (1) be sodium fluoride,
Ammonium fluoride or potassium fluoride.
4. preparation method according to claim 1, which is characterized in that protective gas described in step (2) is nitrogen or argon gas.
5. preparation method according to claim 1, which is characterized in that the concentration of sodium hydroxide solution described in step (2) is 2
~8mol/L.
6. preparation method according to claim 1, which is characterized in that the concentration of ammonia spirit described in step (2) be 5~
10mol/L。
7. preparation method according to claim 1, which is characterized in that digestion time is 24~72h in step (2).
8. preparation method according to claim 1, which is characterized in that dry for vacuum drying, dry temperature described in step (2)
Degree be 90~105 DEG C, drying time be 20~for 24 hours.
9. a kind of nickel cobalt manganese presoma of Fluorin doped, which is characterized in that the presoma is by claim 1~8 any one institute
The method of stating is prepared.
10. a kind of nickel-cobalt lithium manganate cathode material of Fluorin doped, which is characterized in that the positive electrode is as described in claim 9
Fluorin doped nickel cobalt manganese presoma or any one the method is prepared according to claim 1~8 Fluorin doped nickel
Cobalt manganese presoma mixed with lithium source, be sintered after be made.
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| CN111082030A (en) * | 2019-12-31 | 2020-04-28 | 河北科技大学 | Dual-modified nickel-rich ternary material and preparation method and application thereof |
| CN111082030B (en) * | 2019-12-31 | 2023-08-08 | 河北科技大学 | Dual-modified nickel-rich ternary material and preparation method and application thereof |
| CN112993260A (en) * | 2021-05-12 | 2021-06-18 | 蜂巢能源科技有限公司 | Doped ternary precursor, preparation method, anode material and battery |
| CN112993260B (en) * | 2021-05-12 | 2021-08-17 | 蜂巢能源科技有限公司 | Doped ternary precursor, preparation method, anode material and battery |
| WO2022237576A1 (en) * | 2021-05-12 | 2022-11-17 | 蜂巢能源科技股份有限公司 | Doped ternary precursor, positive electrode material, and preparation method |
| CN114212803A (en) * | 2021-10-28 | 2022-03-22 | 广东邦普循环科技有限公司 | Preparation method of fluorine-doped Prussian blue type sodium ion battery positive electrode material |
| CN114212803B (en) * | 2021-10-28 | 2023-09-12 | 广东邦普循环科技有限公司 | Preparation method of fluorine-doped Prussian blue sodium ion battery positive electrode material |
| CN115028211A (en) * | 2022-06-10 | 2022-09-09 | 天津巴莫科技有限责任公司 | Fluorine-doped nickel-cobalt-manganese-lithium ternary material and preparation method thereof |
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