CN107658451A - A kind of 622NCM tertiary cathode materials and preparation method thereof - Google Patents
A kind of 622NCM tertiary cathode materials and preparation method thereof Download PDFInfo
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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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- 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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Abstract
The present invention relates to a kind of 622NCM tertiary cathode materials and preparation method thereof, belong to electrochemical applications technical field.The material structure is submicron order class spherical particles, a diameter of 300nm~800nm.Methods described is：Using the carbonate deposition MnCo (CO of solvent structure manganese containing cobalt3)2, by MnCo (CO3)2After being well mixed with nickel source, lithium source, high-temperature calcination obtains a kind of 622NCM tertiary cathode materials.This method need not control the pH of solution in course of reaction, and simple to operate, cost is cheap；Ethylene glycol or glycerine are both used as solvent in building-up process, are used as dispersant, compared with coprecipitation, improve particle agglomeration problem again；And obtained end-product size uniformity, particle diameter are smaller and have larger specific surface area, are advantageous to the further infiltrating material of electrolyte, so as to improve the chemical property of battery.
Description
Technical field
The present invention relates to a kind of 622NCM tertiary cathode materials and preparation method thereof, belong to electrochemical applications technical field.
Background technology
Lithium ion battery has operating voltage height, self discharge is few, energy density is big, memory effect is small, has extended cycle life, be green
The advantages that colour circle is protected.Relative to lithium ion battery negative material, positive electrode is shown more in terms of capacity and security
Deficiency, positive electrode turns into the key for determining battery overall performance, therefore must further be studied and the improvement of correlated performance.
Wherein, the research for lithium cobaltate cathode material is earliest, and the technology controlling and process such as its synthesis, pattern and compacting has been made suitable
Maturation, have been used for commercially producing, but it has the shortcomings that low specific capacity, cobalt price, production cost are high.
At present, nickel cobalt manganese (NCM) tertiary cathode material is the focus of research, Ni, Co, Mn be with cycle adjacent element, with
Part Ni, Mn substitution Co can reduce material production cost.Ni is+divalent in NCM tertiary cathode materials, and Co is+trivalent, and Mn is+4
Valency, Mn4+Play rock-steady structure, Co3+Be advantageous to improve electronic conductivity, Ni can improve material by redox to be held
Amount.622NCM tertiary cathode materials (LiNi0.6Co0.2Mn0.2O2) in, the increase of nickel content, the capacity of material can be improved, is had
Wider array of development prospect.In the prior art, the preparation of 622NCM tertiary cathode materials mainly utilizes coprecipitation, controls solution
PH value synthesizes the hydroxide precursor of nickel and cobalt containing manganese, then high-temperature calcination obtains final product, material granule after being mixed with lithium source
Size is substantially more than 5 μm.In precipitation process, the change of solution ph has direct shadow to the precipitation of three kinds of elements of nickel cobalt manganese
Ring, too high too low be easily caused is precipitated not exclusively；In addition, solution rotating speed also has considerable influence, rotating speed to the pattern of material
Too low easily to cause particle agglomeration, rotating speed is too high easily to cause Particle Breakage.The pattern and its size of material are to influence
An important factor for 622NCM tertiary cathode material chemical properties, so synthesizing, pattern is good, 622NCM ternarys of size uniformity
Positive electrode is significant to the chemical property for lifting battery.
The content of the invention
In view of this, the present invention provides a kind of preparation method of 622NCM tertiary cathode materials, the material granule prepared
Size is homogeneous and has large specific surface area, and then improves the chemical property of lithium ion battery.
A kind of 622NCM tertiary cathode materials, it is characterised in that：The material structure is submicron order class spherical particles, directly
Footpath is 300nm~800nm.
A kind of preparation method of 622NCM tertiary cathode materials of the present invention, methods described step are as follows：
Manganese source and cobalt source are dissolved in solvent by step (1), are evenly stirred until and are completely dissolved；Then ammonium hydrogen carbonate is added, is stirred
Mix and be uniformly completely dissolved to ammonium hydrogen carbonate, obtain mixed solution；Wherein the mol ratio of manganese atom, cobalt atom and ammonium hydrogen carbonate is 1:
1:15~20；
Step (2) pours into the mixed solution in reactor, at 160~200 DEG C carry out solvent thermal reaction 15~
20h, purple precipitation is obtained, the purple precipitation is rinsed with water and alcohol, filter residue is dried after suction filtration, obtains middle production
Thing；
Nickel source and lithium source are dissolved in absolute ethyl alcohol by step (3), are evenly stirred until after being completely dissolved, and add among described and produce
Thing, heat and be evaporated at 60~80 DEG C, obtain hybrid solid；Wherein the mol ratio of Ni, Co, Mn, Li atom is 0.6:0.2:
0.2:1.05~1.15；
After step (4) grinds the hybrid solid, 10~15h is calcined at 750~850 DEG C, heating rate is 2~5
DEG C/min, obtain a kind of 622NCM tertiary cathode materials.
Preferably, the solvent is ethylene glycol or glycerine.
Preferably, the manganese source is one or more of manganese nitrate, manganese sulfate, manganese acetate and manganese chloride.
Preferably, the cobalt source is one or more of cobalt nitrate, cobaltous sulfate, cobalt acetate and cobalt chloride.
Preferably, the nickel source is one or more of nickel nitrate, nickel sulfate and nickel acetate.
Preferably, the lithium source is one or more of lithium nitrate, lithium hydroxide and lithium carbonate.
Preferably, during calcining, first 3~5h of pre-burning, heating rate are 2~5 DEG C/min at 400~600 DEG C.
Beneficial effect
1. the invention provides a kind of synthetic method of 622NCM tertiary cathode materials, the carbonate containing only cobalt manganese is first synthesized
Precipitate MnCo (CO3)2, i.e., described intermediate product, then by MnCo (CO3)2Uniformly mixed with nickel source, lithium source, high-temperature calcination obtains most
End-product.The pH of solution in course of reaction need not be controlled in course of reaction, simple to operate, cost is cheap.
2. the invention provides a kind of synthetic method of 622NCM tertiary cathode materials, the ethylene glycol or third in building-up process
Triol is both used as solvent, is used as dispersant, compared with coprecipitation, improve particle agglomeration problem again, and obtained carbonate
Precipitate MnCo (CO3)2With good ball-type pattern, good dispersion, size uniformity.
3. this method synthesize a kind of obtained 622NCM tertiary cathode materials ball-type diameter substantially 300nm~800nm it
Between, material specific surface area is big, is advantageous to the further infiltrating material of electrolyte, so as to improve the chemical property of battery.
Brief description of the drawings
Fig. 1 is a kind of X-ray diffractogram of 622NCM tertiary cathode materials made from the embodiment of the present invention 1.
Fig. 2 is the scanning electron microscope diagram of intermediate product made from the embodiment of the present invention 1.
Fig. 3 is a kind of scanning electron microscope diagram of 622NCM tertiary cathode materials made from the embodiment of the present invention 1.
Fig. 4 is a kind of battery of 622NCM tertiary cathode materials assembling made from the embodiment of the present invention 1 under 0.2C multiplying powers
Cycle performance figure.
Embodiment
With reference to specific embodiment, the present invention is further detailed explanation.
Battery assembles and performance test is as follows：
The assembling of battery：By 622NCM tertiary cathode materials made from embodiment and acetylene black, Kynoar (PVDF)
In mass ratio 8:1:1 mixing, addition 1-METHYLPYRROLIDONE (NMP) is ground into uniform slurry and is coated on aluminium foil, at 80 DEG C
Working electrode is used as after drying 24h after cut-parts, rolling, lithium piece is to electrode, and electrolyte is 1M LiPF6Solution, solvent are body
Product is than being 1:1:1 dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC) mixed liquor.In argon gas atmosphere
Glove box in be assembled into the half-cell of model 2025.
(1) SEM (SEM) is tested：Using field emission scanning electron microscope (FESEM, FEI,
Quanta200f) microscopic appearance of material is characterized；
(2) X-ray diffraction (XRD) is tested：Use X-ray diffractometer (XRD；Rigaku Ultima IV-185) to sample
Carry out crystal structure analysis；
(3) battery performance is tested：Constant current charge-discharge test is in blue electric cell tester (LAND-CT2001A)
Upper progress, charging/discharging voltage scope are 2.8~4.3V, 1C=200mAhg-1。
Embodiment 1
Weigh manganese nitrate and each 3mmol of cobalt nitrate is dissolved in 80mL ethylene glycol, stir until being completely dissolved；Then claim
Take 60mmol ammonium hydrogen carbonate to be slowly added into above-mentioned solution, be evenly stirred until that ammonium hydrogen carbonate is completely dissolved, obtain mixed solution.
Mixed solution is poured into reactor, the solvent thermal reaction 20h at 200 DEG C, after question response, the purple that will obtain
Color precipitation water and alcohol respectively rinse 3 times, and filter residue is placed in 80 DEG C of drying in oven after suction filtration, obtains intermediate product.
3mmol nickel acetates, 2.675mmol lithium carbonates are dissolved in 50mL absolute ethyl alcohols, stirred up to being completely dissolved,
Intermediate product described in adding 1mmol, is evaporated in 80 DEG C of heating, obtains hybrid solid；The wherein mol ratio of Ni, Co, Mn, Li atom
For 0.6:0.2:0.2:1.07.
After obtained hybrid solid is ground, it is placed in Muffle furnace and calcines, heating rate is 2 DEG C/min, first at 400 DEG C
5h is calcined, then 12h is calcined at 800 DEG C, obtains a kind of 622NCM tertiary cathode materials.
X-ray diffraction (XRD) result of end-product shows the diffraction maximum for meeting 622NCM tertiary cathode materials, described
622NCM tertiary cathode materials have good α-NaFeO2Six side's layer structures.The SEM of intermediate product
(SEM) result is as shown in Fig. 2 show that intermediate product has good ball-type pattern, good dispersion, particle diameter is substantially 500
Between~1 μm.SEM (SEM) result of 622NCM tertiary cathode materials is as shown in figure 3,622NCM tertiary cathodes
Material is submicron order class spherical particles, and diameter is substantially between 300~600nm.The battery charging and discharging test result assembled
As shown in figure 4, in the range of 2.8~4.3V charging/discharging voltage, under 0.2C multiplying powers, material circulation is after 50 weeks, specific discharge capacity
By 170.7mAhg-1It is changed into 143.8mAhg-1, capability retention 84.2%.
Embodiment 2
Weigh manganese chloride and each 3mmol of cobalt chloride is dissolved in 80mL glycerine, stir until being completely dissolved；Then claim
Take 45mmol ammonium hydrogen carbonate to be slowly added into above-mentioned solution, be evenly stirred until that ammonium hydrogen carbonate is completely dissolved.
Mixed solution is poured into reactor, the solvent thermal reaction 15h at 160 DEG C, after question response, the purple that will obtain
Color precipitation water and alcohol respectively rinse 3 times, and filter residue is placed in 60 DEG C of drying in oven after suction filtration, obtains intermediate product.
3mmol nickel nitrates, 5.25mmol lithium hydroxides are dissolved in 50mL absolute ethyl alcohols, stirred until completely molten
Solution, 1mmol intermediate products are added, is evaporated in 60 DEG C of heating, obtains hybrid solid；The wherein mol ratio of Ni, Co, Mn, Li atom
For 0.6:0.2:0.2:1.05.
After obtained hybrid solid is ground, it is placed in Muffle furnace and calcines, heating rate is 2 DEG C/min, first at 600 DEG C
3h is calcined, then 15h is calcined at 750 DEG C, obtains a kind of 622NCM tertiary cathode materials.
X-ray diffraction (XRD) result of end-product shows the diffraction maximum for meeting 622NCM tertiary cathode materials, described
622NCM tertiary cathode materials have good α-NaFeO2Six side's layer structures.The SEM of intermediate product
(SEM) result shows that intermediate product has a good ball-type pattern, good dispersion, particle diameter substantially 500~900nm it
Between.SEM (SEM) result of the 622NCM tertiary cathode materials shows 622NCM tertiary cathode materials for Asia
Micron order class spherical particles, diameter is substantially between 400~800nm.The battery charging and discharging test result assembled shows 2.8
In the range of~4.3V charging/discharging voltage, under 0.2C multiplying powers, material circulation is after 50 weeks, and specific discharge capacity is by 165.8mAhg-1Become
For 139.3mAhg-1, capability retention 84%.
Embodiment 3
Weigh manganese sulfate and each 3mmol of cobaltous sulfate is dissolved in 80mL ethylene glycol, stir until being completely dissolved；Then claim
Take 54mmol ammonium hydrogen carbonate to be slowly added into above-mentioned solution, be evenly stirred until that ammonium hydrogen carbonate is completely dissolved.
Mixed solution is poured into reactor, the solvent thermal reaction 18h at 180 DEG C, after question response, the purple that will obtain
Color precipitation water and alcohol respectively rinse 3 times, and filter residue is placed in 70 DEG C of drying in oven after suction filtration, obtains intermediate product.
3mmol nickel sulfates, 5.75mmol lithium nitrates are dissolved in 50mL absolute ethyl alcohols, stirred up to being completely dissolved,
1mmol intermediate products are added, is evaporated in 70 DEG C of heating, obtains hybrid solid；The mol ratio of wherein Ni, Co, Mn, Li atom is
0.6:0.2:0.2:1.15。
After obtained hybrid solid is ground, it is placed in Muffle furnace and calcines, heating rate is 2 DEG C/min, first at 550 DEG C
5h is calcined, then 10h is calcined at 850 DEG C, obtains a kind of 622NCM tertiary cathode materials.
X-ray diffraction (XRD) result of end-product shows the diffraction maximum for meeting 622NCM tertiary cathode materials, described
622NCM tertiary cathode materials have good α-NaFeO2Six side's layer structures.The SEM of intermediate product
(SEM) result shows that intermediate product has a good ball-type pattern, good dispersion, particle diameter substantially 400~800nm it
Between.What SEM (SEM) result of the 622NCM tertiary cathode materials showed 622NCM tertiary cathode materials is
Submicron order class spherical particles, diameter is substantially between 300~600nm.The battery charging and discharging test result assembled shows
In the range of 2.8~4.3V charging/discharging voltage, under 0.2C multiplying powers, material circulation is after 50 weeks, and specific discharge capacity is by 167.9mAh
g-1It is changed into 139.4mAhg-1, capability retention 83%.
Embodiment 4
Weigh manganese acetate and each 3mmol of cobalt acetate is dissolved in 80mL ethylene glycol, stir until being completely dissolved；Then claim
Take 60mmol ammonium hydrogen carbonate to be slowly added into above-mentioned solution, be evenly stirred until that ammonium hydrogen carbonate is completely dissolved.
Mixed solution is poured into reactor, the solvent thermal reaction 20h at 180 DEG C, after question response, the purple that will obtain
Color precipitation water and alcohol respectively rinse 3 times, and filter residue is placed in 80 DEG C of drying in oven after suction filtration, obtains intermediate product.
3mmol nickel acetates, 5.35mmol lithium hydroxides are dissolved in 50mL absolute ethyl alcohols, stirred until completely molten
Solution, 1mmol intermediate products are added, is evaporated in 80 DEG C of heating, obtains the mol ratio of hybrid solid, wherein Ni, Co, Mn, Li atom
For 0.6:0.2:0.2:1.07.
After obtained hybrid solid is ground, it is placed in Muffle furnace and calcines, is first raised to 400 with 5 DEG C/min heating rate
DEG C, calcine 5h at 400 DEG C；Then 800 DEG C are raised to 2 DEG C/min heating rate, then 12h is calcined at 800 DEG C, obtain one
Kind 622NCM tertiary cathode materials.
X-ray diffraction (XRD) result of end-product shows the diffraction maximum for meeting 622NCM tertiary cathode materials, described
622NCM tertiary cathode materials have good α-NaFeO2Six side's layer structures.The SEM of intermediate product
(SEM) result shows that intermediate product has a good ball-type pattern, good dispersion, particle diameter substantially 400~900nm it
Between.SEM (SEM) result of the 622NCM tertiary cathode materials shows 622NCM tertiary cathode materials for Asia
Micron order class spherical particles, diameter is substantially between 300~800nm.The battery charging and discharging test result assembled shows 2.8
In the range of~4.3V charging/discharging voltage, under 0.2C multiplying powers, material circulation is after 50 weeks, and specific discharge capacity is by 163.7mAhg-1Become
For 136.2mAhg-1, capability retention 83.2%.
Embodiment 5
Weigh manganese nitrate and each 3mmol of cobalt nitrate is dissolved in 80mL ethylene glycol, stir until being completely dissolved；Then claim
Take 60mmol ammonium hydrogen carbonate to be slowly added into above-mentioned solution, be evenly stirred until that ammonium hydrogen carbonate is completely dissolved.
Mixed solution is poured into reactor, the solvent thermal reaction 20h at 180 DEG C, after question response, the purple that will obtain
Color precipitation water and alcohol respectively rinse 3 times, and filter residue is placed in 60 DEG C of drying in oven after suction filtration, obtains intermediate product.
3mmol nickel nitrates, 5.5mmol lithium nitrates are dissolved in 50mL absolute ethyl alcohols, stirs up to being completely dissolved, adds
Enter 1mmol intermediate products, be evaporated in 80 DEG C of heating, obtain hybrid solid；Wherein the mol ratio of Ni, Co, Mn, Li atom is 0.6:
0.2:0.2:1.1。
After obtained hybrid solid is ground, it is placed in Muffle furnace and calcines, heating rate is 2 DEG C/min, is forged at 800 DEG C
12h is burnt, obtains a kind of 622NCM tertiary cathode materials.
X-ray diffraction (XRD) result of end-product shows the diffraction maximum for meeting 622NCM tertiary cathode materials, described
622NCM tertiary cathode materials have good α-NaFeO2Six side's layer structures.The SEM of intermediate product
(SEM) result shows that intermediate product has a good ball-type pattern, good dispersion, particle diameter substantially 500~800nm it
Between.SEM (SEM) result of the 622NCM tertiary cathode materials shows 622NCM tertiary cathode materials for Asia
Micron order class spherical particles, diameter is substantially between 400~600nm.The battery charging and discharging test result assembled shows 2.8
In the range of~4.3V charging/discharging voltage, under 0.2C multiplying powers, material circulation is after 50 weeks, and specific discharge capacity is by 157.7mAhg-1Become
For 130.3mAhg-1, capability retention 82.6%.
Embodiment 6
Weigh manganese nitrate and each 3mmol of cobalt nitrate is dissolved in 80mL ethylene glycol, stir until being completely dissolved；Then claim
Take 60mmol ammonium hydrogen carbonate to be slowly added into above-mentioned solution, be evenly stirred until that ammonium hydrogen carbonate is completely dissolved.
Mixed solution is poured into 100mL reactors, the hydro-thermal reaction 20h at 200 DEG C；After question response, it will obtain
Purple precipitation water and alcohol respectively rinse 3 times, filter residue is placed in 80 DEG C of drying in oven 24h after suction filtration, obtains intermediate product.
3mmol nickel nitrates, 5.5mmol lithium nitrates are dissolved in 50mL absolute ethyl alcohols, stirs up to being completely dissolved, adds
Enter 1mmol intermediate products, be evaporated in 80 DEG C of heating, obtain hybrid solid；Wherein the mol ratio of Ni, Co, Mn, Li atom is 0.6:
0.2:0.2:1.1。
After obtained hybrid solid is ground, it is placed in Muffle furnace and calcines, heating rate is 2 DEG C/min, first at 480 DEG C
10h is calcined at calcining 5h, then 780 DEG C, obtains a kind of 622NCM tertiary cathode materials.
X-ray diffraction (XRD) result of end-product shows the diffraction maximum for meeting 622NCM tertiary cathode materials, described
622NCM tertiary cathode materials have good α-NaFeO2Six side's layer structures.The SEM of intermediate product
(SEM) result shows, intermediate product is submicron order spherical particles, and diameter is between 300~600nm.The 622NCM ternarys
SEM (SEM) result of positive electrode shows that 622NCM tertiary cathode materials are submicron order class spherical particles,
Diameter is between 300~600nm.The battery charging and discharging test result assembled is such as in 2.8~4.3V charging/discharging voltage scope
Interior, under 0.2C multiplying powers, the first all charge specific capacities of material are 195.3mAhg-1, specific discharge capacity 160.6mAhg-1, first week
Coulombic efficiency is 82.2%；After material circulation 50 weeks, specific discharge capacity is by 160.6mAhg-1It is changed into 135.7mAhg-1, hold
It is 84.5% to measure conservation rate.
Invention include but is not limited to above example, it is every carried out under the spirit and principles in the present invention it is any equivalent
Replacement or local improvement, all will be regarded as within protection scope of the present invention.
Claims (8)
- A kind of 1. 622NCM tertiary cathode materials, it is characterised in that：The material structure is submicron order class spherical particles, diameter For 300nm~800nm.
- 2. prepare a kind of method of 622NCM tertiary cathode materials as claimed in claim 1, it is characterised in that：Methods described walks It is rapid as follows：Manganese source and cobalt source are dissolved in solvent by step (1), are evenly stirred until and are completely dissolved；Then ammonium hydrogen carbonate is added, stirring is equal It is even to be completely dissolved to ammonium hydrogen carbonate, obtain mixed solution；Wherein the mol ratio of manganese atom, cobalt atom and ammonium hydrogen carbonate is 1:1:15 ~20；Step (2) pours into the mixed solution in reactor, and 15~20h of solvent thermal reaction is carried out at 160~200 DEG C, is obtained Precipitated to purple, the purple precipitation is rinsed with water and alcohol, filter residue is dried after suction filtration, obtains intermediate product；Nickel source and lithium source are dissolved in absolute ethyl alcohol by step (3), are evenly stirred until after being completely dissolved, and add the intermediate product, Heat and be evaporated at 60~80 DEG C, obtain hybrid solid；Wherein the mol ratio of Ni, Co, Mn, Li atom is 0.6:0.2:0.2: 1.05~1.15；Step (4) by the hybrid solid grind after, heating rate be 2~5 DEG C/min, at 750~850 DEG C calcining 10~ 15h, obtain a kind of 622NCM tertiary cathode materials.
- A kind of 3. preparation method of 622NCM tertiary cathode materials as claimed in claim 2, it is characterised in that：The solvent is Ethylene glycol or glycerine.
- A kind of 4. preparation method of 622NCM tertiary cathode materials as claimed in claim 2, it is characterised in that：The manganese source is One or more of manganese nitrate, manganese sulfate, manganese acetate and manganese chloride.
- A kind of 5. preparation method of 622NCM tertiary cathode materials as claimed in claim 2, it is characterised in that：The cobalt source is One or more of cobalt nitrate, cobaltous sulfate, cobalt acetate and cobalt chloride.
- A kind of 6. preparation method of 622NCM tertiary cathode materials as claimed in claim 2, it is characterised in that：The nickel source is One or more of nickel nitrate, nickel sulfate and nickel acetate.
- A kind of 7. preparation method of 622NCM tertiary cathode materials as claimed in claim 2, it is characterised in that：The lithium source is One or more of lithium nitrate, lithium hydroxide and lithium carbonate.
- A kind of 8. preparation method of 622NCM tertiary cathode materials as claimed in claim 2, it is characterised in that：During calcining, first 3~5h of pre-burning at 400~600 DEG C.
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| CN110642300A (en) * | 2019-09-30 | 2020-01-03 | 哈尔滨工业大学 | Preparation method of micron-sized carbonate lithium ion battery cathode material |
| CN110867577A (en) * | 2019-11-18 | 2020-03-06 | 西安建筑科技大学 | 811NCM ternary cathode material with three-dimensional nanowire array structure and preparation method thereof |
| CN111377476A (en) * | 2018-12-29 | 2020-07-07 | 广西大学 | Micro-nano material ZnMn2O4Preparation method of (1) |
| CN111668445A (en) * | 2020-06-01 | 2020-09-15 | 广东轻工职业技术学院 | Shape-controllable nickel manganese oxide electrode material and preparation method and application thereof |
| CN114988386A (en) * | 2022-06-16 | 2022-09-02 | 蜂巢能源科技股份有限公司 | Lithium iron manganese phosphate positive electrode material and preparation method and application thereof |
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| CN114988386B (en) * | 2022-06-16 | 2024-02-02 | 蜂巢能源科技股份有限公司 | Lithium iron manganese phosphate positive electrode material, and preparation method and application thereof |
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