CN110615480A - Method for preparing layered lithium manganate material by dynamic hydrothermal method - Google Patents
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
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- 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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Abstract
A preparation method of a layered lithium manganate material comprises the following steps: the first step is as follows: MnO is electrolyzed with the molar ratio of 0.8-1.22Adding divalent manganese salt into water, mixing uniformly, and pouring into a nickel-lined dynamic hydrothermal kettle; the second step is that: pouring sodium ethylene diamine tetracetate and lithium hydroxide into a dynamic hydrothermal kettle, so that the solubility of the lithium hydroxide is 3-6M, the molar ratio of the lithium hydroxide to the total manganese source is 5-10, and the molar ratio of the sodium ethylene diamine tetracetate to the total manganese source is 0.25-0.5; the third step: setting the stirring speed to be more than 100rpm in a dynamic reaction kettle, heating the mixed solution obtained in the second step to 200 ℃ with the heating power of 0.5-1.5 KW, and carrying out hydrothermal reaction at 200 ℃ for more than 3 h; the fourth step: and after the hydrothermal reaction is finished, cooling the obtained reaction mixture to room temperature, and carrying out post-treatment to obtain the pure-phase layered lithium manganate material. The inventionThe preparation method solves the problem of LiMnO2The traditional hydrothermal synthesis process has the problems of long reaction time, large raw material consumption, multiple operation steps and the like.
Description
Technical Field
The invention relates to a layered LiMnO2In particular to a layered LiMnO used as the anode material of the lithium ion battery2A method for preparing the material.
Technical Field
Currently, lithium ion positive electrode materials include olivine-type phosphates and lithium salts of metal oxides of cobalt, manganese, and nickel systems: such as olivine-type LiFePO4Layered LiCoO2Layered ternary materials (NCM and NCA) and spinel-type LiMn2O4The actual specific capacity is 100-180mAh g-1And graphite (372mAh g)-1) Compared with the cathode material, the cathode material is difficult to meet the requirement of the lithium ion battery with high energy density, and the research development is slow, so that the cathode material is a main reason for hindering the improvement of the specific energy of the battery. Because the lithium manganate has the advantages of rich resources, low cost, little pollution, good safety and the like, the lithium manganate is one of the most promising positive electrode materials of the lithium ion battery. The lithium manganate has two structures of spinel and layered, wherein spinel type LiMn2O4Theoretical capacity of 148mAh g-1Due to its low capacity and poor thermal stability, it is not suitable for large-scale application. And layered LiMnO2Theoretical capacity up to 285mAh g-1The requirements of high voltage and high specific capacity anode materials are met, and the method becomes a research hotspot at present.
Disclosure of Invention
The invention aims to provide a method for preparing layered LiMnO by a dynamic hydrothermal method2The method of the material solves the problem of LiMnO2The traditional hydrothermal synthesis process has the defects of long reaction time, large raw material consumption, multiple operation steps and the like.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a layered lithium manganate material comprises the following steps:
the first step is as follows: MnO is to be electrolyzed2And a divalent manganese salt are added into the water,mixing uniformly, pouring into a nickel-lined dynamic hydrothermal kettle, wherein the MnO is electrolyzed2The molar ratio of the divalent manganese salt to the divalent manganese salt is 0.8-1.2;
the second step is that: pouring sodium ethylene diamine tetracetate and lithium hydroxide into a dynamic hydrothermal kettle, so that the solubility of the lithium hydroxide is 3-6 mol/L, the molar ratio of the lithium hydroxide to the total manganese source is 5-10, and the molar ratio of the sodium ethylene diamine tetracetate to the total manganese source is 0.25-0.5;
the third step: setting the stirring speed to be more than 100rpm in a dynamic hydrothermal kettle, heating the mixed solution obtained in the second step to 200 ℃ with the heating power of 0.5-1.5 KW, and carrying out hydrothermal reaction at 200 ℃ for more than 3 h;
the fourth step: and after the hydrothermal reaction is finished, cooling the obtained reaction mixture to room temperature, centrifugally separating solid precipitate, washing until the conductivity of the supernatant is below 30 mu S/cm, and drying the washed product in vacuum to obtain the pure-phase layered lithium manganate material.
Preferably, Carbon Nanotubes (CNTs) are also added into the mixed solution in the first step, and the CNTs are added according to the proportion that the content of the carbon nanotubes in the final product is 1-5 wt%. The addition of the carbon nano tube can improve the electrochemical performance of the layered lithium manganate material.
Preferably, in the first step, the divalent manganese salt is selected from one or a combination of any of the following: MnCl2·4H2O、MnSO4·H2O、Mn(CH3COO)2·4H2O、Mn(NO3)2·4H2O。
In the first step of the present invention, said electrolytic MnO2The molar ratio of the divalent manganese salt to the divalent manganese salt is preferably 1, and the valence of Mn in the theoretical product is 3, so that the target product is favorably obtained.
In the second step of the method, the concentration of the lithium hydroxide is more than 3M, and the molar ratio of the sodium ethylene diamine tetracetate to the total manganese source is more than 0.25, so that pure-phase layered lithium manganate can be obtained. Preferably, the concentration of lithium hydroxide is 3 mol/L. Preferably, the molar ratio of sodium edetate to total manganese source is 0.25.
In the second step of the present invention, the molar ratio of lithium hydroxide to the total manganese source has no influence on the purity of the product, and it is preferable that the molar ratio of lithium hydroxide to the total manganese source is 5 in view of the product yield.
In the third step of the invention, the rotating speed is set to be more than 100rpm, the reaction time is more than 3h, and the pure phase product is favorably obtained. Preferably, the rotation speed is set to 100rpm and the reaction time is 3 h.
Preferably, in the third step, the heating power is 1KW in the dynamic reaction kettle.
Preferably, in the fourth step, the vacuum drying conditions are as follows: the drying temperature was 80 ℃ and the drying time was 12 hours.
The invention particularly preferably discloses a preparation method of the layered lithium manganate material, which comprises the following steps:
the first step is as follows: MnO is to be electrolyzed2Adding divalent manganese salt into water, mixing uniformly, pouring into a nickel-lined dynamic hydrothermal kettle, wherein the electrolytic MnO is2And the divalent manganese salt in a molar ratio of 1;
the second step is that: pouring sodium ethylene diamine tetracetate and lithium hydroxide into a reaction kettle, so that the solubility of the lithium hydroxide is 3mol/L, the molar ratio of the lithium hydroxide to the total manganese source is 5, and the molar ratio of the sodium ethylene diamine tetracetate to the total manganese source is 0.25;
the third step: placing the mixed solution obtained in the second step in a dynamic reaction kettle, wherein the reaction temperature is 200 ℃, the heating power is 1KW, the stirring speed is 100rpm, and the hydrothermal reaction is carried out for 3 hours after the set temperature is reached;
the fourth step: and after the hydrothermal reaction is finished, cooling to room temperature, centrifuging and washing solid precipitates in the obtained reaction mixture until the conductivity of the supernatant is below 30 mu S/cm, and drying the washed product in vacuum to obtain the pure-phase layered lithium manganate material.
The layered lithium manganate material prepared by the method can be used as a lithium ion battery anode material.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides layered LiMnO2The preparation method adopts ethylene diamine tetraacetic acid (EDTA-2Na) as an auxiliary dynamic hydrothermal method to prepare the LiMnO by one step by utilizing common reaction raw materials2WhereinEDTA-2Na not only acts as a complexing agent to inhibit the oxidation of divalent manganese, but also is used as a reducing agent to effectively avoid the generation of a lithium-rich phase, and the method can effectively reduce the reaction time and the consumption of a Li source, is simple and convenient to operate, and is beneficial to LiMnO2The scale production of the method.
(2) According to the invention, the electrochemical performance of the pure-phase layered lithium manganate is improved by adding CNTs, so that the specific capacity and the cycle performance of the pure-phase layered lithium manganate are greatly improved.
Drawings
FIG. 1 is a scheme showing that o-LiMnO was obtained by adding 0.045mol of EDTA-2Na in example 22By electrolysis of MnO with the raw material2XRD pattern of (a);
FIG. 2 is an XRD pattern of the effect of different reaction temperatures on the reaction product;
FIG. 3 is an XRD pattern of the effect of different rotation speeds on the reaction product;
FIG. 4 is an XRD pattern of the effect of different EDTA-2Na additions on the reaction product;
FIG. 5 is an XRD pattern of samples prepared according to examples 2, 8 of the present invention;
FIG. 6 is an SEM image of samples prepared according to examples 2 and 8 of the present invention;
FIG. 7 is a graph showing the electrochemical properties of the samples prepared in examples 2 and 8 of the present invention.
Detailed description of the invention
To further illustrate the present invention, the following examples are provided to describe the preparation of layered lithium manganate by dynamic hydrothermal method according to the present invention.
Layered LiMnO of anode material of lithium ion battery2The preparation method comprises the following steps:
example 1:
the first step is as follows: weighing 7.84g of electrolytic MnO2And 22.06g Mn (AC)2·4H2Adding O into 300ml of deionized water, uniformly mixing, and pouring into a nickel-lined dynamic hydrothermal kettle;
the second step is that: 37.74g of LiOH. H was weighed2O, pouring into a nickel-lined dynamic hydrothermal kettle;
the third step: installing a dynamic hydrothermal kettle, setting the reaction temperature to be 200 ℃, the heating power to be 1KW, the rotating speed to be 100rpm, heating from room temperature to 200 ℃ within 120min, maintaining for 3h when the reaction temperature is increased to 200 ℃, and then closing, heating, standing and cooling to room temperature.
The fourth step: cooling at room temperature, disassembling the reaction device, centrifuging and washing solid precipitate in the obtained reaction mixture for multiple times until the conductivity of supernatant of the centrifugate at the last time is below 30 muS/cm; and drying the washed sample in a vacuum oven for 12 hours, wherein the drying temperature is controlled to be 80 ℃.
Example 2:
the first step is as follows: weighing 7.84g of electrolytic MnO2And 22.06g Mn (AC)2·4H2Adding O into 300ml of deionized water, uniformly mixing, and pouring into a nickel-lined dynamic hydrothermal kettle;
the second step is that: 16.84g of EDTA-2Na (0.045mol) and 37.76g of LiOH. H were weighed2O, pouring into a nickel-lined dynamic hydrothermal kettle;
the third step: installing a dynamic hydrothermal kettle, setting the reaction temperature to be 200 ℃, the heating power to be 1KW, the rotating speed to be 100rpm, heating from room temperature to 200 ℃ within 120min, maintaining for 3h when the reaction temperature is increased to the set temperature of 200 ℃, and then closing, heating, standing and cooling to the room temperature.
The fourth step: cooling at room temperature, disassembling the reaction device, centrifuging and washing solid precipitate in the obtained reaction mixture for multiple times until the conductivity of supernatant of the centrifugate at the last time is below 30 muS/cm; and drying the washed sample in a vacuum oven for 12 hours, wherein the drying temperature is controlled to be 80 ℃.
Example 3:
the first step is as follows: weighing 7.84g of electrolytic MnO2And 22.06g Mn (AC)2·4H2Adding O into 300ml of deionized water, uniformly mixing, and pouring into a nickel-lined dynamic hydrothermal kettle;
the second step is that: 16.84g of EDTA-2Na (0.045mol) and 37.76g of LiOH. H were weighed2O, pouring into a nickel-lined dynamic hydrothermal kettle;
the third step: installing a dynamic hydrothermal kettle, setting the reaction temperature to be 180 ℃, the heating power to be 1KW, the rotating speed to be 100rpm, heating to 180 ℃ from room temperature in 110min, maintaining for 3h when the reaction temperature is increased to the set temperature of 180 ℃, and then closing, heating, standing and cooling to room temperature.
The fourth step: cooling at room temperature, disassembling the reaction device, centrifuging and washing solid precipitate in the obtained reaction mixture for multiple times until the conductivity of supernatant of the centrifugate at the last time is below 30 muS/cm; and drying the washed sample in a vacuum oven for 12 hours, wherein the drying temperature is controlled to be 80 ℃.
Example 4:
the first step is as follows: weighing 7.84g of electrolytic MnO2And 22.06g Mn (AC)2·4H2Adding O into 300ml of deionized water, uniformly mixing, and pouring into a nickel-lined dynamic hydrothermal kettle;
the second step is that: 16.84g of EDTA-2Na (0.045mol) and 37.76g of LiOH. H were weighed2O, pouring into a nickel-lined dynamic hydrothermal kettle;
the third step: installing a dynamic hydrothermal kettle, setting the reaction temperature to be 220 ℃, the heating power to be 1KW, the rotating speed to be 100rpm, heating from room temperature to 220 ℃ in 130min, maintaining for 3h when the reaction temperature is increased to the set temperature of 220 ℃, and then closing, heating, standing and cooling to the room temperature.
The fourth step: cooling at room temperature, disassembling the reaction device, centrifuging and washing solid precipitate in the obtained reaction mixture for multiple times until the conductivity of supernatant of the centrifugate at the last time is below 30 muS/cm; and drying the washed sample in a vacuum oven for 12 hours, wherein the drying temperature is controlled to be 80 ℃.
Example 5:
the first step is as follows: weighing 7.84g of electrolytic MnO2And 22.06g Mn (AC)2·4H2Adding O into 300ml of deionized water, uniformly mixing, and pouring into a nickel-lined dynamic hydrothermal kettle;
the second step is that: 16.84g of EDTA-2Na (0.045mol) and 37.76g of LiOH. H were weighed2O, pouring into a nickel-lined dynamic hydrothermal kettle;
the third step: installing a dynamic hydrothermal kettle, setting the reaction temperature to be 200 ℃, the heating power to be 1KW, the rotating speed to be 0rpm, heating from room temperature to 200 ℃ within 120min, maintaining for 3h when the reaction temperature is increased to the set temperature of 200 ℃, and then closing, heating, standing and cooling to the room temperature.
The fourth step: cooling at room temperature, disassembling the reaction device, centrifuging and washing solid precipitate in the obtained reaction mixture for multiple times until the conductivity of supernatant of the centrifugate at the last time is below 30 muS/cm; and drying the washed sample in a vacuum oven for 12 hours, wherein the drying temperature is controlled to be 80 ℃.
Example 6:
the first step is as follows: weighing 7.84g of electrolytic MnO2And 22.06g Mn (AC)2·4H2Adding O into 300ml of deionized water, uniformly mixing, and pouring into a nickel-lined dynamic hydrothermal kettle;
the second step is that: 16.84g of EDTA-2Na (0.045mol) and 37.76g of LiOH. H were weighed2O, pouring into a nickel-lined dynamic hydrothermal kettle;
the third step: installing a dynamic hydrothermal kettle, setting the reaction temperature to be 200 ℃, the heating power to be 1KW, the rotating speed to be 50rpm, heating from room temperature to 200 ℃ within 120min, maintaining for 3h when the reaction temperature is increased to the set temperature of 200 ℃, and then closing, heating, standing and cooling to the room temperature.
The fourth step: cooling at room temperature, disassembling the reaction device, centrifuging and washing solid precipitate in the obtained reaction mixture for multiple times until the conductivity of supernatant of the centrifugate at the last time is below 30 muS/cm; and drying the washed sample in a vacuum oven for 12 hours, wherein the drying temperature is controlled to be 80 ℃.
Example 7:
the same procedure as in example 2 was repeated except that the amounts of EDTA-2Na added were changed to 0.009mol, 0.018mol and 0.036mol, to obtain a layered lithium manganate material.
FIG. 1 is a scheme showing that o-LiMnO was obtained by adding 0.045mol of EDTA-2Na in example 22By electrolysis of MnO with the raw material2XRD pattern of (A), from which a pure phase of o-LiMnO is seen2Has been prepared without raw material electrolysis of MnO2The residue of (1).
FIG. 2 is an XRD pattern showing the effect of different reaction temperatures on the reaction product in examples 2-4, from which it can be seen that o-LiMnO was produced under different temperature conditions2However, the Li-rich phase exists at the over-high or under-low temperature2MnO3Indicating that a proper reaction temperature is required to generate pure phase o-LiMnO2。
FIG. 3 is an XRD pattern showing the effect of different rotation speeds on the reaction products in examples 2, 5 and 6, and it can be seen that higher rotation speed enables the reaction to proceed more thoroughly, which is beneficial to inhibit the formation of lithium-rich phase.
FIG. 4 shows o-LiMnO prepared in examples 1, 2 and 72The XRD pattern shows that the lithium-rich phase is inhibited more remarkably by EDTA-2Na under the same other conditions along with the increase of the concentration, and the pure phase o-LiMnO can be obtained when the molar ratio of the concentration of EDTA-2Na to the total manganese reaches 0.252And o-LiMnO obtained2Has good crystallinity.
Example 8:
the first step is as follows: weighing 7.84g of electrolytic MnO2、22.06g Mn(AC)2·4H20.8645g of O and carbon nano-tubes are added into 300ml of deionized water to be mixed evenly and poured into a nickel-lined dynamic hydrothermal kettle;
the second step is that: 16.84g of EDTA-2Na (0.045mol) and 37.76g of LiOH. H were weighed2O, pouring into a nickel-lined dynamic hydrothermal kettle;
the third step: installing a dynamic hydrothermal kettle, setting the reaction temperature to be 200 ℃, the heating power to be 1KW, the rotating speed to be 100rpm, heating from room temperature to 200 ℃ within 120min, maintaining for 3h when the reaction temperature is increased to the set temperature of 200 ℃, and then closing, heating, standing and cooling to the room temperature.
The fourth step: cooling at room temperature, disassembling the reaction device, centrifuging the solid precipitate in the obtained solution, and washing for multiple times until the conductivity of the supernatant of the centrifugate at the last time is below 30 muS/cm; and drying the washed sample in a vacuum oven for 12 hours, wherein the drying temperature is controlled to be 80 ℃.
Figure 5 is an XRD pattern of samples prepared according to examples 2, 8 of the present invention. It can be seen from the figure that the addition of CNTs is not to o-LiMnO2The purity of (c) has an effect; FIG. 6 is an SEM image of samples prepared in examples 2 and 8 of the present invention. It can be seen from the figure that the size of the lithium manganate sample prepared in example 2 is substantially in the range of 0.1-1 μm, and the particle size is relatively large. The lithium manganate sample prepared in example 8 has a small particle size, uniform particle size distribution, a size of substantially 100-200 nm, uniform particle-to-particle distances, good dispersibility, and in-situ addition of carbon nanotubesDispersed in the gaps among the material particles to form a better conductive network, which helps to improve the conductivity of the material.
0.2g of the layered lithium manganate and 0.025g of acetylene black prepared in the above examples 2 and 8 were weighed and placed in a mortar, 3mL of NMP glue solution containing 0.025g of PVDF was added after uniform grinding, and after uniform stirring, the mixture was coated on the surface of an aluminum foil of 8cm × 5cm, and after vacuum drying at 120 ℃, the aluminum foil was taken out, and then button cells were assembled using metallic lithium as a counter electrode. The button cell was tested using a lithium ion battery charging and discharging system (LAND CT2001A), and the results are shown in FIG. 7.
As shown in FIG. 7, the circulation capacity of the layered lithium manganate added with 5% carbon nanotubes can be maintained at 210mAh g-1The discharge capacity of the layered lithium manganate sample without the carbon nano tube is only 140mAh g-1Left and right, and capacity decays continuously at later stages. Therefore, the specific capacity and the cycle performance of the pure-phase layered lithium manganate are greatly improved by adding the carbon nano tubes.
Claims (10)
1. A preparation method of a layered lithium manganate material comprises the following steps:
the first step is as follows: MnO is to be electrolyzed2Adding divalent manganese salt into water, mixing uniformly, pouring into a nickel-lined dynamic hydrothermal kettle, wherein the electrolytic MnO is2The molar ratio of the divalent manganese salt to the divalent manganese salt is 0.8-1.2;
the second step is that: pouring sodium ethylene diamine tetracetate and lithium hydroxide into a dynamic hydrothermal kettle, so that the solubility of the lithium hydroxide is 3-6 mol/L, the molar ratio of the lithium hydroxide to the total manganese source is 5-10, and the molar ratio of the sodium ethylene diamine tetracetate to the total manganese source is 0.25-0.5;
the third step: setting the stirring speed to be more than 100rpm in a dynamic hydrothermal kettle, heating the mixed solution obtained in the second step to 200 ℃ with the heating power of 0.5-1.5 KW, and carrying out hydrothermal reaction at 200 ℃ for more than 3 h;
the fourth step: and after the hydrothermal reaction is finished, cooling the obtained reaction mixture to room temperature, centrifugally separating solid precipitate, washing until the conductivity of the supernatant is below 30 mu S/cm, and drying the washed product in vacuum to obtain the pure-phase layered lithium manganate material.
2. The method of claim 1, wherein: in the first step, the divalent manganese salt is selected from one or any combination of the following: MnCl2·4H2O、MnSO4·H2O、Mn(CH3COO)2·4H2O、Mn(NO3)2·4H2O。
3. The method of claim 1, wherein: the electrolytic MnO2And the divalent manganese salt in a molar ratio of 1.
4. The method of claim 3, wherein: in the second step, the concentration of lithium hydroxide is 3mol/L, and the molar ratio of sodium ethylene diamine tetracetate to the total manganese source is 0.25.
5. The method of claim 3, wherein: in the second step, the molar ratio of lithium hydroxide to total manganese source was 5.
6. The method of claim 3, wherein: in the third step, the rotation speed was set to 100rpm, and the reaction time was 3 hours.
7. The method of claim 3, wherein: in the third step, the heating power is 1KW in the dynamic reaction kettle.
8. The preparation method according to claim 3, wherein the preparation method of the layered lithium manganate material comprises the following steps:
the first step is as follows: MnO is to be electrolyzed2Adding divalent manganese salt into water, mixing uniformly, pouring into a nickel-lined dynamic hydrothermal kettle, wherein the electrolytic MnO is2And the divalent manganese salt in a molar ratio of 1;
the second step is that: pouring sodium ethylene diamine tetracetate and lithium hydroxide into a reaction kettle, so that the solubility of the lithium hydroxide is 3mol/L, the molar ratio of the lithium hydroxide to the total manganese source is 5, and the molar ratio of the sodium ethylene diamine tetracetate to the total manganese source is 0.25;
the third step: placing the mixed solution obtained in the second step in a dynamic reaction kettle, wherein the reaction temperature is 200 ℃, the heating power is 1KW, the stirring speed is 100rpm, and the hydrothermal reaction is carried out for 3 hours after the set temperature is reached;
the fourth step: and after the hydrothermal reaction is finished, cooling to room temperature, centrifuging and washing solid precipitates in the obtained reaction mixture until the conductivity of the supernatant is below 30 mu S/cm, and drying the washed product in vacuum to obtain the pure-phase layered lithium manganate material.
9. The method of claim 1, wherein: in the fourth step, the vacuum drying conditions are as follows: the drying temperature was 80 ℃ and the drying time was 12 hours.
10. The method of any one of claims 1 to 9, wherein: and adding carbon nanotubes into the mixed solution in the first step according to the proportion that the content of the carbon nanotubes in the final product is 1-5 wt%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112421011A (en) * | 2020-11-26 | 2021-02-26 | 中北大学 | Method for preparing layered lithium manganate cathode material by low lithium-manganese ratio doping |
| CN112421013A (en) * | 2020-11-26 | 2021-02-26 | 中北大学 | Preparation method of layered lithium manganate cathode material with low lithium-manganese ratio |
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| CN112421011A (en) * | 2020-11-26 | 2021-02-26 | 中北大学 | Method for preparing layered lithium manganate cathode material by low lithium-manganese ratio doping |
| CN112421013A (en) * | 2020-11-26 | 2021-02-26 | 中北大学 | Preparation method of layered lithium manganate cathode material with low lithium-manganese ratio |
| CN112701262A (en) * | 2020-12-29 | 2021-04-23 | 浙江工业大学 | Inert Li2MnO3Phase-doped layered lithium manganate material and preparation and application thereof |
| KR20220100261A (en) * | 2021-01-08 | 2022-07-15 | 고려대학교 산학협력단 | Cathode active material |
| KR20220100315A (en) * | 2021-01-08 | 2022-07-15 | 고려대학교 산학협력단 | Cathode active material |
| KR102536228B1 (en) | 2021-01-08 | 2023-05-23 | 고려대학교 산학협력단 | Cathode active material |
| KR102586288B1 (en) | 2021-01-08 | 2023-10-18 | 고려대학교 산학협력단 | Cathode active material |
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