CN110957486A - Preparation method of superstructure tin-carbon-molybdenum oxide composite material and application of superstructure tin-carbon-molybdenum oxide composite material to electrode - Google Patents
Preparation method of superstructure tin-carbon-molybdenum oxide composite material and application of superstructure tin-carbon-molybdenum oxide composite material to electrode Download PDFInfo
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Abstract
The invention belongs to the technical field of electrode material preparation, and relates to a preparation method of a superstructure tin-carbon-molybdenum oxide composite material and application thereof to an electrode. Firstly, preparing an alkaline solution to enable the pH value to be 8.0-10.5, dissolving phosphomolybdate in the solution, dispersing tin-based nanoparticles in the solution, preparing an isometric dopamine hydrochloride alkaline solution, enabling phosphomolybdic acid and dopamine to perform coordination polymerization reaction, adsorbing the tin-based nanoparticles in the solution, and forming a superstructure precursor through self-assembly; centrifuging, washing and drying the superstructure precursor, and carbonizing in a protective atmosphere to obtain the superstructure precursor. The preparation process is simple, the tin-based nanoparticles are uniformly dispersed in the three-dimensional carbon skeleton by constructing the superstructure, the tin-based nanoparticles can play a role in pore formation while being reduced into the nano tin in the carbonization process, and the volume expansion and pulverization of the tin-based material in the charging and discharging processes can be effectively inhibited; the polydopamine is doped with nitrogen atoms in situ while providing a carbon source, so that the conductivity of the material is improved.
Description
Technical Field
The invention belongs to the technical field of electrode material preparation, and particularly relates to a preparation method of a superstructure tin-carbon-molybdenum oxide composite material and application of the superstructure tin-carbon-molybdenum oxide composite material to an electrode.
Background
Lithium ion batteries have been widely noticed because of their advantages of high voltage, high energy density, good safety, light weight, small self-discharge, long cycle life, no memory effect, no pollution, etc., and the electrode materials of lithium ion batteries have also become the hot point of research in the battery industry. Graphite is a negative electrode material of lithium ion batteries which are commercialized at present, and has good cycle performance. However, the graphite has low capacity, the electrode potential after lithium storage is similar to that of metallic lithium, and when the battery is overcharged, metallic lithium is easily precipitated on the surface of the carbon electrode, and dendrite is formed to cause short circuit.
Tin-based materials are considered to be one of the candidates for a potential replacement for carbon negative electrode materials because of their high capacity, good processability, good conductivity, no solvent co-intercalation problem, rapid charge and discharge capability, and the like. However, the reversible generation and decomposition of Li — Sn alloys are accompanied by a large volume change, which easily causes pulverization of tin particles, causing the active material to fall off from the current collector, resulting in a short cycle life of the tin-based material. Meanwhile, when the tin particles are exposed in the electrolyte, an unstable SEI film is formed on the tin surface, and the cycle performance of the electrode material is reduced. Therefore, if the problems of pulverization, conductivity, unstable SEI formation and the like of the tin cathode in the lithium intercalation and deintercalation process can be solved, a road is laid for the application of the tin cathode in the fields of electronic products and new energy automobiles, and the improvement of life and environment of people can be facilitated.
In order to solve the problems of pulverization, SEI instability and the like of a tin cathode in the process of lithium intercalation and deintercalation, a surface coating method is generally adopted to improve the cycle performance of a tin cathode material. On one hand, the nano tin can reduce the absolute volume change of tin particles caused by lithium ion intercalation and reduce the internal stress of the composite material; on the other hand, coating the material with good conductivity on the surface of the nano tin can increase the conductivity of the nano tin, and simultaneously, the direct contact between the tin and the electrolyte is avoided, so that a stable SEI film is formed. CN2017113176636, "a composite coated nano tin negative electrode material, and a preparation method and an application thereof," adopts nano copper and carbon to cooperatively coat nano tin, so as to avoid direct contact between nano tin and an electrolyte, form stable SEI, and increase the conductivity of an electrode. CN201810028108X Biomass carbon-tin energy storage material and preparation method thereof, provides a biomass carbon-tin energy storage material and preparation method thereof, which takes silkworm excrement as carrier, and hydrolyzes and deposits tin dioxide by stannic chloride, and then carbonizes at high temperature to generate carbon-tin material, and the material has higher specific capacity than the existing graphite cathode material.
Disclosure of Invention
In order to overcome the defects of the prior art and improve the electrochemical stability of the tin cathode, the invention aims to provide a preparation method of a superstructure tin-carbon-molybdenum oxide composite material.
The technical scheme of the invention is as follows:
a preparation method of a superstructure tin-carbon-molybdenum oxide composite material comprises the following steps:
A. preparing an alkaline solution to enable the pH value to be 8.0-10.5, dissolving phosphomolybdate in the phosphomolybdate solution, dispersing tin-based nanoparticles in the phosphomolybdate solution, preparing an isometric dopamine hydrochloride alkaline solution in addition, mixing the two solutions under the stirring condition, wherein the molar ratio of phosphomolybdate to dopamine hydrochloride in the mixed solution is 1: 0.5-5, preferably 1: 1-2, carrying out coordination polymerization reaction on phosphomolybdic acid and dopamine hydrochloride, adsorbing tin-based nanoparticles in a solution, and forming a superstructure precursor through self-assembly, wherein the reaction temperature of the superstructure self-assembly is 20-60 ℃, and the assembly time is 1-4 h;
B. centrifuging, washing and drying the superstructure precursor, and then carbonizing in a protective atmosphere at 500-800 ℃ for 1-4 h, preferably 600-700 ℃ for 2h to obtain the superstructure precursor.
In the preferred embodiment of the invention, the solvent of the alkaline solution prepared in the step A is water or a mixed solution of water and ethanol, the solute is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia water or tris (tris), and the concentration of the ethanol solution is 10-50%.
In a preferred embodiment of the invention, the phosphomolybdate in the step A is one or more of phosphomolybdate hydrate, ammonium phosphomolybdate, sodium phosphomolybdate and potassium phosphomolybdate, and the molar concentration is 0.01-0.1 mol/L.
In the preferred embodiment of the invention, the tin-based nanoparticles in the step A are one or more of tin, stannous oxide or stannic oxide, the radius of the tin-based nanoparticles is 10-500 nm, and the molar concentration is 0.01-0.1 mol/L.
In the preferred embodiment of the invention, the drying treatment in the step B is any one of freeze drying, supercritical drying or thermal drying, the drying temperature is-50-80 ℃, and the drying time is 4-30 h.
Further, the gas of the protective atmosphere in the step B is nitrogen, argon, a nitrogen-hydrogen mixed gas or an argon-hydrogen mixed gas.
According to the invention, the tin-based nanoparticles are uniformly dispersed in the three-dimensional carbon skeleton by constructing the three-dimensional superstructure, the tin-based nanoparticles can play a role in pore formation while being reduced into nano tin in the carbonization process, the volume expansion and pulverization of the tin-based material in the charging and discharging processes can be effectively inhibited, and the polydopamine is doped with nitrogen atoms in situ while providing a carbon source, so that the conductivity of the material is improved; the carbon skeleton can protect tin nanoparticles, has a good conductive effect, improves the chemical activity and the utilization rate of tin, and improves the discharge capacity of the material by doping molybdenum dioxide.
According to the invention, a solution self-assembly technology is adopted to assemble and coat nano tin oxide to form a superstructure material, wherein molybdate ions and dopamine firstly generate complexation, then under the action of oxygen in the environment, dopamine generates polymerization to promote the formation of a high-molecular polymer framework, under the adsorption action of amino on the surface of polydopamine, nano tin oxide particles dispersed in a solution are adsorbed to the surface of the formed polymer framework, and in the self-assembly process of molybdic acid and ion-polydopamine, a large amount of nano tin oxide is adsorbed and wrapped in the structure to form a superstructure product. Through subsequent high-temperature carbonization treatment, the generated product has a complete and stable framework structure and an organic framework is converted into a carbon framework containing nitrogen and molybdenum dioxide, and the nano tin oxide is reduced into a nano metallic tin simple substance.
The superstructure tin-carbon-molybdenum oxide composite material prepared by the preparation method is uniform spherical particles with the radius of 3-5 microns, and nano simple substance tin and molybdenum oxide particles generated by reduction are uniformly distributed in a three-dimensional layered carbon skeleton structure.
Still another object of the present invention is to apply the prepared superstructure tin-carbon-molybdenum oxide composite material to an electrode material.
The resulting composite was mixed with acetylene black and PVDF in a 8: 1: 1, adding a proper amount of NMP solvent dropwise, grinding and uniformly mixing, coating the uniformly mixed slurry on the surface of a copper foil, and then placing the copper foil coated with the slurry in an oven for drying treatment. The obtained pole piece is cut and nursed, then a battery is assembled by taking a metal lithium piece as a counter electrode, a diaphragm adopts a porous polypropylene film, and electrolyte is EC and DMC (1: 1) containing 1M.
Advantageous effects
According to the invention, through constructing the porous superstructure material containing the nanoscale metallic tin simple substance, the shedding and agglomeration of metallic tin particles are avoided, the porous channel in the structure can ensure the sufficient contact of the nano metallic tin and the electrolyte, so that the nano metallic tin has higher electrochemical activity, meanwhile, the porous structure provides an effective space for the volume expansion of the metallic tin in the charging and discharging processes, and also has a certain protection effect on the volume expansion of the metallic tin, so that the material shows high specific capacity, large energy density and good rate characteristics; meanwhile, the preparation process is simple, is beneficial to reducing energy consumption and process cost, and is easy to realize industrial large-scale production.
Drawings
Fig. 1 is an SEM image of a superstructure tin-carbon-molybdenum oxide composite prepared in example 2.
Fig. 2 is a cycle performance test chart of a half cell assembled by taking the superstructure tin-carbon-molybdenum oxide composite material prepared in example 2 as a negative electrode and pure Sn.
Detailed Description
The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
Unless otherwise defined, terms (including technical and scientific terms) used herein should be construed to have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art, and should not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Example 1
A preparation method of a superstructure tin-carbon-molybdenum oxide composite material comprises the following steps:
(1) preparing a trihydroxymethyl aminomethane aqueous solution to ensure that the pH value of the solution is 10;
(2) weighing a proper amount of phosphomolybdic acid hydrate, and dissolving the phosphomolybdic acid hydrate in a trimethylaminomethane water solution, wherein the content of phosphomolybdic acid hydrate is 0.02 mol/L; then weighing a proper amount of nano tin dioxide, and ultrasonically dispersing the nano tin dioxide in the nano tin dioxide, wherein the concentration of the nano tin dioxide is 0.01 mol/L;
(3) preparing a trihydroxymethyl aminomethane aqueous solution of dopamine hydrochloride with the same volume in the step (2), wherein the concentration of the dopamine hydrochloride is 0.02 mol/L;
(4) pouring the dopamine hydrochloride solution obtained in the step (3) into the mixed solution obtained in the step (2), stirring for 5 minutes, and standing for 2 hours;
(5) pouring out the supernatant of the product solution in the step (4), centrifuging the precipitate at the lower layer, washing the precipitate for 2 to 3 times by using deionized water and absolute ethyl alcohol, and drying the precipitate at 70 ℃ by using a forced air drying oven;
(6) and (5) carbonizing the product obtained in the step (5) by using a tube furnace, wherein the carbonizing temperature is 700 ℃, the heating rate is 2 ℃/min, the heat preservation time is 2 hours, and the protective atmosphere is argon-hydrogen mixed gas.
The prepared superstructure tin-carbon-molybdenum oxide composite material is applied to an electrode, and tests show that the content of the tin-carbon-molybdenum oxide composite material is 1A mg-1After 500 cycles of the current, 515 mAh g-1The discharge capacity of (2).
Example 2
A preparation method of a superstructure tin-carbon-molybdenum oxide composite material comprises the following steps:
(1) preparing a sodium hydroxide aqueous solution to ensure that the pH value of the solution is 9.5;
(2) weighing a proper amount of sodium phosphomolybdate hydrate, and dissolving the sodium phosphomolybdate hydrate in a sodium hydroxide aqueous solution, wherein the content of the sodium phosphomolybdate hydrate is 0.02 mol/L; weighing a proper amount of nano tin powder, and ultrasonically dispersing the nano tin powder into the nano tin powder, wherein the concentration of the nano tin powder is 0.01 mol/L;
(3) weighing a proper amount of dopamine hydrochloride, dissolving the dopamine hydrochloride into the sodium hydroxide solution with the same volume as that in the step (2), and stirring to fully dissolve the dopamine hydrochloride, wherein the concentration of the dopamine hydrochloride is 0.02 mol/L;
(4) pouring the dopamine hydrochloride solution obtained in the step (3) into the mixed solution obtained in the step (2), stirring for 5 minutes, and standing for 2 hours;
(5) pouring out the supernatant of the product solution in the step (4), centrifuging the precipitate at the lower layer, washing the precipitate for 2 to 3 times by using deionized water and absolute ethyl alcohol, and then drying the precipitate by using a forced air drying oven at the temperature of 70 ℃;
(6) and (5) carbonizing the product obtained in the step (5) by using a tube furnace, wherein the carbonizing temperature is 700 ℃, the heating rate is 2 ℃/min, the heat preservation time is 2 hours, and the protective atmosphere is argon-hydrogen mixed gas.
The prepared superstructure tin-carbon-molybdenum oxide composite material is applied to an electrode, and tests show that the content of the tin-carbon-molybdenum oxide composite material is 1 A.mg-1After 500 cycles of the current, 520 mAh g-1The discharge capacity of (2).
Example 3
A preparation method of a superstructure tin-carbon-molybdenum oxide composite material comprises the following steps:
(1) preparing a mixed solution of ammonia water and ethanol, wherein the volume ratio of water to ethanol is 1: 1, the pH value of the solution is 10;
(2) weighing a proper amount of phosphomolybdic acid hydrate, and dissolving the phosphomolybdic acid hydrate in a mixed solution of ammonia water and ethanol, wherein the content of phosphomolybdic acid hydrate is 0.2 mol/L; weighing a proper amount of nano tin dioxide, and ultrasonically dispersing the nano tin dioxide in the nano tin dioxide, wherein the concentration of the nano tin dioxide is 0.1 mol/L;
(3) weighing a proper amount of dopamine hydrochloride, dissolving the dopamine hydrochloride into the mixed solution of ammonia water and ethanol with the same volume in the step (2), and stirring to fully dissolve the dopamine hydrochloride, wherein the concentration of the dopamine hydrochloride is 0.2 mol/L;
(4) pouring the dopamine hydrochloride solution obtained in the equal volume step (3) into the mixed solution obtained in the step (2), stirring for 5 minutes, and standing for 2 hours;
(5) pouring out the supernatant of the product solution in the step (4), centrifuging the precipitate at the lower layer, washing the precipitate for 2 to 3 times by using deionized water and absolute ethyl alcohol, and then drying the precipitate by using a forced air drying oven at the temperature of 70 ℃;
(6) and (5) carbonizing the product obtained in the step (5) by using a tubular furnace, wherein the carbonizing temperature is 650 ℃, the heating rate is 2 ℃/min, the heat preservation time is 2 hours, and the protective atmosphere is argon-hydrogen mixed gas.
The prepared superstructure tin-carbon-molybdenum oxide composite material is applied to an electrode, and tests show that the tin-carbon-molybdenum oxide composite material is tin-carbon-molybdenum oxideThe molybdenum composite material is 1 A.mg-1After 500 cycles of the current of (A) and (B), 518 mAh g-1The discharge capacity of (2).
Example 4
A preparation method of a superstructure tin-carbon-molybdenum oxide composite material comprises the following steps:
(1) preparing a potassium hydroxide aqueous solution to ensure that the pH value of the solution is 10;
(2) weighing a proper amount of phosphomolybdic acid hydrate, and dissolving the phosphomolybdic acid hydrate in a potassium hydroxide aqueous solution, wherein the content of the phosphomolybdic acid hydrate is 0.02 mol/L; weighing a proper amount of nano tin dioxide, and ultrasonically dispersing the nano tin dioxide in the nano tin dioxide, wherein the concentration of the nano tin dioxide is 0.01 mol/L;
(3) weighing a proper amount of dopamine hydrochloride, dissolving the dopamine hydrochloride into the potassium hydroxide solution with the same volume in the synchronous step (2), and stirring to fully dissolve the dopamine hydrochloride, wherein the concentration of the dopamine hydrochloride is 0.02 mol/L;
(4) pouring the dopamine hydrochloride solution obtained in the equal volume step (3) into the mixed solution obtained in the step (2), stirring for 5 minutes, and standing for 2 hours;
(5) pouring out the supernatant of the product solution in the step (4), centrifuging the precipitate at the lower layer, washing the precipitate for 2 to 3 times by using deionized water and absolute ethyl alcohol, and then carrying out freeze drying at the temperature of-55 ℃ for 24 hours;
(6) and (5) carbonizing the product obtained in the step (5) by using a tubular furnace, wherein the carbonizing temperature is 600 ℃, the heating rate is 2 ℃/min, the heat preservation time is 4 hours, and the protective atmosphere is argon-hydrogen mixed gas.
The prepared superstructure tin-carbon-molybdenum oxide composite material is applied to an electrode, and tests show that the content of the tin-carbon-molybdenum oxide composite material is 1A mg-1After 500 cycles of the current, 516 mAh g-1The discharge capacity of (2).
Example 5
A preparation method of a superstructure tin-carbon-molybdenum oxide composite material comprises the following steps:
(1) preparing a mixed solution of tris (hydroxymethyl) aminomethane water and ethanol, wherein the volume ratio of water to ethanol is 1: 1, the pH value of the solution is 10;
(2) weighing a proper amount of ammonium phosphomolybdate, and dissolving the ammonium phosphomolybdate in the solution obtained in the step (1), wherein the content of the ammonium phosphomolybdate is 0.2 mol/L; weighing a proper amount of nano tin dioxide, and ultrasonically dispersing the nano tin dioxide in the nano tin dioxide, wherein the concentration of the nano tin dioxide is 0.1 mol/L;
(3) weighing a proper amount of dopamine hydrochloride, dissolving the dopamine hydrochloride into the trihydroxymethyl aminomethane water and ethanol mixed solution with the same volume in the synchronous step (2), and stirring to fully dissolve the dopamine hydrochloride, wherein the concentration of the dopamine hydrochloride is 0.2 mol/L;
(4) pouring the dopamine hydrochloride solution obtained in the equal volume step (3) into the mixed solution obtained in the step (2), stirring for 5 minutes, and standing for 2 hours;
(5) pouring out the supernatant of the product solution in the step (4), centrifuging the precipitate at the lower layer, washing the precipitate for 2 to 3 times by using deionized water and absolute ethyl alcohol, and drying the precipitate by using a forced air drying oven at the temperature of 70 ℃;
(6) and (5) carbonizing the product obtained in the step (5) by using a tubular furnace, wherein the carbonizing temperature is 600 ℃, the heating rate is 2 ℃/min, the heat preservation time is 4 hours, and the protective atmosphere is argon-hydrogen mixed gas.
The prepared superstructure tin-carbon-molybdenum oxide composite material is applied to an electrode, and tests show that the content of the tin-carbon-molybdenum oxide composite material is 1A mg-1After 500 cycles of the current, 525 mAh g-1The discharge capacity of (2).
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (10)
1. A preparation method of a superstructure tin-carbon-molybdenum oxide composite material comprises the following steps:
A. preparing an alkaline solution to enable the pH value to be 8.0-10.5, dissolving phosphomolybdate in the phosphomolybdate solution, dispersing tin-based nanoparticles in the phosphomolybdate solution, preparing an alkaline solution of dopamine hydrochloride with the same volume, mixing the two solutions under the stirring condition, enabling the molar ratio of phosphomolybdate to dopamine hydrochloride in the mixed solution to be 1: 0.5-5, enabling phosphomolybdic acid and dopamine hydrochloride to perform coordination polymerization reaction, adsorbing tin-based nanoparticles in the solution, and forming a superstructure precursor through self-assembly, wherein the reaction temperature of the superstructure self-assembly is 20-60 ℃, and the assembly time is 1-4 h;
B. centrifuging, washing and drying the superstructure precursor, and then carbonizing in a protective atmosphere at 500-800 ℃ for 1-4 h, preferably 600-700 ℃ for 2h to obtain the superstructure precursor.
2. The method for preparing the superstructure tin-carbon-molybdenum oxide composite material according to claim 1, characterized in that: the prepared alkaline solution solvent in the step A is water or a mixed solution of water and ethanol, and the solute is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia water or tris (hydroxymethyl) aminomethane.
3. The method for preparing the superstructure tin-carbon-molybdenum oxide composite material according to claim 2, characterized in that: the concentration of the ethanol solution in the step A is 10-50%.
4. The method for preparing the superstructure tin-carbon-molybdenum oxide composite material according to claim 1, characterized in that: in the step A, the phosphomolybdate is one or more of phosphomolybdate hydrate, ammonium phosphomolybdate, sodium phosphomolybdate or potassium phosphomolybdate, and the molar concentration is 0.01-0.1 mol/L.
5. The method for preparing the superstructure tin-carbon-molybdenum oxide composite material according to claim 1, characterized in that: in the step A, the tin-based nanoparticles are one or more of tin, stannous oxide or stannic oxide, the radius of the tin-based nanoparticles is 10-500 nm, and the molar concentration is 0.01-0.1 mol/L.
6. The method for preparing the superstructure tin-carbon-molybdenum oxide composite material according to claim 1, characterized in that: in the step A, the molar ratio of the phosphomolybdate to the dopamine hydrochloride is 1: 1 to 2.
7. The method for preparing the superstructure tin-carbon-molybdenum oxide composite material according to claim 1, characterized in that: and the drying treatment in the step B is any one of freeze drying, supercritical drying or thermal drying, the drying temperature is-50-80 ℃, and the drying time is 4-30 h.
8. The method for preparing the superstructure tin-carbon-molybdenum oxide composite material according to claim 1, characterized in that: and B, the gas of the protective atmosphere in the step B is nitrogen, argon, a nitrogen-hydrogen mixed gas or an argon-hydrogen mixed gas.
9. A superstructure tin-carbon-molybdenum oxide composite made according to the method of any of claims 1-8.
10. Use of a superstructure tin-carbon-molybdenum oxide composite according to claim 9, wherein: it is applied to an electrode material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113842936A (en) * | 2021-10-22 | 2021-12-28 | 四川大学华西医院 | Platinum-based single-atom electro-catalytic material and preparation method and application thereof |
| CN114256457A (en) * | 2021-12-31 | 2022-03-29 | 国联汽车动力电池研究院有限责任公司 | Lithium-rich manganese-based positive electrode material with homogeneous composite coating layer and preparation method thereof |
| CN114324505A (en) * | 2021-12-09 | 2022-04-12 | 北京市农林科学院智能装备技术研究中心 | Preparation of carbon electrode and detection method and application of plant morin |
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| CN104795545A (en) * | 2015-04-14 | 2015-07-22 | 华东理工大学 | Composite electrode material of molybdenum dioxide quantum dot embedded mesoporous carbon nanosheets, as well as preparation method and application of composite electrode material |
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Cited By (5)
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| CN113842936A (en) * | 2021-10-22 | 2021-12-28 | 四川大学华西医院 | Platinum-based single-atom electro-catalytic material and preparation method and application thereof |
| CN114324505A (en) * | 2021-12-09 | 2022-04-12 | 北京市农林科学院智能装备技术研究中心 | Preparation of carbon electrode and detection method and application of plant morin |
| CN114324505B (en) * | 2021-12-09 | 2023-12-05 | 北京市农林科学院智能装备技术研究中心 | Preparation of carbon electrode, detection method of phytomorin and application |
| CN114256457A (en) * | 2021-12-31 | 2022-03-29 | 国联汽车动力电池研究院有限责任公司 | Lithium-rich manganese-based positive electrode material with homogeneous composite coating layer and preparation method thereof |
| CN114256457B (en) * | 2021-12-31 | 2023-12-05 | 国联汽车动力电池研究院有限责任公司 | Lithium-rich manganese-based positive electrode material with homogeneous composite coating layer and preparation method thereof |
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