CN107275606B - Carbon-coated spinel lithium manganate nanocomposite and preparation method and application thereof - Google Patents
Carbon-coated spinel lithium manganate nanocomposite and preparation method and application thereof Download PDFInfo
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- 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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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a carbon-coated spinel lithium manganate nanocomposite and a preparation method thereof. The application of the nano particles shortens the ion diffusion and transmission path of the material in the charge and discharge process; the carbon coating can improve the conductivity of the active material, simultaneously can prevent the direct contact of the lithium manganate anode and electrolyte, and can greatly improve the rate capability and cycle performance of the lithium ion battery and the hybrid supercapacitor; because the coating layer forms a conductive network, a conductive agent does not need to be additionally added in subsequent application. Compared with the traditional preparation method, the preparation method greatly simplifies the preparation process of the composite material, and the carbon-coated spinel lithium manganate nanocomposite with optimized performance is prepared by a one-step method.
Description
Technical Field
The invention relates to the field of composite materials, in particular to a lithium manganate carbon nano composite material and preparation and application thereof.
Background
In the 21 st century, people are facing serious challenges of energy crisis and environmental problems, and the development of new energy (solar energy, wind energy, biological energy, tidal energy, nuclear energy, geothermal energy) and renewable energy is an important measure for solving environmental pollution and realizing sustainable development. As an important electronic device, an energy storage device plays an important role. Among them, lithium ion batteries, supercapacitors and hybrid supercapacitors formed by combining the two have become the most potential energy storage devices.
Spinel lithium manganate LiMn2O4The lithium ion battery anode material has the advantages of abundant natural resources, low price, high safety, easy preparation and no toxicity, becomes the most potential lithium ion battery anode material, and is widely applied commercially. Spinel LiMn2O4Belongs to a cubic crystal system, the space group is Fd3m, and oxygen atoms form face-centered cubic close packing and occupy the 32e position of the space point group; the manganese ion is positioned at the 16d position of the octahedron, and the 16c position of the octahedron is vacant; the lithium ions are positioned at the 8a position of the tetrahedron, and the 8a position and the 16c position form a three-dimensional channel for lithium ion diffusion, so that the lithium ions are rapidly extracted/inserted in the crystal lattice. Compared with other types of positive electrode materials, the lithium manganate has higher rate performance, but still cannot meet the application requirement in the energy storage field; and Mn on the surface of the material particles in the charging and discharging process3+The dissolution of (2) causes generation of spinel structure defects, so that capacity fading is rapid and cycle life is shortened. In order to solve this problem, methods such as ion doping, nanocrystallization of active materials, and surface coating of highly conductive materials have been widely studied and applied.
The invention discloses an amorphous carbon-coated lithium manganate composite material. Firstly synthesizing lithium manganate powder by a hydrothermal method, then uniformly mixing the powder with glucose, placing the mixture in a tubular furnace, and sintering the mixture for 2 hours at 800 ℃ under the protection of argon atmosphere to obtain the amorphous carbon-coated lithium manganate composite material. However, the product prepared by the method has large particles, long ion diffusion path and hindered ion extraction in the charge and discharge process, is not suitable for high-rate charge and discharge, and cannot meet the requirement of an electronic device on rapid charge and discharge. And the hydrothermal method and the high-temperature carbonization are difficult to realize commercialization due to low production efficiency, harsh conditions and the like.
Li Xinhai et al coated graphite on the surface of the lithium manganate electrode by a magnetron sputtering method. After the conventional electrode is prepared, a layer of graphite is sputtered on the prepared lithium manganate electrode through magnetron sputtering, so that the graphite-coated lithium manganate electrode is prepared. According to the method, the carbon coating layer is only coated on the outermost layer, each lithium manganate particle is not uniformly coated, and a conductive network cannot be formed among the active substance particles, so that the conductivity is not greatly improved; and the commercialized micron-sized lithium manganate is not crushed, and the active substance is still coarse in particle, so that the lithium manganate is not beneficial to the implementation of rapid charge and discharge and the maintenance of structural stability in the circulating process.
Liujianhong and the like invent a graphene-like coated and doped lithium manganate composite positive electrode material and a preparation method thereof (patent number: CN 105655576A), manganese dioxide and lithium carbonate are subjected to ball milling, lithium manganate powder is prepared through solid-phase reaction, then a graphene-like precursor is added into the lithium manganate powder and uniformly mixed, the mixture is calcined at high temperature to obtain graphene/lithium manganate composite powder, and finally the graphene-like coated and doped lithium manganate composite positive electrode material is obtained through heat treatment in the air. The composite material prepared by the method has insufficient graphene coating, and the preparation process has various steps, and high-temperature heat treatment is involved, so that the method is not economical and environment-friendly.
A preparation method of a carbon-coated modified lithium manganate positive electrode material (CN 102916178A) is invented by people of Liutao et al, lithium manganate, an organic carbon source and a carbonization catalyst are prepared into a mixed solution, and the mixed solution is subjected to spray granulation by a spray dryer and then sintered for 0.5 to 4 hours at the temperature of 300 to 450 ℃ to obtain the composite material, so that the composite material is obtained. Effectively improves the conductivity of the electrode and avoids the direct contact of the electrode and electrolyte, but the method does not grind and refine the lithium manganate particles, so that the obtained composite particles are coarse, and the rate performance of the electrode material is seriously influenced.
Liangwenjun et al invented a method for preparing coated lithium manganate (patent No. CN 103996840A), in which the surface of lithium manganate is coated with metal oxide. Adding lithium manganate and the prepared metal oxide into water, dispersing and stirring to obtain turbid liquid, and then centrifugally washing, drying and calcining the product to obtain the metal oxide coated lithium manganate. The electrode material obtained by the method has better high-temperature cycle performance, but the conductivity of the electrode material is still poor, and the rate performance of the battery cannot be improved.
The invention discloses lithium manganate with a core-shell structure and a preparation method thereof (CN 104282902A), manganese carbonate and lithium carbonate are used as raw materials to prepare spinel lithium manganate through high-temperature solid-phase reaction, deionized water is used to uniformly mix the lithium manganate with cobalt oxalate, and after drying, the lithium manganate coated with a cobalt oxide core-shell structure is prepared through heat treatment. The electrode material prepared by the method has the advantages of complex process, incomplete coating, poor conductivity and poor rate performance.
Poplar Donacian et al invented a coated modified lithium manganate and its preparation method (patent No. CN 105655576A). first, uniformly mix lithium manganate with lithium source and boron source required for preparing lithium tetraborate to obtain precursor, then calcine the precursor at high temperature to obtain the lithium tetraborate coated lithium manganate composite material. The material prepared by the method has large particles and poor conductivity, so that the rate capability of the lithium ion battery is poor.
Zhang Jian Feng about LiMn2O4Carbon coating modification and electrochemical performance research of electrode material adopts melting self-mixing method to prepare LiMn2O4Preparing carbon-coated LiMn from powder and glucose as carbon source2O4A material. However, the carbon coating method has complex operation conditions, long time consumption, poor controllability, more influencing factors, difficult achievement of stable performance of different batches, poor economic benefit and difficult batch production and application in recent years.
The existing carbon-coated spinel lithium manganate is generally subjected to carbon coating by pyrolyzing organic compounds, and the carbon coating needs to be carried out at high temperature (600 ℃), but the lithium manganate is easy to cause oxygen atom loss at high temperature, so that the performance is reduced. Coating carbon materials by Chemical Vapor Deposition (CVD) also results in the loss of oxygen atoms. There is an urgent need for a coating process that can be performed at low temperatures.
Disclosure of Invention
In order to overcome the defects, the invention provides a simple and effective one-step method for synthesizing carbon-coated nano lithium manganate and a preparation method and application thereof. The composite material is simple in synthesis method and good in rate capability, and has wide application prospects in the fields of lithium ion batteries and hybrid supercapacitors. The carbon-coated lithium manganate nanocomposite can be prepared in a large scale at normal temperature, and the one-step large-scale preparation of the nanocomposite is realized.
In order to achieve the purpose, the invention adopts the following technical scheme:
the application of the nano-scale carbon material in preparing the carbon-coated spinel lithium manganate nanocomposite by a ball milling method.
The invention also provides a carbon-coated spinel lithium manganate nanocomposite, which is prepared from the following raw materials in parts by weight: 1-3 parts of micron-sized lithium manganate and 1 part of nano-sized carbon material, wherein the lithium manganate and the carbon material are uniformly coated together.
In order to realize the combination of the lithium manganate nanocrystallization technology and the carbon coating technology and simultaneously avoid the oxygen loss of the lithium manganate at high temperature, the invention carries out systematic research on the structure change rule of the lithium manganate in the nanocrystallization and carbon coating processes, and finds out after a large number of experiments: the micron-sized lithium manganate and the nanoscale inorganic carbon material are mixed and ball-milled, so that the electrochemical properties of the lithium manganate, such as specific capacity, rate capability, cycle life and the like, can be effectively improved, and the ball milling can be carried out at room temperature, so that the generation of oxygen defects can be avoided.
The early stage experiment of the invention shows that: ball milling commercial lithium manganate alone causes a certain amount of manganese to be lost, resulting in a decrease in performance. And the nano-scale inorganic carbon material and the micron-scale lithium manganate are mixed in a proportion of 1: 1-3, the loss of manganese element can be effectively prevented when the ball milling is carried out. Therefore, the mixing ratio of the nano-scale inorganic carbon material and the micron-scale lithium manganate is 1: 1-3.
Preferably, the particle size of the composite material is 20nm to 2000 nm.
Preferably, the lithium manganate comprises one or more of spherical, octahedral, commercial spinel lithium manganate;
preferably, the carbon material is one or more of conductive carbon black, graphene, carbon nanotubes, carbon fibers and conductive ink.
The invention also provides a preparation method of the carbon-coated spinel lithium manganate nanocomposite, which comprises the following steps:
and uniformly mixing the micron-sized lithium manganate and the nanoscale carbon material, and performing ball milling to obtain the carbon-coated spinel lithium manganate nanocomposite.
According to the invention, the transmission of lithium ions and electrons can be effectively promoted through the nano-crystallization of lithium manganate: the specific surface area and the surface area/volume ratio of the small-size crystal grains are larger, so that the active substance can be ensured to be fully contacted with the electrolyte, the active substance is fully utilized, and the specific capacity of the active substance is improved; and the nano structure shortens the transmission path of ions, and is beneficial to the rapid de-intercalation of the ions, thereby greatly improving the rate capability of the material. The carbon material coating effectively improves the conductivity between the active material particles. The coating layer can effectively promote lithium ion transmission, maintain structural stability and relieve the dissolution of trivalent manganese ions.
Preferably, the ball milling conditions are as follows: the ball material ratio is 9-10: 1, the rotating speed is 200-;
the ball milling method is simple to operate, has low requirements on production conditions, can be carried out in air at room temperature, has wide raw material sources, and can be used for batch production of the high-rate-performance carbon-coated spinel lithium manganate nanocomposite with stable performance.
Preferably, the ball milling adopts a non-metal ball milling tank and non-metal ball milling beads, preferably agate ball milling tank and agate ball milling beads, wherein the diameter of the small ball is 2-15mm, and the volume of the ball tank is 50-200 ml;
preferably, the ball milling is performed by a high energy ball mill, preferably a planetary ball mill.
The invention also provides the carbon-coated spinel lithium manganate nanocomposite prepared by any one of the methods.
The invention also provides a preparation method of the carbon-coated spinel lithium manganate nanocomposite electrode, which comprises the following steps:
uniformly mixing the micron-sized lithium manganate and the nanoscale carbon material, and performing ball milling to obtain a carbon-coated spinel lithium manganate nanocomposite;
compounding the carbon-coated spinel lithium manganate nanocomposite material serving as an active substance with a binder and a solvent to obtain a coating;
and coating the coating on a substrate electrode to obtain the coating.
The invention also provides application of any carbon-coated spinel lithium manganate nanocomposite in preparation of electrodes, lithium ion batteries and hybrid supercapacitors.
The invention has the advantages of
(1) The lithium manganate used in the invention is commercial lithium manganate, and has wide source and stable performance.
(2) The method utilizes a ball milling method to synthesize the carbon-coated lithium manganate nanocomposite material in one step, and has the advantages of simple operation and low cost.
(3) The carbon-coated lithium manganate synthesized by the method has small size, shortens the ion diffusion and transmission path of the material in the charging and discharging process, and can greatly improve the rate capability of a lithium ion battery and a hybrid supercapacitor.
(4) According to the invention, the lithium manganate particles are coated by carbon, so that the conductivity of the lithium manganate anode material can be obviously improved, and the lithium manganate anode is prevented from being directly contacted with an electrolyte.
(5) According to the invention, the carbon material is directly coated on the surface of the active material to form a uniform conductive network, and no additional conductive agent is required to be added in the subsequent application of the energy storage device.
(6) The invention provides a new method for synthesizing other carbon-coated lithium-containing oxide composite materials, such as carbon-coated lithium iron phosphate, carbon-coated lithium titanate and other nano composite materials.
(7) The preparation method is simple, high in detection efficiency, strong in practicability and easy to popularize.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 is a scanning electron micrograph of an original commercial spherical spinel lithium manganate amplified 20000 times;
FIG. 2 is a scanning electron micrograph of commercial lithium manganate after ball milling at 20000 times;
FIG. 3 is a scanning electron micrograph of conductive carbon black super P-coated lithium manganate nanoparticles magnified 50000 times;
FIG. 4 is a distribution diagram of carbon, manganese and oxygen elements of conductive carbon black super P-coated lithium manganate nanoparticles;
FIG. 5 is a cyclic voltammogram of conductive carbon black super P-coated lithium manganate nanoparticles used as a positive electrode of a water-based hybrid capacitor;
FIG. 6 is a graph showing the rate capability of conductive carbon black super P-coated lithium manganate nanoparticles used as a water system hybrid capacitor.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
A carbon material coated nano lithium manganate composite material and a preparation method and application thereof are disclosed, (1) the material is commercial lithium manganate and a carbon material; (2) crushing commercial micron-sized lithium manganate into nano-sized lithium manganate particles; (3) and directly coating the carbon material on the surfaces of the nano lithium manganate particles by ball milling. The carbon material is uniformly coated on the surfaces of the lithium manganate particles while the lithium manganate particles are crushed and refined, so that the conductivity of the electrode material is improved. The multiplying power performance of the lithium ion battery and the hybrid capacitor is remarkably improved while the cycle performance of the lithium ion battery and the hybrid capacitor is improved.
The preparation method of the carbon material coated nano lithium manganate comprises the following steps:
1) putting commercial lithium manganate and a carbon material into a ball milling tank;
2) preparing a certain proportion of ball milling beads and placing the ball milling beads in the ball milling tank;
3) sealing the cover of the ball mill pot and installing the ball mill pot cover on the ball mill for ball milling
The preparation method of the carbon material coated nano lithium manganate comprises the following steps of (1) preferably, wherein the mass ratio of lithium manganate to the carbon material in the step (1) is 2: 1;
the preparation method of the carbon material coated nano lithium manganate comprises the following steps of (1) preferably, wherein the ball milling pot in the step (1) is an agate ball milling pot;
the preparation method of the carbon material-coated nano lithium manganate comprises the following steps of (1) preferably, wherein the carbon material in the step is conductive carbon black;
the preparation method of the carbon material coated nano lithium manganate comprises the following steps of (1) preparing a carbon material coated nano lithium manganate, wherein preferably, in the step (2), the ball milling beads are preferably agate ball milling beads, and the proportion of the agate ball milling beads is preferably (9-10): 1;
the preparation method of the carbon material coated nano lithium manganate comprises the following steps of (1) preferably carrying out ball milling in air in the step (3) without any protective gas;
the preparation method of the carbon material-coated nano lithium manganate composite material comprises the following steps of (1) preferably, in the step (3), performing ball milling at a ball milling rotation speed of (200-;
the preparation method of the conductive carbon black coated nano lithium manganate composite material comprises the following steps of (1) and (3), wherein the ball mill is preferably a high-energy ball mill, and the ball mill is preferably a high-energy planetary ball mill in the steps (1) and (3);
(1) in step 1, a zirconia ball mill can be used.
(2) In the step 1, the mass ratio of the lithium manganate to the carbon material can be replaced by (1-3) to 1.
(3) In the step 1, a proper amount of absolute ethyl alcohol can be added for wet grinding or a proper amount of grinding aid is added for ball milling.
(4) In the step 2, the ball milling beads can replace zirconia ball milling beads made of the same material as the ball milling tank, and the material ratio and the ball milling bead diameter ratio are adjusted.
(5) And 3, ball milling in air in the step 3 can be replaced by ball milling in nitrogen and argon protective gas.
(6) The ball milling time in step 3 can be replaced by 2-24 h.
(7) The ball mill ball milling in the step 2 and the step 3 can replace the grinding mode in a mortar.
step 1: weighing 808mg of spinel lithium manganate (LiMn)2O4) And 404mg of conductive carbon black (super P) in a 50ml agate jar;
step 2: 3 ball grinding beads with the diameter of 15mm, 1 ball grinding bead with the diameter of 8mm, 2 ball grinding beads with the diameter of 6mm and 10 ball grinding beads with the diameter of 5mm are taken and placed in the ball grinding tank;
and step 3: and sealing the end cover of the proportioned ball mill tank, and installing the end cover in a high-energy ball mill for ball milling at the rotating speed of 450rmp/min for 6 hours. And (4) obtaining conductive carbon black coated nano lithium manganate composite material powder after ball milling.
Embodiment 2, a conductive carbon black and graphene coated nano lithium manganate composite material is prepared, which comprises the following specific steps:
step 1: weighing 808mg of spinel lithium manganate (LiMn)2O4) 202mg of conductive carbon black (super P) and 202mg of graphene powder are placed in a 50ml agate ball milling tank;
step 2: 3 ball grinding beads with the diameter of 15mm, 1 ball grinding bead with the diameter of 8mm, 2 ball grinding beads with the diameter of 6mm and 10 ball grinding beads with the diameter of 5mm are taken and placed in the ball grinding tank;
and step 3: and sealing the cover of the proportioned ball mill tank, and mounting the cover on a high-energy ball mill for ball milling at the rotating speed of 550rmp/min for 6 hours. And (4) obtaining conductive carbon black and graphene coated nano lithium manganate composite material powder after ball milling.
Embodiment 3, a method for preparing a conductive carbon black coated nano lithium manganate composite material comprises the following specific steps:
step 1: weighing 600mg of spinel lithium manganate (LiMn)2O4) And 200mg of conductive carbon black (super P) in an agate mortar.
Step 2: and grinding the powder in a mortar for 1h to fully crush and mix the material to obtain the conductive carbon black coated nano lithium manganate composite material powder.
Example 4, a conductive carbon black coated nano lithium manganate composite material as an organic lithium ion battery anode material, specifically comprises the following steps:
step 1: respectively weighing 90mg of the carbon-coated nano lithium manganate composite material and 10mg of the binder PVDF, placing the materials in a 10ml beaker, adding a certain amount of NMP, and magnetically stirring for 12 hours to uniformly mix the materials to obtain the lithium ion battery anode slurry.
Step 2: and (3) uniformly coating the slurry prepared in the step (1) on an aluminum foil, and drying at 100 ℃ for 6 hours to obtain the lithium manganate electrode.
And step 3: and (3) cutting the electrode in the step (2) into a circular pole piece with the diameter of 10mm, weighing and calculating the mass of the active substance on the pole piece.
And 4, step 4: and (4) assembling the pole piece in the step (3) as a working electrode, and assembling the working electrode and the counter electrode into the button cell in a glove box protected by argon atmosphere.
And 5: and (4) taking out the packaged battery in the step 4 and standing for 24 hours.
Step 6: and (5) mounting the button cell which is well stood in the step (5) on a blue charge-discharge tester, and testing the electrochemical performance of the button cell.
Example 5, a conductive carbon black coated nano lithium manganate composite material as a water system hybrid capacitor, specifically comprising the following steps:
step 1: cutting foamed nickel with the thickness of 1mm into the size of 10mm x 20mm, respectively cleaning the foamed nickel with acetone, dilute hydrochloric acid and deionized water in sequence, then placing the cleaned foamed nickel in a vacuum drying oven for drying for 6 hours at the temperature of 60 ℃, and then using the cleaned foamed nickel as a current collector.
Step 2: weighing 90mg of conductive carbon black coated nano lithium manganate composite material and 16.7mg of Polytetrafluoroethylene (PTFE) aqueous solution binder with the mass fraction of 60%, wherein the mass ratio of active substances to the binder is 9: 1; pouring into a small beaker of 10ml, adding a certain amount of alcohol, and magnetically stirring for 1h to uniformly mix the mixture to obtain the mixed capacitor anode slurry.
And step 3: and (3) uniformly coating the slurry in the step 2 on the surface of the dried foamed nickel in the step 1, wherein the coating area is 10 x 10 mm. Drying at 100 deg.C for 12h to remove alcohol and water solvent, maintaining vacuum state, and taking out when the temperature is reduced to below 40 deg.C to obtain the prepared pole piece.
And 4, step 4: preparing 1mol/L lithium sulfate aqueous solution as electrolyte.
And 5: and (3) forming a three-electrode system by using a saturated calomel electrode as a reference electrode, a platinum electrode as a counter electrode and the pole piece prepared in the step (3) as a working electrode, placing the three-electrode system in an electrolytic cell, adding the electrolyte prepared in the step (4), wherein the electrolyte is required to cover the coated area of the working electrode.
Step 6: and (4) carrying out cyclic voltammetry and constant-current charge and discharge tests to analyze the electrochemical performance of the material.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (8)
1. The preparation method of the carbon-coated spinel lithium manganate nanocomposite is characterized by comprising the following steps: uniformly mixing the micron-sized lithium manganate and the nanoscale carbon material, and performing ball milling to obtain a carbon-coated spinel lithium manganate nanocomposite; the mixing mass ratio of the nano-scale carbon material to the micron-scale lithium manganate is 1: 1-3; the particle size of the composite material is 20 nm-2000 nm; the ball milling is carried out at room temperature; the ball milling conditions are as follows: the ball material ratio is 9-10: 1, the rotating speed is 200-;
according to the method, commercial micron-sized lithium manganate is crushed into nano-sized lithium manganate particles, the carbon material is directly coated on the surfaces of the nano-sized lithium manganate particles through ball milling, the carbon material is uniformly coated on the surfaces of the particles while the lithium manganate particles are crushed and refined, and the conductivity of the electrode material is improved.
2. The method of preparing a carbon-coated spinel lithium manganate nanocomposite of claim 1 wherein said lithium manganate comprises one or more of spherical, octahedral, commercial spinel lithium manganate.
3. The method of preparing a carbon-coated spinel lithium manganate nanocomposite as claimed in claim 1, wherein said carbon material is one or more of conductive carbon black, graphene, carbon nanotubes, carbon fibers, conductive ink.
4. The method of claim 1, wherein the ball milling is performed using a non-metal ball milling pot and non-metal ball milling beads.
5. The method for preparing the carbon-coated spinel lithium manganate nanocomposite as claimed in claim 4, wherein said beads are selected from agate ball-milling jars and agate ball-milling beads, wherein the diameter of the small ball is 2-15mm, and the volume of the ball jar is 50-200 ml.
6. The method of preparing a carbon-coated spinel lithium manganate nanocomposite as claimed in claim 1, wherein said ball milling is carried out by a high energy ball mill.
7. A carbon-coated spinel lithium manganate nanocomposite prepared by the method for preparing a carbon-coated spinel lithium manganate nanocomposite as claimed in any one of claims 1 to 6.
8. The carbon-coated spinel lithium manganate nanocomposite material of claim 7, being used for preparing electrodes, lithium ion batteries or hybrid supercapacitors.
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| CN108470901B (en) * | 2018-05-29 | 2020-09-25 | 山东大学 | Carbon nanotube lithium manganate nanocomposite and preparation method and application thereof |
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| CN115490266A (en) * | 2022-09-27 | 2022-12-20 | 安徽博石高科新材料股份有限公司 | Preparation method of carbon-coated lithium manganate composite material |
| CN116130623B (en) * | 2022-12-20 | 2024-03-19 | 湖南法恩莱特新能源科技有限公司 | Graphene lithium battery composite material and preparation method and application thereof |
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