CN110176595B - Lithium ion battery anode material LiMnO2@ C and preparation method thereof - Google Patents
Lithium ion battery anode material LiMnO2@ C and preparation method thereof Download PDFInfo
- Publication number
- CN110176595B CN110176595B CN201910490654.XA CN201910490654A CN110176595B CN 110176595 B CN110176595 B CN 110176595B CN 201910490654 A CN201910490654 A CN 201910490654A CN 110176595 B CN110176595 B CN 110176595B
- Authority
- CN
- China
- Prior art keywords
- solution
- limno
- lithium ion
- ion battery
- stirring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the field of lithium ion batteries, and particularly provides a layered lithium manganate LiMnO as a lithium ion battery anode material2@ C and preparation method thereof for overcoming defect of layered lithium manganate (LiMnO) of positive electrode material of lithium ion battery2) Difficult preparation, poor electrochemical performance, easy phase transformation of the structure and incapability of high-rate discharge. The invention prepares the hexahedral or cubic MnCO by the hydrothermal reaction of a soft chemical method3The Mn is prepared into high-activity Mn with the same morphology2O3Then, the lithium ion battery is subjected to low-temperature solid-phase reaction with a lithium source, so that the prepared layered lithium manganate particles are hexahedral or cubic structure materials, and the materials are high in crystallinity and excellent in electrochemical performance under a lower multiplying power; meanwhile, carbon coating is carried out to obtain LiMnO capable of discharging at high rate2@ C composite positive electrode material.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, relates to a lithium ion battery anode material and a preparation method thereof, and particularly relates to a layered lithium manganate LiMnO of the lithium ion battery anode material2The preparation method of (1).
Background
With the increasing deterioration of global environment and climate, energy conservation and emission reduction are in need, and countries in the world pay more attention to the development and application of new energy and renewable clean energy. The lithium ion battery is used as an environment-friendly power supply with excellent performance, has the advantages of high energy density, quick charging, small self-discharge, long-time storage, excellent cycle performance, no memory effect and the like, is widely applied to various portable electronic and electrical equipment, and becomes a preferred ideal power supply for future electric vehicles.
At present, a lot of positive electrode materials are applied to lithium ion batteries in batches, and lithium cobaltate (LiCoO) is mainly used2) Lithium nickelate (LiNiO)2) Spinel type lithium manganate (LiMn)2O4) Lithium Nickel Cobalt Manganese (NCM) and lithium iron phosphate (LiFePO)4). Lithium cobaltate is the anode material which is the earliest to realize commercial application, the preparation technology has been developed and matured so far, and the lithium cobaltate is widely applied to small-sized portable electronic products with low power, but the manufacturing cost of the lithium ion battery is high and the environmental pollution is large due to the large toxicity and the lack of resources of cobalt; the nickel acid lithium battery has the worst safety performance due to intolerance of overcharge and discharge, overcharge is easy to ignite, and decomposition is easy at high temperature, so that the nickel acid lithium battery has poor thermal stability and poor cycle performance, and the commercialization process is hindered to a certain extent; although the lithium iron phosphate anode material is environment-friendly and nontoxic, rich in mineral resources, low in raw material cost, excellent in temperature tolerance and excellent in cycle stability, the application and development of the lithium iron phosphate anode material are limited due to poor conductivity, small tap and compaction density, large volume, low energy density and poor low-temperature performance; the spinel type lithium manganate positive electrode material has good safety performance and good low-temperature performance, but has not high theoretical specific capacity (only the spinel type lithium manganate positive electrode material has good safety performance and good low-temperature performance)148mAh/g), a pure-phase product is difficult to prepare, and Jahn-Teller effect is easy to occur in the circulation process, so that the service life of the lithium ion battery is influenced. Especially in a high-temperature environment, the cycle performance of spinel-type lithium manganate is more unstable due to the dissolution of manganese.
Although attention has been focused at home and abroad on lithium nickel cobalt manganese oxide (NCM) and lithium Nickel Cobalt Aluminate (NCA) with higher energy density, particularly on high nickel NCM811 and NCA 815; however, the two materials have high cost due to lack of resources, and have harsh use conditions and poor safety performance due to high nickel content, so that the use of the two materials in future pure electric vehicles is limited.
And spinel type LiMn2O4In contrast, layered LiMnO of trivalent manganese compound2The improved cycle performance is shown, the voltage range is between 2.0 and 4.5V, and no special requirement is imposed on the electrolyte; further, orthorhombic or monoclinic phase layered LiMnO2The lithium ion battery positive electrode material is an attractive rechargeable lithium ion battery positive electrode material, and is considered to be the best potential positive electrode material of a future low-cost high-energy-density lithium ion battery due to high specific capacity (theoretical specific capacity of 285mAh/g), extremely low cost, no toxicity, high energy density, high environmental acceptability and the like. So far, the preparation method of the layered lithium manganate is various, mainly the traditional solid phase method, and the lithium source and the manganese source are respectively Li2CO3、LiOH·H2O、MnO2、MnCO3、Mn2O3Manganese acetate, manganese nitrate, manganese sulfate, and the like; direct production of LiMnO by hydrothermal method2Although reported, hydrothermal method for preparing layered LiMnO2The method is complex and is not suitable for industrial large-scale production; sol-gel method for preparing LiMnO2The cost is high, and environmental pollution can be brought; the pure solid phase method adopts high-temperature sintering after grinding or ball milling is uniform, although the method has simple process and is suitable for commercial production, the particle size distribution of the product is not uniform, the target product with stoichiometric ratio is difficult to prepare, the electrochemical performance is poor, and the phase transformation from a layered structure to a spinel structure is easy to occur in the charge-discharge cycle process. In addition, phase-pure layeringThe lithium manganate has poor conductivity, cannot meet the requirement of high-rate charge and discharge, causes very low power density, and simultaneously has pure-phase layered LiMnO2The material can be activated by 3-10 times of charge-discharge cycles to achieve the best discharge performance; therefore, it is required to explore a new material composition and to prepare layered lithium manganate (LiMnO) having excellent properties of the composition2) A method of preparing a cathode material.
Disclosure of Invention
The invention aims to provide layered lithium manganate (LiMnO) as a positive electrode material of a lithium ion battery2) Is difficult to prepare, has poor electrochemical performance and very easy phase transition of the structure, and provides a layered lithium manganate (LiMnO) as a positive electrode material of a lithium ion battery2) The method combines a hydrothermal method to synthesize a high-activity precursor and a low-temperature solid-phase method to synthesize the nano-structure layered LiMnO2. The lithium ion battery anode material LiMnO synthesized by the invention2Has higher specific discharge capacity and excellent cycling stability, and the carbon-coated layered lithium manganate LiMnO2The @ C can meet the requirements of high energy density, high power density and high-rate charge and discharge, the preparation method overcomes the defects of uneven particle size distribution, poor electrochemical performance and the like of a product prepared by a pure solid-phase synthesis method, and the prepared product has high purity, good chemical uniformity, high crystallization quality, fine and uniform product particles, excellent electrochemical performance and lower manufacturing cost; the phase transformation from a layered structure to a cubic spinel structure does not occur in the charge and discharge processes, and the cycle performance is excellent.
In order to achieve the purpose, the invention adopts the technical scheme that:
lithium ion battery anode material LiMnO2@ C, characterized in that the lithium ion battery positive electrode material LiMnO2@ C is carbon (C) -coated layered lithium manganate (LiMnO)2) A composite material wherein the amount of carbon (C) coated is 0.5 to 2.0 wt%; the crystal structure of the composite material is in a regular hexahedron shape, the surface of the composite material is provided with a point-shaped coating, the maximum side length of the hexahedron is 8-10 um, the minimum side length of the hexahedron is 1-2 um, and the agglomeration phenomenon is avoided.
Even more, the composite material crystal structure is cubic.
The lithium ion battery anode material LiMnO2A preparation method of @ C comprises the following steps:
step 1, adding manganese nitrate into deionized water, and stirring at room temperature to completely dissolve the manganese nitrate to obtain a solution A with the manganese nitrate concentration of 1.0 mol/L;
step 3, adding ammonium fluoride into deionized water, and stirring at room temperature to completely dissolve the ammonium fluoride to obtain a solution C with the ammonium fluoride concentration of 2.0 mol/L;
step 4, adding the solution A, B obtained in the steps 1, 2 and 3 and C together at the speed of 10ml/min, stirring to obtain a mixed solution, and continuously stirring to obtain a mixed suspension, wherein the solution A, B and the solution C are mixed in equal volume;
step 6, placing the white crystal precipitation product obtained in the step 5 into a forced air drying oven, and drying for 5-8 hours at the temperature of 80-120 ℃ to obtain MnCO3A powder;
step 7, the MnCO obtained in the step 6 is processed3Putting the powder into a muffle furnace, and carrying out thermal decomposition for 5-20 h at 450-650 ℃ in air to obtain Mn2O3Powder;
step 9, placing the powder mixture obtained in the step 8 in a ceramic boat, placing the ceramic boat in a tube furnace, and sintering the ceramic boat for 10-24 hours at 650-900 ℃ in an argon atmosphere to obtain a layered lithium manganate target product;
The invention prepares the hexahedral or cubic MnCO by the hydrothermal reaction of a soft chemical method3The Mn is prepared into high-activity Mn with the same morphology2O3Then, the lithium ion battery is subjected to low-temperature solid-phase reaction with a lithium source, so that the prepared layered lithium manganate particles are hexahedral or cubic structure materials, the particle crystallinity is high, and the electrochemical performance is excellent under a lower rate; then obtaining LiMnO capable of discharging under high rate through carbon coating2@ C composite positive electrode material.
In summary, the invention has the following advantages:
1. the invention adopts a process combining a soft chemical hydrothermal method and a low-temperature solid-phase method, prepares precursor powder with hexahedron or cubic appearance through liquid-phase reaction, prepares micron-sized layered lithium manganate particles with the same appearance through sintering by a low-temperature solid-phase method, and finally obtains LiMnO with hexahedron or cubic appearance through carbon coating2@ C composite positive electrode material. The method overcomes the defects of the traditional solid phase synthesis method, and the prepared product has the advantages of excellent crystallization quality, good chemical uniformity, fine particles, high purity and capability of discharging with large current and high rate.
2. The layered lithium manganate serving as the cathode material of the lithium ion battery, prepared by the invention, has higher specific discharge capacity and excellent cycling stability, and is suitable for the charge and discharge requirements of high-energy density batteries; under the room temperature environment, when the constant current charge-discharge rate is 0.1C, the first discharge specific capacity of the layered lithium manganate anode material can reach 216mAh/g, can still reach 206mAh/g after 50 times of circulation, and the capacity retention rate is as high as 95.4%. Carbon-coated layered lithium manganate LiMnO2@ C positiveThe electrode material can obtain higher specific discharge capacity and cycle performance under the multiplying power of 0.5C.
3. The reaction raw materials used in the process are common chemical products, and have the advantages of rich raw material sources, low price and extremely low manufacturing cost. The carbon source is common food-grade sucrose or glucose.
4. The equipment used in the process is simple, no toxic or harmful substance is generated in the preparation process, the green and environment-friendly concept is met, and the large-scale industrial production is easy to realize.
Drawings
FIG. 1 shows that the invention prepares LiMnO which is the anode material of lithium ion battery2The process flow diagram of (1).
FIG. 2 shows that the invention prepares the anode material LiMnO of the lithium ion battery2@ C.
FIG. 3 shows that the invention prepares LiMnO which is the anode material of lithium ion battery2XRD pattern of (a).
FIG. 4 shows that the precursor MnCO for preparing the anode material of the lithium ion battery is prepared by the invention3(left) and LiMnO2SEM picture of @ C (right).
FIG. 5 shows that the invention prepares LiMnO which is the anode material of lithium ion battery2First charge and discharge curves at 0.1C rate.
FIG. 6 shows that LiMnO which is a positive electrode material for a lithium ion battery prepared by the present invention2Tenth charge-discharge curve at 0.1C rate.
FIG. 7 shows that the invention prepares LiMnO which is the anode material of lithium ion battery2Cycling performance at 0.1C rate.
FIG. 8 shows that the invention prepares LiMnO which is the anode material of lithium ion battery2Graph of the cycling performance at 0.5C rate @ C.
Detailed Description
The present invention will be described in further detail with reference to the following detailed description and the accompanying drawings.
Example 1
Adding 0.1mol of manganese nitrate into 100ml of deionized water to prepare a solution A, adding 0.4mol of urea into 100ml of deionized water to prepare a solution B, and adding 0.2mol of ammonium fluoride into 100ml of deionized waterPreparing solution C, adding solution A, solution B and solution C into a beaker at the speed of 10ml/min while stirring, stirring uniformly after adding, transferring into a stainless steel high-pressure reaction kettle lined with polytetrafluoroethylene, filling the stainless steel high-pressure reaction kettle with the filling amount of 80%, sealing the high-pressure reaction kettle, performing hydrothermal reaction for 5 hours at 180 ℃, performing centrifugal separation, and performing cross washing and precipitation with deionized water and absolute ethyl alcohol for three times respectively to obtain MnCO3Precipitating white crystals; mixing MnCO3Putting the white crystal precipitation product into a forced air drying oven, and drying at 90 ℃ for 4h to obtain MnCO3A white powder; mixing MnCO3Placing the white powder in a muffle furnace in air atmosphere for thermal decomposition at 450 ℃ for 2h to obtain Mn2O3And (3) precursor powder. Adding a precursor Mn2O3And LiOH. H2Mixing and grinding O uniformly, and then sintering at the low temperature of 650 ℃ for 12h under the protection of argon to obtain the layered lithium manganate cathode material LiMnO2(ii) a As shown in FIG. 1;
the obtained LiMnO2Adding the anode material into a sucrose solution with the concentration of 20 percent to maintain LiMnO2The carbon content in the anode material is between 0.5 and 2.0 weight percent, the anode material is fully stirred, dried, thermally decomposed for 3 hours at 500 ℃ in the atmosphere of high-purity argon, cooled, ground and sieved to obtain LiMnO2@ C composite positive electrode material; as shown in fig. 2.
FIG. 3 shows that the uncoated lithium ion battery anode material LiMnO prepared by the invention2The XRD pattern of the material is orthorhombic LiMnO as can be seen from FIG. 32The diffraction peak of the characteristic XRD diffraction spectrum of the standard spectrogram is completely coincided with that of the standard spectrogram.
Shown as a precursor MnCO in figure 4 (left)3The scanning electron microscope photograph of (1) shows, from the left image, the precursor MnCO3The surface of the hexahedron is provided with a plurality of point-shaped coatings, the maximum side length of the hexahedron is 8-10 um, the minimum side length of the hexahedron is 1-2 um, and the agglomeration phenomenon is avoided. After the material is inserted into lithium ions, the particle size and the morphology of the material still maintain the precursors of manganese carbonate and Mn2O3The particle size and morphology of (a) are shown in fig. 4 (right).
For the prepared anode of the lithium ion batteryMaterial LiMnO2Constant current charge and discharge tests are carried out, and the test result shows that the anode material has higher specific discharge capacity and excellent cycling stability; under the room temperature environment, when the constant current charge-discharge multiplying power is 0.1C, the first discharge specific capacity of the layered lithium manganate lithium ion battery anode material can reach 155mAh/g (figure 5), the discharge specific capacity at the 10 th cycle can reach 216mAh/g (figure 6), the discharge specific capacity can still reach more than 206mAh/g after 50 cycles (figure 7), and the capacity retention rate is as high as 95.4%. Similarly, for the prepared lithium ion battery anode material LiMnO2The @ C is used for constant current charge and discharge tests, and the test results show that the cathode material has higher rate discharge specific capacity and excellent cycling stability. Under the room temperature environment, when the constant current charge-discharge multiplying power is 0.5C, the carbon-coated layered lithium manganate anode material LiMnO of the lithium ion battery2The specific discharge capacity of @ C for the first time can reach 206.3mAh/g, the specific discharge capacity of 2 nd time can reach 223.2mAh/g, the specific discharge capacity can still reach more than 216.9mAh/g after 50 times of circulation, and the capacity retention rate is as high as 97.2% (figure 8).
Comparative example 1
0.005mol Mn of analytically pure chemical reagent is weighed2O3And 0.011mol of LiOH. H2Mixing and grinding O uniformly, and then sintering for 12h at 650 ℃ under the protection of argon to obtain the layered lithium manganate cathode material LiMnO2. Then the prepared layered lithium manganate LiMnO of the lithium ion battery is added2The positive electrode material is subjected to constant current charge and discharge test, and the test result shows that the positive electrode material has poor discharge specific capacity and poor cycling stability; under the room temperature environment, when the constant current charge-discharge multiplying power is 0.1C, the first discharge specific capacity of the layered lithium manganate lithium ion battery anode material after complete activation is only 103.3mAh/g, the highest discharge specific capacity can reach 105.8mAh/g, the discharge specific capacity after 50 cycles is only 80.2mAh/g, and the capacity retention rate is 77.6%.
Comparative example 2
Weighing 0.1mol of white powder MnCO3Analyzing pure chemical reagent, adding MnCO3Placing the white powder in a muffle furnace in air atmosphere for thermal decomposition at 450 ℃ for 2h to obtain Mn2O3Powder, and then 0.005mol of Mn obtained by weighing2O3And 0.011mol of LiOH. H2Mixing and grinding O uniformly, and then sintering for 12h at 650 ℃ under the protection of argon to obtain the layered lithium manganate cathode material LiMnO2. Then the prepared layered lithium manganate LiMnO of the lithium ion battery is added2The anode material is subjected to constant current charge-discharge test, and the test result shows that the discharge specific capacity and the cycling stability of the anode material are still poor; under the room temperature environment, when the constant current charge-discharge multiplying power is 0.1C, the first discharge specific capacity of the layered lithium manganate lithium ion battery anode material after complete activation is only 121.6mAh/g, the highest discharge specific capacity can reach 123.1mAh/g, the discharge specific capacity after 50 cycles is only 101.3 mAh/g, and the capacity retention rate is 83.3%.
As can be seen from the above comparative examples 1 and 2, either industrial-grade MnCO was used as it is3Preparation of Mn2O3Powder or directly using industrial grade Mn2O3Powder with LiOH H2Layered lithium manganate LiMnO obtained by O mixed sintering2The electrochemical performance of the MnCO is far lower than that of the MnCO in the invention, so that the MnCO in the hexahedron or cube shape is prepared only by strictly adopting the process flow and the process parameters of the invention3Powder and making it into high-activity Mn with same morphology2O3Then carrying out solid phase reaction with a lithium source to prepare the layered lithium manganate LiMnO2The electrochemical performance of the invention is excellent; then the LiMnO capable of discharging at high rate is obtained by carbon coating2@ C composite positive electrode material.
Where mentioned above are merely embodiments of the invention, any feature disclosed in this specification may, unless stated otherwise, be replaced by alternative features serving equivalent or similar purposes; all of the disclosed features, or all of the method or process steps, may be combined in any combination, except mutually exclusive features and/or steps.
Claims (2)
1. Lithium ion battery anode material LiMnO2@ C, characterized in that the lithium ion battery positive electrode materialLiMnO Material2@ C is carbon (C) -coated layered lithium manganate (LiMnO)2) A composite material wherein the amount of carbon (C) coated is 0.5 to 2.0 wt%; the crystal structure of the composite material is in a regular hexahedron shape, the surface of the composite material is provided with a point-shaped coating, the maximum side length of the hexahedron is 8-10 um, the minimum side length of the hexahedron is 1-2 um, and the agglomeration phenomenon is avoided; the lithium ion battery anode material LiMnO2@ C is prepared by the following steps:
step 1, adding manganese nitrate into deionized water, and stirring at room temperature to completely dissolve the manganese nitrate to obtain a solution A with the manganese nitrate concentration of 1.0 mol/L;
step 2, adding urea into deionized water, and stirring at room temperature to completely dissolve the urea to obtain a solution B with the urea concentration of 4.0 mol/L;
step 3, adding ammonium fluoride into deionized water, and stirring at room temperature to completely dissolve the ammonium fluoride to obtain a solution C with the ammonium fluoride concentration of 2.0 mol/L;
step 4, adding the solution A, B obtained in the steps 1, 2 and 3 and C together at the speed of 10ml/min, stirring to obtain a mixed solution, and continuously stirring to obtain a mixed suspension, wherein the solution A, B and the solution C are mixed in equal volume;
step 5, transferring the suspension obtained in the step 4 into a high-pressure reaction kettle, wherein the filling amount is 80%, and sealing the high-pressure kettle; performing hydrothermal reaction at 180 ℃ for 5-12 h to obtain MnCO3Crystal precipitation;
step 6, placing the white crystal precipitation product obtained in the step 5 into a forced air drying oven, and drying for 5-8 hours at the temperature of 80-120 ℃ to obtain MnCO3Powder;
step 7, the MnCO obtained in the step 6 is processed3Putting the powder into a muffle furnace, and carrying out thermal decomposition for 5-20 h at 450-650 ℃ in air to obtain Mn2O3Powder;
step 8, Li according to the mol ratio+/Mn3+= 1.05-1.25 LiOH or Li is weighed2CO3And Mn obtained in step 72O3Uniformly mixing the powder to obtain a powder mixture;
step 9, placing the powder mixture obtained in the step 8 in a ceramic boat, placing the ceramic boat in a tube furnace, and sintering the ceramic boat for 10-24 hours at 650-900 ℃ in an argon atmosphere to obtain a layered lithium manganate target product;
step 10, adding the target product obtained in the step 9 into a sucrose solution, uniformly stirring and drying; then thermally decomposing the mixture for 2 to 5 hours at 500 ℃ in the atmosphere of nitrogen or argon to obtain the lithium ion battery anode material LiMnO2@C。
2. The lithium ion battery positive electrode material LiMnO of claim 12A preparation method of @ C comprises the following steps:
step 1, adding manganese nitrate into deionized water, and stirring at room temperature to completely dissolve the manganese nitrate to obtain a solution A with the manganese nitrate concentration of 1.0 mol/L;
step 2, adding urea into deionized water, and stirring at room temperature to completely dissolve the urea to obtain a solution B with the urea concentration of 4.0 mol/L;
step 3, adding ammonium fluoride into deionized water, and stirring at room temperature to completely dissolve the ammonium fluoride to obtain a solution C with the ammonium fluoride concentration of 2.0 mol/L;
step 4, adding the solution A, B obtained in the steps 1, 2 and 3 and C together at the speed of 10ml/min, stirring to obtain a mixed solution, and continuously stirring to obtain a mixed suspension, wherein the solution A, B and the solution C are mixed in equal volume;
step 5, transferring the suspension obtained in the step 4 into a high-pressure reaction kettle, wherein the filling amount is 80%, and sealing the high-pressure kettle; performing hydrothermal reaction at 180 ℃ for 5-12 h to obtain MnCO3Crystal precipitation;
step 6, placing the white crystal precipitation product obtained in the step 5 into a forced air drying oven, and drying for 5-8 hours at the temperature of 80-120 ℃ to obtain MnCO3Powder;
step 7, the MnCO obtained in the step 6 is processed3Putting the powder into a muffle furnace, and carrying out thermal decomposition for 5-20 h at 450-650 ℃ in air to obtain Mn2O3Powder;
step 8, Li according to the mol ratio+/Mn3+= 1.05-1.25 LiOH or Li is weighed2CO3And Mn obtained in step 72O3Uniformly mixing the powder to obtain a powder mixture;
step 9, placing the powder mixture obtained in the step 8 in a ceramic boat, placing the ceramic boat in a tube furnace, and sintering the ceramic boat for 10-24 hours at 650-900 ℃ in an argon atmosphere to obtain a layered lithium manganate target product;
step 10, adding the target product obtained in the step 9 into a sucrose solution, uniformly stirring and drying; then thermally decomposing the mixture for 2 to 5 hours at 500 ℃ in the atmosphere of nitrogen or argon to obtain the final product of carbon-coated layered lithium manganate LiMnO2@ C composite material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910490654.XA CN110176595B (en) | 2019-06-06 | 2019-06-06 | Lithium ion battery anode material LiMnO2@ C and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910490654.XA CN110176595B (en) | 2019-06-06 | 2019-06-06 | Lithium ion battery anode material LiMnO2@ C and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110176595A CN110176595A (en) | 2019-08-27 |
| CN110176595B true CN110176595B (en) | 2022-06-03 |
Family
ID=67697331
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910490654.XA Active CN110176595B (en) | 2019-06-06 | 2019-06-06 | Lithium ion battery anode material LiMnO2@ C and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110176595B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113517432A (en) * | 2021-03-29 | 2021-10-19 | 浙江工业大学 | Manganese dioxide composite electrode material and preparation method and application thereof |
| CN113629226B (en) * | 2021-06-22 | 2024-03-22 | 北京化工大学 | Core-shell structured potassium manganate/carbon composite material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102800855A (en) * | 2012-08-15 | 2012-11-28 | 北京师范大学 | Preparation method of lithium ion battery positive electrode material layered LiMnO2 |
| CN107331853A (en) * | 2017-08-18 | 2017-11-07 | 郑州大学 | A kind of graphene composite multi-layer spherical manganic acid lithium electrode material with holes and its lithium ion battery of preparation |
| CN108630922A (en) * | 2018-04-27 | 2018-10-09 | 东北大学秦皇岛分校 | A kind of lithium manganese phosphate/carbon composite anode material, preparation method and lithium ion battery |
| WO2019010366A1 (en) * | 2017-07-07 | 2019-01-10 | Ppg Industries Ohio, Inc. | Electrode binder slurry composition for lithium ion electrical storage devices |
-
2019
- 2019-06-06 CN CN201910490654.XA patent/CN110176595B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102800855A (en) * | 2012-08-15 | 2012-11-28 | 北京师范大学 | Preparation method of lithium ion battery positive electrode material layered LiMnO2 |
| WO2019010366A1 (en) * | 2017-07-07 | 2019-01-10 | Ppg Industries Ohio, Inc. | Electrode binder slurry composition for lithium ion electrical storage devices |
| CN107331853A (en) * | 2017-08-18 | 2017-11-07 | 郑州大学 | A kind of graphene composite multi-layer spherical manganic acid lithium electrode material with holes and its lithium ion battery of preparation |
| CN108630922A (en) * | 2018-04-27 | 2018-10-09 | 东北大学秦皇岛分校 | A kind of lithium manganese phosphate/carbon composite anode material, preparation method and lithium ion battery |
Non-Patent Citations (2)
| Title |
|---|
| 类球形正交LiMnO2的制备、微结构和电化学性能;范广新 等;《无机化学学报》;20070610;第963-968页 * |
| 软化学法制备新型正极材料LiMnO2的研究进展;赵宏远;《电池工业》;20130825;第177-180页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110176595A (en) | 2019-08-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8303841B2 (en) | Method for preparing cathode active material of lithium battery | |
| CN101855754B (en) | Lithium manganate particle powder for nonaqueous electrolyte secondary battery, method for producing the same, and nonaqueous electrolyte secondary battery | |
| CN105185954A (en) | LiAlO2 coated LiNi1-xCoxO2 lithium-ion battery positive electrode material and preparation method thereof | |
| CN101752562B (en) | Compound doped modified lithium ion battery anode material and preparation method thereof | |
| CN109119624B (en) | Preparation method of lithium titanium phosphate coated lithium-rich manganese-based positive electrode material | |
| CN102437323A (en) | Anode material of lithium ion battery and preparation method thereof | |
| CN112993241B (en) | Preparation method of single-crystal lithium manganate material | |
| CN108448109A (en) | A kind of stratiform lithium-rich manganese-based anode material and preparation method thereof | |
| CN106910887A (en) | A kind of lithium-rich manganese-based anode material, its preparation method and the lithium ion battery comprising the positive electrode | |
| CN105271424B (en) | Preparation method of needle-like spinel lithium manganese oxide positive electrode material | |
| CN108682844A (en) | A kind of preparation method of lithium ion battery mangaic acid lithium anode material | |
| CN110904495A (en) | Preparation method of monocrystal polyhedral lithium manganate positive electrode material | |
| CN102956883A (en) | AnodePositive electrode material of lithium ion battery with porous laminated structure and preparation method thereof | |
| CN113929070B (en) | Preparation method of high-rate lithium iron phosphate cathode material | |
| CN102299316A (en) | Layered oxide lithium ion battery anode and preparation method thereof | |
| CN111224089A (en) | Ternary cathode material NCM811 for lithium ion battery prepared by molten salt method and preparation method thereof | |
| CN109786693A (en) | A kind of preparation method of carbon nanotube composite lithium iron phosphate cathode material | |
| CN111952562A (en) | LiZr2(PO4)3Method for preparing coated lithium-rich material | |
| CN110176595B (en) | Lithium ion battery anode material LiMnO2@ C and preparation method thereof | |
| CN110190277B (en) | Lithium ion battery anode material LiMnO2@ C and preparation method thereof | |
| CN105185981A (en) | Preparation method of LiNi<x>Mn<2-x>O<4> cathode material | |
| CN108511697A (en) | Cupro-nickel acid lithium anode material and preparation method thereof and lithium ion battery | |
| Jiang et al. | One-pot hydrothermal synthesis of LiMn 2 O 4 cathode material with excellent high-rate and cycling properties | |
| CN104577101A (en) | Preparation method for surface-modified lithium-manganese-rich cathode material of lithium ion battery | |
| CN115312754A (en) | Lamellar cobalt-free lithium-rich manganese-based positive electrode material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |