CN108847481B - Preparation and application of carbon-coated porous manganous oxide cubic cathode material for high-performance lithium ion battery - Google Patents

Preparation and application of carbon-coated porous manganous oxide cubic cathode material for high-performance lithium ion battery Download PDF

Info

Publication number
CN108847481B
CN108847481B CN201810697542.7A CN201810697542A CN108847481B CN 108847481 B CN108847481 B CN 108847481B CN 201810697542 A CN201810697542 A CN 201810697542A CN 108847481 B CN108847481 B CN 108847481B
Authority
CN
China
Prior art keywords
porous
carbon
solution
cubic
coated porous
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
Application number
CN201810697542.7A
Other languages
Chinese (zh)
Other versions
CN108847481A (en
Inventor
李伟善
李淑敏
李晓萍
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China Normal University
Original Assignee
South China Normal University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by South China Normal University filed Critical South China Normal University
Priority to CN201810697542.7A priority Critical patent/CN108847481B/en
Publication of CN108847481A publication Critical patent/CN108847481A/en
Application granted granted Critical
Publication of CN108847481B publication Critical patent/CN108847481B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • 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
    • 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
    • H01M4/48—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
    • H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
    • 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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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

Abstract

The invention belongs to the field of lithium ion batteries, and discloses a carbon-coated porous manganous oxide cubic cathode material (hereinafter referred to as Mn) for a high-performance lithium ion battery2O3@ C) and a preparation method and application thereof. The invention uses phenolic resin as a carbon source and silicon dioxide as a sacrificial template, and prepares a precursor in microemulsion, so that manganese-containing precursor particles are uniform, a nano-scale cubic precursor is obtained, the precursor has a porous structure by subsequent calcination, the crystallinity of the material is improved to a certain extent, the cubic porous material coated with carbon is beneficial to reduction of internal resistance and transmission of electrons, and gaps left after silicon dioxide etching can relieve the stress of volume expansion, thereby greatly improving the electrochemical performance. Resulting carbon-coated porous Mn2O3The cubic cathode material has high specific capacity, high charge-discharge capacity, high first coulombic efficiency and obviously improved capacity attenuation condition.

Description

Preparation and application of carbon-coated porous manganous oxide cubic cathode material for high-performance lithium ion battery
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a carbon-coated porous manganous oxide cubic cathode material (hereinafter referred to as Mn) for a high-performance lithium ion battery2O3@ C) and a preparation method and application thereof.
Background
Among commercial secondary batteries, lithium ion batteries have the highest specific energy and the best cycle performance, and have wide development prospects as energy storage batteries due to the variety of electrode material choices. However, with the progress of science and technology and the continuous development of the market, the demand for the energy density of the battery is increasingly urgent, so that the improvement of the energy density of the lithium battery becomes a new subject which puzzles researchers.
The dramatic increase in fossil fuel consumption threatens the sustainability of energy sources and prompts researchers to develop renewable energy sources to ensure the development of society. Lithium Ion Batteries (LIBs)) Is an excellent power source for hybrid vehicles and portable electronic devices because of its high energy density, low self-discharge, no memory effect, and long cycle life. The theoretical capacity of the commercial graphite as the lithium ion battery cathode material is only 372mA h g-1The interlayer spacing was 0.34nm, which largely limited the large-scale application of commercial graphite. The theoretical specific capacity of the manganese oxide is high (MnO,756mA h g)-1；Mn3O4,937mA h g-1；Mn2O3,1018mA h g-1； and MnO2,1233mA h g-1) The lithium ion battery has the advantages of small voltage lag, environmental friendliness, low price and rich resource reserves, and is a good material for lithium ion batteries. However, the electron conductivity of manganese oxide is poor, and the process of intercalating and deintercalating lithium ions is accompanied by volume change, resulting in poor cyclability and rate capability thereof. Therefore, it is critical to improve the mechanical strength and conductivity of the manganese oxide electrode.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a preparation method of a carbon-coated porous manganous oxide cubic cathode material, the method obtains a cubic manganese carbonate precursor by an emulsion method, the cubic manganese carbonate precursor becomes a porous structure after annealing, silicon dioxide is used as a sacrificial template, phenolic resin is used as a carbon source, the phenolic resin is carbonized by firing in a nitrogen atmosphere, and finally the carbon-coated porous cubic manganous oxide is obtained by etching, a carbon shell, a gap and the porous structure form a triple buffer structure, the volume expansion of the cathode material in the charging and discharging process is well relieved, meanwhile, the carbon shell improves the conductivity of the cathode material, and the cycle stability and the rate capability of the electrode material are greatly improved.
The invention also aims to provide the carbon-coated porous manganous oxide cubic cathode material prepared by the method, which can solve the problems of poor conductivity and volume expansion of the cathode material of the lithium battery.
The invention further aims to provide application of the carbon-coated porous manganous oxide cubic cathode material in preparation of a lithium ion battery.
The purpose of the invention is realized by the following scheme:
a preparation method of a high-performance carbon-coated porous manganese sesquioxide cubic cathode material comprises the following steps:
(1) stirring and mixing a surfactant, a cosurfactant, a solvent and an ammonium bicarbonate aqueous solution to form clear and transparent microemulsion;
(2) adding a water solution of manganese sulfate tetrahydrate into the mixed solution in the step (1), standing and filtering to obtain a precursor precipitate manganese carbonate;
(3) putting the precursor precipitate manganese carbonate obtained in the step (2) into a muffle furnace for high-temperature calcination to obtain porous Mn2O3A cube;
(4) subjecting the porous Mn obtained in step (3)2O3Uniformly dispersing cubes into water, mixing the cubes with an aqueous ammonia solution dissolved with CTAB, adding Tetraethoxysilane (TEOS) under the stirring condition, adding resorcinol and formaldehyde solution, and continuously stirring for 24 hours for aging;
(5) transferring the aged mixed solution in the step (4) to the inner liner of a reaction kettle to perform hydrothermal reaction;
(6) centrifugally drying the solution reacted in the step (5), placing the solution in a tube furnace, and calcining the solution at high temperature in an argon atmosphere to obtain porous Mn coated with carbon and silicon dioxide2O3；
(7) Coating the carbon and silica-coated porous Mn obtained in step (6)2O3Placing the cube in a sodium hydroxide solution for reaction, centrifuging the obtained reaction solution after the reaction is finished, removing supernatant, cleaning the obtained solid, and drying to obtain the carbon-coated porous Mn2O3A cube.
The surfactant in the step (1) can be at least one of cationic surfactants such as cetyl trimethyl quaternary ammonium bromide, octadecyl dimethyl benzyl quaternary ammonium chloride and the like; preferably cetyltrimethylammonium bromide (CTAB);
the cosurfactant in the step (1) can be at least one of n-butanol, isopropanol, isobutanol, n-pentanol, isoamyl alcohol and the like, and is preferably n-butanol;
the solvent in the step (1) is at least one of hydrocarbons such as cyclohexane, normal hexane, isooctane and the like, and is preferably normal hexane;
the concentration of the ammonium bicarbonate aqueous solution in the step (1) is 0.5-1.0 mol/L; preferably 0.8 mol/L;
the dosage of the cosurfactant, the ammonium bicarbonate aqueous solution and the solvent in the step (1) meets the requirement that the volume ratio of the cosurfactant, the ammonium bicarbonate aqueous solution and the solvent is 1-1.5 (1-1.5) to (19-21), and preferably 1:1: 20; the dosage of the surfactant in the step (1) is such that 3-5 g of surfactant is correspondingly added to every 100ml of solvent;
the concentration of the aqueous solution of manganese sulfate tetrahydrate in the step (2) meets the condition that the ratio of the concentration of the aqueous solution of ammonium bicarbonate in the step (1) to the concentration of the aqueous solution of manganese sulfate tetrahydrate is (2-4): (1-2), wherein the using amount of the aqueous solution of manganese sulfate tetrahydrate meets the condition that the volume ratio of the aqueous solution of manganese sulfate tetrahydrate to the volume of the ammonium bicarbonate aqueous solution added in the step (1) is 1: 1;
the standing in the step (2) is standing for 20-30 min;
the high-temperature calcination in the step (3) is to heat the mixture to 550-650 ℃ in air at a heating rate of 2-5 ℃/min, and then keep the mixture for 3-4 hours.
Porous Mn described in step (4)2O3Cubic uniform dispersion in water means porous Mn per 1g2O3The cubes are uniformly dispersed in 20-30 mL of water.
The concentration of CTAB in the aqueous solution of ammonia water dissolved with CTAB in the step (4) is 0.01-0.05 g/mL, wherein the concentration of the aqueous solution of ammonia water is 28%; the formaldehyde solution in the step (4) is a formaldehyde solution with the mass fraction of 37%; porous Mn described in step (4)2O3Cubic, CTAB, Tetraethylorthosilicate (TEOS), resorcinol and formaldehyde solutions are used in amounts that satisfy the porous Mn2O3Cube, CTAB, tetraethyl orthosilicate (TEOS), resorcinol and formaldehyde in a mass ratio of 8:8: (11-15): (0.5-6): (1-8);
the aging in the step (4) refers to the aging of the phenolic resin obtained by polymerization reaction of resorcinol and formaldehyde;
the hydrothermal reaction in the step (5) is a constant temperature reaction at 100-120 ℃ for 18-24 hours;
the high-temperature calcination in the step (6) is to heat up to 550-650 ℃ at a heating rate of 2-5 ℃/min, and then keep for 3-5 h;
the concentration of the sodium hydroxide solution in the step (7) is 3-5 mol/L aqueous solution;
the carbon-and-silica-coated porous Mn described in step (7)2O3The amount of cubic and sodium hydroxide solution used is such that the carbon and silica coated porous Mn is satisfied2O3The mass ratio of the cube to the sodium hydroxide is 1: 10-20;
the reaction in the step (7) is to continuously stir at 60-80 ℃ for 4-6 h;
the cleaning in the step (7) is that water is firstly used for washing and then ethanol is used for washing; the drying refers to drying in an oven at 60-80 ℃ for 10-12 h;
the stirring speed is preferably 400-600 rpm, so that the raw materials are fully contacted with each other;
the unspecified temperatures in the invention refer to room temperature, and the room temperature refers to 23-25 ℃.
The high-performance carbon-coated porous manganous oxide cubic cathode material prepared by the method.
The high-performance carbon-coated porous manganous oxide cubic cathode material is applied to the preparation of lithium ion batteries.
The mechanism of the invention is as follows:
the invention uses phenolic resin as a carbon source and silicon dioxide as a sacrificial template, and prepares a precursor in microemulsion, so that manganese-containing precursor particles are uniform, a nano-scale cubic precursor is obtained, the precursor has a porous structure by subsequent calcination, the crystallinity of the material is improved to a certain extent, the carbon-coated cubic porous material is beneficial to reduction of internal resistance and transmission of electrons, and the silicon dioxide is etchedThe void left later can relieve the stress of volume expansion, and the electrochemical performance is greatly improved. Resulting carbon-coated porous Mn2O3The cubic cathode material has high specific capacity, high charge-discharge capacity, high first coulombic efficiency and obviously improved capacity attenuation condition.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention synthesizes the carbon-coated porous cubic Mn with the grain diameter of about 500nm2O3The structure has a firm cubic frame, and the structural stability of the material is improved. In addition, the internal porous structure of the lithium ion battery facilitates the transmission of lithium ions, provides space for the extraction of the lithium ions, buffers the separation of active materials from a current collector caused by volume expansion in the charging and discharging process, avoids the process of the rapid capacity attenuation of electrode materials, and improves the cycle performance of the electrode materials.
(2) The material synthesized by the invention has the advantages that the carbon has conductivity, so that the coated carbon layer can not only maintain the stability of the structure, but also improve the conductivity of the material, reduce the surface resistance of the material, improve the rate capability of the electrode material and make up for single Mn2O3The shortage of the electrodes. Therefore, the material of the invention has higher specific capacity and excellent cycle performance when being used as the negative electrode material of the lithium ion battery.
Drawings
FIG. 1 is an SEM image of a precursor precipitated manganese carbonate prepared in example 1;
FIG. 2 is porous Mn prepared in example 12O3SEM image of the cube;
FIG. 3 is a carbon-coated porous Mn prepared in example 12O3SEM image of the cube;
FIG. 4 is porous Mn prepared in example 12O3A TEM image of a cube;
FIG. 5 is carbon-coated porous Mn prepared in example 12O3A TEM image of a cube;
FIG. 6 shows porous Mn prepared in example 12O3Cubic and carbon coatingPorous Mn2O3XRD pattern of the cube;
FIG. 7 shows porous Mn prepared in example 12O3Cubic and carbon coated porous Mn2O3The cube is a relation graph of the discharge specific capacity and the cycle number of the lithium ion battery prepared by the negative electrode material.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
The reagents used in the examples are commercially available without specific reference. The temperatures not indicated in the examples are room temperature;
example 1
A preparation method of a carbon-coated porous manganous oxide cubic cathode material for a high-performance lithium ion battery comprises the following steps:
(1) under the stirring condition that the room temperature rotation speed is 400rpm, 4g of Cetyl Trimethyl Ammonium Bromide (CTAB), 5ml of n-butyl alcohol, 100ml of cyclohexane and 5ml of ammonium bicarbonate (0.8M) aqueous solution are uniformly mixed to form clear and transparent microemulsion;
(2) under the stirring condition that the room temperature and the rotating speed are 700rpm, 5ml of 0.4M manganese sulfate tetrahydrate is added into the solution in the step (1), and standing is carried out for 20min after the dropwise addition is finished, so as to obtain precursor precipitate manganese carbonate;
(3) putting the precursor manganese carbonate obtained in the step (2) into a muffle furnace, heating to 550 ℃ in air at a heating rate of 2 ℃/min, keeping the temperature for 3h, and naturally cooling to room temperature to obtain porous Mn2O3A cube;
(4) 0.2g of porous Mn obtained in step (3)2O3The cubes are uniformly dispersed in 5mL of deionized water, then mixed with 10mL of ammonia water (28 wt%) aqueous solution in which 0.2g of CTAB is dissolved, 0.39mL of Tetraethoxysilane (TEOS) is added under the stirring condition of the rotation speed of 400rpm, 0.025g of resorcinol and 0.035mL of formaldehyde solution (37 wt%) are added after continuous stirring for 15min, and then the stirring is continued for 24 h;
(5) transferring the solution in the step (4) into a liner of a reaction kettle, putting the liner into a stainless steel reaction kettle, and keeping the temperature constant for 24 hours at 100 ℃;
(6) centrifugally drying the solution subjected to hydrothermal treatment in the step (5), putting the solution into a tube furnace, heating to 550 ℃ at a heating rate of 2 ℃ in an argon atmosphere, keeping the temperature for 3 hours, and cooling to room temperature to obtain the porous Mn coated with carbon and silicon dioxide2O3；
(7) 0.3g of the carbon-coated porous Mn obtained in step (6)2O3Placing the cube in 25mL of 4M sodium hydroxide solution, and continuously stirring for 4h at the temperature of 60 ℃ and the rotating speed of 500 rpm;
(8) centrifuging the solution in the step (7), removing supernatant, washing with water and ethanol for 3 times, and drying in a 60 ℃ oven for 12h to obtain the carbon-coated porous Mn2O3A cube.
FIGS. 1, 2 and 3 show precipitated manganese carbonate as a precursor prepared in step (2) and porous Mn as a porous Mn as prepared in step (3) in example 1, respectively2O3Cube and carbon-coated porous Mn prepared in step (8)2O3SEM image of the cube; mn can be seen from FIGS. 1 to 32O3Is cubic, has uniform particles with the size of 300-500 nm, and contains Mn after calcination2O3Is porous, and a smooth film appears on the surface after carbon coating.
FIGS. 4 and 5 are views of porous Mn prepared in step (3) of example 1, respectively2O3Cube and carbon-coated porous Mn prepared in step (8)2O3In the TEM image of the cube, from FIG. 4 and FIG. 5, manganese sesquioxide is in a porous structure, and a carbon layer coated on the surface can be clearly seen, the thickness is about 10-15 nm, and the carbon shell and Mn are mixed2O3A void is left before.
FIG. 6 shows porous Mn prepared in example 12O3Cubic and carbon coated porous Mn2O3XRD pattern of the cube; it can be seen from FIG. 6 that the XRD pattern shows that Mn is produced2O3And Mn2O3The xrd peak at @ C was consistent with the standard card and no miscellaneous peaks, and no carbon peak was found, indicating that the carbon was amorphous.
Example 2
A preparation method of a carbon-coated porous manganous oxide cubic cathode material for a high-performance lithium ion battery comprises the following steps:
(1) under the stirring condition that the room temperature rotation speed is 500rpm, 8g of Cetyl Trimethyl Ammonium Bromide (CTAB), 10ml of n-butyl alcohol, 200ml of cyclohexane and 10ml of ammonium bicarbonate (0.8M) aqueous solution are uniformly mixed to form clear and transparent microemulsion;
(2) adding 10ml of tetrahydrate manganese sulfate (0.4M) into the solution in the step (1) under the stirring condition that the room temperature and the rotating speed are 700rpm, and standing for 20min after the dropwise addition is finished to obtain precursor precipitate manganese carbonate;
(3) putting the precursor manganese carbonate obtained in the step (2) into a muffle furnace, heating to 600 ℃ in air at a heating rate of 2 ℃/min, keeping the temperature for 3h, and naturally cooling to room temperature to obtain porous Mn2O3A cube;
(4) 0.25g of porous Mn obtained in step (3)2O3The cubes are uniformly dispersed in 5mL of deionized water, then mixed with 12mL of ammonia water (28 wt%) aqueous solution dissolved with 0.25g of CTAB, 0.40mL of Tetraethoxysilane (TEOS) is added under the stirring condition of the rotating speed of 400rpm, 0.05g of resorcinol and 0.07mL of formaldehyde solution (37 wt%) are added after continuous stirring for 10min, and then the mixture is continuously stirred for 24 h;
(5) transferring the solution in the step (4) into a liner of a reaction kettle, putting the liner into a stainless steel reaction kettle, and keeping the temperature constant for 24 hours at the temperature of 110 ℃;
(6) centrifugally drying the solution subjected to hydrothermal treatment in the step (5), putting the solution into a tube furnace, heating to 550 ℃ at a heating rate of 2 ℃ in an argon atmosphere, keeping the temperature for 4 hours, and cooling to room temperature to obtain the porous Mn coated with carbon and silicon dioxide2O3；
(7) 0.3g of the carbon-coated porous Mn obtained in step (6)2O3Placing the cube in 25mL of 4M sodium hydroxide solution, and continuously stirring for 5h at 70 ℃ under the stirring condition of 500 rpm;
(8) centrifuging the solution in the step (7), removing supernatant, and washing with water and ethanol for 3 timesDrying in a 60 ℃ oven for 12h to obtain the carbon-coated porous Mn2O3A cube.
Example 3
A preparation method of a carbon-coated porous manganous oxide cubic cathode material for a high-performance lithium ion battery comprises the following steps:
(1) under the stirring condition that the room temperature rotation speed is 700rpm, 12g of Cetyl Trimethyl Ammonium Bromide (CTAB), 15ml of n-butyl alcohol, 300ml of cyclohexane and 15ml of ammonium bicarbonate (0.8M) aqueous solution are uniformly mixed to form clear and transparent microemulsion;
(2) under the stirring condition that the room temperature and the rotating speed are 400rpm, 15ml of tetrahydrate manganese sulfate (0.4M) is added into the solution in the step (1), and standing is carried out for 30min after the dropwise addition is finished, so as to obtain precursor precipitate manganese carbonate;
(3) putting the precursor manganese carbonate obtained in the step (2) into a muffle furnace, heating to 550 ℃ in air at a heating rate of 3 ℃/min, keeping the temperature for 3h, and naturally cooling to room temperature to obtain porous Mn2O3A cube;
(4) 0.2g of porous Mn obtained in step (3)2O3The cubes are uniformly dispersed in 5mL of deionized water, then mixed with 11mL of ammonia water (28 wt%) aqueous solution dissolved with 0.2g of CTAB, 0.39mL of Tetraethoxysilane (TEOS) is added under the stirring condition of the rotating speed of 400rpm, 0.033g of resorcinol and 0.047mL of formaldehyde solution (37 wt%) are added after continuous stirring for 10min, and then the mixture is continuously stirred for 24 h;
(5) transferring the solution in the step (4) into a liner of a reaction kettle, putting the liner into a stainless steel reaction kettle, and keeping the temperature constant for 24 hours at 120 ℃;
(6) centrifugally drying the solution subjected to hydrothermal treatment in the step (5), putting the solution into a tube furnace, heating to 600 ℃ at a heating rate of 2 ℃ in an argon atmosphere, keeping the temperature for 5 hours, and cooling to room temperature to obtain the porous Mn coated with carbon and silicon dioxide2O3；
(7) 0.3g of the carbon-coated porous Mn obtained in step (6)2O3Placing the cube in 20mL of 5M sodium hydroxide solution, and continuously stirring for 6h at 80 ℃ under the stirring condition with the rotating speed of 500 rpm;
(8) centrifuging the solution in the step (7), removing supernatant, washing with water and ethanol for 3 times, and drying in a 60 ℃ oven for 12h to obtain the carbon-coated porous Mn2O3A cube.
Example 4
A preparation method of a carbon-coated porous manganous oxide cubic cathode material for a high-performance lithium ion battery comprises the following steps:
(1) under the stirring condition that the room temperature rotation speed is 600rpm, 4g of Cetyl Trimethyl Ammonium Bromide (CTAB), 5ml of n-butyl alcohol, 100ml of cyclohexane and 5ml of ammonium bicarbonate (0.8M) aqueous solution are uniformly mixed to form clear and transparent microemulsion;
(2) under the stirring condition that the room temperature and the rotating speed are 400rpm, 5ml of tetrahydrate manganese sulfate (0.4M) is added into the solution in the step (1), and standing is carried out for 30min after the dropwise addition is finished, so as to obtain precursor precipitate manganese carbonate;
(3) putting the precursor manganese carbonate obtained in the step (2) into a muffle furnace, heating to 550 ℃ in air at a heating rate of 2 ℃/min, keeping the temperature for 3h, and naturally cooling to room temperature to obtain porous Mn2O3A cube;
(4) 0.22g of porous Mn obtained in step (3)2O3The cubes are uniformly dispersed in 5mL of deionized water, then mixed with 13mL of ammonia water (28 wt%) aqueous solution dissolved with 0.22g of CTAB, 0.39mL of Tetraethoxysilane (TEOS) is added under the stirring condition of the rotation speed of 400rpm, 0.1g of resorcinol and 0.14mL of formaldehyde solution (37 wt%) are added after continuous stirring for 10min, and then the mixture is continuously stirred for 24 h;
(5) transferring the solution in the step (4) into a liner of a reaction kettle, putting the liner into a stainless steel reaction kettle, and keeping the temperature constant for 24 hours at 100 ℃;
(6) centrifugally drying the solution subjected to hydrothermal treatment in the step (5), putting the solution into a tube furnace, heating to 650 ℃ at a heating rate of 2 ℃ in an argon atmosphere, keeping the temperature for 3 hours, and cooling to room temperature to obtain the porous Mn coated with carbon and silicon dioxide2O3；
(7) 0.31g of the carbon-coated porous Mn obtained in step (6)2O3The cubes were placed in 25mL of 4M sodium hydroxide solution,continuously stirring for 4h at the temperature of 80 ℃ and the rotating speed of 500 rpm;
(8) centrifuging the solution in the step (7), removing supernatant, washing with water and ethanol for 3 times, and drying in a 60 ℃ oven for 12h to obtain the carbon-coated porous Mn2O3A cube.
Example 5
A preparation method of a carbon-coated porous manganous oxide cubic cathode material for a high-performance lithium ion battery comprises the following steps:
(1) under the stirring condition that the room temperature rotation speed is 500rpm, 4g of Cetyl Trimethyl Ammonium Bromide (CTAB), 5ml of n-butyl alcohol, 100ml of cyclohexane and 5ml of ammonium bicarbonate (0.8M) aqueous solution are uniformly mixed to form clear and transparent microemulsion;
(2) under the stirring condition that the room temperature and the rotating speed are 400rpm, 5ml of tetrahydrate manganese sulfate (0.4M) is added into the solution in the step (1), and standing is carried out for 30min after the dropwise addition is finished, so as to obtain precursor precipitate manganese carbonate;
(3) putting the precursor manganese carbonate obtained in the step (2) into a muffle furnace, heating to 650 ℃ in air at a heating rate of 2 ℃/min, keeping the temperature for 4h, and naturally cooling to room temperature to obtain porous Mn2O3A cube;
(4) 0.22g of porous Mn obtained in step (3)2O3The cubes are uniformly dispersed in 5mL of deionized water, then mixed with 12mL of ammonia water (28 wt%) aqueous solution dissolved with 0.22g of CTAB, 0.35mL of Tetraethoxysilane (TEOS) is added under the stirring condition of the rotation speed of 400rpm, 0.15g of resorcinol and 0.21mL of formaldehyde solution (37 wt%) are added after continuous stirring for 10min, and then the mixture is continuously stirred for 24 h;
(5) transferring the solution in the step (4) into a liner of a reaction kettle, putting the liner into a stainless steel reaction kettle, and keeping the temperature constant for 24 hours at the temperature of 110 ℃;
(6) centrifugally drying the solution subjected to hydrothermal treatment in the step (5), putting the solution into a tube furnace, heating to 550 ℃ at a heating rate of 2 ℃ in an argon atmosphere, keeping the temperature for 3 hours, and cooling to room temperature to obtain the porous Mn coated with carbon and silicon dioxide2O3；
(7) Packing 0.28g of the carbon obtained in the step (6)Coated porous Mn2O3Placing the cube in 25mL of 4M sodium hydroxide solution, and continuously stirring for 5h at 80 ℃ under the stirring condition of 500 rpm;
(8) centrifuging the solution in the step (7), removing supernatant, washing with water and ethanol for 3 times, and drying in a 60 ℃ oven for 12h to obtain the carbon-coated porous Mn2O3A cube.
Example 6
A preparation method of a carbon-coated porous manganous oxide cubic cathode material for a high-performance lithium ion battery comprises the following steps:
(1) under the stirring condition that the room temperature rotation speed is 600rpm, 4g of Cetyl Trimethyl Ammonium Bromide (CTAB), 5ml of n-butyl alcohol, 100ml of cyclohexane and 5ml of ammonium bicarbonate (0.8M) aqueous solution are uniformly mixed to form clear and transparent microemulsion;
(2) under the stirring condition that the room temperature and the rotating speed are 500rpm, 5ml of tetrahydrate manganese sulfate (0.4M) is added into the solution in the step (1), and standing is carried out for 30min after the dropwise addition is finished, so as to obtain precursor precipitate manganese carbonate;
(3) putting the precursor manganese carbonate obtained in the step (2) into a muffle furnace, heating to 550 ℃ in air at a heating rate of 2 ℃/min, keeping the temperature for 3h, and naturally cooling to room temperature to obtain porous Mn2O3A cube;
(4) 0.23g of porous Mn obtained in step (3)2O3The cubes are uniformly dispersed in 5mL of deionized water, then mixed with 10mL of ammonia water (28 wt%) aqueous solution dissolved with 0.23g of CTAB, 0.35mL of Tetraethoxysilane (TEOS) is added under the stirring condition of the rotation speed of 400rpm, 0.017g of resorcinol and 0.023mL of formaldehyde solution (37 wt%) are added after continuous stirring for 10min, and then the stirring is continued for 24 h;
(5) transferring the solution in the step (4) into a liner of a reaction kettle, putting the liner into a stainless steel reaction kettle, and keeping the temperature constant for 24 hours at 120 ℃;
(6) centrifugally drying the solution subjected to hydrothermal treatment in the step (5), putting the solution into a tube furnace, heating to 600 ℃ at the heating rate of 3 ℃ in the argon atmosphere, keeping the temperature for 3 hours, and cooling to room temperature to obtain the porous Mn coated with carbon and silicon dioxide2O3；
(7) 0.31g of the carbon-coated porous Mn obtained in step (6)2O3Placing the cube in 25mL of 4M sodium hydroxide solution, and continuously stirring for 6h at 70 ℃ under the stirring condition with the rotating speed of 500 rpm;
(8) centrifuging the solution in the step (7), removing supernatant, washing with water and ethanol for 3 times, and drying in a 60 ℃ oven for 12h to obtain the carbon-coated porous Mn2O3A cube.
The precursor prepared in the above examples 2 to 6 precipitated manganese carbonate and porous Mn2O3Cubic and carbon coated porous Mn2O3The cube can obtain the similar test result to that of embodiment 1 by comparing with the cube in the same test process as that of embodiment 1, which is not repeated herein.
Test example
(1) Assembling a half cell: carbon-coated porous Mn prepared in example 12O3Cubic negative electrode material and porous Mn prepared in step (3) of example 12O3And the negative electrode material is respectively pulped and coated with acetylene black and PVDF according to the mass ratio of 7:1.5:1.5, and a 2025 button half-cell is assembled by taking a metal lithium sheet as a counter electrode.
(2) And (3) charge and discharge test: carbon-coated porous Mn prepared in example 12O3Cubic negative electrode material and porous Mn prepared in step (3) of example 12O3The negative electrode material is used for charging and discharging the manufactured lithium ion battery under the constant current of 100 mA/g.
FIG. 7 is carbon coated porous Mn prepared in example 12O3Cubic negative electrode material and porous Mn prepared in step (3) of example 12O3The lithium ion battery made of the negative electrode material has a relationship diagram of specific discharge capacity, coulombic efficiency and cycle number. It can be seen from fig. 7 that the first discharge capacity of the negative electrode material prepared in example 1 is 1266.0mAh/g, the first-turn coulombic efficiency is 73.3%, and the capacity fading condition is significantly improved. Porous Mn2O3The first discharge capacity of the negative electrode material is 721.0mAh/g, and the first coulomb efficiency is 57.7%. Show thatCarbon coated porous Mn2O3The cubic cathode material has more excellent electrochemical performance.
In addition, the carbon-coated porous Mn obtained in examples 2 to 6 was used2O3Pulping and coating a cubic cathode material, acetylene black and PVDF according to a mass ratio of 8:1:1, and assembling a half battery by taking a metal lithium sheet as a counter electrode; then, charging and discharging tests are carried out under the constant current of 100mA/g, and the following results are obtained through detection:
the first discharge capacity of the negative electrode material prepared in example 2 is 1492.0mAh/g, and the first coulomb efficiency is 71.2%.
The first discharge capacity of the negative electrode material prepared in example 3 is 1334.0mAh/g, and the first coulomb efficiency is 72%.
The first discharge capacity of the negative electrode material prepared in example 4 is 1012.0mAh/g, and the first coulomb efficiency is 73%.
The first discharge capacity of the negative electrode material prepared in example 5 is 1253.6mAh/g, and the first coulomb efficiency is 72.5%.
The first discharge capacity of the negative electrode material prepared in example 6 was 917.7mAh/g, and the first coulomb efficiency was 75%.
The data show that the carbon-coated porous manganese sesquioxide cube prepared in the embodiments 1-6 of the invention has higher specific capacity and excellent cycle performance as the negative electrode material of the lithium ion battery.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A preparation method of a high-performance carbon-coated porous manganese sesquioxide cubic cathode material is characterized by comprising the following steps:
(1) stirring and mixing a surfactant, a cosurfactant, a solvent and an ammonium bicarbonate aqueous solution to form clear and transparent microemulsion;
(2) adding a water solution of manganese sulfate tetrahydrate into the mixed solution in the step (1), standing and filtering to obtain a precursor precipitate manganese carbonate;
(3) putting the precursor precipitate manganese carbonate obtained in the step (2) into a muffle furnace for high-temperature calcination to obtain porous Mn2O3A cube;
(4) subjecting the porous Mn obtained in step (3)2O3Uniformly dispersing cubes into water, mixing the cubes with an aqueous ammonia solution dissolved with CTAB, adding ethyl orthosilicate under the stirring condition, adding resorcinol and formaldehyde solution, and continuously stirring for 24 hours for aging;
(5) transferring the aged mixed solution in the step (4) to the inner liner of a reaction kettle to perform hydrothermal reaction;
(6) centrifugally drying the solution reacted in the step (5), placing the solution in a tube furnace, and calcining the solution at high temperature in an argon atmosphere to obtain porous Mn coated with carbon and silicon dioxide2O3；
(7) Coating the carbon and silica-coated porous Mn obtained in step (6)2O3Placing the cube in a sodium hydroxide solution for reaction, centrifuging the obtained reaction solution after the reaction is finished, removing supernatant, cleaning the obtained solid, and drying to obtain the carbon-coated porous Mn2O3A cube;
the concentration of the ammonium bicarbonate aqueous solution in the step (1) is 0.5-1.0 mol/L;
the concentration of the aqueous solution of manganese sulfate tetrahydrate in the step (2) meets the condition that the ratio of the concentration of the aqueous solution of ammonium bicarbonate in the step (1) to the concentration of the aqueous solution of manganese sulfate tetrahydrate is (2-4): (1-2), wherein the using amount of the aqueous solution of manganese sulfate tetrahydrate meets the condition that the volume ratio of the aqueous solution of manganese sulfate tetrahydrate to the volume of the aqueous solution of ammonium bicarbonate added in the step (1) is 1: 1.
2. The preparation method of the high-performance carbon-coated porous manganous oxide cubic negative electrode material according to claim 1, characterized by comprising the following steps:
the surfactant in the step (1) is at least one of cetyl trimethyl ammonium bromide, cetyl trimethyl quaternary ammonium bromide and octadecyl dimethyl benzyl quaternary ammonium chloride;
the cosurfactant in the step (1) is at least one of n-butyl alcohol, isopropanol, isobutanol, n-amyl alcohol and isoamyl alcohol;
the solvent in the step (1) is at least one of cyclohexane, normal hexane and isooctane;
the dosage of the surfactant, the cosurfactant, the solvent and the ammonium bicarbonate aqueous solution in the step (1) meets the requirement of the cosurfactant: aqueous ammonium bicarbonate solution: the volume ratio of the solvent is (1-1.5): 19-21.
3. The preparation method of the high-performance carbon-coated porous manganous oxide cubic negative electrode material according to claim 1, characterized by comprising the following steps:
the standing in the step (2) refers to standing for 20-30 min.
4. The preparation method of the high-performance carbon-coated porous manganous oxide cubic negative electrode material according to claim 1, characterized by comprising the following steps:
the high-temperature calcination in the step (3) is to heat the mixture to 550-650 ℃ in air at a heating rate of 2-5 ℃/min, and then keep the mixture for 3 hours.
5. The preparation method of the high-performance carbon-coated porous manganous oxide cubic negative electrode material according to claim 1, characterized by comprising the following steps:
porous Mn described in step (4)2O3Cubic uniform dispersion in water means porous Mn per 1g2O3The cubes are uniformly dispersed in 20-30 mL of water;
the concentration of CTAB in the aqueous solution of ammonia water dissolved with CTAB in the step (4) is 0.01-0.05 g/mL, wherein the concentration of the aqueous solution of ammonia water is 28%; the formaldehyde solution in the step (4) is a formaldehyde solution with the mass fraction of 37%;
porous Mn described in step (4)2O3The mass ratio of the cubes, CTAB, ethyl orthosilicate, resorcinol and formaldehyde is 8:8 (11E)15):(0.5～6):(1～8)。
6. The preparation method of the high-performance carbon-coated porous manganous oxide cubic negative electrode material according to claim 1, characterized by comprising the following steps:
the hydrothermal reaction in the step (5) is a constant temperature reaction at 100-120 ℃ for 18-24 hours.
7. The preparation method of the high-performance carbon-coated porous manganous oxide cubic negative electrode material according to claim 1, characterized by comprising the following steps:
the high-temperature calcination in the step (6) is to heat the mixture to 550-650 ℃ at a heating rate of 2-5 ℃/min, and then keep the mixture for 3-5 hours.
8. The preparation method of the high-performance carbon-coated porous manganous oxide cubic negative electrode material according to claim 1, characterized by comprising the following steps:
the concentration of the sodium hydroxide solution in the step (7) is 3-5 mol/L aqueous solution;
the carbon-and-silica-coated porous Mn described in step (7)2O3The amount of cubic and sodium hydroxide solution used is such that the carbon and silica coated porous Mn is satisfied2O3The mass ratio of the cube to the sodium hydroxide is 1: 10-20;
the reaction in the step (7) is to continuously stir at 60-80 ℃ for 4-6 h;
the cleaning in the step (7) is that water is firstly used for washing and then ethanol is used for washing; the drying is drying in an oven at 60-80 ℃ for 10-12 h.
9. A high-performance carbon-coated porous manganese sesquioxide cubic negative electrode material prepared by the method of any one of claims 1 to 8.
10. The use of the high performance carbon-coated porous manganese sesquioxide cubic negative electrode material of claim 9 in the preparation of a lithium ion battery.
CN201810697542.7A 2018-06-29 2018-06-29 Preparation and application of carbon-coated porous manganous oxide cubic cathode material for high-performance lithium ion battery Active CN108847481B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810697542.7A CN108847481B (en) 2018-06-29 2018-06-29 Preparation and application of carbon-coated porous manganous oxide cubic cathode material for high-performance lithium ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810697542.7A CN108847481B (en) 2018-06-29 2018-06-29 Preparation and application of carbon-coated porous manganous oxide cubic cathode material for high-performance lithium ion battery

Publications (2)

Publication Number Publication Date
CN108847481A CN108847481A (en) 2018-11-20
CN108847481B true CN108847481B (en) 2020-11-24

Family

ID=64199937

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810697542.7A Active CN108847481B (en) 2018-06-29 2018-06-29 Preparation and application of carbon-coated porous manganous oxide cubic cathode material for high-performance lithium ion battery

Country Status (1)

Country Link
CN (1) CN108847481B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110112411B (en) * 2019-04-23 2021-02-26 上海应用技术大学 MnCO3Microspheres and method for preparing same
CN110391405A (en) * 2019-06-19 2019-10-29 华南师范大学 A kind of nano composite oxide, electrode and preparation method thereof
CN110783568B (en) * 2019-11-04 2021-05-04 陕西科技大学 Preparation method and application of hollow carbon-coated molybdenum selenide nanostructure

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103979610A (en) * 2014-05-30 2014-08-13 武汉理工大学 Porous manganic oxide cube as well as preparation method and application thereof
CN105967239A (en) * 2015-12-29 2016-09-28 重庆大学 Porous cubic Mn2O3 sub-micron powder and preparation method thereof
CN106058216A (en) * 2016-08-08 2016-10-26 武汉理工大学 Network-like hierarchical pore structured Mn2O3/C composite material and preparation method thereof
CN106853996A (en) * 2016-12-26 2017-06-16 武汉理工大学 A kind of method of the porous micro-nano structure material of the manganese sesquioxide managnic oxide for preparing morphology controllable
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
CN107507686A (en) * 2017-08-31 2017-12-22 扬州大学 A kind of preparation method of magnetic nano cages

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103979610A (en) * 2014-05-30 2014-08-13 武汉理工大学 Porous manganic oxide cube as well as preparation method and application thereof
CN105967239A (en) * 2015-12-29 2016-09-28 重庆大学 Porous cubic Mn2O3 sub-micron powder and preparation method thereof
CN106058216A (en) * 2016-08-08 2016-10-26 武汉理工大学 Network-like hierarchical pore structured Mn2O3/C composite material and preparation method thereof
CN106853996A (en) * 2016-12-26 2017-06-16 武汉理工大学 A kind of method of the porous micro-nano structure material of the manganese sesquioxide managnic oxide for preparing morphology controllable
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
CN107507686A (en) * 2017-08-31 2017-12-22 扬州大学 A kind of preparation method of magnetic nano cages

Also Published As

Publication number Publication date
CN108847481A (en) 2018-11-20

Similar Documents

Publication Publication Date Title
CN108269982B (en) Composite material, preparation method thereof and application thereof in lithium ion battery
CN105470455A (en) Modified lithium ion battery positive electrode material and preparation method therefor
CN103367719A (en) Yolk-shell structure tin dioxide-nitrogen-doped carbon material and preparation method thereof
CN108598394B (en) Carbon-coated titanium manganese phosphate sodium microspheres and preparation method and application thereof
CN108847481B (en) Preparation and application of carbon-coated porous manganous oxide cubic cathode material for high-performance lithium ion battery
CN109659511B (en) SiO (silicon dioxide)2Coated ternary positive electrode material and preparation method thereof
CN105226267B (en) Three dimensional carbon nanotubes modification spinel nickel lithium manganate material and its preparation method and application
CN114122397B (en) Carbon nanotube-connected double-carbon-layer-coated mesoporous silica composite material and preparation method and application thereof
CN108899541B (en) Magnesium lithium silicate coated modified lithium zinc titanate negative electrode material and preparation method thereof
CN110739446B (en) Silicon/carbon composite anode material and preparation method thereof
CN108400296B (en) Heterogeneous element doped ferroferric oxide/graphene negative electrode material
CN111082013B (en) Preparation method of carbon-coated nitrogen-magnesium doped porous silicon-based composite material and lithium ion battery
CN110854373B (en) Composite negative electrode material and preparation method thereof
CN109360961B (en) Hollow composite microsphere for lithium-sulfur battery positive electrode material and preparation method thereof
CN111613791B (en) Negative electrode active material, silicon-carbon negative electrode piece and high-energy-density quick-charging lithium ion battery
CN111646450B (en) Lithium iron phosphate and preparation method and application thereof
CN114220969A (en) Preparation method of lithium titanium silicate
CN113921783A (en) Long-cycle high-rate silicon-carbon negative electrode material and preparation method thereof
CN109192973B (en) Composite material with silicon-carbon core-shell structure and preparation method and application thereof
CN108767220B (en) Silicon-carbon composite material, preparation method thereof, battery cathode material and battery
CN112038617A (en) Micro-nano double-particle-size porous silicon material and preparation method and application thereof
CN111883762A (en) Graphene-nano TiO2Modified porous SnO2The negative electrode material of the sodium ion battery
CN111293297A (en) Carbon-coated MoSe2Black phosphorus composite material and preparation method thereof
CN113809296B (en) Porous silicon-carbon composite material and preparation thereof
CN113948691B (en) Titanium dioxide composite material and application thereof as energy storage material

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