CN108441652B - Preparation method of mesoporous germanium material - Google Patents
Preparation method of mesoporous germanium material Download PDFInfo
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- CN108441652B CN108441652B CN201810218031.2A CN201810218031A CN108441652B CN 108441652 B CN108441652 B CN 108441652B CN 201810218031 A CN201810218031 A CN 201810218031A CN 108441652 B CN108441652 B CN 108441652B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B41/00—Obtaining germanium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
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- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- 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 relates to a preparation method of a mesoporous germanium material, belonging to the technical field of preparation and application of germanium materials, and the preparation method is advanced in process, precise in data, high in preparation speed, black in product, high in product yield which is 95.2% of mesoporous pore structure, can be used as a lithium ion battery cathode material, and is an ideal method for preparing the mesoporous germanium material.
Description
Technical Field
The invention relates to a preparation method of a mesoporous germanium material, belonging to the technical field of preparation and application of germanium materials.
Background
The mesoporous germanium material has good structure adjustability and electrochemical activity, is incomparable with other materials, has higher specific surface area and larger pore volume, and is widely applied to the fields of adsorption, catalysis and electricity.
The synthesis method and the process of the mesoporous germanium material can directly influence the structural characteristics and the performance of the material, the selection of the synthesis method and the template agent is a decisive influence factor, and the reaction temperature, the reaction time and the roasting temperature also have important influence on the pore channel structure of the porous germanium material.
The template is a basic component for preparing the mesoporous germanium material, and the precursor and the template form a mesoporous structure through supermolecular force or chemical action. The structure and the type of the template will influence the pore structure of the mesoporous germanium material, so the selection and the use of the template are very important.
In the process of synthesizing the mesoporous germanium material by taking germanium tetrachloride as a precursor, a soft template or a hard template is mostly needed to be used as a structure directing agent, and due to the fact that different selected chemical substances, different synthesis parameters, different synthesis processes and roasting temperature from 600 ℃ to 1000 ℃, the obtained mesoporous germanium material has large difference in chemical and physical properties, the requirement of synthetic substances is difficult to meet, and the application of the material is greatly limited.
Disclosure of Invention
The invention aims to solve the problems, the invention adopts a novel metal reduction synthesis method, sodium-potassium alloy is used as a metal reducing agent, germanium tetrachloride is used as a precursor, the mixture is stirred at room temperature, the obtained black powder is roasted at high temperature by a tube furnace to prepare a mesoporous germanium material, the pore channel structure of the germanium material can be adjusted by controlling the roasting temperature, the chemical and physical properties are improved, and the material can be used as a lithium ion battery cathode material.
The technical scheme of the invention is as follows: a preparation method of a mesoporous germanium material comprises the following chemical substance materials: metal sodium, metal potassium, germanium tetrachloride, toluene, ethanol and deionized water;
the combined dosage is as follows: taking g and ml as the measurement unit,
the preparation method comprises the following steps:
(1) preparing a sodium-potassium alloy: weighing 0.4g +/-0.03 g of metal sodium, weighing 1.6g +/-0.04 g of metal potassium, and stirring for 1min to prepare a sodium-potassium alloy;
(2) synthesizing a mesoporous germanium material: under the protection of nitrogen, firstly stirring and reducing at room temperature, then filtering to obtain a solid, and finally roasting at high temperature under the condition of nitrogen to obtain a roasted product;
(3) washing and suction filtration:
(4) and (3) vacuum drying: drying to obtain the mesoporous germanium material;
(5) detection, analysis and characterization: the shape, the components and the chemical and physical properties of the prepared mesoporous germanium material are detected, analyzed and characterized.
The step (2) specifically comprises the following steps:
A. preparing a mixed reaction mixture: weighing 2.4 +/-0.04 g of germanium tetrachloride and 1.8 +/-0.03 g of sodium-potassium alloy, weighing 200mL +/-5 mL of toluene, and adding the toluene into a round-bottom flask to obtain a mixed reaction solution;
B. starting magnetic stirring, stirring for 4 hours, and reacting the mixed reaction solution, wherein the reaction equation is as follows:
GeCl4+4Na＝4NaCl+Ge
GeCl4+4K＝4KCl+Ge
C. after the reaction is finished, stopping stirring, and adding 100ml of ethanol; and (3) suction filtration: placing the reacted mixture into a Buchner funnel of a filter flask, carrying out suction filtration by using a microporous filter membrane, and pumping the residual product, namely the filter cake waste liquid on the filter membrane into the filter flask; roasting: the obtained filter cake is roasted in a tubular furnace at the temperature of 300-600 ℃.
The concrete steps of washing and suction filtration in the step (3) are as follows: placing the roasted product in a beaker, adding 100mL of deionized water, stirring and washing for 5 min; placing the washing liquid in a Buchner funnel of a filter flask, performing suction filtration by using a microporous filter membrane, reserving a product filter cake on the filter membrane, pumping the washing liquid into the filter flask, and performing washing and suction filtration for 2 times; and placing the product filter cake in a beaker, adding 100mL of deionized water, stirring and washing for 5min, and washing and filtering for 2 times.
The vacuum drying in the step (4) comprises the following specific steps: and (3) placing the washed product filter cake into a quartz container, and then placing the quartz container into a vacuum drying oven for drying at the drying temperature of 50 +/-1 ℃ under the vacuum degree of 50Pa for 10 hours.
The mesoporous germanium material can be applied to a lithium ion battery cathode material.
The invention has the beneficial effects that: compared with the prior art, the method has obvious advancement, adopts germanium tetrachloride as a germanium source, adopts sodium-potassium alloy as a reducing agent, adopts toluene as a solvent, prepares a reaction solution by magnetic stirring at room temperature, and prepares the mesoporous germanium material by suction filtration, high-temperature roasting, washing and vacuum drying.
Drawings
The invention will be further described with reference to the accompanying drawings.
The above objects, advantages and features of the present invention will become more apparent by referring to the following detailed description of the embodiments taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a schematic structural diagram of a glass round-bottom flask required for synthesis and preparation of a mesoporous germanium material;
1. the device comprises an iron clamp, 2 parts of a round-bottom flask, 3 parts of a stirring table, 4 parts of a fixing rod, 5 parts of a magnetic stirrer, 6 parts of a plastic rubber plug, 7 parts of a stirrer base, 8 parts of a display screen, 9 parts of an indicator light, 10 parts of a power switch and 11 parts of a rotating speed regulator.
FIG. 2 is a schematic view of a tubular furnace structure required for synthesis and preparation of a mesoporous germanium material;
1, 2, a vacuumizing port, 3, a flange, 4, a protective cover, 5, a handle, 6, an ammeter, 7 control buttons, 8, a draw buckle, 9, a temperature controller, 10, a pressure gauge and 11, wherein the vacuumizing port is arranged on the upper part of the shell;
FIG. 3 is an X-ray diffraction pattern of a mesoporous germanium material;
FIG. 4 is a graph showing nitrogen adsorption and desorption curves of a mesoporous germanium material;
FIG. 5 is a transmission electron microscope photograph of a mesoporous germanium material;
fig. 6 is a graph showing the cycle performance of the mesoporous germanium material as a negative electrode material of a lithium ion battery.
Detailed Description
Hereinafter, specific embodiments of the present invention will be described in detail with reference to the accompanying drawings.
FIG. 1 and FIG. 2 show the state diagram of the synthesis and preparation of the mesoporous germanium material, in which the positions of the components are correct, proportioned by weight, and operated sequentially; the amount of chemical substance used for preparation is determined in a preset range, and the measured unit is gram and milliliter.
The synthesis of the mesoporous germanium material is carried out in a glass round-bottom flask and a tubular furnace and is finished by stirring at room temperature and roasting at high temperature under inert atmosphere;
referring to fig. 1, the stirrer is rectangular, a round-bottomed flask 2 is fixed on a fixing rod 4 of a stirring table 3 by an iron clamp 1, a magnetic stirrer 5 is placed at the bottom of the flask, and the mouth of the round-bottomed flask is sealed by a plastic plug 6. The stirrer base 7 is provided with a display screen 8, an indicator light 9, a power switch 10 and a rotating speed regulator 11.
As shown in FIG. 2, the high temperature calcination is performed in a tube, using nitrogen as the shielding gas, and the calcination temperature is 300-600 ℃. 1, 2, a vacuumizing port, 3, a flange, 4, a protective cover, 5, a handle, 6, an ammeter, 7 control buttons, 8, a draw buckle, 9, a temperature controller, 10, a pressure gauge and 11, wherein the vacuumizing port is arranged on the upper part of the shell;
the chemical materials used were: the preparation method comprises the following steps of (1) preparing sodium metal, potassium metal, germanium tetrachloride, toluene, ethanol and deionized water in a combined preparation amount: taking g and ml as measurement unit
The preparation method comprises the following steps:
(1) selecting chemical materials
The chemical material used for preparation is selected and subjected to quality purity control:
(2) preparation of sodium-potassium alloy
Weighing 0.4g +/-0.03 g of metal sodium, weighing 1.6g +/-0.04 g of metal potassium, and stirring for 1min to obtain a sodium-potassium alloy;
(3) synthesis of mesoporous germanium materials
The synthesis of the mesoporous germanium material is carried out under the protection of nitrogen, and the mesoporous germanium material is firstly stirred and reduced at room temperature, then filtered to obtain solid, and finally roasted at high temperature under the condition of nitrogen.
① preparing mixed reaction mixture
Weighing 2.4 +/-0.04 g of germanium tetrachloride and 1.8 +/-0.03 g of sodium-potassium alloy, and weighing 200mL +/-5 mL of toluene;
adding the mixture into a round-bottom flask to obtain a mixed reaction solution;
②, starting magnetic stirring, stirring for 4h, mixing the reaction solution to react, and the reaction equation is as follows:
GeCl4+4Na＝4NaCl+Ge
GeCl4+4K＝4KCl+Ge
③ after the reaction, the stirring was stopped, and 100ml of ethanol was added
(4) Suction filtration
Placing the reacted mixture into a Buchner funnel of a filter flask, carrying out suction filtration by using a microporous filter membrane, remaining a product filter cake on the filter membrane, and pumping the waste liquid into the filter flask;
(5) roasting
And roasting the filter cake obtained in the last step in a tubular furnace at the temperature of 300-600 ℃.
(6) Washing and suction filtering
Placing the roasted product in a beaker, adding 100mL of deionized water, stirring and washing for 5 min;
placing the washing liquid in a Buchner funnel of a filter flask, carrying out suction filtration by using a microporous filter membrane, reserving a product filter cake on the filter membrane, and pumping the washing liquid into the filter flask;
washing and filtering for 2 times;
putting the product filter cake into a beaker, adding 100mL of deionized water, and stirring and washing for 5 min;
washing and filtering for 2 times;
(7) vacuum drying
Putting the washed product filter cake into a quartz container, and then putting the quartz container into a vacuum drying oven for drying at the drying temperature of 50 +/-1 ℃ under the vacuum degree of 50Pa for 10 hours;
drying to obtain the mesoporous germanium material;
(8) detection, analysis, characterization
Detecting, analyzing and representing the morphology, components and chemical and physical properties of the prepared mesoporous germanium material;
carrying out structural analysis on the material by using an X-ray diffractometer; the result is shown in fig. 3, which is an X-ray diffraction pattern of the mesoporous germanium material, and it can be seen in fig. 3 that the obtained germanium material has a crystalline structure.
Analyzing the pore structure of the material by using a nitrogen physical adsorption instrument; as shown in fig. 4, which is a graph showing nitrogen adsorption and desorption of the mesoporous germanium material, it can be seen that the obtained germanium material has a mesoporous channel structure.
Carrying out microstructure analysis on the material by using a transmission electron microscope; the result is shown in fig. 5, which is a transmission electron microscope photograph of the mesoporous germanium material, and it can be seen that the obtained germanium material has a pore channel structure. The figures are all processed by a material studio software program;
(9) lithium ion battery performance study
The active material, conductive carbon material and binder are mixed in a ratio of 70: 15: 15 portions of the electrode slurry are uniformly coated on the copper foil. The electrochemical property is obtained from a CR2016 type button cell, a polypropylene film is used as a diaphragm, a lithium foil is used as a counter electrode, and 1mol L of the lithium foil is used-1LiPF6Dissolved in a mixed solution of diethyl carbonate, ethylene carbonate and dimethyl carbonate (volume ratio 1: 1) and fluoroethylene carbonate (FEC, volume fraction 10%) as an electrolyte additive, the cell was circulated at a constant current of 0.01-1.50V.
The conclusion is that: the synthesized germanium material at room temperature is black powder, the material has a mesoporous channel structure, and the product yield is 95.2%;
(10) product storage
The prepared mesoporous germanium material is stored in a brown transparent glass container, is stored in a closed and dark place, and needs to be waterproof, moistureproof, sun-proof and acid, alkali and salt corrosion resistant, the storage temperature is 20 +/-2 ℃, and the relative humidity is less than or equal to 10%.
Fig. 6 shows the cycle performance of the mesoporous germanium material as a lithium ion battery negative electrode material, and fig. 6 shows that the obtained germanium material shows better electrochemical performance when being used as a lithium ion battery negative electrode material.
Although the present invention has been described in conjunction with the preferred embodiments thereof, it will be understood by those skilled in the art that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention. Accordingly, the present invention should not be limited by the above-described embodiments, but should be defined by the appended claims and their equivalents.
Claims (4)
1. A preparation method of a mesoporous germanium material is characterized by comprising the following chemical substance materials: metal sodium, metal potassium, germanium tetrachloride, toluene, ethanol and deionized water;
the combined dosage is as follows: taking g and ml as the measurement unit,
the synthesis of the mesoporous germanium material is carried out in a closed reactor at room temperature in the process of magnetic stirring;
the preparation method comprises the following steps:
(1) preparing a sodium-potassium alloy: weighing 0.4g +/-0.03 g of metal sodium, weighing 1.6g +/-0.04 g of metal potassium, and stirring for 1min to prepare a sodium-potassium alloy;
(2) synthesizing a mesoporous germanium material: under the protection of nitrogen, firstly stirring and reducing at room temperature, then filtering to obtain a solid, and finally roasting at high temperature under the condition of nitrogen to obtain a roasted product;
(3) washing and suction filtration:
(4) and (3) vacuum drying: drying to obtain the mesoporous germanium material;
(5) detection, analysis and characterization: detecting, analyzing and representing the morphology, components and chemical and physical properties of the prepared mesoporous germanium material;
the step (2) specifically comprises the following steps:
A. preparing a mixed reaction mixture: weighing 2.4 +/-0.04 g of germanium tetrachloride and 1.8 +/-0.03 g of sodium-potassium alloy, weighing 200mL +/-5 mL of toluene, and adding the toluene into a round-bottom flask to obtain a mixed reaction solution;
B. starting magnetic stirring, stirring for 4 hours, and reacting the mixed reaction solution, wherein the reaction equation is as follows:
GeCl4+4Na＝4NaCl+Ge
GeCl4+4K＝4KCl+Ge
C. after the reaction is finished, stopping stirring, and adding 100ml of ethanol; and (3) suction filtration: placing the reacted mixture into a Buchner funnel of a filter flask, carrying out suction filtration by using a microporous filter membrane, and pumping the residual product, namely the filter cake waste liquid on the filter membrane into the filter flask; roasting: the obtained filter cake is roasted in a tubular furnace at the temperature of 300-600 ℃.
2. The method for preparing the mesoporous germanium material according to claim 1, wherein the washing and suction filtration in step (3) specifically comprises the following steps: placing the roasted product in a beaker, adding 100mL of deionized water, stirring and washing for 5 min; placing the washing liquid in a Buchner funnel of a filter flask, performing suction filtration by using a microporous filter membrane, reserving a product filter cake on the filter membrane, pumping the washing liquid into the filter flask, and performing washing and suction filtration for 2 times; and placing the product filter cake in a beaker, adding 100mL of deionized water, stirring and washing for 5min, and washing and filtering for 2 times.
3. The method for preparing a mesoporous germanium material according to claim 1, wherein the vacuum drying in step (4) comprises the following steps: and (3) placing the washed product filter cake into a quartz container, and then placing the quartz container into a vacuum drying oven for drying at the drying temperature of 50 +/-1 ℃ under the vacuum degree of 50Pa for 10 hours.
4. The mesoporous germanium material prepared by the preparation method according to claim 1, which can be applied to a lithium ion battery cathode material.
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