CN112174108B - Preparation method of communicated mesoporous carbon-based composite electrode material - Google Patents

Preparation method of communicated mesoporous carbon-based composite electrode material Download PDF

Info

Publication number
CN112174108B
CN112174108B CN202010992044.2A CN202010992044A CN112174108B CN 112174108 B CN112174108 B CN 112174108B CN 202010992044 A CN202010992044 A CN 202010992044A CN 112174108 B CN112174108 B CN 112174108B
Authority
CN
China
Prior art keywords
electrode material
communicated
based composite
carbon
fumed silica
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
CN202010992044.2A
Other languages
Chinese (zh)
Other versions
CN112174108A (en
Inventor
余彦
王斌
杨海
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.)
University of Science and Technology of China USTC
Original Assignee
University of Science and Technology of China USTC
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 University of Science and Technology of China USTC filed Critical University of Science and Technology of China USTC
Priority to CN202010992044.2A priority Critical patent/CN112174108B/en
Publication of CN112174108A publication Critical patent/CN112174108A/en
Application granted granted Critical
Publication of CN112174108B publication Critical patent/CN112174108B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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 application provides a preparation method of a communicated mesoporous carbon-based composite electrode material, which comprises the following steps: a) complexing and crosslinking a complexing agent, dihydric alcohol, water and optional metal salt to obtain uniform precursor gel; b) fully mixing the precursor gel and the fumed silica to obtain a mixture; c) pyrolyzing the mixture to obtain an intermediate state nano material; d) and etching the intermediate state nano material to etch out the fumed silica so as to obtain the nano carbon-based composite electrode material with communicated mesopores. The method for synthesizing the communicated mesoporous carbon composite material has wide raw material sources and universality. Meanwhile, the carbon-based nano material synthesized by the method has higher capacity and stability when being used as a sodium and potassium ion battery at low temperature.

Description

Preparation method of communicated mesoporous carbon-based composite electrode material
Technical Field
The invention relates to the technical field of nano materials, in particular to a preparation method and application of a carbon-based composite electrode material.
Background
The development of the high-performance low-temperature sodium/potassium ion battery has important technical significance for key applications such as national defense, aerospace, large-scale energy storage and the like. However, the electrochemical performance of sodium/potassium ion batteries is very poor due to the very slow desolvation reaction of sodium potassium ions during ion transport at low temperatures. Therefore, it is important to develop a high-capacity, high-rate, long-cycle-life sodium/potassium ion battery electrode material. At low temperatures, increasing the specific capacity of the negative electrode is considered an attractive approach to increasing the energy density of the battery.
Taking an alloy-based cathode as an example, the alloy-based cathode has been widely paid attention by researchers, not only can provide high capacity, but also provides a proper working voltage platform, which is beneficial to preventing the formation of sodium/potassium dendrites and improving the safety of the battery. However, the alloy-based negative electrode has short plates with large volume expansion in the circulation process, poor stability in the circulation process and the like, and the carbon-based alloy composite material can well solve the problems by reserving the expansion volume, maintaining the structure stability and the like. 386mAh g of metal bismuth negative electrode-1Specific volume ofVolume and high capacity 3800mAh cm-3The material is an electrode material with wide application prospect. Therefore, from the viewpoint of material selection and electrode material design, the ideal low-temperature sodium potassium ion negative electrode material should have rich ion transmission channels, high specific capacity and high chemical stability.
Most of the synthesis of the nano-scale alloy-based materials reported so far focuses on the bottom-up process, including the ultrasonic-filtration method, the solvothermal method, the chemical dealloying method, and the like. Although these strategies have been successful in producing nanoalloy-based materials with uniformly controllable particle size, these strategies rarely consider building abundant ion transport channels in the material to achieve low temperature energy storage with high requirements for ion transport. It is particularly important to develop a synthetic method for producing a carbon-based composite electrode material having interconnected mesopores, uniform metal particles, and low cost.
Disclosure of Invention
The invention aims to provide a preparation method of a connected mesoporous carbon-based composite electrode material, and the preparation method of the carbon nano composite material provided by the application has universality.
The application provides a preparation method of a communicated mesoporous carbon-based composite electrode material, which comprises the following steps: complexing and crosslinking a complexing agent (such as citric acid), dihydric alcohol, water and metal salt to obtain uniform precursor gel, then fully mixing the precursor gel with fumed silica to obtain a mixture, pyrolyzing the mixture to obtain an intermediate state nano material, and finally etching the intermediate state nano material to etch away the fumed silica to obtain the nanocarbon composite electrode material with communicated mesopores.
Preferably, the complexing agent is selected from anhydrous citric acid, ethylenediaminetetraacetic acid or tartaric acid, and the like.
Preferably, the glycol is selected from ethylene glycol or propylene glycol, and the like.
Preferably, the metal salt is a nitrate, more preferably a nitrate selected from Bi, Co or Mn.
The carbon nano-material provided by the application has the advantages of easily available raw materials, mild reaction conditions and wide applicability. Furthermore, the carbon composite metal in the carbon-based nano material prepared by the method has the activity of embedding sodium and potassium, so that the carbon composite metal has excellent electrochemical activity when used as a sodium-potassium ion battery; meanwhile, the communicated mesopores provided in the carbon nanomaterial not only improve the structural stability of the whole material, but also provide a shorter ion diffusion path and a faster ion transmission rate in the low-temperature charging and discharging process, so that the carbon nanomaterial provided by the application has better capacity and stability at low temperature as an electrode material of a sodium-potassium ion battery.
Drawings
Fig. 1 is an energy storage schematic diagram of a connected mesoporous carbon-based composite electrode material prepared in embodiment 1 of the present disclosure;
fig. 2 is a scanning electron micrograph of the interconnected mesoporous carbon-based composite electrode material prepared in example 1 of the present disclosure;
fig. 3 is a transmission electron micrograph of the connected mesoporous carbon-based composite electrode material prepared in example 1 of the present disclosure;
FIG. 4 is a scanning electron micrograph of fumed silica used in example 1 of the present disclosure;
fig. 5 is a nitrogen adsorption and desorption isotherm of the connected mesoporous carbon-based composite electrode material prepared in example 1 of the present disclosure;
fig. 6 is a graph of pore size distribution of the interconnected mesoporous carbon-based composite electrode material prepared in example 1 of the present disclosure;
fig. 7 is a cycle performance diagram of the connected mesoporous carbon-based composite electrode material prepared in example 1 of the present disclosure for energy storage of a low-temperature sodium potassium ion battery;
fig. 8 is a scanning electron micrograph and a transmission electron micrograph of the interconnected mesoporous carbon-based composite electrode material prepared in example 4 of the present disclosure;
fig. 9 is a scanning electron micrograph and a transmission electron micrograph of the interconnected mesoporous carbon-based composite electrode material prepared in example 5 of the present disclosure;
fig. 10 is a graph of rate performance of the connected mesoporous carbon-based composite electrode material prepared in example 1 of the present disclosure and the nanocarbon-based composite electrode material prepared in comparative example 1 for energy storage of a low-temperature sodium-potassium ion battery; and
fig. 11 is a scanning electron micrograph and a transmission electron micrograph of the interconnected mesoporous carbon electrode material prepared in example 6 of the present disclosure.
Detailed Description
For a further understanding of the present invention, reference will now be made to the following preferred embodiments of the invention in conjunction with the examples, but it is to be understood that the description is intended to further illustrate the features and advantages of the invention and is not intended to limit the scope of the claims which follow.
The embodiment of the invention discloses a synthetic method of a communicated mesoporous carbon-based composite electrode material, which comprises the following steps:
a) complexing and crosslinking a complexing agent, dihydric alcohol, water and optional metal salt to obtain uniform precursor gel;
b) fully mixing the precursor gel and the fumed silica to obtain a mixture;
c) pyrolyzing the mixture to obtain an intermediate state nano material;
d) and etching the intermediate state nano material to etch out the fumed silica so as to obtain the nano carbon-based composite electrode material with communicated mesopores.
The complexing agent refers to an agent capable of complexing with metal ions from a metal salt under about neutral pH conditions to give a homogeneous solution. In the present disclosure, examples of the complexing agent include any one selected from anhydrous citric acid, ethylenediaminetetraacetic acid, tartaric acid, or the like.
The diol is used as a solvent and a crosslinking agent in the production method of the present disclosure, and examples thereof include any one preferably selected from ethylene glycol or propylene glycol and the like.
In the disclosure, the fumed silica can be a commercially available product, and preferably, the fumed silica has a primary particle size of 7-10nm and a specific surface area of 300-400m2/g。
The nano carbon-based composite electrode material obtained by the present disclosure has elongated through holes, and the diameter of the through holes can be 7-10nm, and the length of the through holes is more than 100nm and is communicated with each other.
The metal ion may be capable of complexing with a complexing agent such as citric acidThe metal ions are appropriately used for the electrode material, and examples thereof include Bi, Co, Mn, and the like. The metal ions may be used in the form of metal salts. Illustratively, the metal salt is selected from Bi (NO)3)3·5H2O、Co(NO3)2·6H2O or 50% Mn (NO)3)2Aqueous solutions, and the like. 50% Mn (NO)3)2The aqueous solution means Mn (NO) with a mass concentration of 50%3)2An aqueous solution, which may be a commercial raw material purchased directly.
Preferably, the "pyrolysis" described in step c) of the preparation method of the present disclosure is carried out by: raising the temperature of the mixture to 500-600 ℃ at a speed of 10-20 ℃/min under the protective atmosphere of argon or nitrogen, and keeping the temperature for 0.5-1.5 h; then raising the temperature to 700-900 ℃ at the speed of 3-5 ℃/min, keeping the temperature for 2-6h, and then cooling to the room temperature to obtain the intermediate state nano material.
The "etching" described in step d) of the preparation method of the present disclosure refers to a process of removing fumed silica, and an etching process commonly used in the art may be used. Preferably, in step d) of the preparation method of the present disclosure, the etchant used is an alkaline solution, preferably NaOH solution, the etching time is 4-24h, and the etching temperature is not particularly limited, and may be, for example, 40-80 ℃.
In some specific embodiments, the application provides a method for preparing a carbon-based nano electrode material by complexing metal ions with citric acid and adopting a fumed silica template.
In the process of preparing the carbon-based nano electrode material, anhydrous citric acid, metal salt, ethylene glycol and deionized water are mixed, and ammonia water is dripped to adjust the pH value to 7, so that the citric acid is complexed with metal ions to obtain a uniform solution; the process is to fully complex citric acid and metal ions to obtain a uniform solution; the complexing is a technique known to those skilled in the art, and the present application is not particularly limited. The pH value is adjusted to 7 by dropping ammonia water, so that the complexing effect of citric acid on metal ions can be effectively promoted.
The solvent is an organic solvent well known to those skilled in the art, and the present application is not particularly limited, and in the examples, the solvent is selected from ethylene glycol.
In step a), after obtaining a homogeneous solution, heating and stirring the homogeneous solution to obtain a homogeneous gel. In one embodiment, "obtaining a uniform gel after further heating and stirring the uniform solution" may be preferably performed by: the obtained solution is stirred for 2-6h at 70-90 ℃ and for 10-40h at 110-130 ℃ step by step, the uniform solution is converted into uniform gel through the esterification and crosslinking of citric acid and glycol, and the water is evaporated to dryness through the stirring of an oil bath at 110-130 ℃. The term "homogeneous solution" or "homogeneous solution" refers to a solution in which the composition and properties are identical or nearly identical throughout. The term "homogeneous gel" refers to a gel that is identical or nearly identical in composition and properties throughout.
After the uniform gel is obtained, the gel and the fumed silica template are fully mixed, including multiple batch mixing. The mixing process can adopt a grinding mode to obtain a uniform mixture, and then the mixture is carbonized and decomposed at high temperature under a protective atmosphere to obtain the intermediate state nano material. The preparation of the intermediate state nano material comprises the following specific steps:
the mass ratio of the gel to the fumed silica is 2: 0.2-2, and preferably, the mass ratio of the gel to the fumed silica is 2: 1. The fumed silica is a nano material widely applied in commerce, the source of the fumed silica is not particularly limited, and in the aspect of specification, the primary particle size is 7-10nm, and the specific surface area is 300-400m2The white carbon black in the gas phase is/g.
According to the method, the intermediate state nano material obtained after high-temperature pyrolysis is etched to obtain a carbon-based nano material with communicated mesopores; the process adopts an etching agent to etch the fumed silica templateThe etchant in the process mainly etches away the fumed silica template, which is an alkaline solution, and more specifically, the etchant can be KOH or NaOH. The etchant is sodium hydroxide, and the following reaction occurs: 2NaOH + H2O+SiO2＝Na2SiO3+H2And then obtaining the porous carbon-based nano material with mesopores. Adding the carbon nano material with mesopores into a 2M NaOH solution with the volume of 30-50 mL, stirring for 20h for etching, then carrying out suction filtration and washing, washing to be neutral, and drying to obtain the communicated mesoporous carbon-based composite electrode material.
In the scheme, the communicated mesoporous carbon-based nano material containing different metals is prepared by using anhydrous citric acid, ethylene glycol, water, metal salt and gas-phase white carbon black as raw materials.
The application also provides the application of the carbon nano material prepared by the preparation method in the scheme in the energy storage of a low-temperature sodium-potassium ion battery as an electrode material.
Without being bound by any theory, the inventors of the present application believe that: in the synthetic carbon nano material, the fumed silica template is used and is based on the characteristics of the fumed silica: 1) the original grain size of the fumed silica is about 7-10 nm; 2) the primary particles of the fumed silica are connected with each other to form a linear structure. The prepared carbon-based nano material has more communicated mesopores, and the communicated mesopore channels provide a shorter ion diffusion path and a faster ion transmission rate in the charge and discharge process of the low-temperature sodium-potassium ion battery on the one hand, and relieve the volume expansion in the charge and discharge process of the electrode material on the other hand, so that the electrode material has higher structural stability. Therefore, the communicated mesoporous carbon-based nano electrode material prepared by the scheme has higher charge and discharge capacity and cycle stability at low temperature.
Examples
For further understanding of the present invention, the following examples are provided to illustrate the synthesis method of heterogeneous carbon-based nano-materials, and the scope of the present invention is not limited by the following examples.
The raw materials in the following examples are all commercial products, wherein fumed silica is purchased from Texaco A380 hydrophilic fumed silica.
Example 1
a. 20g of anhydrous citric acid, 21.8g of Bi (NO)3)3·5H2Dispersing O in 25g of deionized water and 25mL of glycol, uniformly stirring, and then dropwise adding ammonia water to adjust the pH value to 7 to obtain a uniform solution; the homogeneous solution was then transferred to a 250mL beaker, which was heated in a water bath at 80 ℃ for 4h, then heated to 120 ℃ for 20h in an oil bath to give a homogeneous gel.
b. And mixing the obtained 10g of gel with 5g of fumed silica template, wherein the mixing process is carried out for 3-4 times, and a uniform mixture is obtained by a grinding mode.
c. Transferring the obtained uniform mixture into a quartz crucible or a quartz sleeve, putting the quartz crucible or the quartz sleeve into a tube furnace, introducing nitrogen or argon as protective gas, heating the tube furnace to 500 ℃ at the speed of 20 ℃/min, and keeping the temperature for 1 h; heating to 800 ℃ at the speed of 5 ℃/min, preserving the heat for 4h, and then cooling to room temperature; the pressure in the tube furnace is kept constant. Obtaining an intermediate state nano material;
d. transferring the intermediate state nano material into a beaker, adding about 100mL of 3M NaOH solution, and stirring for 20 hours to perform alkali etching; and then, carrying out suction filtration on the solution, washing to be neutral, and drying at 80 ℃ to obtain the communicated mesoporous carbon-based composite electrode material containing the nano bismuth particles.
FIG. 2 is a scanning electron micrograph of the interconnected mesoporous carbon-based composite electrode material prepared in example 1 of the present invention;
FIG. 3 is a TEM image of the interconnected mesoporous carbon-based composite electrode material prepared in example 1 of the present invention;
FIG. 4 is a scanning electron microscope photograph of fumed silica used in example 1 of the present invention;
fig. 5 is a nitrogen adsorption and desorption isotherm of the connected mesoporous carbon-based composite electrode material prepared in example 1 of the present invention;
FIG. 6 is a graph showing the pore size distribution of the interconnected mesoporous carbon-based composite electrode material prepared in example 1 of the present invention;
fig. 7 is a cycle performance diagram of the connected mesoporous carbon-based composite electrode material prepared in example 1 of the present invention for energy storage of a low temperature sodium potassium ion battery. The communicated mesoporous carbon-based nano electrode material has higher charge and discharge capacity and cycle stability when being applied to a potassium ion battery at low temperature, can still realize the ultra-long cycle life of 2000 circles at the temperature of minus 20 ℃ and under the huge current density of 10A/g, and can still maintain 86 percent of capacity after 2000 circles of cycles.
As can be seen from fig. 2 and 3, the carbon nanomaterial prepared in this embodiment has an obvious connected mesoporous structure left after the fumed silica is etched.
Example 2
a. 20g of anhydrous citric acid, 21.8g of Bi (NO)3)3·5H2Dispersing O in 25g of deionized water and 25mL of glycol, uniformly stirring, and then dropwise adding ammonia water to adjust the pH value to 7 to obtain a uniform solution; the homogeneous solution was then transferred to a 250mL beaker, which was heated in a water bath at 80 ℃ for 4h, then heated to 120 ℃ for 20h in an oil bath to give a homogeneous gel.
b. And mixing the obtained 10g of gel with 1g of fumed silica template, wherein the mixing process is carried out for 3-4 times, and a uniform mixture is obtained by a grinding mode.
c. Transferring the obtained uniform mixture into a quartz crucible or a quartz sleeve, putting the quartz crucible or the quartz sleeve into a tube furnace, introducing nitrogen or argon as a protective gas, heating the tube furnace to 500 ℃ at the speed of 20 ℃/min, and keeping the temperature for 1 h; heating to 800 ℃ at the speed of 5 ℃/min, preserving the heat for 4h, and then cooling to room temperature; the pressure in the tube furnace is kept constant. Obtaining an intermediate state nano material;
d. transferring the intermediate state nano material into a beaker, adding about 100mL of 3M NaOH solution, and stirring for 20 hours to perform alkali etching; and then, carrying out suction filtration on the solution, washing to be neutral, and drying at 80 ℃ to obtain the communicated mesoporous carbon-based composite electrode material containing the nano bismuth particles.
Compared with example 1, the interconnected mesoporous carbon-based nano electrode material prepared by the embodiment can maintain more than 90% of the capacity of example 1 when being applied to the potassium ion battery at low temperature, and can realize long cycle life of more than 1000 circles.
Example 3
a. 20g of anhydrous citric acid, 21.8g of Bi (NO)3)3·5H2Dispersing O in 25g of deionized water and 25mL of glycol, uniformly stirring, and then dropwise adding ammonia water to adjust the pH value to 7 to obtain a uniform solution; the homogeneous solution was then transferred to a 250mL beaker, which was heated in a water bath at 80 ℃ for 4h, then heated to 120 ℃ for 20h in an oil bath to give a homogeneous gel.
b. And mixing the obtained 10g of gel with 10g of fumed silica template, wherein the mixing process is carried out for 3-4 times, and a uniform mixture is obtained by a grinding mode.
c. Transferring the obtained uniform mixture into a quartz crucible or a quartz sleeve, putting the quartz crucible or the quartz sleeve into a tube furnace, introducing nitrogen or argon as a protective gas, heating the tube furnace to 500 ℃ at the speed of 20 ℃/min, and keeping the temperature for 1 h; heating to 800 ℃ at the speed of 5 ℃/min, preserving the heat for 4h, and then cooling to room temperature; the pressure in the tube furnace is kept constant. Obtaining an intermediate state nano material;
d. transferring the intermediate state nano material into a beaker, adding about 100mL of 3M NaOH solution, and stirring for 20 hours to perform alkali etching; and then, carrying out suction filtration on the solution, washing to be neutral, and drying at 80 ℃ to obtain the communicated mesoporous carbon-based composite electrode material containing the nano bismuth particles.
The communicated mesoporous carbon-based nano electrode material prepared by the embodiment can realize the same capacity and cycling stability as those of the embodiment 1 when being applied to the potassium ion battery at low temperature.
Example 4
a. 20g of anhydrous citric acid, 19.6g of Co (NO)3)2·6H2Dispersing O in 25g of deionized water and 25mL of glycol, uniformly stirring, and then dropwise adding ammonia water to adjust the pH value to 7 to obtain a uniform solution; the homogeneous solution was then transferred to a 250mL beaker, which was heated in a water bath at 80 ℃ for 4h, then the temperature was raised to 120 ℃ for a 20h oil bathHeating to obtain uniform gel.
b. And mixing the obtained 10g of gel with 5g of fumed silica template, wherein the mixing process is carried out for 3-4 times, and a uniform mixture is obtained by a grinding mode.
c. Transferring the obtained uniform mixture into a quartz crucible or a quartz sleeve, putting the quartz crucible or the quartz sleeve into a tube furnace, introducing nitrogen or argon as a protective gas, heating the tube furnace to 500 ℃ at the speed of 20 ℃/min, and keeping the temperature for 1 h; heating to 800 ℃ at the speed of 5 ℃/min, preserving the heat for 4h, and then cooling to room temperature; the pressure in the tube furnace is kept constant. Obtaining an intermediate state nano material;
d. transferring the intermediate state nano material into a beaker, adding about 100mL of 3M NaOH solution, and stirring for 20 hours to perform alkali etching; and then, filtering the solution, washing to be neutral, and drying at 80 ℃ to obtain the communicated mesoporous carbon-based composite electrode material containing the nano cobalt particles.
Fig. 8 is a scanning electron microscope picture and a transmission electron microscope picture of the connected mesoporous carbon-based composite electrode material prepared in example 4 of the present invention. The cobalt sulfide electrode material obtained by carrying out subsequent vulcanization treatment on the connected mesoporous carbon-based composite electrode material containing the nano cobalt particles obtained in the embodiment has higher capacity and longer cycle life through tests.
Example 5
a. 20g of anhydrous citric acid, 26g of 50% Mn (NO)3)2Dispersing the aqueous solution in 12g of deionized water and 25mL of ethylene glycol, uniformly stirring, and then dropwise adding ammonia water to adjust the pH value to 7 to obtain a uniform solution; the homogeneous solution was then transferred to a 250mL beaker, which was heated in a water bath at 80 ℃ for 4h, then heated to 120 ℃ for 20h in an oil bath to give a homogeneous gel.
b. And mixing the obtained 10g of gel with 5g of fumed silica template, wherein the mixing process is carried out for 3-4 times, and a uniform mixture is obtained by a grinding mode.
c. Transferring the obtained uniform mixture into a quartz crucible or a quartz sleeve, putting the quartz crucible or the quartz sleeve into a tube furnace, introducing nitrogen or argon as a protective gas, heating the tube furnace to 500 ℃ at the speed of 20 ℃/min, and keeping the temperature for 1 h; then heating to 800 ℃ at the speed of 5 ℃/min, preserving the heat for 4h, and then cooling to room temperature; the pressure in the tube furnace is kept constant. Obtaining an intermediate state nano material;
d. transferring the intermediate state nano material into a beaker, adding about 100mL of 3M NaOH solution, and stirring for 20 hours to perform alkali etching; and then, carrying out suction filtration on the solution, washing to be neutral, and drying at 80 ℃ to obtain the communicated mesoporous carbon-based composite electrode material containing the nano manganese oxide.
Fig. 9 is a scanning electron micrograph and a transmission electron micrograph of the interconnected mesoporous carbon-based composite electrode material prepared in example 5 of the present invention.
Comparative example 1
a. 20g of anhydrous citric acid, 21.8g of Bi (NO)3)3·5H2Dispersing O in 25g of deionized water and 25mL of glycol, uniformly stirring, and then dropwise adding ammonia water to adjust the pH value to 7 to obtain a uniform solution; the homogeneous solution was then transferred to a 250mL beaker, which was heated in a water bath at 80 ℃ for 4h, then heated to 120 ℃ for 20h in an oil bath to give a homogeneous gel.
b. Transferring the obtained uniform gel into a quartz crucible or a quartz sleeve, putting the quartz crucible or the quartz sleeve into a tube furnace, introducing nitrogen or argon as a protective gas, heating the tube furnace to 500 ℃ at the speed of 20 ℃/min, and keeping the temperature for 1 h; heating to 800 ℃ at the speed of 5 ℃/min, preserving the heat for 4h, and then cooling to room temperature; the pressure in the tube furnace is kept constant. Obtaining the carbon-based composite electrode material containing the nano bismuth particles.
Fig. 10 is a graph of rate performance of the connected mesoporous carbon-based composite electrode material prepared in example 1 of the present invention and the carbon-based composite electrode material containing nano bismuth particles prepared in comparative example 1 for energy storage of a low-temperature sodium potassium ion battery, and it can be seen that the electrode material of example 1 has more excellent rate performance compared to comparative example 1.
Example 6
a. Dispersing 20g of anhydrous citric acid in 25g of deionized water and 25mL of ethylene glycol, uniformly stirring, and then dropwise adding ammonia water to adjust the pH value to 7 to obtain a uniform solution; the homogeneous solution was then transferred to a 250mL beaker, which was heated in a water bath at 80 ℃ for 4h, then heated to 120 ℃ for 20h in an oil bath to give a homogeneous gel.
b. And mixing the obtained 10g of gel with 5g of fumed silica template, wherein the mixing process is carried out for 3-4 times, and a uniform mixture is obtained by a grinding mode.
c. Transferring the obtained uniform mixture into a quartz crucible or a quartz sleeve, putting the quartz crucible or the quartz sleeve into a tube furnace, introducing nitrogen or argon as a protective gas, heating the tube furnace to 500 ℃ at the speed of 20 ℃/min, and keeping the temperature for 1 h; then heating to 800 ℃ at the speed of 5 ℃/min, preserving the heat for 4h, and then cooling to room temperature; the pressure in the tube furnace is kept constant. Obtaining an intermediate state nano material;
d. transferring the intermediate state nano material into a beaker, adding about 100mL of 3M NaOH solution, and stirring for 20 hours to perform alkali etching; and then, filtering the solution, washing to be neutral, and drying at 80 ℃ to obtain the communicated mesoporous carbon electrode material.
Fig. 11 is a scanning electron micrograph and a transmission electron micrograph of the interconnected mesoporous carbon electrode material prepared in example 6 of the present invention.
The embodiment proves that the metal salt used in the method is optional, the preparation of the pure carbon nano material can be realized under the condition of not adding the metal salt, and the connected mesoporous carbon electrode material is applied to a sodium-potassium ion electrode material, and has excellent reversible capacity and cycle life.
Example 7
a. 20g of anhydrous citric acid, 21.8g of Bi (NO)3)3·5H2Dispersing O in 25g of deionized water and 25mL of glycol, stirring uniformly, and then dropwise adding ammonia water to adjust the pH value to 7 to obtain a uniform solution; the homogeneous solution was then transferred to a 250mL beaker, which was heated in a water bath at 80 ℃ for 4h, then heated to 120 ℃ for 20h in an oil bath to give a homogeneous gel.
b. And mixing the obtained 10g of gel with 5g of fumed silica template, wherein the mixing process is carried out for 3-4 times, and a uniform mixture is obtained by a grinding mode.
c. Transferring the obtained uniform mixture into a quartz crucible or a quartz sleeve, putting the quartz crucible or the quartz sleeve into a tube furnace, introducing nitrogen or argon as protective gas, heating the tube furnace to 500 ℃ at the speed of 20 ℃/min, preserving the heat for 4h, and then cooling to room temperature; the pressure in the tube furnace is kept constant. Obtaining an intermediate state nano material;
d. transferring the intermediate state nano material into a beaker, adding about 100mL of 3M NaOH solution, and stirring for 20 hours to perform alkali etching; and then, filtering the solution, washing to be neutral, and drying at 80 ℃ to obtain the communicated mesoporous carbon-based composite electrode material containing the nano bismuth particles.
The electrode material prepared in this example 7 had a lower capacity and cycle life than example 1, indicating that step pyrolysis in step c of example 1 is a technological means by which further capacity and cycle life improvements can be achieved.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Industrial applicability
The method for synthesizing the communicated mesoporous carbon composite material has the advantages of wide raw material source and universality, and the synthesized carbon-based nano material has higher capacity and stability when being used as a sodium-potassium ion battery at low temperature. Therefore, the method has potential wide application prospect in the industrial field.

Claims (9)

1. A preparation method of a communicated mesoporous carbon-based composite electrode material comprises the following steps:
a) complexing and crosslinking a complexing agent, dihydric alcohol, water and optional metal salt to obtain uniform precursor gel, wherein the complexing agent is selected from anhydrous citric acid, ethylenediamine tetraacetic acid or tartaric acid;
b) fully mixing the precursor gel with the fumed silica to obtain a mixture;
c) pyrolyzing the mixture to obtain an intermediate state nano material;
d) and etching the intermediate state nano material to etch the fumed silica to obtain the nano carbon-based composite electrode material with communicated mesopores.
2. The production method according to claim 1, wherein the metal salt is a nitrate of Bi, Co, or Mn.
3. The method of claim 1, wherein the complex crosslinking in step a) is performed by: dropwise adding ammonia water to the mixed sample to adjust the pH value to 6-8; then the sample is stirred for 2-6h at 70-90 ℃ and for 10-40h at 110-130 ℃ in steps.
4. The method according to claim 1, wherein the mixing in step b) is to mix the gel and the fumed silica in powder form into a uniform phase by grinding.
5. The method of claim 1, wherein step c) is:
under the protective atmosphere of argon or nitrogen, raising the temperature of the mixture to 500-600 ℃ at the speed of 10-20 ℃/min, and keeping the temperature for 0.5-1.5 h; then raising the temperature to 700-900 ℃ at 3-5 ℃/min, and keeping the temperature for 2-6h to obtain the intermediate state nano material.
6. The preparation method according to claim 1, wherein in step d), the etching agent for etching is alkaline solution, and the etching time is 4-24 h.
7. The preparation method according to claim 1, wherein in the step b), the mass ratio of the gel to the gas-phase white carbon black is 2: (0.2-2).
8. The production method according to claim 1, wherein the diol is selected from ethylene glycol or propylene glycol.
9. The application of the communicated mesoporous carbon-based composite material prepared by the preparation method of any one of claims 1-8 in low-temperature sodium potassium ion battery energy storage as an electrode material.
CN202010992044.2A 2020-09-18 2020-09-18 Preparation method of communicated mesoporous carbon-based composite electrode material Active CN112174108B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010992044.2A CN112174108B (en) 2020-09-18 2020-09-18 Preparation method of communicated mesoporous carbon-based composite electrode material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010992044.2A CN112174108B (en) 2020-09-18 2020-09-18 Preparation method of communicated mesoporous carbon-based composite electrode material

Publications (2)

Publication Number Publication Date
CN112174108A CN112174108A (en) 2021-01-05
CN112174108B true CN112174108B (en) 2022-07-15

Family

ID=73956240

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010992044.2A Active CN112174108B (en) 2020-09-18 2020-09-18 Preparation method of communicated mesoporous carbon-based composite electrode material

Country Status (1)

Country Link
CN (1) CN112174108B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113206253A (en) * 2021-04-29 2021-08-03 陕西科技大学 Foam copper potassium ion battery material and preparation method thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106694019B (en) * 2016-12-16 2019-05-21 荆楚理工学院 A kind of preparation method of the nitrogen-doped carbon nano material of metallic cobalt modification
CN108480657B (en) * 2018-05-21 2021-05-04 许昌学院 Bismuth nanosheet, and preparation method and application thereof
CN108878813B (en) * 2018-06-15 2020-07-28 华南理工大学 Silicon dioxide/lignin porous carbon composite material, preparation method thereof and application thereof in lithium ion battery cathode material
CN111320193B (en) * 2020-02-27 2023-12-29 东南大学 Metal oxide nanoparticle and method for producing metal nanoparticle

Also Published As

Publication number Publication date
CN112174108A (en) 2021-01-05

Similar Documents

Publication Publication Date Title
CN109755482B (en) Silicon/carbon composite material and preparation method thereof
CN109244427B (en) Preparation method of carbon-coated zinc sulfide loaded graphene as potassium ion battery cathode
CN112349899B (en) Silicon-based composite negative electrode material, preparation method thereof and lithium ion battery
CN109103443B (en) Silicon-based negative electrode material and preparation method thereof
CN110683522B (en) Transition metal chalcogen family carbon-based heterostructure composite material with regular morphology and preparation method and application thereof
CN110518213A (en) A kind of porous silicon-carbon nano tube compound material and its preparation method and application
CN110048106B (en) Cobalt sulfide and multilevel carbon nanostructure composite material and preparation method and application thereof
CN108987729B (en) Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery
CN108390048B (en) Nitrogen-phosphorus co-doped carbon-coated MoO3-x and preparation method thereof
CN109748282B (en) Method for preparing nano silicon carbide at low temperature
CN110707301A (en) Vanadium trioxide/carbon composite material with nanosphere structure and preparation method and application thereof
CN111769272A (en) Bi @ C hollow nanosphere composite material and preparation method and application thereof
CN112786865A (en) MoS2Preparation method and application of quasi-quantum dot/nitrogen-sulfur co-doped biomass carbon composite nano material
CN108565131B (en) Method for preparing nitrogen-doped graphitized carbon
CN111162266B (en) Carbon-coated two-dimensional silicon and preparation method and application thereof
CN113629245A (en) Novel compounding method of carbon material and transition metal compound, composite material and application
CN112174108B (en) Preparation method of communicated mesoporous carbon-based composite electrode material
CN111682215B (en) Preparation method of nitrogen-doped yolk-shaped phenolic resin-based derivative carbon spheres
CN111584838B (en) Porous silicon/silicon-carbon composite material and preparation method and application thereof
CN113526566A (en) Preparation method of nano carbon sphere composite cobalt oxide negative electrode material
CN109768233B (en) NiCo of lithium ion battery2S4Preparation method of/graphene composite negative electrode material
CN108091838B (en) Method for preparing core-shell structure nano α -Fe2O3@ C composite material in one step
CN110600710A (en) Iron sulfide-carbon composite material and preparation method thereof, lithium ion battery negative electrode material, lithium ion battery negative electrode piece and lithium ion battery
CN112750627B (en) Carbon nano tube and preparation method and application thereof
CN113422059B (en) High-voltage carbon fluoride composite cathode material and preparation method 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