CN111416119A - Ultra-high dispersion Co-containing3S4Nanoparticle porous carbon and carbon nanotube sponge hybrid and preparation method and application thereof - Google Patents

Ultra-high dispersion Co-containing3S4Nanoparticle porous carbon and carbon nanotube sponge hybrid and preparation method and application thereof Download PDF

Info

Publication number
CN111416119A
CN111416119A CN201910011168.5A CN201910011168A CN111416119A CN 111416119 A CN111416119 A CN 111416119A CN 201910011168 A CN201910011168 A CN 201910011168A CN 111416119 A CN111416119 A CN 111416119A
Authority
CN
China
Prior art keywords
hybrid
carbon
sponge
carbon nanotube
ultra
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.)
Pending
Application number
CN201910011168.5A
Other languages
Chinese (zh)
Inventor
曹安源
张慧
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.)
Peking University
Original Assignee
Peking 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 Peking University filed Critical Peking University
Priority to CN201910011168.5A priority Critical patent/CN111416119A/en
Publication of CN111416119A publication Critical patent/CN111416119A/en
Pending legal-status Critical Current

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
    • H01M4/62—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention provides a catalyst containing ultra-high dispersion Co3S4Nanoparticle porous carbon and carbon nanotube sponge hybrid and preparation method and application thereof. The preparation method comprises the following steps: 1) functionalizing the carbon nanotube sponge; 2) adding the ZIF-67 precursor solution into the functionalized carbon nanotube sponge to react to obtain a carbon nanotube sponge and a ZIF-67 nanoparticle hybrid; 3) carbonizing and vulcanizing the hybrid of the carbon nano tube sponge and the ZIF-67 nano particle to obtain the hybrid containing the ultra-high dispersion Co3S4Nanoparticle porous carbon and carbon nanotube sponge hybrids. The preparation method is novel and can be used for mass production, and when the hybrid is used as the anode material of the lithium-sulfur battery, the specific capacity and the cycling stability can respectively reach 850mAh g during the charging and discharging of 5C high current density‑1And 75% capacity retention rate after 1000 cycles, the rate and long-cycle stability of the battery are remarkably improved.

Description

Ultra-high dispersion Co-containing3S4Nanoparticle porous carbon and carbon nanotube sponge hybrid and preparation method and application thereof
Technical Field
The invention belongs to the technical field of carbon materials and application, and relates to a material containing ultrahigh-dispersion Co3S4A method for preparing a nano particle porous carbon and carbon nano tube sponge hybrid.
Background
With the development of society and the continuous progress of science and technology, lithium ion batteries can not meet the requirements of people gradually due to lower specific capacity and energy density, so that novel secondary batteries are produced at the same time, and lithium sulfur batteries are one of the lithium sulfur batteries. The working principle of the lithium-sulfur battery is that the charging and discharging are realized by the chemical conversion reaction of elemental sulfur and lithium ions, so that the energy density and the power density have obvious advantages compared with the lithium-ion battery. However, the dissolution of polysulfide as an intermediate product, poor conductivity of elemental sulfur and sulfide, large volume collision of elemental sulfur in the charging and discharging processes, and slow polysulfide conversion reaction rate greatly influence the cycle stability and rate capability of the lithium-sulfur battery.
In order to solve the above problems, a method of coating sulfur with a porous carbon material has been introduced, so as to improve the conductivity of an electrode material and the volume expansion of elemental sulfur while alleviating the dissolution of polysulfide, thereby improving the cycle stability of a lithium-sulfur battery. However, the coated carbon layer, while protecting the polysulfide, also reduces the kinetics of polysulfide conversion, losing the rate capability of the lithium sulfur battery. The previous research results show that the rate performance of the lithium-sulfur battery can be remarkably improved by introducing the catalyst into the electrode material, but the design of the catalyst is particularly important. Such as Co3S4The catalytic action on polysulfide conversion is obviously better than that of Co, and Co is increased3S4The specific surface area of (a) can improve the catalytic efficiency thereof. Therefore, in order to improve the rate performance of the lithium-sulfur battery while ensuring the cycling stability of the lithium-sulfur battery, introducing a suitable catalyst into the porous carbon material is an effective method.
Disclosure of Invention
The invention aims to provide a catalyst containing ultra-high dispersion Co3S4A method for preparing a hybrid of nanoparticle porous carbon and carbon nanotube sponge that can convert a hybrid of ZIF-67 nanoparticles and carbon nanotube sponge into a hybrid containing highly dispersed Co by a simple carbonization-first and sulfurization-second method3S4The composite of porous carbon of nano particles and carbon nano tube sponge can increase the specific surface area of catalyst particles as much as possibleWhen the method is used, the composition of the carbon nano tube sponge and the carbon nano tube sponge is not influenced. Thereby realizing the synchronous improvement of the multiplying power and the long-cycle stability of the lithium-sulfur battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
ultra-high dispersion Co-containing3S4Nanoparticle porous carbon and carbon nanotube sponge hybrids, carbon nanotubes passing through porous carbon, Co3S4The nanoparticles are uniformly dispersed in the porous carbon.
Ultra-high dispersion Co-containing3S4A method for preparing a nanoparticle porous carbon and carbon nanotube sponge hybrid, the method comprising the steps of:
1) functionalizing the carbon nanotube sponge;
2) adding the ZIF-67 precursor solution into the functionalized carbon nanotube sponge to react to obtain a carbon nanotube sponge and a ZIF-67 nanoparticle hybrid;
3) carbonizing and vulcanizing the hybrid of the carbon nano tube sponge and the ZIF-67 nano particle to obtain the hybrid containing the ultra-high dispersion Co3S4Nanoparticle porous carbon and carbon nanotube sponge hybrids.
Further, the functionalization is a treatment with high temperature acidification.
Preferably, the high-temperature acidification temperature is 80-120 ℃, and the reaction time is 12-24 h.
Preferably, the ZIF-67 precursor mixed solution is formed by mixing cobalt nitrate hexahydrate and hexadecylammonium bromide aqueous solution with 2-methylimidazole ethanol solution.
Preferably, in step 3), the carbonization is performed under the protection of inert gas.
Preferably, in the step 3), the carbonization temperature is 550-650 ℃, the carbonization time is 0-5min, and the heating rate of heating to the carbonization temperature is 5-10 ℃/min.
Preferably, in step 3), the vulcanization is carried out using a thiourea solution.
The invention also provides a catalyst containing ultra-high dispersion Co3S4Nanoparticle porous carbon and carbon nanotube spongeUse of a hybrid in a lithium sulphur battery.
The material of the present invention, when used as a positive electrode material for a lithium sulfur battery, is at 5C (about 8A g)-1) When the heavy current density is charged and discharged, the specific capacity can reach 850mAh g-1。
The material of the invention is used as the positive electrode material of a lithium-sulfur battery at 5C (about 8A g)-1) The capacity retention rate can reach 75% after 1000 cycles when the battery is charged and discharged at high current density.
According to a preferred embodiment of the present invention, a composition comprising ultra-high dispersed Co3S4The preparation method of the nanoparticle porous carbon and carbon nanotube sponge hybrid comprises the steps of firstly acidifying carbon nanotube sponge by concentrated nitric acid to enable the surface of a carbon nanotube to contain functional groups such as hydroxyl, carboxyl and the like, and then growing ZIF-67 nanoparticles in situ in the functionalized carbon nanotube sponge to obtain the three-dimensional hybrid with the mutually penetrated carbon nanotube sponge and ZIF-67 particles. ZIF-67 in this hybrid was converted to porous carbon containing ultra-highly dispersed Co nanoparticles by carbonization, followed by sulfidation, and the porous carbon containing ultra-highly dispersed Co nanoparticles was further converted to porous carbon containing ultra-highly dispersed Co3S4The nano particle porous carbon realizes the content of ultra-high dispersion Co3S4And (3) preparing a nano particle porous carbon and carbon nano tube sponge hybrid.
The preparation method comprises the following specific steps:
firstly, preparing a functionalized carbon nanotube sponge: soaking carbon nanotube sponge in a high-pressure reaction kettle filled with concentrated nitric acid, acidifying at high temperature for a period of time (the high-temperature acidification temperature is 80-120 ℃, and the high-temperature acidification time is 12-24h), cleaning with deionized water, and replacing. Finally, freeze drying the carbon nano tube sponge to obtain functionalized carbon nano tube sponge;
secondly, preparing a carbon nano tube sponge and ZIF-67 nano particle hybrid: and (3) fully mixing the ZIF-67 precursor solution, and then dropwise adding the mixed solution into the functionalized carbon nanotube sponge to perform in-situ reaction in the carbon nanotube. Washing the reacted product with ethanol, replacing the product with deionized water, and freeze-drying to obtain a carbon nano tube sponge and ZIF-67 nano particle hybrid;
preparing a porous carbon and carbon nanotube sponge hybrid containing the ultra-high dispersion Co nano particles: slowly heating the obtained hybrid of the carbon nano tube sponge and the ZIF-67 nano particles in an inert atmosphere, and carbonizing the hybrid at a high temperature for a period of time to obtain a hybrid of the porous carbon containing the ultra-high dispersion Co nano particles and the carbon nano tube sponge;
fourthly, containing ultra-high dispersion Co3S4Preparing a nano particle porous carbon and carbon nano tube sponge hybrid: soaking the porous carbon containing the ultra-high dispersion Co nano particles and the carbon nano tube sponge hybrid in thiourea solution with a certain concentration, and carrying out high-temperature hydrothermal reaction for 24 hours. Then washing by deionized water and freeze drying to obtain the product containing ultra-high dispersion Co3S4Nanoparticle porous carbon and carbon nanotube sponge hybrids.
In the second step, the precursor mixed solution of ZIF-67 was prepared by mixing an aqueous solution of 2m L cobalt nitrate hexahydrate (0.06g) and ammonium hexadecylbromide (0.001g) with an ethanol solution of 9m L2-methylimidazole (0.896g) (or equivalent concentration).
In the third step, the inert atmosphere for carbonizing the hybrid of the carbon nano tube sponge and the ZIF-67 nano particle is 100% argon, the temperature is 550-650 ℃, the heating rate is 5-10 ℃/min, and the time is 0-5 min.
In the fourth step, the concentration of thiourea is 150m L g-1。
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a catalyst containing ultra-high dispersion Co3S4The method for preparing the nano particle porous carbon and carbon nano tube sponge hybrid has the advantages that the specific surface area of the hybrid is larger, the catalyst particles are highly dispersed, and the catalytic efficiency can be greatly improved.
2. The ultra-high dispersion Co-containing material prepared by the invention3S4The preparation method of the nano particle porous carbon and carbon nano tube sponge hybrid is simple, can realize mass production, and is expected to realize practical production and application.
3. The ultra-high dispersion Co-containing material prepared by the invention3S4When the nanoparticle porous carbon and carbon nanotube sponge hybrid is used as a positive electrode material of a lithium-sulfur battery, the rate capability and the cycling stability of the battery can be improved at the same time, and the hybrid has potential application prospects in the energy-related field.
Drawings
FIG. 1 shows the results of example 1, wherein the ultra-high dispersion Co is contained3S4Scanning electron microscope images of nanoparticle porous carbon and carbon nanotube sponge hybrids;
FIG. 2 shows the results of example 3, which shows that the catalyst contains ultra-high dispersion Co3S4Transmission electron microscopy images of nanoparticle porous carbon and carbon nanotube sponge hybrids;
FIG. 3 shows the results of example 2, wherein the ultra-high dispersion Co is contained3S4Transmission electron microscopy images of nanoparticle porous carbon and carbon nanotube sponge hybrids;
FIG. 4 shows the results of example 1, wherein the ultra-high dispersion Co is contained3S4The nano particle porous carbon and carbon nano tube sponge hybrid is used as a long cycle curve of the lithium-sulfur battery anode material under high current density.
Detailed Description
Any feature disclosed in this specification may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. Unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features. The description is only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention.
The invention is described in further detail below with reference to the figures and the detailed description.
Example 1
In this example, the ultra-high dispersion Co is contained3S4The preparation method of the nano particle porous carbon and carbon nano tube sponge hybrid is realized according to the following steps:
firstly, preparing a functionalized carbon nanotube sponge: pouring the concentrated nitric acid solution immersed in the carbon nanotube sponge into a high-pressure reaction kettle, placing the high-pressure reaction kettle in an oven, heating to 120 ℃ and keeping for 12 hours, then replacing the high-pressure reaction kettle with deionized water, and cleaning until the pH value is about 7. Then, freeze-drying the carbon nano tube sponge to obtain functionalized carbon nano tube sponge;
secondly, preparing a carbon nanotube sponge and ZIF-67 nano particle hybrid, namely mixing and stirring ZIF-67 precursor solution (2m L cobalt nitrate hexahydrate (0.06g) and hexadecylammonium bromide (0.001g) aqueous solution and 9m L2-methylimidazole (0.896g) ethanol solution) uniformly, adding the mixture into functionalized carbon nanotube sponge in a dropwise manner until the sponge is filled with a whole block, then placing the sponge on a shaking bed for reacting overnight, then washing the product with ethanol for three times, replacing the ethanol with deionized water, and finally freeze-drying the mixture to obtain the carbon nanotube sponge and the ZIF-67 nano particle hybrid;
porous carbon (about 5000 Co in each cubic block) containing ultrahigh-dispersion Co nanoparticles3S4Nanoparticles) and carbon nanotube sponge hybrid preparation: slowly heating the obtained hybrid of the carbon nano tube sponge and the ZIF-67 nano particles in 100% argon at 5 ℃/min, and quickly cooling after the temperature is raised to 550 ℃, so that the hybrid of the porous carbon containing the ultra-high dispersion Co nano particles and the carbon nano tube sponge can be obtained;
fourthly, containing ultra-high dispersion Co3S4The preparation of the porous carbon and carbon nanotube sponge hybrid of the nano particles comprises the step of soaking the porous carbon and carbon nanotube sponge hybrid containing the ultra-high dispersion Co nano particles in 150m L g-1Carrying out high-temperature hydrothermal reaction on the thiourea solution for 24 hours, washing the solution by using deionized water, and carrying out freeze drying to obtain the solution containing the ultrahigh-dispersion Co3S4The scanning electron microscope image of the nanoparticle porous carbon and carbon nanotube sponge hybrid is shown in fig. 1, and as can be seen from fig. 1, after the hybrid, the carbon nanotube passes through the porous carbon; the long cycling curve of the lithium-sulfur battery cathode material under high current density is shown in fig. 4, and as can be seen from fig. 4, the battery shows very excellent cycling stability, and after 1000 cycles, the battery capacity retention rate can still reach 75%.
Example 2
In this example, the ultra-high dispersion Co is contained3S4The preparation method of the nano particle porous carbon and carbon nano tube sponge hybrid is realized according to the following steps:
firstly, preparing a functionalized carbon nanotube sponge: pouring the concentrated nitric acid solution immersed in the carbon nanotube sponge into a high-pressure reaction kettle, placing the high-pressure reaction kettle in an oven, heating to 80 ℃ and keeping for 24 hours, then replacing the high-pressure reaction kettle with deionized water, and cleaning until the pH value is about 7. Then, freeze-drying the carbon nano tube sponge to obtain functionalized carbon nano tube sponge;
secondly, preparing a carbon nanotube sponge and ZIF-67 nano particle hybrid, namely mixing and stirring ZIF-67 precursor solution (2m L cobalt nitrate hexahydrate (0.06g) and hexadecylammonium bromide (0.001g) aqueous solution and 9m L2-methylimidazole (0.896g) ethanol solution) uniformly, adding the mixture into functionalized carbon nanotube sponge in a dropwise manner until the sponge is filled with a whole block, then placing the sponge on a shaking bed for reacting overnight, then washing the product with ethanol for three times, replacing the ethanol with deionized water, and finally freeze-drying the mixture to obtain the carbon nanotube sponge and the ZIF-67 nano particle hybrid;
preparing a porous carbon and carbon nanotube sponge hybrid containing the ultra-high dispersion Co nano particles: slowly heating the obtained hybrid of the carbon nano tube sponge and the ZIF-67 nano particles in 100% argon at 5 ℃/min, and quickly cooling after the temperature is raised to 550 ℃, so that the hybrid of the porous carbon containing the ultra-high dispersion Co nano particles and the carbon nano tube sponge can be obtained;
fourthly, containing ultra-high dispersion Co3S4Nanoparticle porous carbon (about 5000 Co per cube)3S4Nano particles) and carbon nano tube sponge hybrid, namely soaking the obtained porous carbon and carbon nano tube sponge hybrid containing the ultra-high dispersion Co nano particles in 150m L g-1Carrying out high-temperature hydrothermal reaction on the thiourea solution for 24 hours, washing the solution by using deionized water, and carrying out freeze drying to obtain the solution containing the ultrahigh-dispersion Co3S4The transmission electron micrograph of the nanoparticle porous carbon and carbon nanotube sponge hybrid is shown in fig. 3, and it can be seen from fig. 3 that sulfur is effectively loaded into the porous carbon.
Example 3
In this example, the ultra-high dispersion Co is contained3S4The preparation method of the nano particle porous carbon and carbon nano tube sponge hybrid is realized according to the following steps:
firstly, preparing a functionalized carbon nanotube sponge: pouring the concentrated nitric acid solution immersed in the carbon nanotube sponge into a high-pressure reaction kettle, placing the high-pressure reaction kettle in an oven, heating to 120 ℃ and keeping for 12 hours, then replacing the high-pressure reaction kettle with deionized water, and cleaning until the pH value is about 7. Then, freeze-drying the carbon nano tube sponge to obtain functionalized carbon nano tube sponge;
secondly, preparing a carbon nanotube sponge and ZIF-67 nano particle hybrid, namely mixing and stirring ZIF-67 precursor solution (2m L cobalt nitrate hexahydrate (0.06g) and hexadecylammonium bromide (0.001g) aqueous solution and 9m L2-methylimidazole (0.896g) ethanol solution) uniformly, adding the mixture into functionalized carbon nanotube sponge in a dropwise manner until the sponge is filled with a whole block, then placing the sponge on a shaking bed for reacting overnight, then washing the product with ethanol for three times, replacing the ethanol with deionized water, and finally freeze-drying the mixture to obtain the carbon nanotube sponge and the ZIF-67 nano particle hybrid;
preparing a porous carbon and carbon nanotube sponge hybrid containing the ultra-high dispersion Co nano particles: slowly heating the obtained hybrid of the carbon nano tube sponge and the ZIF-67 nano particles in 100% argon at the speed of 10 ℃/min, and quickly cooling after the temperature is raised to 550 ℃, so that the hybrid of the porous carbon containing the ultra-high dispersion Co nano particles and the carbon nano tube sponge can be obtained;
fourthly, containing ultra-high dispersion Co3S4Nanoparticle porous carbon (about 5000 Co per cube)3S4Nano particles) and carbon nano tube sponge hybrid, namely soaking the obtained porous carbon and carbon nano tube sponge hybrid containing the ultra-high dispersion Co nano particles in 150m L g-1Carrying out high-temperature hydrothermal reaction on the thiourea solution for 24 hours, washing the solution by using deionized water, and carrying out freeze drying to obtain the solution containing the ultrahigh-dispersion Co3S4Nanoparticle porous carbon and carbon nanotube spongeThe hybrid, a transmission electron micrograph of which is shown in FIG. 2, can be seen from FIG. 2, a large amount of Co3S4The nanoparticles were homogeneously dispersed in porous carbon, with approximately 5000 Co in a cube3S4Nanoparticles.
Example 4
In this example, the ultra-high dispersion Co is contained3S4The preparation method of the nano particle porous carbon and carbon nano tube sponge hybrid is realized according to the following steps:
firstly, preparing a functionalized carbon nanotube sponge: pouring the concentrated nitric acid solution immersed in the carbon nanotube sponge into a high-pressure reaction kettle, placing the high-pressure reaction kettle in an oven, heating to 120 ℃ and keeping for 12 hours, then replacing the high-pressure reaction kettle with deionized water, and cleaning until the pH value is about 7. Then, freeze-drying the carbon nano tube sponge to obtain functionalized carbon nano tube sponge;
secondly, preparing a carbon nanotube sponge and ZIF-67 nano particle hybrid, namely mixing and stirring ZIF-67 precursor solution (2m L cobalt nitrate hexahydrate (0.06g) and hexadecylammonium bromide (0.001g) aqueous solution and 9m L2-methylimidazole (0.896g) ethanol solution) uniformly, adding the mixture into functionalized carbon nanotube sponge in a dropwise manner until the sponge is filled with a whole block, then placing the sponge on a shaking bed for reacting overnight, then washing the product with ethanol for three times, replacing the ethanol with deionized water, and finally freeze-drying the mixture to obtain the carbon nanotube sponge and the ZIF-67 nano particle hybrid;
preparing a porous carbon and carbon nanotube sponge hybrid containing the ultra-high dispersion Co nano particles: slowly heating the obtained hybrid of the carbon nano tube sponge and the ZIF-67 nano particles to 550 ℃ at a speed of 5 ℃/min in 100% argon, and quickly cooling after heat preservation for 5min to obtain a hybrid of the porous carbon containing the ultra-high dispersion Co nano particles and the carbon nano tube sponge;
fourthly, containing ultra-high dispersion Co3S4Nanoparticle porous carbon (about 5000 Co per cube)3S4Nanoparticles) and carbon nanotube sponge hybrid preparation: the obtained porous carbon and carbon containing the ultra-high dispersion Co nano particlesSoaking the sponge hybrid of nanotube at 150m L g-1Carrying out high-temperature hydrothermal reaction on the thiourea solution for 24 hours, washing the solution by using deionized water, and carrying out freeze drying to obtain the solution containing the ultrahigh-dispersion Co3S4Nanoparticle porous carbon and carbon nanotube sponge hybrids.
The method can be realized by upper and lower limit values and interval values of intervals of process parameters (such as temperature, time and the like), and embodiments are not listed.
Conventional technical knowledge in the art can be used for the details which are not described in the present invention.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (9)

1. Ultra-high dispersion Co-containing3S4Nanoparticle porous carbon and carbon nanotube sponge hybrid characterized in that carbon nanotubes pass through porous carbon, Co3S4The nanoparticles are uniformly dispersed in the porous carbon.
2. The ultra-high dispersion Co-containing alloy of claim 13S4A method for preparing a nanoparticle porous carbon and carbon nanotube sponge hybrid, the method comprising the steps of:
1) carbonizing and vulcanizing the hybrid of the carbon nano tube sponge and the ZIF-67 nano particle to obtain the hybrid containing the ultra-high dispersion Co3S4Nanoparticle porous carbon and carbon nanotube sponge hybrids.
3. The method of claim 2, wherein the functionalization is a treatment with high temperature acidification.
4. The preparation method according to claim 3, wherein the high-temperature acidification temperature is 80-120 ℃ and the reaction time is 12-24 h.
5. The method according to claim 2, wherein the ZIF-67 precursor mixed solution is prepared by mixing an aqueous solution of cobalt nitrate hexahydrate and ammonium cetylbromide with an ethanol solution of 2-methylimidazole.
6. The method according to claim 2, wherein in the step 3), the carbonization is performed under an inert gas atmosphere.
7. The method as claimed in claim 2, wherein the carbonization temperature in step 3) is 550-650 ℃, the carbonization time is 0-5min, and the heating rate for heating to the carbonization temperature is 5-10 ℃/min.
8. The method according to claim 2, wherein in step 3), the vulcanization is performed using a thiourea solution.
9. The ultra-high dispersion Co-containing alloy of claim 13S4Application of nanoparticle porous carbon and carbon nanotube sponge hybrid in lithium-sulfur battery.
CN201910011168.5A 2019-01-07 2019-01-07 Ultra-high dispersion Co-containing3S4Nanoparticle porous carbon and carbon nanotube sponge hybrid and preparation method and application thereof Pending CN111416119A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910011168.5A CN111416119A (en) 2019-01-07 2019-01-07 Ultra-high dispersion Co-containing3S4Nanoparticle porous carbon and carbon nanotube sponge hybrid and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910011168.5A CN111416119A (en) 2019-01-07 2019-01-07 Ultra-high dispersion Co-containing3S4Nanoparticle porous carbon and carbon nanotube sponge hybrid and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN111416119A true CN111416119A (en) 2020-07-14

Family

ID=71494035

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910011168.5A Pending CN111416119A (en) 2019-01-07 2019-01-07 Ultra-high dispersion Co-containing3S4Nanoparticle porous carbon and carbon nanotube sponge hybrid and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN111416119A (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103456929A (en) * 2013-09-04 2013-12-18 中南大学 Anode material of lithium-sulfur battery and preparation method thereof
CN106450200A (en) * 2016-10-25 2017-02-22 福建师范大学 Cos@carbon nano-cage as well as preparation method and application thereof
CN108336308A (en) * 2017-01-20 2018-07-27 华为技术有限公司 A kind of lithium-sulphur cell positive electrode protection materials and its application
CN108878854A (en) * 2018-07-20 2018-11-23 西南科技大学 The hollow micro-structure Co of negative electrode of lithium ion battery is made of MOF template3S4@C@MoS2Preparation method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103456929A (en) * 2013-09-04 2013-12-18 中南大学 Anode material of lithium-sulfur battery and preparation method thereof
CN106450200A (en) * 2016-10-25 2017-02-22 福建师范大学 Cos@carbon nano-cage as well as preparation method and application thereof
CN108336308A (en) * 2017-01-20 2018-07-27 华为技术有限公司 A kind of lithium-sulphur cell positive electrode protection materials and its application
CN108878854A (en) * 2018-07-20 2018-11-23 西南科技大学 The hollow micro-structure Co of negative electrode of lithium ion battery is made of MOF template3S4@C@MoS2Preparation method

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
HUI ZHANG等: "3D，Mutually Embedded MOF@Carbon Nanotube Hybrid Networks for High-Performance Lithium-Sulfur Batteries", 《ADV. ENERGY MATER.》 *
JUN PU等: "Multifunctional Co3S4@sulfur nanotubes for enhanced lithium-sulfur battery performance", 《NANO ENERGY》 *
SHIQIANG LUO等: "A 3D conductive network of porous carbon nanoparticles interconnected with carbon nanotubes as the sulfur host for long cycle life lithium-sulfur batteries", 《NANOSCALE》 *

Similar Documents

Publication Publication Date Title
CN109755482B (en) Silicon/carbon composite material and preparation method thereof
CN101420023B (en) Electrochemical lithium ionic insertion/deinsertion electrode and production method thereof
CN108336308A (en) A kind of lithium-sulphur cell positive electrode protection materials and its application
CN110683522B (en) Transition metal chalcogen family carbon-based heterostructure composite material with regular morphology and preparation method and application thereof
CN108987729B (en) Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery
Wei et al. Self-assembled ZnO-carbon dots anode materials for high performance nickel-zinc alkaline batteries
CN111146424B (en) Metal sulfide/carbon composite material, and preparation method and application thereof
CN109473651B (en) Synthesis of bimetallic sulfide Co by ZIF-67 derivatization8FeS8Method for preparing/N-C polyhedral nano material
CN112928260B (en) Molybdenum disulfide/iron sulfide/nitrogen-doped carbon composite material and preparation and application thereof
CN110880589B (en) Carbon nanotube @ titanium dioxide nanocrystal @ carbon composite material and preparation method and application thereof
CN110660981B (en) Graphene-coated bimetallic selenide material and preparation method and application thereof
Duan et al. MOF-71 derived layered Co-CoP/C for advanced Li-S batteries
CN113871598B (en) MOF composite material and preparation method and application thereof
CN108987733B (en) Preparation method of active porous carbon @ FeS of lithium ion battery cathode material
CN108767203B (en) Titanium dioxide nanotube-graphene-sulfur composite material and preparation method and application thereof
CN113629245A (en) Novel compounding method of carbon material and transition metal compound, composite material and application
CN110739429A (en) Preparation method of functional interlayer of lithium-sulfur battery
CN110581264A (en) High-performance nickel-zinc battery negative electrode active material and preparation method thereof
CN109285998B (en) Silicon/silicon iron oxide/ferric oxide/carbon core-shell composite structure material and preparation method thereof
Ren et al. Effect of zinc-based active sites on porous carbon and electrochemical properties in lithium-sulfur batteries
CN110729478B (en) Antimony trisulfide nano-dot/sulfur-doped carbon composite material, preparation method thereof and application thereof in sodium/potassium ion battery
CN109473634A (en) Solid phase heat together synthesizes two selenizing molybdenums/N doping carbon-point method
CN111952569B (en) Silicon oxide-based negative electrode material for lithium ion battery and preparation method thereof
CN106299287B (en) A kind of carbonization silkworm excrement/MILs composite sulfur positive electrodes and preparation method thereof
CN111416119A (en) Ultra-high dispersion Co-containing3S4Nanoparticle porous carbon and carbon nanotube sponge hybrid and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20200714