CN108039460B - Three-dimensional dendritic nitrogen-doped graphene nanotube and preparation method thereof - Google Patents
Three-dimensional dendritic nitrogen-doped graphene nanotube and preparation method thereof Download PDFInfo
- Publication number
- CN108039460B CN108039460B CN201711170934.XA CN201711170934A CN108039460B CN 108039460 B CN108039460 B CN 108039460B CN 201711170934 A CN201711170934 A CN 201711170934A CN 108039460 B CN108039460 B CN 108039460B
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- heating
- doped graphene
- nanotube
- dimensional
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a three-dimensional dendritic nitrogen-doped graphene nanotube and a preparation method thereof, and the graphene nanotube is prepared by a template method. The invention uses one-dimensional nickel nano-rods as templates to prepare graphene nanotubes, and uses a cyanate decomposition method to grow nitrogen-doped graphene nanotubes on the surface, and the application of the nitrogen-doped graphene nanotubes as a positive electrode material in a lithium-sulfur battery. The three-dimensional dendritic nitrogen-doped graphene nanotube prepared by the invention utilizes the graphene nanotube with excellent conductivity to enhance the conductivity of sulfur, and simultaneously reserves space for volume expansion of sulfur, thereby preventing cracking caused by internal stress; the nitrogen element doped on the outer layer dendritic carbon nano tube can effectively adsorb lithium polysulfide and prevent the lithium polysulfide from dissolving and diffusing, and the charge-discharge efficiency and the capacity cycling stability of the anode are improved through comprehensive action.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to the field of lithium-sulfur batteries, and particularly relates to a preparation method of a three-dimensional dendritic nitrogen-doped graphene nanotube and application of the three-dimensional dendritic nitrogen-doped graphene nanotube in a positive electrode material of a lithium-sulfur battery.
Background
With the development of modern society, the requirements of people on clean and renewable energy sources are more and more urgent. As a common secondary battery, the specific capacity of the lithium ion battery is increasingly unable to meet the requirements of people for power storage, especially for the endurance support of mobile intelligent electronic devices and electric vehicles. People are forced to choose between frequent charging frequency or larger battery weight, which seriously reduces the use experience of consumers and also becomes important limitation for restricting the mobile intelligent device. Therefore, the development of next-generation secondary batteries having a large capacity and stable performance is more and more urgent.
Compared with the traditional lithium ion battery, the lithium sulfur battery is a new generation secondary battery, the specific capacity of the lithium sulfur battery is about ten times of that of the lithium ion battery, and the lithium sulfur battery is a very competitive secondary battery. In addition, compared with lithium cobaltate and lithium iron phosphate cathode materials used in the traditional lithium ion battery, the sulfur element used by the lithium sulfur battery is more abundant in earth crust storage, low in price and free of heavy metal pollution, and is considered as a battery cathode material with great development potential.
But three drawbacks of sulfur itself restrict its application to positive electrode materials. First, sulfur itself is an insulator, so electrons are difficult to transmit to the surface of sulfur to generate electrochemical reaction, so that the electrode polarization is severe and the reaction efficiency of the electrode is extremely low. Secondly, the sulfur forms lithium sulfide during charging, which has a density less than that of sulfur, causing the electrode to expand in volume, up to 80% volumetric expansion. Repeated volume scaling during charging and discharging can cause micro-cracks to occur in the electrode material, and finally the material is collapsed, so that the cycle capacity is reduced. Finally, the lithium polysulfide, an intermediate product of the reaction between sulfur and lithium, is easily dissolved in the organic electrolyte, and shuttles back and forth between the positive electrode and the negative electrode along with the electrolyte in the charging and discharging processes, namely, the shuttle effect. This ultimately leads to a continuous decrease in the positive electrode active material and a continuous decrease in the charge-discharge efficiency of the battery.
To address these three drawbacks, researchers have employed a number of methods to improve the performance of sulfur electrodes. Firstly, people prepare sulfur into particles or even nano-particles to reduce internal stress caused by volume expansion and avoid collapse failure of electrode materials; secondly, the sulfur-carbon composite material is combined with a material with higher conductivity to improve the conductivity of sulfur and accelerate the electrochemical reaction rate of sulfur, for example, the sulfur and carbon particles are mixed to form a sulfur-carbon composite material; thirdly, polysulfide adsorbent is added into the sulfur anode material or the electrode structure is changed to inhibit the dissolution of polysulfide, for example, nitrogen-doped graphene is added to adsorb polysulfide, or carbon is prepared into a hollow microsphere carbon shell to wrap sulfur in the shell to inhibit the precipitation of polysulfide.
Disclosure of Invention
The invention aims to solve the problem that the shuttle effect of the sulfur anode material of the lithium ion battery is easy to generate, so that the cycle performance of the battery is unstable.
The invention provides a preparation method of a three-dimensional dendritic nitrogen-doped graphene nanotube, which comprises the following steps:
A. preparing one-dimensional nickel nano-rods from soluble nickel salt, a water-soluble high polymer soft template and hydrazine hydrate by a hydrothermal method,
B. preparing the graphene nano-tube coated with the one-dimensional nickel nano-rod by a chemical vapor deposition method,
C. then soaking the graphene nano tube in an inorganic salt precursor solution to obtain the graphene nano tube wrapped with the inorganic salt precursor coating,
D. heating the graphene nano tube with the coating obtained in the step C to promote the decomposition of the inorganic salt precursor coating, growing a nitrogen-doped carbon nano tube outside the graphene nano tube to obtain a dendritic nitrogen-doped graphene nano tube,
E. and finally, compounding the solution dissolved with sulfur and the dendritic nitrogen-doped graphene nanotube by using a melting method to obtain the three-dimensional dendritic nitrogen-doped graphene nanotube.
In the technical scheme of the invention, the method in the step A specifically comprises the following steps:
a-1, dissolving a water-soluble high polymer soft template in hydrazine hydrate, performing ultrasonic oscillation, and simultaneously heating and keeping the temperature constant;
a-2, preparing a soluble nickel salt solution, dropwise adding the soluble nickel salt solution into the solution of A-1, and continuing ultrasonic oscillation for 30 minutes after dropwise adding;
and A-3, taking out the reactant in the A-2, centrifuging, washing the obtained solid with ethanol and distilled water for several times, and drying to obtain the one-dimensional nickel nanorod.
Preferably, the soluble nickel salt is selected from nickel sulfate and nickel nitrate, and the concentration of the soluble nickel salt (calculated by the concentration of nickel ions) is 0.1-3 mol/L;
the water-soluble high polymer soft template is polyvinylpyrrolidone (PVP), the concentration of the water-soluble high polymer soft template is 0.5-5g/mL, the concentration of hydrazine hydrate is 10-50% (mass fraction), and the heating temperature in the A-1 is 50-120 ℃.
In the technical scheme of the invention, the method in the step B specifically comprises the following steps:
b-1, placing the one-dimensional nickel nano rod in a mixed gas flow of argon and hydrogen, heating to a certain temperature, keeping the temperature,
b-2, then introducing methane gas for a period of time, then closing the introduction of the methane gas, stopping heating, cooling the solid to room temperature,
and B-3, adding dilute hydrochloric acid into the solid, heating, fully reacting, centrifuging, washing the obtained solid with ethanol and distilled water in sequence, and finally drying to obtain the graphene nanotube.
In the method of the step B, in the step B-1, the flow ratio of the hydrogen to the argon is 1:1-1:10, and the certain temperature is 750-; the constant temperature time is 1-30 minutes;
in the step B-2, the gas flow ratio of the introduced methane gas to the argon gas is 1:100-1:600, and the introduction time is 1-30 minutes;
the concentration of the dilute hydrochloric acid added in the B-3 is 0.5-5 mol/L.
In the technical scheme of the invention, the inorganic salt precursor in the step C comprises but is not limited to potassium ferrocyanide and sodium ferrocyanide, and the concentration of the inorganic salt precursor solution is 0.5-10 g/L.
In the technical scheme of the invention, in the step D, heating and dehydrating for a period of time under the nitrogen atmosphere, wherein the heating and dehydrating temperature is 100-200 ℃, and the dehydrating time is 6-36 hours;
the growth temperature of the nitrogen-doped graphene nanotube is 700-1200 ℃, and the growth time is 3-24 hours.
In the technical scheme, step E is that the three-dimensional dendritic nitrogen-doped graphene nanotube is dispersed in a sulfur carbon disulfide solution, and then the carbon disulfide is completely evaporated by stirring and heating to obtain a solid; then heating the solid in a nitrogen atmosphere to obtain a composite positive electrode material for the lithium-sulfur battery; wherein the concentration of the carbon disulfide solution of sulfur is 0.1-2 g/mL; the heating temperature is 100-200 ℃ under the nitrogen atmosphere, and the heating time is 2-24 h.
The invention also provides a three-dimensional dendritic nitrogen-doped graphene nanotube positive electrode material which has high specific capacity and good cycle performance and can be used for the lithium-sulfur battery.
In the technical scheme of the invention, the diameter of the main body of the graphene nanotube is 20-200nm, the length of the main body of the graphene nanotube is 50-500nm, and the wall thickness of the main body of the graphene nanotube is 1-10 carbon atom layers.
In the technical scheme of the invention, the diameter of the nitrogen-doped carbon nanotube branch is 20-100nm, the length is 5-800nm, and the wall thickness is 5-100 nm.
A third aspect of the present invention provides a lithium sulfur battery comprising: the battery comprises a battery positive and negative electrode shell, a diaphragm, electrolyte, an elastic sheet, a steel sheet, positive and negative electrode current collectors and positive and negative electrode materials, wherein the positive electrode material is the positive electrode material.
The three-dimensional dendritic nitrogen-doped graphene nanotube anode material of the lithium-sulfur battery is prepared by compounding a sulfur simple substance by taking the graphene nanotube as a trunk and the nitrogen-doped graphene nanotube as a branch. The hollow structure of the graphene nanotube can effectively relieve the volume expansion of sulfur in the discharge process and improve the conductivity of sulfur; the nitrogen-doped graphene nanotube can effectively adsorb polysulfide and prevent the shuttle effect from occurring, so that the cycle performance of the lithium-sulfur battery is remarkably improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings, there is shown in the drawings,
FIG. 1 is a schematic diagram of the overall structure of a three-dimensional dendritic nitrogen-doped graphene nanotube according to the present invention;
fig. 2 is one of the flow charts of the preparation of the three-dimensional dendritic nitrogen-doped graphene nanotube according to the present invention.
In the figure, 1 is a graphene nanotube, 2 is a nitrogen-doped graphene nanotube, 3 is sulfur, 4 is a nickel nanorod, and 5 is an inorganic salt precursor coating.
Detailed Description
The following describes embodiments of the present invention with reference to the drawings.
Example 1
The invention provides a preparation method of the anode active material, which comprises the following specific steps:
(1) dissolving 1-50g of water-soluble high polymer soft template in 10-50% (mass fraction) of hydrazine hydrate, performing ultrasonic oscillation, simultaneously heating to 90-120 ℃, and keeping the temperature;
(2) preparing a soluble nickel salt solution with the concentration of 0.1-3mol/L (by nickel ion concentration), dropwise adding the mixed solution in the step (1), and continuing constant-temperature ultrasonic oscillation for 30 minutes after dropwise adding is finished;
(3) and (3) taking out the reactant in the step (2), centrifuging, washing the obtained solid for 3-5 times by using ethanol and distilled water in sequence, and drying to obtain the one-dimensional nickel nanorod.
(4) Placing the one-dimensional nickel nano rod under mixed gas flow with the gas flow ratio of hydrogen to argon being 1:1-1:10, and heating to 750-;
(5) after the high temperature in the step (4) is reached, keeping the temperature for 1-30 minutes, then introducing methane gas, wherein the gas flow ratio of the methane gas to the hydrogen gas is 1:100-1:600, and the introduction time is 1-30 minutes;
(6) the methane gas was turned off while the heating was stopped. Cooling the solid obtained in the step (2) to room temperature, taking out, adding dilute hydrochloric acid with the concentration of 0.5-5mol/L, heating, centrifuging the solution after full reaction, washing the obtained solid with ethanol and distilled water for 3-5 times, and drying to obtain a graphene nanotube;
(7) soaking the graphene nano tube in a solution of an inorganic salt precursor with the concentration of 0.5-10g/L, and then filtering and drying the solution to deposit a layer of inorganic salt precursor outside the graphene nano tube;
(8) heating the product obtained in the step (7) to 100-200 ℃ in a nitrogen atmosphere for dehydration for 6-36 hours, then heating to 700-1200 ℃ and keeping the temperature for 3-24 hours, so that the inorganic salt precursor coating is decomposed and the nitrogen-doped graphene nanotube is grown, and the three-dimensional dendritic nitrogen-doped graphene nanotube is obtained;
(9) dispersing the three-dimensional dendritic nitrogen-doped graphene nanotube obtained in the step (7) in a carbon disulfide solution of sulfur with the concentration of 0.5-2g/mL, and then stirring while heating to evaporate carbon disulfide;
(10) and (3) heating the solid obtained in the step (2) to 100-200 ℃ in a nitrogen atmosphere to obtain the composite positive active material for the lithium-sulfur battery.
Example 2
(1) Dissolving 1g of water-soluble high polymer soft template in 40 percent (mass fraction) of hydrazine hydrate, carrying out ultrasonic oscillation, simultaneously heating to 95 ℃, and keeping the temperature;
(2) 25mL of soluble nickel salt solution with the concentration of 0.8mol/L (by nickel ion concentration) is prepared, the mixed solution in the step (1) is dripped, and constant-temperature ultrasonic oscillation is continued for 30 minutes after the dripping is finished;
(3) and (3) taking out the reactant in the step (2), centrifuging, washing the obtained solid for 3 times by using ethanol and distilled water in sequence, and drying to obtain the one-dimensional nickel nanorod.
(4) Placing the one-dimensional nickel nano rod under mixed gas flow with the gas flow ratio of hydrogen to argon being 1:4, and heating to 950 ℃;
(5) after the high temperature in the step (4) is reached, keeping the temperature for 10 minutes, then introducing methane gas, wherein the gas flow ratio of the methane gas to the hydrogen gas is 1:500, and the introduction time is 10 minutes;
(6) the methane gas was turned off while the heating was stopped. And (3) cooling the solid obtained in the step (2) to room temperature, taking out, adding 1mol/L diluted hydrochloric acid, heating, fully reacting, centrifuging the solution, washing the obtained solid with ethanol and distilled water for 3 times, and drying to obtain the graphene nanotube.
(7) And soaking the graphene nanotube in a solution of an inorganic salt precursor with the concentration of 3g/L, and filtering and drying the solution to deposit a layer of the inorganic salt precursor outside the graphene nanotube.
(8) And (3) heating the product obtained in the step (7) to 120 ℃ in a nitrogen atmosphere for 12 hours of dehydration, then heating to 850 ℃ and keeping the temperature constant for 20 hours, so that the inorganic salt precursor coating is decomposed and the nitrogen-doped graphene nanotube is grown, and the three-dimensional dendritic nitrogen-doped graphene nanotube is obtained.
(9) Dispersing the three-dimensional dendritic nitrogen-doped graphene nanotube obtained in the step (7) in 5mL of sulfur carbon disulfide solution with the concentration of 0.2g/mL, and then stirring and heating to evaporate carbon disulfide;
(10) and (3) heating the solid obtained in the step (2) to 140 ℃ in a nitrogen atmosphere to obtain the composite positive electrode active material for the lithium-sulfur battery.
Example 2
(1) Dissolving 0.5g of water-soluble high polymer soft template in 50 percent (mass fraction) of hydrazine hydrate, carrying out ultrasonic oscillation, simultaneously heating to 90 ℃, and keeping the temperature;
(2) 25mL of soluble nickel salt solution with the concentration of 0.5mol/L (by nickel ion concentration) is prepared, the mixed solution in the step (1) is dripped, and constant-temperature ultrasonic oscillation is continued for 30 minutes after the dripping is finished;
(3) taking out the reactant in the step (2), centrifuging, washing the obtained solid with ethanol and distilled water for 3 times, and drying to obtain the one-dimensional nickel nanorod;
(4) placing the one-dimensional nickel nano rod under mixed gas flow with the gas flow ratio of hydrogen to argon being 1:4, and heating to 950 ℃;
(5) after the high temperature in the step (4) is reached, keeping the temperature for 10 minutes, then introducing methane gas, wherein the gas flow ratio of the methane gas to the hydrogen gas is 1:500, and the introduction time is 6 minutes;
(6) the methane gas was turned off while the heating was stopped. Cooling the solid obtained in the step (2) to room temperature, taking out, adding 1mol/L diluted hydrochloric acid, heating, fully reacting, centrifuging the solution, washing the obtained solid with ethanol and distilled water for 4 times, and drying to obtain the graphene nanotube;
(7) soaking the graphene nano tube in a solution of an inorganic salt precursor with the concentration of 4g/L, and filtering and drying the solution to deposit a layer of inorganic salt precursor outside the graphene nano tube;
(8) heating the product obtained in the step (7) to 150 ℃ in a nitrogen atmosphere for dehydration for 18 hours, then heating to 900 ℃ and keeping the temperature constant for 16 hours, so that the inorganic salt precursor coating is decomposed and a nitrogen-doped graphene nanotube is grown, and the three-dimensional dendritic nitrogen-doped graphene nanotube is obtained;
(9) dispersing the three-dimensional dendritic nitrogen-doped graphene nanotube obtained in the step (7) in 4mL of sulfur carbon disulfide solution with the concentration of 0.3g/mL, and then stirring and heating to evaporate carbon disulfide;
(10) and (3) heating the solid obtained in the step (2) to 160 ℃ in a nitrogen atmosphere to obtain the composite positive electrode active material for the lithium-sulfur battery.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited by the foregoing examples, which are provided to illustrate the principles of the invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention, which is also intended to be covered by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. A preparation method of a three-dimensional dendritic nitrogen-doped graphene nanotube comprises the following steps:
A. preparing one-dimensional nickel nano-rods from soluble nickel salt, a water-soluble high polymer soft template and hydrazine hydrate by a hydrothermal method,
the step A is as follows:
a-1, dissolving a water-soluble high polymer soft template in hydrazine hydrate, performing ultrasonic oscillation, and simultaneously heating and keeping the temperature constant;
a-2, preparing a soluble nickel salt solution, dropwise adding the soluble nickel salt solution into the solution of A-1, and continuing ultrasonic oscillation for 30 minutes after dropwise adding;
a-3, taking out the reactant in the A-2, centrifuging, washing the obtained solid with ethanol and distilled water successively for several times, and drying to obtain the one-dimensional nickel nanorod;
B. preparing the graphene nano-tube coated with the one-dimensional nickel nano-rod by a chemical vapor deposition method,
the step B is as follows:
b-1, placing the one-dimensional nickel nano rod in a mixed gas flow of argon and hydrogen, heating to 750-,
b-2, then introducing methane gas for a period of time, then closing the introduction of the methane gas, stopping heating, cooling the solid to room temperature,
b-3, adding dilute hydrochloric acid into the solid, heating, fully reacting, centrifuging, and sequentially using ethanol and ethanol to obtain the solid
Washing with distilled water, and finally drying to obtain the graphene nanotube;
C. then soaking the graphene nanotube in an inorganic salt precursor solution to obtain the graphene nanotube wrapped with an inorganic salt precursor coating, wherein the inorganic salt precursor is selected from potassium ferrocyanide and sodium ferrocyanide;
D. heating the graphene nano tube with the coating obtained in the step C to promote the decomposition of the inorganic salt precursor coating, growing a nitrogen-doped carbon nano tube outside the graphene nano tube to obtain a dendritic nitrogen-doped graphene nano tube,
E. and finally, compounding the solution dissolved with sulfur and the dendritic nitrogen-doped graphene nanotube by using a melting method to obtain the three-dimensional dendritic nitrogen-doped graphene nanotube.
2. The method of claim 1, wherein the soluble nickel salt is selected from the group consisting of nickel sulfate, nickel nitrate; the water-soluble high polymer soft template is polyvinylpyrrolidone, and the heating temperature in the step A-1 is 50-120 ℃.
3. The method according to claim 1, wherein in the step B-1, the flow ratio of hydrogen to argon is 1:1 to 1:10, and the constant temperature is maintained for 1 to 30 minutes;
in the step B-2, the ratio of the introduced methane gas to the argon gas is 1:100-1:600, and the introduction time is 1-30 minutes.
4. The method as claimed in claim 1, wherein in the step D, the dehydration is performed by heating under nitrogen atmosphere at 100-200 ℃ for 6-36 hours;
the growth temperature of the nitrogen-doped graphene nanotube is 700-.
5. The preparation method according to claim 1, wherein the step E is that the three-dimensional dendritic nitrogen-doped graphene nanotubes are dispersed in a sulfur carbon disulfide solution, and then the carbon disulfide is completely evaporated by stirring and heating to obtain a solid; then heating the solid in a nitrogen atmosphere to obtain a composite positive electrode material for the lithium-sulfur battery; wherein the heating temperature is 100-200 ℃ under the nitrogen atmosphere.
6. The three-dimensional dendritic nitrogen-doped graphene nanotube prepared by the preparation method according to any one of claims 1 to 5.
7. A lithium sulfur battery, comprising: the positive and negative electrode shells of the battery, the diaphragm, the electrolyte, the elastic sheet, the steel sheet, the positive and negative electrode current collectors and the positive and negative electrode materials, wherein the positive electrode material is the three-dimensional dendritic nitrogen-doped graphene nanotube prepared by the method of any one of claims 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711170934.XA CN108039460B (en) | 2017-11-22 | 2017-11-22 | Three-dimensional dendritic nitrogen-doped graphene nanotube and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711170934.XA CN108039460B (en) | 2017-11-22 | 2017-11-22 | Three-dimensional dendritic nitrogen-doped graphene nanotube and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108039460A CN108039460A (en) | 2018-05-15 |
| CN108039460B true CN108039460B (en) | 2020-10-23 |
Family
ID=62093282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711170934.XA Active CN108039460B (en) | 2017-11-22 | 2017-11-22 | Three-dimensional dendritic nitrogen-doped graphene nanotube and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108039460B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734079B (en) * | 2019-03-12 | 2022-05-24 | 湖南医家智烯新材料科技有限公司 | Dendritic graphene and preparation method thereof |
| CN114538433B (en) * | 2022-02-25 | 2023-11-10 | 中南大学 | Method for preparing quick graphite filling with single metal doping defect |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1590291A (en) * | 2003-09-01 | 2005-03-09 | 三星Sdi株式会社 | Carbon-nano tube structure, method of manufacturing the same, and field emitter and display device each adopting the same |
| CN104841924A (en) * | 2014-02-19 | 2015-08-19 | 中国科学院大连化学物理研究所 | Preparation method of carbon entirely-packaged metal nanoparticles |
| CN106163980A (en) * | 2013-11-05 | 2016-11-23 | 加利福尼亚大学董事会 | Mixing CNT and graphene nano structure |
| CN106399874A (en) * | 2016-08-31 | 2017-02-15 | 宁波新睦新材料有限公司 | Preparing method of high-performance iron-based composite material |
| CN106653390A (en) * | 2016-12-22 | 2017-05-10 | 温州大学 | Nitrogen and phosphorus co-doped composite material, preparation method and application and capacitor electrode |
-
2017
- 2017-11-22 CN CN201711170934.XA patent/CN108039460B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1590291A (en) * | 2003-09-01 | 2005-03-09 | 三星Sdi株式会社 | Carbon-nano tube structure, method of manufacturing the same, and field emitter and display device each adopting the same |
| CN106163980A (en) * | 2013-11-05 | 2016-11-23 | 加利福尼亚大学董事会 | Mixing CNT and graphene nano structure |
| CN104841924A (en) * | 2014-02-19 | 2015-08-19 | 中国科学院大连化学物理研究所 | Preparation method of carbon entirely-packaged metal nanoparticles |
| CN106399874A (en) * | 2016-08-31 | 2017-02-15 | 宁波新睦新材料有限公司 | Preparing method of high-performance iron-based composite material |
| CN106653390A (en) * | 2016-12-22 | 2017-05-10 | 温州大学 | Nitrogen and phosphorus co-doped composite material, preparation method and application and capacitor electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108039460A (en) | 2018-05-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Constructing ultra-thin Ni-MOF@ NiS2 nanosheets arrays derived from metal organic frameworks for advanced all-solid-state asymmetric supercapacitor | |
| Zhang et al. | Recent progress in self‐supported metal oxide nanoarray electrodes for advanced lithium‐ion batteries | |
| Guang et al. | Three-dimensional P-doped carbon skeleton with built-in Ni2P nanospheres as efficient polysulfides barrier for high-performance lithium-sulfur batteries | |
| Wu et al. | Sb@ C/expanded graphite as high-performance anode material for lithium ion batteries | |
| Wang et al. | One-step fabrication of in situ carbon-coated NiCo2O4@ C bilayered hybrid nanostructural arrays as free-standing anode for high-performance lithium-ion batteries | |
| Li et al. | Flexible self-supporting Ni2P@ N-doped carbon anode for superior rate and durable sodium-ion storage | |
| CN111302402A (en) | Hydroxyl ferric oxide/two-dimensional carbide crystal MXene negative electrode material and preparation method and application thereof | |
| Zhuang et al. | Scalable synthesis of nano-Si embedded in porous C and its enhanced performance as anode of Li-ion batteries | |
| CN110957490A (en) | Preparation method of carbon-coated sodium iron phosphate electrode material with hollow structure | |
| CN110993362A (en) | Novel three-dimensional electrode material, preparation method thereof and application thereof in super capacitor | |
| CN111354929A (en) | Preparation of carbon fiber-tin disulfide electrode material with multilayer core-shell structure | |
| CN112216828A (en) | Carbon nanotube/MOF silicon carbon composite material and preparation method and application thereof | |
| Xiang et al. | Design and synthesis of Cr2O3@ C@ G composites with yolk-shell structure for Li+ storage | |
| Ma et al. | To achieve controlled specific capacities of silicon-based anodes for high-performance lithium-ion batteries | |
| CN105070923A (en) | Co3O4/Ru composite electrode with nano structure and preparation method and application of Co3O4/Ru composite electrode | |
| Li et al. | Construction of a novel three-dimensional porous lead-carbon network for improving the reversibility of deep discharge lead-carbon batteries | |
| CN108039460B (en) | Three-dimensional dendritic nitrogen-doped graphene nanotube and preparation method thereof | |
| Bekhit et al. | Nickel selenide nanorod arrays as an electrode material for lithium-ion batteries and supercapacitors | |
| Chen et al. | Nickel-decorated TiO 2 nanotube arrays as a self-supporting cathode for lithium-sulfur batteries | |
| CN112366298B (en) | Carbon-assembled zinc sulfide cobalt sulfide hollow nano polyhedral framework material and preparation and application thereof | |
| CN113809286B (en) | Metal Organic Framework (MOF) catalyzed growth carbon nanotube coated nickel-tin alloy electrode material and preparation method and application thereof | |
| CN106024403A (en) | Supercapacitor carbon pipe/molybdenum carbide combination electrode material and preparation method thereof | |
| Du et al. | Anchoring 1T/2H MoS 2 nanosheets on carbon nanofibers containing Si nanoparticles as a flexible anode for lithium–ion batteries | |
| CN110474023B (en) | Fibrous nickel-bismuth battery and preparation method thereof | |
| CN109817954A (en) | A kind of 3-D ordered multiporous carbon embeds the preparation method of oxide material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |