CN108831757B - A kind of preparation method of N and S codope graphene/carbon nano-tube aeroge - Google Patents
A kind of preparation method of N and S codope graphene/carbon nano-tube aeroge Download PDFInfo
- Publication number
- CN108831757B CN108831757B CN201810841339.2A CN201810841339A CN108831757B CN 108831757 B CN108831757 B CN 108831757B CN 201810841339 A CN201810841339 A CN 201810841339A CN 108831757 B CN108831757 B CN 108831757B
- Authority
- CN
- China
- Prior art keywords
- carbon nano
- graphene
- preparation
- added
- tube
- 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
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a kind of preparation methods of N and S codope graphene/carbon nano-tube aeroge, belong to electrode material preparation technical field.After first mixing carboxylic acid carbon nano tube and graphene oxide, deionized water is added, obtains mixed liquor after ultrasound is uniform；Pyrroles and thiophene are added into mixed liquor, carries out a hydro-thermal reaction, obtains hydrogel；Obtained hydrogel is put into the KNO of 2M3In solution, secondary hydro-thermal reaction is carried out, after being cooled to room temperature, using filter, washing and freeze-drying；Products therefrom thermal cracking in argon atmosphere after being freeze-dried, is made N the and S codope graphene/carbon nano-tube aeroge.Present invention N and S in graphene aerogel, wherein the codope of N and S can further enhance the reactivity and electric conductivity of carbon material, compared to single N or S dopant material, by introducing more active sites, to improve its chemical property, it is expected in the electrode material applied to supercapacitor.
Description
Technical field
The invention belongs to electrode material preparation technical fields, and in particular to a kind of N and S codope graphene/carbon nano-tube
The preparation method of aeroge.
Background technique
In all carbon materials, as carbon nanotube, nanofiber, porous carbon, hollow nano-sphere, carbon paste capsule, graphene are received
Rice piece, graphene nanobelt and its composite material, graphene are better than other carbon materials due to its outstanding electronics and mechanical performance
Material.Although graphene has been achieved for sizable progress in supercapacitor, performance is still barely satisfactory.This is because
Strong Van der Waals force and the interaction of π-π lamination between graphene layer form graphite-like structure so that they are easy aggregation, thus
The loss for leading to effective ratio area reduces its specific capacitance.Therefore, in order to make full use of the chemical property of graphene, it is necessary to
Effectively inhibit it from stack-up issue.
Graphene aerogel represents a kind of novel globality carbonaceous material, flourishing hole, ultralow density with
And excellent conductive characteristic imparts the graphene aerogel application wide in fields such as the energy, environmental protection and catalysis
Prospect is research hotspot in recent years.
Summary of the invention
It is an object of the invention in view of the shortcomings of the prior art, providing a kind of N and S codope graphene/carbon nano-tube gas
The preparation method of gel.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of preparation method of N and S codope graphene/carbon nano-tube aeroge, specifically includes the following steps:
(1) preparation of carboxylic acid carbon nano tube；
(2) preparation of graphene oxide；
(3) it after mixing graphene oxide made from carboxylic acid carbon nano tube made from step (1) and step (2), is added
Deionized water obtains the mixed liquor that concentration is 2mg/mL after ultrasound is uniform；
(4) pyrroles and thiophene are added into the mixed liquor that step (3) obtains, carries out a hydro-thermal reaction, reaction temperature is
160 ~ 180 DEG C, the reaction time is 4 ~ 6h, obtains hydrogel；
(5) hydrogel that step (4) obtains is put into the KNO of 2M3In solution, secondary hydro-thermal reaction, reaction temperature are carried out
It is 120 ~ 140 DEG C, the reaction time is 2 ~ 3h, after being cooled to room temperature, using filter, washing and freeze-drying；
(6) by products therefrom thermal cracking 2h at 1050 ~ 1100 DEG C in argon atmosphere after step (5) freeze-drying, system
Obtain N the and S codope graphene/carbon nano-tube aeroge.
Carboxylic acid carbon nano tube described in step (1) the preparation method comprises the following steps: by 1 g multi-walled carbon nanotube (MWCNTs) plus
Enter to the dense HNO of 80 mL3In, 12 h then are condensed back in 120 DEG C of oil bath pans, gained black mixture is washed into pumping repeatedly
Filter to pH=7 take filter residue.
Graphene oxide described in step (2) the preparation method comprises the following steps: graphite is uniformly mixed with the concentrated sulfuric acid/concentrated phosphoric acid system
Afterwards, it is slowly added to potassium permanganate, after uniform stirring 0.5h, in 50 DEG C of stirred in water bath 12h, is slowly added to deionized water, and protect
Temperature is held lower than 100 DEG C, the hydrogen peroxide of 5wt% is added dropwise, when mixed liquor becomes golden yellow, salt acid elution, reaction 5 is added
After minute, it is washed with deionized to neutrality, and use BaCl2Detect the presence of SO4 2-Residual, then oxidation is made in freeze-drying for 24 hours
Powdered graphite；Graphite oxide powder obtained is add to deionized water, ultrasonic 1h, then under the revolving speed of 2000r/min
Be centrifuged 10min, remove lower sediment thing, take upper liquid, after upper liquid is freezed 12h at 0 DEG C, be placed in freeze drier into
Row freeze-drying 36h, obtains the graphene oxide.
In the concentrated sulfuric acid/concentrated phosphoric acid system, the volume ratio of the concentrated sulfuric acid and concentrated phosphoric acid is 9:1.
The mass ratio of carboxylic acid carbon nano tube described in step (3) and graphene oxide is 1:1.
The mass ratio of pyrroles described in step (4) and thiophene is 1:1, and wherein the additional amount of pyrroles is graphene oxide
1wt%。
N and S codope graphene/carbon nano-tube aeroge obtained is used in electrode material, specific steps are as follows: by N
The ratio for being 90:5:5 according to mass ratio with S codope graphene/carbon nano-tube aeroge, acetylene black, ptfe emulsion
It is added in same weighing bottle, is uniformly mixed and sample is blown to paste with hair dryer, using nickel foam as collector, by paste
Material is coated in nickel foam, is dried in vacuo at 120 DEG C for 24 hours, final that required electrode is made.
The beneficial effects of the present invention are:
(1) present invention is inserted into carbon nanotube between graphene synusia, helps to improve the electric conductivity of graphene layer, and
Carbon nanotube can be used as spacer also to prevent the aggregation of graphene layer；In addition, low-dimensional carbon material is self-assembled into three-dimensional porous receive
Rice structural network, can greatly improve its specific surface area, big electrode/electrolyte contact area is provided for charge transfer reaction,
Shorten ion transport length, to improve chemical property；
(2) present invention N and S in graphene aerogel, wherein the codope of N and S can further enhance carbon material
Reactivity and electric conductivity, compared to single N or S dopant material, by introducing more active sites, to improve its electrification
Learn performance.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited only to these embodiments.
Embodiment 1
A kind of preparation method of N and S codope graphene/carbon nano-tube aeroge, specifically includes the following steps:
(1) 1 g multi-walled carbon nanotube (MWCNTs) preparation of carboxylic acid carbon nano tube: is added to the dense HNO of 80 mL3
In, 12 h then are condensed back in 120 DEG C of oil bath pans, gained black mixture is washed to suction filtration to pH=7 repeatedly and takes filter residue；
(2) preparation of graphene oxide: after evenly mixing by graphite and the concentrated sulfuric acid/concentrated phosphoric acid system (v/v=9:1), slowly
Potassium permanganate is added, after uniform stirring 0.5h, in 50 DEG C of stirred in water bath 12h, is slowly added to deionized water, and keep temperature low
In 100 DEG C, the hydrogen peroxide of 5wt% is added dropwise, when mixed liquor becomes golden yellow, salt acid elution is added, reaction after five minutes, is used
Deionized water is washed to neutrality, and uses BaCl2Detect the presence of SO4 2-Residual, then graphite oxide powder is made in freeze-drying for 24 hours；
Graphite oxide powder obtained is add to deionized water, then ultrasonic 1h is centrifuged 10min under the revolving speed of 2000r/min,
Lower sediment thing is removed, upper liquid is taken, after upper liquid is freezed 12h at 0 DEG C, is placed in freeze drier and is freeze-dried
36h obtains the graphene oxide；
(3) graphene oxide made from carboxylic acid carbon nano tube made from 50mg step (1) and 50mg step (2) is taken to mix
Afterwards, 50mL deionized water is added, the mixed liquor that concentration is 2mg/mL is obtained after ultrasound is uniform；
(4) pyrroles of 0.5mg and the thiophene of 0.5mg are added into the mixed liquor that step (3) obtains, it is anti-to carry out a hydro-thermal
It answers, reaction temperature is 160 DEG C, and reaction time 6h obtains hydrogel；
(5) hydrogel that step (4) obtains is put into the KNO of 2M3In solution, secondary hydro-thermal reaction, reaction temperature are carried out
It is 120 DEG C, reaction time 3h, after being cooled to room temperature, using filter, washing and freeze-drying；
(6) by products therefrom thermal cracking 2h at 1050 DEG C in argon atmosphere after step (5) freeze-drying, it is made described
N and S codope graphene/carbon nano-tube aeroge.
Embodiment 2
A kind of preparation method of N and S codope graphene/carbon nano-tube aeroge, specifically includes the following steps:
(1) 1 g multi-walled carbon nanotube (MWCNTs) preparation of carboxylic acid carbon nano tube: is added to the dense HNO of 80 mL3
In, 12 h then are condensed back in 120 DEG C of oil bath pans, gained black mixture is washed to suction filtration to pH=7 repeatedly and takes filter residue；
(2) preparation of graphene oxide: after evenly mixing by graphite and the concentrated sulfuric acid/concentrated phosphoric acid system (v/v=9:1), slowly
Potassium permanganate is added, after uniform stirring 0.5h, in 50 DEG C of stirred in water bath 12h, is slowly added to deionized water, and keep temperature low
In 100 DEG C, the hydrogen peroxide of 5wt% is added dropwise, when mixed liquor becomes golden yellow, salt acid elution is added, reaction after five minutes, is used
Deionized water is washed to neutrality, and uses BaCl2Detect the presence of SO4 2-Residual, then graphite oxide powder is made in freeze-drying for 24 hours；
Graphite oxide powder obtained is add to deionized water, then ultrasonic 1h is centrifuged 10min under the revolving speed of 2000r/min,
Lower sediment thing is removed, upper liquid is taken, after upper liquid is freezed 12h at 0 DEG C, is placed in freeze drier and is freeze-dried
36h obtains the graphene oxide；
(3) graphene oxide made from carboxylic acid carbon nano tube made from 50mg step (1) and 50mg step (2) is taken to mix
Afterwards, 50mL deionized water is added, the mixed liquor that concentration is 2mg/mL is obtained after ultrasound is uniform；
(4) pyrroles of 0.5mg and the thiophene of 0.5mg are added into the mixed liquor that step (3) obtains, it is anti-to carry out a hydro-thermal
It answers, reaction temperature is 180 DEG C, and reaction time 4h obtains hydrogel；
(5) hydrogel that step (4) obtains is put into the KNO of 2M3In solution, secondary hydro-thermal reaction, reaction temperature are carried out
It is 140 DEG C, reaction time 2h, after being cooled to room temperature, using filter, washing and freeze-drying；
(6) by products therefrom thermal cracking 2h at 1100 DEG C in argon atmosphere after step (5) freeze-drying, it is made described
N and S codope graphene/carbon nano-tube aeroge.
Embodiment 3
A kind of preparation method of N and S codope graphene/carbon nano-tube aeroge, specifically includes the following steps:
(1) 1 g multi-walled carbon nanotube (MWCNTs) preparation of carboxylic acid carbon nano tube: is added to the dense HNO of 80 mL3
In, 12 h then are condensed back in 120 DEG C of oil bath pans, gained black mixture is washed to suction filtration to pH=7 repeatedly and takes filter residue；
(2) preparation of graphene oxide: after evenly mixing by graphite and the concentrated sulfuric acid/concentrated phosphoric acid system (v/v=9:1), slowly
Potassium permanganate is added, after uniform stirring 0.5h, in 50 DEG C of stirred in water bath 12h, is slowly added to deionized water, and keep temperature low
In 100 DEG C, the hydrogen peroxide of 5wt% is added dropwise, when mixed liquor becomes golden yellow, salt acid elution is added, reaction after five minutes, is used
Deionized water is washed to neutrality, and uses BaCl2Detect the presence of SO4 2-Residual, then graphite oxide powder is made in freeze-drying for 24 hours；
Graphite oxide powder obtained is add to deionized water, then ultrasonic 1h is centrifuged 10min under the revolving speed of 2000r/min,
Lower sediment thing is removed, upper liquid is taken, after upper liquid is freezed 12h at 0 DEG C, is placed in freeze drier and is freeze-dried
36h obtains the graphene oxide；
(3) graphene oxide made from carboxylic acid carbon nano tube made from 50mg step (1) and 50mg step (2) is taken to mix
Afterwards, 50mL deionized water is added, the mixed liquor that concentration is 2mg/mL is obtained after ultrasound is uniform；
(4) pyrroles of 0.5mg and the thiophene of 0.5mg are added into the mixed liquor that step (3) obtains, it is anti-to carry out a hydro-thermal
It answers, reaction temperature is 170 DEG C, and reaction time 5h obtains hydrogel；
(5) hydrogel that step (4) obtains is put into the KNO of 2M3In solution, secondary hydro-thermal reaction, reaction temperature are carried out
It is 130 DEG C, reaction time 2.5h, after being cooled to room temperature, using filter, washing and freeze-drying；
(6) by products therefrom thermal cracking 2h at 1080 DEG C in argon atmosphere after step (5) freeze-drying, it is made described
N and S codope graphene/carbon nano-tube aeroge.
Comparative example 1
A kind of preparation method of N doped graphene/carbon nanotube aerogel, specifically includes the following steps:
(1) 1 g multi-walled carbon nanotube (MWCNTs) preparation of carboxylic acid carbon nano tube: is added to the dense HNO of 80 mL3
In, 12 h then are condensed back in 120 DEG C of oil bath pans, gained black mixture is washed to suction filtration to pH=7 repeatedly and takes filter residue；
(2) preparation of graphene oxide: after evenly mixing by graphite and the concentrated sulfuric acid/concentrated phosphoric acid system (v/v=9:1), slowly
Potassium permanganate is added, after uniform stirring 0.5h, in 50 DEG C of stirred in water bath 12h, is slowly added to deionized water, and keep temperature low
In 100 DEG C, the hydrogen peroxide of 5wt% is added dropwise, when mixed liquor becomes golden yellow, salt acid elution is added, reaction after five minutes, is used
Deionized water is washed to neutrality, and uses BaCl2Detect the presence of SO4 2-Residual, then graphite oxide powder is made in freeze-drying for 24 hours；
Graphite oxide powder obtained is add to deionized water, then ultrasonic 1h is centrifuged 10min under the revolving speed of 2000r/min,
Lower sediment thing is removed, upper liquid is taken, after upper liquid is freezed 12h at 0 DEG C, is placed in freeze drier and is freeze-dried
36h obtains the graphene oxide；
(3) graphene oxide made from carboxylic acid carbon nano tube made from 50mg step (1) and 50mg step (2) is taken to mix
Afterwards, 50mL deionized water is added, the mixed liquor that concentration is 2mg/mL is obtained after ultrasound is uniform；
(4) pyrroles of 1mg is added into the mixed liquor that step (3) obtains, carries out a hydro-thermal reaction, reaction temperature is
170 DEG C, reaction time 5h obtains hydrogel；
(5) hydrogel that step (4) obtains is put into the KNO of 2M3In solution, secondary hydro-thermal reaction, reaction temperature are carried out
It is 130 DEG C, reaction time 2.5h, after being cooled to room temperature, using filter, washing and freeze-drying；
(6) by products therefrom thermal cracking 2h at 1080 DEG C in argon atmosphere after step (5) freeze-drying, it is made described
N doped graphene/carbon nanotube aerogel.
Comparative example 2
A kind of preparation method of S doped graphene/carbon nanotube aerogel, specifically includes the following steps:
(1) 1 g multi-walled carbon nanotube (MWCNTs) preparation of carboxylic acid carbon nano tube: is added to the dense HNO of 80 mL3
In, 12 h then are condensed back in 120 DEG C of oil bath pans, gained black mixture is washed to suction filtration to pH=7 repeatedly and takes filter residue；
(2) preparation of graphene oxide: after evenly mixing by graphite and the concentrated sulfuric acid/concentrated phosphoric acid system (v/v=9:1), slowly
Potassium permanganate is added, after uniform stirring 0.5h, in 50 DEG C of stirred in water bath 12h, is slowly added to deionized water, and keep temperature low
In 100 DEG C, the hydrogen peroxide of 5wt% is added dropwise, when mixed liquor becomes golden yellow, salt acid elution is added, reaction after five minutes, is used
Deionized water is washed to neutrality, and uses BaCl2Detect the presence of SO4 2-Residual, then graphite oxide powder is made in freeze-drying for 24 hours；
Graphite oxide powder obtained is add to deionized water, then ultrasonic 1h is centrifuged 10min under the revolving speed of 2000r/min,
Lower sediment thing is removed, upper liquid is taken, after upper liquid is freezed 12h at 0 DEG C, is placed in freeze drier and is freeze-dried
36h obtains the graphene oxide；
(3) graphene oxide made from carboxylic acid carbon nano tube made from 50mg step (1) and 50mg step (2) is taken to mix
Afterwards, 50mL deionized water is added, the mixed liquor that concentration is 2mg/mL is obtained after ultrasound is uniform；
(4) thiophene of 0.1mg is added into the mixed liquor that step (3) obtains, carries out a hydro-thermal reaction, reaction temperature is
170 DEG C, reaction time 5h obtains hydrogel；
(5) hydrogel that step (4) obtains is put into the KNO of 2M3In solution, secondary hydro-thermal reaction, reaction temperature are carried out
It is 130 DEG C, reaction time 2.5h, after being cooled to room temperature, using filter, washing and freeze-drying；
(6) by products therefrom thermal cracking 2h at 1080 DEG C in argon atmosphere after step (5) freeze-drying, it is made described
S doped graphene/carbon nanotube aerogel.
By N and S codope graphene/carbon nano-tube aeroge obtained above, N doped graphene/carbon nanotube airsetting
Glue and S doped graphene/carbon nanotube aerogel are used in electrode material, specific steps are as follows: by N and S codope graphene/carbon
Nanotube aeroge (or N doped graphene/carbon nanotube aerogel, S doped graphene/carbon nanotube aerogel), acetylene black,
Ptfe emulsion is added in same weighing bottle according to the ratio that mass ratio is 90:5:5, is uniformly mixed and uses hair dryer
Sample is blown to paste, using nickel foam as collector, pastes is coated in nickel foam, is dried in vacuo at 120 DEG C
For 24 hours, final that required electrode is made.
Electrode obtained is subjected to density, specific surface area and electrochemical property test, the results are shown in Table 1.
The properties of 1 silica aerogel electrode of table
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (4)
1. a kind of preparation method of N and S codope graphene/carbon nano-tube aeroge, it is characterised in that: specifically include following step
It is rapid:
(1) preparation of carboxylic acid carbon nano tube；
(2) preparation of graphene oxide；
(3) will graphene oxide made from carboxylic acid carbon nano tube made from step (1) and step (2) mix after, addition go from
Sub- water obtains the mixed liquor that concentration is 2mg/mL after ultrasound is uniform；
(4) pyrroles and thiophene are added into the mixed liquor that step (3) obtains, carries out a hydro-thermal reaction, reaction temperature is 160 ~
180 DEG C, the reaction time is 4 ~ 6h, obtains hydrogel；
(5) hydrogel that step (4) obtains is put into the KNO of 2M3In solution, secondary hydro-thermal reaction is carried out, reaction temperature is 120 ~
140 DEG C, the reaction time is 2 ~ 3h, after being cooled to room temperature, using filter, washing and freeze-drying；
(6) by products therefrom thermal cracking 2h at 1050 ~ 1100 DEG C in argon atmosphere after step (5) freeze-drying, institute is made
State N and S codope graphene/carbon nano-tube aeroge；
Carboxylic acid carbon nano tube described in step (1) the preparation method comprises the following steps: that 1 g multi-walled carbon nanotube is added to 80 mL is dense
HNO3In, 12 h then are condensed back in 120 DEG C of oil bath pans, gained black mixture is washed to suction filtration to pH=7 repeatedly and takes filter
Slag；
The mass ratio of carboxylic acid carbon nano tube described in step (3) and graphene oxide is 1:1；
The mass ratio of pyrroles described in step (4) and thiophene is 1:1, and wherein the additional amount of pyrroles is graphene oxide
1wt%。
2. the preparation method of N and S codope graphene/carbon nano-tube aeroge according to claim 1, feature exist
In: graphene oxide described in step (2) the preparation method comprises the following steps: after evenly mixing by graphite and the concentrated sulfuric acid/concentrated phosphoric acid system, delaying
It is slow to be added potassium permanganate, after uniform stirring 0.5h, in 50 DEG C of stirred in water bath 12h, it is slowly added to deionized water, and keep temperature
Lower than 100 DEG C, the hydrogen peroxide of 5wt% is added dropwise, when mixed liquor becomes golden yellow, salt acid elution is added, reacts after five minutes,
It is washed with deionized to neutrality, and uses BaCl2Detect the presence of SO4 2-Residual, then graphite oxide powder is made in freeze-drying for 24 hours
End；Graphite oxide powder obtained is add to deionized water, then ultrasonic 1h is centrifuged under the revolving speed of 2000r/min
10min, remove lower sediment thing, take upper liquid, after upper liquid is freezed 12h at 0 DEG C, be placed in freeze drier carry out it is cold
Dry 36h is lyophilized, obtains the graphene oxide.
3. the preparation method of N and S codope graphene/carbon nano-tube aeroge according to claim 2, feature exist
In: in the concentrated sulfuric acid/concentrated phosphoric acid system, the volume ratio of the concentrated sulfuric acid and concentrated phosphoric acid is 9:1.
4. N and S codope graphene/carbon nano-tube aeroge is in electricity made from a kind of preparation method as described in claim 1
Application in the material of pole, it is characterised in that: by N and S codope graphene/carbon nano-tube aeroge, acetylene black, polytetrafluoroethylene (PTFE)
Lotion is added in same weighing bottle according to the ratio that mass ratio is 90:5:5, is uniformly mixed and is blown to sample with hair dryer
Pastes is coated in nickel foam by paste using nickel foam as collector, is dried in vacuo at 120 DEG C for 24 hours, final to be made
Required electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810841339.2A CN108831757B (en) | 2018-07-27 | 2018-07-27 | A kind of preparation method of N and S codope graphene/carbon nano-tube aeroge |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810841339.2A CN108831757B (en) | 2018-07-27 | 2018-07-27 | A kind of preparation method of N and S codope graphene/carbon nano-tube aeroge |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108831757A CN108831757A (en) | 2018-11-16 |
| CN108831757B true CN108831757B (en) | 2019-09-13 |
Family
ID=64141235
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810841339.2A Active CN108831757B (en) | 2018-07-27 | 2018-07-27 | A kind of preparation method of N and S codope graphene/carbon nano-tube aeroge |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108831757B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110127665A (en) * | 2019-05-18 | 2019-08-16 | 黑龙江八一农垦大学 | Multi-walled carbon nanotube/graphene aerogel and its method for detecting organophosphorus pesticide |
| CN110316720B (en) * | 2019-06-27 | 2021-03-30 | 沈健民 | Sulfur and nitrogen double-doped carbon nanotube film and preparation method thereof |
| CN114220670B (en) * | 2021-12-16 | 2023-09-12 | 福州大学 | Preparation method of non-covalent hybridized MOF graphene aerogel/molybdenum capacitor electrode material |
| CN115472440B (en) * | 2022-08-18 | 2024-03-15 | 兰州大学 | Graphene-based N, S doped electrode material and preparation method thereof |
| CN115536009B (en) * | 2022-10-14 | 2023-08-08 | 安徽科技学院 | Preparation method of nitrogen-sulfur co-doped graphene multiwall carbon nanotube composite film |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104860294A (en) * | 2015-04-20 | 2015-08-26 | 复旦大学 | Three-dimensional graphene nanoribbon/carbon nanoribbon bridged structural material, and preparation method and application thereof |
| CN105047427B (en) * | 2015-08-06 | 2017-07-18 | 清华大学 | Ultracapacitor combination electrode material and preparation method thereof and ultracapacitor |
| CN106025210A (en) * | 2016-06-06 | 2016-10-12 | 复旦大学 | Molybdenum selenide/graphene/carbon nanotube composite material and preparation method thereof |
| CN106684389A (en) * | 2016-12-30 | 2017-05-17 | 温州大学 | Sulfur-nitrogen dual-doped graphene nano material and preparation method and application thereof |
| CN107416800A (en) * | 2017-08-15 | 2017-12-01 | 东南大学 | A kind of method that hydro-thermal method prepares N and S codope three-dimensional grapheme materials |
-
2018
- 2018-07-27 CN CN201810841339.2A patent/CN108831757B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108831757A (en) | 2018-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108831757B (en) | A kind of preparation method of N and S codope graphene/carbon nano-tube aeroge | |
| CN107204445B (en) | A kind of lithium ion battery three-dimensional porous silicon-carbon cathode material and preparation method thereof | |
| Tang et al. | Facile synthesis of 3D reduced graphene oxide and its polyaniline composite for super capacitor application | |
| CN102941042B (en) | A kind of Graphene/metal oxide hybrid aeroge, preparation method and application thereof | |
| CN104916826B (en) | A kind of graphene coated silicium cathode material and preparation method thereof | |
| CN105552371B (en) | The preparation and application of nitrogen-doped graphene carbon nanohorn composite | |
| CN109830661B (en) | Selenium-doped MXene composite nano material and preparation method and application thereof | |
| CN104973596B (en) | A kind of Heteroatom doping hollow ball graphene composite material and preparation method and application | |
| CN109003826A (en) | N and S codope graphene-graphene nanobelt aeroge preparation method | |
| CN104466134B (en) | The preparation method of self-supporting graphene/carbon nano-tube hybrid foam support amino anthraquinones base polymer | |
| CN108258210B (en) | Preparation method of 3D porous graphene/carbon nanotube-nano silicon aerogel lithium ion battery cathode material | |
| CN109461915A (en) | A kind of preparation method of the positive electrode of lithium-sulfur cell | |
| CN104835963B (en) | Lithium ion battery composite anode material and preparation method thereof | |
| CN107221654A (en) | A kind of three-dimensional porous nest like silicon-carbon composite cathode material and preparation method thereof | |
| CN104176783B (en) | The preparations and applicatio method of the coated manganese dioxide nanowire of a kind of nitrogen carbon material | |
| CN104319371A (en) | Preparation method of lithium ion battery SnS2/CNTs/PPy composite anode material | |
| CN110416539A (en) | Polypyrrole coats three-dimensional grapheme cobaltosic oxide lithium cell negative pole material preparation method | |
| CN108878167A (en) | A kind of supercapacitor CoNi2S4/ graphene composite material and preparation method thereof | |
| CN111883366A (en) | Polypyrrole nanosphere @ titanium carbide composite material and preparation method and application thereof | |
| CN109860526A (en) | The preparation method of graphite type material doping metals oxalates lithium battery composite negative pole material | |
| CN108511201A (en) | A kind of ultra-thin MoS2Nanometer sheet/CNT composite material and preparation methods | |
| CN108597891A (en) | Composite material and preparation method and application are covered in a kind of double load double-contractings of silica@metal oxides/graphene aerogel | |
| CN108539143A (en) | A method of quickly preparing high-capacity lithium ion cell silicon based anode material | |
| CN105789628B (en) | A kind of azepine graphene and manganese dioxide hybrid aerogel and its preparation method and application | |
| CN110078130B (en) | Preparation method of hollow-structure iron-based compound and application of hollow-structure iron-based compound as cathode material of supercapacitor |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200805 Address after: No. 3001, south section of Century Avenue, Luoshan street, Jinjiang City, Quanzhou City, Fujian Province Patentee after: FUJIAN CHENQI NEW MATERIAL TECHNOLOGY Co.,Ltd. Address before: 350108, No. 2 School Road, Minhou New District, Fuzhou County, Fuzhou, Fujian Patentee before: FUZHOU University |
|
| TR01 | Transfer of patent right |