CN110391087A - A kind of preparation method and applications of three kinds of element doping porous oxidation grapheme materials of nitrogen sulphur phosphorus - Google Patents
A kind of preparation method and applications of three kinds of element doping porous oxidation grapheme materials of nitrogen sulphur phosphorus Download PDFInfo
- Publication number
- CN110391087A CN110391087A CN201910673244.9A CN201910673244A CN110391087A CN 110391087 A CN110391087 A CN 110391087A CN 201910673244 A CN201910673244 A CN 201910673244A CN 110391087 A CN110391087 A CN 110391087A
- Authority
- CN
- China
- Prior art keywords
- kinds
- porous oxidation
- nitrogen
- graphene
- sulphur phosphorus
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- 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
-
- 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
-
- 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 method and applications of three kinds of element doping porous oxidation grapheme materials of nitrogen sulphur phosphorus, the present invention is using graphene oxide as raw material, pore-creating is carried out under hydrothermal conditions by the way that hydrogen peroxide is added, the porous oxidation grapheme material of three kinds of element dopings is prepared in the dopant for adding three kinds of elements of Nitrogen-and Phosphorus-containing sulphur, is applied to the electrode material of supercapacitor.The present invention utilizes the hydrogen peroxide with strong oxidizing property to etch three-dimensional porous structure on the surface of graphene, and then improve the specific surface area of grapheme material, dopant after obtained porous oxidation graphene ultrasonic disperse with three kinds of elements of Nitrogen-and Phosphorus-containing sulphur is sufficiently mixed, nitrogen, sulphur, phosphorus heteroatoms are introduced into porous oxidation graphene improvement graphene chemical property, it is supported on it in conductive current collector and prepares electrode of super capacitor, so that capacitor is obtained better capacitive property, but also makes it have good cyclical stability.
Description
Technical field
The present invention relates to carbon material preparation technical fields, porous more particularly, to a kind of three kinds of element dopings of nitrogen sulphur phosphorus
The preparation method and applications of graphene oxide composite material.
Background technique
It is the important topic of 21 century that advanced energy storage technology, which is explored, with the Science & Technology Demands for adapting to continue to develop.Current
In energy storage device, supercapacitor is because it is with energy density height, and the charge and discharge time is short, has extended cycle life, non-maintaining, self discharge
Many advantages, such as property is small, has a safety feature, environmental-friendly, illustrates huge development prospect, has attracted extensive research interest.
However the lower energy density of supercapacitor especially double electric layers supercapacitor is the main reason for hindering its development.For
For the performance for improving supercapacitor, since the superiority and inferiority of electrode material performance largely determines performance of the supercapacitor
Quality, therefore it is significant to rationally design the high performance electrode material of exploitation.
Currently, commercial electrode material for super capacitor is mainly active carbon, but its lower specific capacitance expire it can not
The demand of sufficient high specific capacitance, high-energy density.Therefore, design has high specific capacitance, the electrode of super capacitor material of high stability
Material is the key that supercapacitor applications.Graphene as typical two-dimentional carbon material because with excellent electric conductivity, it is higher
Specific surface area (theoretical specific capacity is up to 550 F/g), is ideal electrode material for super capacitor, but graphene film with
Strong π~pi-conjugated effect makes it easily reunite between piece, and greatly reducing its effective ratio area leads to poor capacitive character
Can, it is restricted it in the application aspect of electrode material for super capacitor.
For the modification of graphene-based electrode material, the method reported at present mainly has: (1) designing porous graphene；
(2) Heteroatom doping modified graphene.Specifically, design porous graphene can be further improved the specific surface of graphene
Product is conducive to the electrochemistry of the conduction improvement material of ion and charge by the porous graphene of reasonable pore-size distribution
Energy.On the other hand, using Heteroatom doping graphene, hetero atom is mainly introduced by graphene sheet layer by suitable method
In singly adulterated or more doped graphenes, and then improve the distribution of charges accelerated charge transmitting of graphene surface, improve graphite
The electric conductivity of alkene electrode material.In addition, adulterating porous graphene answering in terms of supercapacitor for nitrogen sulphur phosphorus three at present
With there is presently no document reports.
Summary of the invention
For existing Heteroatom doping porous oxidation grapheme material preparation there are technological gap, the present invention provides one
Kind, can quick, high yield acquisition nitrogen, three kinds of sulphur, phosphorus element doping porous oxidation graphene materials using graphene oxide as raw material
Preparation method for material, this method is simple, condition is controllable, advantage of lower cost, is expected to realize industrialized production.
Another object of the present invention is to be to provide the nitrogen sulphur phosphorus three kinds of element doping porous oxidation graphene materials
The application of material can prepare the supercapacitor of electrochemical performance as electrode material.
The present invention is realized by the following scheme:
A kind of three kinds of element doping porous oxidation grapheme materials of nitrogen sulphur phosphorus, it is composed of the following components: graphene oxide, hydrogen peroxide
With the dopant of three kinds of elements containing nitrogen phosphate and sulfur.
A kind of preparation method of three kinds of element doping porous oxidation grapheme materials of nitrogen sulphur phosphorus, mainly comprises the steps that
S1. it weighs appropriate graphene oxide ultrasonic disperse and obtains graphene oxide dispersion in deionized water, pore creating material is added
After be transferred into hydrothermal reaction kettle, stirring, reaction, be cooled to room temperature after having reacted；
S2. step S1 products therefrom is centrifugated, is washed, freeze-drying obtains three-dimensional porous graphene oxide, again by it
For secondary ultrasonic disperse in aqueous solution, the dopant that three kinds of elements containing nitrogen phosphate and sulfur are then added under strong agitation continues stirring and dissolving
Obtain mixed solution；
S3. the resulting mixed solution of step S2 is subjected to hydro-thermal reaction, is cooled to room temperature after having reacted；
S4. the resulting reaction product of step S3 is centrifugated, washing is freeze-dried up to the three of nitrogenous three kinds of elements of sulphur phosphorus
Adulterate porous oxidation graphene.
Three kinds of element doping porous oxidation graphenes of nitrogen sulphur phosphorus of the present invention are made of porous oxidation graphene film,
And nitrogen sulphur phosphorus heteroatoms are successfully introduced into graphene oxide on piece by simple water-heat process, it is this that there is reasonable aperture point
The porous Heteroatom doping graphene oxide of cloth can effectively improve the agglomeration of graphene, increase electrode material and electrolysis
The contact area of matter, while the hetero atom introduced can provide additional fake capacitance, and then improve the chemical property of graphene.
Up to now, there is not been reported as electrode material for super capacitor for the doping of nitrogen sulphur phosphorus three porous oxidation graphene.
Further, graphene oxide dispersion concentration obtained in step S1 is 0.1~4 mg/mL, the addition
The volume ratio of pore creating material and graphene oxide dispersion is 1: 5~50.
Preferably, graphene oxide dispersion concentration obtained in step S1 is 0.5~2mg/mL, the pore-creating of the addition
The volume ratio of agent and graphene oxide dispersion is 1: 5~10.
Further, reaction temperature is 100~200 DEG C in step S1, and the reaction time is 2~12h.
Preferably, reaction temperature is 100~150 DEG C in step S1, and the reaction time is 2~6h.
Further, pore creating material described in step S1 is hydrogen peroxide, and the hydrogen peroxide concentration is 20 ~ 40wt%.
Preferably, the hydrogen peroxide concentration is 30wt%.
The pore-creating modes such as nitrogen, organic solvent are used compared to other, it is more controllable using hydrogen peroxide pore-creating, control can be passed through
The time of reaction is made to control the size of hole, enhances the controllability of pore-creating.
Further, the dopant of three kinds of elements of Nitrogen-and Phosphorus-containing sulphur described in step S2 is phosphate and sulfurous organic compound.
Preferably, the porous oxidation graphene that is added in step S2, sulfurous organic compound, phosphatic mass ratio be 1: 1~
10: 1~10.
It is further preferred that the porous oxidation graphene being added in step S2, sulfurous organic compound, phosphatic mass ratio are
1: 1~4: 1~4.
Further, the phosphate can be diammonium hydrogen phosphate, ammonium dihydrogen phosphate or ammonium phosphate salt, and the sulfur-bearing is organic
Object can be cysteine, thiocarbamide or thioacetamide.
Preferably, the sulfurous organic compound is L-cysteine, and the phosphate is ammonium dihydrogen phosphate.
Further, in step S3 hydrothermal temperature be 100~200 DEG C, the reaction time be 2~for 24 hours.
Preferably, hydrothermal temperature is 150~180 DEG C in step S3, and the reaction time is 2~6h.
Three kinds of element doping porous oxidation grapheme materials of nitrogen sulphur phosphorus that the present invention is prepared can be as electrode material
Material is applied to supercapacitor.Three kinds of element doping porous oxidation graphenes of nitrogen sulphur phosphorus, binder PVDF and conductive black are pressed
Mass ratio 60~80: 10~20: 10~20 mixes, and is applied in nickel sheet, that is, can be made into electrode of super capacitor.
Compared with the prior art, technical solution of the present invention bring advantageous effects:
The invention by three kinds of element dopings into graphene oxide dispersion, with single doping, compared with codope, three mix
It is miscellaneous to introduce more hetero atoms to improve graphene surface cloud density enhancing electric conductivity, and different hetero atoms is mixed
Miscellaneous that different modified effects can be generated to graphene, the coordinating effect between three foreign atoms can further improve graphene performance,
For corresponding supercapacitor, three doped graphenes can provide more fake capacitances to reach higher specific capacitance.
Graphene agglomeration can be alleviated to a certain extent by introducing the hetero atoms such as nitrogen, sulphur, phosphorus, moreover it is possible to play raising material
The specific surface area of material, as electrode material for super capacitor in use, the hetero atom introduced can also increase electrolyte to material
Wetness degree, while providing additional fake capacitance.In addition, compared with singly doping or codope graphene, three doped graphenes
Provide surface charge more abundant, improve charge-conduction rate, at the same between each hetero atom mutual synergistic effect presence, into
The chemical property of one step improvement graphene.
Sulphur and P elements are doped into that graphene surface distribution of charges can be improved by the present invention, while can slow down stone
The agglomeration of black alkene, and the degree of wetting of Graphene electrodes material can be improved, the final electricity for improving Graphene electrodes material
Chemical property.After being sufficiently mixed after graphene oxide ultrasonic disperse with hydrogen peroxide solution by this method, it is placed in 50~180 °C
Thermal and hydric environment in activate pore-creating, it is more to etch three-dimensional on the surface of graphene using the dioxygen water and steam with strong oxidizing property
Pore structure, to improve the specific surface area of grapheme material.By after obtained porous oxidation graphene ultrasonic disperse with half Guang of L-
Propylhomoserin and ammonium dihydrogen phosphate are sufficiently mixed, and are placed in 140~200 °C of hydrothermal reaction kettle and are carried out Heteroatom doping, utilize doping
The thermogenetic NH of agent water3、H2S、PH3It is with the effect of porous oxidation graphene surface functional group that nitrogen, sulphur, phosphorus heteroatoms introducing is porous
Graphene oxide improves graphene performance.Three, which adulterate porous oxidation graphenes and binder, is made into electrode slurry according to certain mass ratio
Material, is supported in conductive current collector and prepares electrode of super capacitor, further decrease reunion degree of the graphene on pole piece, obtain
Obtained good capacitive property.
The present invention successfully prepares three kinds of element doping porous oxidation graphite of nitrogen sulphur phosphorus using graphene oxide as raw material for the first time
Alkene material is with a wide range of applications to the development of super capacitor industry；Secondly three kinds of element doping porous oxidations of nitrogen sulphur phosphorus
The preparation method of grapheme material is simple and quick, efficient high yield, and condition is controllable, and it is low in cost, be advantageously implemented industrial metaplasia
It produces；Three kinds of element doping porous oxidation grapheme materials of nitrogen sulphur phosphorus of preparation are used to prepare supercapacitor as electrode material,
With excellent properties such as high specific capacitance, high circulation stability, high magnifications.
Detailed description of the invention
Fig. 1 is the SEM figure of three kinds of element doping porous oxidation graphenes of nitrogen sulphur phosphorus that example 2 is prepared.
Fig. 2 is the BET nitrogen adsorption desorption of three kinds of element doping porous oxidation graphenes of nitrogen sulphur phosphorus that example 2 is prepared
Figure.
Fig. 3 is the XPS map for three kinds of element doping porous oxidation graphenes of nitrogen sulphur phosphorus that example 2 is prepared.
Fig. 4 is that three kinds of element doping porous oxidation graphenes of nitrogen sulphur phosphorus that example 2 is prepared are negative as supercapacitor
10000 cycle charge discharge electrographs of the pole material under 3A/g current density.
Specific embodiment
It is explained further and illustrates below with reference to embodiment, but specific embodiment does not have any type of limit to the present invention
It is fixed.Unless otherwise specified, method and apparatus used in embodiment is ability conventional method and equipment, raw materials used is routine
Marketable material.
Embodiment 1
S1. in deionized water, obtained graphene oxide dispersion concentration is ultrasonic disperse after weighing raw material graphene oxide
Then 0.5 mg/mL is added 30wt% hydrogen peroxide as pore creating material in strong mixing, the volume and graphene oxide of hydrogen peroxide is added
The volume ratio of dispersion liquid is 1: 5, then mixed liquor is transferred in hydrothermal reaction kettle, is persistently stirred to react, reaction temperature 100
DEG C, reaction time 2h is cooled to room temperature after having reacted.
S2. the product after reaction obtained by above-mentioned steps S1 is centrifugated, is washed with deionized, is freeze-dried to obtain the final product
Three-dimensional porous graphene oxide, by the three-dimensional porous graphene oxide solid powder sample of gained again ultrasonic disperse to deionized water
In, dopant L-cysteine, ammonium dihydrogen phosphate, porous oxidation graphene, L-cysteine, phosphorus are then added under strong agitation
The mass ratio of acid dihydride ammonium is 1: 1: 1, continues stirring and dissolving and obtains mixed solution.
S3. then mixed solution obtained by step S2 is transferred in hydrothermal reaction kettle and carries out hydro-thermal reaction, reaction temperature is
100 DEG C, reaction time 6h is cooled to room temperature after having reacted.
S4. the resulting reaction product of step S3 is centrifugated, is washed with deionized, freeze-drying, which is collected, to be contained
The three doping porous oxidation graphenes of three kinds of elements of nitrogen sulphur phosphorus.
By active material (the nitrogen sulphur phosphorus three of preparation adulterates porous oxidation graphene), acetylene black, PVDF in mass ratio 80: 10
: 10 ratio mixing is added a small amount of NMP and stirs to being mixed thoroughly, then said mixture is uniformly coated in bubble
On foam nickel, the negative electrode material for claiming supercapacitor is made finally in the processing of 10MPa lower sheeting in 120 DEG C of hollow dry 12h.
Embodiment 2
S1. in deionized water, obtained graphene oxide dispersion concentration is ultrasonic disperse after weighing raw material graphene oxide
Then 2 mg/mL are added 30wt% hydrogen peroxide as pore creating material in strong mixing, the volume and graphene oxide point of hydrogen peroxide are added
The volume ratio of dispersion liquid is 1: 5, then mixed liquor is transferred in hydrothermal reaction kettle, is persistently stirred to react, and reaction temperature is 100 DEG C,
Reaction time is 2h, is cooled to room temperature after having reacted.
S2. the product after reaction obtained by above-mentioned steps S1 is centrifugated, is washed with deionized, is freeze-dried to obtain the final product
Three-dimensional porous graphene oxide, by the three-dimensional porous graphene oxide solid powder sample of gained again ultrasonic disperse to deionized water
In, dopant L-cysteine, ammonium dihydrogen phosphate, porous oxidation graphene, L-cysteine, phosphorus are then added under strong agitation
The mass ratio of acid dihydride ammonium is 1: 1: 1, continues stirring and dissolving and obtains mixed solution.
S3. then mixed solution obtained by step S2 is transferred in hydrothermal reaction kettle and carries out hydro-thermal reaction, reaction temperature is
140 DEG C, reaction time 2h is cooled to room temperature after having reacted.
S4. the resulting reaction product of step S3 is centrifugated, is washed with deionized, freeze-drying collection obtains nitrogenous
The three doping porous oxidation graphenes of three kinds of elements of sulphur phosphorus.
By the active material nitrogen sulphur phosphorus three of preparation (adulterate porous oxidation graphene), acetylene black, PVDF in mass ratio 80:
The ratio of 10:10 mixes, and a small amount of NMP is added and stirs to being mixed thoroughly, is then uniformly coated in said mixture
In nickel foam, the negative electrode material of supercapacitor is made finally in the processing of 10MPa lower sheeting in 120 DEG C of hollow dry 12h.
Embodiment 3
S1. in deionized water, obtained graphene oxide dispersion concentration is ultrasonic disperse after weighing raw material graphene oxide
Then 0.5 mg/mL is added 30wt% hydrogen peroxide as pore creating material in strong mixing, the volume and graphene oxide of hydrogen peroxide is added
The volume ratio of dispersion liquid is 1: 5, then mixed liquor is transferred in hydrothermal reaction kettle, is persistently stirred to react, reaction temperature 100
DEG C, reaction time 2h is cooled to room temperature after having reacted.
S2. the product after reaction obtained by above-mentioned steps S1 is centrifugated, is washed with deionized, is freeze-dried up to three
Tie up porous oxidation graphene, by the three-dimensional porous graphene oxide solid powder sample of gained again ultrasonic disperse to deionized water
In, dopant L-cysteine, ammonium dihydrogen phosphate, porous oxidation graphene, L-cysteine, phosphorus are then added under strong agitation
The mass ratio of acid dihydride ammonium is 1: 2: 3, continues stirring and dissolving and obtains mixed solution.
S3. then mixed solution obtained by step S2 is transferred in hydrothermal reaction kettle and carries out hydro-thermal reaction, reaction temperature is
140 DEG C, reaction time 2h is cooled to room temperature after having reacted.
S4. the resulting reaction product of step S3 is centrifugated, is washed with deionized, freeze-drying, which is collected, to be contained
The three doping porous oxidation graphenes of three kinds of elements of nitrogen sulphur phosphorus.
By the active material nitrogen sulphur phosphorus three of preparation (adulterate porous oxidation graphene), acetylene black, PVDF in mass ratio 80:
The ratio of 10:10 mixes, and a small amount of NMP is added and stirs to being mixed thoroughly, is then uniformly coated in said mixture
In nickel foam, the negative electrode material for claiming supercapacitor is made finally in the processing of 10MPa lower sheeting in 120 DEG C of hollow dry 12h.
Embodiment 4
S1. in deionized water, obtained graphene oxide dispersion concentration is ultrasonic disperse after weighing raw material graphene oxide
Then 2 mg/mL are added 30wt% hydrogen peroxide as pore creating material in strong mixing, the volume and graphene oxide point of hydrogen peroxide are added
The volume ratio of dispersion liquid is 1: 5, then mixed liquor is transferred in hydrothermal reaction kettle, is persistently stirred to react, and reaction temperature is 100 DEG C,
Reaction time is 2h, is cooled to room temperature after having reacted.
S2. the product after reaction obtained by above-mentioned steps S1 is centrifugated, is washed with deionized, is freeze-dried to obtain the final product
Three-dimensional porous graphene oxide, by the three-dimensional porous graphene oxide solid powder sample of gained again ultrasonic disperse to deionized water
In, dopant L-cysteine, ammonium dihydrogen phosphate, porous oxidation graphene, L-cysteine, phosphorus are then added under strong agitation
The mass ratio of acid dihydride ammonium is 1: 2: 3, continues stirring and dissolving and obtains mixed solution.
S3. then mixed solution obtained by step S2 is transferred in hydrothermal reaction kettle and carries out hydro-thermal reaction, reaction temperature is
140 DEG C, reaction time 6h is cooled to room temperature after having reacted.
S4. the resulting reaction product of step S3 is centrifugated, is washed with deionized, freeze-drying, which is collected, to be contained
The three doping porous oxidation graphenes of three kinds of elements of nitrogen sulphur phosphorus.
By the active material nitrogen sulphur phosphorus three of preparation (adulterate porous oxidation graphene), acetylene black, PVDF in mass ratio 80:
The ratio of 10:10 mixes, and a small amount of NMP is added and stirs to being mixed thoroughly, is then uniformly coated in said mixture
In nickel foam, the negative electrode material for claiming supercapacitor is made finally in the processing of 10MPa lower sheeting in 120 DEG C of hollow dry 12h.
Embodiment 5
S1. in deionized water, obtained graphene oxide dispersion concentration is ultrasonic disperse after weighing raw material graphene oxide
Then 2 mg/mL are added 30wt% hydrogen peroxide as pore creating material in strong mixing, the volume and graphene oxide point of hydrogen peroxide are added
The volume ratio of dispersion liquid is 1: 5, then mixed liquor is transferred in hydrothermal reaction kettle, is persistently stirred to react, and reaction temperature is 100 DEG C,
Reaction time is 4h, is cooled to room temperature after having reacted.
S2. the product after reaction obtained by above-mentioned steps S1 is centrifugated, is washed with deionized, is freeze-dried to obtain the final product
Three-dimensional porous graphene oxide, by the three-dimensional porous graphene oxide solid powder sample of gained again ultrasonic disperse to deionized water
In, dopant L-cysteine, ammonium dihydrogen phosphate, porous oxidation graphene, L-cysteine, phosphorus are then added under strong agitation
The mass ratio of acid dihydride ammonium is 1: 1: 1, continues stirring and dissolving and obtains mixed solution.
S3. then mixed solution obtained by step S2 is transferred in hydrothermal reaction kettle and carries out hydro-thermal reaction, reaction temperature is
180 DEG C, reaction time 2h is cooled to room temperature after having reacted.
S4. the resulting reaction product of step S3 is centrifugated, is washed with deionized, freeze-drying, which is collected, to be contained
The three doping porous oxidation graphenes of three kinds of elements of nitrogen sulphur phosphorus.
By the active material nitrogen sulphur phosphorus three of preparation (adulterate porous oxidation graphene), acetylene black, PVDF in mass ratio 80:
The ratio of 10:10 mixes, and a small amount of NMP is added and stirs to being mixed thoroughly, is then uniformly coated in said mixture
In nickel foam, the negative electrode material for claiming supercapacitor is made finally in the processing of 10MPa lower sheeting in 120 DEG C of hollow dry 12h.
Embodiment 6
S1. in deionized water, obtained graphene oxide dispersion concentration is ultrasonic disperse after weighing raw material graphene oxide
Then 0.1mg/mL is added 20wt% hydrogen peroxide as pore creating material in strong mixing, the volume and graphene oxide of hydrogen peroxide is added
The volume ratio of dispersion liquid is 1: 10, then mixed liquor is transferred in hydrothermal reaction kettle, is persistently stirred to react, reaction temperature 150
DEG C, reaction time 6h is cooled to room temperature after having reacted.
S2. the product after the resulting reaction of above-mentioned steps S1 is centrifugated, is washed with deionized, freeze-drying is
Three-dimensional porous graphene oxide, by the three-dimensional porous graphene oxide solid powder sample of gained again ultrasonic disperse to deionization
In water, then under strong agitation be added dopant L-cysteine, ammonium dihydrogen phosphate, porous oxidation graphene, L-cysteine,
The mass ratio of ammonium dihydrogen phosphate is 1: 4: 10, continues stirring and dissolving and obtains mixed solution.
S3. then mixed solution obtained by step S2 is transferred in hydrothermal reaction kettle and carries out hydro-thermal reaction, reaction temperature is
150 DEG C, the reaction time is for 24 hours, to be cooled to room temperature after having reacted.
S4. the resulting reaction product of step S3 is centrifugated, is washed with deionized, freeze-drying collection obtains nitrogenous
The three doping porous oxidation graphenes of three kinds of elements of sulphur phosphorus.
By the active material nitrogen sulphur phosphorus three of preparation (adulterate porous oxidation graphene), acetylene black, PVDF in mass ratio 80:
The ratio of 10:10 mixes, and a small amount of NMP is added and stirs to being mixed thoroughly, is then uniformly coated in said mixture
In nickel foam, the negative electrode material for claiming supercapacitor is made finally in the processing of 10MPa lower sheeting in 120 DEG C of hollow dry 12h.
Embodiment 7
S1. in deionized water, obtained graphene oxide dispersion concentration is ultrasonic disperse after weighing raw material graphene oxide
Then 4 mg/mL are added 40wt% hydrogen peroxide as pore creating material in strong mixing, the volume and graphene oxide point of hydrogen peroxide are added
The volume ratio of dispersion liquid is 1: 50, then mixed liquor is transferred in hydrothermal reaction kettle, is persistently stirred to react, reaction temperature 200
DEG C, reaction time 12h is cooled to room temperature after having reacted.
S2. the product after the resulting reaction of above-mentioned steps S1 is centrifugated, is washed with deionized, freeze-drying is
Three-dimensional porous graphene oxide, by the three-dimensional porous graphene oxide solid powder sample of gained again ultrasonic disperse to deionization
In water, then under strong agitation be added dopant L-cysteine, ammonium dihydrogen phosphate, porous oxidation graphene, L-cysteine,
The mass ratio of ammonium dihydrogen phosphate is 1: 10: 4, continues stirring and dissolving and obtains mixed solution.
S3. then mixed solution obtained by step S2 is transferred in hydrothermal reaction kettle and carries out hydro-thermal reaction, reaction temperature is
200 DEG C, reaction time 2h is cooled to room temperature after having reacted.
S4. the resulting reaction product of step S3 is centrifugated, is washed with deionized, freeze-drying collection obtains nitrogenous
The three doping porous oxidation graphenes of three kinds of elements of sulphur phosphorus.
By active material (the nitrogen sulphur phosphorus three of preparation adulterates porous oxidation graphene), acetylene black, PVDF in mass ratio 80: 10
: 10 ratio mixing is added a small amount of NMP and stirs to being mixed thoroughly, then said mixture is uniformly coated in bubble
On foam nickel, the negative electrode material for claiming supercapacitor is made finally in the processing of 10MPa lower sheeting in 120 DEG C of hollow dry 12h.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description
To make other variations or changes in different ways.There is no necessity and possibility to exhaust all the enbodiments.It is all this
Made any modifications, equivalent replacements, and improvements etc., should be included in the claims in the present invention within the spirit and principle of invention
Protection scope within.
Claims (10)
1. a kind of three kinds of element doping porous oxidation grapheme materials of nitrogen sulphur phosphorus, which is characterized in that formed including following components: oxygen
The dopant of graphite alkene, hydrogen peroxide and three kinds of elements containing nitrogen phosphate and sulfur.
2. the preparation method of three kinds of element doping porous oxidation grapheme materials of nitrogen sulphur phosphorus as described in claim 1, feature
It is, comprising the following steps:
S1. it weighs appropriate graphene oxide ultrasonic disperse and obtains graphene oxide dispersion in deionized water, pore creating material is added
After be transferred into hydrothermal reaction kettle, stirring, reaction, be cooled to room temperature after having reacted；
S2. step S1 products therefrom is centrifugated, is washed, freeze-drying obtains three-dimensional porous graphene oxide, again by it
For secondary ultrasonic disperse in aqueous solution, the dopant that three kinds of elements containing nitrogen phosphate and sulfur are then added under strong agitation continues stirring and dissolving
Obtain mixed solution；
S3. the resulting mixed solution of step S2 is subjected to hydro-thermal reaction, is cooled to room temperature after having reacted；
S4. the resulting reaction product of step S3 is centrifugated, washing is freeze-dried up to the three of nitrogenous three kinds of elements of sulphur phosphorus
Adulterate porous oxidation graphene.
3. the preparation method of three kinds of element doping porous oxidation grapheme materials of nitrogen sulphur phosphorus according to claim 2, special
Sign is that graphene oxide dispersion concentration obtained in step S1 is 0.1~4 mg/mL, the pore creating material and graphite oxide
The volume ratio of alkene dispersion liquid is 1: 5~50.
4. the preparation method of three kinds of element doping porous oxidation grapheme materials of nitrogen sulphur phosphorus according to claim 2, special
Sign is that reaction temperature is 100~200 DEG C in step S1, and the reaction time is 2~12h.
5. the preparation method of three kinds of element doping porous oxidation grapheme materials of nitrogen sulphur phosphorus according to claim 2, special
Sign is that pore creating material described in step S1 is hydrogen peroxide, and the hydrogen peroxide concentration is 20 ~ 40wt%, and preferably hydrogen peroxide concentration is
30wt%。
6. the preparation method of three kinds of element doping porous oxidation grapheme materials of nitrogen sulphur phosphorus according to claim 2, special
Sign is that the dopant of three kinds of elements of Nitrogen-and Phosphorus-containing sulphur described in step S2 is phosphate and sulfurous organic compound.
7. the preparation method of three kinds of element doping porous oxidation grapheme materials of nitrogen sulphur phosphorus according to claim 6, special
Sign is that porous oxidation graphene, sulfurous organic compound, the phosphatic mass ratio being added in step S2 are 1: 1~10: 1~10.
8. the preparation method of three kinds of element doping porous oxidation grapheme materials of nitrogen sulphur phosphorus according to claim 6, special
Sign is that the phosphate can be diammonium hydrogen phosphate, ammonium dihydrogen phosphate or ammonium phosphate salt, and the sulfurous organic compound can be half
Cystine, thiocarbamide or thioacetamide；The preferably described sulfurous organic compound is L-cysteine, and the phosphate is biphosphate
Ammonium.
9. the preparation method of three kinds of element doping porous oxidation grapheme materials of nitrogen sulphur phosphorus according to claim 2, special
Sign is, reaction temperature is 100~200 DEG C in step S3, the reaction time is 2~for 24 hours.
10. three kinds of element doping porous oxidation grapheme materials of nitrogen sulphur phosphorus described in claim 1 ~ 9 are used for super capacitor electrode
Pole material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910673244.9A CN110391087A (en) | 2019-07-24 | 2019-07-24 | A kind of preparation method and applications of three kinds of element doping porous oxidation grapheme materials of nitrogen sulphur phosphorus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910673244.9A CN110391087A (en) | 2019-07-24 | 2019-07-24 | A kind of preparation method and applications of three kinds of element doping porous oxidation grapheme materials of nitrogen sulphur phosphorus |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110391087A true CN110391087A (en) | 2019-10-29 |
Family
ID=68287368
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910673244.9A Pending CN110391087A (en) | 2019-07-24 | 2019-07-24 | A kind of preparation method and applications of three kinds of element doping porous oxidation grapheme materials of nitrogen sulphur phosphorus |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110391087A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110817850A (en) * | 2019-12-21 | 2020-02-21 | 桂林理工大学 | Nitrogen-phosphorus co-doped graphene quantum dot and preparation method thereof |
| CN111155146A (en) * | 2019-12-26 | 2020-05-15 | 浙江大学 | Preparation method of vanadium-doped nickel phosphide composite nitrogen-sulfur double-doped reduced graphene oxide electrocatalytic material |
| CN111508721A (en) * | 2020-04-24 | 2020-08-07 | 刘庆信 | Graphene modified aniline-pyrrole copolymer electrode material and preparation method thereof |
| CN112520730A (en) * | 2020-12-03 | 2021-03-19 | 东华大学 | Polyatomic co-doped graphene, preparation method and application |
| CN114014306A (en) * | 2021-12-15 | 2022-02-08 | 陇东学院 | Preparation method and application of oxygen-enriched layered porous graphene |
| WO2022042667A1 (en) * | 2020-08-27 | 2022-03-03 | 中国石油化工股份有限公司 | Carbon-supported platinum group metal catalyst, preparation method therefor and use thereof |
| CN114479521A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Carbon material, platinum-carbon catalyst, and preparation method and application thereof |
| CN114512706A (en) * | 2021-12-24 | 2022-05-17 | 合肥国轩高科动力能源有限公司 | Lithium ion battery diaphragm slurry and lithium ion battery diaphragm |
| CN115231558A (en) * | 2022-07-12 | 2022-10-25 | 苏州大学 | Graphene material with high sulfur atom doping degree and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106044754A (en) * | 2016-05-31 | 2016-10-26 | 中国科学院山西煤炭化学研究所 | Preparation method of heteroatom doped graphene hierarchical pore carbon material |
| CN106744838A (en) * | 2016-12-06 | 2017-05-31 | 武汉工程大学 | The method that one step hydro thermal method prepares N doping porous graphene |
| CN108232116A (en) * | 2017-12-15 | 2018-06-29 | 江苏大学 | A kind of preparation method of nitrogen, phosphor codoping Graphene gel electrochemistry storage sodium electrode |
| CN109678139A (en) * | 2017-10-18 | 2019-04-26 | 天津大学 | Fluorine nitrogen codope porous graphene hydrogel and preparation method thereof for electrode of super capacitor |
| CN109971470A (en) * | 2019-03-19 | 2019-07-05 | 集美大学 | A method of preparing nitrogen, sulphur, phosphorus, chlorine co-doped graphene quantum dot |
-
2019
- 2019-07-24 CN CN201910673244.9A patent/CN110391087A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106044754A (en) * | 2016-05-31 | 2016-10-26 | 中国科学院山西煤炭化学研究所 | Preparation method of heteroatom doped graphene hierarchical pore carbon material |
| CN106744838A (en) * | 2016-12-06 | 2017-05-31 | 武汉工程大学 | The method that one step hydro thermal method prepares N doping porous graphene |
| CN109678139A (en) * | 2017-10-18 | 2019-04-26 | 天津大学 | Fluorine nitrogen codope porous graphene hydrogel and preparation method thereof for electrode of super capacitor |
| CN108232116A (en) * | 2017-12-15 | 2018-06-29 | 江苏大学 | A kind of preparation method of nitrogen, phosphor codoping Graphene gel electrochemistry storage sodium electrode |
| CN109971470A (en) * | 2019-03-19 | 2019-07-05 | 集美大学 | A method of preparing nitrogen, sulphur, phosphorus, chlorine co-doped graphene quantum dot |
Non-Patent Citations (1)
| Title |
|---|
| FATEMEH RAZMJOOEI ET AL: ""Enhanced electrocatalytic activity due to additional phosphorous doping in nitrogen and sulfur-doped graphene: A comprehensive study"", 《CARBON》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110817850A (en) * | 2019-12-21 | 2020-02-21 | 桂林理工大学 | Nitrogen-phosphorus co-doped graphene quantum dot and preparation method thereof |
| CN111155146A (en) * | 2019-12-26 | 2020-05-15 | 浙江大学 | Preparation method of vanadium-doped nickel phosphide composite nitrogen-sulfur double-doped reduced graphene oxide electrocatalytic material |
| CN111508721A (en) * | 2020-04-24 | 2020-08-07 | 刘庆信 | Graphene modified aniline-pyrrole copolymer electrode material and preparation method thereof |
| WO2022042667A1 (en) * | 2020-08-27 | 2022-03-03 | 中国石油化工股份有限公司 | Carbon-supported platinum group metal catalyst, preparation method therefor and use thereof |
| CN114479521A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Carbon material, platinum-carbon catalyst, and preparation method and application thereof |
| CN114479521B (en) * | 2020-10-26 | 2023-05-05 | 中国石油化工股份有限公司 | Carbon material, platinum-carbon catalyst, and preparation method and application thereof |
| CN112520730A (en) * | 2020-12-03 | 2021-03-19 | 东华大学 | Polyatomic co-doped graphene, preparation method and application |
| CN112520730B (en) * | 2020-12-03 | 2022-06-21 | 东华大学 | Polyatomic co-doped graphene, preparation method and application |
| CN114014306B (en) * | 2021-12-15 | 2022-08-09 | 陇东学院 | Preparation method and application of oxygen-enriched layered porous graphene |
| CN114014306A (en) * | 2021-12-15 | 2022-02-08 | 陇东学院 | Preparation method and application of oxygen-enriched layered porous graphene |
| CN114512706A (en) * | 2021-12-24 | 2022-05-17 | 合肥国轩高科动力能源有限公司 | Lithium ion battery diaphragm slurry and lithium ion battery diaphragm |
| CN114512706B (en) * | 2021-12-24 | 2023-08-04 | 合肥国轩高科动力能源有限公司 | Lithium ion battery diaphragm slurry and lithium ion battery diaphragm |
| CN115231558A (en) * | 2022-07-12 | 2022-10-25 | 苏州大学 | Graphene material with high sulfur atom doping degree and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110391087A (en) | A kind of preparation method and applications of three kinds of element doping porous oxidation grapheme materials of nitrogen sulphur phosphorus | |
| CN107393725B (en) | A kind of carbon material supported NiCo of porous, electrically conductive2O4Composite material and its preparation method and application | |
| CN103413689B (en) | Prepare graphene aerogel and the method for graphene/metal oxide aeroge | |
| Hang et al. | Ni 0.33 Co 0.67 MoS 4 nanosheets as a bifunctional electrolytic water catalyst for overall water splitting | |
| CN106229521B (en) | A kind of FeCx@NC catalyst with core-casing structure and preparation method thereof | |
| CN103346024B (en) | The preparation method of high-conductivity flexible graphene membrane electrode | |
| CN106334501A (en) | Three-dimensional N/S double-doped graphene aerogel as well as preparation method and application thereof | |
| CN108389728A (en) | A kind of preparation method of nitrogen/phosphorus/oxygen heterogeneous element codope carbon electrode material | |
| CN109967100A (en) | A kind of metal-doped CoP3, preparation method and application | |
| CN107731566A (en) | A kind of preparation method and application of three-dimensional petal-shaped nickel cobalt sulfide electrode material | |
| CN105679552B (en) | A kind of thiocarbamide urea formaldehyde based super capacitor electrode material and its preparation method and application | |
| CN110474050B (en) | Preparation method of doped carbon/manganese sulfide composite material | |
| CN106492843A (en) | A kind of ultra-dispersed MoS2The preparation method of/rGO nano hybridization water electrolysis hydrogen production catalyst | |
| CN103632857A (en) | Preparation method for nickel-oxide/ reduced-graphene-oxide nanosheet composite materials | |
| Yao et al. | Template-assisted synthesis of hierarchically porous Co3O4 with enhanced oxygen evolution activity | |
| CN109850896A (en) | A kind of preparation method and application of primary Eichhornia crassipes biomass carbon porous electrode material | |
| CN108336374A (en) | Nitrogenous carbon material of a kind of high-performance ternary Fe-Co-Ni codopes and its preparation method and application | |
| CN104091931A (en) | Multi-edge MoS2 nano piece/graphene composite nanomaterial and preparation method thereof | |
| CN105883925B (en) | A kind of mesoporous mangano-manganic oxide and preparation method thereof | |
| Zhang et al. | Melamine-assisted synthesis of paper mill sludge-based carbon nanotube/nanoporous carbon nanocomposite for enhanced electrocatalytic oxygen reduction activity | |
| Zhang et al. | N-doped biomass carbon materials as superior catalyst to improve electrochemical performance of vanadium redox flow battery | |
| Jia et al. | One-step synthesis of Co2P/NP co-doped porous carbon composites derived from soybean derivatives as acidic and alkaline HER electrocatalysts | |
| CN104091936B (en) | A kind of MoS2nanometer watt/graphene composite nano material and preparation method thereof | |
| Wang et al. | Mesopore-dominated N, S co-doped carbon as advanced oxygen reduction reaction electrocatalysts for Zn-air battery | |
| Shang et al. | Constructing hierarchical structure electrocatalyst for efficient hydrogen evolution and selective oxidation of benzylamine |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191029 |