CN109503420A - A kind of dual graft azobenzene/graphene composite energy-storage material and preparation method - Google Patents
A kind of dual graft azobenzene/graphene composite energy-storage material and preparation method Download PDFInfo
- Publication number
- CN109503420A CN109503420A CN201710833709.3A CN201710833709A CN109503420A CN 109503420 A CN109503420 A CN 109503420A CN 201710833709 A CN201710833709 A CN 201710833709A CN 109503420 A CN109503420 A CN 109503420A
- Authority
- CN
- China
- Prior art keywords
- graphene
- azobenzene
- storage material
- energy
- dual graft
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
- C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/11—Compounds covalently bound to a solid support
Abstract
The present invention discloses a kind of dual graft azobenzene/graphene composite energy-storage material and preparation method, and two kinds of azo molecules of monomer molecule are covalently grafted to graphene surface, and every 30~60 carbon atoms are grafted an azo molecules；The preparation of two kinds first azo molecules；Then redox graphene pre-processes；Finally carry out the preparation of dual graft azobenzene/graphene composite material.The isomerization rate of energy storage material of the present invention is up to 94%, improves 30% than monomer molecule；Storage density is up to 150Wh/kg, improves nearly 60% than monomer molecule, has surmounted the energy density of common lithium battery.More traditional single azo molecules are greatly improved in energy value and half-life period, are conducive to that the sun is made full use of to can be carried out energy stores.
Description
Technical field
The invention belongs to composite functional material fields, more particularly, it is multiple to be related to a kind of dual graft azobenzene/graphene
Energy storage material and preparation method are closed, before future has important application in Solar use and in terms of making long-range photo-thermal switch
Scape.
Background technique
Solar energy is a kind of inexhaustible eco-friendly power source, although solar radiation is to the energy of earth atmosphere
Only 1st/2200000000th of its total radiation energy, but it has been up to 173000TW, that is to say, that the sun is irradiated on the earth each second
Energy be equivalent to 5,000,000 tons of coals, the energy per second for being irradiated to the earth is then 1.465 × 10^14 coke.Tellurian wind energy,
Water energy, ocean thermal energy, wave energy and biomass energy are all derived from the sun；Even tellurian fossil fuel (such as coal, stone
Oil, natural gas etc.) solar energy to get off basically and since time immemorial has been stored, so model included by the solar energy of broad sense
It encloses very greatly, the solar energy of narrow sense is then limited to the photo-thermal, photoelectricity and photochemical direct conversion of solar radiant energy.
The rapid development of China's economy so that increase in demand to the energy, caused by environmental problem it is also urgently to be resolved.In order to
The use of the non-renewable energy resources such as coal petroleum gas is reduced, the dependence to these energy is reduced, in this case, development is new
The energy and renewable energy are very urgent.Solar energy advantage mainly has: (1) universal: solar light cultivated illumination the earth, the not limit of region
System, no matter land or ocean, no matter high mountain or island, all have everywhere, can directly develop and utilize, and need not convenient for acquisition
Exploitation and transport.(2) harmless: development and utilization solar energy does not pollute the environment, it is most one of clean energy resource, is got in environmental pollution
Come more serious today, this point is extremely valuable.(3) huge: the annual solar radiant energy about phase reached on earth surface
When in 130,000,000,000,000 tons of coals, total amount belongs to the maximum energy that can be developed in the world now.(4) permanent: the core generated according to the sun
Can rate estimation, the reserves of hydrogen maintain over ten billion year enough, and the service life of the earth is also about tens years, in this sense
It says, it may be said that the energy of the sun is nexhaustible.
Azobenzene is a kind of light responsive material with along anti-two kinds of configurations.Under the ultraviolet light of specific wavelength, instead
The azobenzene of formula configuration can be changed into cis-configuration；Later under conditions of light or heat, cis-configuration can be restored to anti-configuration.
There are the difference of energy between two kinds of configurations, by it is trans- be transitioned into it is cis- can store energy, otherwise heat can be discharged.It utilizes
Graphene is template, the energy generated by cis-trans isomerism.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of dual graft azobenzene/compound storages of graphene
Energy material and preparation method have high-energy density, the characteristic of long half-lift.
Technical purpose of the invention is achieved by following technical proposals:
Dual graft azobenzene/graphene composite energy-storage material is made of, two kinds graphene and two kinds of monomer azobenzene molecules
Monomer azobenzene molecule is covalently grafted to graphene surface, and every 30~60 carbon atoms are grafted azobenzene point
Son, structural formula are as follows:
In dual graft azobenzene/graphene composite energy-storage material of the invention, restore to obtain stone using graphene oxide
Black alkene, so that damaged structure occurs in the benzene ring structure of composition graphene, there is some carbon original in fine and close hexatomic ring (phenyl ring) structure
The missing of son forms vacancy, provides reaction site for the grafting of two kinds of azobenzene molecules, preferably every 40~50 carbon atoms grafting
One azobenzene molecule.
The structural formula of first azobenzene molecule (i.e. the first monomer) is as follows:
The structural formula of second azobenzene molecule (i.e. second comonomer) is as follows:
Dual graft azobenzene/graphene composite energy-storage material preparation method, is prepared as steps described below:
In the aqueous solution of methyl pyrrolidone be added graphene, the first azo benzene monomer, the second azo benzene monomer and
NaOH is simultaneously evenly dispersed, is reacted under inert protective gas atmosphere, and reaction temperature is 100-150 degrees Celsius, so that two kinds
Azo benzene monomer is covalently grafted to the reaction site of graphene surface, and it is compound to obtain dual graft azobenzene/graphene
Energy storage material；Wherein graphene uses sodium borohydride and sodium carbonate redox graphene for graphene, so that composition graphene
Benzene ring structure there is damaged structure, there is the missing of carbon atom in fine and close hexatomic ring (phenyl ring) structure, forms vacancy, is two kinds
The grafting of azo benzene monomer provides reaction site；First azo benzene monomer is double carboxyl azobenzenes, and the second azo benzene monomer is double
Trifluoromethyl azobenzene, the amino on two kinds of azo benzene monomers is reacted with reaction site respectively, so that it is covalently keyed to graphite
In alkene structure.
In the above-mentioned technical solutions, 20-30 mass parts graphene is added, each mass parts are 1mg, the first azo benzene monomer
Molar ratio with sodium hydroxide is 1:(1-1.2), the molar ratio of the second azo benzene monomer and sodium hydroxide is 1:(1-1.2).
In the above-mentioned technical solutions, in the aqueous solution of methyl pyrrolidone, methyl pyrrolidone concentration is 0.3-
0.9mg/mL。
In the above-mentioned technical solutions, inert protective gas atmosphere is nitrogen, helium or argon gas.
In the above-mentioned technical solutions, reaction temperature be 120-140 degrees Celsius, the reaction time be 5-10 hours, preferably 7-
8 hours.
In the above-mentioned technical solutions, after the completion of reaction, decompression filters, acetone washing 3-5 times, obtains purpose product pair and connects
Branch azobenzene/graphene composite material.
In the above-mentioned technical solutions, graphene uses sodium borohydride and sodium carbonate redox graphene for graphene, tool
For body, graphene oxide is placed in water to and is added sodium carbonate adjusting pH to 7-9, sodium borohydride aqueous solution is added to oxidation stone
Black alkene carries out reduction treatment, and the concentration of sodium borohydride is 10-20mg/ml (sodium borohydride quality, mg/ water volume, ml), in 75-
It is placed 6-8 hours under 90 degrees Celsius；By centrifugation, filtering, distilled water is washed to obtain required redox graphene (i.e. stone
Black alkene)；Then it is dispersed in water again ultrasound is passed through.
First azo benzene monomer is double carboxyl azobenzenes, is prepared as steps described below: by 3,5 dicarboxyanylines, Asia
Sodium nitrate and sodium hydroxide are evenly dispersed in deionized water, and hydrochloric acid is added dropwise, and ice bath reaction adds 3,5 two after carrying out azo
Reaction obtains double carboxyl azobenzenes under inert protective gas atmosphere in aminoanisole, as follows:
Specifically, 3,5 dicarboxyanylines, sodium nitrite and sodium hydroxide are equimolar ratio, 3,5 dicarboxyanylines and chlorine
The molar ratio for changing hydrogen is 1:(4-6), 3,5 dicarboxyanylines and 3, the molar ratio of 5 dimethoxyanilines is 1:(1-2), 3,5 two
Carboxyanilino is 10-30 molar parts, and each molar part is 1mmol；Ice bath reaction temperature is 0-2 degrees Celsius, when ice bath reacts
Between be 1-3 hours；Hydrogen cloride concentration is 1mol/L in hydrochloric acid.In the reaction by it is faint yellow just formed it is dark red or orange-red
Azo reaction, adds 3,5-dimethoxyanilines and is reacted, while adjusting pH to 6-7, generates yellow mercury oxide, i.e., double carboxylics
Base azobenzene.
Second azo benzene monomer is bis trifluoromethyl azobenzene, is prepared as steps described below: by 3,5 two trifluoromethyls
Aniline, sodium nitrite and hydrochloric acid are added in methanol, keep its miscible uniformly；It is added dropwise to sodium nitrite, ice bath reaction carries out azo
After add in 3,5 dimethoxyanilines the reaction under inert protective gas atmosphere and obtain bis trifluoromethyl azobenzene, following institute
Show:
Specifically, starting 3,5 two 5-trifluoromethylanilines and sodium nitrite when charging is equimolar ratio, 3,5 two fluoroforms
The molar ratio of base aniline and the sodium nitrite of dropwise addition is 1:(1-2), the molar ratio of 3,5 two 5-trifluoromethylanilines and hydrogen chloride is
1:(4-6), methanol is 4-10 parts by volume, and each parts by volume is 1ml, and 3,5 two 5-trifluoromethylanilines are 10-30 molar parts, often
One molar part is 1mmol；Ice bath reaction temperature is 0-2 degrees Celsius, and the ice bath reaction time is 1-3 hours；Hydrogen chloride in hydrochloric acid
Concentration is 1mol/L.
Dual graft azobenzene/graphene composite energy-storage material of the invention can efficient storage solar energy, have high-energy
The characteristics of density, controlled thermal release, carries out energy stores and release using cis-trans isomerism, as follows:
Dual graft azobenzene/graphene composite energy-storage material is subjected to ultraviolet spectra characterization, as shown in Fig. 1, absorption peak
For the absorption of the π-π * under trans- state.By dual graft azobenzene/graphene composite energy-storage material DSC (differential scanning calorimetry
Method), it is discharged using the heat that differential scan calorimeter carries out temperature programmed control measurement material, is then released exothermic peak integral
Energy, then make comparisons with quality, obtain the storage density of material, as shown in Fig. 2, show the material really and have along anti-
Structure has the effect of heat accumulation simultaneously.By azobenzene/graphene Jing Guo ultraviolet light and azobenzene/graphite without heat accumulation
Alkene is placed on to be observed in thermal station with thermal infrared imager respectively, the variation of directly accurate shooting recording materials exothermic process temperature, storage
Azobenzene/grapheme material of heat is 15 DEG C higher than the temperature without heat accumulation, and exothermal effect is quite obvious.It is of the invention through calculating
Dual graft azobenzene/graphene composite energy-storage material energy storage density improves closely up to 130-150Wh/kg than monomer molecule
60%, surmount the energy density of common lithium battery.It is filled with the ultraviolet light irradiation 10min of 260W energy storage material of the invention
Heat discharges the heat of storage by thermostimulation, heat accumulating is in 80 DEG C of beginning heat releases in DSC scanning process.
The quality that redox graphene is first weighed before azo molecules and redox graphene are compound, is denoted as m0, the
After a kind of azo molecules are reacted with redox graphene, the azo molecules of absorption are washed off, weigh quality after drying again, remembered
For m1, second azo molecules and front were grafted the graphite alkene reaction of azo, and washed off the molecule of absorption, weigh quality after drying
For m2, the relative molecular mass of azo molecules is M, and the relative atomic mass 12 of C atom, grafting rate calculation formula is γ1=12
(m1-m0)/M*m0, γ1=12 (m2-m1)/M*m0；Isomerization is calculated further according to the ratio of energy energy storage and release in cis-trans isomerism
How much rate is changed into cis-structure in whole transconfigurations, isomerization rate reaches as high as 94-96%, improves than monomer molecule
30%.
The present invention discloses a kind of novel dual graft azobenzene/graphene composite material and preparation method, by double carboxyanilinos
With bis trifluoromethyl aniline respectively with 3,5 dimethoxyanilines reaction synthesis branch azobenzene, then with pretreated oxygen reduction
Graphite alkene is compound, obtained dual graft azobenzene/graphene composite material.It is multiple in heterocycle azo benzene/graphene of the invention
In condensation material, grafting azobenzene is carried out using graphene oxide also original structure, restores to obtain graphene using graphene oxide, with
The benzene ring structure for forming graphene is set damaged structure occur, lacking for some carbon atom occurs in fine and close hexatomic ring (phenyl ring) structure
It loses, forms vacancy, provide reaction site for the grafting of azobenzene；Two kinds of grafting azobenzenes in dual graft energy storage material of the invention
Between form intermolecular hydrogen bonding, the composite material of more traditional single grafting azobenzene has in energy value with half-life period to be changed greatly very much
It is kind, be conducive to that the sun is made full use of to can be carried out energy stores, and can be answered by the graft ratio of two kinds of azo benzene monomers
The adjustment of condensation material performance.
Detailed description of the invention
Fig. 1 is dual graft azobenzene/graphene composite material ultra-violet absorption spectrum.
Fig. 2 is dual graft azobenzene/graphene composite material DSC figure.
Fig. 3 is the nmr spectrum of bis trifluoromethyl used in the present invention.
Specific embodiment
Technical solution of the present invention is further illustrated combined with specific embodiments below.Preparing double carboxyl azobenzene processes
In, with 3,5 dicarboxyanylines mole on the basis of, equivalent, 1-2 equivalent are one times and 1-2 of 3,5 dicarboxyanylines mole
Times.During preparing bis trifluoromethyl azobenzene, with 3,5 two 5-trifluoromethylanilines mole on the basis of, equivalent, 1-2 work as
Amount is one times and 1-2 times of 3,5 2 5-trifluoromethylanilines mole.During preparing azobenzene, in the reaction by it is faint yellow just
Dark red or orange-red azo reaction is formed, 3,5-dimethoxyanilines is added and is reacted, while adjusting pH to 6-
7, generate inclined yellow mercury oxide.
Embodiment 1
1) preparation of double carboxyl azobenzenes: by the sodium nitrite of 3,5 dicarboxyanylines of 30mmol and equivalent and etc. work as
The sodium hydroxide of amount is dissolved in deionized water, is added dropwise to the hydrochloric acid of 6 equivalent 1mol/L, and ice bath reacts 3 hours, is added to 2 and works as
Reaction obtains double carboxyl azobenzenes under argon gas in 3,5 dimethoxyanilines of amount；
2) preparation of bis trifluoromethyl azobenzene: by 3,5 2 5-trifluoromethylanilines of 30mmol and the nitrous acid of equivalent
In the 1mol/L hydrochloric acid of sodium and 6 equivalents, 6ml methanol is added to keep its miscible, be then added dropwise to 2 equivalent sodium nitrites, ice bath reaction 3 is small
When, the 3 of 2 equivalents are added to, is reacted under argon gas in 5 dimethoxyanilines and obtains bis trifluoromethyl azobenzene；
3) redox graphene pre-processes: the aqueous sodium carbonate for being 30% with mass percent is by graphene oxide
Aqueous solution adjusts pH to 9, and the graphene oxide water solution that the pH of 40ml is mixed up is added in 20mg/ml sodium borohydride aqueous solution,
And it is placed 8 hours under 90 degrees Celsius；By centrifugation, filtering, distilled water is washed to obtain the required RGO (oxidation restored
Graphene)；Then it is dispersed in water again ultrasound is passed through；
4) dual graft azobenzene/graphene composite material preparation: add in 0.9mg/mL methyl pyrrolidone aqueous solution
Enter that the above-mentioned RGO of 20mg is evenly dispersed to be placed in reactor；Azo molecules, the 0.6mmol step that 0.6mmol step 1) is obtained
2) azo molecules and equimolar NaOH obtained are added to reactor；N2It is reacted 5 hours under protection at 140 DEG C；Decompression filters, and third
Ketone washs 3-5 times, obtains purpose product dual graft azobenzene/graphene composite material.Storage density reaches 150Wh/kg.
Embodiment 2
1) preparation of double carboxyl azobenzenes: by the sodium nitrite of 3,5 dicarboxyanylines of 10mmol and equivalent and etc. work as
The sodium hydroxide of amount is dissolved in deionized water, is added dropwise to the hydrochloric acid of 4 equivalent 1mol/L, and ice bath reacts 1 hour, is added to 1 and works as
Reaction obtains double carboxyl azobenzenes under argon gas in 3,5 dimethoxyanilines of amount；
2) preparation of bis trifluoromethyl azobenzene: by 3,5 2 5-trifluoromethylanilines of 10mmol and the nitrous acid of equivalent
In the 1mol/L hydrochloric acid of sodium and 4 equivalents, 4ml methanol is added to keep its miscible, be then added dropwise to 1 equivalent sodium nitrite, ice bath reaction 1 is small
When, the 3 of 1 equivalent are added to, is reacted under argon gas in 5 dimethoxyanilines and obtains bis trifluoromethyl azobenzene；
3) redox graphene pre-processes: the aqueous sodium carbonate for being 20% with mass percent is by graphene oxide
Aqueous solution adjusts pH to 7, and the graphene oxide water solution that the pH of 30ml is mixed up is added in 10mg/ml sodium borohydride aqueous solution,
And it is placed 6 hours under 75 degrees Celsius；By centrifugation, filtering, distilled water is washed to obtain the required RGO (oxidation restored
Graphene)；Then it is dispersed in water again ultrasound is passed through；
4) dual graft azobenzene/graphene composite material preparation: add in 0.3mg/mL methyl pyrrolidone aqueous solution
Enter that the above-mentioned RGO of 25mg is evenly dispersed to be placed in reactor；Azo molecules, the 0.2mmol step that 0.2mmol step 1) is obtained
2) azo molecules and equimolar NaOH obtained are added to reactor；N2It is reacted 10 hours under protection at 120 DEG C；Decompression filters,
Acetone washing 3-5 times obtains purpose product dual graft azobenzene/graphene composite material.Storage density reaches 140Wh/kg.
Embodiment 3
1) preparation of double carboxyl azobenzenes: by the sodium nitrite of 3,5 dicarboxyanylines of 20mmol and equivalent and etc. work as
The sodium hydroxide of amount is dissolved in deionized water, is added dropwise to the hydrochloric acid of 5 equivalent 1mol/L, and ice bath reacts 2 hours, is added to 2 and works as
Reaction obtains double carboxyl azobenzenes under argon gas in 3,5 dimethoxyanilines of amount；
2) preparation of bis trifluoromethyl azobenzene: by 3,5 2 5-trifluoromethylanilines of 20mmol and the nitrous acid of equivalent
In the 1mol/L hydrochloric acid of sodium and 5 equivalents, 5ml methanol is added to keep its miscible, be then added dropwise to 1 equivalent sodium nitrite, ice bath reaction 2 is small
When, the 3 of 1 equivalent are added to, is reacted under argon gas in 5 dimethoxyanilines and obtains bis trifluoromethyl azobenzene；
3) redox graphene pre-processes: the sodium carbonate for being 20%-30% with mass fraction is by the water of graphene oxide
Solution adjusts pH to 7-9, the solution that the pH of 30-40ml is mixed up is added in 10-20mg/ml sodium borohydride solution, and in 75-90
It is placed 6-8 hours under degree Celsius；By centrifugation, filtering, distilled water is washed to obtain required RGO；Then heavy by ultrasound
Newly it is dispersed in water；
4) dual graft azobenzene/graphene composite material preparation: add in 0.6mg/mL methyl pyrrolidone aqueous solution
Enter that the above-mentioned RGO of 25mg is evenly dispersed to be placed in reactor；Azo molecules, the 0.6mmol step that 0.4mmol step 1) is obtained
2) azo molecules and 0.6mmol NaOH obtained are added to reactor；N2It is reacted 8 hours under protection at 120 DEG C；Decompression filters,
Acetone washing 3-5 times obtains purpose product dual graft azobenzene/graphene composite material.Storage density reaches 130Wh/kg.
Content carries out the adjustment of technological parameter according to the present invention, can prepare dual graft azobenzene/graphene composite material,
And show almost the same energy storage-release performance.Illustrative description has been done to the present invention above, it should explanation,
In the case where not departing from core of the invention, any simple deformation, modification or other skilled in the art can not be spent
The equivalent replacement of expense creative work each falls within protection scope of the present invention.
Claims (10)
1. dual graft azobenzene/graphene composite energy-storage material, which is characterized in that by graphene and two kinds of monomer azobenzene molecules
Composition, two kinds of monomer azobenzene molecules are covalently grafted to graphene surface, and every 30~60 carbon atoms are grafted one
Azobenzene molecule restores to obtain graphene using graphene oxide, so that there is damaged structure in the benzene ring structure of composition graphene,
There is the missing of some carbon atom in fine and close six-membered ring structure, forms vacancy, and the grafting for two kinds of azobenzene molecules provides reaction
Site；Structural formula is as follows:
The structural formula of first azobenzene molecule is as follows:
The structural formula of second azobenzene molecule (i.e. second comonomer) is as follows:
2. dual graft azobenzene/graphene composite energy-storage material according to claim 1, which is characterized in that every 40~50
A carbon atom is grafted an azobenzene molecule.
3. dual graft azobenzene/graphene composite energy-storage material preparation method, which is characterized in that made as steps described below
It is standby: graphene, the first azo benzene monomer, the second azo benzene monomer and NaOH and equal being added in the aqueous solution of methyl pyrrolidone
Even dispersion is reacted under inert protective gas atmosphere, and reaction temperature is 100-150 degrees Celsius, so that two kinds of azobenzene lists
Body is covalently grafted to the reaction site of graphene surface, obtains dual graft azobenzene/graphene composite energy-storage material；
Wherein graphene uses sodium borohydride and sodium carbonate redox graphene for graphene, so that the benzene ring structure of composition graphene
There is damaged structure, the missing of carbon atom occurs in fine and close hexatomic ring (phenyl ring) structure, forms vacancy, is two kinds of azo benzene monomers
Grafting provide reaction site；First azo benzene monomer is double carboxyl azobenzenes, and the second azo benzene monomer is that bis trifluoromethyl is even
Pyridine.
4. the preparation method of dual graft azobenzene/graphene composite energy-storage material according to claim 3, feature exist
In graphene uses sodium borohydride and sodium carbonate redox graphene for graphene, and specifically, graphene oxide is placed in
In water and sodium carbonate adjusting pH to 7-9 is added, sodium borohydride aqueous solution is added, reduction treatment, hydroboration is carried out to graphene oxide
The concentration of sodium is 10-20mg/ml, is placed 6-8 hours under 75-90 degrees Celsius；By centrifugation, filtering, distilled water is washed to obtain
Required redox graphene (i.e. graphene)；Then it is dispersed in water again ultrasound is passed through.
5. the preparation method of dual graft azobenzene/graphene composite energy-storage material according to claim 3, feature exist
In the first azo benzene monomer is double carboxyl azobenzenes, is prepared as steps described below: by 3,5 dicarboxyanylines, sodium nitrite
It is evenly dispersed in deionized water with sodium hydroxide, hydrochloric acid is added dropwise, ice bath reaction adds 3,5 dimethoxys after carrying out azo
Reaction obtains double carboxyl azobenzenes under inert protective gas atmosphere in aniline；Second azo benzene monomer is bis trifluoromethyl azo
Benzene is prepared as steps described below: 3,5 two 5-trifluoromethylanilines, sodium nitrite and hydrochloric acid being added in methanol, keep its miscible
Uniformly；It is added dropwise to sodium nitrite, ice bath reaction adds in 3,5 dimethoxyanilines after carrying out azo in inert protective gas
Reaction obtains bis trifluoromethyl azobenzene under atmosphere.
6. the preparation method of dual graft azobenzene/graphene composite energy-storage material according to claim 3, feature exist
In 20-30 mass parts graphene being added, each mass parts are 1mg, and the molar ratio of the first azo benzene monomer and sodium hydroxide is 1:
The molar ratio of (1-1.2), the second azo benzene monomer and sodium hydroxide is 1:(1-1.2).
7. the preparation method of dual graft azobenzene/graphene composite energy-storage material according to claim 3, feature exist
In in the aqueous solution of methyl pyrrolidone, methyl pyrrolidone concentration is 0.3-0.9mg/mL.
8. the preparation method of dual graft azobenzene/graphene composite energy-storage material according to claim 3, feature exist
In inert protective gas atmosphere is nitrogen, helium or argon gas.
9. the preparation method of dual graft azobenzene/graphene composite energy-storage material according to claim 3, feature exist
In reaction temperature is 120-140 degrees Celsius, and the reaction time is 5-10 hours, preferably 7-8 hours.
10. dual graft azobenzene/graphene composite energy-storage material as described in claim 1 is in preparing solar energy heat-storage material
Application, which is characterized in that energy storage density reaches as high as 94-96% up to 130-150Wh/kg, isomerization rate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710833709.3A CN109503420A (en) | 2017-09-15 | 2017-09-15 | A kind of dual graft azobenzene/graphene composite energy-storage material and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710833709.3A CN109503420A (en) | 2017-09-15 | 2017-09-15 | A kind of dual graft azobenzene/graphene composite energy-storage material and preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109503420A true CN109503420A (en) | 2019-03-22 |
Family
ID=65744977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710833709.3A Pending CN109503420A (en) | 2017-09-15 | 2017-09-15 | A kind of dual graft azobenzene/graphene composite energy-storage material and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109503420A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113174241A (en) * | 2020-10-29 | 2021-07-27 | 山西大同大学 | Graphene synergistic heat storage composite material and preparation method and application thereof |
| CN113173864B (en) * | 2020-10-30 | 2023-06-30 | 山西大同大学 | Graphene synergistic photo-thermal energy storage composite material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870467A (en) * | 2010-06-02 | 2010-10-27 | 天津大学 | Optical responsive azobenzene graft grapheme material and preparation method thereof |
| CN105969321A (en) * | 2016-05-30 | 2016-09-28 | 天津大学 | Double-branch azobenzene/graphene energy storage material and preparing method |
| CN106047307A (en) * | 2016-05-24 | 2016-10-26 | 天津大学 | Tri-branched azobenzene/graphene composite energy storage material and preparation method thereof |
| CN106966929A (en) * | 2017-03-14 | 2017-07-21 | 天津大学 | A kind of Linear Double branch azobenzene/graphene composite material and preparation method and application |
-
2017
- 2017-09-15 CN CN201710833709.3A patent/CN109503420A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870467A (en) * | 2010-06-02 | 2010-10-27 | 天津大学 | Optical responsive azobenzene graft grapheme material and preparation method thereof |
| CN106047307A (en) * | 2016-05-24 | 2016-10-26 | 天津大学 | Tri-branched azobenzene/graphene composite energy storage material and preparation method thereof |
| CN105969321A (en) * | 2016-05-30 | 2016-09-28 | 天津大学 | Double-branch azobenzene/graphene energy storage material and preparing method |
| CN106966929A (en) * | 2017-03-14 | 2017-07-21 | 天津大学 | A kind of Linear Double branch azobenzene/graphene composite material and preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| WEN LUO等: "A high energy density azobenzene/graphene hybrid: a nano-templated platform for solar thermal storage", 《J.MATER.CHEM.A》 * |
| WEN LUO等: "High-energy, stable and recycled molecular solar thermal storage materials using AZO/graphene hybrids by optimizing hydrogen bonds", 《NANOSCALE》 * |
| 罗文: "偶氮苯-石墨烯杂化材料的合成及其氢键调控分子储能研究", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113174241A (en) * | 2020-10-29 | 2021-07-27 | 山西大同大学 | Graphene synergistic heat storage composite material and preparation method and application thereof |
| CN113174241B (en) * | 2020-10-29 | 2022-04-08 | 山西大同大学 | Graphene synergistic heat storage composite material and preparation method and application thereof |
| CN113173864B (en) * | 2020-10-30 | 2023-06-30 | 山西大同大学 | Graphene synergistic photo-thermal energy storage composite material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Martindale et al. | Enhancing light absorption and charge transfer efficiency in carbon dots through graphitization and core nitrogen doping | |
| Srinivasan et al. | Long term cycling behavior of titanium doped NaAlH4 prepared through solvent mediated milling of NaH and Al with titanium dopant precursors | |
| Dincer et al. | Solar based hydrogen production systems | |
| CN102838085B (en) | High-capacity high-molecular polymer hydrogen storing material and preparation method thereof | |
| CN110586183B (en) | Method for preparing TiO by using supercritical carbon dioxide2Method for preparing/COF catalytic material | |
| Jiang et al. | Surface modification of porous gC 3 N 4 materials using a waste product for enhanced photocatalytic performance under visible light | |
| CN107201214A (en) | A kind of heterocycle azo benzene/graphene solar energy heat-storage material and preparation method | |
| CN109503420A (en) | A kind of dual graft azobenzene/graphene composite energy-storage material and preparation method | |
| CN111804338B (en) | Triazinyl D-A type nitrogen-containing organic conjugated porous polymer photocatalytic material and preparation and application thereof | |
| CN109503419A (en) | A kind of alternately bilayer azobenzene/graphene composite energy-storage material and preparation method | |
| Shi et al. | Boosting photothermal-assisted photocatalytic water/seawater splitting into hydrogen based on greenhouse-induced photothermal effect | |
| CN111298824B (en) | Graphite-like carbon nitride-based photocatalytic composite material and preparation method and application thereof | |
| CN112547125B (en) | CdS/NiPc photocatalyst for water photolysis and preparation method thereof | |
| Yuan et al. | Selective oxidation of 5-hydroxymethylfurfural to furan-2, 5-dicarbaldehyde using chitosan-based biochar composite cadmium sulfide quantum dots | |
| AU742693B2 (en) | Carbothermal production of alkali metals | |
| CN108927197B (en) | g-C with high catalytic performance3N4Preparation method and use of | |
| Feng et al. | Using coal coke for N-sorption with an Al-based nitrogen carrier during chemical looping ammonia generation | |
| CN111790369B (en) | Silver-loaded black indium-based composite photothermal catalytic material for methane coupling and preparation method and application thereof | |
| CN110639587B (en) | Preparation method and application of carbon-bridged modified carbon nitride photocatalytic material | |
| CN111686779A (en) | Tungsten selenide/carbon nitride composite nanosheet and preparation method and application thereof | |
| CN101348726B (en) | Coal direct liquefaction method | |
| CN115138392B (en) | Multifunctional biochar catalyst rich in oxygen-containing functional groups and preparation method thereof | |
| CN109503486A (en) | A kind of heterocycle azo benzene/graphene solar energy heat-storage material and preparation method | |
| Liu et al. | Fabrication of CdS/ZnS/g-C3N4 composites for enhanced visible-light photocatalytic degradation performance | |
| CN103980928B (en) | bio-oil and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190322 |