CN107611364A - A kind of polyimides/graphene flexible composite and its preparation method and application - Google Patents
A kind of polyimides/graphene flexible composite and its preparation method and application Download PDFInfo
- Publication number
- CN107611364A CN107611364A CN201710622253.6A CN201710622253A CN107611364A CN 107611364 A CN107611364 A CN 107611364A CN 201710622253 A CN201710622253 A CN 201710622253A CN 107611364 A CN107611364 A CN 107611364A
- Authority
- CN
- China
- Prior art keywords
- polyimides
- graphene
- flexible composite
- preparation
- graphene flexible
- 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.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 87
- 239000004642 Polyimide Substances 0.000 title claims abstract description 68
- 229920001721 polyimide Polymers 0.000 title claims abstract description 68
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000012530 fluid Substances 0.000 claims abstract description 14
- 239000007772 electrode material Substances 0.000 claims abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 7
- 239000004952 Polyamide Substances 0.000 claims abstract 2
- 229920002647 polyamide Polymers 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 35
- 238000010438 heat treatment Methods 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 238000006068 polycondensation reaction Methods 0.000 claims description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 229920005575 poly(amic acid) Polymers 0.000 claims description 12
- 238000005253 cladding Methods 0.000 claims description 8
- 238000010790 dilution Methods 0.000 claims description 8
- 239000012895 dilution Substances 0.000 claims description 8
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 2
- -1 oxygen Graphite alkene Chemical class 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000007669 thermal treatment Methods 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 230000002441 reversible effect Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 3
- 238000003786 synthesis reaction Methods 0.000 abstract 3
- 239000002253 acid Substances 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 239000012286 potassium permanganate Substances 0.000 description 4
- 239000004317 sodium nitrate Substances 0.000 description 4
- 235000010344 sodium nitrate Nutrition 0.000 description 4
- 238000013517 stratification Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to a kind of polyimides/graphene flexible composite, its preparation process includes：The synthesis of viscous fluid of polyamide acid, polyimides coat the synthesis of graphene oxide composite material, the synthesis of polyimides/graphene flexible composite；The polyimides/graphene flexible composite may be used as the flexible self-supporting electrode material of lithium ion battery.The preparation method of the present invention is simple, and easily operated, cost is low, environmental protection；The polyimides that the present invention obtains/graphene flexible composite has preferable pliability and electric conductivity, has higher reversible capacity and excellent cyclical stability.
Description
Technical field
The invention belongs to carbon nano-composite material field, more particularly to a kind of polyimides/graphene flexible composite
And its preparation method and application.
Background technology
In order to meet the sustainable development of social economy and ecology, discharge, the consumption of fossil fuel of carbon dioxide are reduced,
Exploitation renewable and clean energy resource device becomes the focus of scientist's research.Lithium ion battery is that one kind utilizes lithium ion in positive pole
The secondary cell of migration storage electric energy between negative pole, because of the advantages that it has extended cycle life, output power, high energy density
Have broad application prospects.However, with the continuous lifting that people are required lithium ion battery energy-storage property, commercially available electrode material
Material can not meet the needs of people, so exploitation high performance electrode material is always the emphasis studied.Graphene is big because of its
Specific surface area, good electric conductivity, excellent mechanical performance the advantages that and be widely used in catalyst carrier, macromolecule is received
The fields such as the flexible base material of nano composite material, energy conversion and memory device, it is considered to be most potential new material it
One.
Polyimides is a kind of typical conjugation ladder polymer, because of its excellent mechanical performance, high heat endurance, knot
Structure stability, excellent chemical property be widely used in Aero-Space, national defense and military, biological medicine and microelectronics,
The fields such as energy storage.However, as electrode material its specific surface area of poorly conductive, film or particle to be present small, make its active sites
Point can not sufficiently be exposed, and have a strong impact on energy stores performance.Therefore, by with high-specific surface area, good conduction
Property, compound to improve its electric conductivity, increasing specific surface area significant for the graphene of very good mechanical properties and polyimides.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of polyimides/graphene flexible composite and its preparation
Methods and applications, the preparation method is simple, and cost is cheap, and prepared polyimides/graphene flexible composite has excellent
Different chemical property.
A kind of polyimides/graphene flexible composite of the present invention, has three-dimensional intercommunication loose structure, polyimides
It is coated on graphene.
A kind of preparation method of polyimides/graphene flexible composite of the present invention, is comprised the following steps that：
(1) by pyromellitic acid anhydride and p-phenylenediamine with mol ratio 1:1-1:3 are added in solvent, dissolving, nitrogen ring
Polycondensation reaction obtains polyamic acid solution under border, and obtained polyamic acid solution and graphene oxide are mixed to form homogeneous sticky
The mass ratio of liquid, wherein pyromellitic acid anhydride and graphene oxide is 15:1-35:1；
(2) viscous fluid in step (1) is added in solvent and diluted, hydro-thermal reaction, cooling obtains polyimides cladding
Graphene oxide composite material；
(3) graphene oxide dissolving is taken to form graphene oxide solution in a solvent, by the polyimides bag in step (2)
Graphene oxide composite material is covered with graphene oxide solution with than for 1g:10mL-3g:10mL is mixed, and is filtered, under nitrogen environment
Heat treatment, obtains polyimides/graphene flexible composite.
Solvent is N,N-dimethylformamide in the step (1), (2), (3).
The solid content of step (1) polycondensation reaction is 10%-20%, and the time of polycondensation reaction is 15-25h, and polycondensation is anti-
The temperature answered is -5 DEG C.
The solid content of polycondensation reaction is 15% in the step (1), and the time of polycondensation reaction is 20h.
The concentration of dilution is 9.1-45.5mg/mL in the step (2)；The technological parameter of hydro-thermal reaction：Hydro-thermal reaction temperature
Spend for 180 DEG C, constant temperature time 6-12h, heating rate is 5 DEG C/min.
The concentration of dilution is 27.3mg/mL in the step (2).
The concentration of graphene oxide solution is 2mg/mL in the step (3).
Process of thermal treatment parameter in the step (3)：Heat treatment temperature is 300-400 DEG C, constant temperature time 2h, heating
Speed is 5 DEG C/min.
A kind of polyimides/graphene flexible composite of the present invention may be used as the flexible self-supporting of lithium ion battery
Electrode material.
A kind of polyimides/graphene flexible composite of the present invention has good electric conductivity, high-specific surface area, uses
The electric conductivity of polyimides can be substantially improved, fully expose avtive spot by making electrode material, be advantageous to the expansion of electrolyte ion
Dissipate and adsorb；In addition, the good electric conductivity and mechanical performance of graphene improve polyimides/graphene flexible composite
Overall mechanical flexibility and electric conductivity.Therefore, it is polyimides and graphene progress is effectively compound, collaboration well can be reached and increased
Use is pretended, to prepare the combination electrode material of excellent performance.
Beneficial effect
(1) preparation method of the invention is simple, and easily operated, cost is low, environmental protection；
(2) present invention obtains the porous polyimides of three-dimensional intercommunication/graphene flexible composite；
(3) polyimides/graphene flexible composite that the present invention obtains has preferable pliability and electric conductivity, has
There are higher reversible capacity and excellent cyclical stability, be the ideal electrode material of the new energy devices such as lithium ion battery.
Brief description of the drawings
Fig. 1 is the picture of (A) polyimides/graphene flexible composite in embodiment 1, (B) polyimides/graphene
The SEM figures in flexible composite section, the SEM figures of (C) polyimides cladding graphene oxide composite material；
Fig. 2 is the FTIR figures of polyimides cladding graphene oxide composite material in embodiment 1；
Fig. 3 is polyimide powder and contrast in polyimides in embodiment 1/graphene flexible composite, comparative example 1
Graphene film is respectively 100mA g in current density in example 2-1Under cycle performance figure.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1
(1) prepared using Hummers methods, graphite, sodium nitrate, the concentrated sulfuric acid are well mixed in ice-water bath, added in batches
Addition deionized water stirring is cooled to room temperature and adds hydrogen peroxide solution after potassium permanganate 35 DEG C of reactions 2h, 98 DEG C of reaction 20min,
Stirring, stratification, suction filtration, pickling, washing repeatedly obtain graphene oxide.
(2) pyromellitic acid anhydride (3.34g) and p-phenylenediamine (3.34g) are added to molten in N,N-dimethylformamide
Solution, 10%, polycondensation reaction 20h obtains polyamic acid solution under the conditions of nitrogen environment and -5 DEG C, takes step for solid content control
(1) the graphene oxide 0.1g in is mixed to form homogeneous viscous fluid with obtained polyamic acid solution.
(3) it is 9.1mg/mL the viscous fluid in step (2) to be added in DMF and be diluted to concentration, will
Viscous fluid after dilution carries out hydro-thermal reaction, and water heating kettle volume 40mL, loading 30mL, the temperature of hydro-thermal reaction is 180 DEG C,
Heating rate is 5 DEG C/min, constant temperature time 6h, naturally cools to room temperature and obtains polyimides cladding graphene oxide composite wood
Material.
(4) take the graphene oxide 0.1g in step (1) to be dissolved in N,N-dimethylformamide and form graphene oxide
Solution, the concentration of the solution is 2mg/mL, and the polyimides in step (3) is coated into graphene oxide composite material 1.0g with being somebody's turn to do
Solution 10.0mL is mixed, and is filtered, and is heat-treated under nitrogen environment, and the temperature of heat treatment is 300 DEG C, and heating rate is 5 DEG C/min, permanent
The warm time is 2h, obtains polyimides/graphene flexible composite.
Prepared using SEM (SEM), FTIS (FTIR) to characterize the present embodiment 1
Obtained polyimides/the pattern of graphene flexible composite, structure, its result are as follows：
(1) SEM test results show in Fig. 1：The polyimides prepared in the present embodiment 1/graphene flexible composite
With three-dimensional intercommunication loose structure, polyimides is coated on graphene.
(2) FTIR test results show in Fig. 2：The polyimides cladding graphite oxide prepared in the present embodiment 1 exists
1774cm-1, 1709cm-1The vibration peak at place belongs to the symmetrical and asymmetric peak of polyimides cyclocarbonyl (C=O)；In 1372cm-1The vibration peak at place belongs to the absorption vibration peak of polyimides ring C-N keys；In 1124cm-1, 725cm-1The vibration peak ownership at place
In polyimides ring torsional deformation vibration peak.The infrared signature vibration peak, which absolutely proves, is successfully prepared polyimides coated graphite
Alkene.
Embodiment 2
(1) prepared using Hummers methods, graphite, sodium nitrate, the concentrated sulfuric acid are well mixed in ice-water bath, added in batches
Addition deionized water stirring is cooled to room temperature and adds hydrogen peroxide solution after potassium permanganate 35 DEG C of reactions 2h, 98 DEG C of reaction 20min,
Stirring, stratification, suction filtration, pickling, washing repeatedly obtain graphene oxide.
(2) pyromellitic acid anhydride (3.34g) and p-phenylenediamine (5.01g) are added to molten in N,N-dimethylformamide
Solution, 15%, polycondensation reaction 20h obtains polyamic acid solution under the conditions of nitrogen environment and -5 DEG C, takes step for solid content control
(1) the graphene oxide 0.15g in is mixed to form homogeneous viscous fluid with obtained polyamic acid solution.
(3) it is 27.3mg/mL the viscous fluid in step (2) to be added in DMF and be diluted to concentration,
Viscous fluid after dilution is subjected to hydro-thermal reaction, water heating kettle volume 40mL, loading 30mL, the temperature of hydro-thermal reaction is 180
DEG C, heating rate is 5 DEG C/min, constant temperature time 9h, naturally cool to room temperature obtain polyimides cladding graphene oxide answer
Condensation material.
(4) take the graphene oxide 0.15g in step (1) to be dissolved in N,N-dimethylformamide and form graphene oxide
Solution, the concentration of the solution is 2mg/mL, and the polyimides in step (3) is coated into graphene oxide composite material 1.5g with being somebody's turn to do
Solution 10.0mL is mixed, and is filtered, and is heat-treated under nitrogen environment, and the temperature of heat treatment is 350 DEG C, and heating rate is 5 DEG C/min, permanent
The warm time is 2h, obtains polyimides/graphene flexible composite.
Embodiment 3
(1) prepared using Hummers methods, graphite, sodium nitrate, the concentrated sulfuric acid are well mixed in ice-water bath, added in batches
Addition deionized water stirring is cooled to room temperature and adds hydrogen peroxide solution after potassium permanganate 35 DEG C of reactions 2h, 98 DEG C of reaction 20min,
Stirring, stratification, suction filtration, pickling, washing repeatedly obtain graphene oxide.
(2) pyromellitic acid anhydride (3.34g) and p-phenylenediamine (6.68g) are added to molten in N,N-dimethylformamide
Solution, 20%, polycondensation reaction 20h obtains polyamic acid solution under the conditions of nitrogen environment and -5 DEG C, takes step for solid content control
(1) the graphene oxide 0.2g in is mixed to form homogeneous viscous fluid with obtained polyamic acid solution.
(3) it is 45.5mg/mL the viscous fluid in step (2) to be added in DMF and be diluted to concentration,
Viscous fluid after dilution is subjected to hydro-thermal reaction, water heating kettle volume 40mL, loading 30mL, the temperature of hydro-thermal reaction is 180
DEG C, heating rate is 5 DEG C/min, constant temperature time 12h, naturally cool to room temperature obtain polyimides cladding graphene oxide answer
Condensation material.
(4) take the graphite oxide 0.2g alkene in step (1) to be dissolved in N,N-dimethylformamide and form graphene oxide
Solution, the concentration of the solution is 2mg/mL, and the polyimides in step (3) is coated into graphene oxide composite material 2.0g with being somebody's turn to do
Solution 10.0mL is mixed, and is filtered, and is heat-treated under nitrogen environment, and the temperature of heat treatment is 400 DEG C, and heating rate is 5 DEG C/min, permanent
The warm time is 2h, obtains polyimides/graphene flexible composite.
Comparative example 1
(1) pyromellitic acid anhydride (3.34g) and p-phenylenediamine (3.34g) are added to molten in N,N-dimethylformamide
Solution, solid content control is 10%, and polycondensation reaction 20h obtains polyamic acid solution under the conditions of nitrogen environment and -5 DEG C.
(2) polyamic acid solution in step (1) is added in N,N-dimethylformamide and is diluted to concentration and is
9.1mg/mL, by after dilution viscous fluid carry out hydro-thermal reaction, water heating kettle volume 40mL, loading 30mL, hydro-thermal reaction
Temperature is 180 DEG C, and heating rate is 5 DEG C/min, constant temperature time 6h, naturally cools to room temperature and obtains polyimide solution.
(3) polyimide solution in step (2) is filtered, be heat-treated under nitrogen environment, the temperature of heat treatment is 300
DEG C, heating rate is 5 DEG C/min, constant temperature time 2h, obtains polyimide powder.
Comparative example 2
(1) prepared using Hummers methods, graphite, sodium nitrate, the concentrated sulfuric acid are well mixed in ice-water bath, added in batches
Addition deionized water stirring is cooled to room temperature and adds hydrogen peroxide solution after potassium permanganate 35 DEG C of reactions 2h, 98 DEG C of reaction 20min,
Stirring, stratification, suction filtration, pickling, washing repeatedly obtain graphene oxide.
(2) take the graphene oxide 0.1g in step (1) to be dissolved in N,N-dimethylformamide and form graphene oxide
Solution, the concentration of the solution is 2mg/mL, is filtered, and is heat-treated under nitrogen environment, and the temperature of heat treatment is 300 DEG C, heating rate
For 5 DEG C/min, constant temperature time 2h, graphene film is obtained.
In electro-chemical test, respectively with polyimides/graphene flexible composite of the preparation of embodiment 1, comparative example 1
Graphene film prepared by the polyimide powder and this comparative example 2 of preparation is as positive pole, and lithium piece is as the electricity of negative pole assembling button half
Pond, using the capacitance of battery charging and discharging CURVE STUDY composite.
Electrochemical results show in Fig. 3：The polyimides prepared in embodiment 1/graphene flexible composite tool
There are higher reversible capacity value and preferable cyclical stability.After 200 circle charge and discharge cycles, its reversible capacity value still may be up to
53mA h g-1.The structure of this polyimides for showing to have three-dimensional intercommunication loose structure/graphene flexible composite can to it
The raising of inverse capability value and cyclical stability has highly important effect.
Claims (10)
1. a kind of polyimides/graphene flexible composite, it is characterised in that there is three-dimensional intercommunication loose structure, polyamides Asia
Amine is coated on graphene.
2. a kind of preparation method of polyimides/graphene flexible composite, is comprised the following steps that：
(1) by pyromellitic acid anhydride and p-phenylenediamine with mol ratio 1:1-1:3 are added in solvent, dissolving, under nitrogen environment
Polycondensation reaction obtains polyamic acid solution, and obtained polyamic acid solution is mixed to form homogeneous viscous fluid with graphene oxide,
Wherein the mass ratio of pyromellitic acid anhydride and graphene oxide is 15:1-35:1；
(2) viscous fluid in step (1) is added in solvent and diluted, hydro-thermal reaction, cooling obtains polyimides cladding oxidation
Graphene composite material；
(3) take graphene oxide dissolving to form graphene oxide solution in a solvent, the polyimides in step (2) is coated into oxygen
Graphite alkene composite is with graphene oxide solution with than for 1g:10mL-3g:10mL is mixed, and is filtered, under nitrogen environment at heat
Reason, obtains polyimides/graphene flexible composite.
3. according to a kind of preparation method of polyimides/graphene flexible composite described in claim 2, its feature exists
In solvent is DMF in the step (1), (2), (3).
4. according to a kind of preparation method of polyimides/graphene flexible composite described in claim 2, its feature exists
In the solid content of polycondensation reaction is 10%-20% in the step (1), and the time of polycondensation reaction is 15-25h, polycondensation reaction
Temperature is -5 DEG C.
5. according to a kind of preparation method of polyimides/graphene flexible composite described in claim 2, its feature exists
In the solid content of polycondensation reaction is 15% in the step (1), and the time of polycondensation reaction is 20h.
6. according to a kind of preparation method of polyimides/graphene flexible composite described in claim 2, its feature exists
In the concentration of dilution is 9.1-45.5mg/mL in the step (2)；The technological parameter of hydro-thermal reaction：Hydrothermal temperature is
180 DEG C, constant temperature time 6-12h, heating rate is 5 DEG C/min.
7. according to a kind of preparation method of polyimides/graphene flexible composite described in claim 2, its feature exists
In the concentration of dilution is 27.3mg/mL in the step (2).
8. according to a kind of preparation method of polyimides/graphene flexible composite described in claim 2, its feature exists
In the concentration of graphene oxide solution is 2mg/mL in the step (3).
9. according to a kind of preparation method of polyimides/graphene flexible composite described in claim 2, its feature exists
In process of thermal treatment parameter in the step (3)：Heat treatment temperature is 300-400 DEG C, constant temperature time 2h, heating rate
For 5 DEG C/min.
10. a kind of application of polyimides/graphene flexible composite as claimed in claim 1, it is characterised in that be used as
The flexible self-supporting electrode material of lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710622253.6A CN107611364B (en) | 2017-07-27 | 2017-07-27 | polyimide/graphene flexible composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710622253.6A CN107611364B (en) | 2017-07-27 | 2017-07-27 | polyimide/graphene flexible composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107611364A true CN107611364A (en) | 2018-01-19 |
| CN107611364B CN107611364B (en) | 2019-12-10 |
Family
ID=61059587
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710622253.6A Expired - Fee Related CN107611364B (en) | 2017-07-27 | 2017-07-27 | polyimide/graphene flexible composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107611364B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109088062A (en) * | 2018-08-14 | 2018-12-25 | 河北省科学院能源研究所 | A kind of preparation method of the modified nickel ion doped material of polyimides cladding, Dopants |
| CN109524652A (en) * | 2018-11-16 | 2019-03-26 | 华南师范大学 | A kind of covalent organic frame/graphene compositing organic material and preparation method and the application in lithium/anode material of lithium-ion battery |
| CN109802078A (en) * | 2019-01-24 | 2019-05-24 | 上海应用技术大学 | A kind of soft graphite alkenyl composite polyimide material of membrane structure, preparation method and applications |
| CN110931790A (en) * | 2019-10-25 | 2020-03-27 | 合肥国轩高科动力能源有限公司 | Conjugated trapezoidal polymer-carbon nanotube composite material and preparation method and application thereof |
| CN111556597A (en) * | 2020-05-27 | 2020-08-18 | 安徽宇航派蒙健康科技股份有限公司 | Method for preparing graphene heating film for battery on surface of polyimide insulating substrate |
| CN111584851A (en) * | 2020-05-26 | 2020-08-25 | 苏州凌威新能源科技有限公司 | Positive electrode composite material and preparation method thereof |
| CN114229805A (en) * | 2021-11-03 | 2022-03-25 | 深圳市本征方程石墨烯技术股份有限公司 | Preparation method and application of nitrogen-doped porous carbon-coated cobalt diselenide composite material |
| CN114300681A (en) * | 2021-12-31 | 2022-04-08 | 齐鲁工业大学 | Graphene composite polyimide electrode material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102268134A (en) * | 2011-04-21 | 2011-12-07 | 扬中市华鑫氟塑电器设备有限公司 | Preparation method for polyimide/graphene nanocomposite material |
| CN103319892A (en) * | 2013-07-12 | 2013-09-25 | 中国科学院长春应用化学研究所 | Polyimide foamed composite and preparation method thereof |
| KR20130141168A (en) * | 2012-06-15 | 2013-12-26 | 경북대학교 산학협력단 | Poly amic acid composition comprising graphane oxide and preparation method thereof |
| CN104355302A (en) * | 2014-10-21 | 2015-02-18 | 复旦大学 | Preparation method of graphene/polyimide-based carbon aerogel |
| CN105273403A (en) * | 2015-10-13 | 2016-01-27 | 中国科学院宁波材料技术与工程研究所 | High-conductivity polyimides-graphene composite material and preparation method thereof |
-
2017
- 2017-07-27 CN CN201710622253.6A patent/CN107611364B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102268134A (en) * | 2011-04-21 | 2011-12-07 | 扬中市华鑫氟塑电器设备有限公司 | Preparation method for polyimide/graphene nanocomposite material |
| KR20130141168A (en) * | 2012-06-15 | 2013-12-26 | 경북대학교 산학협력단 | Poly amic acid composition comprising graphane oxide and preparation method thereof |
| CN103319892A (en) * | 2013-07-12 | 2013-09-25 | 中国科学院长春应用化学研究所 | Polyimide foamed composite and preparation method thereof |
| CN104355302A (en) * | 2014-10-21 | 2015-02-18 | 复旦大学 | Preparation method of graphene/polyimide-based carbon aerogel |
| CN105273403A (en) * | 2015-10-13 | 2016-01-27 | 中国科学院宁波材料技术与工程研究所 | High-conductivity polyimides-graphene composite material and preparation method thereof |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109088062A (en) * | 2018-08-14 | 2018-12-25 | 河北省科学院能源研究所 | A kind of preparation method of the modified nickel ion doped material of polyimides cladding, Dopants |
| CN109524652A (en) * | 2018-11-16 | 2019-03-26 | 华南师范大学 | A kind of covalent organic frame/graphene compositing organic material and preparation method and the application in lithium/anode material of lithium-ion battery |
| CN109524652B (en) * | 2018-11-16 | 2020-06-30 | 华南师范大学 | Covalent organic framework/graphene composite organic material, preparation method and application in lithium/sodium ion battery cathode material |
| CN109802078A (en) * | 2019-01-24 | 2019-05-24 | 上海应用技术大学 | A kind of soft graphite alkenyl composite polyimide material of membrane structure, preparation method and applications |
| CN110931790A (en) * | 2019-10-25 | 2020-03-27 | 合肥国轩高科动力能源有限公司 | Conjugated trapezoidal polymer-carbon nanotube composite material and preparation method and application thereof |
| CN110931790B (en) * | 2019-10-25 | 2022-05-06 | 合肥国轩高科动力能源有限公司 | Conjugated trapezoidal polymer-carbon nanotube composite material and preparation method and application thereof |
| CN111584851A (en) * | 2020-05-26 | 2020-08-25 | 苏州凌威新能源科技有限公司 | Positive electrode composite material and preparation method thereof |
| CN111584851B (en) * | 2020-05-26 | 2021-10-26 | 苏州凌威新能源科技有限公司 | Positive electrode composite material and preparation method thereof |
| CN111556597A (en) * | 2020-05-27 | 2020-08-18 | 安徽宇航派蒙健康科技股份有限公司 | Method for preparing graphene heating film for battery on surface of polyimide insulating substrate |
| CN114229805A (en) * | 2021-11-03 | 2022-03-25 | 深圳市本征方程石墨烯技术股份有限公司 | Preparation method and application of nitrogen-doped porous carbon-coated cobalt diselenide composite material |
| CN114229805B (en) * | 2021-11-03 | 2023-07-25 | 深圳市本征方程石墨烯技术股份有限公司 | Preparation method and application of nitrogen-doped porous carbon-coated cobalt diselenide composite material |
| CN114300681A (en) * | 2021-12-31 | 2022-04-08 | 齐鲁工业大学 | Graphene composite polyimide electrode material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107611364B (en) | 2019-12-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107611364A (en) | A kind of polyimides/graphene flexible composite and its preparation method and application | |
| CN104934610B (en) | A kind of lithium ion battery self-supporting flexible composite electrode material preparation method | |
| Huo et al. | Progress and prospects for low-grade heat recovery electrochemical technologies | |
| Liu et al. | Effects of organic additives with oxygen-and nitrogen-containing functional groups on the negative electrolyte of vanadium redox flow battery | |
| CN105742658B (en) | The preparation method of electrode material for all-vanadium flow battery | |
| CN105552333B (en) | A kind of preparation method of graphene/silicon/conducting polymer composite negative pole material | |
| CN102024965B (en) | Method for improving stability of fuel cell catalyst and utilization rate of catalyst | |
| CN103579638B (en) | Air electrode catalyst of lithium-air battery and preparation method thereof | |
| CN111276678B (en) | Single-layer graphene coated FeS2Preparation method and application of carbon nanotube material | |
| CN108091861B (en) | Preparation method of organic electrode material based on polyimide structure | |
| CN103560019B (en) | A kind of zinc ion hybrid super capacitor | |
| CN103682381B (en) | Eelctro-catalyst and preparation method thereof | |
| CN106299369A (en) | A kind of aqueous solution organic cathode material for sodium ion battery and preparation method thereof | |
| CN106935826A (en) | The lithium ion battery preparation method of nano cupric oxide graphene composite material | |
| CN104993160A (en) | Preparing method for non-precious metal ion complexation Schiff base graphene catalyst | |
| CN111326779A (en) | Method for improving transmission performance of eutectic solvent electrolyte flow battery and flow battery | |
| CN106058182B (en) | A kind of preparation method of the good lithium titanate/polyaniline composite material of high rate performance | |
| CN109346729B (en) | Water system semi-flow battery | |
| CN106653382A (en) | Flexible electrode material and preparation method and application thereof | |
| CN111740126A (en) | Chemical doping modification method for graphite felt electrode material of vanadium battery | |
| CN108766791A (en) | A kind of preparation method of the ultracapacitor based on graphene/polyaniline laminated film | |
| CN108346806A (en) | Electrode of liquid flow cell and preparation method thereof and flow battery | |
| CN107579211A (en) | Lithium ion battery negative material VO2The preparation method of/CNTs microballoons | |
| CN104064366A (en) | Graphene-hard carbon composite material, preparation method thereof and application thereof | |
| CN104538620B (en) | A kind of fluorinated graphene coats the preparation method of manganese cobalt lithium anode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20191210 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |