CN108597894B - preparation method of boron-doped porous carbon material - Google Patents
preparation method of boron-doped porous carbon material Download PDFInfo
- Publication number
- CN108597894B CN108597894B CN201810529256.XA CN201810529256A CN108597894B CN 108597894 B CN108597894 B CN 108597894B CN 201810529256 A CN201810529256 A CN 201810529256A CN 108597894 B CN108597894 B CN 108597894B
- Authority
- CN
- China
- Prior art keywords
- carbon material
- porous carbon
- boric acid
- boron
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000004327 boric acid Substances 0.000 claims abstract description 46
- 239000002131 composite material Substances 0.000 claims abstract description 31
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- 229920001721 polyimide Polymers 0.000 claims abstract description 23
- 239000004642 Polyimide Substances 0.000 claims abstract description 20
- 239000012528 membrane Substances 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 44
- 239000000758 substrate Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 2
- 229920002647 polyamide Polymers 0.000 claims 2
- 238000009826 distribution Methods 0.000 abstract description 11
- 239000011148 porous material Substances 0.000 abstract description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052796 boron Inorganic materials 0.000 abstract description 8
- 239000003990 capacitor Substances 0.000 abstract description 8
- PQMFVUNERGGBPG-UHFFFAOYSA-N (6-bromopyridin-2-yl)hydrazine Chemical compound NNC1=CC=CC(Br)=N1 PQMFVUNERGGBPG-UHFFFAOYSA-N 0.000 abstract 2
- 238000003763 carbonization Methods 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 13
- 238000000059 patterning Methods 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a preparation method of a boron-doped porous carbon material, which comprises the following steps: (1) preparing a mixed solution; (2) preparing a polyamic acid (PAA)/boric acid composite film; (3) preparing a Polyimide (PI)/boric acid composite membrane; (4) preparing a boron-doped porous carbon material; the porous carbon material can be directly used for preparing a high-performance micro super capacitor. The method is rapid and simple, has low cost, and the prepared porous carbon material has high specific surface area, adjustable pore size distribution and good conductivity, can be directly patterned, has a certain amount of boron doped, and can be used for preparing high-performance micro supercapacitors.
Description
Technical Field
The invention relates to the field of supercapacitors, in particular to a preparation method of a boron-doped porous carbon material.
Background
The porous carbon material has large specific surface area and good conductivity, so that the porous carbon material is widely applied to lithium ion batteries, lithium sulfur batteries and super capacitors, and the good mechanical property of the carbon material also enables the porous carbon material to become a candidate material for flexible energy storage and flexible electronic devices. Researches show that the electrochemical performance of the porous carbon material can be further improved by improving the specific surface area of the porous carbon material, adjusting the pore size distribution of the porous carbon material and doping hetero atoms to improve the conductivity and the electrochemical activity.
At present, there are many methods for improving conductivity and electrochemical activity by doping heteroatoms, mainly high-temperature carbonization in an inert atmosphere, chemical vapor deposition and the like, and these methods can obtain porous carbon materials with high specific surface area, good conductivity and adjustable doping proportion, but these methods are difficult to directly form films and pattern them to prepare micro energy storage devices and electronic devices, so it is necessary to develop simpler carbonization and patterning technologies.
Disclosure of Invention
The invention aims to solve the technical problems and provides a preparation method of a porous carbon material, which is quick and simple and has low cost, and the prepared porous carbon material has the advantages of high specific surface area, adjustable pore size distribution, good conductivity, direct patterning, a certain amount of boron doped and capability of being used for preparing a high-performance micro supercapacitor.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
A preparation method of a boron-doped porous carbon material comprises the following steps:
(1) preparing a mixed solution: mixing boric acid and a polyamic acid solution, and dissolving the boric acid to obtain a mixed solution;
(2) Preparing a polyamic acid (PAA)/boric acid composite film: uniformly dripping the mixed solution on a clean substrate, and placing the substrate until the solvent is completely volatilized to obtain a PAA/boric acid composite membrane;
(3) polyimide (PI)/boric acid composite film: heating the obtained PAA/boric acid composite membrane for reaction to obtain a polymerized polyimide and boric acid composite membrane;
(4) preparing a boron-doped porous carbon material: performing laser irradiation on the polyimide/boric acid composite membrane by adopting continuous wave laser to carbonize the polyimide/boric acid composite membrane, thus obtaining a boron-doped porous carbon material; the porous carbon material can be directly used for preparing a high-performance micro super capacitor.
Specifically, in the step (1), the mass ratio of the boric acid to the polyamic acid is 0-30: 100.
Specifically, in the step (1), boric acid and a polyamic acid solution are mixed and dissolved at a temperature of 25-100 ℃.
Specifically, in the step (2), the substrate is a glass substrate, a silicon substrate, a metal substrate, or another heat-resistant substrate.
Specifically, in the step (2), the substrate is placed at 45-80 ℃ until the solvent is completely volatilized.
Specifically, in the step (3), the heating is performed by heating at a heating rate of 0-20 ℃/min and keeping the temperature at 120-250 ℃ to react the PAA/boric acid composite film.
More specifically, the power of the continuous wave laser in the step (4) is 30-5000 mW, and the continuous wave laser is visible light and ultraviolet light with the wavelength of less than 600 nm.
The laser direct writing technology is a non-contact, rapid and one-step preparation technology, does not need a mask, post-treatment and a complex clean room, can directly carry out patterning preparation on a device structure, and is compatible with the existing electronic industry. With the rapid development of laser technology, the laser cost is greatly reduced, and the laser power and wavelength can be selected in a large range, thereby laying a foundation for the application of the laser direct writing technology. At present, the laser direct writing technology is used for preparing a patterned conductive film fused by noble metal nanoparticles, reduction and patterning of graphene oxide, carbonization of polymers, a micro supercapacitor and the like, and if a high-performance solid flexible carbon-based micro supercapacitor is prepared by directly writing a polyimide film in air and argon gas by a continuous wave laser in our unit, a very high surface capacitance is obtained, but still needs to be improved; the group of Tours subjects of the university of rice in usa adopts a pulse laser to prepare the boron-doped carbon material, the regulation and control of the pore structure are not obvious, the specific surface area is low, the purchase cost of the pulse laser is high, and the energy utilization efficiency of carbonization is low. In view of this, the preparation technology of the porous carbon material is optimized, so that the performance of the obtained porous carbon material is improved, and carbonization doping and patterning can be further realized by a laser direct writing technology.
Compared with the prior art, the invention has the following beneficial effects:
(1) Compared with a commercial pure polyimide film, after the boric acid is doped into the polyimide film and is washed by laser direct writing, part of boric acid which does not participate in boron doping can be washed out, and the boric acid plays a role of a pore-making agent, so that the purposes of increasing the specific surface area of the porous carbon material and ensuring uniform pore size distribution are achieved. And the doping of the boron element also improves the electronic structure of the carbon material, so that the charge transmission performance of the laser carbonization structure is improved, and the performance of the porous carbon material is further improved.
(2) The preparation method is quick and simple, has low cost and does not need expensive equipment. In addition, the method can generate any pattern for directly preparing the microelectrode while carbonizing the polymer, and a high-performance micro supercapacitor is obtained.
(3) The laser direct writing method (namely step 4) adopted by the invention is simple and rapid, the carbonization doping, the aperture distribution regulation and control and the patterning can be simultaneously realized in one step, and the used laser is a low-cost continuous wave laser, so that the cost is lower compared with pulse laser, the carbonization energy utilization efficiency is higher, and the laser is easy to integrate with the existing electronic industrial system. In addition, the laser direct writing obtained micro super capacitor achieves high surface capacitance, can be directly applied to the production of micro energy storage elements in a flexible electronic system, and has high practical value and popularization value.
(4) In the preparation process, the mass ratio of the boric acid to the polyamic acid is determined after a large number of experiments, the polyimide/boric acid composite film with better flexibility can be formed only when the boric acid percentage is within 30 percent and is used for laser direct writing, and the polyimide/boric acid composite film is easy to be brittle when the boric acid percentage is higher than 30 percent, and the film can be brittle due to photo-thermal stress during laser direct writing, so that the film can not be combined with a laser direct writing technology, and the carbonization doping and patterning effects can not be achieved.
(5) The temperature conditions of the steps in the invention are determined by abundant knowledge storage and a large number of experiments of the inventor: the mixing temperature condition of the boric acid and the polyamic acid solution is set to be 25-100 ℃, so that the solubility of the boric acid in the PAA solution is remarkably increased along with the increase of the temperature, the dissolution process is very slow due to the excessively low temperature (such as lower than 25 ℃), and meanwhile, a large number of experiments show that if the temperature exceeds 100 ℃, the PAA polymerization is initiated, and the subsequent film-making treatment cannot be carried out; the volatilization of the solvent is set to be 45-80 ℃, the solvent in the solution can be uniformly volatilized, so that a uniform PAA/boric acid composite film can be formed, once the temperature exceeds the temperature range, the volatilization time is long due to too low temperature, the efficiency is influenced, but the film forming uniformity is influenced due to too high temperature higher than 80 ℃, and the fluctuation phenomenon can occur; the temperature of the film polymerization is set to be 120-250 ℃, the temperature is the polymerization temperature of polyamic acid, the polymerization degree is poor below 120 ℃, a polyimide/boric acid composite film with high polymerization degree is difficult to form, and the temperature higher than 250 ℃ exceeds the heat-resistant temperature of polyimide, so that the film is aged and even decomposed. Therefore, the control of each temperature is particularly important in the invention, and the key parameters of whether the porous carbon material with uniform pore size distribution and adjustable pore size can be formed can be determined, and whether the obtained porous carbon material can be patterned by using the laser direct writing technology can also be determined.
(6) an interdigital electrode structure is written on the boron-doped porous carbon material film prepared by the method by adopting a laser direct writing method, and the surface capacitance of the obtained micro super capacitor reaches 71mF/cm 2, which is almost the highest value of the current micro super capacitor based on the carbon material.
Drawings
FIG. 1 is a flow chart of the present invention for preparing boron-doped porous carbon material and a micro supercapacitor.
FIG. 2 is a morphology characterization diagram of the boron-doped porous carbon material prepared by the present invention.
FIG. 3 is an XRD pattern of the boron-doped porous carbon material prepared by the present invention.
FIG. 4 is a Raman spectrum of the boron-doped porous carbon material prepared by the present invention.
FIG. 5 is an XPS spectrum of a boron-doped porous carbon material prepared according to the present invention.
FIG. 6 is a comparison of pore size distributions of boron doped and undoped porous carbon materials prepared in accordance with the present invention.
FIG. 7 is a photograph of a boron-doped porous carbon material micro supercapacitor made in accordance with the present invention.
FIG. 8 shows the comparison of the performance of the boron-doped porous carbon material micro supercapacitor prepared according to the present invention and the carbon-based micro supercapacitor prepared according to the commercialized Kapton 500H
Detailed Description
The present invention will be further described with reference to the following description and examples, which include but are not limited to the following examples.
In order to solve the problems that the preparation of a porous carbon material is difficult to directly form a film, the porous carbon material is difficult to pattern and the cost of the existing laser direct writing technology is high in the prior art, the embodiment provides a preparation method of a porous carbon material, which can directly form a film and can realize carbonization doping, aperture distribution regulation and control and patterning through the laser direct writing technology (a scheme of using the laser direct writing technology to regulate and control the aperture distribution of the porous carbon material does not exist in the prior art) so as to prepare a micro energy storage device and an electronic device. The method is a method of adopting boric acid and polyamic acid with a certain weight ratio to carry out composite high-temperature polymerization to form a film and utilizing laser direct writing carbonization. The boron-doped porous carbon material obtained after laser direct writing has the characteristics of large specific surface area, reasonable pore size distribution, good conductivity and the like, and can be used for directly preparing a high-performance micro supercapacitor.
Specifically, as shown in fig. 1, the specific process for preparing the boron-doped porous carbon material in this example is as follows:
(1) preparing a mixed solution: mixing boric acid and polyamic acid solution according to the weight ratio of the boric acid to the polyamic acid of 15:100, and fully dissolving the boric acid at 45 ℃ to obtain a mixed solution; wherein, the reagents are purchased from chemical reagent companies, and the purity is generally required to be not less than 99%;
(2) Preparing a PAA/boric acid composite film: uniformly dripping the mixed solution on a clean substrate, and standing on a hot plate at 55 ℃ for 3h until the solvent is completely volatilized to obtain a PAA/boric acid composite membrane;
(3) Polyimide (PI)/boric acid composite film: heating the obtained PAA/boric acid composite membrane to 180 ℃ at the speed of 5 ℃/min, keeping the temperature for 1 hour, and reacting to obtain a polymerized polyimide and boric acid composite membrane;
(4) Preparing a boron-doped porous carbon material: and (3) performing laser irradiation on the composite membrane by adopting 157mW 405nm blue-violet continuous wave laser to carbonize the composite membrane, thus obtaining the boron-doped porous carbon material.
2 2The porous carbon material is observed by an electron microscope, a transmission electron microscope and a high-resolution transmission electron microscope in a shape characterization manner, so that a scanning photograph of the porous carbon material under a microscope with different resolutions as shown in fig. 2 is obtained, and it can be obviously seen that the obtained porous carbon material structure is a micro-nano hierarchical pore channel structure, and further the porous carbon material is detected, so that an XRD (X-ray diffraction) spectrum as shown in fig. 3, a Raman spectrum as shown in fig. 4 and an XPS (X-ray diffraction) spectrum as shown in fig. 5 can be obtained, the obtained porous carbon material is an amorphous or graphitized carbon material from fig. 3 and fig. 4, the obtained porous carbon material contains carbon, nitrogen, oxygen and a small amount of boron, the boron content is about 0.9%, and boron doping is confirmed.
The performance of the obtained micro supercapacitor is compared with that of a carbon-based micro supercapacitor prepared by a commercialized Kapton 500H film by the same method to obtain a comparison graph shown in fig. 8, and it can be seen from the graph that the micro supercapacitor made of the porous carbon material prepared by the method shows higher surface capacitance which reaches 71mF/cm 2 and is almost the highest value of the current micro supercapacitor based on the carbon material.
In the embodiment, a simple preparation method of the boric acid and polyimide composite membrane is adopted, and a direct-writing laser method capable of directly patterning one-step carbonization doping is combined, so that the boron-doped porous carbon material with high specific surface area and uniform pore size distribution is obtained. The method is easily integrated with the existing electronics industry for the production of energy supply units in flexible electronics. Compared with the prior art, the method has the characteristics that the porous carbon material film is simply and uniformly prepared, and the laser carbonization preparation material and the patterning preparation device are synchronously prepared. In addition, the embodiment also proves that the boron-doped porous carbon material micro supercapacitor prepared synchronously by the method shows very high surface capacitance, cycling stability and flexibility.
in order to illustrate the application value of the method and the prepared material, the embodiment provides an application example of the boron-doped porous carbon material prepared by the method in the aspect of a micro super capacitor, namely, an interdigital electrode structure is written on the polyimide and boric acid composite film prepared by the method by adopting a laser direct writing method, and the surface capacitance of the obtained micro super capacitor reaches 71mF/cm 2.
the above-mentioned embodiment is only one of the preferred embodiments of the present invention, and should not be used to limit the scope of the present invention, but all the insubstantial modifications or changes made within the spirit and scope of the main design of the present invention, which still solve the technical problems consistent with the present invention, should be included in the scope of the present invention.
Claims (3)
1. A preparation method of a boron-doped porous carbon material is characterized by comprising the following steps:
(1) Preparing a mixed solution: dissolving and mixing boric acid and a polyamic acid solution at a mass ratio of 0-30: 100 at 25-100 ℃ to obtain a mixed solution after the boric acid is dissolved;
(2) Preparing a polyamic acid/boric acid composite film: uniformly dripping the mixed solution on a clean substrate at the temperature of 45-80 ℃, and placing the substrate until the solvent is completely volatilized to obtain a polyamide acid/boric acid composite film;
(3) Polyimide/boric acid composite film: heating the obtained polyamide acid/boric acid composite membrane at the heating rate of 0-20 ℃/min, and keeping the temperature to react when the temperature reaches 120-250 ℃ so as to obtain a polymerized polyimide and boric acid composite membrane;
(4) Preparing a boron-doped porous carbon material: and (3) performing laser irradiation on the polyimide/boric acid composite membrane by adopting continuous wave laser to carbonize the polyimide/boric acid composite membrane, thus obtaining the boron-doped porous carbon material.
2. The method according to claim 1, wherein in the step (2), the substrate is a glass substrate, a silicon substrate, or a metal substrate.
3. The method for preparing a boron-doped porous carbon material according to claim 2, wherein the power of the continuous wave laser in the step (4) is 30-5000 mW, and the continuous wave laser is visible light and ultraviolet light with the wavelength of less than 600 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810529256.XA CN108597894B (en) | 2018-05-26 | 2018-05-26 | preparation method of boron-doped porous carbon material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810529256.XA CN108597894B (en) | 2018-05-26 | 2018-05-26 | preparation method of boron-doped porous carbon material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108597894A CN108597894A (en) | 2018-09-28 |
| CN108597894B true CN108597894B (en) | 2019-12-10 |
Family
ID=63630072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810529256.XA Active CN108597894B (en) | 2018-05-26 | 2018-05-26 | preparation method of boron-doped porous carbon material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108597894B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111217351B (en) * | 2018-11-26 | 2022-11-08 | 中国科学院大连化学物理研究所 | Method for preparing magnetic porous carbon by laser ablation method |
| CN114229824B (en) * | 2021-12-14 | 2023-06-27 | 中国石油大学(华东) | Porous carbon material and preparation method thereof, lithium-sulfur battery modified diaphragm and preparation method thereof, and lithium-sulfur battery |
| CN114395766B (en) * | 2022-01-28 | 2023-06-20 | 常州大学 | Method for rapidly forming alkaline hydrogen evolution carbon-loaded doped anti-spinel ferroferric oxide film |
| CN114988716B (en) * | 2022-06-15 | 2023-11-07 | 中国科学院合肥物质科学研究院 | Tungsten carbide/graphene composite material and preparation method thereof |
| CN115537027B (en) * | 2022-10-19 | 2024-03-29 | 天津泰合利华材料科技有限公司 | Preparation method of boron doped fluorinated polyimide film applied to super capacitor |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103038835A (en) * | 2010-03-08 | 2013-04-10 | 威廉马歇莱思大学 | Transparent electrodes based on graphene and grid hybrid structures |
| CN103288073A (en) * | 2013-05-13 | 2013-09-11 | 厦门大学 | Method and device for preparing graphene by LCVD (laser chemical vapor deposition) method |
| CN103980528A (en) * | 2014-05-29 | 2014-08-13 | 哈尔滨工业大学 | Method for preparing low dielectric polyimide film by using electrodeposited polyamide acid |
| CN106232520A (en) * | 2014-02-17 | 2016-12-14 | 威廉马歇莱思大学 | The grapheme material of induced with laser and they purposes in an electronic |
| WO2017223217A1 (en) * | 2016-06-21 | 2017-12-28 | William Marsh Rice University | Laser-induced graphene scrolls (ligs) materials |
-
2018
- 2018-05-26 CN CN201810529256.XA patent/CN108597894B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103038835A (en) * | 2010-03-08 | 2013-04-10 | 威廉马歇莱思大学 | Transparent electrodes based on graphene and grid hybrid structures |
| CN103288073A (en) * | 2013-05-13 | 2013-09-11 | 厦门大学 | Method and device for preparing graphene by LCVD (laser chemical vapor deposition) method |
| CN106232520A (en) * | 2014-02-17 | 2016-12-14 | 威廉马歇莱思大学 | The grapheme material of induced with laser and they purposes in an electronic |
| CN103980528A (en) * | 2014-05-29 | 2014-08-13 | 哈尔滨工业大学 | Method for preparing low dielectric polyimide film by using electrodeposited polyamide acid |
| WO2017223217A1 (en) * | 2016-06-21 | 2017-12-28 | William Marsh Rice University | Laser-induced graphene scrolls (ligs) materials |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108597894A (en) | 2018-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108597894B (en) | preparation method of boron-doped porous carbon material | |
| Cai et al. | Laser direct writing of heteroatom-doped porous carbon for high-performance micro-supercapacitors | |
| Xie et al. | Tuning the properties of graphdiyne by introducing electron‐withdrawing/donating groups | |
| Cai et al. | Laser direct writing and selective metallization of metallic circuits for integrated wireless devices | |
| Liang et al. | Hierarchical porous nitrogen-doped carbon microspheres after thermal rearrangement as high performance electrode materials for supercapacitors | |
| Qiu et al. | Large-scale production of aligned long boron nitride nanofibers by multijet/multicollector electrospinning | |
| Cong et al. | Growth and extension of one-step sol–gel derived molybdenum trioxide nanorods via controlling citric acid decomposition rate | |
| Yang et al. | Preparation and application of PANI/N-doped porous carbon under the protection of ZnO for supercapacitor electrode | |
| CN107034663A (en) | A kind of tungsten disulfide/carbon nano-fiber composite material and its production and use | |
| CN108461725B (en) | Carbon-limited vanadium trioxide hollow microsphere and preparation method and application thereof | |
| CN110713176A (en) | Preparation of three-dimensional grading porous carbon material and method for regulating and controlling pore diameter of three-dimensional grading porous carbon material | |
| CN113436912B (en) | Method for improving specific capacitance of laser-induced graphene-based capacitor and laser-induced graphene-based capacitor | |
| Jiang et al. | A Simple and Green Preparation Method of Nitrogen‐Doped Carbon Nanocages for Supercapacitor Application | |
| Cai et al. | Low-cost and high-performance electrospun carbon nanofiber film anodes | |
| Liu et al. | N/P codoped carbon materials with an ultrahigh specific surface area and hierarchical porous structure derived from durian peel for high-performance supercapacitors | |
| CN109110744B (en) | Preparation method of hollow tubular polyaniline-based carbon material | |
| Dhandapani et al. | Carbon-quantum-dots-anchored poly (aniline-co-indole) composite electrodes for high-performance supercapacitor applications | |
| Xu et al. | Novel Preoxidation-Assisted Mechanism to Preciously Form and Disperse Bi2O3 Nanodots in Carbon Nanofibers for Ultralong-Life and High-Rate Sodium Storage | |
| Gao et al. | In Situ Synthesis of ZnO/Porous Carbon Microspheres and Their High Performance for Lithium‐Ion Batteries | |
| CN111825070B (en) | In-situ hybridized coordination polymer derived porous flower-like Co 2 P 2 O 7 Preparation method of/C composite material | |
| CN110610812B (en) | B, N double-doped carbon aerogel based on methyl cellulose and preparation method and application thereof | |
| Li et al. | Fe3O4/Nitrogen‐Doped Carbon Electrodes from Tailored Thermal Expansion toward Flexible Solid‐State Asymmetric Supercapacitors | |
| CN102568849B (en) | Carbon counter electrode for dye-sensitized solar cell and preparation method for carbon counter electrode | |
| Phan et al. | Functional groups distributed on carbon nanotube surfaces using vacuum plasma for the high-capacitance supercapacitor electrode | |
| Liu et al. | Research and development of double layer P-doped laser induced graphene thin film electrode for flexible micro-supercapacitor applications |
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 |