CN111137890A - Preparation method of biomass hierarchical pore nano-ring microstructure carbon-based supercapacitor electrode material - Google Patents
Preparation method of biomass hierarchical pore nano-ring microstructure carbon-based supercapacitor electrode material Download PDFInfo
- Publication number
- CN111137890A CN111137890A CN202010039658.9A CN202010039658A CN111137890A CN 111137890 A CN111137890 A CN 111137890A CN 202010039658 A CN202010039658 A CN 202010039658A CN 111137890 A CN111137890 A CN 111137890A
- Authority
- CN
- China
- Prior art keywords
- biomass
- electrode material
- room temperature
- stems
- carbon
- 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.)
- Withdrawn
Links
- 239000002028 Biomass Substances 0.000 title claims abstract description 57
- 239000007772 electrode material Substances 0.000 title claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 35
- 239000002063 nanoring Substances 0.000 title claims abstract description 35
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001816 cooling Methods 0.000 claims abstract description 24
- 239000012043 crude product Substances 0.000 claims abstract description 24
- 244000017020 Ipomoea batatas Species 0.000 claims abstract description 20
- 235000002678 Ipomoea batatas Nutrition 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 238000002791 soaking Methods 0.000 claims abstract description 14
- 239000002699 waste material Substances 0.000 claims abstract description 13
- 239000000706 filtrate Substances 0.000 claims abstract description 12
- 239000011261 inert gas Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 230000007935 neutral effect Effects 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000000197 pyrolysis Methods 0.000 claims abstract description 10
- 230000003213 activating effect Effects 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 81
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 62
- 238000010438 heat treatment Methods 0.000 claims description 44
- 229910052757 nitrogen Inorganic materials 0.000 claims description 31
- 230000004913 activation Effects 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 11
- 238000007605 air drying Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- 239000012190 activator Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 8
- 239000003575 carbonaceous material Substances 0.000 abstract description 6
- 239000003990 capacitor Substances 0.000 abstract description 5
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 abstract 1
- 229910052573 porcelain Inorganic materials 0.000 description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 34
- 229910052759 nickel Inorganic materials 0.000 description 17
- 239000000243 solution Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 239000012498 ultrapure water Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical group [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
-
- 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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- 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
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- 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)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of a biomass hierarchical pore nano-ring microstructure carbon-based supercapacitor electrode material, which comprises the steps of cleaning, drying and crushing waste biomass sweet potato stems, leaves and the like into uniform powder; carrying out constant-temperature pyrolysis treatment for 2h under the protection of 600 ℃ inert gas, and naturally cooling to room temperature to obtain biomass carbide; mixing carbide and solid KOH in a container, adding water, fully soaking, and drying to obtain a carbide/KOH mixture; activating for 2 hours under the protection of inert gas at the temperature of 600-900 ℃, and naturally cooling to room temperature to obtain a crude product; and putting the crude product into a container containing hydrochloric acid solution, soaking for 24h, washing with deionized water until the filtrate is neutral, and drying at 80 ℃ for 24h to obtain the hierarchical pore nano-ring microstructure carbon-based supercapacitor electrode material. The super capacitor electrode material prepared by the invention is a nitrogen-oxygen co-doped high-grade carbon material with a hierarchical pore and nano-ring microstructure, and has good electrochemical performance when used for the super capacitor electrode material.
Description
Technical Field
The invention belongs to the technical field of preparation of electrode materials of supercapacitors, and particularly relates to a preparation method of a biomass hierarchical pore nano-ring microstructure carbon-based supercapacitor electrode material.
Background
Energy is an important material basis on which human society relies for survival and sustained development. As a novel energy storage device, the super capacitor can complete the charging and discharging process within several seconds based on high power, is free from maintenance for a long time, can be used within a wide temperature range, has high safety and other excellent energy storage performances, has huge application value and market potential in the fields of new energy electric vehicles, uninterruptible power supplies, intelligent start-stop, aerospace, transportation, electric power energy, engineering machinery, military industry and national defense and the like, and the key factor determining the performance of the super capacitor is an electrode material. The hierarchical porous carbon material is one of the ideal carbon-based electrode materials of the super capacitor. The structure of the material is distributed with interconnected micropores, mesopores and macropores. The micropores determine the capacitance effect of the electric double layer, the mesopores provide channels for the transmission of ions, and the macropores are equivalent to an ion storage bank, so that the diffusion distance of the ions is shortened. The macroporous-mesoporous-microporous interconnected structural material overcomes the defects of single-level pore structures such as the traditional activated carbon. The oxygen, nitrogen and other doped atomic groups can improve the wetting capacity, the conductivity and the Faraday effect of the surface of the carbon material and the electrolyte solution to increase the specific capacity of the electrode material. At present, a template method is a commonly used main technology for preparing a hierarchical pore structure carbon material, but has the series problems of long preparation process period, complex process, environmental friendliness and the like. The invention prepares the oxygen-nitrogen heteroatom-doped hierarchical pore nano-ring microstructure carbon-based supercapacitor electrode material with excellent capacitance performance by using an economic, environment-friendly, simple and feasible process technology.
Disclosure of Invention
The invention solves the technical problem of providing a preparation method of a biomass multilevel pore nano ring microstructure carbon-based supercapacitor electrode material with simple process and low cost.
The invention adopts the following technical scheme for solving the technical problems, and the preparation method of the biomass hierarchical pore nano-ring microstructure carbon-based supercapacitor electrode material is characterized by comprising the following specific processes:
step S1: cleaning waste sweet potato stems, stems and leaves with deionized water, placing the cleaned waste sweet potato stems, stems and leaves in a forced air drying oven, drying the waste sweet potato stems, stems and leaves for 24 hours at 65 ℃ to remove water in a sample, and crushing dried biomass into biomass powder by a crusher for later use;
step S2: putting the biomass powder obtained in the step S1 into a tubular furnace, heating the biomass powder from room temperature to 600 ℃ at a heating rate of 5 ℃/min under the protection of inert gas, pyrolyzing the biomass powder for 2 hours at a constant temperature, and naturally cooling the biomass powder to room temperature to obtain biomass carbide;
step S3: mixing the biomass carbide obtained in the step S2 with an activating agent potassium hydroxide according to a mass ratio of 1: 3-5, adding water to soak the mixture, placing the mixture in a blast drying oven for drying, placing the mixture in a tubular furnace, heating the mixture from room temperature to 600-900 ℃ at a heating rate of 10 ℃/min under the protection of inert gas, carrying out constant-temperature activation treatment for 2 hours, and then naturally cooling the mixture to room temperature to obtain a crude product;
step S4: and (4) soaking the crude product obtained in the step (S3) in a 2mol/L hydrochloric acid solution for 24h, washing with deionized water until the filtrate is neutral, and then placing in a forced air drying oven to dry to obtain the electrode material of the multistage pore nano-ring microstructure carbon-based supercapacitor.
Preferably, the inert gas in steps S2 and S3 is nitrogen or argon.
Preferably, the mass ratio of the biomass carbide to the activator potassium hydroxide in the step S3 is 1: 4.
Preferably, the constant temperature activation treatment temperature in step S3 is 700 ℃.
Preferably, the preparation method of the biomass hierarchical pore nano-ring microstructure carbon-based supercapacitor electrode material is characterized by comprising the following specific steps:
step S1: cleaning waste sweet potato stems, stems and leaves with deionized water, placing the cleaned waste sweet potato stems, stems and leaves in a forced air drying oven, drying the waste sweet potato stems, stems and leaves for 24 hours at 65 ℃ to remove water in a sample, and crushing dried biomass into biomass powder by a crusher for later use;
step S2: placing 9g of the biomass powder obtained in the step S1 in a tubular furnace, heating the biomass powder from room temperature to 600 ℃ at a heating rate of 5 ℃/min under the protection of inert gas, carrying out constant-temperature pyrolysis for 2h, and naturally cooling the biomass powder to room temperature to obtain biomass carbide;
step S3: mixing 1g of the biomass carbide obtained in the step S2 with 4g of activating agent potassium hydroxide, adding 10mL of water, soaking for 24h, placing in a forced air drying oven, drying at 120 ℃, placing the mixture in a tubular furnace, heating from room temperature to 700 ℃ at a heating rate of 10 ℃/min under the protection of inert gas, carrying out constant-temperature activation treatment for 2h, and then naturally cooling to room temperature to obtain a crude product;
step S4: soaking the crude product obtained in the step S3 in 2mol/L hydrochloric acid solution for 24h, washing with deionized water until the filtrate is neutral, and then drying in a forced air drying oven at 80 ℃ to obtain the electrode material of the multistage pore nano-ring microstructure carbon-based supercapacitor;
the specific surface area of the electrode material of the multistage-hole nano-ring microstructure carbon-based supercapacitor is up to 3115m2In a constant current charge and discharge test, the specific capacitance of 1A/g under a constant current density is 532.5F/g, the specific capacitance of 264F/g can be released under a large current density of 30A/g, and the specific capacitance retention rate reaches 95.1 percent after 10000 cycles when the current density is 30A/g.
Compared with the prior art, the invention has the following beneficial effects:
1. the raw materials used in the invention are cheap, the preparation process is simple, and the specific surface area and the pore size distribution of the carbon material can be controlled by regulating the proportion of the biomass and the activating agent and the activation temperature;
2. the biomass hierarchical pore nano-ring microstructure carbon-based supercapacitor electrode material prepared by the method has the advantages of stable structure, excellent electrochemical performance, long cycle life, high specific capacitance and the like, and is very suitable for being used as a supercapacitor electrode material;
3. the oxygen-nitrogen co-doped nano-ring microstructure carbon material is obtained by self-doping in biomass and externally doping activated oxygen, and the specific surface area is as high as 3115m2G, in constant current charge and discharge test, at a constant current density of 1A/gThe specific capacitance of the electrode is 532.5F/g, the 264F/g specific capacitance can still be released under the large current density of 30A/g, the specific capacitance retention rate of the electrode reaches 95.1 percent after 10000 cycles when the current density is 30A/g, and the carbon supercapacitor electrode material prepared by the method has potential application prospects.
Drawings
FIG. 1 is a field emission scanning electron microscope image of the electrode material of the carbon-based supercapacitor with the hierarchical porous nanoring microstructure prepared in example 4;
FIG. 2 is a transmission electron microscope image of the electrode material of the carbon-based supercapacitor with the hierarchical porous nanoring microstructure prepared in example 4;
FIG. 3 is a pore size distribution diagram of the electrode material of the carbon-based supercapacitor with the multilevel pore nano-ring microstructure prepared in example 4;
FIG. 4 is an infrared spectrum of the multi-level pore nanoring microstructure carbon-based supercapacitor electrode material prepared in examples 2 to 5 and 7;
FIG. 5 is a mass specific capacitance diagram of the multi-level pore nano-ring microstructure carbon-based supercapacitor electrode material prepared in examples 3 to 5 under different current densities.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
(1) Putting 9g of sweet potato stem leaf powder into a porcelain boat, putting the porcelain boat into a tubular furnace, vacuumizing the porcelain boat, replacing air in the tubular furnace with nitrogen, heating the porcelain boat to 600 ℃ from room temperature at a heating rate of 5 ℃/min under the protection of normal-pressure nitrogen, carrying out constant-temperature pyrolysis treatment for 2 hours, and naturally cooling the porcelain boat to room temperature to obtain biomass carbide, which is recorded as BLSC-0;
(2) putting 1g of BLSC-0 and 3g of solid KOH into a container, adding 10mL of deionized water, fully stirring and mixing uniformly, standing at room temperature for 24h, and drying at 120 ℃ to obtain a biomass BLSC-0/KOH mixture;
(3) transferring the BLSC-0/KOH mixture into a nickel boat, placing the nickel boat into a tubular furnace, vacuumizing the nickel boat, replacing air in the tubular furnace with nitrogen, heating the mixture from room temperature to 600 ℃ at a heating rate of 10 ℃/min under the protection of normal-pressure nitrogen, carrying out constant-temperature activation treatment for 2 hours, and naturally cooling the mixture to room temperature to obtain a crude product;
(4) and adding the crude product into a container containing 2mol/L hydrochloric acid solution, soaking for 24h, filtering, washing with high-purity water until the filtrate is neutral, and drying at 80 ℃ for 24h to obtain the electrode material BLSC-1 of the hierarchical pore nano-ring microstructure carbon supercapacitor.
Example 2
(1) Putting 9g of sweet potato stem leaf powder into a porcelain boat, putting the porcelain boat into a tubular furnace, vacuumizing the porcelain boat, replacing air in the tubular furnace with nitrogen, heating the porcelain boat to 600 ℃ from room temperature at a heating rate of 5 ℃/min under the protection of normal-pressure nitrogen, carrying out constant-temperature pyrolysis treatment for 2 hours, and naturally cooling the porcelain boat to room temperature to obtain biomass carbide, which is recorded as BLSC-0;
(2) putting 1g of BLSC-0 and 3g of solid KOH into a container, adding 10mL of deionized water, fully stirring and mixing uniformly, standing at room temperature for 24h, and drying at 120 ℃ to obtain a BLSC-0/KOH mixture;
(3) transferring the BLSC-0/KOH mixture into a nickel boat, placing the nickel boat into a tube furnace, vacuumizing the tube furnace, replacing air in the tube furnace with nitrogen, heating the tube furnace to 700 ℃ from room temperature at a heating rate of 10 ℃/min under the protection of normal-pressure nitrogen, carrying out constant-temperature activation treatment for 2 hours, and naturally cooling the tube furnace to room temperature to obtain a crude product;
(4) and adding the crude product into a container containing 2mol/L hydrochloric acid solution, soaking for 24h, filtering, washing with high-purity water until the filtrate is neutral, and drying at 80 ℃ for 24h to obtain the electrode material BLSC-2 of the hierarchical pore nano-ring microstructure carbon supercapacitor.
Example 3
(1) Putting 9g of sweet potato stem leaf powder into a porcelain boat, putting the porcelain boat into a tubular furnace, vacuumizing the porcelain boat, replacing air in the tubular furnace with nitrogen, heating the porcelain boat to 600 ℃ from room temperature at a heating rate of 5 ℃/min under the protection of normal-pressure nitrogen, carrying out constant-temperature pyrolysis treatment for 2 hours, and naturally cooling the porcelain boat to room temperature to obtain biomass carbide, which is recorded as BLSC-0;
(2) putting 1g of BLSC-0 and 4g of solid KOH into a container, adding 10mL of deionized water, fully stirring and mixing uniformly, standing at room temperature for 24h, and drying at 120 ℃ to obtain a BLSC-0/KOH mixture;
(3) transferring the BLSC-0/KOH mixture into a nickel boat, placing the nickel boat into a tubular furnace, vacuumizing the nickel boat, replacing air in the tubular furnace with nitrogen, heating the mixture from room temperature to 600 ℃ at a heating rate of 10 ℃/min under the protection of normal-pressure nitrogen, carrying out constant-temperature activation treatment for 2 hours, and naturally cooling the mixture to room temperature to obtain a crude product;
the above example describes that in the step (4), the crude product is added into a container containing 2mol/L hydrochloric acid solution to be soaked for 24 hours, filtered, washed by high-purity water until the filtrate is neutral, and then dried for 24 hours at 80 ℃ to obtain the electrode material BLSC-3 of the hierarchical pore nano-ring microstructure carbon supercapacitor.
Example 4
(1) Putting 9g of sweet potato stem leaf powder into a porcelain boat, putting the porcelain boat into a tubular furnace, vacuumizing the porcelain boat, replacing air in the tubular furnace with nitrogen, heating the porcelain boat to 600 ℃ from room temperature at a heating rate of 5 ℃/min under the protection of normal-pressure nitrogen, carrying out constant-temperature pyrolysis treatment for 2 hours, and naturally cooling the porcelain boat to room temperature to obtain biomass carbide, which is recorded as BLSC-0;
(2) putting 1g of BLSC-0 and 4g of solid KOH into a container, adding 10mL of deionized water, fully stirring and mixing uniformly, standing at room temperature for 24h, and drying at 120 ℃ to obtain a BLSC-0/KOH mixture;
(3) transferring the BLSC-0/KOH mixture into a nickel boat, placing the nickel boat into a tube furnace, vacuumizing the tube furnace, replacing air in the tube furnace with nitrogen, heating the tube furnace to 700 ℃ from room temperature at a heating rate of 10 ℃/min under the protection of normal-pressure nitrogen, carrying out constant-temperature activation treatment for 2 hours, and naturally cooling the tube furnace to room temperature to obtain a crude product;
(4) and adding the crude product into a container containing 2mol/L hydrochloric acid solution, soaking for 24h, filtering, washing with high-purity water until the filtrate is neutral, and drying at 80 ℃ for 24h to obtain the electrode material BLSC-4 of the hierarchical pore nano-ring microstructure carbon supercapacitor.
Example 5
(1) Putting 9g of sweet potato stem leaf powder into a porcelain boat, putting the porcelain boat into a tubular furnace, vacuumizing the porcelain boat, replacing air in the tubular furnace with nitrogen, heating the porcelain boat to 600 ℃ from room temperature at a heating rate of 5 ℃/min under the protection of normal-pressure nitrogen, carrying out constant-temperature pyrolysis treatment for 2 hours, and naturally cooling the porcelain boat to room temperature to obtain biomass carbide, which is recorded as BLSC-0;
(2) putting 1g of BLSC-0 and 4g of solid KOH into a container, adding 10mL of deionized water, fully stirring and mixing uniformly, standing at room temperature for 24h, and drying at 120 ℃ to obtain a BLSC-0/KOH mixture;
(3) transferring the BLSC-0/KOH mixture into a nickel boat, placing the nickel boat into a tube furnace, vacuumizing the tube furnace, replacing air in the tube furnace with nitrogen, heating the tube furnace to 800 ℃ from room temperature at a heating rate of 10 ℃/min under the protection of normal-pressure nitrogen, carrying out constant-temperature activation treatment for 2 hours, and naturally cooling the tube furnace to room temperature to obtain a crude product;
(4) and adding the crude product into a container containing 2mol/L hydrochloric acid solution, soaking for 24h, filtering, washing with high-purity water until the filtrate is neutral, and drying at 80 ℃ for 24h to obtain the electrode material BLSC-5 of the hierarchical pore nano-ring microstructure carbon supercapacitor.
Example 6
(1) Putting 9g of sweet potato stem leaf powder into a porcelain boat, putting the porcelain boat into a tubular furnace, vacuumizing the porcelain boat, replacing air in the tubular furnace with nitrogen, heating the porcelain boat to 600 ℃ from room temperature at a heating rate of 5 ℃/min under the protection of normal-pressure nitrogen, carrying out constant-temperature pyrolysis treatment for 2 hours, and naturally cooling the porcelain boat to room temperature to obtain biomass carbide, which is recorded as BLSC-0;
(2) putting 1g of BLSC-0 and 4g of solid KOH into a container, adding 10mL of deionized water, fully stirring and mixing uniformly, standing at room temperature for 24h, and drying at 120 ℃ to obtain a BLSC-0/KOH mixture;
(3) transferring the BLSC-0/KOH mixture into a nickel boat, placing the nickel boat into a tubular furnace, vacuumizing the nickel boat, replacing air in the tubular furnace with nitrogen, heating the mixture from room temperature to 900 ℃ at a heating rate of 10 ℃/min under the protection of normal-pressure nitrogen, carrying out constant-temperature activation treatment for 2 hours, and naturally cooling the mixture to room temperature to obtain a crude product;
(4) and adding the crude product into a container containing 2mol/L hydrochloric acid solution, soaking for 24h, filtering, washing with high-purity water until the filtrate is neutral, and drying at 80 ℃ for 24h to obtain the electrode material BLSC-6 of the hierarchical pore nano-ring microstructure carbon supercapacitor.
Example 7
(1) Putting 9g of sweet potato stem leaf powder into a porcelain boat, putting the porcelain boat into a tubular furnace, vacuumizing the porcelain boat, replacing air in the tubular furnace with nitrogen, heating the porcelain boat to 600 ℃ from room temperature at a heating rate of 5 ℃/min under the protection of normal-pressure nitrogen, carrying out constant-temperature pyrolysis treatment for 2 hours, and naturally cooling the porcelain boat to room temperature to obtain biomass carbide, which is recorded as BLSC-0;
(2) putting 1g of BLSC-0 and 5g of solid KOH into a container, adding 10mL of deionized water, fully stirring and mixing uniformly, standing at room temperature for 24h, and drying at 120 ℃ to obtain a BLSC-0/KOH mixture;
(3) transferring the BLSC-0/KOH mixture into a nickel boat, placing the nickel boat into a tube furnace, vacuumizing the tube furnace, replacing air in the tube furnace with nitrogen, heating the tube furnace to 700 ℃ from room temperature at a heating rate of 10 ℃/min under the protection of normal-pressure nitrogen, carrying out constant-temperature activation treatment for 2 hours, and naturally cooling the tube furnace to room temperature to obtain a crude product;
(4) and adding the crude product into a container containing 2mol/L hydrochloric acid solution, soaking for 24h, filtering, washing with high-purity water until the filtrate is neutral, and drying at 80 ℃ for 24h to obtain the electrode material BLSC-7 of the hierarchical pore nano-ring microstructure carbon supercapacitor.
The basic principles, principal features and advantages of the invention, it should be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only for the purpose of illustrating the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention, which fall within the scope of the invention.
Claims (5)
1. A preparation method of a biomass hierarchical pore nano-ring microstructure carbon-based supercapacitor electrode material is characterized by comprising the following specific steps:
step S1: cleaning waste sweet potato stems, stems and leaves with deionized water, placing the cleaned waste sweet potato stems, stems and leaves in a forced air drying oven, drying the waste sweet potato stems, stems and leaves for 24 hours at 65 ℃ to remove water in a sample, and crushing dried biomass into biomass powder by a crusher for later use;
step S2: putting the biomass powder obtained in the step S1 into a tubular furnace, heating the biomass powder from room temperature to 600 ℃ at a heating rate of 5 ℃/min under the protection of inert gas, pyrolyzing the biomass powder for 2 hours at a constant temperature, and naturally cooling the biomass powder to room temperature to obtain biomass carbide;
step S3: mixing the biomass carbide obtained in the step S2 with an activating agent potassium hydroxide according to a mass ratio of 1: 3-5, adding water to soak the mixture, placing the mixture in a blast drying oven for drying, placing the mixture in a tubular furnace, heating the mixture from room temperature to 600-900 ℃ at a heating rate of 10 ℃/min under the protection of inert gas, carrying out constant-temperature activation treatment for 2 hours, and then naturally cooling the mixture to room temperature to obtain a crude product;
step S4: and (4) soaking the crude product obtained in the step (S3) in a 2mol/L hydrochloric acid solution for 24h, washing with deionized water until the filtrate is neutral, and then placing in a forced air drying oven to dry to obtain the electrode material of the multistage pore nano-ring microstructure carbon-based supercapacitor.
2. The preparation method of the biomass hierarchical pore nano-ring microstructure carbon-based supercapacitor electrode material according to claim 1, characterized in that: the inert gas in steps S2 and S3 is nitrogen or argon.
3. The preparation method of the biomass hierarchical pore nano-ring microstructure carbon-based supercapacitor electrode material according to claim 1, characterized in that: the mass ratio of the biomass carbide to the activator potassium hydroxide in step S3 is 1: 4.
4. The preparation method of the biomass hierarchical pore nano-ring microstructure carbon-based supercapacitor electrode material according to claim 1, characterized in that: the constant temperature activation treatment temperature in step S3 was 700 ℃.
5. The preparation method of the biomass hierarchical pore nano-ring microstructure carbon-based supercapacitor electrode material according to claim 1, which is characterized by comprising the following specific steps:
step S1: cleaning waste sweet potato stems, stems and leaves with deionized water, placing the cleaned waste sweet potato stems, stems and leaves in a forced air drying oven, drying the waste sweet potato stems, stems and leaves for 24 hours at 65 ℃ to remove water in a sample, and crushing dried biomass into biomass powder by a crusher for later use;
step S2: placing 9g of the biomass powder obtained in the step S1 in a tubular furnace, heating the biomass powder from room temperature to 600 ℃ at a heating rate of 5 ℃/min under the protection of inert gas, carrying out constant-temperature pyrolysis for 2h, and naturally cooling the biomass powder to room temperature to obtain biomass carbide;
step S3: mixing 1g of the biomass carbide obtained in the step S2 with 4g of activating agent potassium hydroxide, adding 10mL of water, soaking for 24h, placing in a forced air drying oven, drying at 120 ℃, placing the mixture in a tubular furnace, heating from room temperature to 700 ℃ at a heating rate of 10 ℃/min under the protection of inert gas, carrying out constant-temperature activation treatment for 2h, and then naturally cooling to room temperature to obtain a crude product;
step S4: soaking the crude product obtained in the step S3 in 2mol/L hydrochloric acid solution for 24h, washing with deionized water until the filtrate is neutral, and then drying in a forced air drying oven at 80 ℃ to obtain the electrode material of the multistage pore nano-ring microstructure carbon-based supercapacitor;
the specific surface area of the electrode material of the multistage-hole nano-ring microstructure carbon-based supercapacitor is up to 3115m2In a constant current charge and discharge test, the specific capacitance of 1A/g under a constant current density is 532.5F/g, the specific capacitance of 264F/g can be released under a large current density of 30A/g, and the specific capacitance retention rate reaches 95.1 percent after 10000 cycles when the current density is 30A/g.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010039658.9A CN111137890A (en) | 2020-01-15 | 2020-01-15 | Preparation method of biomass hierarchical pore nano-ring microstructure carbon-based supercapacitor electrode material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010039658.9A CN111137890A (en) | 2020-01-15 | 2020-01-15 | Preparation method of biomass hierarchical pore nano-ring microstructure carbon-based supercapacitor electrode material |
Publications (1)
Publication Number | Publication Date |
---|---|
CN111137890A true CN111137890A (en) | 2020-05-12 |
Family
ID=70524964
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010039658.9A Withdrawn CN111137890A (en) | 2020-01-15 | 2020-01-15 | Preparation method of biomass hierarchical pore nano-ring microstructure carbon-based supercapacitor electrode material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111137890A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111704131A (en) * | 2020-07-14 | 2020-09-25 | 广西臻净新材料科技有限公司 | Preparation method of carbon material prepared from bamboo |
CN113430565A (en) * | 2021-06-16 | 2021-09-24 | 江西师范大学 | Method for preparing carbon-based transition metal nano composite catalyst from tremella |
CN114709430A (en) * | 2022-03-07 | 2022-07-05 | 哈尔滨理工大学 | Application of sweet potato three-dimensional electrode in microbial fuel cell |
CN114758900A (en) * | 2022-04-27 | 2022-07-15 | 深圳大学 | Biomass porous carbon material, preparation method thereof and supercapacitor |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20080085605A (en) * | 2007-03-20 | 2008-09-24 | 전남대학교산학협력단 | Activated carbon with ultra-high specific surface area from corn and production method of thereof |
CN103641113A (en) * | 2013-11-11 | 2014-03-19 | 中南大学 | Preparation method of biomass-based formed activated carbon |
CN105609327A (en) * | 2015-12-19 | 2016-05-25 | 湘潭大学 | Porous active carbon/copper ion super-capacitor preparation method |
CN106430186A (en) * | 2016-09-16 | 2017-02-22 | 大连理工大学 | Preparation method and application of sweet potato leaf based active carbon |
CN107910200A (en) * | 2017-10-23 | 2018-04-13 | 河南师范大学 | A kind of preparation method of multi-stage porous nitrogen oxygen doping carbon supercapacitor electrode material |
CN108922794A (en) * | 2018-06-05 | 2018-11-30 | 江苏海基新能源股份有限公司 | A kind of preparation method of N doping biology base active carbon electrode material |
CN110028069A (en) * | 2019-04-18 | 2019-07-19 | 河南师范大学 | A kind of preparation method of the advanced carbon electrode material of multi-stage porous for supercapacitor |
CN110127696A (en) * | 2019-06-11 | 2019-08-16 | 吉林化工学院 | A kind of preparation method and applications of biomass-based nitrogen-doped porous carbon material |
CN110668441A (en) * | 2019-10-17 | 2020-01-10 | 北京化工大学 | Crop tuber-based porous carbon material and preparation method and application thereof |
-
2020
- 2020-01-15 CN CN202010039658.9A patent/CN111137890A/en not_active Withdrawn
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20080085605A (en) * | 2007-03-20 | 2008-09-24 | 전남대학교산학협력단 | Activated carbon with ultra-high specific surface area from corn and production method of thereof |
CN103641113A (en) * | 2013-11-11 | 2014-03-19 | 中南大学 | Preparation method of biomass-based formed activated carbon |
CN105609327A (en) * | 2015-12-19 | 2016-05-25 | 湘潭大学 | Porous active carbon/copper ion super-capacitor preparation method |
CN106430186A (en) * | 2016-09-16 | 2017-02-22 | 大连理工大学 | Preparation method and application of sweet potato leaf based active carbon |
CN107910200A (en) * | 2017-10-23 | 2018-04-13 | 河南师范大学 | A kind of preparation method of multi-stage porous nitrogen oxygen doping carbon supercapacitor electrode material |
CN108922794A (en) * | 2018-06-05 | 2018-11-30 | 江苏海基新能源股份有限公司 | A kind of preparation method of N doping biology base active carbon electrode material |
CN110028069A (en) * | 2019-04-18 | 2019-07-19 | 河南师范大学 | A kind of preparation method of the advanced carbon electrode material of multi-stage porous for supercapacitor |
CN110127696A (en) * | 2019-06-11 | 2019-08-16 | 吉林化工学院 | A kind of preparation method and applications of biomass-based nitrogen-doped porous carbon material |
CN110668441A (en) * | 2019-10-17 | 2020-01-10 | 北京化工大学 | Crop tuber-based porous carbon material and preparation method and application thereof |
Non-Patent Citations (1)
Title |
---|
XIANJUN WEI ET AL.: "Biomass-derived interconnected carbon nanoring electrochemical capacitors with high performance in both strongly acidic and alkaline electrolytes", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111704131A (en) * | 2020-07-14 | 2020-09-25 | 广西臻净新材料科技有限公司 | Preparation method of carbon material prepared from bamboo |
CN113430565A (en) * | 2021-06-16 | 2021-09-24 | 江西师范大学 | Method for preparing carbon-based transition metal nano composite catalyst from tremella |
CN114709430A (en) * | 2022-03-07 | 2022-07-05 | 哈尔滨理工大学 | Application of sweet potato three-dimensional electrode in microbial fuel cell |
CN114758900A (en) * | 2022-04-27 | 2022-07-15 | 深圳大学 | Biomass porous carbon material, preparation method thereof and supercapacitor |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108483442B (en) | Preparation method of nitrogen-doped carbon electrode material with high mesoporous rate | |
CN111137890A (en) | Preparation method of biomass hierarchical pore nano-ring microstructure carbon-based supercapacitor electrode material | |
CN109081342B (en) | Date palm leaf biomass porous activated carbon and preparation method and application thereof | |
CN108529587B (en) | Preparation method and application of phosphorus-doped biomass graded porous carbon material | |
CN109081340B (en) | Pine-based biomass activated carbon, preparation method thereof and application thereof in electrochemical energy storage | |
CN107522200B (en) | Preparation method and application of active biomass carbon material | |
CN107555430B (en) | Pine needle-based activated carbon for supercapacitor and one-step carbonization preparation method thereof | |
CN113603078A (en) | Porous carbon, preparation method and application thereof | |
CN109467082B (en) | Preparation method of graphitized porous corncob derived carbon electrode material | |
CN104064369B (en) | Preparation of natural nutshell carbon material and application of natural nutshell carbon material in electrochemical capacitors | |
CN111137887B (en) | Preparation method of biomass carbon dot nano-array embedded structure carbon-based supercapacitor electrode material | |
CN110127695A (en) | A kind of preparation method of supercapacitor wood sawdust base porous charcoal | |
CN110697709B (en) | Porous carbon prepared from biomass unburned carbon and application of porous carbon in super capacitor | |
CN115231568A (en) | Graphene-like carbon nanosheet macroporous cross-linked cotton stalk biomass carbon electrode material and preparation method thereof | |
CN113200544B (en) | Preparation method of biomass charcoal-based supercapacitor electrode material | |
CN111153403A (en) | Alginate-based porous carbon and preparation method and application thereof | |
CN110589823A (en) | Shaddock peel porous carbon material and preparation method and application thereof | |
CN112563042B (en) | Biomass carbon aerogel-MnOxPreparation method and application of composite electrode material | |
CN107154498B (en) | Preparation method and application of microporous carbon structure electrode material prepared from plant material | |
CN109319762A (en) | The preparation of biomass porous carbon material with superhigh specific surface area and application as electrode material | |
CN112635202A (en) | Nickel cobaltate @ graphene @ China fir composite material electrode and preparation method and application thereof | |
CN111968863A (en) | Preparation method of rare earth composite biomass-based capacitance carbon material | |
CN111547719A (en) | 3D porous carbon material and preparation method and application thereof | |
CN116553539A (en) | Preparation method of camphor tree seed-based activated carbon for super capacitor | |
CN116053047A (en) | Method for preparing biomass porous carbon for super capacitor based on cistanche deserticola and application of biomass porous carbon |
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 | ||
WW01 | Invention patent application withdrawn after publication |
Application publication date: 20200512 |
|
WW01 | Invention patent application withdrawn after publication |