CN112520736A - Method for preparing high-performance carbon-based electrode material by biomass full-component pyrolysis - Google Patents
Method for preparing high-performance carbon-based electrode material by biomass full-component pyrolysis Download PDFInfo
- Publication number
- CN112520736A CN112520736A CN202011409077.6A CN202011409077A CN112520736A CN 112520736 A CN112520736 A CN 112520736A CN 202011409077 A CN202011409077 A CN 202011409077A CN 112520736 A CN112520736 A CN 112520736A
- Authority
- CN
- China
- Prior art keywords
- pyrolysis
- stem
- leaf
- biomass
- pyrolysis product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 71
- 239000002028 Biomass Substances 0.000 title claims abstract description 51
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 39
- 239000007772 electrode material Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 9
- 238000007873 sieving Methods 0.000 claims abstract description 3
- 230000001360 synchronised effect Effects 0.000 claims abstract 2
- 239000003575 carbonaceous material Substances 0.000 claims description 50
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 238000006722 reduction reaction Methods 0.000 claims description 10
- 240000001592 Amaranthus caudatus Species 0.000 claims description 8
- 235000009328 Amaranthus caudatus Nutrition 0.000 claims description 8
- 239000004178 amaranth Substances 0.000 claims description 8
- 235000012735 amaranth Nutrition 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000012983 electrochemical energy storage Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 240000008436 Ipomoea aquatica Species 0.000 claims description 3
- 244000017020 Ipomoea batatas Species 0.000 claims description 3
- 235000019004 Ipomoea aquatica Nutrition 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 claims description 2
- 244000300264 Spinacia oleracea Species 0.000 claims 1
- 235000009337 Spinacia oleracea Nutrition 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 18
- 239000011148 porous material Substances 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 9
- 239000000446 fuel Substances 0.000 description 7
- 125000005842 heteroatom Chemical group 0.000 description 7
- 239000003990 capacitor Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 230000003213 activating effect Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000013043 chemical agent Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 235000015097 nutrients Nutrition 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 235000013311 vegetables Nutrition 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 240000002900 Arthrospira platensis Species 0.000 description 1
- 235000016425 Arthrospira platensis Nutrition 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 229940082787 spirulina Drugs 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 239000002699 waste material Substances 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
- C01B32/318—Preparation characterised by the starting materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a method for preparing a high-performance carbon-based electrode material by biomass full-component pyrolysis. The method comprises the following steps: (1) separating leaves and stems of fresh herbaceous biomass, drying, crushing and sieving to obtain a leaf sample and a stem sample respectively; (2) the leaf sample or the stem sample is taken as a raw material, is put into a pyrolysis furnace, is subjected to synchronous pyrolysis reaction under the protection of inert gas, and is cooled to room temperature to obtain a leaf pyrolysis product or a stem pyrolysis product; (3) and respectively washing and drying the leaf pyrolysis product or the stem pyrolysis product, and grinding the washed and dried leaf pyrolysis product or stem pyrolysis product into powder to obtain two high-performance carbon-based electrode materials with different purposes. According to the invention, the herbaceous biomass is subjected to leaf and stem separation and respectively pyrolyzed, the natural structure and element distribution characteristics of the herbaceous biomass are fully exerted, self-activation and self-doping regulation and control in the pyrolyzing process are realized, and further carbon-based electrode materials with different electrochemical properties are obtained and are used in different fields according to product characteristics.
Description
Technical Field
The invention relates to the technical field of high-valued utilization of biomass, in particular to a method for preparing a high-performance carbon-based electrode material by full-component pyrolysis of biomass.
Background
Carbon elements widely exist in nature, and carbon atoms can be stacked and gathered in different ways to form carbon materials with various structures, so that the carbon materials become the first choice of functional materials. With the increasing sharpness of energy and environmental problems, the carbon material is used as a basis, and the developed high-efficiency and low-pollution novel functional material is widely applied to a plurality of fields of sewage treatment, soil optimization, gas adsorption, catalysis, electrochemical energy storage and the like.
With the continuous development of carbon material research, carbon electrode materials with simpler preparation method, lower price and more excellent performance gradually become a research hotspot in the electrochemical field. With the expansion of the application field of the carbon material, different applications put forward different requirements on the composition, structure and morphology of the carbon material, for example, the rich pore structure can endow the carbon material with a higher specific surface area, so that the specific capacitance performance of the carbon material can be improved, and the carbon material has a wide application prospect in the field of supercapacitors.
The main component element of the biomass is carbon element, and the carbon element is used for preparing electricityThe carbon source of the carbon electrode material is good, and has the advantages of wide source, low price, unique renewable carbon source and the like. The preparation of high-efficiency electrode carbon materials by using biomass is applied to different fields, and at present, in order to obtain the high-efficiency electrode carbon material with a certain specific surface area, different activating agents, such as ZnCl, need to be added in the pyrolysis process of a biomass raw material2、KOH、K2CO3、H3PO4NaOH, etc. For example, Chinese patent CN 109081340A uses pine-based biomass as raw material, and the raw material is treated with NaOH and HNO3After treatment by different activators, the high surface area of the biochar can be used for sodium ion negative electrode materials or double electric layer capacitor materials; chinese patent CN 110400939A uses spirulina as raw material, and after activation, the raw material is mixed with g-C3N4And performing secondary pyrolysis after mixing to prepare the high-performance biomass nitrogen-doped oxygen reduction catalyst which can be used for cathode materials of zinc-air batteries, fuel batteries and the like.
Generally, when biomass is used for preparing a charcoal material, most of the biomass needs an activating agent to adjust the pore structure size and pore distribution or perform heteroatom doping by using other chemical agents, but on one hand, the introduction of the chemical agents causes equipment corrosion, increases the preparation cost and is not beneficial to the industrial production of the high-performance charcoal material, on the other hand, the introduction and removal of the chemical agents increase the process complexity and cause secondary environmental problems, and in addition, the use of the chemical agents also reduces the charcoal yield and affects the substrate conversion efficiency. At present, the existing research on the biochar electrode material does not utilize the characteristic advantages of biomass raw materials to the maximum extent and directionally differentiate and utilize the biomass to prepare high-performance materials. Therefore, a method for preparing a high-performance carbon-based electrode material by full-component pyrolysis with simple synthetic method, less pollution and high efficiency of biomass energy conversion is needed to be developed.
Disclosure of Invention
The invention provides a method for preparing a high-performance carbon-based electrode material by full-component pyrolysis by taking herbaceous biomass as a raw material, which is used for synchronously and respectively obtaining two capacitance carbon materials with rich pore structures and electrode carbon materials for heteroatom-doped catalytic oxygen reduction reaction. The method meets the requirements of green and environment-friendly development of the carbon material industry, low cost and contribution to industrial production.
The invention provides a method for preparing a performance carbon-based electrode material by biomass full-component pyrolysis, which comprises the following steps:
(1) separating leaves and stems of fresh herbaceous biomass, drying, crushing and sieving to obtain a leaf sample and a stem sample respectively;
(2) taking a leaf sample and a stem sample, respectively placing the leaf sample and the stem sample in a pyrolysis furnace, and carrying out pyrolysis reaction under the protection of inert gas, wherein the pyrolysis conditions are as follows: the heating rate is as follows: 3-15 ℃/min, pyrolysis temperature range: keeping the temperature at 700-1000 ℃ for a period of time: cooling to room temperature for 1-3h to obtain leaf pyrolysis product and stem pyrolysis product.
(3) Washing, filtering, drying and grinding the leaf pyrolysis product or stem pyrolysis product obtained in the step (2) into powder respectively to obtain two high-performance carbon-based electrode materials, which are respectively: the super capacitor is made of electrochemical energy storage carbon material and fuel cell air cathode oxygen reduction reaction electrode carbon material.
According to the invention, the herbaceous biomass is subjected to leaf and stem separation and respectively pyrolyzed, the natural structure and element distribution characteristics of the herbaceous biomass are fully exerted, self-activation and self-doping regulation and control in the pyrolyzing process are realized, and further carbon-based electrode materials with different electrochemical properties are obtained and are used in different fields according to product characteristics.
The invention utilizes the advantages of natural structure and element composition of herbaceous biomass, carries out in-situ utilization, directly carries out pyrolysis in one step, and prepares carbon by using materials to obtain the high-performance carbon-based electrode material. The leaf part of the herbaceous biomass contains high-concentration amino acid, chlorophyll, trace elements and other nutrient substances, the stem part of the herbaceous biomass has a natural porous structure, and the herbaceous biomass is a natural transportation channel for the nutrient substances required by the growth of the herbaceous biomass, particularly fresh grass, is rich in water, provides convenient conditions for self doping and self activation in the pyrolysis process, does not need an exogenous heteroatom supply agent and an exogenous activator, and can be pyrolyzed in one step to obtain carbon-based electrode materials with different performances.
Preferably, the herbaceous biomass in the step (1) is selected from more than one of amaranth, water spinach and sweet potato seedlings.
Preferably, the mesh number of the crushing and screening sieve in the step (1) is 50-300 meshes.
Preferably, the inert gas in step (2) is one of nitrogen and argon.
Preferably, the specific steps of washing and suction filtering the leaf pyrolysis product or stem pyrolysis product in the step (3) are as follows: and washing the leaf pyrolysis product or the stem pyrolysis product for 24 hours by using hydrochloric acid or phosphoric acid in sequence, washing by using ammonia water and distilled water, and performing suction filtration to be neutral, wherein the concentration of the hydrochloric acid is 0.5-2mol/L, and the mass concentration of the ammonia water is 25-28%.
Preferably, in the step (3), the leaf pyrolysis product or stem pyrolysis product obtained in the step (2) is respectively washed, dried and ground into powder, so as to obtain two high-performance carbon-based electrode materials with different purposes, and the specific steps are as follows: and (3) washing, filtering, drying and grinding the pyrolysis product of the leaf pyrolysis product obtained in the step (2) to powder to obtain the high-performance biomass-based electro-catalytic oxidation-reduction reaction carbon material for the field of energy conversion, washing, filtering, drying and grinding the pyrolysis product of the stem obtained in the step (2) to powder to obtain the high-performance biomass-based capacitance carbon material for the field of energy storage. The electrode materials with different performances in the step (3) are mainly used as electrochemical energy storage carbon materials for super capacitors and air cathode oxygen reduction reaction electrode carbon materials for fuel cells.
The invention also protects the application of the high-performance carbon-based electrode material in electrochemical energy storage and energy conversion.
Compared with the prior art, the invention has the beneficial effects that:
(1) the precursor adopted by the invention is herbaceous biomass, has low price and wide source, has a renewable effect, efficiently utilizes biomass energy, and provides possibility for industrial preparation of different high-performance carbon-based electrode materials.
(2) The invention fully utilizes the structural characteristics and the component characteristics of the full components of the biomass, utilizes the natural pore channel structure to prepare the high-performance biomass-based capacitance carbon material, can be used in the field of super capacitors, utilizes the rich heteroatom doping to prepare the high-performance heteroatom-doped electro-catalysis carbon material, and can be applied in the field of electro-catalysis oxygen reduction.
(3) The preparation process provided by the invention has simple steps and is green and environment-friendly, compared with the existing biomass-based carbon material preparation technology, the introduction of chemical reagents is avoided, the energy waste and the environmental problems in the preparation process are reduced, the advantages of biomass are more efficiently utilized, and the large-scale production and sustainable development of the full-component oriented preparation of the electrode carbon material are facilitated.
(4) The natural structure and the heteroatoms of the herbaceous biomass can be self-doped and self-activated in the pyrolysis process, so that the porous structure of the herbaceous biomass is enriched, the fast diffusion of electrolyte ions is facilitated, the natural activating agent is more uniform in distribution than an exogenous activating agent and a heteroatom additive, the doping effect is stronger, and the distribution of carbon pore channels of a product and the doping regulation and control of the heteroatoms are facilitated.
(5) The technological parameters related to the herbaceous biomass researched by the invention provide valuable experience for preparing the high-performance carbon-based electrode material and subsequent research by utilizing the structure and composition characteristics of the biomass.
Drawings
FIG. 1 is a scanning electron micrograph of a high performance electrocatalytic carbon material (a) and a capacitive carbon material (b) prepared in example 1 of the present invention;
FIG. 2 is N of leaf char and stem char materials in example 1 of the present invention2An isothermal adsorption-desorption curve (a) and a pore size distribution diagram (b);
FIG. 3 is XPS N1S peak profiles and P2P (c) and S2P (d) peak profiles of high performance leaf char (a) and stem char (b) materials prepared in example 1 of the present invention;
FIG. 4 is a graph showing the electrocatalytic oxygen reduction performance of the leaf carbon material in example 1 of the present invention;
FIG. 5 is a diagram showing the operation cycle of a microbial fuel cell using leaf carbon material as a cathode prepared in example 1 of the present invention;
FIG. 6 is a cyclic voltammogram of a carbon stem material in example 1 of the present invention;
FIG. 7 is a graph of the electrocatalytic oxygen reduction performance of the leaf carbon material prepared in example 2 of the present invention.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof. The equipment and reagents used in the present invention are, unless otherwise specified, conventional commercial products in the art.
Example 1
Adopts fresh amaranth purchased from a certain vegetable market in Guangzhou city. Taking amaranth raw materials with certain mass, separating leaves (AL) and stems (AS), putting into an oven with the temperature of 80 ℃, drying, and grinding to powder with the mesh size of 50-300 to obtain a leaf sample and a stem sample for later use. And then, respectively putting the leaf sample and the stem sample into crucibles, pyrolyzing the materials in a tubular furnace under the protection of inert gas at the heating rate of 3 ℃/min at the pyrolysis temperature of 800 ℃ for 2h at the constant temperature, washing the materials with 2mol/L HCl and 25% concentrated ammonia water in sequence after cooling to the room temperature, and performing suction filtration to neutrality with deionized water to obtain a high-performance electro-catalytic carbon material (ALC, leaf carbon material) and a capacitance carbon material (ASC, stem carbon material).
The surface morphology and the internal structure of the biochar ALC and the ASC are observed by a scanning electron microscope (SEM, Hitachi s-4800) and are shown in figure 1, and information such as the specific surface area and the pore size distribution of the obtained carbon material preparation material is obtained by further combining a full-automatic specific surface area and pore size distribution instrument (ASIQMO002-2) and adopting a Brunnauer-Emmett-Teller (BET) method and a Barrett-Joynenrr-Halenda (BJH) method and is shown in figure 2 and table 1. The electrochemical performance test is completed by connecting a CHI 660C electrochemical workstation with a three-electrode system by Cyclic Voltammetry (CV) and Linear Voltammetry (LSV). The performance of the fuel cell is tested by taking an assembled Microbial Fuel Cell (MFC) as an example, ALC is an electrocatalytic material loaded on the surface of cathode carbon cloth, and the operation condition of the cell is monitored on line.
TABLE 1
As can be seen from FIGS. 1 and 2, the pyrolysis products of the feedstocks AL and AS both exhibit a porous structure, the longitudinal pore structure and the channels of the ASCThe depth is more obvious, the micropore structure of the sheet layer on the ALC surface is more remarkable, probably because of the requirement of transporting nutrient substances, the pore channel structure of the stem is more abundant, and the original pore channel structure is reserved by pyrolysis products. Analysis of the data in conjunction with table 1 shows: both carbons have microporous and mesoporous structures. However, the pore structure of ASC is more abundant and thus has a larger specific surface area (2749.27 m)2/g), about 3.8 times that of ALC. This is probably because the stems of the plants have abundant natural structures due to the need of transporting nutrients, and the original structural characteristics are maintained after pyrolysis at high temperature, so that more pores are generated, which is helpful for reducing the ion diffusion resistance of the electrolyte and is more suitable for the structure of the super capacitor.
Fig. 3 is an element distribution analysis of ASC and ALC, both carbon materials contain nitrogen (fig. 3a and 3b), the nitrogen content of ALC is superior to that of ASC, and further nitrogen morphology analysis shows that nitrogen in ALC exists mainly in the form of pyridine nitrogen, graphite nitrogen and pyrrole nitrogen, which play an important role in oxygen reduction reaction, and ASC also has a certain amount of nitrogen oxide. In addition, in the further XPS analysis of P2P and S2P, 132.8eV and 134.8eV are a P-C bond and a P-O bond, respectively, and 167.9eV and 169.3eV are assigned to-C-SO2and-C-SO4. In addition, the biochar surface was examined with SEM/EDS and TEM/MAPPING, respectively, and found that ALC had P contents of 0.43 wt% and 0.13 wt%, S contents of 1.34 wt% and 0.24 wt%, and ASC had P contents of almost zero and sulfur contents of only 0.23 wt% and 0.15 wt%. In the heteroatom-doped biochar, due to the fact that electronegativity is different from that of carbon, electron action among elements changes electron cloud distribution around carbon atoms, and a synergistic effect exists among different doping elements, for example, the electronegativity of N is larger than that of C, so that C atoms beside N show certain Lewis acidity, the electronegativity of P is smaller than that of C, C-P bonds with polarity opposite to that of C-N bonds can be formed, and more defect sites and active sites different from those caused by nitrogen doping are generated. The doping of S atoms can cause spin asymmetry of adjacent carbon atoms, promoting the coupling of O2Adsorption of (3). The co-doping of different heteroatoms can generate stronger synergistic effect, and the electrocatalytic performance of the carbon material is further improved. As shown in fig. 4: ALC showsElectrocatalytic oxygen reduction activity comparable to that of conventional oxygen reduction catalysts. In addition, ALC exhibits excellent electrocatalytic properties for ORR over a wide pH range.
Fig. 5 shows that the prepared high-performance electrocatalytic carbon material ALC is applied to voltage cycle operation of a microbial fuel cell, and the maximum voltage of a battery system is 0.41V and the battery system stably operates for 200h under the external resistance of a battery pack loaded with 1000 ohms, and basically has no attenuation.
FIG. 6 is a cyclic voltammetry curve of the prepared high-performance capacitance carbon material ASC in a neutral solution, which shows that the material has good electrochemical behavior and the specific capacity is 186F/g.
Example 2
Adopts sweet potato seedlings purchased from a certain dish market in Guangzhou city. Taking a certain mass of sweet potato seedling raw material, separating leaves (KL) and stems (KS), putting into an oven at 80 ℃, drying, and grinding to powder of 50-300 meshes to obtain a leaf sample and a stem sample for later use. Then, the leaf sample and the stem sample are respectively put into a crucible and pyrolyzed in a tube furnace under the protection of inert gas. And carrying out pyrolysis reaction, wherein the heating rate of pyrolysis is 3 ℃/min, the pyrolysis temperature is 800 ℃, the constant temperature time is 2h, cooling to room temperature, washing with 1mol/L HCl, and carrying out suction filtration with deionized water to neutrality to obtain a high-performance electro-catalytic carbon material (KLC) and a capacitance carbon material (KSC).
The electrochemical test method was the same as in experimental example 1.
FIG. 7 is the LSV curve of KLC catalyst in neutral (50mM PBS) solution at 1600 rpm. The starting potential of KLC was 0.183V (vs. SCE), respectively.
Example 3
Adopts fresh amaranth purchased from a certain vegetable market in Guangzhou city. Taking amaranth with a certain mass, separating leaves (AL) and stems (AS), putting into an oven with the temperature of 80 ℃, drying, and grinding to powder of 50-300 meshes to obtain a leaf sample and a stem sample for later use. And then, respectively putting the leaf sample and the stem sample into crucibles, pyrolyzing the materials in a tubular furnace under the protection of inert gas, wherein the heating rate is 5 ℃/min, the pyrolysis temperature is 700 ℃, the constant temperature time is 3h, after cooling to the room temperature, washing the materials with 0.5mol/L HCl and concentrated ammonia water with the mass concentration of 28% in sequence, and performing suction filtration with deionized water to be neutral to obtain the high-performance electro-catalytic carbon material (ALC, leaf carbon material) and capacitance carbon material (ASC, stem carbon material).
Example 4
Adopts fresh amaranth purchased from a certain vegetable market in Guangzhou city. Taking amaranth with a certain mass, separating leaves (AL) and stems (AS), putting into an oven with the temperature of 80 ℃, drying, and grinding to powder of 50-300 meshes to obtain a leaf sample and a stem sample for later use. And then, respectively putting the leaf sample and the stem sample into crucibles, pyrolyzing the materials in a tubular furnace under the protection of inert gas, wherein the heating rate is 15 ℃/min, the pyrolysis temperature is 1000 ℃, the constant temperature time is 1h, after cooling to the room temperature, washing the materials by sequentially using 2mol/L HCl and 25% concentrated ammonia water, and performing suction filtration by using deionized water until the materials are neutral to obtain a high-performance electro-catalytic carbon material (ALC, leaf carbon material) and a capacitance carbon material (ASC, stem carbon material).
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (7)
1. A method for preparing a high-performance carbon-based electrode material by biomass full-component pyrolysis is characterized by comprising the following steps of:
(1) separating leaves and stems of fresh herbaceous biomass, drying, crushing and sieving to obtain a leaf sample and a stem sample respectively;
(2) taking the leaf sample or the stem sample obtained in the step (1) as a raw material, putting the raw material into a pyrolysis furnace, and carrying out synchronous pyrolysis reaction under the protection of inert gas, wherein the pyrolysis conditions are as follows: the heating rate is as follows: 3-15 ℃/min, pyrolysis temperature range: keeping the temperature at 700-1000 ℃ for a period of time: cooling to room temperature after 1-3h to obtain leaf pyrolysis products or stem pyrolysis products;
(3) and (3) respectively washing and drying the leaf pyrolysis product or stem pyrolysis product obtained in the step (2), and grinding the washed and dried leaf pyrolysis product or stem pyrolysis product into powder, so as to obtain two high-performance carbon-based electrode materials with different purposes.
2. The method for preparing the high-performance carbon-based electrode material by full-component pyrolysis of the biomass according to claim 1, wherein the herbaceous biomass in the step (1) is selected from one or more of amaranth, water spinach, spinach and sweet potato seedlings.
3. The method for preparing the high-performance carbon-based electrode material by full-component pyrolysis of the biomass according to claim 1, wherein the mesh number of the crushed and sieved mesh in the step (1) is 50-300 meshes.
4. The method for preparing the high-performance carbon-based electrode material by full-component pyrolysis of the biomass according to claim 2, wherein the inert gas in the step (2) is one of nitrogen and argon.
5. The method for preparing the high-performance carbon-based electrode material by full-component pyrolysis of biomass according to claim 1, wherein the specific steps of washing and suction filtering of the leaf pyrolysis product or the stem pyrolysis product in the step (3) are as follows: and washing the leaf pyrolysis product or the stem pyrolysis product for 24 hours by using hydrochloric acid or phosphoric acid in sequence, washing by using ammonia water and distilled water, and performing suction filtration to be neutral, wherein the concentration of the hydrochloric acid is 0.5-2mol/L, and the mass concentration of the ammonia water is 25-28%.
6. The method for preparing the high-performance carbon-based electrode material by full-component biomass pyrolysis according to claim 1, wherein the leaf pyrolysis product or stem pyrolysis product obtained in the step (2) is respectively washed, dried and ground into powder to obtain two high-performance carbon-based electrode materials with different purposes, and the specific steps are as follows: and (3) washing, suction-filtering, drying and grinding the pyrolysis product of the leaf pyrolysis product obtained in the step (2) to powder to obtain the high-performance biomass-based electro-catalytic oxygen reduction reaction carbon material for energy conversion, washing, suction-filtering, drying and grinding the pyrolysis product of the stem obtained in the step (2) to powder to obtain the high-performance biomass-based capacitance carbon material for energy storage.
7. Use of the high performance carbon-based electrode material of claim 1 in electrochemical energy storage and energy conversion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011409077.6A CN112520736A (en) | 2020-12-03 | 2020-12-03 | Method for preparing high-performance carbon-based electrode material by biomass full-component pyrolysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011409077.6A CN112520736A (en) | 2020-12-03 | 2020-12-03 | Method for preparing high-performance carbon-based electrode material by biomass full-component pyrolysis |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112520736A true CN112520736A (en) | 2021-03-19 |
Family
ID=74997649
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011409077.6A Pending CN112520736A (en) | 2020-12-03 | 2020-12-03 | Method for preparing high-performance carbon-based electrode material by biomass full-component pyrolysis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112520736A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114436253A (en) * | 2022-01-04 | 2022-05-06 | 中冶南方都市环保工程技术股份有限公司 | Method for preparing activated carbon by pyrolysis and self-activation of cobalt-containing biomass and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130023409A1 (en) * | 2010-01-11 | 2013-01-24 | The University Of Surrey | Activated Charcoal |
| EA201591549A1 (en) * | 2013-03-22 | 2016-05-31 | Торэй Индастриз, Инк. | POROUS CARBON MATERIAL, PREDICTOR OF POROUS CARBON MATERIAL, METHOD FOR OBTAINING PRECONDENT POROUS CARBON MATERIAL AND METHOD FOR OBTAINING POROUS CARBON MATERIAL |
| 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 |
| CN106744936A (en) * | 2016-12-05 | 2017-05-31 | 天津大学 | A kind of method that biomass cauline leaf separation prepares absorbent charcoal material |
| WO2018120067A1 (en) * | 2016-12-30 | 2018-07-05 | The University Of Hong Kong | Waste biomass-derived metal-free catalysts for oxygen reduction reaction |
-
2020
- 2020-12-03 CN CN202011409077.6A patent/CN112520736A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130023409A1 (en) * | 2010-01-11 | 2013-01-24 | The University Of Surrey | Activated Charcoal |
| EA201591549A1 (en) * | 2013-03-22 | 2016-05-31 | Торэй Индастриз, Инк. | POROUS CARBON MATERIAL, PREDICTOR OF POROUS CARBON MATERIAL, METHOD FOR OBTAINING PRECONDENT POROUS CARBON MATERIAL AND METHOD FOR OBTAINING POROUS CARBON MATERIAL |
| 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 |
| CN106744936A (en) * | 2016-12-05 | 2017-05-31 | 天津大学 | A kind of method that biomass cauline leaf separation prepares absorbent charcoal material |
| WO2018120067A1 (en) * | 2016-12-30 | 2018-07-05 | The University Of Hong Kong | Waste biomass-derived metal-free catalysts for oxygen reduction reaction |
Non-Patent Citations (1)
| Title |
|---|
| SHUYAN GAO, ET AL.: "Transforming organic-rich amaranthus waste into nitrogen-doped carbon with superior performance of the oxygen reduction reaction", 《ENERGY &ENVIRONMENTAL SCIENCE》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114436253A (en) * | 2022-01-04 | 2022-05-06 | 中冶南方都市环保工程技术股份有限公司 | Method for preparing activated carbon by pyrolysis and self-activation of cobalt-containing biomass and application |
| CN114436253B (en) * | 2022-01-04 | 2024-01-02 | 中冶南方都市环保工程技术股份有限公司 | Method for preparing activated carbon by pyrolysis and self-activation of cobalt-containing biomass and application of activated carbon |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109081342B (en) | Date palm leaf biomass porous activated carbon and preparation method and application thereof | |
| CN108117073B (en) | Method for preparing porous carbon material by using water hyacinth and application | |
| CN108529587B (en) | Preparation method and application of phosphorus-doped biomass graded porous carbon material | |
| CN108483442B (en) | Preparation method of nitrogen-doped carbon electrode material with high mesoporous rate | |
| 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 | |
| CN104386691B (en) | A kind of method preparing ultracapacitor hollow tubular active carbon electrode material | |
| CN111017927A (en) | Preparation and application method of nitrogen-doped porous carbon based on straw hydrothermal carbonization | |
| CN107244664B (en) | Preparation method and application of graphene-like structure carbon electrode material | |
| CN111453726A (en) | Nitrogen-doped porous carbon material and preparation method and application thereof | |
| CN109467082B (en) | Preparation method of graphitized porous corncob derived carbon electrode material | |
| CN106629723A (en) | Biomass-based N, S and P-containing co-doped porous carbon and application thereof | |
| CN110648854B (en) | Boron-nitrogen co-doped carbon/manganese oxide composite nanosheet material, and preparation method and application thereof | |
| CN111584251B (en) | Duckweed-based carbon-coated metal oxide electrode material and preparation method thereof | |
| CN107958797A (en) | A kind of preparation method of the biomass-based active carbon electrode material of highly basic ammonia co-activating | |
| CN111333068A (en) | Preparation method and application of biomass porous carbon material based on nut shells | |
| CN111268677A (en) | Preparation method and application of novel lithium ion battery negative electrode material carbonized grape seed | |
| CN110668441A (en) | Crop tuber-based porous carbon material and preparation method and application thereof | |
| CN110127695A (en) | A kind of preparation method of supercapacitor wood sawdust base porous charcoal | |
| CN114538408B (en) | Method for preparing high-electrocatalytic active biochar by micro-oxygen pyrolysis | |
| CN112520736A (en) | Method for preparing high-performance carbon-based electrode material by biomass full-component pyrolysis | |
| CN111524716B (en) | Preparation and application of composite electrode material with manila herb as carbon source | |
| CN112479205A (en) | Narrow-pore bamboo sheath activated carbon and preparation method thereof | |
| CN113479879B (en) | Activated carbon material based on secondary fermentation vinasse and preparation method and application thereof | |
| CN113838678B (en) | Doped porous biomass charcoal electrode material, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210319 |
|
| RJ01 | Rejection of invention patent application after publication |