CN114715890A - Momordica grosvenori shell based biomass porous carbon and preparation method and application thereof - Google Patents
Momordica grosvenori shell based biomass porous carbon and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 76
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- 239000002028 Biomass Substances 0.000 title claims abstract description 50
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 241001409321 Siraitia grosvenorii Species 0.000 title claims abstract 20
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 53
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 38
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
-
- 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 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- 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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- 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
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- 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
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- Environmental & Geological Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a momordica grosvenori shell based biomass porous carbon, which is prepared by using momordica grosvenori shells as raw materials through pre-carbonization and activation treatment, and a momordica grosvenori shell based biomass porous carbon material with a cellular structure in a micro-morphology is obtained; the content of pyrrole N is 30-32%; i isD/IGThe value range is 1.07-1.08, the specific surface area range is 3900-2·g‑1The pore size distribution range is 1.8-2.0 nm. The preparation method comprises the following steps: 1. pre-carbonizing a momordica grosvenori shell-based precursor; 2. and (3) preparing the momordica grosvenori shell based biomass porous carbon. As a super capacitorUse of a device at 0.5A g‑1The specific capacitance value range is 350-370F-g‑1(ii) a After 10000 cycles, the specific capacitance retention rate is 95-97%. As the application of the symmetrical super capacitor, the power density is 240-260 W.kg‑1When the energy density is high, the maximum energy density can reach 21-22 Wh/kg‑1(ii) a The energy density is 15-16 Wh/kg‑1When the maximum power density can reach 5000-‑1。
Description
Technical Field
The invention relates to the field of electrochemical energy storage, in particular to a shell-based Supercapacitor (SCs) porous carbon material and a preparation method and a performance test thereof.
Background
Since this century, various electronic products have been developed, the output of electronic components has been increasing, and the conventional energy storage devices have a slow release rate of stored electric energy and have a negative effect on the environment. Therefore, the market needs an energy storage material with high energy and high power density to meet the demand of the economic society developing at a high speed. The super capacitor is one of the new energy storage devices. The main performance of the super capacitor is determined by the electrode material, so that the search for the cheap and efficient electrode material has application value and research prospect.
At present, there are three major types of electrode materials used in supercapacitors: carbon-based materials, metal oxides, and conductive polymers. The porous carbon material in the carbon-based material is the most widely applied electrode material at present, and has the characteristics of good physical and chemical properties, such as large specific surface area, controllable pore structure, stable chemical property, high heat conductivity, high electric conductivity, rich raw materials and the like. In order to achieve the goals of carbon peak reaching and carbon neutralization according to the development direction of green and low carbon, the biomass raw material has attracted extensive attention as a research object for preparing carbon-based materials due to the characteristics of natural green, wide sources, unique morphology, carbon structure and the like.
The preparation of the carbon material by using biomass and the application of the carbon material to the super capacitor have been studied, for example, the subject group of the present invention works in the early stage, and the prior document 1 (Xufen, Xueshuan, Sujixian, etc..) discloses a preparation method and an application of a shaddock pulp and peel-based porous carbon material [ P]Chinese patent: CN108584947A, 2018.9.28.), xufen and the like, prepare a carbon precursor from the pomelo fruit flesh skin, treat the carbon precursor with an alkaline inorganic substance, and prepare the porous carbon material from the pomelo fruit flesh skin by calcining. The specific surface area of the material is 1529 m2·g -1The average pore diameter was 1.84 nm. When the material is used as an electrode material of a super capacitor, the current density is 0.5 A.g -1When the specific capacitance is 315F · g-1. At 20 A.g -1At high current density, the specific capacitance value reaches 210 F.g -1The specific capacity retention after 10000 cycles was 93%. However, the technology has the common technical problem that the specific surface area of the porous carbon is not high, and the performance of the supercapacitor is further influenced.
In order to solve the problems, the invention combines the knowledge related to graphene and nitrogen doping technology, utilizes the high specific surface property of graphene, screens raw materials and controls a preparation process to realize the preparation of the carbon material rich in the graphene structure by using biomass as the raw material.
Such as prior art document 2 (Dianching Duan, Hu Fang, Jianojun Ma, et al. A factor one-pot method to prepare reagent and fluorine co-processed needle-dimensional graphics-materials for supercapacitors [ J]Journal of Materials Science-Materials in Electron 2019, 30(21): 19505-2Melamine and polytetrafluoroethylene are directly pyrolyzed in the flow, and the nitrogen and fluorine co-doped three-dimensional (3D) graphene-like material MP-700 is successfully prepared. The specific surface area of the 3D graphene material can reach 1309 m2·g -1And the material is at 0.5A · g -1The specific capacitance is 230F g -1At a current density of 20 A.g -1Then, the specific capacity retention rate after 10000 cycles was 86.3%. The prior art shows that the performance of the supercapacitor is improved by the method for preparing the nitrogen-doped graphene.
According to the existing research, the nitrogen element doped carbon material is used for the oxidation-reduction reaction which can be obtained, which is beneficial to improving the conductivity and further improving the electrochemical performance.
Such as the prior document 3 (Wangguanqiang, Houshuo, Zhang Juan, etc.. preparation of nitrogen-doped graphene nano-sheets and electrochemical properties [ J ]]The physical science report 2016, 65(17): 178102-0-178102-7), Wangcui Qiang and the like take graphite sheets as raw materials to prepare the nitrogen-doped graphene nanosheets by a mechanical needle milling method in a nitrogen atmosphere. Through testing, the specific surface area of the nitrogen-doped graphene nanosheet is 674.7 m2·g -1(ii) a When the charge-discharge current density is 0.3 A.g -1Then, the specific capacitance of the nitrogen-doped graphene nanosheet electrode was calculated to be 202.8F g -1. The prior art shows that the performance of the super capacitor can be improved by carrying out nitrogen doping on the graphene.
Therefore, in the field of nitrogen doping of carbon materials, the aim is mainly to obtain carbon materials with graphite or graphene structures, namely graphite N. Similarly, the preliminary work of the subject group of the present invention has also realized a nitrogen-doped carbon material of a graphite or graphene structure.
For example, the preparation and application of a carbon-coated Co-Ru nano material with a hollow structure [ P ] in the prior document 4 (Sunlixian, buiting, Xufen)]Chinese patent: CN112295572A, 2021.02.02.), ZIF-67 is adopted as a precursor of a supporting material, and Ru is loaded3+And carrying out bonding coating by using dopamine hydrochloride, and carrying out high-temperature carbonization to obtain the carbon-coated Co-Ru nano material with the hollow structure. XRD detection shows that the element C in the material is graphitized carbon.
And the prior document 5 (Sunlizian, Yuyuqian, Xufen. a graphene shell-coated Co-MOF-74 composite material, a preparation method and application [ P ] Chinese patent: application No. 2022103574248.), prepares the graphene-coated Co-MOF-74 by a hydrothermal method, obtains the graphene shell-coated Co-MOF-74 composite material by activation, and obtains the material in a microscopic shape of a rod-shaped bouquet with a rough surface. The graphene is coated, and the catalytic efficiency and stability are improved.
However, the inventor has found that nitrogen doped into the carbon material may exist in the form of pyrrole N and pyridine N in addition to graphite N. Also, the role played by nitrogen-doped forms in carbon materials is different.
The graphite N has the main function of improving the performance of the super capacitor by improving the conductivity of the material; the role of pyrrole N is mainly to improve the electron acceptor/donor structure of the material so as to play a main role in the pseudocapacitance performance of the supercapacitor.
Meanwhile, the subject group of the invention also carries out related research aiming at the preparation of the carbon material by taking the biomass as the raw material.
For example, as shown in prior document 6 (Penghuang, Hufang, and Buddha's bud, etc.; a fermented bean curd-based porous carbon material, and a method for producing the same and use thereof [ P ]]Chinese patent: CN112938967A, 2021.06.11.), the fermented bean curd is used as a raw material, and a porous structure formed by fermented bean curd is reserved after pre-carbonization to form a carbon precursor; and performing alkali treatment, activation and calcination on the carbon precursor to obtain the fermented bean curd-based porous carbon material, wherein the microscopic morphology of the fermented bean curd-based porous carbon material is in a 3D ant nest shape, and the specific surface area of the fermented bean curd-based porous carbon material is 3080.2 m2·g -1. The material is proved to have an amorphous carbon structure by tests.
The research shows that the structure of the biomass material is damaged due to the high-temperature carbonization process, so that the carbon material with an amorphous structure is obtained, wherein the amorphous carbon also has a graphite structure, namely graphite N is obtained. Therefore, a technical problem to be solved at present is how to obtain pyrrole N from biomass.
According to the present invention, the preliminary investigation of the subject group shows that, since pyrrole is a basic structural unit of heme, chlorophyll, bile pigment, specific amino acid, alkaloid and specific enzyme, it is required to satisfy the following requirements for obtaining a carbonaceous material containing pyrrole N, and the components of biomass for preparing the carbonaceous material include, but are not limited to, heme, chlorophyll, bile pigment, specific amino acid, alkaloid and specific enzyme.
The bioactive components of the momordica grosvenori are researched and found to mainly comprise cucurbitane triterpenoids, flavonoids, protein amino acids, polysaccharides and the like by combining the prior document 7 (tang yanping, shuangli, zhangtai, wang courage, momordica grosvenori bioactive components, pharmacological action and product processing research progress [ J ]. beverage industry 2020, 23(06): 67-70). The prior art shows that the momordica grosvenori shells meet the requirement of obtaining pyrrole N.
Through the research of the inventor, the saponin and the amino acid in the fructus momordicae are beneficial to improving the performance of the carbon material; the content of unsaturated fatty acid and linoleic acid is highest, and the unsaturated fatty acid and linoleic acid are rich in N element, so that the unsaturated fatty acid and linoleic acid are naturally beneficial to the development and growth of pores. In the compounds, acids containing benzene rings can be subjected to neutralization reaction with an activating agent KOH in the activation process to generate steam, and phenols and esters are dissolved with water and react with KOH to synthesize pyrrole N and generate a large amount of heat, so that the carbonization process of biomass is accelerated. Meanwhile, the carbonyl group contained in the ester organic matter can generate pseudo capacitance, and the hydroxyl group contained in the aldehyde organic matter improves the surface wettability of carbon.
Therefore, the method adopts the momordica grosvenori shells as the raw material to prepare the biomass porous carbon material, retains the porous structure after carbonization, has larger specific surface area, can synthesize rich pyrrole N, and is an ideal electrode material of the supercapacitor.
Disclosure of Invention
The invention aims to provide a momordica grosvenori shell based biomass porous carbon, and a preparation method and application thereof, so that the comprehensive utilization rate of agricultural and sideline product waste is improved, the economic added value of momordica grosvenori shells is increased, and the production cost of electrode materials is reduced while the content of pyrrole N is enriched, the specific surface area is high, and the performance of a super capacitor is improved.
In order to achieve the purpose, the invention adopts the technical scheme that:
1. the fructus Siraitiae Grosvenorii shell contains cellulose and lignin, so that its pore structure is not destroyed during carbonization. The momordica grosvenori shells contain a large amount of acidic components, wherein the content of unsaturated fatty acid and linoleic acid is highest, and the momordica grosvenori shells are rich in N elements, so that the momordica grosvenori shells are beneficial to synthesizing and enriching pyrrole N.
2. The stable three-dimensional porous carbon material is synthesized by using the momordica grosvenori shells as a carbon source, using an alkaline inorganic substance KOH as an activating agent and using a chemical activation method. The KOH activating agent is combined, the optimal mass ratio is explored, the pore size distribution of the carbon material is adjusted, and the pyrrole N content and the conductivity of the carbon material are improved, so that the specific surface area of the material is increased as much as possible, a large-area double electric layer is formed, and the performance of the supercapacitor is improved.
In order to realize the purpose, the invention adopts the technical scheme that:
a fructus momordicae shell based biomass porous carbon material is prepared by using fructus momordicae shells as raw materials, and carrying out pre-carbonization and activation treatment on the fructus momordicae shells to obtain the fructus momordicae shell based biomass porous carbon material with a cellular structure in a microscopic appearance; in the obtained momordica grosvenori shell based biomass porous carbon, the content of pyrrole N is 30-32%; the micro-morphology honeycomb structure is specifically as followsD/IGThe value range is 1.07-1.08, the specific surface area range is 3900-2·g -1The pore size distribution range is 1.8-2.0 nm.
A preparation method of fructus momordicae shell based biomass porous carbon comprises the following steps:
the pre-carbonization condition is that under the nitrogen condition, the temperature is 3 ℃ min-1The temperature rise rate is that the pre-carbonization temperature is 300-400 ℃, and the pre-carbonization time is 2-3 h;
the mass ratio of MGCs and KOH obtained in the step 1 is 1 (3-4);
the calcining condition is that under the condition of nitrogen, the temperature rising rate is 5 ℃ per minute-1The calcination temperature is 750-850 ℃, and the calcination time is 2-3 h.
Application of fructus momordicae shell based biomass porous carbon as supercapacitor at 0.5 A.g -1The specific capacitance value range is 350-370F-g -1(ii) a After 10000 cycles, the specific capacitance retention rate is 95-97%.
The application of the porous carbon of the fructus momordicae shell-based biomass as the symmetrical supercapacitor is characterized in that: at a power density of 240- -1When the energy density is high, the maximum energy density can reach 21-22 Wh/kg -1；
The energy density is 15-16 Wh/kg -1When the maximum power density can reach 5000- -1。
The experimental test of the obtained momordica grosvenori shell based biomass carbon material has the following results:
XRD (X-ray diffraction) tests show that standard peaks of carbon appear at positions of 30 degrees and 43 degrees in a spectrum, and the standard peaks correspond to (002) and (101) crystal faces of the carbon material, so that the sample is proved to be the carbon material.
Raman test shows that graph shows ID/IG=1.07-1.08, which indicates that the C atom crystal has defects, and the disordered amorphous structure of the sample is proved.
XPS tests show that the sample consists of C, N, O elements, and the N content of pyrrole is as high as 30-32%; the N content of the graphite is 40-42%.
SEM and TEM tests show that the material has a cellular porous structure and uniformly distributed pores.
BET test shows that the sample has a high specific surface area which can reach 3900-2·g -1A large number of micropores and a proper amount of mesopores, wherein the average pore diameter range is 1.8-2.0 nm, and the micropore volume is 1.2-1.3 cm3·g -1。
The cyclic voltammetry test of the momordica grosvenori shell based biomass carbon material shows that under different scanning rates, a cyclic voltammetry curve keeps a good rectangular-like shape, and the sample has good double electric layer performance.
Constant current charge and discharge tests show that the content of the momordica grosvenori shell based biomass carbon material is 0.5 A.g -1The specific capacitance range is 360-370F-g -1(ii) a At a current density of 20A g -1While the specific capacitance is still maintained at 250-270F-g -1。
The cycle stability test of the momordica grosvenori shell based biomass carbon material shows that the content of the momordica grosvenori shell based biomass carbon material is 5 A.g -1After 10000 cycles, the specific capacitance retention rate is 95-97%.
According to the test results, the preparation method and the obtained product have the following advantages and beneficial effects:
1. the invention selects the waste momordica grosvenori shells as the carbon source, improves the comprehensive utilization rate of the momordica grosvenori shells, increases the economic added value and reduces the production cost of the electrode material. The fructus momordicae is mainly produced in Guangxi Guilin, and has high yield, storage resistance, easy obtaining and low cost. The momordica grosvenori shells contain a large amount of acidic components, wherein the content of unsaturated fatty acid and linoleic acid is highest, and the momordica grosvenori shells are rich in N elements and naturally beneficial to the development and growth of pores.
2. The fructus momordicae shell-based porous carbon prepared by the method has rich pyrrole N content ranging from 30 to 32 percent and high specific surface area ranging from 3900-2·g -1Abundant micropores, a proper amount of mesoporous structures and uniform average pore size distribution within the range of 1.8-2.0 nm are beneficial to increasing the specific surface area, so that the performance of the double-electric-layer capacitor of the supercapacitor is improved.
3. The super capacitor electrode material is applied when the current density is 0.5 A.g−1The specific capacitance value range is 360-−1And has good cycle stability and rate capability.
Aiming at the limitation of the process for preparing the carbon material in the prior art, the method takes the momordica grosvenori shells as the carbon source, and the carbon material is etched by alkaline inorganic matters at high temperature to formAnd the gas generated by etching is favorable for forming abundant pore structures and increasing the surface area, and finally the momordica grosvenori shell-based porous carbon material is formed. When the porous carbon material is used as an electrode material of a super capacitor, micropores in the porous carbon material mainly provide a larger specific surface, mesopores are transmission channels of electrolyte ions, and a macroporous structure can play a role of an electrolyte buffer pool, so that the good rate performance of the super capacitor is realized, and the rate performance is 20 A.g -1The specific capacitance is still kept at 250-270F-g -1。
Therefore, the invention has wide application prospect in the field of super capacitor materials.
Drawings
FIG. 1 is a summary of the XRD images of example 1, comparative example 2 and comparative example 3;
FIG. 2 is Raman spectra of example 1, comparative example 2 and comparative example 3;
FIG. 3 is XPS measurement spectra of example 1, comparative example 2, and comparative example 3;
figure 4 is a high resolution XPS spectrum of N1s of MGCs-2 material in example 1;
FIG. 5 shows an SEM image of carbon material MGCs-2 prepared in example 1;
figure 6 is a TEM image of MGCs-2 material in example 1 with a high resolution image;
FIG. 7 is a graph showing isothermal nitrogen adsorption and desorption curves of example 1, comparative example 2 and comparative example 3;
FIG. 8 is a pore size distribution plot for example 1, comparative example 2, and comparative example 3;
FIG. 9 shows MGCs-0, MGCs-1, MGCs-2, and MGCs-3 CV at 100 mV. multidot.s-1A lower curve image;
figure 10 is a graph of CV for MGCs-2 material of example 1 at various scan rates;
FIG. 11 shows that MGCs-0, MGCs-1, MGCs-2 and MGCs-3 are at 0.5 A.g -1(ii) the lower GCD plot;
figure 12 is a GCD plot of MGCs-2 material of example 1 at different current densities;
FIG. 13 is a graph of the specific capacitance of the MGCs-2 material of example 1 at different current densities;
FIG. 14 shows the current density of the MGCs-2 material of example 1 at 5A g -1A temporal cycling stability map;
figure 15 is a CV curve at different scan rates for a symmetrical supercapacitor made from MGCs-2 material of example 1;
FIG. 16 is a GCD curve of a symmetrical supercapacitor made of MGCs-2 material of example 1 at different current densities;
FIG. 17 is a graph of the specific capacitance of a symmetrical supercapacitor made of MGCs-2 material in example 1 at different current densities;
figure 18 is a graph of the energy density and power density of a symmetrical supercapacitor made of MGCs-2 material in example 1;
FIG. 19 is an SEM image of MGCs-0 of the carbon material prepared in comparative example 1;
FIG. 20 is an SEM image of MGCs-1 of the carbon material prepared in comparative example 2;
FIG. 21 is an SEM image of MGCs-3, a carbon material prepared in comparative example 3.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings, which are given by way of examples, but are not intended to limit the present invention.
Example 1
A preparation method of a momordica grosvenori shell based biomass porous carbon comprises the following specific preparation steps:
To demonstrate the compositional characteristics of the material of the present invention, XRD testing was performed on MGCs-2. As shown in fig. 1, a broad diffraction peak exists at 2 θ =30 °, which is the (002) crystal plane of the carbon material, and an unobvious camel-type diffraction peak at 2 θ = 43 ° is assigned to the (101) crystal plane of graphite. Experimental results show that MGCs-2 is in an amorphous structure.
To further demonstrate the disordered amorphous structure of the material of the present invention, Raman testing was performed on MGCs-2. Test results are shown in FIG. 2 and Table 1, I of MGCs-2D/IGMaximum value of about 1.076, intensity ratio of D band and G band (I)D/IG) Can reflect the defect structure in the graphitized structure, therefore, the experimental result shows that MGCs-2 is in a disordered amorphous structure.
Watch (A)
Comparison table of sample specific surface area and pore size
Note: a: the ratio of the specific surface area of the micropores to the mesopores of the experimental sample (on SSA)
b：ID/IGFor the experimental sample Raman characteristic intensity peak (D peak/G peak)
To demonstrate the elemental composition of the material of the invention, the MGCs-2 was subjected to XPS testing. As shown in fig. 3 and fig. 4, MGCs-2 has N, C and O elements, where N1s is formed by stacking 4 peaks, specifically including pyridine N, pyrrole N, graphite N, and oxidized N. According to the common knowledge, the redox reaction obtained by doping nitrogen elements is beneficial to improving the conductivity and the additional pseudocapacitance and improving the performance of the super capacitor, but researches show that the N elements in all states can not obtain obvious technical effect improvement, and the researches show that the pyrrole N plays a main role in improving the pseudocapacitance performance of the super capacitor by improving the electron acceptor/donor structure; in addition, graphite N can increase the conductivity of the sample. The pyrrole N content of MGCs-2 is up to 31.1 percent according to XPS experiment result calculation; the graphite N content was 40.33%.
In order to prove the microscopic morphology and morphological characteristics of the material, scanning SEM and TEM tests are carried out on the MGCs-2 obtained in the step 2. The test results are shown in fig. 5 and fig. 6, respectively, MGCs-2 is a porous material having a microporous structure, and is a property of amorphous carbon in combination with the feature of no lattice fringes; furthermore, the porous material is characterized by developed internal porosity, uniform pore structure development, developed transverse hole expansion and developed depth development, complete pore structure and no existence of more through holes.
According to the common knowledge in the field, micropores and mesopores can increase the specific surface area, which is beneficial to the rapid diffusion of electrolyte ions and improves the capacity of storing charges, so that the BET test is carried out on MGCs-2 in order to further confirm the micropore structure and parameters of the material. As shown in FIG. 7, FIG. 8 and Table 1, the nitrogen sorption and desorption curves of MGCs-2 exhibit typical type I isotherms and the maximum of the sorption volume exceeds 1200 cm3·g -1The experimental result shows that a large number of micropores exist in MGCs-2, so that the adsorption capacity is effectively improved; PSD curve of MGCs-2 further proves that MGCs-2 are mainly microporous; the specific surface area of MGCs-2 was 3996.4 m2·g -1Average pore diameter of 1.89 nm and micropore volume of 1.28 cm3·g -1。
In order to prove the electrochemical performance of the material, cyclic voltammetry CV test, constant current charge and discharge GCD test and cyclic stability test are respectively carried out on MGCs-2.
CV test results As shown in FIGS. 9 and 10, the CV curve is in a rectangular-like shape with a slightly wider Faraday peak between-0.8V and-0.6V, which is generally interpreted as ideal electrical double-layer capacitance and pseudocapacitance behavior; as the scan rate increases, even at 100 mV · s -1The CV curve of MGCs-2 still maintains a symmetrical and rectangular-like shape at high scan rates, which indicates that due to nitrogen doping and porosityThe structure forms an electrical double layer, good rate capability and low internal resistance.
The GCD test result is shown in figures 11 and 12, the curve presents a symmetrical triangle, the bottom side length of the triangle indicates that the sample has good cycle reversibility, which is a great advantage when the carbon material is used as an electrode material; the specific capacitance at different current densities is 0.5 A.g, as shown in FIG. 13 -1MGC-2 has a specific capacitance value of 367F g at the current density of (1) -1(ii) a At a high current density of 20A g -1While the capacitance of MGC-2 is still maintained at 260F g -1The capacity retention was 70.8%, showing excellent high rate capability.
The method of the cycle stability test is to repeat the GCD test to obtain the cycle stability of MGCs-2, and the test result is shown in fig. 14. At 5 A.g -1The specific capacity retention ratio after 10000 cycles of the current density of (1) was 96.02%. The excellent cycle stability of the composite material can be attributed to the fact that MGCs-2 has a three-dimensional porous structure, a proper micropore content and a large specific surface area, a short and unobstructed path is provided for the diffusion and migration of electrolyte ions, and the electrolyte ions are allowed to be adsorbed and desorbed on the surface of the material very quickly.
From the above, it can be seen that the Grosvenor momordica shell based biomass porous carbon MGCs-2 has excellent capacitance (at 0.5A · g) -1Can reach 367 F.g at the current density -1) And high cycle stability (specific capacity retention 96.02% after 10000 cycles). Due to the proper proportion of the micropores and the mesopores, a diffusion channel of electrolyte ions is optimized, so that the contact area of the electrolyte and an electrode is increased, and the electrochemical performance of MGCs-2 is improved.
In order to further prove the electrochemical performance of MGCs-2, a symmetrical supercapacitor test was performed under the specific test conditions of CV test and GCD test in 6M KOH solution, respectively.
The CV test results are shown in FIG. 15, where the CV curve is in a rectangular-like shape with a slightly wider Faraday peak between-0.8V and-0.6V. When the scan rate is increased, even at 100 mV · s -1At high scan rates, the CV curve of MGCs-2// MGCs-2 still maintains a symmetrical and rectangular-like shape, indicating that it has a good profileRate capability and low internal resistance.
The GCD test results are shown in fig. 16, fig. 17 and fig. 18, and the curves show symmetrical triangles, which indicates that the material has good cycle reversibility, which is also a great advantage when the carbon material is used as an electrode material.
Symmetric MGCS-2// MGCS-2 at 0.5 A.g -1The specific capacitance at the current density of (A) is 152F · g -1Based on the average weight of the two electrode active materials.
At a high current density of 20A g -1The capacitance of MGCs-2// MGCs-2 is still kept at 89 Fg -1The capacity retention was 58.6%.
At a power density of 250 W.kg -1The maximum energy density of the MGCs-2// MGCs-2 symmetrical supercapacitor is 21.04 Wh kg -1。
At an energy density of 15.42 Wh/kg -1When the power density reaches 5047 W.kg -1。
The experimental results prove that the MGCs-2 meets the requirements of practical application, and the MGCs-2// MGCs-2 symmetrical super capacitor has 21.04 Wh.kg -1High energy density.
In order to demonstrate the effect of KOH on the performance of the porous momordica grosvenori shell based biomass carbon, comparative example 1, the porous momordica grosvenori shell based biomass carbon prepared without adding KOH, was provided.
Comparative example 1
The preparation method of the momordica grosvenori shell based biomass porous carbon is the same as that of the example 1 in the preparation steps which are not particularly described, and the difference is that: KOH is not added in the step 2, and the obtained material is called MGCs-0 for short.
The results of the SEM test of MGCs-0 are shown in FIG. 19, which shows that MGCs-0 has a relatively smooth surface and no porous structure is observed, i.e., MGCs-0 is a non-porous material. The result shows that KOH is not added for activation, MGCs-0 does not have a pore structure, so that the material does not have an electrolyte ion channel inside, the contact area between the electrolyte and an electrode is small, and the capacity of storing charges is weak.
The BET test results of MGCs-0 are shown in FIG. 7, FIG. 8 and Table 1, and the nitrogen desorption curve and pore size distribution curve of MGCs-0 have low values andthe variation is not large. The specific surface area of MGCs-0 shown in Table 1 was 1.1 m2·g -1The volume of the micro-pores is almost zero, and the sample can be basically determined to be a non-porous material. This indicates that MGCs-0 is a non-porous material, which results in a small amount of nitrogen adsorption and a small specific surface area of the sample.
As compared with example 1, it is clear that a porous structure can be obtained by adding KOH.
The CV test results for MGCs-0 are shown in FIG. 9 at a scan rate of 100 mV. multidot.s -1The CV curve exhibits a triangle-like shape, which indicates that the sample does not exhibit electrical double-layer capacitance and pseudocapacitance behavior.
The GCD test result of MGCs-0 is shown in FIG. 11, the curve shows a symmetrical triangle with a shorter base and a charging and discharging time of less than 600 s. The specific capacitance at different current densities is shown in FIG. 13 and is at 0.5A g−1At a current density of (3), the specific capacitance of MGCs-0 is 112F g−1。
Compared to example 1, it is clear that the porous structure obtained by the addition of KOH directly affects the electrochemical performance.
To demonstrate the effect of KOH ratio on the performance of the porous momordica grosvenori shell-based biomass carbon, comparative examples 2 and 3 were provided, the porous momordica grosvenori shell-based biomass carbon having a precursor and KOH ratio of 1:1.5 and 1:3.5, respectively.
Comparative example 2
A preparation method of Momordica grosvenori shell based biomass porous carbon with MGCs and KOH mass ratio of 1:1.5 is the same as example 1 in preparation steps and test sequence which are not particularly described, and the difference is that: the addition amount of KOH in the step 2 is 1.5 g, and the obtained material is called MGCs-1 for short.
The SEM test result of MGCs-1 is shown in fig. 20, which shows that MGCs-1 begins to have some micropores and mesopores after KOH activation etching, and the existence of the porous structure is favorable for the rapid diffusion of electrolyte ions, thereby improving the charge storage capacity.
The BET test results of MGCs-1 are shown in FIG. 7, FIG. 8 and Table 1, the nitrogen adsorption and desorption curve of MGCs-1 is type I, and the absorption volume value range is 200-400 cm3·g -1Experiment, experiment ofThe result shows that part of micropores exist in MGCs-1, so that the adsorption capacity is improved; pore Size Distribution (PSD) curves further prove that the interior of MGCs-1 is mainly microporous; MGCs-1 has a specific surface area of 1150.5 m2·g -1The micropore volume is 0.47 cm3·g -1。
As compared with example 1, it is understood that, since the number of micropores and mesopores provided in MGCs-1 is decreased due to the decrease in the addition amount of KOH, and the specific surface area and the micropore volume are relatively low, the amount of adsorption is relatively small, which means that the contact area between the active material and the electrolyte is increased, and the ability to store electric charge is weaker than that of MGCs-2.
The CV test result of MGCs-1 is shown in FIG. 9, the CV curve is in a rectangle-like shape, and a slightly wider Faraday peak is between-0.8V and-0.6V, which is generally interpreted as ideal electric double-layer capacitance and pseudocapacitance behavior; as the scan rate increases, even at 100 mV · s -1The CV curve of MGCs-1 still maintains a symmetrical and rectangular-like shape at high scan rates, which indicates the formation of an electrical double layer, good rate performance and low internal resistance due to nitrogen doping and porous structure.
The GCD test result of MGCs-1 is shown in FIG. 11, the curve presents a symmetrical triangle, the bottom side length of the triangle shows that the sample has good cycle reversibility, which is also a great advantage when carbon materials are used as electrode materials; the specific capacitance at different current densities is 0.5 A.g, as shown in FIG. 13−1At a current density of (3), the specific capacitance value of MGCs-1 is 298F g−1。
As compared with example 1, the number and specific surface area of MGCs-1 micropores are far less than those of MGCs-2 due to the reduction of the addition amount of KOH; MGCs-1 has electric double-layer capacitance and pseudocapacitance behaviors, but the discharge time is relatively short, and the specific capacitance value is relatively small, which shows that the electrochemical performance of MGCs-1 is weaker than that of MGCs-2.
Comparative example 3
A method for preparing momordica grosvenori shell based biomass porous carbon with MGCs and KOH in a weight ratio of 1:3.5, wherein the steps which are not particularly described are the same as those in example 1, except that: in the step 2, the addition amount of KOH is 3.5 g, and the obtained material is called MGCs-3 for short.
The results of the SEM test of MGCs-3 are shown in FIG. 21, where many micropores and mesopores are destroyed and fragments appear on the surface due to the activation of excess KOH, and the BET test is performed for further quantitative analysis.
The BET test results are shown in FIG. 7, FIG. 8 and Table 1, the nitrogen adsorption and desorption curves of MGCs-3 show typical type I isotherms, and the absorption volume range is 400-800 cm3·g -1The experimental result shows that a large number of micropores exist inside MGCs-3; pore Size Distribution (PSD) curves further demonstrate that MGCs-3 are predominantly microporous; the specific surface area of MGCs-3 is 2251.6 m2·g -1Micropore volume of 0.40 cm3·g -1。
As compared with example 1, it is understood that, since the addition amount of KOH was too large, part of the micropores of MGCs-3 were destroyed and the specific surface area and the micropore volume were small relative to those of MGCs-2, the amount of adsorption was relatively small, meaning that the contact area of the active material with the electrolyte was increased and the ability to store electric charge was weaker than that of MGCs-2.
The CV test results of MGCs-3 are shown in FIG. 9, 100 mV. multidot.s -1The lower CV curve is in a rectangle-like shape, and a slightly wider Faraday peak is arranged between-0.8V and-0.6V, which indicates that MGCs-3 has electric double-layer capacitance and pseudocapacitance behaviors.
The GCD test results of MGCs-3 are shown in FIG. 11, where the curve shows a symmetrical triangle, indicating that the sample has good cycle reversibility. The specific capacitance at different current densities is 0.5 A.g, as shown in FIG. 13−1At a current density of (3), the specific capacitance value of MGCs-3 is 258F g−1。
Compared with the example 1, the activation of excessive KOH causes the micro-pores of MGCs-3 to be broken partially, so that the specific surface area is far less than that of MGCs-2; MGCs-3 has electrical double-layer capacitance and pseudocapacitance behavior, but the discharge time is relatively short, and the specific capacitance value is relatively small, which shows that the electrochemical performance of MGCs-3 is weaker than that of MGCs-2.
According to the experimental results of the example 1, the comparative example 2 and the comparative example 3, the MGCs-2 activated by KOH with proper dosage has developed porosity, lateral hole expansion and depth development, and compared with other comparative examples, the pore structure is more complete and no more through holes exist.
MGCs-2 specific surface area (3996.4 m)2·g -1) And bulk density (1.28 cm)3·g -1) Compared with other comparative examples, the composite material is more excellent, so that the contact area of the active material and the electrolyte is increased, and the capacity of storing charges with large adsorption quantity is more remarkable.
MGCs-2 has excellent capacitance (at 0.5A g) -1Can reach 367 F.g at the current density -1) And high cycling stability (specific capacity retention 96.02% after 10000 cycles). At 0.5 A.g -1Under the condition (1), the discharge time sequence of the electrodes is displayed according to a GCD curve: MGCs-0< MGCs-3 < MGCs-1 <MGCs-2, corresponding to their specific capacitance values of 112, 258, 298 and 367F g, respectively -1. And MGCs-2 is at 20 A.g -1Under the condition (2), the specific capacitance still has 260F g -1The capacity retention ratio was 70.8%.
Because the appropriate proportion of the micropores to the mesopores is 2.61, a diffusion channel of electrolyte ions is optimized, the contact area of the electrolyte and an electrode is increased, and the electrochemical performance of MGCs-2 is improved.
Claims (10)
1. A porous carbon of fructus momordicae shell-based biomass is characterized in that: the momordica grosvenori shell based biomass porous carbon material with a cellular structure in a microscopic morphology is obtained by using momordica grosvenori shells as raw materials and carrying out pre-carbonization and activation treatment.
2. The momordica grosvenori shell based biomass porous carbon of claim 1, wherein: in the obtained momordica grosvenori shell based biomass porous carbon, the content of pyrrole N is 30-32%.
3. The momordica grosvenori shell based biomass porous carbon of claim 1, wherein: the micro-morphology honeycomb structure is specifically as followsD/IGThe value range is 1.07-1.08, the specific surface area range is 3900-2·g -1The pore size distribution range is 1.8-2.0 nm.
4. A preparation method of fructus momordicae shell based biomass porous carbon is characterized by comprising the following steps:
step 1, pre-carbonizing a momordica grosvenori shell-based precursor, washing and drying the momordica grosvenori shell base, crushing the momordica grosvenori shell base into momordica grosvenori powder, and then pre-carbonizing the momordica grosvenori powder under certain conditions to obtain the momordica grosvenori shell-based precursor, wherein the obtained material is named as MGCs;
step 2, preparing the momordica grosvenori shell based biomass porous carbon, and mixing and grinding MGCs and KOH uniformly according to a certain mass ratio of MGCs and KOH obtained in the step 1; and then, calcining under a certain condition, washing by using an HCl solution, carrying out suction filtration to remove excessive alkali and inorganic salt, and drying to obtain the momordica grosvenori shell-based biomass porous carbon.
5. The production method according to claim 3, characterized in that: the pre-carbonization condition of the step 1 is that under the nitrogen condition, the temperature is 3 ℃ min-1The temperature rise rate is 400 ℃ at the pre-carbonization temperature of 300 ℃ and the pre-carbonization time of 2-3 h.
6. The production method according to claim 3, characterized in that: in the step 2, the mass ratio of MGCs to KOH is 1 (3-4); the calcining condition is that under the condition of nitrogen, the temperature rising rate is 5 ℃ per minute-1The calcination temperature is 750-850 ℃, and the calcination time is 2-3 h.
7. The application of the porous carbon of the momordica grosvenori shell-based biomass as the supercapacitor is characterized in that: at 0.5 A.g -1The specific capacitance value range is 350-370F-g -1。
8. Use according to claim 6, characterized in that: after 10000 cycles, the specific capacitance retention rate is 95-97%.
9. The application of the porous carbon of the fructus momordicae shell-based biomass as the symmetrical supercapacitor is characterized in that: at a power density of 240-260 W·kg -1When the energy density is high, the maximum energy density can reach 21-22 Wh/kg -1。
10. The application of the porous carbon of the fructus momordicae shell-based biomass as the symmetrical supercapacitor is characterized in that: at an energy density of 15-16 Wh/kg -1When the maximum power density can reach 5000- -1。
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