CN110942924A - Yeast cell-based Ni-Co-S-loaded porous carbon material and preparation method and application thereof - Google Patents

Yeast cell-based Ni-Co-S-loaded porous carbon material and preparation method and application thereof Download PDF

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CN110942924A
CN110942924A CN201911233244.3A CN201911233244A CN110942924A CN 110942924 A CN110942924 A CN 110942924A CN 201911233244 A CN201911233244 A CN 201911233244A CN 110942924 A CN110942924 A CN 110942924A
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porous carbon
yeast
yeast cells
cobalt
yeast cell
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向翠丽
杨学英
邹勇进
徐芬
孙立贤
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Guilin University of Electronic Technology
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Guilin University of Electronic Technology
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/24Electrodes characterised by structural features, e.g. forms, shapes, surface areas, porosities or dimensions, of the materials making up or comprised in the electrodes; characterised by the structural features of powders or particles used therefor
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/05Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their materials
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their materials
    • H01G11/32Carbon-based, e.g. activated carbon materials
    • H01G11/34Carbon-based, e.g. activated carbon materials characterised by carbonisation or activation of carbon
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their materials
    • H01G11/32Carbon-based, e.g. activated carbon materials
    • H01G11/42Powders or particles, e.g. composition thereof
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their materials
    • H01G11/32Carbon-based, e.g. activated carbon materials
    • H01G11/44Raw materials therefor, e.g. resins or coal
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

Abstract

The invention discloses a yeast cell-based Ni-Co-S loaded porous carbon material, which is prepared by preparing carbonized yeast cell porous carbon, performing hydrothermal reaction on the carbonized yeast cell porous carbon, cobalt nitrate, nickel nitrate and urea, and then oxidizing and vulcanizing the carbonized yeast cell porous carbon, wherein the obtained material is in a core-shell structure, and cobalt and nickel elements are NiCo2S4Form is uniformThe ground is loaded on the surface of porous carbon of the yeast cells; the shell-core structure is formed by carbonizing ellipsoidal unicellular fungus yeast, and yeast cells after carbonization are in a hollow carbon sphere structure. The preparation method comprises the following steps: 1) preparing porous carbon of the yeast cells; 2) porous carbon of yeast cells adsorbs cobalt nickel metal ions; 3) sulfurizing porous carbon of yeast cell with adsorbed cobalt and nickel metal ions. The high-performance super capacitor is applied to a super capacitor, the super capacitor is charged and discharged within the range of-0.2-0.5, and the specific capacitance is 700-800F/g when the discharge current density is 1A/g. Has the following advantages: no harm to human body; solves the problem of the tolerance of the metal salt solution of the yeast cells.

Description

Yeast cell-based Ni-Co-S-loaded porous carbon material and preparation method and application thereof
Technical Field
The invention relates to the technical field of supercapacitors, in particular to a yeast cell-based Ni-Co-S loaded porous carbon material for research of a supercapacitor.
Background
With the proliferation of demand for advanced electric vehicles and large energy systems, energy storage/conversion and its environmental impact have become two of the most important issues in recent years. In this regard, new and sustainable energy storage/conversion technologies are needed to meet the rapidly growing global energy demand ring. However, clean and sustainable energy technologies that are closely related to renewable resources face several challenges. These challenges, such as low reliability and high cost, have hindered their commercial application. However, the super capacitor has the advantages of high power, long cycle, low maintenance cost, and the like, and is considered to be a promising energy conversion device.
For supercapacitors, high specific capacitance, green and renewable and performance issues are important concerns for researchers. The super capacitor based on the high-molecular conductive polymer has higher specific capacitance, but has the technical problems of poor stability, toxic and polluted raw materials and harsh polymerization conditions, for example, polypyrrole can be polymerized under the ice bath condition.
In order to solve the technical problem of poor stability, the carbonization of the high-molecular conductive polymer is an effective method for improving the stability of the material. However, carbonization causes a new technical problem, namely a large reduction in the specific capacitance. Aiming at the new technical problem, the introduction of the transition metal sulfide to improve the specific capacitance of the composite material is an effective method.
In addition, aiming at the technical problems of toxicity and pollution of raw materials and harsh polymerization conditions, the biomass is used as the substrate carbon material, so that the material is nontoxic, is a high molecular compound with a specific morphology, does not need to be subjected to polymerization treatment, and can be directly carbonized for use.
Therefore, combining the above two methods, the use of metal sulfide in combination with biomass carbon material for a supercapacitor can effectively solve the above technical problems. Prior art Yu et al (advancing electrochemical activity of activated carbon derived from pop by NiCo)2S4nanoparticle coating》Applied Surface Science, 4631001-1010-doi: 10.1016/j.apsusc.2018.09.037) loaded with NiCo as a biomass carbon source2S4The specific capacitance of the nano-particles reaches 605.2F/g. The substrate carbon material in the work is popcorn, and compared with the preparation process of graphene, carbon nanotubes and the like, the preparation process is more environment-friendly. Second NiCo2S4Belongs to transition metal sulfide, is used for supercapacitor electrode material, has rich valence transition and comprises Co2+/ Co3+And Ni2+/Ni3+By adopting the method, the performance is improved by about fifty percent. NiCo2S4The working principle in alkaline electrolyte is as follows:
CoS+OH-1=CoSOH-1+e-1
CoSOH-1+OH-1=CoSO+H2O+e-1
NiS+OH-1=NiSOH+e-1
however, the technique still has the following two problems: the popcorn does not have a specific micro-appearance, and the carbonized material does not have a specific appearance; in the high-temperature carbonization process, the structure is easy to damage, and the agglomeration phenomenon is generated to ensure that the NiCo is2S4The amount of nanoparticles attached to the surface is reduced, so that the electrochemical performance of the composite material is only 605.2F/g, and the expected effect cannot be achieved.
For the reasons, the substrate material which has a specific shape structure and can keep the shape structure in the preparation process can better solve the problem of shapePoor appearance retention. Lejia (mycelial group doped carbon material prepared based on microorganism enrichment and electrochemical performance research thereof) [ D ]]Southwest university of science and technology, 2018.)) takes hyphae formed by germination of fungal spores as a biomass carbon source, microorganisms enrich heteroatom precursors in the growth process of the fungi, a new idea is provided for preparation of the doped biomass carbon material, Fe/N co-doped carbon fiber is prepared by a biological enrichment method of chelating ferrous iron with glycine by the fungi, and the highest specific capacitance is 211 Fg-1. The work uses live fungal spore source material that can adsorb metals during the culture process. The method can better maintain the original appearance of the fungal spores, but the specific capacitance of the obtained material is extremely low. The inventor analyzes and finds that the appearance is shrunk due to the osmosis of the cell wall surface caused by the excessive concentration of the metal salt in the culture medium, so that the adsorption effect of the fungal spores on the metal particles is extremely poor, and the specific capacitance is low.
Therefore, when biomass is used as an electrode material of a supercapacitor, the technical problem that must be solved is to select biomass having a micro morphology suitable for the supercapacitor and a carbonization process can effectively maintain the morphology, and when the biomass is used as a raw material of the supercapacitor, the following problems need to be solved:
1) most microorganisms have weak metal tolerance, and the adsorption effect of the viable bacteria on metal ions is poor;
2) many microorganisms are highly harmful to the human body, such as helicobacter pylori, escherichia coli, and the like.
Disclosure of Invention
The invention aims to provide a yeast cell-based Ni-Co-S loaded porous carbon material for a supercapacitor.
Aiming at the technical problems in the prior art, the invention adopts the following modes to solve the problems:
1. firstly, yeast cells are carbonized by using the principle of taking the yeast cells as a self-template, and a spherical structure is kept in the carbonization process;
2. the yeast cells are carbonized and then are compounded with a metal salt solution, and the method can solve the problem that the yeast cells cannot resist the metal salt solution;
3. in addition, in order to overcome the damage of experimental raw materials to human body in the experimental or production process, especially the damage of intestinal balance of human body caused by some biomass raw materials, such as escherichia coli, etc., a biomass which is not harmful to human body needs to be selected.
In order to achieve the purpose of the invention, the invention adopts the technical scheme that:
a porous carbon material based on yeast cells and loaded with Ni-Co-S is prepared through preparing carbonized porous carbon of yeast cells, hydrothermal reaction on cobalt nitrate, nickel nitrate and urea, oxidizing and sulfurizing to obtain the material in core-shell structure with NiCo and Ni elements2S4The shell-core structure is formed by carbonizing ellipsoidal unicellular fungus yeast, and the carbonized yeast cell is in a hollow carbon sphere structure.
A preparation method of a Ni-Co-S loaded porous carbon material based on yeast cells comprises the following steps:
step 1) preparing porous carbon of yeast cells, preparing a glucose solution with the concentration of 0.02-0.03g/mL, adding yeast powder, pretreating the yeast cells under the water bath condition that the water bath temperature is 30-50 ℃ and the water bath time is 20-50min, washing and drying to obtain the pretreated yeast cells, dispersing the pretreated yeast cells in a glutaraldehyde aqueous solution according to a certain proportion to prepare a solution with the concentration of 0.01-0.03g/mL of the yeast cells and the concentration of 2-4% of the glutaraldehyde aqueous solution, carrying out ultrasonic treatment for 5-15min to uniformly disperse the yeast cells, carrying out hydrothermal reaction for 4-6h under the condition that the temperature is 150-, calcining for 1-3h at the temperature of 700-900 ℃ under the condition of nitrogen, and carrying out carbonization treatment to obtain porous carbon of the yeast cells;
step 2), adsorbing cobalt and nickel metal ions by porous carbon of the yeast cell so as to meet the requirement that the ratio of the mass of the porous carbon of the yeast cell to the sum of the mass of cobalt nitrate hexahydrate and nickel nitrate hexahydrate is 1: 2, the mass ratio of the cobalt nitrate hexahydrate to the nickel nitrate hexahydrate to the urea is 10: 5: 18, adding the porous carbon of the yeast cells, cobalt nitrate, nickel nitrate and urea obtained in the step 1 into an aqueous solution, uniformly mixing and stirring, carrying out hydrothermal reaction for 4-6h at the temperature of 150-;
and 3) vulcanizing the porous carbon of the yeast cells adsorbing the cobalt-nickel metal ions, namely putting the porous carbon of the yeast cells adsorbing the cobalt-nickel metal ions in the step 2 into an aqueous solution, and mixing the sodium sulfide nonahydrate with nickel nitrate hexahydrate and cobalt nitrate hexahydrate according to the mass ratio of 4: 1: 2, adding sodium sulfide nonahydrate, carrying out hydrothermal reaction for 5-7h at the temperature of 150-250 ℃, and finally carrying out suction filtration, washing and drying to obtain the Ni-Co-S loaded porous carbon material of the yeast cells.
The yeast cell-based Ni-Co-S loaded porous carbon material is applied to a super capacitor as the super capacitor, and is charged and discharged within the range of-0.2 to 0.5, and when the discharge current density is 1A/g, the specific capacitance is 700-800F/g.
The invention can be known through detection of SEM, XRD, CV, GCD, EIS and the like that: compared with the prior art, the invention has the following advantages:
1) the yeast cell food-grade biomass material has no harm to human body;
2) the yeast cells keep the structure unchanged after carbonization by utilizing the self spherical structure, the spherical structure is beneficial to loading other substances on the surface, and the problem of tolerance of the metal salt solution of the yeast cells can be solved after carbonization;
3) the transition metal sulfide has higher surface capacitance but poor conductivity, however, after yeast cells are carbonized, cell walls of the yeast cells have rich protein, so that the carbon material is doped with N, and the conductivity of the material can be enhanced.
Therefore, compared with the prior art, the composite electrode material has better capacitance performance and sustainable development performance, improves the capacitance performance of the composite electrode material, and has a new research prospect in the field of application of biomass and transition metal sulfide in the field of supercapacitors.
Description of the drawings:
FIG. 1 is a SEM photograph of yeast cells not subjected to carbonization treatment in example 1;
FIG. 2 is a photograph of a CY SEM of carbon-treated yeast cells of example 1;
FIG. 3 is an SEM photograph of CY-Co-Ni-S in example 1;
FIG. 4 is an SEM-mapping chart of CY-Co-Ni-S in example 1;
FIG. 5 is an XRD pattern of CY-Co-Ni-S in example 1;
FIG. 6 is an EIS diagram of CY-Co-Ni-S in example 1, comparative example 2 and comparative example 3;
FIG. 7 is the 5m Vs of CY-Co-Ni-S in example 1-1CV curve of time;
FIG. 8 shows the chemical formula of CY-Co-Ni-S in 1 Ag in example 1-1A GCD curve of time;
FIG. 9 shows 1 Ag of Y-Co-Ni-S in comparative example 1-1A GCD curve of time;
FIG. 10 shows CY-Co-S at 1 Ag in comparative example 2-1A GCD curve of time;
FIG. 11 is a graph of CY-Ni-S at 1 Ag for comparative example 3-1A GCD curve of time;
FIG. 12 is an SEM photograph of Y-Co-Ni-S in comparative example 1.
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 yeast cell-based Ni-Co-S loaded porous carbon material for a supercapacitor material comprises the following steps:
step 1) preparing porous carbon of yeast cells, preparing 0.024g/mL glucose solution, adding yeast powder, preserving heat in a water bath at 37 ℃ for 30min to pretreat the yeast cells, washing and drying to obtain the pretreated yeast cells, dispersing the pretreated yeast cells with the concentration of 0.017g/mL in a 3% glutaraldehyde water solution, performing ultrasonic treatment for 10min to uniformly disperse the yeast cells, performing hydrothermal reaction at 180 ℃ for 5h, washing and drying the obtained precipitate after the reaction is finished, finally calcining at 300 ℃ for 2h in air atmosphere, and calcining at 800 ℃ for 2h in nitrogen to obtain the porous carbon of yeast cells;
step 2) adsorbing cobalt and nickel metal ions by porous carbon of the yeast cell, weighing 0.5g of the porous carbon of the yeast cell obtained in the step 1 according to a certain proportion relation, respectively weighing 2.5mmol, 1.25mmol and 4.5mmol of cobalt nitrate, nickel nitrate and urea, adding the weighed materials into an aqueous solution, uniformly mixing and stirring, reacting for 5 hours at 180 ℃, and finally calcining for 1-3 hours at 300 ℃ in the air to obtain the porous carbon of the yeast cell adsorbing the cobalt and nickel metal ions;
and 3) vulcanizing the porous carbon of the yeast cell adsorbing the cobalt and nickel metal ions, placing the porous carbon of the yeast cell adsorbing the cobalt and nickel metal ions in the step 2 into an aqueous solution, adding 5mmol of sodium sulfide nonahydrate, carrying out hydrothermal reaction for 6 hours at 180 ℃, and finally carrying out suction filtration, washing and drying to obtain the Ni-Co-S loaded porous carbon material of the yeast cell.
In order to demonstrate that the initial structure of the yeast cells is spherical and the spherical structure is maintained after carbonization, the pretreated yeast cells and CY are subjected to SEM characterization, the test results are respectively shown in FIGS. 1 and 2, and it is obvious from FIGS. 1 and 2 that CY still has a spherical structure, which is beneficial to NiCo2S4Distributed on the surface;
in order to prove the successful loading of metal cobalt nickel on the surface of CY, the CY-Co-Ni-S is subjected to SEM characterization, as shown in FIG. 3. In the figure, it can be clearly seen that a layer is attached to the originally smooth surface to form a core-shell structure, and the originally smooth surface becomes very rough.
Meanwhile, the SEM-mapping graph of CY-Co-Ni-S in FIG. 4 also confirms that C, Co, Ni and S elements are successfully attached to the surface of CY.
To demonstrate that the CY surface-loaded species is NiCo2S4XRD testing was performed on CY-Co-Ni-S composites as shown in FIG. 5. By dividing the XRD patternAs can be seen, the crystal planes (220), (311), (400), (511), (440) and (444) are all NiCo2S4The corresponding crystal plane.
NiCo2S4The electrochemical performance test method of the loaded porous carbon composite material of the yeast cells comprises the following specific steps: 0.008 g of NiCo is weighed2S4Loading a porous carbon composite material of yeast cells, 0.001 g of acetylene black and 0.001 g of polytetrafluoroethylene micropowder into a small agate grinding bowl, and adding 0.5 mL of ethanol for grinding; and pressing the ground sample with a foamed nickel current collector with the thickness of 1 mm under the pressure of 5 kPa, drying in air at room temperature, cutting into 2 cm multiplied by 2 cm to obtain the supercapacitor electrode, and testing the electrochemical performance of the supercapacitor electrode.
The detection results are as follows:
as shown in FIG. 7, to demonstrate the rate capability of CY-Co-Ni-S composites, CV testing was performed. At 5mVs-1An oxidation-reduction peak appears, which shows that CY-Co-Ni-S has better rate capability.
It can also be seen from the GCD curve of CY-Co-Ni-S in FIG. 8 that CY-Co-Ni-S has a longer discharge time, 411S discharge time and 747F/g specific capacitance. The CY-Co-Ni-S is proved to have higher capacitance performance.
In order to investigate the effect of carbonized yeast cells as a base carbon material and yeast cells not subjected to carbonization as a base carbon material on a supercapacitor, NiCo supported on porous carbon of yeast cells not subjected to carbonization was prepared by comparative example 12S4The material is marked as Y-Co-Ni-S.
Comparative example 1
Yeast cell porous carbon loaded NiCo without carbonization treatment2S4The materials were prepared by the same procedure as in example 1 except that: after the porous carbon of the yeast cells was pretreated, 1g of the yeast cells pretreated in step 1 were directly weighed and compounded with metallic cobalt nickel, which was recorded as Y-Co-Ni-S, without the operation of washing the yeast in step 1 described in example 1.
To demonstrate the porous carbon-loaded NiCo of yeast cells without carbonation treatment2S4And (3) performing SEM appearance characterization on Y-Co-Ni-S instead of a core-shell structure, as shown in FIG. 12. It is found from FIG. 12 that NiCo2O4The combination of the formed continuous agglomerates and the porous carbon of the yeast cells without carbonization treatment is irregular, and the comparison with FIG. 3 proves that Y-Co-Ni-S is not in a core-shell structure.
The electrochemical test was carried out on Y-Co-Ni-S in the same manner as in example 1, and the results of the test are shown in FIG. 9, in which the charge and discharge were carried out in a range of-0.1 to 0.45V and the specific capacitances were 265F/g, respectively, at a discharge current density of 1A/g.
Therefore, under the same current density, the discharge time of the CY-Co-Ni-S electrode material is obviously longer than that of the Y-Co-Ni-S electrode material, and the specific capacitance is improved by about 2.8 times, which shows that the yeast cells keep the spherical structure of the original cells after carbonization treatment, and are compounded with metal cobalt and nickel to better improve the electrochemical performance of the material, thereby proving that the CY-Co-Ni-S composite material has good super-capacitance performance.
Through the comparative example 1, the capacitance performance of the yeast cells which are not carbonized and compounded with cobalt-nickel ions is lower than that of CY-Co-Ni-S, and the specific capacitance of Y-Co-Ni-S is only 265F/g, which proves that the yeast cells are compounded with cobalt-nickel after being carbonized to be an effective way for improving the specific capacitance of the composite material.
To prove NiCo2S4The performance of the loaded yeast cell porous carbon material is superior to the performance of the loaded yeast cell porous carbon material after the cobalt monometal is vulcanized, and the yeast cell porous carbon material loaded with the cobalt monometal and the nickel sulfide is prepared by the comparative examples 2 and 3 respectively.
Comparative example 2
A preparation method of yeast cell porous carbon loaded with single metal cobalt sulfide is the same as example 1 in the steps which are not particularly described, except that: and 2.5mmol of cobalt nitrate hexahydrate is added in the step 2, and nickel nitrate hexahydrate is not added. The sample of comparative example 2 was designated CY-Co-S.
The electrochemical test of the obtained CY-Co-S composite material is carried out, the test method is the same as that of the example 1, the detection results are shown in figure 10, the composite material is charged and discharged within the range of-0.1-0.45V, when the discharge current density is 1A/g, the specific capacitance is 190F/g respectively, the specific capacitance of the CY-Co-Ni-S composite material is 747F/g, which is 3.9 times of that of CY-Co-S, and the electrochemical performance of the bimetal cobalt-nickel loaded yeast cell porous carbon is proved to be remarkably superior to that of the single metal cobalt load.
Comparative example 3
A preparation method of yeast cell porous carbon loaded with single metal cobalt sulfide is the same as example 1 in the steps which are not particularly described, except that: and (3) adding 1.25mmol of nickel nitrate hexahydrate in the step (2) without adding cobalt nitrate hexahydrate. The sample of comparative example 2 was designated CY-Ni-S.
The CY-Ni-S composite material obtained was subjected to an electrochemical test in the same manner as in example 1, and the results of the test are shown in FIG. 11, in which the composite material was charged and discharged at-0.1 to 0.45V, and the specific capacitances were 538F/g, respectively, at a discharge current density of 1A/g. The specific capacitance of the CY-Co-Ni-S composite material is 747F/g, which is 1.38 times of that of CY-Ni-S, and the electrochemical performance of the bimetal cobalt-nickel loaded yeast cell porous carbon is proved to be remarkably superior to that of single metal nickel loaded yeast cell porous carbon.
Through comparative examples 2 and 3, the specific capacitance of CY-Ni-S and CY-Co-S is added (the specific capacitance is 728F/g), and compared with the specific capacitance of CY-Co-Ni-S (747F/g) in example 1, the specific capacitance of CY-Co-Ni-S in example 1 is still larger than the effect of single-metal cobalt sulfide load, so that the addition of bimetal can prove to play a synergistic role in the electrochemical performance of the composite material.
In order to examine the electron transport resistance of the three samples CY-Co-Ni-S, CY-Co-S, CY-Ni-S, the samples of example 1, comparative examples 2 and 3 were subjected to an AC impedance test, and the results are shown in FIG. 6. In fig. 6, the slope of CY-Co-Ni-S may be larger in the low frequency region, indicating better capacitance performance, and the curve semicircle may be smaller in the high frequency region, indicating that the electron transport resistance of CY-Co-Ni-S is small in these three samples.
Therefore, the electrochemical performance of the obtained composite material can be fully exerted only by the process technology provided by the invention.

Claims (7)

1. A porous carbon material loaded with Ni-Co-S based on yeast cells,the method is characterized in that: the material is prepared by preparing carbonized yeast cell porous carbon, performing hydrothermal reaction on the yeast cell porous carbon, cobalt nitrate, nickel nitrate and urea, and then oxidizing and vulcanizing, wherein the obtained material is in a core-shell structure, and cobalt and nickel elements are NiCo2S4The form is uniformly loaded on the surface of porous carbon of the yeast cells.
2. The yeast cell-based Ni-Co-S-loaded porous carbon material according to claim 1, wherein: the shell-core structure is formed by carbonizing ellipsoidal unicellular fungus yeast, and yeast cells after carbonization are in a hollow carbon sphere structure.
3. A preparation method of a Ni-Co-S loaded porous carbon material based on yeast cells is characterized by comprising the following steps:
step 1) preparing porous carbon of yeast cells, namely preparing a glucose solution with a certain concentration, adding yeast powder, pretreating the yeast cells under a certain condition, washing and drying to obtain the pretreated yeast cells, dispersing the pretreated yeast cells in a glutaraldehyde aqueous solution according to a certain proportion, performing ultrasonic treatment for 5-15min to uniformly disperse the yeast cells, performing hydrothermal reaction under a certain condition, washing and drying the obtained precipitate after the reaction is finished, and finally performing carbonization treatment under a certain condition to obtain the porous carbon of the yeast cells;
step 2) adsorbing cobalt and nickel metal ions by the porous carbon of the yeast cell, adding the porous carbon of the yeast cell, cobalt nitrate, nickel nitrate and urea obtained in the step 1 into an aqueous solution according to a certain proportion relationship, mixing and stirring uniformly, carrying out hydrothermal reaction under a certain condition, and finally calcining under a certain condition to obtain the porous carbon of the yeast cell adsorbing cobalt and nickel metal ions;
and 3) vulcanizing the porous carbon of the yeast cell adsorbing the cobalt and nickel metal ions, placing the porous carbon of the yeast cell adsorbing the cobalt and nickel metal ions in the step 2 into an aqueous solution, adding sodium sulfide nonahydrate according to a certain substance quantity ratio, carrying out hydrothermal reaction under a certain condition, and finally carrying out suction filtration, washing and drying to obtain the Ni-Co-S loaded porous carbon material of the yeast cell.
4. The production method according to claim 3, characterized in that: the concentration of the glucose solution in the step 1) is 0.02-0.03 g/mL; the conditions of the pretreatment of the yeast cells in the step 1) are that water bath is carried out at the water bath temperature of 30-50 ℃ for 20-50 min; the water solution in the hydrothermal process in the step 1) needs to meet the requirements that the concentration of yeast cells is 0.01-0.03g/mL, the concentration of glutaraldehyde water solution is 2% -4%, the temperature of hydrothermal reaction is 150-; the carbonization treatment in the step 1) is performed under the conditions that calcination is performed for 1-3h at the temperature of 200-400 ℃ in the air atmosphere and calcination is performed for 1-3h at the temperature of 700-900 ℃ in the nitrogen atmosphere.
5. The production method according to claim 3, characterized in that: in the step 2), the ratio of the mass of porous carbon of the yeast cell to the sum of the mass of cobalt nitrate hexahydrate and nickel nitrate hexahydrate is 1: 2, the mass ratio of the cobalt nitrate hexahydrate to the nickel nitrate hexahydrate to the urea is 10: 5: 18; the temperature of the hydrothermal reaction in the step 2) is 150-250 ℃, and the time of the hydrothermal reaction is 4-6 h; the calcining condition in the step 2) is calcining for 1-3h at the temperature of 200-400 ℃ under the air condition.
6. The method of claim 4, wherein: the mass ratio of the added sodium sulfide nonahydrate to the nickel nitrate hexahydrate and the cobalt nitrate hexahydrate in the step 3) is 4: 1: 2; the hydrothermal reaction condition of the step 3) is that the hydrothermal reaction is carried out for 5-7h at the temperature of 150-250 ℃.
7. The application of the yeast cell-based Ni-Co-S loaded porous carbon material as a super capacitor is characterized in that: the discharge is carried out in the range of-0.2 to 0.5, and the specific capacitance is 700-.
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