CN111210997A - Novel MnOmPreparation method and application of @ BCCNFs composite material - Google Patents
Novel MnOmPreparation method and application of @ BCCNFs composite material Download PDFInfo
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- CN111210997A CN111210997A CN202010090185.5A CN202010090185A CN111210997A CN 111210997 A CN111210997 A CN 111210997A CN 202010090185 A CN202010090185 A CN 202010090185A CN 111210997 A CN111210997 A CN 111210997A
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- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title description 9
- 229920002749 Bacterial cellulose Polymers 0.000 claims abstract description 30
- 239000005016 bacterial cellulose Substances 0.000 claims abstract description 26
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002134 carbon nanofiber Substances 0.000 claims abstract description 11
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 10
- 235000020415 coconut juice Nutrition 0.000 claims abstract description 9
- 238000000855 fermentation Methods 0.000 claims abstract description 8
- 235000015097 nutrients Nutrition 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 230000004151 fermentation Effects 0.000 claims abstract description 7
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
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- 150000001875 compounds Chemical class 0.000 claims description 2
- 235000021419 vinegar Nutrition 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- 239000002023 wood Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 18
- 241000589220 Acetobacter Species 0.000 abstract description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 25
- 239000003990 capacitor Substances 0.000 description 15
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 238000002484 cyclic voltammetry Methods 0.000 description 10
- 239000007772 electrode material Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000003575 carbonaceous material Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229960004887 ferric hydroxide Drugs 0.000 description 6
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 244000235858 Acetobacter xylinum Species 0.000 description 4
- 235000002837 Acetobacter xylinum Nutrition 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical class [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 239000001963 growth medium Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
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- 238000009826 distribution Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
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- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004966 Carbon aerogel Substances 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- 241000764238 Isis Species 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 108010076039 Polyproteins Proteins 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 229940041514 candida albicans extract Drugs 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
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- 238000000227 grinding Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000009630 liquid culture Methods 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
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- 238000013507 mapping Methods 0.000 description 1
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- 239000012452 mother liquor Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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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
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Abstract
The invention discloses a novel BCCNFs @ MnOmThe preparation method of the composite material comprises taking Hainan natural coconut water as nutrient solution, and directly coating transition metal oxide (M) dispersed in the nutrient solution with product generated by static metabolic fermentation of acetobacter xylinumnOm) Colloidal particles, forming a gel (M) of bacterial cellulose-coated transition metal oxide colloidal particlesnOm@ BC). The gel is subjected to freeze drying and high-temperature annealing treatment to obtain a coating structure of bacterial cellulose carbon nanofiber-coated transition metal oxide nanoparticlesComposite material (M)nOm@ BCCNFs) and is applied in the field of supercapacitors.
Description
Technical Field
The invention belongs to the technical field of materials, relates to a super capacitor electrode material, and particularly relates to a bacterial cellulose carbon material prepared by using natural coconut water as a nutrient solution.
Background
The super capacitor can be divided into two types according to different energy storage modes, one type is an Electric Double Layer Capacitor (EDLCs), and the super capacitor realizes energy storage through electric charges and an electric double layer formed on the surface of an electrode by electrolyte ions; the other type is a pseudo-capacitance capacitor which realizes energy storage through oxidation-reduction reaction of electroactive substances on the surface of an electrode. The electric quantity or electric energy stored by the pseudo capacitor is far larger than that of the electric double layer capacitor. At present, commercial super capacitors are mainly EDLCs capacitors, and the energy density of the capacitors is relatively low, so that the capacitors cannot meet the increasing production and living needs. Therefore, the development of a supercapacitor with high energy density is urgently required. To improve the energy density of the super capacitor, the key is to improve the specific capacitance of the electrode material and the working voltage of the device.
The electrode material of the super capacitor is mainly carbon material, metal oxide, conductive polymer and the like. The carbon material is an ideal electrode material of the double-electric-layer capacitor and has been widely applied to the super capacitor due to the advantages of good conductivity, large specific surface area, abundant sources, low cost and the like. Commonly used carbon materials include activated carbon, activated carbon fibers, carbon fibrils, carbon aerogels, carbon honeycombs, and the like. However, the theoretical specific capacitance of the carbon material is low, and the carbon material is often applied to asymmetric and hybrid supercapacitors.
The metal oxide stores electric energy (pseudo capacitance) through oxidation-reduction reaction, and the theoretical specific capacitance is higher. A commonly used metal oxide is Co3O4、NiO、MnO2、CuO、Fe2O3And the like. However, metal oxides have poor conductivity and often need to be compounded with materials having good conductivity, such as carbon materials, to improve conductivity.
Bacterial Cellulose (BC) is a natural high molecular compound having a three-dimensional network space structure cross-linked with each other, and can be produced in large quantities by microbial fermentation. The bacterial cellulose carbon material obtained after carbonization of bacterial cellulose has the characteristics of porosity, high specific surface area, good electric conductivity, low density and the like.
Disclosure of Invention
The invention provides a method for preparing transition metal oxide M by microorganism in-situ fermentation technologynOmThe nanoparticles are wrapped in bacterial cellulose, and then the BCCNFs @ M is prepared by program temperature control carbonizationnOmA composite material.
In order to achieve the purpose, the technical scheme of the invention is as follows: novel BCCNFs @ MnOmThe preparation method of the composite material comprises the steps of taking natural coconut water as nutrient solution, and directly coating transition metal oxide (M) dispersed in the nutrient solution by a product generated by static metabolic fermentation of acetobacter xylinumnOm) Colloidal particles, forming a gel (M) of bacterial cellulose-coated transition metal oxide colloidal particlesnOm@ BC), the gel is subjected to freeze drying and high-temperature annealing treatment to obtain the novel coating structure (M) of the bacterial cellulose carbon nanofiber-coated transition metal oxide nano particlesnOm@ BCCNFs).
The specific reaction steps are that coconut water is used as a culture medium, static culture is carried out at 30 ℃, and M dispersed in the culture solution is directly coated by virtue of a bacterial cellulose three-dimensional network structure generated by microbial fermentationnOmNanoparticles to give MnOm@ BC primary product. The product is frozen and dried, and then carbonized at a certain heating rate and a set temperature to finally obtain the bacterial cellulose carbon nanofiber composite material M with a three-dimensional network structurenOm@BCCNFs。
Another object of the present invention is to provide MnOmApplication of the @ BCCNFs composite material in a supercapacitor.
The invention has the following beneficial effects:
(1) the most common coconut water in Hainan is used as a liquid culture medium, and the natural fermentation process of microorganisms is used for directly performing MnOmGrowing bacterial cellulose on the surface of the nano particle in situ, and preparing M by program temperature control carbonizationnOm@ BCCNFs composite material. In the preparation method of the material, the method isIs innovative, and the used raw materials are environment-friendly and nontoxic, thereby providing a new idea for commercial production.
(2) Using MnOmThe @ BCCNFs composite material has stronger circulation stability as a supercapacitor electrode material, and meanwhile, the specific capacitance is also obviously improved.
Drawings
FIG. 1 is a scanning electron microscope image of the material prepared by the present invention; wherein: (a) BCCNFs; (b) (c) Fe3O4@ BCCNFs composite;
FIG. 2 is Fe3O4The element analysis and distribution diagram of the @ BCCNFs composite material; wherein: (d) selecting a region; (e-g) are mapping graphs respectively representing the distribution of Fe, O and C elements; (h) fe3O4EDS energy spectrogram of @ BCCNFs composite material;
FIG. 3 is Fe3O4An electrode physical diagram of the @ BCCNFs composite material;
FIG. 4 is a plot of cyclic voltammetry for materials prepared according to the present invention; wherein: (A) fe3O4The cyclic voltammogram of the @ BCCNFs composite material at different sweep rates; (B) fe3O4The cyclic voltammogram of the @ BCCNFs composite material and the pure BCCNFs at a sweep rate of 20 mV/s;
FIG. 5 is a constant current charge-discharge curve diagram of the material prepared by the present invention; wherein: (A) fe3O4The constant current charge-discharge curve diagram of the @ BCCNFs composite material under different current densities; (B) fe3O4A constant current charge-discharge curve chart of the @ BCCNFs composite material and pure BCCNFs at the current density of 1A/g;
FIG. 6 shows the charge-discharge cycle stability and AC impedance spectrum of the material prepared according to the present invention; wherein: (A) fe3O4@ BCCNFs composite material is in the range of 2 A.g-1Cycling stability under current density conditions; (B) fe3O4The alternating current impedance spectrogram of the @ BCCNFs composite material and the pure BCCNFs;
FIG. 7 shows MnO2Scanning electron microscope picture of @ BCCNFs composite material; wherein: (a) (b) MnO2@ BCCNFs; (c) EDS element analysis;
FIG. 8 shows MnO2、BCCNFs and MnO2XRD patterns of @ BCCNFs;
FIG. 9 shows MnO2The cyclic voltammogram (A) and the charge-discharge curve (B) of the @ BCCNFs composite material.
Detailed Description
One, Fe3O4Preparation of @ BCCNFs electrode
1. Culture of acetic acid bacteria
Collecting acetic acid bacteria culture medium (containing polyprotein 5g, yeast extract 5g, glucose 5g, mannitol 5g, and MgSO 5g4O7H2O1 g and pH 6.6-7.0)21g into 1000mL of distilled water, autoclaving at 121 deg.C for 15min to obtain acetic acid bacteria culture solution, and cooling to room temperature. Under aseptic operation, the acetobacter xylinum strain is inoculated into the culture solution, and cultured for 7 days at 30 ℃ to obtain a mother solution of acetobacter xylinum which is propagated and grown in a large quantity.
2.Fe3O4Preparation of @ BCCNFs electrode material
0.8g FeCl was weighed3.6H2And adding O into 4mL of distilled water, dissolving, then dropping 20mL of boiling water, and naturally cooling for 2min to obtain the ferric hydroxide colloid.
Purchasing fresh green coconut on the market, and carrying out suction filtration to obtain coconut water. Placing 0.6mL ferric hydroxide colloid and 30mL purified coconut water in a culture bottle, sterilizing at 121 deg.C for 15min, inoculating 5mL Acetobacter xylinum mother liquor into the culture bottle under aseptic condition, and culturing in 30 deg.C incubator for seven days to obtain Fe3O4@ BC bacterial cellulosic material. Taking out the material, repeatedly washing with deionized water, soaking in deionized water for two days, and freeze drying for 24 hr. Freeze drying the Fe3O4@ BC bacterial cellulose Material at 2 ℃. min under Nitrogen atmosphere-1The temperature is raised to 500 ℃ at a speed, and then the temperature is kept for 1 h; then at 5 ℃ for min-1The temperature is raised to 700 ℃ at the speed rate, and then the constant temperature is kept for 2 hours, thus obtaining the Bacterial Cellulose Carbon Nanofibers (BCCNFs) 3 4Coated FeO composites 3 4Carbon-containing material FeO @ BCCNFs. Pure BCCNFsMethod for producing a material and Fe3O4@ BCCNFs same as the above except that no additives are required in the preparation processAdding ferric hydroxide colloid.
3.Fe3O4Preparation of @ BCCNFs electrode
Taking the grinded Fe3O4Mixing the @ BCCNFs composite material, acetylene black and PTFE emulsion with a proper amount of absolute ethyl alcohol according to a mass ratio of 80:15:5, grinding into a film with the size of 1cm multiplied by 1cm, attaching the film to a foamed nickel current collector, tabletting by using a powder tabletting machine under the pressure of 4MPa, and drying in a vacuum drying oven at 60 ℃ for 24 hours.
II, Fe3O4Characterization of the @ BCCNFs electrode
Fe prepared by the invention3O4The @ BCCNFs electrode is uniform and dense, and the microstructure is shown in FIG. 1. FIG. 1(a) is a scanning electron microscope image of pure bacterial cellulose carbon nanofibers obtained by using coconut water as a liquid medium, performing static fermentation culture, performing freeze drying, calcining at 500 ℃ for 1 hour under nitrogen atmosphere, and continuously heating to 700 ℃ for calcining for 2 hours. FIGS. 1(b) and (c) are scanning electron micrographs of bacterial cellulose carbon nanofiber composites obtained by adding ferric hydroxide colloid to the culture medium and fermenting and calcining the mixture by acetobacter xylinum. The diameter of the bacterial cellulose carbon nano-fiber is 10-20nm, the bacterial cellulose carbon nano-fiber and the bacterial cellulose carbon nano-fiber are mutually crosslinked to form a three-dimensional network structure, and the diameter of the bacterial cellulose carbon nano-fiber is 200-300nm of Fe3O4The particles are encapsulated in a fibrous network.
The elemental distributions of FIG. 2(e-g) and the EDS spectroscopy analysis of (h) demonstrate that the composite material is composed primarily of Fe, O, C elements. Dehydrating ferric hydroxide colloid at high temperature to generate ferric oxide, calcining bacterial cellulose carbon nanofiber at high temperature under nitrogen atmosphere to form graphite carbon, and reacting graphite carbon with ferric oxide to finally obtain Fe3O4The @ BCCNFs composite material has the following reaction formula:
colloidal particles of ferric hydroxide in culture solutionCan stably exist for a long time, thereby avoiding the problem that the metal oxide particles are easy to sink in the process of culturing the microorganisms, and ensuring that the metal oxide particles can be completely coated by the bacterial cellulose. FIG. 3 is a graph showing the use of Fe3O4An electrode picture made of the @ BCCNFs composite material. III, Fe3O4Electrochemical performance of @ BCCNFs composite material
Fig. 4, 5 and 6 are electrochemical performance test results of the prepared materials. The test procedure used a 3-electrode system. Fe3O4The @ BCCNFs composite material and the pure BCCNFs electrode are respectively a working electrode, a platinum sheet is a counter electrode, a saturated calomel electrode is a reference electrode, a potential window is-1-0V, and the electrolyte is 6 mol. L-1KOH solution. FIG. 4(A) shows Fe3O4The results of the cyclic voltammetry scans of the @ BCCNFs at different scan rates show that the cyclic voltammetry curves are similar to rectangles, the areas of the cyclic voltammetry curves increase with the increase of the scan rate, but the shapes of the cyclic voltammetry curves are basically unchanged, and typical capacitance characteristics are shown. Thus, Fe3O4@ BCCNFs are capacitive type materials like pure BCCNFs as shown in FIG. 4 (B). FIG. 5(A) shows Fe3O4@ BCCNFs constant current charge-discharge curves at different current densities. According to the constant current charging and discharging curve and the following formula
Wherein I is a current (A), Δ t is a discharge time(s), m is a mass (g) of the electrode active material, and Δ V is a potential window (V) of charge and discharge. Calculating to obtain Fe3O4@ BCCNFs composites at 1, 2 and 5A · g-1The specific capacitances at the current densities were 215.3, 123.6 and 97.2 Fg-1. Under the same conditions (1A · g)-1) The specific capacitance of BCCNFs is only 130.4F g-1(FIG. 5B). It can be seen that BCCNFs and Fe3O4After recombination, the specific capacitance is from 130.4 F.g-1Increased to 215.3 F.g-1(1A·g-1) The effect is obvious by increasing 65 percent, which is Fe3O4The pseudocapacitance contribution of (a).
The cycling stability is another important index for measuring the performance of the electrode material of the supercapacitor. FIG. 6(A) is Fe3O4@ BCCNFs electrode material is 2 A.g-1The specific capacitance change curve of 500 charge-discharge cycles at the current density of (2). As can be seen from the figure, after 500 times of charge and discharge, Fe3O4The specific capacitance of the @ BCCNFs electrode material still keeps 99.4% of the initial value, and the good stability is shown. Electrochemical impedance spectroscopy measurement shows that Fe3O4The interface electron transfer resistance of the @ BCCNFs electrode is small, about 0.215 Ω (fig. 6B), and the charge and discharge processes are controlled by the diffusion of electrolyte ions.
Applying the above method to MnO2Nanoparticles, likewise giving MnO2@ BCCNFs composite, as shown in FIG. 7. FIG. 8 shows the results of XRD measurements, which also demonstrates that the material produced is MnO2@ BCCNFs. The cyclic voltammetry test result shows that MnO2@ BCCNFs electrode Cyclic voltammogram and Fe at different sweep rates3O4@ BCCNFs same, quasi-rectangular in shape (FIG. 9A), indicating MnO2@ BCCNFs also belong to capacitive materials. The specific capacitance value of the material is calculated according to the constant current charging and discharging curve (fig. 9B) and the formula (1) and is listed in table 1. As can be seen from the table, (1A. g) under the same conditions-1),MnO2Specific capacitance of @ BCCNFs composite Material (206.6F g)-1) And pure BCCNFs (130.4F g)-1) Compared with the prior art, the method is also obviously improved. Thus, the method of the invention for preparing bacterial cellulose carbon nanofiber composites for energy storage applications can be extended to all transition metal oxides MnOm。
TABLE 1 MnO2Specific capacitance value of @ BCCNFs composite material under different current densities
Claims (2)
1. Novel MnOmThe preparation method of the @ BCCNFs composite material is characterized by comprising the following steps of: using natural coconut water as nutrient solution, and making the nutrient solution pass through wood vinegar rodThe product generated by the static metabolic fermentation of the bacteria directly wraps the transition metal oxide M dispersed in the nutrient solutionnOmColloidal particles, forming a gel M of bacterial cellulose-coated transition metal oxide colloidal particlesnOm@ BC, the gel is subjected to freeze drying and high-temperature annealing treatment to obtain the novel M with the coating structure of the bacterial cellulose carbon nanofiber-coated transition metal oxide nano particlesnOm@ BCCNFs composite material.
2. A novel compound according to claim 1nOmApplication of the @ BCCNFs composite material in a supercapacitor.
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