CN110767960B - Flexible device integrating microbial fuel cell and hybrid supercapacitor, and preparation method and application thereof - Google Patents
Flexible device integrating microbial fuel cell and hybrid supercapacitor, and preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M16/00—Structural combinations of different types of electrochemical generators
- H01M16/003—Structural combinations of different types of electrochemical generators of fuel cells with other electrochemical devices, e.g. capacitors, electrolysers
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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
- H01G11/08—Structural combinations, e.g. assembly or connection, of hybrid or EDL capacitors with other electric components, at least one hybrid or EDL capacitor being the main component
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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
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02B90/10—Applications of fuel cells in buildings
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a flexible device integrating a microbial fuel cell and a hybrid super capacitor and a method for manufacturing the sameA preparation method and application. The anode material of the microbial fuel cell and the hybrid supercapacitor device is PNCOxThe cathode material is 3DPG nano material. The PNCO is directly prepared on the flexible carbon cloth carrier by the flexible devicexThe specific surface area of the electrode material is increased by the nano electrode material and the 3DPG nano electrode material, so that the performances of the hybrid super capacitor and the microbial fuel cell are improved; in addition, by setting the temperature and time of in-situ phosphating, oxygen vacancies and phosphate ions are introduced on the surface of the NCO nano material, so that the active sites and the conductivity of the NCO nano material are increased, and the reversible capacity, the rate capability and the cycle stability of the hybrid supercapacitor and the microbial fuel cell are greatly improved. The flexible device can be applied to the technical field of electrochemical energy storage and conversion.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy conversion and storage integration, and particularly relates to a flexible device integrating a microbial fuel cell and a hybrid supercapacitor, a preparation method and application thereof.
Background
With the rapid increase of the world population and the continuous development of the human society, various demands of people on energy sources are increasing day by day, and the traditional fossil energy sources obviously cannot meet the various demands of the future society on the energy sources. In addition, with the rapid development of electronic technology and the great popularization of various portable electronic products, people have an increasing demand for chemical power sources and an increasing demand for performance. However, a series of new green energy sources such as wind energy, solar energy, geothermal energy, ocean energy, etc. often have the problem of uneven distribution of regions, and usually need to be converted into electric energy for convenient use. Therefore, the deep development and the efficient utilization of new energy are realized, and the development of a high-specific-energy, clean and safe chemical power system becomes an important requirement for social development.
Among various power generation facilities, the microbial fuel cell is a technology for directly decomposing organic wastes by biological oxidation and simultaneously generating electric energy, and has a good development prospect. However, the output power density of the microbial fuel cell as a power generating device is relatively low as compared with other energy conversion devices, which is a problem that limits practical applications thereof. In the aspect of energy storage, the hybrid super capacitor device is concerned with due to the remarkable characteristics of high power density, long service life, good safety, moderate energy density and the like. Unfortunately, the current hybrid supercapacitor devices suffer from a significant amount of positive electrode materials. Therefore, a microbial fuel cell with high power density and a hybrid supercapacitor device with high energy density are urgently needed to make further breakthrough in the aspect of high-performance cathode materials. Moreover, the integration of the microbial fuel cell and the hybrid supercapacitor device into one system having the same material and structure would be very advantageous for the collection and storage of high power output renewable energy. Therefore, the development of a high-performance flexible device integrating a microbial fuel cell and a hybrid supercapacitor is urgently needed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a flexible device integrating a microbial fuel cell and a hybrid supercapacitor, so as to solve the problem of collection and storage of renewable energy with high power output and realize the purpose of integration of energy conversion and storage.
The invention also aims to provide a preparation method of the flexible device integrating the microbial fuel cell and the hybrid supercapacitor.
The invention further aims to provide application of the flexible device integrating the microbial fuel cell and the hybrid supercapacitor.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of a flexible device integrating a microbial fuel cell and a hybrid super capacitor comprises the following steps: the microbial fuel cell is connected in series with a hybrid supercapacitor.
The number of the microbial fuel cells is preferably more than one.
The microbial fuel cell is preferably a single-chamber microbial fuel cell, and more preferably 4 × 5 × 5cm in size3The single-cell microbial fuel cell of (1).
The microbial fuel cell preferably comprises a chamber, a single-sided membrane cathode, an anode and anolyte.
The chamber is preferably made of polymethyl methacrylate.
The anode is preferably a 3DPG anode.
The sizes of the single-sided membrane cathode and the 3DPG anode are preferably 4 x 4cm2。
The preparation method of the single-sided membrane cathode comprises the following steps: PNCO (phosphorus-carbon monoxide)xThe nano material is tightly attached to the cation exchange membrane by a hot pressing method to obtain the single-face membrane cathode.
The preparation method of the anolyte comprises the following steps: 10.0g NaHCO was taken3、11.2gNaH2PO4·2H2And putting O, 10.0g of glucose and 5.0g of yeast extract into a beaker, adding 5mmol of 2-hydroxy-1, 4-naphthoquinone (HNQ), uniformly stirring, and fixing the volume in a 1000mL volumetric flask to obtain the anolyte.
The anolyte preferably also comprises a bacterial liquid.
The preparation method of the bacterial liquid comprises the following steps: activated E.coli (Escherichia coli) was inoculated into a medium without oxygen and cultured at 37 ℃ for 18 hours under anaerobic conditions.
The Escherichia coli is preferably Escherichia coli K12.
The inoculum size of the Escherichia coli is preferably 1/9 of the volume of the culture medium.
The oxygen removal is preferably performed by introducing nitrogen into the culture medium for 20 minutes.
The preparation method of the culture medium comprises the following steps: taking peptone, NaCl and beef powder, adding distilled water to a constant volume, enabling the concentrations of the peptone, the NaCl and the beef powder to be 10g/L, 5g/L and 3g/L respectively, and sterilizing at 121 ℃ for 20min for later use.
The hybrid supercapacitor is preferably prepared by the following method: and packaging the positive electrode material, the negative electrode material and the solid electrolyte to obtain the hybrid supercapacitor.
The shape of the positive electrode material and the negative electrode material is preferably a rectangle of 0.5cm × 2 cm.
SaidThe anode material is preferably NiCo modified by oxygen vacancy and phosphate ions2O4(PNCOx) And (3) nano materials.
The negative electrode material is preferably a three-dimensional mesoporous graphene (3DPG) nano material.
The solid electrolyte is preferably PVA/LiCl gel.
The encapsulation is preferably done by an encapsulation machine.
The PNCOxThe nanomaterial is preferably prepared by the following steps:
(1) preparation of NiCo2O4(NCO) nanowire array materials;
(2) preparation of PNCOxAnd (3) nano materials.
The NCO nanowire array material in the step (1) is preferably prepared on a flexible carbon cloth substrate by a hydrothermal method, and the specific steps are as follows:
placing the flexible carbon cloth in absolute ethyl alcohol for ultrasonic treatment to prepare a flexible carbon cloth substrate;
② Ni (NO)3)2·6H2O，Co(NO3)2·6H2O, thiourea and NH4F is dissolved in water to obtain a solution A; immersing the flexible carbon cloth substrate obtained in the step I into the solution A to perform hydrothermal reaction;
and taking out the flexible carbon cloth, cooling, washing and airing to obtain the NCO nanometer material.
The dissolving condition in the step (II) is preferably dissolving at room temperature.
The room temperature is preferably 10-30 ℃; more preferably 24 to 26 ℃.
The water in the step (II) is preferably deionized water.
Ni (NO) as described in step (II)3)2·6H2The mass (g) volume (L) ratio of O to water is preferably 5-150: 3; more preferably 10: 1.
Co (NO) as described in step (II)3)2·6H2The mass (g) volume (L) ratio of O to water is preferably 10-240: 3; more preferably 20: 1.
The preferable ratio of the thiourea to the water in the second step is 5-150: 3 according to the mass (g) and volume (L); more preferably 10: 1.
NH described in step 24The mass (g) volume (L) ratio of F to water is preferably 5-150: 3; more preferably 10: 1.
The hydrothermal reaction condition in the step II is preferably 80-200 ℃ for 6-36 h; more preferably at 120 ℃ for 12 h.
The cooling in the third step is preferably natural cooling.
And the washing in the step (III) is preferably carried out by adopting deionized water.
PNCO described in step (2)xThe nano material is preferably prepared by introducing oxygen vacancies and phosphate ions to the surface of the NCO nano material prepared in the step (1) through an in-situ phosphating technology, and the specific steps are as follows:
(A) putting the NCO nano material growing on the flexible carbon cloth obtained in the step (1) into a tube, and adding NaH into the tube2PO2·H2O, then vacuumizing the tube;
(B) injecting N into the evacuated tube2Reacting, cooling and stopping N injection2To obtain PNCOxAnd (3) nano materials.
The tube described in step (a) is preferably a quartz tube.
The specification of the flexible carbon cloth in the step (A) is preferably 2 x 3cm2The flexible carbon cloth of (2).
NaH as defined in step (A)2PO2·H2The amount of O used is preferably 2 g.
The evacuation described in step (A) is preferably to 20 mTorr.
N in step (B)2The injection flow rate of (3) is preferably 100 mL/min.
The reaction condition in the step (B) is preferably heating reaction at 200-300 ℃ for 3 h; more preferably, the reaction is carried out by heating at 300 ℃ for 3 hours.
The cooling in step (B) is preferably natural cooling.
The 3DPG nano material is preferably prepared by the following steps:
(I) preparing graphene oxide by a Hummers method, and then adding deionized water for dispersion to obtain a graphene oxide suspension;
(II) uniformly mixing the graphene oxide suspension with KOH, and putting the mixture and a piece of carbon cloth into a reaction kettle for reaction to obtain graphene gel;
and (III) freezing and drying the obtained graphene gel to obtain the 3DPG nano material.
The Hummers method described in step (I) for preparing graphene oxide is preferably referred to paragraph 12 of patent CN 108395578A.
The preferable mass ratio of the graphene oxide to KOH in the step (II) is 40-60: 148.1; more preferably 60: 148.1.
the specification of the carbon cloth in the step (II) is 2 x 3cm2。
The reaction condition in the step (II) is preferably 160-220 ℃ for 3-8 h; more preferably, the reaction is carried out for 5 hours at 160-180 ℃; most preferably 180 ℃ for 5 h.
A flexible device integrating a microbial fuel cell and a hybrid supercapacitor is obtained through the preparation method.
The flexible device integrating the microbial fuel cell and the hybrid supercapacitor comprises the microbial fuel cell and the hybrid supercapacitor.
The anode material of the microbial fuel cell and the hybrid supercapacitor device is NiCo modified by oxygen vacancy and phosphate ions2O4Nanowire array materials (PNCO)xNanomaterial), and the cathode material of the microbial fuel cell and the hybrid supercapacitor device is a three-dimensional mesoporous graphene (3DPG) nanomaterial.
The flexible device integrating the microbial fuel cell and the hybrid supercapacitor is applied to the technical field of electrochemical energy storage and conversion.
Compared with the prior art, the invention has the following advantages and effects:
1. the invention directly prepares PNCO on the flexible carbon cloth carrierxThe nano electrode material and the 3DPG nano electrode material improve the specific surface area of the electrode material, thereby effectively improving the hybrid super capacitor and the hybrid super capacitorThe performance of the microbial fuel cell can be applied to the assembly of a flexible device integrated by the microbial fuel cell and a hybrid super capacitor; setting the temperature and time of the hydrothermal reaction to grow a uniform NCO nanowire array on the flexible carbon cloth substrate; in addition, by setting the temperature and time of in-situ phosphating, oxygen vacancies and phosphate ions are introduced on the surface of the NCO nano material, so that the active sites and the conductivity of the NCO nano material are further increased, and the reversible capacity, the rate capability and the cycling stability of the hybrid super capacitor and the microbial fuel cell are greatly improved.
2. The invention provides a flexible device integrating a microbial fuel cell and a hybrid supercapacitor for collecting and storing high-power-output renewable energy, which has the advantages of high energy density, good flexibility and the like, and the total power density, the energy density and the cycle life can meet the expected requirements on collection and storage of the high-power-output renewable energy; can be applied to the technical field of electrochemical energy storage and conversion.
Drawings
FIG. 1 is a scanning electron micrograph of 3DPG of example 1 taken on a scale of 50 μm.
FIG. 2 is a Raman spectrum and a C1s high resolution XPS of 3DPG in example 1: wherein a is a Raman spectrogram; b is a high resolution XPS plot of C1 s.
FIG. 3 is a graph showing PNCO in example 1 at 500nm at 2 μm on a scalexScanning electron microscopy of (2): wherein, the picture outside the dotted line frame is the PNCO of example 1 with 2 μm scalexScanning electron microscope images of; the picture in the dotted line box is the PNCO of example 1 at 500nm on the scalexScanning electron micrograph (c).
FIG. 4 is NCO and PNCOxThe detection map of (1); wherein a is the value of PNCO in example 1 at a scale of 100nmxTransmission electron microscopy images of; b is on the scale of 2nm, PNCO in example 1xHigh resolution transmission electron microscopy images; c is NCO and PNCO in example 1xX-ray powder diffractogram of (a); d is NCO and PNCO in example 1xA raman spectrum of (a).
FIG. 5 shows PNCO in example 1xOf X-ray energyAnd (4) spectrum analysis chart.
FIG. 6 is NCO and PNCOxAn identification map of (1); wherein a is NCO and PNCO in example 1xThe full spectrogram of the X-ray photoelectron spectrum; b is the high resolution XPS map for Ni 2P in example 1, c is the high resolution XPS map for Co 2P in example 1, d is the high resolution XPS map for O1s in example 1, and e is the high resolution XPS map for P2P in example 1; f is NCO and PNCO in example 1xElectron paramagnetic resonance spectrum of (a).
Fig. 7 is a graph of rate performance of the hybrid supercapacitor of example 1: the graph is a double-Y-axis X-axis graph, wherein the left Y-axis is volume capacity, and the right Y-axis is coulombic efficiency; in the figure, a point set pointing to the left Y axis with a left arrow corresponds to the volume capacity of the hybrid supercapacitor device, and a point set pointing to the right Y axis with a right arrow corresponds to the coulomb efficiency of the hybrid supercapacitor device.
Fig. 8 is a graph of the long cycle performance of the hybrid supercapacitor of example 1: the graph is a double-Y-axis X-axis graph, wherein the left Y-axis is the capacity retention rate, and the right Y-axis is the coulombic efficiency; in the figure, a point set pointed to the left Y axis by the left arrow corresponds to the capacity retention ratio of the hybrid supercapacitor device, and a point set pointed to the right Y axis by the right arrow corresponds to the coulombic efficiency of the hybrid supercapacitor device.
Fig. 9 is a polarization curve versus power curve for the microbial fuel cell of example 1: the graph is a double-Y-axis X-axis graph, wherein the left Y-axis is the voltage of the microbial fuel cell, and the right Y-axis is the power density; in the figure, the line with the left arrow pointing to the left Y-axis corresponds to the voltage of the microbial fuel cell, and the line with the right arrow pointing to the right Y-axis corresponds to the power density of the microbial fuel cell.
FIG. 10 shows the use of different numbers of PNCOs in example 1xThe/3 DPG microbial fuel cell device is PNCOxA schematic diagram of charging a/3 DPG hybrid supercapacitor device.
FIG. 11 shows the use of different numbers of PNCOs in example 1xThe/3 DPG microbial fuel cell device is PNCOxA/3 DPG hybrid supercapacitor device charging curve.
FIG. 12 shows the benefits of example 1With 1 PNCOxThe/3 DPG microbial fuel cell device is PNCOxA schematic diagram of charging a/3 DPG hybrid supercapacitor device.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The reagents used in the present invention are all commercially available.
Example 1
1. Preparation of 3DPG nano material:
(1) preparing graphene oxide by Hummers method (refer to paragraph 12 in patent CN 108395578A), and then adding deionized water to disperse (the mass (mg) of graphene oxide is 3 times of the volume (mL) of deionized water) to obtain graphene oxide suspension with a concentration of 3 mg/mL;
(2) uniformly mixing 20mL of 3mg/mL graphene oxide suspension with 20mL of 0.132mol/L KOH, and mixing with a block of 2X 3cm2Putting the carbon cloth into a reaction kettle together for hydrothermal reaction at 180 ℃ for 5 hours to obtain graphene gel;
(3) and (3) freeze-drying the obtained graphene gel for 2 days to obtain the 3DPG nano material.
2、PNCOxPreparing a nano material:
(1) preparing an NCO nano material:
preparing a flexible carbon cloth substrate: the size of the particles is 2 x 3cm2The flexible carbon cloth is placed in absolute ethyl alcohol for ultrasonic treatment to prepare a flexible carbon cloth substrate;
② mixing 1.0g of Ni (NO)3)2·6H2O，2.0g Co(NO3)2·6H2O, 1.0g Thiourea and 1.0g NH4Dissolving F in 100mL of deionized water at 24-26 ℃ to obtain a solution A; immersing a flexible carbon cloth substrate into the solution A, and carrying out hydrothermal reaction for 12h at 120 ℃;
and thirdly, taking out the flexible carbon cloth, naturally cooling, washing with deionized water, and airing to obtain the NCO nano material.
(2)PNCOxPreparing a nano material:
taking the raw material obtained in the step (1)Placing NCO nanometer material on flexible carbon cloth in quartz tube, placing 2g NaH in the quartz tube2PO2·H2O, then vacuumizing the quartz tube to 20 mTorr;
② injecting N into the vacuumized quartz tube2Is a reaction of N2The flow rate of the reaction solution is controlled to be 100mL/min, the reaction is carried out for 3h at the temperature of 300 ℃, and the N injection is stopped after the reaction solution is naturally cooled2To obtain PNCOxAnd (3) nano materials.
3. Assembly of flexible device integrating microbial fuel cell and hybrid supercapacitor
(1) Assembling the hybrid super capacitor:
respectively mixing the 3DPG nano material prepared in the step 1 and the step 2 with PNCOxCutting the nanometer material into 0.5cm × 2cm rectangle, taking 3DPG nanometer material as cathode material, PNCOxAnd (3) packaging the nano material serving as the anode material and the PVA/LiCl gel serving as the solid electrolyte by a packaging machine to obtain the all-solid-state flexible mixed type super capacitor.
(2) Assembling the microbial fuel cell:
the microbial fuel cell is assembled by using a single chamber (4 × 5 × 5 cm)3) Microbial fuel cell, chamber made of polymethyl methacrylate, single-face membrane cathode (4X 4 cm)2) 3DPG anode (4X 4 cm)2) And anolyte.
The preparation method of the single-face membrane cathode comprises the following steps: PNCO (phosphorus-carbon monoxide)xThe nano material is tightly attached to the cation exchange membrane by a hot pressing method to obtain the single-face membrane cathode.
The preparation method of the anolyte comprises the following steps: 10.0g NaHCO was taken3、11.2g NaH2PO4·2H2And putting O, 10.0g of glucose and 5.0g of yeast extract into a beaker, adding 5mmol of 2-hydroxy-1, 4-naphthoquinone (HNQ), uniformly stirring, and fixing the volume in a 1000mL volumetric flask to obtain the anolyte.
The anolyte also comprises bacterial liquid.
The preparation method of the bacterial liquid comprises the following steps: after the medium was purged with nitrogen for 20 minutes to remove oxygen, 2mL of activated Escherichia coli (Escherichia coli) K12 was inoculated into 18mL of the medium and cultured at 37 ℃ for 18 hours under anaerobic conditions; the preparation method of the culture medium comprises the following steps: taking peptone, NaCl and beef powder, adding distilled water to a constant volume, enabling the concentrations of the peptone, the NaCl and the beef powder to be 10g/L, 5g/L and 3g/L respectively, and sterilizing at 121 ℃ for 20min for later use.
(3) Assembly of flexible device integrating microbial fuel cell and hybrid supercapacitor
And (3) connecting the microbial fuel cell and the hybrid super capacitor according to the schematic diagram shown in the attached figure 10 to obtain the flexible device integrating the microbial fuel cell and the hybrid super capacitor.
Examples 2 to 4
Examples 2-4 were prepared in the same manner as in example 1, except that NaH was used for in situ phosphating2PO2·H2The mass of O. Specific NaH in preparation methods of examples 2 to 42PO2·H2The quality control of O is shown in Table 1. PNCO was investigated by referring to the same constant current charge/discharge test method as in the above-mentioned Effect example 1xElectrochemical properties of the nanomaterial. PNCO prepared in example 1xThe nano material is at 2mA/cm2The specific capacity corresponding to the specific reaction time is 2.97F/cm2PNCO prepared in examples 2 to 4 was testedxThe nano material is at 2mA/cm2The corresponding area is specific to capacity.
TABLE 1 in situ phosphating of NaH2PO2·H2Quality control of O
Examples 5 to 6
Examples 5-6 were prepared in the same manner as example 1, except for the temperature used for in situ phosphating. Specific temperature control in the preparation methods of examples 5 to 6 is shown in Table 2. PNCO was investigated by referring to the same constant current charge/discharge test method as in the above-mentioned Effect example 1xElectrochemical properties of the nanomaterial. PNCO prepared in example 1xThe nano material is at 2mA/cm2The specific area capacity is 2.97F/cm2EXAMPLES 5 to 6Prepared PNCOxThe nano material is at 2mA/cm2The corresponding area is specific to capacity.
TABLE 2 temperature control of in-situ phosphating
Examples 7 to 10
The preparation methods of examples 7 to 10 are the same as those of example 1, except for the concentration of graphene oxide. Specific concentration control of graphene oxide in the preparation methods of examples 7-10 is shown in table 3. The electrochemical performance of the 3DPG nano material is researched by referring to the constant current charge and discharge test method which is the same as that of the effect example 1. 3DPG nanomaterial prepared in example 1 at 1.5mA/cm2The specific capacity of the corresponding area is 0.556F/cm2The 3DPG nano material prepared in the test examples 7-10 is tested at 2mA/cm2The corresponding area is specific to capacity.
Table 3 concentration regulation of graphene oxide
Examples 11 to 14
The preparation methods of examples 11 to 14 were the same as in example 1, except for the temperature of hydrothermal reaction for preparing 3 DPG. The specific temperature control in the preparation methods of examples 11 to 13 is shown in Table 4. The electrochemical performance of the 3DPG nano material is researched by referring to the constant current charge and discharge test method which is the same as that of the effect example 1. 3DPG nanomaterial prepared in example 1 at 1.5mA/cm2The specific capacity corresponding to the specific reaction time is 0.556F/cm23DPG nanomaterials prepared in examples 11-13 were tested at 2mA/cm2The corresponding area is specific to capacity.
TABLE 43 temperature control of DPG hydrothermal reaction
Fruit with high effectExample 13 DPG nanomaterial, PNCOxCharacterization detection of nanomaterials
1. The 3DPG nanomaterial prepared in example 1 was subjected to scanning electron microscopy and the results are shown in fig. 1: the 3DPG nano material is shown to be in the shape of three-dimensional mesopores.
2. The 3DPG nanomaterial prepared in example 1 was subjected to raman spectroscopy and high resolution XPS characterization and detection, and the results are shown in fig. 2: FIG. 2a shows the ratio I of two peak intensities of 3DPG nano-materialD：IG0.93 is reached, indicating that 3DPG has very abundant defects in the edges and planes of graphite sheets; fig. 2b shows that the peak C1s was fit into four peaks, corresponding to the C-C bond, C-OH bond, C ═ O bond, and C ═ O-OH bond that occupied the major components.
3. For the PNCO prepared in example 1xThe nano material is tested by a scanning electron microscope, and the result is shown in fig. 3: a uniform nanowire array was grown on the flexible carbon cloth fiber.
4. For the PNCO prepared in example 1xThe nano material is characterized by a Transmission Electron Microscope (TEM), a high-resolution transmission electron microscope (HRTEM), X-ray powder diffraction (XRD) and a Raman spectrum, and the result is shown in figure 4: FIG. 4a shows PNCOxThe nano material is a mesoporous material, and the one-dimensional nano wire consists of a great number of small nano particles; FIG. 4b shows PNCOxHas an interlayer spacing of 0.47nm, and generates lattice defects due to the introduction of oxygen vacancies and phosphate ions; FIG. 4c shows that the crystal structure of NCO nanomaterials remained the same before and after in situ phosphating, whereas the PNCO obtained after in situ phosphatingxThe crystalline strength of (a) is reduced; FIG. 4d shows NCO nanomaterials 550cm after in situ phosphating–1The Raman peak at (A) becomes smaller and broader, indicating PNCOxThe nanomaterial introduces oxygen vacancies.
5. For the PNCO prepared in example 1xThe nanomaterials were characterized by X-ray spectroscopy (EDS) and the results are shown in fig. 5: indicating that phosphate ions have been successfully introduced onto the surface of the NCO nanowire array.
6. For the PNCO prepared abovexThe nanometer material is subjected to X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonanceThe vibration spectrum is characterized, and the result is shown in figure 6: indicating that oxygen vacancies and phosphate ions have been successfully introduced into the surface of the NCO nanowire array.
Effect example 2 hybrid supercapacitor, microbial fuel cell, and flexible device performance measurement of integration of microbial fuel cell with hybrid supercapacitor
The energy storage performance of the hybrid supercapacitor prepared in the embodiment 1 is researched by adopting a constant current charging and discharging test method, the constant current charging and discharging test of the hybrid supercapacitor device is completed by a CHI 760D electrochemical workstation in Shanghai Chen at room temperature, and the voltage window of the test is 0-1.6V.
As can be seen from FIG. 7, the capacity of the hybrid supercapacitor device prepared in example 1 ranged from 2mA/cm28.76F/cm3Change to 20mA/cm26.49F/cm3And after 30 times of deep charging and discharging, when the current density is recovered to 2mA/cm2In the process, the reversible capacity can still be recovered to the original capacity, and the corresponding coulombic efficiency is over 95 percent, which shows that the reversible capacity has good reversibility and rate capability.
As can be seen from FIG. 8, the hybrid supercapacitor device is at 10mA/cm2The capacity retention rate of 95.2 percent is still maintained after 10000 times of continuous charging and discharging under the current density, which shows that the flexible quasi-solid hybrid super capacitor device has good cycle stability.
As can be seen from FIG. 9, the open circuit voltage of the microbial fuel cell can reach 0.59V, which is very close to 0.60V of Pt/C-MFC. And at 2.13mA/cm2The maximum output power can reach 3276.1mW/cm under the current density of (2)22375mW/cm higher than that of Pt/C-MFC2But still high.
Driven by the development of self-driven energy devices, further attempts to combine hybrid supercapacitors with microbial fuel cells in order to achieve energy conversion of chemical energy to electrical energy at the microbial fuel cells and simultaneous storage of electrical energy at the supercapacitors were made, and the results of charging the hybrid supercapacitors with different numbers of microbial fuel cells for 414 seconds are shown in fig. 11: it can be seen that the voltage of the hybrid supercapacitor device can be rapidly charged to 0.3V, 0.6V and 0.9V respectively by using one, two or three microbial fuel cells, and the charging mode is similar to constant voltage charging.
In conclusion, the flexible device integrated by the microbial fuel cell and the hybrid supercapacitor has the characteristics of collecting and storing renewable energy with high power output, has the advantages of high energy density, good flexibility and the like, and has a great application prospect in the technical field of electrochemical energy storage and conversion.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a flexible device integrating a microbial fuel cell and a hybrid super capacitor is characterized by comprising the following steps: connecting a microbial fuel cell in series with a hybrid supercapacitor;
the number of the microbial fuel cells is more than one;
the microbial fuel cell is a single-chamber microbial fuel cell and consists of a chamber, a single-side membrane cathode, an anode and anolyte;
the hybrid supercapacitor is prepared by the following method: packaging the positive electrode material, the negative electrode material and the solid electrolyte to obtain a hybrid supercapacitor;
the anode material is NiCo modified by oxygen vacancy and phosphate radical ions2O4A nanowire array material;
the negative electrode material is a three-dimensional mesoporous graphene nano material;
the solid electrolyte is PVA/LiCl gel.
2. The method of manufacturing a hybrid supercapacitor integrated flexible device with a microbial fuel cell according to claim 1, wherein:
the NiCo modified by the oxygen vacancy and the phosphate radical ion2O4The nanowire array material is prepared by the following steps:
preparation of NiCo2O4A nanowire array material;
(2) preparation of oxygen vacancy and phosphate ion modified NiCo2O4Nanowire array materials nanomaterials.
3. The method of manufacturing a flexible device integrating a microbial fuel cell and a hybrid supercapacitor according to claim 2, wherein:
NiCo described in step (1)2O4The nanowire array material is prepared on a flexible carbon cloth substrate by a hydrothermal method, and the method comprises the following specific steps:
step (ii) of
The dissolving condition is dissolving at room temperature;
the room temperature is 10-30 ℃;
step (ii) of
The water in (1) is deionized water;
step (ii) of
Ni (NO) as defined in3)2∙6H2The mass volume ratio of O to water is 5-150: 3;
step (ii) of
Co (NO) as described in (1)3)2∙6H2The mass volume ratio of O to water is 10-240: 3;
step (ii) of
The mass volume ratio of the thiourea to the water is 5-150: 3;
step (ii) of
NH as described in (1)4F and water are in a mass-to-volume ratio of 5-150: 3;
step (ii) of
The hydrothermal reaction condition is that the reaction is carried out for 6-36 h at the temperature of 80-200 ℃;
step (ii) of
The cooling in (1) is natural cooling;
step (ii) of
The washing in (1) adopts deionized water for washing;
the NiCo modified by oxygen vacancy and phosphate radical ions in the step (2)2O4The nanowire array material is NiCo prepared in the step (1) through an in-situ phosphating technology2O4The preparation method of the nano material by introducing oxygen vacancy and phosphate radical ions on the surface comprises the following specific steps:
(A) taking the NiCo grown on the flexible carbon cloth obtained in the step (1)2O4The nano material is placed in a tube, NaH is added into the tube2PO2·H2O, then vacuumizing the tube;
(B) injecting N into the evacuated tube2Reacting, cooling and stopping N injection2Obtaining NiCo modified by oxygen vacancy and phosphate radical ions2O4Nano-wire array material nano-material;
the tube in step (A) is a quartz tube;
the specification of the flexible carbon cloth in the step (A) is 2 multiplied by 3cm2The flexible carbon cloth of (2);
NaH as defined in step (A)2PO2·H2The dosage of O is 2 g;
the vacuumizing in the step (A) is vacuumizing to 20 mTorr;
n in step (B)2The injection flow rate of (2) is 100 mL/min;
the reaction condition in the step (B) is heating reaction at 200-300 ℃ for 3 h;
the cooling in the step (B) is natural cooling.
4. The method of manufacturing a hybrid supercapacitor integrated flexible device with a microbial fuel cell according to claim 3, wherein:
the room temperature is 24-26 ℃;
step (ii) of
Ni (NO) as defined in3)2∙6H2The mass volume ratio of O to water is 10: 1;
step (ii) of
Co (NO) as described in (1)3)2∙6H2The mass volume ratio of O to water is 20: 1;
step (ii) of
The mass volume ratio of the thiourea to the water is 10: 1;
step (ii) of
NH as described in (1)4F and water in a mass-to-volume ratio of 10: 1;
step (ii) of
The hydrothermal reaction condition in (1) is reaction at 120 ℃ for 12 h;
the reaction condition in the step (B) is heating reaction at 300 ℃ for 3 h.
5. The method of manufacturing a hybrid supercapacitor integrated flexible device with a microbial fuel cell according to claim 1, wherein:
the three-dimensional mesoporous graphene nano material is prepared by the following steps:
（
) Preparing graphene oxide by a Hummers method, and then adding deionized water for dispersion to obtain a graphene oxide suspension;
（
) Taking oxidized stoneUniformly mixing the graphene suspension with KOH, and putting the mixture and a piece of carbon cloth into a reaction kettle for reaction to obtain graphene gel;
（
) Freeze-drying the obtained graphene gel to obtain a three-dimensional mesoporous graphene nano material;
the mass ratio of the graphene oxide to KOH in the step (II) is 40-60: 148.1;
the reaction condition in the step (II) is that the reaction is carried out for 3-8 h at 160-220 ℃;
the specification of the carbon cloth in the step (II) is 2 x 3cm2。
6. The method for preparing a flexible device integrating a microbial fuel cell and a hybrid supercapacitor according to claim 5, wherein:
the mass ratio of the graphene oxide to KOH in the step (II) is 60: 148.1;
the reaction condition in the step (II) is 160-180 ℃ for 5 hours.
7. The method of manufacturing a hybrid supercapacitor integrated flexible device with a microbial fuel cell according to claim 1, wherein:
the anode is a three-dimensional mesoporous graphene anode;
the preparation method of the single-sided membrane cathode comprises the following steps: NiCo modified with oxygen vacancy and phosphate ion2O4The nanowire array material nanomaterial is tightly attached to a cation exchange membrane by a hot pressing method to obtain a single-sided membrane cathode;
the preparation method of the anolyte comprises the following steps: 10.0g NaHCO was taken3、11.2gNaH2PO4∙2H2Putting O, 10.0g of glucose and 5.0g of yeast extract into a beaker, adding 5mmol of 2-hydroxy-1, 4-naphthoquinone, uniformly stirring, and fixing the volume in a 1000mL volumetric flask to obtain anolyte;
the anolyte also comprises a bacterial liquid;
the preparation method of the bacterial liquid comprises the following steps: inoculating activated Escherichia coli into oxygen-free culture medium, and culturing at 37 deg.C for 18 hr under anaerobic condition;
the Escherichia coli is Escherichia coli K12;
the inoculation amount of the escherichia coli is 1/9 of the volume of the culture medium;
the oxygen is removed by introducing nitrogen into the culture medium for 20 minutes;
the preparation method of the culture medium comprises the following steps: taking peptone, NaCl and beef powder, adding distilled water to a constant volume, enabling the concentrations of the peptone, the NaCl and the beef powder to be 10g/L, 5g/L and 3g/L respectively, and sterilizing at 121 ℃ for 20min for later use.
8. The method of manufacturing a hybrid supercapacitor integrated flexible device with a microbial fuel cell according to claim 1, wherein:
the single-chamber microbial fuel cell is 4 multiplied by 5cm in size3The single-cell microbial fuel cell of (1);
the chamber is made of polymethyl methacrylate;
the size of the single-sided membrane cathode and the three-dimensional mesoporous graphene anode is 4 multiplied by 4cm2；
The shape of the anode material and the cathode material is a rectangle of 0.5cm multiplied by 2 cm;
the packaging is completed by a packaging machine.
9. A flexible device integrating a microbial fuel cell and a hybrid supercapacitor is characterized in that: the preparation method of any one of claims 1 to 8.
10. The use of the microbial fuel cell of claim 9 in the field of electrochemical energy storage and conversion technology in combination with a hybrid supercapacitor integrated flexible device.
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| PCT/CN2020/071047 WO2021093155A1 (en) | 2019-11-15 | 2020-01-09 | Flexible device made by integration of microbial fuel cell and hybrid supercapacitor, preparation method therefor, and application thereof |
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| CN112908715B (en) * | 2021-01-18 | 2022-11-29 | 广东轻工职业技术学院 | Difunctional defective manganese dioxide nanorod cathode material as well as preparation method and application thereof |
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| US20170214076A1 (en) * | 2016-01-27 | 2017-07-27 | Ankush Dhawan | Microbial fuel cell light assembly |
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