CN106409538A - Biomass energy conversion and storage integrated device and preparation method thereof - Google Patents
Biomass energy conversion and storage integrated device and preparation method thereof Download PDFInfo
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- CN106409538A CN106409538A CN201610913103.6A CN201610913103A CN106409538A CN 106409538 A CN106409538 A CN 106409538A CN 201610913103 A CN201610913103 A CN 201610913103A CN 106409538 A CN106409538 A CN 106409538A
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 23
- 239000002028 Biomass Substances 0.000 title claims abstract description 22
- 238000003860 storage Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000446 fuel Substances 0.000 claims abstract description 46
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 19
- 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 claims abstract description 13
- 239000008103 glucose Substances 0.000 claims abstract description 13
- 229920000767 polyaniline Polymers 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- 108010050375 Glucose 1-Dehydrogenase Proteins 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 10
- 108010029541 Laccase Proteins 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011245 gel electrolyte Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000003990 capacitor Substances 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- VWWQXMAJTJZDQX-UYBVJOGSSA-N flavin adenine dinucleotide Chemical compound C1=NC2=C(N)N=CN=C2N1[C@@H]([C@H](O)[C@@H]1O)O[C@@H]1CO[P@](O)(=O)O[P@@](O)(=O)OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C2=NC(=O)NC(=O)C2=NC2=C1C=C(C)C(C)=C2 VWWQXMAJTJZDQX-UYBVJOGSSA-N 0.000 claims description 4
- 235000019162 flavin adenine dinucleotide Nutrition 0.000 claims description 4
- 239000011714 flavin adenine dinucleotide Substances 0.000 claims description 4
- 229940093632 flavin-adenine dinucleotide Drugs 0.000 claims description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- QXYRRCOJHNZVDJ-UHFFFAOYSA-N 4-pyren-1-ylbutanoic acid Chemical compound C1=C2C(CCCC(=O)O)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 QXYRRCOJHNZVDJ-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- -1 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000007974 sodium acetate buffer Substances 0.000 claims description 3
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- 238000005253 cladding Methods 0.000 claims description 2
- 239000002551 biofuel Substances 0.000 claims 2
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 238000004146 energy storage Methods 0.000 abstract description 5
- 108090000790 Enzymes Proteins 0.000 abstract description 4
- 102000004190 Enzymes Human genes 0.000 abstract description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract 1
- 239000010409 thin film Substances 0.000 abstract 1
- 238000007600 charging Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000005611 electricity Effects 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NBPGPQJFYXNFKN-UHFFFAOYSA-N 4-methyl-2-(4-methylpyridin-2-yl)pyridine Chemical group CC1=CC=NC(C=2N=CC=C(C)C=2)=C1 NBPGPQJFYXNFKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006386 memory function Effects 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G17/00—Structural combinations of capacitors or other devices covered by at least two different main groups of this subclass with other electric elements, not covered by this subclass, e.g. RC combinations
-
- 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
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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
- H01G11/48—Conductive polymers
-
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- 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
- H01G11/84—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
-
- 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
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The present invention belongs to the biomass energy conversion and storage device technical field and relates to an integrated device provided with an enzyme type glucose/oxygen biological fuel cell for biomass energy conversion and a supercapacitor for biomass energy storage and a preparation method of the integrated device. The integrated device is integrated on a base and comprises the biological fuel cell and the supercapacitor connected with each other through a wire; the integrated device can realize the conversion and storage of biomass energy; the biological fuel cell is composed of glucose dehydrogenase and laccase-modified and multiwalled carbon nanotube-based Buck paper electrodes; and polymer gel is sandwiched and molded between a multiwalled carbon nanotube electrode and a polyaniline thin film electrode, so that the supercapacitor can be formed. The integrated device of the invention has the advantages of lightness and flexibility, and has a good application prospect in the portable power supply and wearable power supply field.
Description
Technical field
The invention belongs to biomass energy conversion and memory device technical field, specifically refer to a kind of biomass energy conversion
Enzyme type glucose/oxygen biological fuel cell and storage the integrated device of ultracapacitor and preparation method thereof.
Background technology
The increasingly depleted of fossil fuel, and its brought environmental problem of burning gradually obtains the attention of countries in the world, sends out
Open up its alternative energy source also to be put on agenda already.Compared with fossil fuel, biomass fuel is the most cheap, be easy to get can be again
The raw energy, the huge energy wherein contained can be discharged by constructing suitable biological fuel cell, and then obtains
Green, the new bio energy of environmental protection.Therefore, biological fuel cell is just subject to each developed country early in eighties of last century the eighties
Most attention, attracted the interest of a large amount of researchers, be expected to be applied to the fields such as biomedicine, compact power.But
It is relatively low energy output density and stability leads to its application to be restricted.
However as the high speed development of advanced nanotechnology, efficient enzyme technique for fixing, the output of biological fuel cell
Density has been obtained for unprecedented raising.Therefore develop the device with the conversion of efficient biomass energy and energy storage function
Part can effectively strengthen the application of biological fuel cell.So so that device storage when not needing electric discharge is electric
Can, and when needing to discharge, export the electric energy of relatively high power.Ultracapacitor, as a kind of energy storage device, has energy storage density
High, the advantages of have extended cycle life.The integrated device of development biological fuel cell and ultracapacitor is particularly important.In recent years
There is researcher that the two-plate of the biological anode of biological fuel cell and biological-cathode and ultracapacitor is integrated in two respectively
Prop up on electrode.But this device architecture should not carry out single optimization to two devices, has had a strong impact on the overall performance of device.
Content of the invention
Present invention aim at providing a kind of enzyme type glucose/oxygen biological fuel cell of biomass energy conversion and storage
Integrated device of ultracapacitor deposited and preparation method thereof.
For achieving the above object, the technical solution used in the present invention is：
A kind of biomass energy conversion and the integrated device of storage, integrated device is to be integrated in substrate, and passes through wire
The biological fuel cell connecting and ultracapacitor；Wherein, biological fuel cell is glucose dehydrogenase and laccase is modified respectively
Multi-walled carbon nano-tubes Bark paper electrode composition, ultracapacitor be multi-walled carbon nano-tubes/polyaniline film two interpolar folder moulds
High-molecular gel.
Described biological fuel cell is one or more；Wherein, multiple biological fuel cells are formed in the form of connecting.
Described substrate is glass or flexible polyethylene terephthalate.
The glucose dehydrogenase (FAD-GDH) that described biological fuel cell is relied on flavin adenine dinucleotide (FAD) modify in
Bark paper electrode as biological anode, modify in Bark paper electrode as biological-cathode by laccase.
A kind of preparation method of the integrated device of biomass energy conversion and storage it is characterised in that：
Step 1：Will be fully dispersed for effective for multi-wall carbon nano-tube ethanol, through vacuum filtration, wash, be dried to obtain based on many walls carbon
The Bark paper of nanotube；
Step 2：Using cladding process, FAD-GDH, Os electron mediator and cross-linking agent are modified in above-mentioned acquisition based on many walls
On the Bark paper of CNT, after being dried, obtain biological anode；Laccase is fixed on above-mentioned acquisition by 1- pyrene butanoic acid active ester
Obtain biological-cathode based on the Bark paper of multi-walled carbon nano-tubes, and then obtain biological fuel cell；
Step 3：By polymer gel electrolyte folder mould multi-walled carbon nano-tubes/polyaniline film the two poles of the earth super capacitor
Device；Polymer gel electrolyte can be polyvinyl alcohol-phosphoric acid (PVA-H3PO4).
Step 4：Biological fuel cell and ultracapacitor are attached using copper conductor, are then integrated in and obtain in substrate
Integrated device.
Described FAD-GDH, Os electron mediator and the total addition of cross-linking agent are 0.2-1.0mg/cm2, three's mass ratio is
2:2:1-3:3:1.
When described integrated device charges, the biological fuel cell 0.1M Acetic acid-sodium acetate containing 30mM glucose for the insertion is delayed
Rush in liquid (pH=5.5).
Preparation biology anode described in above-mentioned steps 2, detailed process is：10 μ L FAD-GDH (10mg/mL), 20 μ L contain Os
The electron mediator (5mg/mL) of coordination compound and 10 μ L polyethyleneglycol diglycidylether (5mg/mL) mixing, take 10 μ L mixture to apply
Overlaying on area is 0.25cm2Bark paper electrode on, drying at room temperature 24 hours.
In the ultracapacitor of the present invention, polymer gel electrolyte can be polyvinyl alcohol-phosphoric acid (PVA-H3PO4).Gu
The use of body electrolyte, greatly increases the charging voltage of ultracapacitor, and reduces its internal resistance, thus improve super electricity
The electric capacity of container the energy loss during reducing energy storage.
The operation principle of integrated device of the present invention is：Biological anode and the biological-cathode buffering containing glucose for the insertion
Liquid, after connecting wire 1 and 3, glucose is aoxidized under the catalysis of FAD-GDH on biological anode, and then ejected electron；
Oxygen is reduced under the catalytic action of laccase on biological-cathode simultaneously, and then produces positive charge.Then biological anode and
The super capacitor plate that the electronics producing respectively on biological-cathode and positive charge are moved closer to by wire, realizes super electricity
The charging process of container, that is, biological fuel cell the chemical energy in glucose is converted into electrical energy for storage in ultracapacitor
In.It is then turned off the external equipments such as wire 1 and 3, connection wire 1 and 2, and outer meeting resistance, realize ultracapacitor and set to external
Standby it is powered.
Beneficial effects of the present invention are：
Biological fuel cell and ultracapacitor are organically incorporated into one by the present invention, are simultaneously achieved the biology of energy
The conversion in mass-energy source and memory function.In the integrated device that the present invention provides, biological fuel cell can be connected multiple, and it is with two
As a example individual biological fuel cell series connection, when the later OCP of series connection and peak power output density are up to 1.4V and 326 μ W
cm-2, the ratio electric capacity of ultracapacitor reaches 329Fg-1；This two biological fuel cells charge for ultracapacitor, and charging voltage can
Reach 0.8V.The peak power output density of integrated device is up to 602 μ W cm-2, obtained close to two biological fuel cell series connection
The twice of peak power output density.Charge to ultracapacitor after two groups of biological fuel cell series connection, it is possible to obtain bigger
Charging voltage, and the peak power output density of device is greatly improved, enrich the range of application of biological fuel cell；Can
See that integrated device has relatively low weight and preferably flexible, there is miniaturization, lightweight, flexible, can conduct
Portable or wearable power supply application.
Brief description
Fig. 1 is the structural representation of biological fuel cell provided in an embodiment of the present invention and ultracapacitor integrated device；
The electrode of wherein biological fuel cell and ultracapacitor is fixed on glass or flexible PET base, and passes through copper conductor
Connect, realize the combination of energy conversion and storage.
Fig. 2 is the power of single group (a) provided in an embodiment of the present invention and two groups (b) glucose/oxygen biological fuel cell
Densogram.
Fig. 3 be integrated two groups of biological fuel cells provided in an embodiment of the present invention and ultracapacitor charging schematic diagram and
(constant-current discharge electric current is 0.8mA cm to charging and discharging curve-2).
Specific embodiment
Specific examples below is used for further illustrating the present invention, but the present invention is only limitted to absolutely not these examples, and it can be according to
According in scope defined by the claims of the present invention, carry out various conversion and change.
Embodiment 1
The constructing of glucose/oxygen biological fuel cell
It is based on multi-walled carbon nano-tubes (purity >=98%, carbon pipe diameter 20-40nm, length 10-30 μ by prior art preparation
M) Bark paper；Or will be fully dispersed for effective for multi-wall carbon nano-tube ethanol, through vacuum filtration, wash, be dried to obtain based on many walls
The Bark paper of CNT also may be used；
1. the preparation of biological anode
Above-mentioned acquisition is cut into 0.25cm based on the Bark paper of multi-walled carbon nano-tubes2Size.By 10 μ L FAD-GDH
(10mg/mL), 20 μ L contain the electron mediator of Os coordination compound【Os (4,4 '-dimethyl -2,2 '-bipyridyl)2(polyvinyl miaow
Azoles)10Chlorine, 5mg/mL】Mix with 10 μ L polyethyleneglycol diglycidylether (5mg/mL), after mixing, take 10 μ L mixture uniformly to apply
Overlaying on area is 0.25cm2Bark paper electrode on, under room temperature be dried 24 hours be obtained biology anode.
2. the preparation of biological-cathode
Above-mentioned acquisition is cut into 0.25cm based on the Bark paper of multi-walled carbon nano-tubes2Size.Then immerse excessive containing
1 hour in the DMSO solution of 10mM 1- pyrene butanoic acid active ester, then take out, more gently rinsed with DMSO, deionized water dry successively
Only, it is then immersed in 2 hours in 7.5mg/mL laccase solution.Take out electrode, deionized water is gently rinsed well and repaiied
The biological-cathode of decorations laccase.
Biological anode and biological-cathode are inserted the 0.1M Acetic acid-sodium acetate buffer (pH=containing 30mM glucose
5.5) assembling glucose/oxygen biological fuel cell in.And test cell power density such as Fig. 2.The OCP of single group battery
With maximum power density respectively up to 0.71V and 204 μ W cm-2, two Battery packs series connection after OCP and maximum power density
Respectively up to 1.4V and 326 μ W cm-2.
Embodiment 2
The preparation of ultracapacitor：
First Bark paper immersion described in embodiment 1 is contained in the 1M hydrochloric acid solution of 0.2M aniline (analysis is pure), after 5 minutes
To above-mentioned solution slowly Deca isopyknic 0.2M Ammonium persulfate. (analysis is pure) solution.Then above-mentioned solution is placed in 05 DEG C
Reaction 12 hours.Finally Bark paper is taken out, use water, acetone, washing with alcohol respectively, and be dried 12 hours at 80 DEG C, obtain
Multi-walled carbon nano-tubes/polyaniline film.
PVA-H3PO4Gel electrolyte is prepared as follows：5g PVA (mean molecule quantity 4000) is dissolved in 50mL
In ionized water and add it to, in 3mL strong phosphoric acid (purity 85%), then mixed liquor be heated under 90 DEG C, stirring and drive gas away
Bubble, obtains PVA-H after cooling3PO4Gel electrolyte.
Polymer gel electrolyte folder is moulded super electricity is obtained between two multi-walled carbon nano-tubes/Polyaniline Thin Film-Coated Electrodes
Container.
Above-mentioned acquisition ultracapacitor after measured its than electric capacity up to 329Fg-1.
Embodiment 3
Referring to Fig. 1, connect two groups with wire and obtain biological fuel cell according to above-described embodiment, then pass through again wire with
Ultracapacitor is connected, and obtains integrated device, also can further biological fuel cell and ultracapacitor be integrated in substrate,
Obtain integrated device.Described substrate is glass or flexible polyethylene terephthalate.
Then connect the wire 1 and 3 of above-mentioned integrated device, and bioelectrode is inserted the 0.1M vinegar containing 30mM glucose
In acid-sodium-acetate buffer (pH=5.5).Record charging process with electrochemical workstation connecting wire 1 and 2；After charging terminates,
Break line 1 and 3, controls ultracapacitor to carry out constant current discharge and record discharge process with electrochemical workstation, repeats two
Individual circulation.(constant-current discharge electric current is 0.8mA cm for gained charging schematic diagram and charging and discharging curve-2) see Fig. 3.
As seen from Figure 3, charging interval about 0.7 hour, charging voltage is up to 0.8V.Can from discharge curve
Go out, voltage drop very little, show that ultracapacitor has the internal resistance of very little, therefore reduce the energy loss of discharge process.
Peak power output density (the P of discharge processmax) can be calculated by below equation：
Pmax=(Vcharge-iR)×I
Wherein VchargeFor charging voltage, iR is voltage drop, and I is discharge current.Calculate PmaxFor 608 μ W cm-2.Table
Bright integrated device according to the present invention, compared with single biological fuel cell, can export bigger power density, and electricity
Can storing the longer time in the capacitor it is ensured that externally carrying out high-power power supply when needing power supply, expanding device
Range of application.
In sum, the present invention obtains the integrated device of biological fuel cell and ultracapacitor first, and colleague achieves
Chemical energy in biomass fuel is converted into electrical energy for storage.The peak power output density of device is 608 μ W cm-2,
Far above single biological fuel cell.And one can be entered by what the optimization of device architecture parameter and technique was obtained with performance
Step lifting.Effective conversion of biomass energy and store efficient utilization beneficial to the energy, in compact power and wearable electricity
Source domain has higher using value.
Above in conjunction with accompanying drawing, the preferred embodiments of the disclosure and embodiment are described in detail, but this
Bright be not limited to the above-described embodiment and examples, made under other any spirit without departing from the present invention and principle
Change, modify, substitute, combine, simplify, all should be equivalent substitute mode, be included within protection scope of the present invention.
Claims (7)
1. a kind of conversion of biomass energy and storage integrated device it is characterised in that：Integrated device is to be integrated in substrate, and
The biological fuel cell being connected by wire and ultracapacitor；Wherein, biological fuel cell is glucose dehydrogenase and laccase
The Bark paper electrode composition based on multi-walled carbon nano-tubes modified respectively, ultracapacitor is that multi-walled carbon nano-tubes/polyaniline is thin
High-molecular gel moulded by film two interpolar folder.
2. as described in claim 1 biomass energy conversion and storage integrated device it is characterised in that：Described bio-fuel
Battery is one or more；Wherein, multiple biological fuel cells are formed in the form of connecting.
3. as described in claim 1 biomass energy conversion and storage integrated device it is characterised in that：Described substrate is glass
Glass or flexible polyethylene terephthalate.
4. as described in claim 1 biomass energy conversion and storage integrated device it is characterised in that：Described bio-fuel
The glucose dehydrogenase (FAD-GDH) that battery is relied on using flavin adenine dinucleotide (FAD) is modified in Bark paper electrode as biological sun
Pole, laccase is modified in Bark paper electrode as biological-cathode.
5. described in a kind of claim 1 biomass energy conversion and storage integrated device preparation method it is characterised in that：
Step 1：Will be fully dispersed for effective for multi-wall carbon nano-tube ethanol, through vacuum filtration, wash, be dried to obtain based on multi-wall carbon nano-tube
The Bark paper of pipe；
Step 2：Using cladding process, FAD-GDH, Os electron mediator and cross-linking agent are modified and received based on many walls carbon in above-mentioned acquisition
On the Bark paper of mitron, after being dried, obtain biological anode；Laccase by 1- pyrene butanoic acid active ester be fixed on above-mentioned acquisition based on
Obtain biological-cathode on the Bark paper of multi-walled carbon nano-tubes, and then obtain biological fuel cell；
Step 3：Polymer gel electrolyte folder is moulded and obtains super capacitor between multi-walled carbon nano-tubes/polyaniline film the two poles of the earth
Device；
Step 4：Biological fuel cell and ultracapacitor are attached using copper conductor, being then integrated in substrate must be integrated
Device.
6. as described in claim 5 biomass energy conversion and storage integrated device preparation method it is characterised in that：Institute
Stating FAD-GDH, Os electron mediator and the total addition of cross-linking agent is 0.2-1.0mg/cm2, three's mass ratio is 2:2:1-3:3:
1.
7. as described in claim 5 biomass energy conversion and storage integrated device preparation method it is characterised in that：Institute
State when integrated device charges and biological fuel cell is inserted the 0.1M Acetic acid-sodium acetate buffer (pH=containing 30mM glucose
5.5) in.
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| CN111244490B (en) * | 2020-01-09 | 2021-03-16 | 中国人民解放军军事科学院军事医学研究院 | Bamboo-shaped hollow N-doped carbon nanotube and C3N4Nanosheet cross-linked composite material and preparation method and application thereof |
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