CN205231175U - Surface titanium / mesoporous graphite alkene aerogel electrode of nitrogen doping - Google Patents
Surface titanium / mesoporous graphite alkene aerogel electrode of nitrogen doping Download PDFInfo
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- CN205231175U CN205231175U CN201520961029.6U CN201520961029U CN205231175U CN 205231175 U CN205231175 U CN 205231175U CN 201520961029 U CN201520961029 U CN 201520961029U CN 205231175 U CN205231175 U CN 205231175U
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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
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Abstract
The utility model discloses a surface titanium / mesoporous graphite alkene aerogel electrode of nitrogen doping belongs to the electrode field. The utility model discloses a surface titanium / mesoporous graphite alkene aerogel electrode of nitrogen doping, including two steps of preparation oxidation graphite alkene and surface titanium / mesoporous graphite alkene aerogel electrode of nitrogen doping. The utility model discloses an it is great that surface titanium / mesoporous graphite alkene aerogel electrode of nitrogen doping has electrode surface activation area, and increase microorganism and electrode surface electrostatic action within a definite time increases little biosorption nature, and the catalysis performance is good to improve electric quantity output, and reduction in production cost's characteristics.
Description
Technical field
The utility model relates to a kind of electrode, particularly the mesoporous graphene aerogel electrode of a kind of surperficial titanium/N doping.
Background technology
Along with continuing to increase of world population number, the mankind are subject to the impact of energy resources deficiency and ecological deterioration day by day, therefore tap a new source of energy and are paid attention to widely, and utilize reproducible biomass power generation to be a kind of effective means.Microbiological fuel cell (Microbialfuelcells, MFC), as a kind of new method utilizing microbial metabolism to produce electric energy, receives the concern of more people in recent years.It is a kind of device utilizing microbe to be electric energy as catalyst by converts chemical energy, and microbe can metabolism organic substance, produces electric energy simultaneously.But existing microbiological fuel cell generally has the low shortcoming of electrogenesis amount; Anode surface area of the prior art is general less simultaneously, be unfavorable for a large amount of attachments of microbe, and catalysis efficiency applicable surface is narrow; In prior art, the platinum that adopts as cathod catalyst more, although excellent catalytic effect, too expensive.
Utility model content
Utility model object of the present utility model is: for above-mentioned Problems existing, there is provided a kind of electrode surface active area larger, increase the electrostatic interaction between microbe and electrode surface, increase microorganism adsorption, catalytic performance is good, thus improve electricity output, and reduce the mesoporous graphene aerogel electrode of one surface titanium/N doping of production cost.
The technical solution adopted in the utility model is as follows:
The mesoporous graphene aerogel electrode of the surperficial titanium/N doping of one of the present utility model, is prepared from by following steps:
Step one: by the concentrated sulfuric acid: graphite powder: sodium nitrate mass ratio 65:1:0.6 adds graphite powder and sodium nitrate under the condition of ice bath in the concentrated sulfuric acid, after stirring and dissolving 30min, according to graphite powder: potassium permanganate mass ratio 1:5, potassium permanganate is added in mixed solution, after stirring 10h, according to the concentrated sulfuric acid: deionized water volume ratio 1:1 adds deionized water in mixed solution, mixture being placed in vacuum degree is under the condition of 0.93, 52 DEG C are slowly warming up to according to the speed of 1.2 DEG C/h, after keeping 52 DEG C of constant temperature to continue to stir 22h, in mixed solution, hydrogen peroxide is added than hydrogen peroxide volume ratio 1:0.1 according to the concentrated sulfuric acid, centrifugal stir 2.5h at 52 DEG C of temperature after, Separation of Solid and Liquid is got solid, solid uses watery hydrochloric acid and the deionized water rinsing of 5% respectively, graphene oxide is obtained after drying,
Step 2: graphene oxide is configured to the solution that concentration is 1.3mg/mL with deionized water; in solution, tetrazotization Tritanium/Trititanium is added according to mass ratio 8:1; after the ultrasonic 2h of room temperature; after reacting 10min under the condition of microwave reaction 100W; mixed solution is placed in teflon-lined thermal response still; be filled with argon gas to seal as after protection gas; vacuumize and reach vacuum degree 0.8; be warming up to 180 DEG C of reaction 36h; normal temperature is cooled to, the obtained mesoporous graphene aerogel of surperficial titanium/N doping under argon shield gas exists.
Owing to have employed technique scheme, three-dimensional grapheme good conductivity, biocompatibility is high, the aerogel structure that easy formation is three-dimensional porous, the mesoporous graphene aerogel of titanium/N doping has hydrophilic surface, and reduce surface of graphene oxide hydrophobicity, electrolyte more easily infiltrates, conductivity is better, improves its reactivity area in anolyte.
The mesoporous graphene aerogel electrode of the surperficial titanium/N doping of one of the present utility model, described surperficial titanium/N doping mesoporous graphene aerogel electrode has three-dimensional netted loose structure, and pore size is 9 μm.
Owing to have employed technique scheme, electrode surface active area is comparatively large, increases the electrostatic interaction between microbe and electrode surface, and increase microorganism adsorption, catalytic performance is good; Tridimensional network there will not be disintegration phenomenon; Pore size is 9 μm, and applicable bacterium enters.
The mesoporous graphene aerogel electrode of the surperficial titanium/N doping of one of the present utility model, this application of electrode is in the method based on the microbiological fuel cell to TMAO medium, described based on comprising setting reactor in the enclosure and the anode be arranged on outside shell and battery cathode to the microbiological fuel cell of TMAO medium, the bottom of described anode is connected to one end of reactor; The bottom of described battery cathode is connected to the other end of reactor; Described reactor comprises capsul and the anode be arranged in capsul and negative electrode, described anode and cathode surface are attached with microbe, amberplex is provided with between described anode and negative electrode, described anode is connected with anode, described negative electrode is connected with battery cathode, is full of medium in described capsul; Filled media is full of between described shell and capsul; Described anode is the mesoporous graphene aerogel of surperficial titanium/N doping, and described negative electrode is VO
2/ S-AC nickel foam air cathode; Described microbe is Shewanella putrefaciens, and described medium is to TMAO.
Owing to have employed technique scheme, reactor is separated into anode chamber and cathode chamber by amberplex, under anode chamber's anaerobic environment, under the effect of TMAO Shewanella putrefaciens, degraded produces trimethylamine, and then generate dimethylamine and formaldehyde etc., oxygen in cathode chamber, under the catalytic action of negative electrode, obtains electronics and is reduced and is combined into water with proton, and reactor produces electric energy, loop can be formed, the electric energy release produced by reactor by connection anode and battery cathode.
The mesoporous graphene aerogel electrode of the surperficial titanium/N doping of one of the present utility model, is provided with flame-resistant insulation layer between described anode and battery cathode, described flame-resistant insulation layer is overlying on capsul upper surface; The bottom of described shell is provided with media exchanger, and described media exchanger is connected with capsul inside by passage.
Owing to have employed technique scheme, flame-resistant insulation layer by flame-resistant insulation, can improve the security performance of battery; Can constantly supplement new medium by media exchanger and enter reactor, ensure the continuous firing of battery, extend the useful life of battery.
The mesoporous graphene aerogel electrode of the surperficial titanium/N doping of one of the present utility model, described flame-resistant insulation layer 10 comprises 37% vinylite, 21% silica gel, 5% plasticiser, 3% dibasic lead stearate, 5% containing oxygen silicone oil, 2% platinum complex, 5% ethynylcyclohexanol, 3% mica, 9% siloxane oligomer and 10% repefral.
Owing to have employed technique scheme, this flame-resistant insulation layer has the features such as waterproof, fire-retardant, high temperature resistant, resist chemical, and lighter weight.
The mesoporous graphene aerogel electrode of the surperficial titanium/N doping of one of the present utility model, ionic membrane exchange membrane comprises cell nafion proton membrane one, the lower floor of cell nafion proton membrane one is coated with silicon dioxide layer, and the lower floor of silicon dioxide is coated with cell nafion proton membrane two; The thickness of silicon dioxide layer is 450nm, and cell nafion proton membrane one surface is covered with PDDA layer, and cell nafion proton membrane two surface is covered with PSS layer.
Owing to have employed technique scheme, SiO
2the sulfonate radical on surface hydroxyl and cell nafion proton membrane surface interacts and serves physical crosslinking polymer effect, PDDA layer and PSS layer can realize being cross-linked sulfonic acid group in cell nafion proton membrane, improve the water content of film, proton is more easily freely passed through, improve proton conductivity and the energy efficiency of ionic membrane, avoid microbial metabolic products to the pollution of ionic membrane simultaneously, ensure that the proton conductivity of ionic membrane, improve the energy efficiency of battery.
The mesoporous graphene aerogel electrode of the surperficial titanium/N doping of one of the present utility model, described VO
2the VO on/S-AC nickel foam air cathode surface
2/ S-AC layer is nanometer thin sheet, described VO
2the thickness of/S-AC layer is 300nm, described VO
2the dimethyl silicone polymer on/S-AC nickel foam air cathode surface and the load capacity of carbon black are 6.25mg/cm
2and 1.56mg/cm
2.
Owing to have employed technique scheme, cathode catalysis performance is good, and the price of vanadium is lower than platinum, reduces production cost.
Of the present utility model a kind of apply above-mentioned electrode based on the microbiological fuel cell to TMAO medium, the anode comprising setting reactor in the enclosure and be arranged on outside shell and battery cathode, the bottom of described anode is connected to one end of reactor; The bottom of described battery cathode is connected to the other end of reactor; Described reactor comprises capsul and the anode be arranged in capsul and negative electrode, described anode and cathode surface are attached with microbe, amberplex is provided with between described anode and negative electrode, described anode is connected with anode, described negative electrode is connected with battery cathode, is full of medium in described capsul; Filled media is full of between described shell and capsul; Described anode is the mesoporous graphene aerogel of surperficial titanium/N doping, and described negative electrode is VO
2/ S-AC nickel foam air cathode; Described microbe is Shewanella putrefaciens, and described medium is to TMAO; Be provided with flame-resistant insulation layer between described anode and battery cathode, described flame-resistant insulation layer is overlying on capsul upper surface; The bottom of described shell is provided with media exchanger, and described media exchanger is connected with capsul inside by passage.
In sum, owing to have employed technique scheme, the beneficial effects of the utility model are:
1, electrode surface active area is comparatively large, increases the electrostatic interaction between microbe and electrode surface, and increase microorganism adsorption, catalytic performance is good, and electric energy productive rate is high.
2, reduce the production cost of anode of microbial fuel cell, be more close to the practical application of microbiological fuel cell, under the prerequisite of control electrode cost, obtain the efficiency of fuel cell generation of higher microbiological fuel cell.
3, have employed the microbiological fuel cell of this electrode, electricity output is improved, and the proton conductivity of battery improves, and the security performance of battery is high, long service life.
Accompanying drawing explanation
Fig. 1 is the structural representation based on the microbiological fuel cell to TMAO medium of the mesoporous graphene aerogel electrode of a kind of application surface titanium/N doping;
Fig. 2 is the operation principle schematic diagram based on the microbiological fuel cell to TMAO medium of the mesoporous graphene aerogel electrode of a kind of application surface titanium/N doping;
Fig. 3 is the SEM figure of the three-dimensional netted loose structure of the mesoporous graphene aerogel of surperficial titanium/N doping;
Fig. 4 is VO
2the VO on/S-AC nickel foam air cathode surface
2the SEM figure of/S-AC layer.
Mark in figure: 1 is reactor, and 2 is anode, and 3 is negative electrode, and 4 is microbe, and 5 is medium, 6 is capsul, and 7 is amberplex, and 8 is anode, and 9 is battery cathode, and 10 is flame-resistant insulation layer, 11 is shell, and 12 is filled media, and 13 is media exchanger, and 14 is passage.
Embodiment
Below in conjunction with accompanying drawing, the utility model is described in detail.
In order to make the object of utility model, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the utility model is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the utility model, and be not used in restriction the utility model.
Embodiment 1
The mesoporous graphene aerogel electrode of a kind of surperficial titanium/N doping, is prepared from by following steps:
Step one: by the concentrated sulfuric acid: graphite powder: sodium nitrate mass ratio 65:1:0.6 adds graphite powder and sodium nitrate under the condition of ice bath in the concentrated sulfuric acid, after stirring and dissolving 30min, according to graphite powder: potassium permanganate mass ratio 1:5, potassium permanganate is added in mixed solution, after stirring 10h, according to the concentrated sulfuric acid: deionized water volume ratio 1:1 adds deionized water in mixed solution, mixture being placed in vacuum degree is under the condition of 0.93, 52 DEG C are slowly warming up to according to the speed of 1.2 DEG C/h, after keeping 52 DEG C of constant temperature to continue to stir 22h, in mixed solution, hydrogen peroxide is added than hydrogen peroxide volume ratio 1:0.1 according to the concentrated sulfuric acid, centrifugal stir 2.5h at 52 DEG C of temperature after, Separation of Solid and Liquid is got solid, solid uses watery hydrochloric acid and the deionized water rinsing of 5% respectively, graphene oxide is obtained after drying,
Step 2: graphene oxide is configured to the solution that concentration is 1.3mg/mL with deionized water; in solution, tetrazotization Tritanium/Trititanium is added according to mass ratio 8:1; after the ultrasonic 2h of room temperature; after reacting 10min under the condition of microwave reaction 100W; mixed solution is placed in teflon-lined thermal response still; be filled with argon gas to seal as after protection gas; vacuumize and reach vacuum degree 0.8; be warming up to 180 DEG C of reaction 36h; normal temperature is cooled to, the obtained mesoporous graphene aerogel of surperficial titanium/N doping under argon shield gas exists.
As shown in Figure 3, a kind of surperficial titanium/N doping mesoporous graphene aerogel electrode has three-dimensional netted loose structure, and pore size is 9 μm.
Embodiment 2
As shown in Figures 1 to 4, the mesoporous graphene aerogel electrode of a kind of surperficial titanium/N doping, this application of electrode is in the method based on the microbiological fuel cell to TMAO medium, a kind of based on the microbiological fuel cell to TMAO medium, comprise and be arranged on reactor in shell 11 1 and the anode 8 be arranged on outside shell 11 and battery cathode 9, the bottom of anode 8 is connected to one end of reactor 1; The bottom of battery cathode 9 is connected to the other end of reactor 1.
Reactor 1 comprises capsul 6 and the anode 2 be arranged in capsul 6 and negative electrode 3, anode 2 and negative electrode 3 surface attachment have microbe 4, and be provided with amberplex 7 between anode 2 and negative electrode 3, anode 2 is connected with anode 8, negative electrode 3 is connected with battery cathode 9, is full of medium 5 in capsul 6.
Anode 2 is the mesoporous graphene aerogel of surperficial titanium/N doping, and negative electrode 3 is VO
2/ S-AC nickel foam air cathode.
Microbe 4 is Shewanella putrefaciens, and medium 5 is to TMAO.Medium 5 TMAO is under the effect of Shewanella putrefaciens 4, and degraded produces trimethylamine, and then generates dimethylamine and formaldehyde etc., and the oxygen in cathode chamber, under the catalytic action of negative electrode, obtains electronics and is reduced and is combined into water with proton.Make when external circuit and anode 8 are connected with battery cathode 9, electronics moves generation current, thus the electric energy release that reactor is produced.
Flame-resistant insulation layer 10 is provided with between anode 8 and battery cathode 9, flame-resistant insulation layer 10 is overlying on capsul 6 upper surface, flame-resistant insulation layer 10 comprises 37% vinylite, 21% silica gel, 5% plasticiser, 3% dibasic lead stearate, 5% containing oxygen silicone oil, 2% platinum complex, 5% ethynylcyclohexanol, 3% mica, 9% siloxane oligomer and 10% repefral; Filled media 12 is full of between shell 11 and capsul 6, filled media 12 is identical with the material of flame-resistant insulation layer 10, filled media 12 comprises 37% vinylite, 21% silica gel, 5% plasticiser, 3% dibasic lead stearate, 5% containing oxygen silicone oil, 2% platinum complex, 5% ethynylcyclohexanol, 3% mica, 9% siloxane oligomer and 10% repefral; The bottom of shell 11 is provided with media exchanger 13, media exchanger 13 is connected with capsul 6 inside by passage 14, medium 5 TMAO can under the effect of media exchanger 13, constantly add in reactor, and the unnecessary water of generation in reactor is by under the effect of media exchanger 13, leave reactor, thus ensure the work of reactor continuous and effective.
Ionic membrane exchange membrane 7 comprises cell nafion proton membrane one, and the lower floor of cell nafion proton membrane one is coated with silicon dioxide layer, and the lower floor of silicon dioxide is coated with cell nafion proton membrane two; The thickness of silicon dioxide layer is 450nm, and cell nafion proton membrane one surface is covered with PDDA layer, and cell nafion proton membrane two surface is covered with PSS layer.
Titanium/N doping mesoporous graphene aerogel in surface has three-dimensional netted loose structure, and pore size is 9 μm; VO
2the VO on/S-AC nickel foam air cathode surface
2/ S-AC layer is nanometer thin sheet, VO
2the thickness of/S-AC layer is 300nm, VO
2the dimethyl silicone polymer on/S-AC nickel foam air cathode surface and the load capacity of carbon black are 6.25mg/cm
2and 1.56mg/cm
2.
The foregoing is only preferred embodiment of the present utility model; not in order to limit the utility model; all do within spirit of the present utility model and principle any amendment, equivalent to replace and improvement etc., all should be included within protection range of the present utility model.
Claims (6)
1. the mesoporous graphene aerogel electrode of surperficial titanium/N doping, is characterized in that: described surperficial titanium/N doping mesoporous graphene aerogel electrode is made up of three-dimensional netted loose structure, and described pore size is 9 μm; The mesoporous graphene aerogel electrode of described surperficial titanium/N doping has hydrophilic surface layer.
2. the mesoporous graphene aerogel electrode of a kind of surperficial titanium/N doping as claimed in claim 1, it is characterized in that: this application of electrode is in based on the microbiological fuel cell to TMAO medium, described based on comprising the reactor (1) that is arranged in shell (11) to the microbiological fuel cell of TMAO medium and being arranged on shell (11) anode outward (8) and battery cathode (9), the bottom of described anode (8) is connected to one end of reactor (1); The bottom of described battery cathode (9) is connected to the other end of reactor (1); Described reactor (1) comprises capsul (6) and the anode (2) that is arranged in capsul (6) and negative electrode (3), described anode (2) and negative electrode (3) surface attachment have microbe (4), amberplex (7) is provided with between described anode (2) and negative electrode (3), described anode (2) is connected with anode (8), described negative electrode (3) is connected with battery cathode (9), is full of medium (5) in described capsul (6); Filled media (12) is full of between described shell (11) and capsul (6); Described anode (2) is the mesoporous graphene aerogel of surperficial titanium/N doping, and described negative electrode (3) is VO
2/ S-AC nickel foam air cathode; Described microbe (4) is Shewanella putrefaciens, and described medium (5) is to TMAO.
3. the mesoporous graphene aerogel electrode of a kind of surperficial titanium/N doping as claimed in claim 2, it is characterized in that: be provided with flame-resistant insulation layer (10) between described anode (8) and battery cathode (9), described flame-resistant insulation layer (10) is overlying on capsul (6) upper surface; The bottom of described shell (11) is provided with media exchanger (13), and described media exchanger (13) is connected with capsul (6) inside by passage (14).
4. the mesoporous graphene aerogel electrode of a kind of surperficial titanium/N doping as claimed in claim 3, it is characterized in that: ionic membrane exchange membrane (7) comprises cell nafion proton membrane one, the lower floor of cell nafion proton membrane one is coated with silicon dioxide layer, and the lower floor of silicon dioxide is coated with cell nafion proton membrane two; The thickness of silicon dioxide layer is 450nm, and cell nafion proton membrane one surface is covered with PDDA layer, and cell nafion proton membrane two surface is covered with PSS layer.
5. the mesoporous graphene aerogel electrode of a kind of surperficial titanium/N doping as claimed in claim 4, is characterized in that: described VO
2the VO on/S-AC nickel foam air cathode surface
2/ S-AC layer is nanometer thin sheet, described VO
2the thickness of/S-AC layer is 300nm, described VO
2the dimethyl silicone polymer on/S-AC nickel foam air cathode surface and the load capacity of carbon black are 6.25mg/cm
2and 1.56mg/cm
2.
6. application a kind of surperficial titanium/N doping as claimed in claim 5 mesoporous graphene aerogel electrode based on the microbiological fuel cell to TMAO medium, it is characterized in that: comprise the reactor (1) that is arranged in shell (11) and be arranged on shell (11) anode outward (8) and battery cathode (9), the bottom of described anode (8) is connected to one end of reactor (1); The bottom of described battery cathode (9) is connected to the other end of reactor (1); Described reactor (1) comprises capsul (6) and the anode (2) that is arranged in capsul (6) and negative electrode (3), described anode (2) and negative electrode (3) surface attachment have microbe (4), amberplex (7) is provided with between described anode (2) and negative electrode (3), described anode (2) is connected with anode (8), described negative electrode (3) is connected with battery cathode (9), is full of medium (5) in described capsul (6); Filled media (12) is full of between described shell (11) and capsul (6); Described anode (2) is the mesoporous graphene aerogel of surperficial titanium/N doping, and described negative electrode (3) is VO
2/ S-AC nickel foam air cathode; Described microbe (4) is Shewanella putrefaciens, and described medium (5) is to TMAO; Be provided with flame-resistant insulation layer (10) between described anode (8) and battery cathode (9), described flame-resistant insulation layer (10) is overlying on capsul (6) upper surface; The bottom of described shell (11) is provided with media exchanger (13), and described media exchanger (13) is connected with capsul (6) inside by passage (14).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201520961029.6U CN205231175U (en) | 2015-11-28 | 2015-11-28 | Surface titanium / mesoporous graphite alkene aerogel electrode of nitrogen doping |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201520961029.6U CN205231175U (en) | 2015-11-28 | 2015-11-28 | Surface titanium / mesoporous graphite alkene aerogel electrode of nitrogen doping |
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| Publication Number | Publication Date |
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| CN205231175U true CN205231175U (en) | 2016-05-11 |
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhou Lianfa Inventor before: Zeng Li |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170918 Address after: Shunde District Guangdong city Foshan province 528314 Chen Cun Zhen Shi Zhou Cun Wei Hui Bai Chen Lu Shi Gang Zhou section North Industrial Zone No. 2 C3 block three layer, one of the three Patentee after: Foshan Jiaying Battery Co. Address before: 610000 Sichuan city of Chengdu province Wuhou District Wuhou Park Zone Vuko East Road No. 15 Building 2 1 unit 2 floor No. 231 Patentee before: CHENGDU JIUSHIDU INDUSTRIAL PRODUCT DESIGN CO., LTD. |