CN108134094A - A kind of application of porous carbon materials in bromo flow battery - Google Patents
A kind of application of porous carbon materials in bromo flow battery Download PDFInfo
- Publication number
- CN108134094A CN108134094A CN201611089176.4A CN201611089176A CN108134094A CN 108134094 A CN108134094 A CN 108134094A CN 201611089176 A CN201611089176 A CN 201611089176A CN 108134094 A CN108134094 A CN 108134094A
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- China
- Prior art keywords
- porous carbon
- lamella
- carbon materials
- flow battery
- bromo
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
- H01M4/8626—Porous electrodes characterised by the form
- H01M4/8631—Bipolar electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based 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
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
-
- 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 present invention relates to a kind of application of two-dimensional slice porous carbon materials in flow battery, the lamella porous carbon materials are as application of electrode in flow battery, the lamella porous carbon materials are by porous carbon materials of the pattern for sheet, lamellar spacing is 5 300nm in porous carbon materials, and the length of side of lamella is 100 5000nm.Such material has that preparation method is simple, and device is simple, and low energy consumption, the period is short, can amplify it is beneficial the characteristics of, therefore the bromo flow battery that the material assembles is with higher voltage efficiency, energy efficiency and cyclical stability.
Description
Technical field
The present invention relates to electrode of liquid flow cell Material Fields, and in particular to a kind of electrode material answering in bromo battery
With.
Technical background
In order to realize double requirements of the people to the energy and environment, Devoting Major Efforts To Developing and utilization wind energy, solar energy etc. can be again
The raw energy meets the requirement of people as a kind of very effective approach.However these energy have discontinuous, unstability,
Direct grid-connected is difficult to, leads to abandon wind and abandons light rate height, the wasting of resources.Therefore, it is necessary to be combined to ensure to supply with efficient energy storage technology
The smooth output of electricity.Energy storage technology is to improve renewable energy utilization rate and stability with release by the storage of energy, is
Develop and use the key technology of new energy.Flow battery is a kind of electrochemical energy storage technology for being suitable for extensive energy storage, special
Point be energy storage in the electrolytic solution, realize power and energy it is mutual indepedent.
Bromo flow battery is by Br2/Br-With another electricity to a kind of flow battery of composition.Since bromine reserves are larger, into
This is low, and higher electrode potential simultaneously has higher solubility, therefore such battery has low cost, high open circuit voltage and energy
The advantages that density.Such as：Zinc bromine liquid flow energy storage battery theoretical open circuit voltage 1.83V or so, theoretical energy density 430Wh/kg.
But there are still a part of problems to need further to research and solve method for bromo flow battery.It is wherein relatively low
Br2/Br-Electricity leads to reaction rate that the activation polarization of battery is larger, and voltage efficiency is relatively low.Therefore its current density is relatively low, and one
As be less than 40mA/cm2So that the power density of battery is relatively low, therefore the material utilization amount of battery system is higher, so as to reduce it
The advantage of cost.Therefore it is exploitation high power density, inexpensive bromo flow battery, design prepares high bromo electrode material living
The reaction rate of raising bromine electricity pair is gone as a kind of effective method, reduces activation polarization, realizes pushing away for bromo flow battery
Extensively.
Invention content
In order to solve the above technical problems, present invention aims at provide a kind of bromo liquid for having high activity and high conductivity
The electrode material of galvanic battery.
Realize above-mentioned purpose, the specific technical solution of the present invention is as follows：
A kind of application of two-dimensional slice porous carbon materials in flow battery, the two-dimensional slice porous carbon materials are by shape
Looks are the porous carbon materials of sheet, and thickness 5-300nm, preferably 100-200nm, the length of side of lamella is 100-5000nm, excellent
Select 1000-2000nm.
Porous carbon blanking aperture is 0.1-30nm, and preferably 1-5nm, the specific surface area of porous carbon materials is 50-3000m2/
Kg, preferably 1000-2000m2/kg。
It is reacted in a solvent with zinc salt and 2-methylimidazole and is prepared into sheet zeolite organometallic skeletal, and use water vapour
The aperture of the method control lamella carbon material of activation, carbon dioxide activation or alkali activation, prepares lamella porous carbon materials.
The zinc salt includes the one or two or more kinds in zinc acetate, zinc chloride, zinc nitrate；Zinc salt and methylimidazole
Molar ratio is 100-1, and lamella porous carbon material precursor is the sheet zeolite organometallic skeletal being prepared.
The lamella porous carbon materials are prepared according to the following procedure：
1) by zinc salt and methylimidazole disperse respectively in a solvent, temperature for be sufficiently stirred 0.1 at 20-100 DEG C-
48h, a concentration of 0.1-50wt% of zinc salt template in solution；
2) it will be mixed in two solution of step 1), be sufficiently stirred 0.5-72h at 20-100 DEG C, it is more to obtain sheet
Hole carbon materials material precursor；
3) the lamella zeolite organometallic skeletal presoma prepared in step 2) is calcined into 1- under the conditions of 700-1200 DEG C
5h；It is activated, activation method is：It is activated in carbon dioxide, 0.5-5h, temperature 500-1500 is activated in carbon dioxide
℃；Or, steam activation, 10min-8h is activated in vapor, temperature is 100-500 DEG C；Or, alkali activation, it is activated in alkali
5min-5h, temperature are 100-1500 DEG C；Alkali includes one or more of potassium hydroxide, sodium hydroxide, ammonia；
The solvent is the one or two or more kinds in water, methanol, ethyl alcohol and N,N-dimethylformamide (DMF)；Acid is molten
Liquid is nitric acid, the one or two or more kinds in sulfuric acid, hydrochloric acid.
The flow battery is bromo flow battery, and lamella porous carbon materials are as application of electrode in bromo flow battery
In.
The bromine electricity of the bromo flow battery is to for Br2/Br-Or/and Br-/Br3-。
Beneficial effects of the present invention：
1) two-dimensional slice structure is prepared using the zeolites organometallic skeletal of lamella as presoma and from template is sacrificed, led to
Cross and shorten electronics conduction distance and provide more reaction site for reaction, construction reactant diffusion admittance realization electronics and from
The high-transmission ability of son is intended so as to fulfill the high catalytic activity to bromine electricity pair by shortening electron-transport distance, and construction reactant expands
The high-transmission ability of channel realization electronics and ion is dissipated so as to fulfill the high catalytic activity to bromine electricity pair.
2) such material is simple with preparation method, good conductivity, and ion diffusion is fast, the good beneficial spy of chemical stability
Point, therefore the bromo flow battery of material assembling has higher voltage efficiency, energy efficiency and cyclical stability.
3) by regulating and controlling the pore size of porous carbon materials, the catalytic performance of carbon material is improved, so as to preferably make
Apply in bromo battery system.
4) zinc salt range of choice of the invention is big, at low cost.
5) water can be used as solvent in the present invention, and the method reacted under room temperature, method is simple, and low energy consumption, environmental-friendly to be easy to
Amplification.
Description of the drawings
Fig. 1 is lamella porous carbon materials preparation process schematic diagram of the present invention；
Fig. 2 is zinc-bromine bettery battery performance figure prepared by embodiment 1.
Specific embodiment
Embodiment 1
By 0.5g zinc nitrates, 2g methylimidazoles are dispersed in the water of 100g respectively, are sufficiently stirred at being 25 DEG C in temperature
0.5h；
Two kinds of solution in step 1) are mixed into preparation, are then sufficiently stirred 12h at 60 DEG C, centrifuges, is used in combination
Ethyl alcohol and water wash three times respectively, then dry in 60 degree of baking ovens；
The lamella zeolite organometallic skeletal presoma prepared in step 2) is calcined into 1h under the conditions of 900 DEG C, in dioxy
Change and 1h is activated in carbon, temperature is 1200 degree.
Step 3) lamella porous carbon materials are added in the hydrochloric acid of 1mol/L, stir 12h.
The lamella length of side that conclusion obtains be 1*2um, thickness be 200nm layered porous carbon material, the ratio of porous carbon materials
Surface is 2000m2/ g, aperture 2nm.
It is scratched on film using the caged porous carbon materials of preparation, zinc-bromine flow battery is assembled, wherein being double using graphite cake
Pole plate；Carbon plastic clad plate is collector；The effective area of film is 9cm2；Positive and negative anodes electrolyte volume is 30mL, wherein bromide ion
A concentration of 3mol/L.In charge-discharge test, current density 60mA/cm2, coulombic efficiency 85%, voltage efficiency is
95%, energy efficiency 80.8%.
Comparative example 1
By the carbon material preparation condition in embodiment 1,0.5h is activated in carbon dioxide, temperature is 1000 degree.It will prepare
Porous carbon materials scratch on film, assemble zinc-bromine flow battery, wherein using graphite cake as bipolar plates；Carbon plastic clad plate is afflux
Body；The effective area of film is 9cm2；Positive and negative anodes electrolyte volume is a concentration of 3mol/L of 30mL, wherein bromide ion.Charge and discharge
In experiment, current density 60mA/cm2, coulombic efficiency 85%, voltage efficiency 86%, energy efficiency 73.1%.
Table 1
Claims (8)
1. a kind of application of porous carbon materials in bromo flow battery, it is characterised in that：
The lamella porous carbon materials as application of electrode in flow battery, the lamella porous carbon materials be by pattern be piece
The porous carbon materials of stratiform, lamellar spacing is 5-300nm in porous carbon materials, and the length of side of lamella is 100-5000nm.
2. application according to claim 1, it is characterised in that：Porous carbon blanking aperture be 0.1-30nm, porous carbon materials
Specific surface area be 50-3000m2/kg。
3. application according to claim 1, it is characterised in that：
It is reacted in a solvent with zinc salt and 2-methylimidazole and is prepared into sheet zeolite organometallic skeletal, and lived with water vapour
Change, the aperture of method control lamella carbon material that carbon dioxide activation or alkali activate, prepare lamella porous carbon materials.
4. application according to claim 3, it is characterised in that：The zinc salt is included in zinc acetate, zinc chloride, zinc nitrate
It is one or two or more kinds of；The molar ratio of zinc salt and methylimidazole is 100-1, and lamella porous carbon material precursor is is prepared
Sheet zeolite organometallic skeletal.
5. application according to claim 3 or 4, it is characterised in that：The lamella porous carbon materials are made according to the following procedure
It is standby to form：
1) zinc salt and methylimidazole are disperseed respectively in a solvent, 0.1-48h to be sufficiently stirred at being 20-100 DEG C in temperature, it is molten
A concentration of 0.1-the 50wt% of zinc salt in liquid；
2) it will be mixed in two solution of step 1), be sufficiently stirred 0.5-72h at 20-100 DEG C, obtain flake porous carbon
Material precursor；
3) the lamella zeolite organometallic skeletal presoma prepared in step 2) is calcined into 1-5h under the conditions of 700-1200 DEG C；It will
It is activated, and activation method is：It is activated in carbon dioxide, 0.5-5h is activated in carbon dioxide, temperature is 500-1500 DEG C；
Or, steam activation, 10min-8h is activated in vapor, temperature is 100-500 DEG C；
Or, alkali activation, 5min-5h is activated in alkali, temperature is 100-1500 DEG C；Alkali includes potassium hydroxide, sodium hydroxide, ammonia
One or more of.
6. application according to claim 5, it is characterised in that：
The solvent is the one or two or more kinds in water, methanol, ethyl alcohol and N,N-dimethylformamide (DMF)；Acid solution is
One or two or more kinds in nitric acid, sulfuric acid, hydrochloric acid.
7. application according to claim 1, it is characterised in that：The flow battery is bromo flow battery, and lamella is porous
Carbon material is as application of electrode in bromo flow battery.
8. application according to claim 1, it is characterised in that：The bromine electricity of the bromo flow battery is to for Br2/Br‐Or/
And Br‐/Br3‐。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611089176.4A CN108134094A (en) | 2016-12-01 | 2016-12-01 | A kind of application of porous carbon materials in bromo flow battery |
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|---|---|---|---|
| CN201611089176.4A CN108134094A (en) | 2016-12-01 | 2016-12-01 | A kind of application of porous carbon materials in bromo flow battery |
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| CN108134094A true CN108134094A (en) | 2018-06-08 |
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| CN201611089176.4A Pending CN108134094A (en) | 2016-12-01 | 2016-12-01 | A kind of application of porous carbon materials in bromo flow battery |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106025239A (en) * | 2016-07-25 | 2016-10-12 | 国家纳米科学中心 | Two-dimensional nitrogen-doped hierarchical pore carbon nano-sheet as well as preparation method and application thereof to lithium/sulfur battery |
-
2016
- 2016-12-01 CN CN201611089176.4A patent/CN108134094A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106025239A (en) * | 2016-07-25 | 2016-10-12 | 国家纳米科学中心 | Two-dimensional nitrogen-doped hierarchical pore carbon nano-sheet as well as preparation method and application thereof to lithium/sulfur battery |
Non-Patent Citations (2)
| Title |
|---|
| 杜祥琬总主编: "《中国可再生能源发展战略研究丛书·风能卷》", 30 November 2008, 北京：中国电力出版社 * |
| 薛智勇主编: "《农业固体废物处理与处置》", 30 November 2016, 郑州：河南科学技术出版社 * |
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Application publication date: 20180608 |