CN103825033B - A kind of flow battery electrode material processing method - Google Patents
A kind of flow battery electrode material processing method Download PDFInfo
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- CN103825033B CN103825033B CN201410093401.6A CN201410093401A CN103825033B CN 103825033 B CN103825033 B CN 103825033B CN 201410093401 A CN201410093401 A CN 201410093401A CN 103825033 B CN103825033 B CN 103825033B
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- electrode material
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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
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
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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
- H01M4/96—Carbon-based electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- 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 kind of flow battery electrode material processing method, use low temperature normal atmosphere plasma technology that electrode material is carried out surface process, use gas flow regulation plasma intensity, and adjust surface treatment effect by the distance and relative movement speed adjusting electrode material and discharge of plasma in low temperature device nozzle.Electrode material processes and performs etching at normal temperatures, it is to avoid the high temperature damage to electrode material itself；Surface treatment effect i.e. can be control effectively by plasma technique only adjusting gas flow and nozzle distance；Vacuum environment and airtight cavity need not be set, can be to the continuous treatment of material；Processing procedure need not inorganic and organic solvent, it is only necessary to consuming electric energy and oxygen, energy consumption is low, safety and environmental protection；Material surface processes uniformly, processes the time short, is very easy to carry out large-scale production, and technique is simple, with low cost.
Description
Technical field
The present invention relates to flow battery technology field, be specifically related to a kind of flow battery electrode material processing method.
Background technology
Electric energy is modern society human lives and produces requisite secondary energy sources.Along with socioeconomic development and people
People's growth in the living standard, increases day by day to the demand of electric power.For the sustainable development of entire society, fully develop
The most urgent demand is had become as with utilizing regenerative resource.For ensureing the stable power-supplying of renewable energy system,
And sufficiently effective utilize its generating capacity, it is necessary to regulated in the way of electric power storage energy storage.It addition, the peak clipping of electrical network
Fill out paddy, balanced load also in the urgent need to our exploitation scale energy storage technology.
Flow battery has following characteristics: 1) power output of battery depends on the size and number of pile, stored energy capacitance
Depending on electrolyte reserves and concentration, design is very flexible, power output to be increased, only need to increase pile area and
The quantity of pile, stored energy capacitance to be increased, only need to increase the volume of electrolyte.2) active material of flow battery is molten
The metal ion of solution different valence state in the aqueous solution, during flow battery charge and discharge, only ionic valence condition occurs
Change, not undergoing phase transition, discharge and recharge answer speed is fast.3) battery is long, electrolyte solution regenerating easily
Recycle.4) charging-discharging performances is good, can deep discharge and do not damage battery, self discharge is low.It is in pass in system
Close pattern, the electrolyte in storage tank is without self-discharge phenomenon.5) the addressing free degree is big, and system can be run by Full automatic sealing,
Pollution-free, to safeguard simple, running cost is low.6) electrolyte solution is the aqueous solution, battery system without potential blast or
Fire hazard, security is high.7) battery system state-of-charge (SOC), beneficially electrical network can in real time, be accurately monitored
It is managed, dispatches.
Electrode material used by flow battery is mainly material with carbon element.The material of most common of which is that carbon felt, graphite felt etc. are many
Hole carbon stereo electrod material.Such material has the advantage that resistivity is low, good stability, specific surface area are big.But,
Carbon felt or graphite felt materials are currently used primarily in insulation industry at present, are applied to flow battery and there is also electrode reaction at it
The problem such as the activity on surface is low.In order to improve carbon felt or the graphite felt materials electrochemical redox for vanadium metal ion
Activity, needs carbon felt or graphite felt are modified activation process, improves electro-chemical activity and battery performance.From mesh
From the point of view of front document, the mechanism that electrode material activity improves is to increase oxygen-containing functional group, such as carboxyl, carbonyl on its surface
Deng.
For reaching above-mentioned purpose, the activating treatment method used at present generally includes: noble metal decorated, acid treatment, heat
Process and Anodic facture etc..Noble metal decorated complex process, needs high temperature sintering, it is difficult on a large scale should
With, it is suitable for carrying out laboratory research.The effect that acid activation processes is pretty good, but needs in processing procedure to produce in a large number
Spent acid, cause environmental pollution.Heat treatment operation technological requirement is higher, and oxidation reaction process is wayward, transition oxygen
Change can reduce stability and the service life of electrode material.Electrochemical process for treating equipment cost is higher, and uses sulphur
Acid is electrolyte, and fiber surface oxidation reaction can be caused more violent, and fiber surface etching phenomenon is serious, can reduce material
The service life of material.
Summary of the invention
The present invention is directed to the problems referred to above, propose a kind of surface treatment method improving electrode of liquid flow cell material activity.Should
Method need not heating, without using the corrosive solutions such as sulfuric acid, normal temperature is carried out, and technological parameter regulation is simple.Pass through
The electrode material surface that the method processes can be greatly improved, and the wettability of material is obviously improved, beneficially flow battery
The electrolyte abundant infiltration to electrode material, electrode material activity is obviously improved.
" normal temperature " in " normal temperature is carried out " of the present invention refers to that the surface of electrode material processes and operates at normal temperatures.
A kind of flow battery electrode material processing method, uses low temperature normal atmosphere plasma technology to carry out electrode material
Surface processes.
The producing method of low temperature plasma has: glow discharge, corona discharge, dielectric barrier discharge, radio frequency discharge,
Slip arc discharge, jet discharges, Atomospheric pressure glow discharge, subatmospheric glow discharge etc..Embodiment of the present invention institute
Discharge of plasma in low temperature device use " dielectric barrier discharge " mode, but technical scheme is also
Being not limited to this, the generating means of other discharge mode is also applied for the present invention.
Further, described method temperature controlling range is 1 × 104K≤ion temperature≤2 × 104K, 1 × 104K≤electricity
Sub-temperature≤2 × 104K。
Further, described method uses gas flow to regulate plasma intensity, and described gas flow is preferably
0.1m3/h-10m3/h。
Further, the gas source that described method uses is the oxygen that content is not less than 99.9%.
Further, described method is when processing electrode material, by adjusting electrode material and discharge of plasma in low temperature
The distance of device nozzle adjusts surface treatment effect.
Described electrode material is preferably 5mm-10mm with the distance of discharge of plasma in low temperature device nozzle.
Further, described method is also by the relative movement speed adjusting discharge of plasma in low temperature device nozzle and material
Rate adjusts surface treatment effect.
Further, described nozzle is preferably 1mm/s-150mm/s with the relative movement speed of material.
Further, the open-assembly time that described electrode material surface processes is not less than 5s.
Open-assembly time of the present invention refers to the time that electrode material processes through plasma jet, and it depends on electrode material
The translational speed of material and number of processes.
Further, described electrode material includes but not limited to graphite felt or charcoal felt.
1) electrode material processes and performs etching at normal temperatures, it is to avoid the high temperature damage to electrode material itself；
2) process adjustments is easy, and surface treatment effect i.e. can effectively be controlled by only adjusting gas flow and nozzle distance
System；
3) vacuum environment and airtight cavity need not be set, can be to the continuous treatment of material；
4) processing procedure need not inorganic and/or organic solvent, only consumes electric energy and oxygen, and energy consumption is low, safety and environmental protection；
5) material surface processes uniformly, processes the time short, easy large-scale production, and technique is simple, with low cost.
Detailed description of the invention
Following non-limiting example can make those of ordinary skill in the art that the present invention be more fully understood, but not with
Any mode limits the present invention.
Embodiment 1
Graphite felt is placed on plasma producing apparatus platform, uses lower temperature plasma technology, regulate plasma
Body generator parameter is: source of the gas uses the oxygen of 99.99%, and flow is 0.5m3/h, nozzle and graphite felt surface distance
For 5mm, nozzle translational speed is 20mm/s, and the open-assembly time of electrode material is not less than 5s.Stone after application process
Ink felt assembles 1kW all-vanadium flow monocell, at 80mA/cm2Under the conditions of run, evaluate battery energy conversion efficiency
(energy efficiency: battery carries out charge and discharge cycles with rated power, battery releases energy divided by being filled with energy), and with not
Surface treated graphite felt battery performance contrasts, as shown in the table:
| Sample | Energy conversion efficiency (%) |
| Before process | 77.61 |
| After process | 85.17 |
As can be seen from the above table, before processing, energy content of battery efficiency is 77.61, and after process, energy content of battery efficiency is 85.17%,
Energy efficiency effectively improves.
Embodiment 2
Charcoal felt is placed on plasma producing apparatus platform, uses lower temperature plasma technology, regulation plasma to send out
Raw device parameter is: source of the gas uses the oxygen of 99.9%, and flow is 2.5m3/h, and nozzle and graphite felt surface distance are 8mm,
Nozzle translational speed is 50mm/s, and the open-assembly time of electrode material is not less than 5s.Graphite felt after application processes assembles
1kW all-vanadium flow monocell, at 80mA/cm2Under the conditions of run, evaluate battery energy conversion efficiency (energy efficiency:
Battery carries out charge and discharge cycles with rated power, and battery releases energy divided by being filled with energy), and with the most surface treated
Charcoal felt battery performance contrasts, as shown in the table:
| Sample | Energy conversion efficiency (%) |
| Before process | 80.5 |
| After process | 86.2 |
As can be seen from the above table, before processing, energy content of battery efficiency is 80.5, and after process, energy content of battery efficiency is 86.2%,
Energy efficiency effectively improves.
Claims (4)
1. a flow battery electrode material processing method, it is characterised in that use low temperature normal atmosphere plasma technology
Electrode material is carried out surface process；
Process conditions are: 1 × 10K4≤ ion temperature≤2 × 104K, 1 × 104K≤electron temperature≤2 × 104K；Gas
Flow is 0.1m3/h-10m3/h；Described electrode material with the distance of discharge of plasma in low temperature device nozzle is
5mm-10mm；Described nozzle is 1mm/s-150mm/s with the relative movement speed of material.
Method the most according to claim 1, it is characterised in that described method use gas source be content not
Oxygen less than 99.9%.
Method the most according to claim 1, it is characterised in that during the exposure that described electrode material surface processes
Between be not less than 5s.
Method the most according to claim 1, it is characterised in that described electrode material is graphite felt or charcoal felt.
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| CN103825033B true CN103825033B (en) | 2016-09-07 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110416554B (en) * | 2018-04-26 | 2021-02-02 | 大连融科储能装备有限公司 | Modification method of carbon felt for all-vanadium redox flow battery electrode |
| CN108878915B (en) * | 2018-08-30 | 2021-01-26 | 成都先进金属材料产业技术研究院有限公司 | Porous carbon material for covering carbon nanotube layer for vanadium battery and vanadium battery |
| CN114976059A (en) * | 2022-06-21 | 2022-08-30 | 华中科技大学 | Electrode method for parallel plate type dielectric barrier discharge plasma modified flow battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101009376A (en) * | 2006-01-25 | 2007-08-01 | 中国科学院大连化学物理研究所 | Integrated pole dual-pole board for oxidation deoxidization liquid energy-storing battery and its preparation |
| CN101481871A (en) * | 2008-12-29 | 2009-07-15 | 南通三信塑胶装备科技有限公司 | Energy-saving environment friendly low temperature normal atmosphere plasma continuous treater |
| CN101821020A (en) * | 2007-09-06 | 2010-09-01 | 布鲁塞尔大学 | Method of depositing fluorinated layer from precursor monomer |
-
2014
- 2014-03-13 CN CN201410093401.6A patent/CN103825033B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101009376A (en) * | 2006-01-25 | 2007-08-01 | 中国科学院大连化学物理研究所 | Integrated pole dual-pole board for oxidation deoxidization liquid energy-storing battery and its preparation |
| CN101821020A (en) * | 2007-09-06 | 2010-09-01 | 布鲁塞尔大学 | Method of depositing fluorinated layer from precursor monomer |
| CN101481871A (en) * | 2008-12-29 | 2009-07-15 | 南通三信塑胶装备科技有限公司 | Energy-saving environment friendly low temperature normal atmosphere plasma continuous treater |
Non-Patent Citations (4)
| Title |
|---|
| cation on carbon felt electrodes for use in vanadium redox fl * |
| Ki Jae Kim等.The effects of surface modifi * |
| ow batteries.《Materials Chemistry and Physics》.2011,第131卷(第1-2期),第547–553页. * |
| The Atmospheric-Pressure Plasma Jet: A Review and Comparison to Other Plasma Sources;Andreas Schutze等;《IEEE TRANSACTIONS ON PLASMA SCIENCE》;19981231;第26卷(第6期);第1685-1694页 * |
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