CN110416554A - A kind of method of modifying of vanadium redox flow battery electrode carbon felt - Google Patents
A kind of method of modifying of vanadium redox flow battery electrode carbon felt Download PDFInfo
- Publication number
- CN110416554A CN110416554A CN201810385706.2A CN201810385706A CN110416554A CN 110416554 A CN110416554 A CN 110416554A CN 201810385706 A CN201810385706 A CN 201810385706A CN 110416554 A CN110416554 A CN 110416554A
- Authority
- CN
- China
- Prior art keywords
- carbon felt
- spray head
- oxygen
- modifying
- flow rate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
The present invention relates to energy-storage battery fields, and in particular to a kind of method of modifying of vanadium redox flow battery electrode carbon felt.Using plasma spray gun carries out pipeline processes to coiled Carbon felt surface, greatly reduction Operating Complexity, hence it is evident that improves carbon felt electrode hydrophily and chemical stability.The present invention realizes full-automatic production, and the more stable nothing of the performance of carbon felt obviously fluctuates after activation, and without human intervention and real-time monitoring, safety and stability is at low cost and yield is significantly increased and obvious simplifies production procedure.
Description
Technical field
The present invention relates to energy-storage battery fields, are exclusively used in entirely more particularly to all-vanadium flow battery field, especially one kind
The method of modifying of vanadium flow battery electrode carbon felt.
Background technique
All-vanadium flow battery is a kind of novel extensive energy-storage battery, and, power height independent with capacity, the service life is long and easily grasps
The advantages that making.Critical component one of of the electrode as flow battery, the performance quality of electrode material, directly affects electrolyte distribution
Uniformity, disperse state, the rate of the internal resistance of cell and electrochemical reaction, and then influence polarization of electrode degree and battery
Internal resistance, the final energy conversion efficiency for influencing battery, the stability of electrode material also influences the service life of battery.
Vanadium redox flow battery electrode material mainly has vitreous carbon, carbon felt, graphite, graphite felt, carbon paper, carbon cloth in the prior art
Deng.Carbon felt or graphite felt are formed by carbon fiber textile, have good mechanical strength, and true specific surface area is much larger than collection table
Area can provide biggish electrochemical reaction area, add good chemical stability and electric conductivity, become full vanadium
One of the research hotspot of electrode of liquid flow cell material.But if being directly used for all-vanadium flow battery, electrochemistry is living
Property, invertibity are lower.Therefore, it is necessary to carry out modification appropriate to it to improve its hydrophily and electro-chemical activity.Currently,
There are gaseous cyaniding, liquid phase oxidation, electrochemical oxidation process, gamma-rays method, hydro-thermal method, surface heavy the main means that it is modified
Area method etc..But in large-scale application, the problems such as there are complicated for operation, modified effect is unobvious, higher cost.
Summary of the invention
For overcome the deficiencies in the prior art, the present invention provides a kind of modification side of vanadium redox flow battery electrode carbon felt
Method carries out pipeline processes to coiled Carbon felt surface using air/oxygen/nitrogen/gaseous mixture plasma torch, greatly reduces
Operating Complexity, hence it is evident that improve carbon felt electrode hydrophily and chemical stability.
Inventive concept of the invention is: gas and carbon felt carbon fiber surface high-activity amorphous carbon atom reacted,
It can be by adjusting activated gas species, flow velocity, ion spray gun power, temperature, spray head and Carbon felt surface distance, spray head scanning frequency etc.
Factor, the degree that control carbon felt carbon fiber surface carbon is oxidized, so that the oxygen-containing functional group type of carbon felt carbon fiber surface growth
And ratio is optimal, carbon felt is optimal activation degree.
To achieve the above object, the invention adopts the following technical scheme:
By without the coiled carbon felt of activation processing, it is driven and is sent into region of activation by 20-80 DEG C of gas etc. by roller bearing
Ion spray gun is activated, and grows oxygen-containing functional group (- COH ,-C=O ,-COOH ,-COOR etc.) in carbon felt carbon fiber surface,
Middle plasma gun activation process conditional are as follows: one or more kinds of gases are as gas source, gas using in air, oxygen, nitrogen
Body flow velocity 0.1-100ml/min, spray head and Carbon felt surface distance 0.1-10cm, spray head walking speed 0.1-50cm/s, plasma gun
Power 2000-25000W.
Further, gas flow rate 20-100ml/min, spray head and Carbon felt surface distance 1-10cm, spray head walking speed 20-
50cm/s, plasma gun power 2500-8000W.
During continuous productive process, according to the settable one or more plasma gunes of production efficiency demand, plasma spray
The arrangement of horizontally-arranged or vertical setting of types can be used in rifle.
Preferably, vanadium redox flow battery electrode Carbon felt surface oxygen-containing functional group percentage composition ratio is-C=O:-COH:-
COOR=2:1:1.
As a preferred embodiment, when gas source is air and nitrogen, air and nitrogen flow rate ratio are 9:1, overall flow rate
20ml/min, spray head and Carbon felt surface are set as 1cm, spray head walking speed 20cm/s.
As a preferred embodiment, when gas source is oxygen and nitrogen, oxygen and nitrogen flow rate ratio are 1:1, overall flow rate
50ml/min, spray head and Carbon felt surface are set as 5cm, spray head walking speed 50cm/s.
There are many limitations, such as gaseous cyaniding to have strictly for temperature and time for traditional carbon felt method of modifying
Requirement, the temperature of gaseous cyaniding is generally 400 DEG C, and temperature is excessively high or the time is long will lead to Carbon felt surface excessive oxidation quarter
Erosion.Traditional gaseous cyaniding temperature and time is not easy to accurately control, industrially during continuous production, especially flowing water
It is difficult to apply in operation.However the present invention uses plasma spraying method changing for vanadium redox flow battery electrode carbon felt for the first time
Property.The method of modifying can operate at normal temperature, and condition be it is artificial controllable, by control spray gas flow velocity,
Spray head scanning frequency and power can adjust oxygen content, control activation condition, prepare oxygen-containing containing variety classes and different proportion
The carbon felt of functional group is suitable for the design of different demands all-vanadium flow battery.Either still change from production cost, mode of operation
Property effect from the point of view of, method of the invention is more suitable for serialization continuous productive process, be suitable for industrialized production.
Compared with the prior art, the beneficial effects of the invention are that:
1. the present invention realizes full-automatic production, using pipelining, carbon felt after activation relative to conventional activation mode
The more stable nothing of performance obviously fluctuate, without human intervention and real-time monitoring, safety and stability is at low cost and yield is significantly increased
It is obvious to simplify production procedure.
2. relative to conventional high-temperature furnace internal oxidition activation method, plasma cation has high excitation state, it is easier to
A large amount of oxygen-containing functional groups are generated in conjunction with the carbon of carbon felt carbon fiber surface.Simply change the i.e. controllable carbon felt carbon fiber of activation parameter
Surface oxygen functional group type and ratio can prepare the electrode of different demands to control carbon felt overall performance.
3. confirming optimal activation condition by serial experiment, carbon felt performance has compared with conventional activation method and obviously mentions after activation
It rises.
Detailed description of the invention
Fig. 1 is the modified carbon felt schematic device of plasma spraying.Wherein a is perspective view, and b is main view.
Specific embodiment
The present invention is described in detail below by specific embodiment, but is not limited the scope of the invention.Unless otherwise specified, originally
Experimental method used by inventing is conventional method, and experiment equipment used, material, reagent etc. commercially obtain.
Embodiment 1
3mm thickness is not carried out activate after coiled finished product carbon felt is put into the effect of uncoiling machine production line, is driven to be sent by roller bearing and be lived
Change in area, purged using plasma gun, activate carbon felt, activates region normal-temperature.Plasma output power 3500w is set, it is empty
Gas and nitrogen flow rate ratio 9:1, overall flow rate 20ml/min, spray head and Carbon felt surface are set as 1cm, spray head walking speed 20cm/s.
Embodiment 2
5mm thickness is not carried out activate after coiled finished product carbon felt is put into the effect of uncoiling machine production line, is driven to be sent by roller bearing and be lived
Change in area, purged using plasma gun, activate carbon felt, activates region normal-temperature.Set plasma output power 5000w, oxygen
Gas and nitrogen flow rate ratio 1:1, overall flow rate 50ml/min, spray head and Carbon felt surface are set as 5cm, spray head walking speed 50cm/s.
Embodiment 3
7mm thickness is not carried out activate after coiled finished product carbon felt is put into the effect of uncoiling machine production line, is driven to be sent by roller bearing and be lived
Change in area, purged using plasma gun, activate carbon felt, activates region normal-temperature.Plasma output power 8000w is set, it is empty
Gas velocity 100ml/min, spray head and Carbon felt surface are set as 8cm, spray head walking speed 30cm/s.
Comparative example 1
5mm thickness is not carried out activate after coiled finished product carbon felt is put into the effect of uncoiling machine production line, is driven to be sent by roller bearing and be lived
Change in area, is purged using plasma gun, activate carbon felt.Set plasma output power 5000w, oxygen and nitrogen flow rate
Than 1:1, overall flow rate 250ml/min, spray head and Carbon felt surface are set as 5cm, spray head walking speed 50cm/s.
Comparative example 2
5mm thickness is not carried out activate after coiled finished product carbon felt is put into the effect of uncoiling machine production line, is driven to be sent by roller bearing and be lived
Change in area, is purged using plasma gun, activate carbon felt.Set plasma output power 5000w, oxygen and nitrogen flow rate
Than 1:1, overall flow rate 50ml/min, spray head and Carbon felt surface are set as 25cm, spray head walking speed 50cm/s.
Comparative example 3
Using traditional hot-air oxidative treatment carbon felt.Carbon felt thickness 3mm, dry air 100ml/min flow velocity, 400 DEG C
Lower heat treatment 4h.
Comparative example 4
Using traditional concentrated sulfuric acid oxidative treatment carbon felt.Carbon felt thickness 3mm impregnates carbon felt electrode in the 4mol/L concentrated sulfuric acid
It is washed with deionized water again after 12h, 80 DEG C of dry 12h.
Following performance evaluation is carried out to embodiment 1-3 and comparative example 1-4 modified product.
1 performance evaluation of table
| Characteristic manner | Performance indicator |
| Thermogravimetric | Phosphorus content |
| XPS | Oxygen-containing functional group type and content |
| Resistivity | Resistivity tester |
| Battery efficiency | Monocell test macro |
Experimental test result is as shown in table 2.
2 embodiment of table and comparative example performance parameter
By above-mentioned experimental data it is found that gas flow rate, spray head scanning frequency, spray head and carbon felt surface distance and power to carbon
Vital influence is played in felt modification, is closely related between each parameter.It can be obtained by the adjustment to above-mentioned parameter
The carbon felt of variety classes and different proportion oxygen-containing functional group obtains the production of different single battery voltage efficiency, energy efficiency, resistivity
Product adapt to the design of different demands all-vanadium flow battery.In general, method of the invention is more suitable for serialization flowing water work
It is modified to be suitable for high-volume carbon felt for industry.
The preferable specific embodiment of the above, only the invention, but the protection scope of the invention is not
It is confined to this, anyone skilled in the art is in the technical scope that the invention discloses, according to the present invention
The technical solution of creation and its inventive concept are subject to equivalent substitution or change, should all cover the invention protection scope it
It is interior.
Claims (7)
1. a kind of method of modifying of vanadium redox flow battery electrode carbon felt, which comprises the following steps: will be without making a living
The coiled carbon felt for changing processing is driven in feeding region of activation by roller bearing and is activated by gas plasma spray gun, in carbon felt carbon
Fiber surface grows oxygen-containing functional group, wherein plasma gun activation process conditional are as follows: with a kind of in air, oxygen, nitrogen
Or two or more gases are as gas source, gas flow rate 0.1-100ml/min, spray head and Carbon felt surface distance 0.1-10cm, spray head
Scanning frequency 0.1-50cm/s, plasma gun power 2000-25000W.
2. method of modifying according to claim 1, which is characterized in that the oxygen-containing functional group include-COH ,-C=O ,-
COOH、-COOR。
3. method of modifying according to claim 1, which is characterized in that oxygen-containing functional group percentage composition ratio is-C=O:-
COH:-COOR=2:1:1.
4. method of modifying according to claim 1, which is characterized in that gas flow rate 20-100ml/min, spray head and carbon felt
Surface distance 1-10cm, spray head walking speed 20-50cm/s, plasma gun power 2500-8000W.
5. method of modifying according to claim 1, which is characterized in that when gas source is air and nitrogen, air and nitrogen stream
Speed ratio is 9:1, overall flow rate 20ml/min, and spray head and Carbon felt surface are set as 1cm, spray head walking speed 20cm/s.
6. method of modifying according to claim 1, which is characterized in that when gas source is oxygen and nitrogen, oxygen and nitrogen stream
Speed ratio is 1:1, overall flow rate 50ml/min, and spray head and Carbon felt surface are set as 5cm, spray head walking speed 50cm/s.
7. method of modifying according to claim 1, which is characterized in that temperature is 20-80 DEG C in region of activation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810385706.2A CN110416554B (en) | 2018-04-26 | 2018-04-26 | Modification method of carbon felt for all-vanadium redox flow battery electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810385706.2A CN110416554B (en) | 2018-04-26 | 2018-04-26 | Modification method of carbon felt for all-vanadium redox flow battery electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110416554A true CN110416554A (en) | 2019-11-05 |
| CN110416554B CN110416554B (en) | 2021-02-02 |
Family
ID=68345712
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810385706.2A Active CN110416554B (en) | 2018-04-26 | 2018-04-26 | Modification method of carbon felt for all-vanadium redox flow battery electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110416554B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114695833A (en) * | 2022-03-01 | 2022-07-01 | 北京化工大学 | Lithium dendrite inhibition device, system and method for lithium metal battery negative electrode material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103441288A (en) * | 2013-09-16 | 2013-12-11 | 大连理工高邮研究院有限公司 | Method for producing carbon felt electrode material for flow battery |
| CN103825033A (en) * | 2014-03-13 | 2014-05-28 | 大连融科储能技术发展有限公司 | Electrode material treating method for electrochemical flow cell |
| US20180108916A1 (en) * | 2016-10-18 | 2018-04-19 | Lockheed Martin Advanced Energy Storage, Llc | Flow batteries having an electrode with differing hydrophilicity on opposing faces and methods for production and use thereof |
-
2018
- 2018-04-26 CN CN201810385706.2A patent/CN110416554B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103441288A (en) * | 2013-09-16 | 2013-12-11 | 大连理工高邮研究院有限公司 | Method for producing carbon felt electrode material for flow battery |
| CN103825033A (en) * | 2014-03-13 | 2014-05-28 | 大连融科储能技术发展有限公司 | Electrode material treating method for electrochemical flow cell |
| US20180108916A1 (en) * | 2016-10-18 | 2018-04-19 | Lockheed Martin Advanced Energy Storage, Llc | Flow batteries having an electrode with differing hydrophilicity on opposing faces and methods for production and use thereof |
Non-Patent Citations (2)
| Title |
|---|
| WENYUELI等: "Reduced graphene oxide with tunable C/O ratio and its activity towards vanadium redox pairs for an all vanadium redox flow battery", 《CARBON》 * |
| YUQING HUANG等: "N, O Co-doped carbon felt for high-performance all-vanadium redox flow battery", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114695833A (en) * | 2022-03-01 | 2022-07-01 | 北京化工大学 | Lithium dendrite inhibition device, system and method for lithium metal battery negative electrode material |
| CN114695833B (en) * | 2022-03-01 | 2024-04-26 | 北京化工大学 | Lithium dendrite suppression device, system and method for negative electrode material of lithium metal battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110416554B (en) | 2021-02-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105484012B (en) | A kind of polyacrylonitrile carbon fiber surface treatment method and device | |
| CN112609199A (en) | Electrocatalysis H2O2Solution preparation method and device | |
| CN106757174A (en) | A kind of electro-deposition prepares the method and device of metal dust | |
| CN104409738A (en) | Making method of conductive carbon black/nanometer carbon fiber composite electrode for all-vanadium redox flow battery | |
| CN104928709A (en) | Electrolytic system of manganese dioxide and production method of manganese dioxide | |
| CN109607705A (en) | A kind of industry water dechlorination method | |
| WO2011120441A1 (en) | Paired electrosynthetic method for producing butanedioic acid and sulfuric acid | |
| CN110416554A (en) | A kind of method of modifying of vanadium redox flow battery electrode carbon felt | |
| CN209276647U (en) | It is a kind of to utilize decomposing water with solar energy device for producing hydrogen | |
| CN105297395A (en) | Method and apparatus for liquid phase plasma continuous treatment of surface of carbon fiber | |
| CN214141734U (en) | H2O2Solution electrocatalysis preparation and sewage treatment integrated system | |
| CN105063108B (en) | A kind of intensifying method of biology electrodialysis production malic acid | |
| CN205873976U (en) | Electric catalytic oxidation reaction unit who contains many react unit | |
| CN110747487A (en) | Water electrolysis oxygen generation system and air quality control system of closed space | |
| CN103560255B (en) | Carrier material of a kind of oxygen reduction catalyst for zinc-air battery and preparation method thereof | |
| CN103825033B (en) | A kind of flow battery electrode material processing method | |
| EP3856955A1 (en) | Method for removing non-proton cationic impurities from an electrochemical cell and an electrochemical cell | |
| CN105624727A (en) | Method for simultaneously producing electrolytic manganese metal and electrolytic manganese dioxide in one electrolysis bath | |
| CN115275217A (en) | Semi-continuous core-shell structure catalyst preparation device | |
| CN202164492U (en) | Single-tow fiber surface treatment device | |
| CN211394645U (en) | Water electrolysis oxygen production equipment | |
| CN210458383U (en) | Device suitable for inorganic salt electrolysis | |
| CN110863212A (en) | Water electrolysis oxygen generation system and air quality control system of closed space | |
| CN219099334U (en) | Movable hydrogen peroxide preparation facilities | |
| CN202152430U (en) | Multi-tow fiber surface treatment device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |