CN102956899A - Phosphor doping method of graphite felt electrode for all-vanadium redox flow battery - Google Patents
Phosphor doping method of graphite felt electrode for all-vanadium redox flow battery Download PDFInfo
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- CN102956899A CN102956899A CN2012104652382A CN201210465238A CN102956899A CN 102956899 A CN102956899 A CN 102956899A CN 2012104652382 A CN2012104652382 A CN 2012104652382A CN 201210465238 A CN201210465238 A CN 201210465238A CN 102956899 A CN102956899 A CN 102956899A
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Abstract
The invention relates to a phosphor doping method of a graphite felt electrode for an all-vanadium redox flow battery. The method comprises the steps of: ultrasonically cleaning a graphite felt; drying the ultrasonically cleaned graphite felt; shearing the graphite felt according to a specified dimension and placing the graphite felt into a reaction chamber as a basal body (or a substrate); vacuumizing the reaction chamber; introducing inertial gases containing phosphorus at a certain flow in reaction; and treating the graphite felt by sputtering into the phosphorus containing atmosphere by using a linear ion beam source device or a sealed electron cyclotron resonance plasma sputtering device so as to increase the number of phosphorus containing functional groups on the surface of the graphite felt and the phosphorus content. The phosphor doping method of the graphite felt electrode for the all-vanadium redox flow battery provided by the invention has the advantages of novel concept and environment-friendly method. On the one hand, impurities on the surface of the graphite felt can be removed, the phosphorus content on the surface of the graphite felt is increased and the electrochemical performance of the graphite felt is improved. On the other hand, the regularity of carbon material is improved, and the cyclizing process of the graphite felt material is promoted and the number of pores of the graphite felt is increased.
Description
Technical field
The present invention relates to the processing method of the graphite felt electrode in all-vanadium flow battery field, particularly a kind of method of used for all-vanadium redox flow battery graphite felt electrode phosphorus doping.
Background technology
In recent years, along with to the going deep into of material with carbon element research, it is found that the material with carbon element body mutually in introducing oxygen, nitrogen, sulphur and phosphorus etc., can improve chemical property, mechanical performance, the optical property of material with carbon element.And at foreign atoms such as carbon material surface introducing oxygen, nitrogen, sulphur and phosphorus, can significantly increase the carbon material surface activity, make its aspect such as adsorption process at electric transmission flow and reaction medium all show better performance, and then become the study hotspot of electrochemical cell electrode material.
The all-vanadium flow battery of using now adopts graphite felt as battery electrode usually.According to the knowledge of the applicant, graphite felt need to strengthen its electro-chemical activity by modification because electro-chemical activity is not strong.Graphite felt modification commonly used has air oxidation process, strong acid oxidizing process and ammoniation process etc.
Wherein, air oxidation process causes the graphite felt surface etch easily; The strong acid oxidizing process is even more serious to the corrosion on graphite felt surface, as being published in the technical method of document " chemical modification of graphite felt electrode and the electrochemical behavior in the acid vanadium solution thereof " introduction on the China YouSe Acta Metallurgica Sinica in August, 2005, the concrete application of adopting exactly the strong acid oxidizing process that graphite felt is processed, the applicant finds through research, this technical method is applied to suitability for industrialized production, environmental requirement is high, and can cause the carbon fiber surface vigorous reaction, make fiber surface corrosion occur, can cause the consequence that reduces the materials'use life-span; And it is very tight to the reaction condition requirement to adopt ammoniation process that graphite felt is carried out modification, for example a kind of ammonification processing method of master's thesis of Central South University in 2011 " research of all-vanadium flow battery graphite felt electrode modification " introduction is exactly like this, the method is used reactor that graphite felt is carried out ammonification and is processed, but the nitrogen element content of graphite felt is not high after processing, and reaction condition is very harsh.
At present, the research of mixing phosphorus in the material with carbon element is less, during " mixing preparation and the behavior of embedding lithium thereof of phosphorus material with carbon element ", adopt by the document that is published in battery magazine in August, 2000 one-step method to prepare thermosetting phenolic resin, determine suitable carburizing temperature by charge-discharge test, and then prepared the doping phenolic resins pyrolysis carbon of different phosphorus contents.The result shows that the ordering degree of material with carbon element improves, and surface activity strengthens, and improves the embedding lithium ability of lithium battery.Wherein, phosphorus mainly links to each other with carbocyclic ring with covalent bond, mix but the method belongs to body, and if the method be used for graphite felt, will the preparation technology of graphite felt be made amendment, can increase the production process of graphite felt, reduce the production efficiency of graphite felt.
Chinese patent literature CN 101182678A(number of patent application 200710202374.1) disclosed " graphite felt surface modifying method and modified graphite felt " provides a kind of modification processing method that can improve simultaneously graphite felt wettability and electro-chemical activity.The method adopts the modification of electrochemistry negative electrode to combine with traditional Anodic modification the graphite felt electrode surface to be carried out modification, its wettability and electro-chemical activity are improved, thus voltage efficiency and discharge performance in the raising battery charge and discharge process.The graphite felt surface modifying treatment that provides: before the anodic oxidation modification, carry out first electrochemistry negative electrode modification.Further, may further comprise the steps: a. the electrochemistry cathode treatment: take graphite felt as negative electrode, alkali lye is electrolyte, passes into direct current graphite felt is carried out electrochemistry negative electrode modification, then cleans the alkali lye on graphite felt surface with distilled water; B. electrochemical anodic oxidation modification: cleaned clean graphite felt is made anode, take the sulfuric acid solution of 0.05 ~ 4M as electrolyte, pass into direct current graphite felt is carried out the anodic oxidation modification.Can clean the acid on its surface according to actual conditions needs and subsequent treatment needs, quicker in order to clean, totally wherein, temperature when passing into direct current in a step graphite felt being carried out electrochemistry negative electrode modification is 50 ~ 90 ℃, and current density is 75 ~ 160mA/cm
2, the processing time is 4 ~ l0min.The described electrolyte of a step is at least a in the strong base solution of alkali metal salt soln, 10 ~ 40g/l.Electrolyte can be selected: at least a in the sodium phosphate of the NaOH of 10 ~ 40g/l, the sodium carbonate of 0.1 ~ 20g/1,0.1 ~ 20g/1.Concrete kind and consumption that electrolyte adds can be adjusted definite according to the needs of basicity.In order effectively to process the larger graphite felt of lipophile, can in the described electrolyte of a step, add emulsifying agent 1 ~ 2g/l.Mentioned emulsifier is preferably in soap, odium stearate, the lauryl sodium sulfate at least a.Wherein, the concentration of sulfuric acid solution is preferably 1M in the b step.Graphite felt after the modification has been improved electro-chemical activity greatly as electrode in for the preparation of vanadium redox battery, improve the voltage efficiency of battery discharge, the efficient of the energy content of battery, improved simultaneously its stable discharging time, thereby so that the charge-discharge performance of vanadium redox battery be greatly improved; And operation is simple for the method, do not need special installation, with low cost.Its modification to graphite felt is to carry out electrochemistry negative electrode modification before the anodic oxidation modification, but it has used NaOH and this class of sulfuric acid to have the chemical substance of severe corrosive.Use therein sodium phosphate is that graphite felt is carried out the anode modification during as electrolyte, increases the oxy radical quantity on graphite felt surface, rather than for increasing phosphorus element content in the graphite felt surface.
Summary of the invention
The objective of the invention is, for the problem that above-mentioned prior art exists, propose and study a kind of method of used for all-vanadium redox flow battery graphite felt electrode phosphorus doping.The method environmental protection is convenient to implement.The method is to the graphite felt electrode surface reforming, directly improved the phosphorous number of functional groups in graphite felt surface that participates in reaction, effective controlled doping degree, and the efficient height, and do not damage machinery and the chemical property of graphite felt.
Technical solution of the present invention is, adopt the Ultrasonic Cleaning graphite felt, it is characterized in that, will be through the clean graphite felt oven dry of Ultrasonic Cleaning, put in accordance with regulations reative cell after the size cutting as matrix or substrate, reative cell is vacuumized, pass into the inert gas that contains P elements in the reaction, adopt Linear ion beam source device or closed electronics cyclotron resonance plasma sputter equipment, by sputtering in the phosphorous atmosphere graphite felt is processed, thereby increased the graphite felt phosphorous number of functional groups in surface and phosphorus element content.
It is characterized in that the inert gas that contains P elements that passes in the reaction is the argon gas that contains the part phosphorus compound.
It is characterized in that the voltage or the current parameters that contain the flow of inert gas of P elements and flow-rate ratio, reaction time, instrument by change are adjusted reaction flow and reaction time.
It is characterized in that reative cell vacuumizes rear air pressure and needs less than 5 * 10
-5Handkerchief, the flow velocity that passes into the inert gas that contains P elements is 10ml/min～100ml/min.
It is characterized in that the operating current of Linear ion beam source device is made as 0.1 A～0.5A, operating voltage is controlled at 1400V ± 50V, and the workpiece negative pressure is-100V～-200V, the operating time is 10min～600min.
It is characterized in that, adopt closed electronics cyclotron resonance plasma sputter equipment, when processing as the graphite felt of substrate putting into reative cell, substrate adopts floating potential, perhaps add-120V～+ bias voltage of 120V.
Innovative point of the present invention is: 1, adopt Linear ion beam source device or closed electronics cyclotron resonance plasma sputter equipment that graphite felt is processed.2, use the present invention that graphite felt is carried out phosphatization and process, can increase the phosphorus element content on graphite felt surface.3, the present invention can remove the impurity such as amorphous carbon on graphite felt surface, and the graphite felt surface is not caused damage, thus the chemism of Effective Raise graphite felt.
Advantage of the present invention is, and is novel, the method environmental protection.The present invention processes the graphite felt electrode, can remove the impurity on graphite felt surface on the one hand, increases the content of graphite felt surface P elements, improves the chemical property of graphite felt.The phosphorus that mixes on the other hand can enter in the carbon-coating space of graphite felt, has improved the systematicness of material with carbon element, promotes simultaneously the cyclization process of graphite felt material, and wetability and the electro-chemical activity of graphite felt can improve in phosphorous functional group, and increases the micropore quantity of graphite felt.
Embodiment
Below, describe embodiments of the invention in detail:
The present invention adopts the Ultrasonic Cleaning graphite felt, will be through the clean graphite felt oven dry of Ultrasonic Cleaning, put in accordance with regulations reative cell after the size cutting as matrix or substrate, reative cell is vacuumized, pass into the inert gas that contains P elements with certain flow in the reaction, adopt Linear ion beam source device or closed electronics cyclotron resonance plasma sputter equipment, by sputtering in the phosphorous atmosphere graphite felt is processed, thereby increase the graphite felt phosphorous number of functional groups in surface and phosphorus element content.
Embodiment 1:
(1) graphite felt is put into deionized water, ultrasonic 15min, then drying uses deionized water rinsing, dry for standby.
The graphite felt that (2) will be cut into suitable size is put into reative cell as matrix, and reative cell is vacuumized, and reative cell vacuumizes rear air pressure and needs less than 5 * 10
-5Handkerchief, the speed with 30ml/min during reaction passes into the argon gas (a kind of inert gas) that contains 10% hydrogen phosphide, and the flow velocity that passes into the inert gas that contains P elements is 10 ml/min～100ml/min.Adopt Linear ion beam source device by the method for (linear ion bundle mixing magnetic control) sputter the graphite felt surface to be processed.Wherein, the operating current of Linear ion beam source device is made as 0.2A, and operating voltage is controlled at 1400 V ± 50V, and the workpiece negative pressure is-200V that the reaction time is 50min.
(3) use distilled water to clean treated graphite felt, dry 12h in 120 ℃ of baking ovens.
The graphite felt that use the present invention obtains is as the electrode fabrication material of vanadium cell.
Embodiment 2:
(1) graphite felt is put into deionized water, ultrasonic 15min, then drying uses deionized water rinsing, dry for standby.
The graphite felt that (2) will be cut into suitable size is put into reative cell as substrate, and reative cell is vacuumized, and reative cell vacuumizes rear air pressure and needs less than 5 * 10
-5Handkerchief, the speed with 30ml/min during reaction passes into the argon gas (a kind of inert gas) that contains 10% hydrogen phosphide, and the flow velocity that passes into the inert gas that contains P elements is 10ml/min～100ml/min.Adopt closed electronics cyclotron resonance plasma sputter equipment, by the method for (closed electronics cyclotron resonance plasma) sputter the graphite felt surface is processed, the reaction time is 200min.
The vacuum degree of reative cell is 2 * 10 before processing
-6Pa, the vacuum degree when being filled with the laggard row reaction of gas is 2 * 10
-2Pa.
(3) use distilled water to clean treated graphite felt, dry 12h in 120 ℃ of baking ovens.
Adopt closed electronics cyclotron resonance plasma sputter equipment, when processing as the graphite felt of substrate putting into reative cell, substrate can be floating potential, also can add-120V～+ bias voltage of 120V.
The graphite felt that use the present invention obtains is as the electrode fabrication material of vanadium cell.
Claims (6)
1. the method for a used for all-vanadium redox flow battery graphite felt electrode phosphorus doping, adopt the Ultrasonic Cleaning graphite felt, it is characterized in that, will be through the clean graphite felt oven dry of Ultrasonic Cleaning, put in accordance with regulations reative cell after the size cutting as matrix or substrate, reative cell is vacuumized, pass into the inert gas that contains P elements with certain flow in the reaction, adopt Linear ion beam source device or closed electronics cyclotron resonance plasma sputter equipment, by sputtering in the phosphorous atmosphere graphite felt is processed, thereby increased the graphite felt phosphorous number of functional groups in surface and phosphorus element content.
2. the method for a kind of used for all-vanadium redox flow battery graphite felt electrode phosphorus doping according to claim 1 is characterized in that, the inert gas that contains P elements that passes into certain flow in the reaction is the argon gas that contains the part phosphorus compound.
3. the method for a kind of used for all-vanadium redox flow battery graphite felt electrode phosphorus doping according to claim 1, it is characterized in that the voltage or the current parameters that contain the flow of inert gas of P elements and flow-rate ratio, reaction time, instrument by change are adjusted reaction flow and time.
4. the method for a kind of used for all-vanadium redox flow battery graphite felt electrode phosphorus doping according to claim 1 is characterized in that, reative cell vacuumizes rear air pressure and needs less than 5 * 10
-5Handkerchief, the flow velocity that passes into the inert gas that contains P elements is 10 ml/min ~ 100ml/min.
5. the method for a kind of used for all-vanadium redox flow battery graphite felt electrode phosphorus doping according to claim 1, it is characterized in that, the operating current of Linear ion beam source device is made as 0.1A～0.5A, operating voltage is controlled at 1400V ± 50V, the workpiece negative film press for-100V～-200V, the operating time is 10min～600min.
6. the method for a kind of used for all-vanadium redox flow battery graphite felt electrode phosphorus doping according to claim 1 is characterized in that, for closed electronics cyclotron resonance plasma sputter equipment, substrate can be floating potential, also can add-120V～+ bias voltage of 120V.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106654235A (en) * | 2017-02-08 | 2017-05-10 | 深圳市贝特瑞新能源材料股份有限公司 | Composite graphite material and preparation method thereof and lithium-ion battery comprising composite graphite material |
| CN108539210A (en) * | 2017-03-03 | 2018-09-14 | 湖南省银峰新能源有限公司 | Heteroatom doping flow battery electrode material |
| CN109216709A (en) * | 2017-06-29 | 2019-01-15 | 中国科学院金属研究所 | A kind of dig pit effect construction method and its application of high-ratio surface carbon fiber felt |
| CN109244483A (en) * | 2018-02-08 | 2019-01-18 | 成都理工大学 | A kind of bigger serface N doping carbon cloth electrode and preparation method thereof, application |
| CN110534757A (en) * | 2019-09-11 | 2019-12-03 | 上海交通大学 | High performance carbon electrode and preparation method thereof |
| CN114555853A (en) * | 2019-10-09 | 2022-05-27 | 欧瑞康表面处理解决方案股份公司普费菲孔 | Method for manufacturing cast iron brake disc with high corrosion and wear resistance |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106654235A (en) * | 2017-02-08 | 2017-05-10 | 深圳市贝特瑞新能源材料股份有限公司 | Composite graphite material and preparation method thereof and lithium-ion battery comprising composite graphite material |
| CN106654235B (en) * | 2017-02-08 | 2020-01-24 | 深圳市贝特瑞新能源材料股份有限公司 | Composite graphite material, preparation method thereof and lithium ion battery containing composite graphite material |
| CN108539210A (en) * | 2017-03-03 | 2018-09-14 | 湖南省银峰新能源有限公司 | Heteroatom doping flow battery electrode material |
| CN109216709A (en) * | 2017-06-29 | 2019-01-15 | 中国科学院金属研究所 | A kind of dig pit effect construction method and its application of high-ratio surface carbon fiber felt |
| CN109244483A (en) * | 2018-02-08 | 2019-01-18 | 成都理工大学 | A kind of bigger serface N doping carbon cloth electrode and preparation method thereof, application |
| CN110534757A (en) * | 2019-09-11 | 2019-12-03 | 上海交通大学 | High performance carbon electrode and preparation method thereof |
| CN114555853A (en) * | 2019-10-09 | 2022-05-27 | 欧瑞康表面处理解决方案股份公司普费菲孔 | Method for manufacturing cast iron brake disc with high corrosion and wear resistance |
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