CN108054390A - A kind of method of modifying of efficiently and effectively graphite felt for vanadium cell - Google Patents
A kind of method of modifying of efficiently and effectively graphite felt for vanadium cell Download PDFInfo
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- CN108054390A CN108054390A CN201711221783.6A CN201711221783A CN108054390A CN 108054390 A CN108054390 A CN 108054390A CN 201711221783 A CN201711221783 A CN 201711221783A CN 108054390 A CN108054390 A CN 108054390A
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- graphite felt
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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
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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
A kind of method of modifying of efficiently and effectively graphite felt for vanadium cell, this method is that graphite felt is immersed in containing Bi3+Solution in；And modified vanadium redox battery electrode is obtained in graphite felt surface electrodeposit metals bismuth using constant-voltage method.Compared with prior art, the beneficial effects of the invention are as follows：1) vanadium redox battery of the modified graphite felt of method using the present invention as electrode, voltage efficiency, the energy efficiency of battery significantly improve, so that the electro-chemical activity of vanadium redox battery improves, activation polarization reduces.2) method of modifying of vanadium redox battery graphite felt of the invention it is faster, evenly, it is more cheap, by the suitable bismuth metal of the uniform electro-deposition in graphite felt surface, achieve the purpose that the electro-chemical activity for improving graphite felt electrode.
Description
Technical field
The present invention relates to vanadium redox battery field more particularly to a kind of efficiently and effectively vanadium cell graphite
The method of modifying of felt.
Background technology
In recent years, wind energy and solar energy are widely developed and utilized, but no matter wind energy or solar energy, because scarce
The large-scale energy-storage battery of few function admirable is matched and cannot efficiently utilize application.Vanadium redox battery is a kind of
Can depth charge and discharge secondary cell, be a kind of model electrochemical energy storage device, have that energy efficiency is high, service life is long and ring
The features such as border is friendly, it is considered to be the most large-scale energy-storage battery of application prospect more and more attracts attention.
Critical material of the electrode as vanadium redox battery, hydrophily and electro-chemical activity affect full vanadium
The chemical property of redox flow batteries.At present, graphite felt electrode with its high temperature resistant, it is corrosion-resistant, conduct electricity very well etc. it is excellent
Point becomes most common electrode in vanadium redox battery, but poor hydrophily and electro-chemical activity limit graphite
The application of felt.Therefore, it is of great significance for the study on the modification of graphite felt electrode.
At present, the method for full vanadium oxidation flow battery graphite felt electrode modification mainly has and increases active function groups, carries
Height reaction effective area and addition surface catalyst, but the agility of above-mentioned processing method and uniformity are all to be improved.
The content of the invention
The object of the present invention is to provide a kind of method of modifying of efficiently and effectively graphite felt for vanadium cell, for improving full vanadium
The electro-chemical activity of redox flow batteries graphite felt electrode.
To achieve the above object, the present invention is realized using following technical scheme：
A kind of method of modifying of efficiently and effectively graphite felt for vanadium cell, this method is that graphite felt is immersed in containing Bi3+
Solution in；And modified vanadium redox electricity is obtained in graphite felt surface electrodeposit metals bismuth using constant-voltage method
Pond electrode, specific method are as follows：
1) Bi is prepared3+Solution：In the dilute hydrochloric acid solution for being 1~3mol/L in concentration, room temperature makes Bi3+Concentration is
The Bi of 0.05~0.2mol/L3+Solution；
2) graphite felt surface carries out electro-deposition：Graphite felt Jing Guo cleaning pretreatment is impregnated into prepare 0.05~
The Bi of 0.2mol/L3+In solution, 30~50min is disperseed with the frequency ultrasound of 1~100kHz with ultrasonic washing instrument；By two pieces
Graphite felt after dipping is connected to the positive and negative anodes of constant voltage supply and submerges Bi3+In solution, constant voltage is passed to；Graphite felt table
Face deposited metal bismuth particle；Graphite felt after electro-deposition is removed, is stood, it is spare.
The Bi3+Solution is by BiCl3Or Bi2O3It is formulated with the dilute hydrochloric acid of 1~3mol/L.
Constant voltage≤the 1.6V.
Graphite felt passes to sedimentation time≤30min after constant voltage.
Compared with prior art, the beneficial effects of the invention are as follows：
1) vanadium redox battery of the modified graphite felt of method using the present invention as electrode, battery
Voltage efficiency, energy efficiency significantly improve, so that the electro-chemical activity of vanadium redox battery improves, electrochemistry pole
Changing reduces.
2) method of modifying of vanadium redox battery graphite felt of the invention it is faster, evenly, it is more cheap,
By the suitable bismuth metal of the uniform electro-deposition in graphite felt surface, achieve the purpose that the electro-chemical activity for improving graphite felt electrode.
Description of the drawings
Fig. 1 is the operation chart of the method for modifying of graphite felt of the present invention.
Specific embodiment
The present invention is described in detail below in conjunction with the accompanying drawings, it should be noted that the present invention implementation be not limited to it is following
Embodiment.
A kind of method of modifying of efficiently and effectively graphite felt for vanadium cell, this method is that graphite felt is immersed in containing Bi3+
Solution in；And modified vanadium redox electricity is obtained in graphite felt surface electrodeposit metals bismuth using constant-voltage method
Pond electrode, specific method are as follows：
Graphite felt first carries out cleaning pretreatment：The purpose that cleaning pretreatment is carried out to graphite felt is to remove graphite felt surface
Graphite felt is put into deionized water cleans 40min with microwave cleaning device with the frequency ultrasonic wave concussion of 10kHz first by impurity,
To remove the insoluble impurities on graphite felt surface, and make soluble impurity soluble in water；Then graphite felt is placed in 1mol/L
1h is impregnated in 80 DEG C of water-baths in NaOH solution, to remove organic impurities, takes out graphite felt, is cleaned multiple times with deionized water to PH
=7, it is put into 80 DEG C of dryings in drying box.However, the invention is not limited thereto, it can be equal to the method for graphite felt cleaning pretreatment
It can.
1) Bi is prepared3+Solution：In the dilute hydrochloric acid solution for being 1~3mol/L in concentration, room temperature makes Bi3+Concentration is
The Bi of 0.05~0.2mol/L3+Solution；
2) graphite felt surface carries out electro-deposition：Graphite felt Jing Guo cleaning pretreatment is impregnated into prepare 0.05~
The Bi of 0.2mol/L3+In solution, 30~50min is disperseed with the frequency ultrasound of 1~100kHz with ultrasonic washing instrument；By two pieces
Graphite felt after dipping is connected to the positive and negative anodes of constant voltage supply and submerges Bi3+In solution, constant voltage is passed to；Graphite felt table
Face deposited metal bismuth particle；Graphite felt after electro-deposition is removed, is stood, it is spare.
In order to ensure Bi in solution3+Concentration will not be changed due to the volatilization of HCl, stand and electrodeposition process in
Bi3+Solution should be sealed.
In order to ensure constant pressure electro-deposition and the linear relationship of deposition voltage, the Bi of 0.05~0.2mol/L3+Solution should be unified
The Bi for preparing and more renewing before each electro-deposition3+Solution；The pattern of graphite felt used, size should be consistent, and soak completely
Not yet.
The Bi3+Solution is by BiCl3Or Bi2O3It is formulated with the dilute hydrochloric acid of 1~3mol/L.
Prepare Bi3+During solution, the BiCl of certain mass is weighed3Or Bi2O3It is dissolved in the dilute hydrochloric acid of respective volume, under room temperature
It stirs to mixing BiCl3Or Bi2O3It is completely dissolved in dilute hydrochloric acid, is configured to the BiCl of 0.05~0.2mol/L water white transparencies3Solution.
Constant voltage≤the 1.6V.Preferred voltage is 1.2V.
Graphite felt passes to sedimentation time≤30min after constant voltage.It is preferred that the sedimentation time is 10min.
The graphite felt that the present invention is modified is applied to a kind of vanadium redox battery, which includes：Electrode, just
Pole electrolyte, electrolyte liquid and membrane.The basis material of electrode is graphite felt and is electrodeposited in matrix surface as catalysis
The bismuth metal of agent.Positive and negative anodes electrolyte is vanadium ion and the mixed electrolytic solution of sulfuric acid solution, and 1MV may be employed in anode electrolyte4+
+3MH2SO4, 1MV may be employed in electrolyte liquid3++3MH2SO4。
Embodiment 1：
3cm × 3cm graphite felts after cleaning pretreatment are impregnated into the fresh 0.1mol/L BiCl of 200ml3In solution, use
Ultrasonic washing instrument disperses 40min with the frequency ultrasound of 10kHz；Graphite felt after two pieces of dippings is connected to constant voltage supply
Positive and negative anodes and submerge the BiCl of 0.1mol/L3In solution, the constant voltage of 0.8V is passed to；After 10min, graphite felt surface deposition
The bismuth metal particle of corrresponding quality；Graphite felt after electro-deposition is removed, is stood.By the use of treated graphite felt as entirely
The negative electrode assembling monocell of vanadium oxide reduction flow battery, in 20-80mA/cm2Current density under carry out charge and discharge electrical measurement
The monocell assembled with untreated graphite felt, current density 20mA/cm are compared in examination2When voltage efficiency improve 4.60%；Electricity
Current density is 80mA/cm2When voltage efficiency improve 15.98%, energy efficiency improve 42.38%.
Embodiment 2：
3cm × 3cm graphite felts after cleaning pretreatment are impregnated into the fresh 0.1mol/L BiCl of 200ml3In solution, use
Ultrasonic washing instrument disperses 40min with the frequency ultrasound of 10kHz；Graphite felt after two pieces of dippings is connected to constant voltage supply
Positive and negative anodes and submerge BiCl3In solution, the constant voltage of 1.2V is passed to；After 10min, graphite felt surface deposited corrresponding quality
Bismuth metal particle；Graphite felt after electro-deposition is removed, is stood.By the use of treated graphite felt as whole vanadium oxide reduction
The negative electrode assembling monocell of flow battery, in 20-80mA/cm2Current density under carry out charge-discharge test, compare with not
Handle the monocell of graphite felt assembling, current density 20mA/cm2When voltage efficiency improve 8.58%, energy efficiency improve
3.05%；Current density is 80mA/cm2When voltage efficiency improve 35.31%, energy efficiency improve 63.90%.
Embodiment 3：
3cm × 3cm graphite felts after cleaning pretreatment are impregnated into the fresh 0.1mol/L BiCl of 200ml3In solution, use
Ultrasonic washing instrument disperses 40min with the frequency ultrasound of 10kHz；Graphite felt after two pieces of dippings is connected to constant voltage supply
Positive and negative anodes and submerge BiCl3In solution, the constant voltage of 1.6V is passed to；After 10min, graphite felt surface deposited corrresponding quality
Bismuth metal particle；Graphite felt after electro-deposition is removed, is stood.By the use of treated graphite felt as whole vanadium oxide reduction
The negative electrode assembling monocell of flow battery, in 20-80mA/cm2Current density under carry out charge-discharge test, compare with not
The monocell of graphite felt assembling is handled, energy efficiency can improve 1.31%.
In conclusion using the vanadium redox battery modified electrode of the method for the present invention, electro-chemical activity
It improves, activation polarization reduction, passes to the modified electrode of the constant voltage 10min of 1.2V, the voltage efficiency and energy of battery
Efficiency all significantly improves, and this phenomenon becomes apparent at higher current densities.
Although having been combined exemplary embodiment above describes the present invention, those skilled in the art should be clear
Chu in the case where not departing from the requirement of spirit and scope by the claims, can carry out various modifications above-described embodiment.
Claims (4)
1. a kind of method of modifying of efficiently and effectively graphite felt for vanadium cell, which is characterized in that this method is to impregnate graphite felt
Containing Bi3+Solution in；And it is aoxidized using constant-voltage method in graphite felt surface electrodeposit metals bismuth to obtain modified full vanadium
Electrode of liquid flow cell is reduced, specific method is as follows：
1) Bi is prepared3+Solution：In the dilute hydrochloric acid solution for being 1~3mol/L in concentration, room temperature makes Bi3+Concentration for 0.05~
The Bi of 0.2mol/L3+Solution；
2) graphite felt surface carries out electro-deposition：Graphite felt Jing Guo cleaning pretreatment is impregnated into prepare 0.05~
The Bi of 0.2mol/L3+In solution, 30~50min is disperseed with the frequency ultrasound of 1~100kHz with ultrasonic washing instrument；By two pieces of leachings
Graphite felt after stain is connected to the positive and negative anodes of constant voltage supply and submerges Bi3+In solution, constant voltage is passed to；Graphite felt surface
Deposited metal bismuth particle；Graphite felt after electro-deposition is removed, is stood, it is spare.
A kind of 2. method of modifying of efficiently and effectively graphite felt for vanadium cell according to claim 1, which is characterized in that institute
The Bi stated3+Solution is by BiCl3Or Bi2O3It is formulated with the dilute hydrochloric acid of 1~3mol/L.
A kind of 3. method of modifying of efficiently and effectively graphite felt for vanadium cell according to claim 1, which is characterized in that institute
Constant voltage≤the 1.6V stated.
A kind of 4. method of modifying of efficiently and effectively graphite felt for vanadium cell according to claim 1, which is characterized in that stone
Black felt passes to sedimentation time≤30min after constant voltage.
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Cited By (5)
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|---|---|---|---|---|
| CN111653799A (en) * | 2020-07-16 | 2020-09-11 | 盐城工学院 | Pretreatment method of tin cathode of tin-based alkaline flow battery |
| CN112054215A (en) * | 2020-08-05 | 2020-12-08 | 深圳大学 | Composite electrode for redox flow battery based on all vanadium and preparation method thereof |
| CN114497580A (en) * | 2020-11-12 | 2022-05-13 | 中国科学院大连化学物理研究所 | Electrode and application of electrode as negative electrode in all-vanadium redox flow battery |
| CN115472849A (en) * | 2022-10-25 | 2022-12-13 | 辽宁金谷炭材料股份有限公司 | Preparation method of composite carbon felt electrode of all-vanadium redox flow battery |
| CN115632132A (en) * | 2022-10-25 | 2023-01-20 | 辽宁金谷炭材料股份有限公司 | Preparation method of composite electrode of iron-chromium flow battery |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111653799A (en) * | 2020-07-16 | 2020-09-11 | 盐城工学院 | Pretreatment method of tin cathode of tin-based alkaline flow battery |
| CN111653799B (en) * | 2020-07-16 | 2022-03-15 | 盐城工学院 | Pretreatment method of tin cathode of tin-based alkaline flow battery |
| CN112054215A (en) * | 2020-08-05 | 2020-12-08 | 深圳大学 | Composite electrode for redox flow battery based on all vanadium and preparation method thereof |
| CN114497580A (en) * | 2020-11-12 | 2022-05-13 | 中国科学院大连化学物理研究所 | Electrode and application of electrode as negative electrode in all-vanadium redox flow battery |
| CN114497580B (en) * | 2020-11-12 | 2023-09-19 | 中国科学院大连化学物理研究所 | Electrode and application of electrode serving as negative electrode in all-vanadium redox flow battery |
| CN115472849A (en) * | 2022-10-25 | 2022-12-13 | 辽宁金谷炭材料股份有限公司 | Preparation method of composite carbon felt electrode of all-vanadium redox flow battery |
| CN115632132A (en) * | 2022-10-25 | 2023-01-20 | 辽宁金谷炭材料股份有限公司 | Preparation method of composite electrode of iron-chromium flow battery |
| CN115632132B (en) * | 2022-10-25 | 2023-10-24 | 辽宁金谷炭材料股份有限公司 | Preparation method of composite electrode of iron-chromium flow battery |
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