CN104319406A - Preparation method of high-performance composite carbon felt - Google Patents
Preparation method of high-performance composite carbon felt Download PDFInfo
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- CN104319406A CN104319406A CN201410608152.XA CN201410608152A CN104319406A CN 104319406 A CN104319406 A CN 104319406A CN 201410608152 A CN201410608152 A CN 201410608152A CN 104319406 A CN104319406 A CN 104319406A
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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
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
- H01M4/8668—Binders
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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 relates to the field of electrode materials for vanadium redox batteries (VRB), in particular to a preparation method of high-performance composite carbon felt, and solves the problems that the existing carbon felt electrode for the vanadium battery is poor in hydrophilicity, small in active area, low in electrochemical activity and conductivity, poor in vanadium ion electric catalytic performance, and low in single battery performance. The preparation method comprises the following steps: taking commercial carbon felt as a raw material, and using a method that a binder is used for binding to prepare the functionalized carbon tube composite carbon felt. The composite carbon felt prepared by the method disclosed by the invention has the advantages of good hydrophilicity, electrochemical catalysis performance, conductivity, chemical stability and single VRB performance. The preparation method disclosed by the invention is simple and easy in operation, the product cost is low, industrialized production is facilitated, environment friendliness is achieved, and the high-performance composite carbon felt can be widely applied to the field of the vanadium redox batteries.
Description
Technical field
The present invention relates to vanadium redox battery (VRB) and use electrode Material Field, specifically a kind of preparation method of suitable high-performance composite carbon felt.
Background technology
Along with the fast development of economy, new energy materials, with its advantage such as environmental friendliness, aboundresources, causes extensive concern.But wherein the renewable energy power generation such as wind energy, solar energy process has discontinuous and unstable shortcoming, in order to address this problem must develop efficient, cheap, pollute less with safe and reliable extensive energy storage technology.Vanadium redox battery (VRB) because its power and energy are independent, have extended cycle life, energy efficiency is high, maintenance cost is low, can the advantage such as fast deep discharge and recharge and be widely used in the energy storage device of wind energy, solar power generation process, power station energy storage, the aspects such as peak load regulation network.Electrode material is one of critical material of restriction vanadium cell development, and a kind of good vanadium cell electrode material should possess the advantages such as good chemical stability, good mechanical performance, superior electro-chemical activity, active electrode response area are large and with low cost.Traditional metal material electrochemical reversibility difference or be easily passivated, although and the noble metal such as platinum, iridium electro-chemical activity is high, good reversibility and chemical stability good, the high cost of this metalloid restricts its large-scale application.Present stage, carbon class material studied widely as graphite felt, graphite, carbon cloth and carbon fiber etc. cause with its good stability and cheap cost, it is the electrode material that application is maximum at present, but this kind of material direct application process electro-chemical activity is low, and battery performance is poor.So modification must be carried out to this kind of material, improve the electro-chemical activity of this kind of material with it.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of high-performance composite carbon felt is provided, solve in prior art that the carbon felt hydrophily existed is poor, poor stability, conductivity are low, electro-chemical activity is low and the problem such as single VRB poor performance.
The preparation method of a kind of high-performance composite carbon felt provided by the invention, comprises the steps:
(1) CNT (carbon nano-tube) after drying process is dissolved in strong acid solution, soak at room temperature certain hour;
(2) CNT (carbon nano-tube) that strong acid in step (1) soaked is carried out suction filtration process, then repeatedly use washed with de-ionized water;
(3) CNT (carbon nano-tube) of step (2) gained is put into a certain amount of deionized water, ultrasonic 30min-60min, add a certain amount of functional group carrier, be made into the solution that mass fraction is 0.2-6%, stir 2-6h;
(4) a certain amount of concentrated hydrochloric acid is added in step (3) gained solution, stir 2-5h;
(5) heating steps (4) gained solution, control temperature scope is 0 ~ 100 DEG C, then adds natrium nitrosum, and the solution of preparation 0.05-2.5%, controls described temperature range between 0 ~ 90 DEG C, reaction 3-9h;
(6) filtration step (5) gained solution, is precipitated thing, then repeatedly cleans described sediment with the ammonium sulfate that concentration is 0.2mol/L-1.5mol/L;
(7) deionized water cleaning step (6) gained sediment is repeatedly utilized;
(8) by step (7) gained drying precipitate, functionalization CNT (carbon nano-tube) is obtained;
(9) be dissolved in deionized water by the functionalization CNT (carbon nano-tube) of step (8) gained, preparation mass fraction is the solution of 5%-35%;
(10) a certain amount of Nafion solution is added in step (9) gained solution;
(11) dried carbon felt is immersed in the solution of step (10) gained, soaks 30min-60min;
(12) the carbon felt drying process after step (11) being soaked.
In further technical scheme, the preparation method of described high-performance composite carbon felt also comprises repetition 3-6 step (11) and step (12).
In further technical scheme, in step (1), the temperature of drying nano carbon pipe is 60-100 DEG C.
In further technical scheme, in step (1), strong acid is the mixed liquor of the concentrated sulfuric acid, red fuming nitric acid (RFNA) or the concentrated sulfuric acid and red fuming nitric acid (RFNA).
In further technical scheme, the functional group's carrier in step (3) be sulfanilic acid, p-aminobenzoic acid, p-phenylenediamine (PPD), tetrabromoaniline, p-aminophenyl boric acid, p-aminophenyl phosphonic acids one or more.
In further technical scheme, adding volume ratio shared by concentrated hydrochloric acid in step (4) is 1/20-1/5.
In further technical scheme, in step (8), the temperature range of dry sediment is 40 ~ 90 DEG C.
In further technical scheme, the temperature range of step (12) and the middle dried carbon felt of step (11) is 40 ~ 100 DEG C.
In further technical scheme, the described Nafion liquid quality fraction added in step (10) is 5%.
In further technical scheme, the described Nafion solution added in step (10) is 1-10ml.
The preparation method of a kind of high-performance composite carbon felt that the present invention proposes, compared with prior art, the present invention has following significant advantage:
1. the present invention take CNT (carbon nano-tube) as raw material, adopt the method for chemical graft, prepare functionalized nano carbon pipe, and with Nafion as binding agent, prepare the carbon felt combination electrode material of functionalized carbon tube modification, this electrode material has that good hydrophilic property, conductivity are high, the active advantages of higher of good stability, electrochemical catalysis.
2. the present invention's method preparing composite carbon felt used, raw material is easy to get, with low cost, operation is simple, is applicable to extensive development.
In a word, the present invention, by being raw material with CNT (carbon nano-tube), adopting chemical graft process, prepares functionalized nano carbon pipe, adopt Nafion binding agent, the carbon felt combination electrode of preparation CNT (carbon nano-tube) modification, improves the conductivity of carbon felt, hydrophilicity, effective active area, electrochemical catalysis performance, therefore in single VRB battery, efficiency for charge-discharge is high, has extended cycle life; Utilize the CNT (carbon nano-tube) of high-specific surface area, high conductivity, adopt simple chemical method grafting functional group, prepare functionalized nano carbon pipe, and utilize Nafion binding agent to be compound on carbon felt material with this, prepare high performance combination electrode.These class methods are raw materials used to be easy to get, with low cost and applicable extensive industrialized development.
Accompanying drawing explanation
Fig. 1 is single vanadium cell efficiency and cycle-index figure that carbon felt and functionalized carbon felt are housed in the specific embodiment of the invention.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
The present invention utilizes CNT (carbon nano-tube) for raw material, adopts the method for chemical graft, prepares functionalization CNT (carbon nano-tube), be bonded on carbon felt with Nafion, preparation compound carbon felt electrode.This electrode material has that conductivity is high, hydrophilicity good, electro-chemical activity is high and the advantage such as single vanadium cell charge-discharge performance is good.
Embodiment 1
The preparation method of a kind of high-performance composite carbon felt that the present invention proposes, comprises the following steps:
1. the preparation of functionalization CNT (carbon nano-tube): first dried 200mg CNT (carbon nano-tube) is put into 500-1000 ml deionized water, stirs 20-30 minute; Then take 600mg sulfanilic acid, add 2ml hydrochloric acid after stirring 1h, above-mentioned solution is heated 3h in 30 DEG C of waters; Taking 1g natrium nitrosum adds in above-mentioned solution, at 30 DEG C of waters reaction 3h; Then by this solution suction filtration, ammonium sulfate, sulfuric acid and deionized water rinsing is recycled, then dry under 50 DEG C of conditions, obtain functionalization CNT (carbon nano-tube).
2. the preparation of functionalization CNT (carbon nano-tube) solution: take 50mg functionalization CNT (carbon nano-tube), adds in 150ml deionized water, then adds the Nafion solution that 5ml mass fraction is 5%, ultrasonic process 30min, for subsequent use after then stirring 2h.
3. the preparation of carbon modified felt: by 500mg carbon felt vacuum drying treatment 6 hours at 70 DEG C, be then immersed in above-mentioned functionalization CNT (carbon nano-tube) solution, soak time is 48 hours, then 80 DEG C of dryings in an oven, and repeatedly soak dry process 4 times.
In the present embodiment, each raw material of composite carbon felt of acquisition combines good, do not have CNT (carbon nano-tube) obscission, and the correlated performance data of the present embodiment is as follows:
Recording the internal resistance of barrier film in vanadium redox battery under room temperature is 0.56 Ω/cm
2, composite membrane surface resistance prepared by this ratio is less than former carbon felt (0.68 Ω/cm
2), the battery performance in VRB, far away higher than former carbon felt, adapts to the application requirement of VRB.
As shown in Figure 1, the single VRB battery of carbon modified felt combination electrode material is housed, has very high coulombic efficiency, energy efficiency in charge and discharge process, through repeatedly circulating, its battery efficiency does not decay; Carbon modified felt is energy stable existence in the concentrated sulfuric acid solution of VRB battery pentavalent vanadium, has good chemical stability.So this composite carbon felt can be good at adapting to vanadium cell system, and its cheap price, good battery performance can promote that the industrialization of vanadium cell is produced.
Embodiment 2:
Difference from Example 1 is:
In the preparation of 1, functionalization CNT (carbon nano-tube), CNT (carbon nano-tube) quality becomes 400mg.
2, after adopting embodiment 1, same step prepares composite carbon felt.
Recording the internal resistance of barrier film in vanadium redox battery under room temperature is 0.85 Ω/cm
2, composite membrane surface resistance prepared by this ratio is higher than former carbon felt (0.68 Ω/cm
2), the battery performance in VRB and former carbon felt almost, adapt to the application requirement of VRB.CNT (carbon nano-tube) functionalization degree prepared by this ratio is low, so proton conductivity declines to some extent, hydrophilicity declines to some extent, and in battery charge and discharge process, voltage efficiency can decrease.
Embodiment 3
Difference from Example 1 is:
20mg functionalization CNT (carbon nano-tube) is added in the preparation of 1, functionalization CNT (carbon nano-tube) solution.
2, after adopting embodiment 1, same step prepares composite carbon felt.
In preparation process, because functionalization CNT (carbon nano-tube) addition reduces, under the same conditions, on combination electrode, functionalization nano-carbon tube load amount reduces, and therefore this combination electrode proton conductivity can decline, lower than embodiment 1.Therefore recording the internal resistance of barrier film in vanadium redox battery under room temperature is 0.62 Ω/cm
2, composite membrane surface resistance prepared by this ratio is lower than former carbon felt (0.68 Ω/cm
2), the cell voltage efficiency in VRB, higher than former carbon felt, adapts to the application requirement of VRB substantially.But it is lower that this ratio prepares functionalization nano-carbon tube load amount in composite carbon felt, long-time battery charging and discharging circulation rear stability declines, and functionalization CNT (carbon nano-tube) has partial exfoliation, and therefore this ratio has much room for improvement.
Embodiment 4
Difference from Example 1 is:
100mg functionalization CNT (carbon nano-tube) is added in the preparation of 1, functionalization CNT (carbon nano-tube) solution.
2, after adopting embodiment 1, same step prepares composite carbon felt.
Recording the internal resistance of barrier film in vanadium redox battery under room temperature is 0.86 Ω/cm
2, composite membrane surface resistance prepared by this ratio is higher than former carbon felt (0.68 Ω/cm
2), the cell voltage efficiency in VRB is lower than former carbon felt.Main cause is that this ratio is prepared in composite carbon felt process, adds more functionalization CNT (carbon nano-tube), can increase the reunion between carbon pipe, and cross-linking reaction occurs, and the combination electrode of preparation will conductivity decline, and internal resistance increases.
Embodiment result shows, the present invention for raw material with carbon felt, by chemical graft process, prepares functionalization CNT (carbon nano-tube), utilizes Nafion as binding agent, functionalization CNT (carbon nano-tube) be compound on carbon felt, prepare combination electrode material.Combination electrode prepared by the present invention has good conductivity, hydrophilicity, chemical property, vanadium ion electricity to advantages such as catalytic performance, chemical stability and single VRB battery performance are good.Operation is simple for preparation method of the present invention, low raw-material cost, is easy to industrialization production and advantages of environment protection, can be widely used in vanadium redox battery field.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (10)
1. a preparation method for high-performance composite carbon felt, is characterized in that, comprises the steps
(1) CNT (carbon nano-tube) after drying process is dissolved in strong acid solution, soak at room temperature certain hour;
(2) CNT (carbon nano-tube) that strong acid in step (1) soaked is carried out suction filtration process, then repeatedly use washed with de-ionized water;
(3) CNT (carbon nano-tube) of step (2) gained is put into a certain amount of deionized water, ultrasonic 30min-60min, add a certain amount of functional group carrier, be made into the solution that mass fraction is 0.2-6%, stir 2-6h;
(4) a certain amount of concentrated hydrochloric acid is added in step (3) gained solution, stir 2-5h;
(5) heating steps (4) gained solution, control temperature scope is 0 ~ 100 DEG C, then adds natrium nitrosum, and the solution of preparation 0.05-2.5%, controls described temperature range between 0 ~ 90 DEG C, reaction 3-9h;
(6) filtration step (5) gained solution, is precipitated thing, then repeatedly cleans described sediment with the ammonium sulfate that concentration is 0.2mol/L-1.5mol/L;
(7) deionized water cleaning step (6) gained sediment is repeatedly utilized;
(8) by step (7) gained drying precipitate, functionalization CNT (carbon nano-tube) is obtained;
(9) be dissolved in deionized water by the functionalization CNT (carbon nano-tube) of step (8) gained, preparation mass fraction is the solution of 5%-35%;
(10) a certain amount of Nafion solution is added in step (9) gained solution;
(11) dried carbon felt is immersed in the solution of step (10) gained, soaks 30min-60min;
(12) the carbon felt drying process after step (11) being soaked.
2. the preparation method of a kind of high-performance composite carbon felt according to claim 1, is characterized in that, repeats 3-6 step (11) and step (12).
3. the preparation method of a kind of high-performance composite carbon felt according to claim 1, is characterized in that, in step (1), the temperature of drying nano carbon pipe is 60-100 DEG C.
4. the preparation method of a kind of high-performance composite carbon felt according to claim 1, is characterized in that, in step (1), strong acid is the mixed liquor of the concentrated sulfuric acid, red fuming nitric acid (RFNA) or the concentrated sulfuric acid and red fuming nitric acid (RFNA).
5. the preparation method of a kind of high-performance composite carbon felt according to claim 1, it is characterized in that, the functional group's carrier in step (3) be sulfanilic acid, p-aminobenzoic acid, p-phenylenediamine (PPD), tetrabromoaniline, p-aminophenyl boric acid, p-aminophenyl phosphonic acids one or more.
6. the preparation method of a kind of high-performance composite carbon felt according to claim 1, is characterized in that, adding volume ratio shared by concentrated hydrochloric acid in step (4) is 1/20-1/5.
7. the preparation method of a kind of high-performance composite carbon felt according to claim 1, is characterized in that, in step (8), the temperature range of dry sediment is 40 ~ 90 DEG C.
8. the preparation method of a kind of high-performance composite carbon felt according to claim 1, is characterized in that, the temperature range of step (12) and the middle dried carbon felt of step (11) is 40 ~ 100 DEG C.
9. the preparation method of a kind of high-performance composite carbon felt according to claim 1, is characterized in that, the described Nafion liquid quality fraction added in step (10) is 5%.
10. the preparation method of a kind of high-performance composite carbon felt according to claim 1, is characterized in that, the described Nafion solution added in step (10) is 1-10ml.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108352507A (en) * | 2015-11-13 | 2018-07-31 | 阿瓦隆电池（加拿大）公司 | Modified electrode for redox flow batteries |
| CN108598500A (en) * | 2018-05-29 | 2018-09-28 | 辽宁金谷炭材料股份有限公司 | The production method of high-performance graphite felt for vanadium cell |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102867967A (en) * | 2011-07-05 | 2013-01-09 | 中国科学院大连化学物理研究所 | Electrode material for all vanadium redox energy storage battery and application thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102867967A (en) * | 2011-07-05 | 2013-01-09 | 中国科学院大连化学物理研究所 | Electrode material for all vanadium redox energy storage battery and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| GUANJIE WEI, ET AL.: "Carbon felt supported carbon nanotubes catalysts composite electrode for vanadium redox flow battery application", 《JOURNAL OF POWER SOURCES》 * |
| 金劭，骞伟中等: "官能团化碳纳米管的表征", 《北京化工大学学报（自然科学版）》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108352507A (en) * | 2015-11-13 | 2018-07-31 | 阿瓦隆电池（加拿大）公司 | Modified electrode for redox flow batteries |
| CN108598500A (en) * | 2018-05-29 | 2018-09-28 | 辽宁金谷炭材料股份有限公司 | The production method of high-performance graphite felt for vanadium cell |
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