CN104319406B - A kind of high-performance is combined the preparation method of carbon felt - Google Patents
A kind of high-performance is combined the preparation method of carbon felt Download PDFInfo
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- CN104319406B CN104319406B CN201410608152.XA CN201410608152A CN104319406B CN 104319406 B CN104319406 B CN 104319406B CN 201410608152 A CN201410608152 A CN 201410608152A CN 104319406 B CN104319406 B CN 104319406B
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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 present invention relates to vanadium redox battery (VRB) electrode material field, a kind of high-performance is combined the preparation method of carbon felt, and present stage vanadium cell carbon felt electrode hydrophilic is poor, effective area is low, electro-chemical activity is low, electrical conductivity is low in solution, vanadium ion is electric to problems such as catalytic performance difference and monocell performance are low；The present invention, with commercialization carbon felt as raw material, utilizes the method that binding agent bonds, and prepares functionalized carbon tube and is combined carbon felt；Compound carbon felt prepared by the present invention has the advantages such as good hydrophilicity, electrochemical catalysis performance, electrical conductivity, chemical stability and good single VRB battery performance.The preparation method of the present invention has that operation is simple, and low cost product, it is easy to industrialization production and advantages of environment protection can be widely used in vanadium redox battery field.
Description
Technical field
The present invention relates to vanadium redox battery (VRB) electrode Material Field, specifically a kind of
Suitable high-performance is combined the preparation method of carbon felt.
Background technology
Along with economic fast development, 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 solve this problem must develop efficient, cheap, pollute less extensive with safe and reliable
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 wind energy, too
Sun can the energy storage device of power generation process, power station energy storage, the aspect such as peak load regulation network.Electrode material is restriction vanadium electricity
One of critical material of pond development, a kind of good vanadium cell electrode material should possess good chemical stability,
The advantages such as good mechanical performance, superior electro-chemical activity, active electrode response area are big and with low cost.
Traditional metal material electrochemical reversibility is poor or is easily passivated, although and the noble metal electrochemistry such as platinum, iridium
Activity is high, good reversibility and chemical stability good, but the high cost of this metalloid restricts it and on a large scale should
With.Present stage carbons material such as graphite felt, graphite, carbon cloth and carbon fiber etc. are with its good stability and low
Honest and clean cost causes to be studied widely, is to apply most electrode materials at present, but this kind of material directly should
Low with process electro-chemical activity, battery performance is poor.So must be modified this kind of material processing, with it
Improve the electro-chemical activity of this kind of material.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of high-performance is combined the preparation of carbon felt
Method, solves that carbon felt hydrophilic is poor, poor stability, electrical conductivity are low, electrochemistry is alive present in prior art
Property is low and the problem such as single VRB poor performance.
A kind of high-performance that the present invention provides is combined the preparation method of carbon felt, comprises the steps:
(1) CNT after dried is dissolved in strong acid solution, soak at room temperature certain time；
(2) CNT that strong acid in step (1) soaked is carried out sucking filtration process, the most repeatedly spend
Ionized water cleans；
(3) CNT of step (2) gained is put in a certain amount of deionized water, ultrasonic 30min
-60min, adds a certain amount of functional group carrier, is made into the solution that mass fraction is 0.2-6%, stirs 2-6
h；
(4) a certain amount of concentrated hydrochloric acid is added in step (3) gained solution, stir 2-5h；
(5) heating steps (4) gained solution, controlling temperature range is 0～100 DEG C, is subsequently adding nitrous
Acid sodium, the solution of preparation 0.05-2.5%, control described temperature range between 0～90 DEG C, react 3-9h；
(6) filtration step (5) gained solution, is precipitated thing, is then 0.2mol/L-1.5mol/L by concentration
Ammonium sulfate repeatedly clean described precipitate；
(7) deionized water cleaning step repeatedly (6) gained precipitate is utilized；
(8) by step (7) gained drying precipitate, sense dough CNT is obtained；
(9) the sense dough CNT of step (8) gained is dissolved in deionized water, prepares quality
Mark 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 dried after step (11) being soaked.
In further technical scheme, described high-performance is combined the preparation method of carbon felt and also includes repeating 3-6
Secondary 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 be concentrated sulphuric acid, concentrated nitric acid or concentrated sulphuric acid with
The mixed liquor of concentrated nitric acid.
In further technical scheme, the functional group's carrier in step (3) is p-aminobenzene sulfonic acid, to ammonia
Yl benzoic acid, p-phenylenediamine, tetrabromoaniline, p-aminophenyl boric acid, the one of p-aminophenyl phosphonic acids or many
Kind.
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, step (12) and step (11) are dried the temperature range of carbon felt
It it is 40～100 DEG C.
In further technical scheme, the described Nafion solution mass fraction added in step (10) is
5%,.
In further technical scheme, the described Nafion solution added in step (10) is 1-10ml.
A kind of high-performance that the present invention proposes is combined the preparation method of carbon felt, compared with prior art, the present invention
There is following significant advantage:
1. the present invention is with CNT as raw material, the method using chemical graft, prepares functionalized nano carbon pipe,
And with Nafion as binding agent, prepare the carbon felt combination electrode material that functionalized carbon tube is modified, this electrode material
Material has good hydrophilic property, electrical conductivity height, good stability, electrochemical catalysis activity advantages of higher.
2. the method for the compound carbon felt of present invention preparation used, raw material is easy to get, with low cost, operation is simple,
It is suitable for extensive development.
In a word, the present invention, by with CNT as raw material, uses chemical graft process, prepares functionalization and receive
Rice carbon pipe, uses Nafion binding agent, prepares the carbon felt combination electrode that CNT is modified, improves carbon felt
Electrical conductivity, hydrophilicity, effective active area, electrochemical catalysis performance, in the most single VRB battery
Efficiency for charge-discharge is high, has extended cycle life；Utilize the CNT of high-specific surface area, high conductivity, use letter
Single chemical method grafting functional group, prepares functionalized nano carbon pipe, and utilizes Nafion binding agent to incite somebody to action with this
It is compound on carbon felt material, prepares high performance combination electrode.This kind of method is raw materials used to be easy to get, cost
Cheap and applicable extensive industrialized development.
Accompanying drawing explanation
Fig. 1 be in the specific embodiment of the invention equipped with carbon felt and functionalization carbon felt single vanadium cell efficiency with follow
Ring number of times figure.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further.
The present invention utilizes CNT for raw material, and the method using chemical graft, preparation official can dough nano-sized carbon
Pipe, is bonded in carbon felt with Nafion, the compound carbon felt electrode of preparation.This electrode material have electrical conductivity high,
The advantage such as hydrophilicity is good, electro-chemical activity is high and single vanadium cell charge-discharge performance is good.
Embodiment 1
A kind of high-performance that the present invention proposes is combined the preparation method of carbon felt, comprises the following steps:
1. the preparation of official's energy dough CNT: first dried 200mg CNT is put into
In 500-1000 ml deionized water, stir 20-30 minute；Then 600mg p-aminobenzene sulfonic acid is weighed,
Add 2ml hydrochloric acid after stirring 1h, above-mentioned solution is heated in 30 DEG C of waters 3h；Weigh 1g sodium nitrite
Add in above-mentioned solution, react 3h in 30 DEG C of waters；Then by this solution sucking filtration, recycle ammonium sulfate,
Sulphuric acid and deionized water rinsing, be then dried under the conditions of 50 DEG C, obtain sense dough CNT.
2. the preparation of official's energy dough CNT solution: weigh 50mg official's energy dough CNT, add 150
In ml deionized water, it is subsequently adding the Nafion solution that 5ml mass fraction is 5%, supersound process 30min,
Then standby after stirring 2h.
3. the preparation of modified carbon felt: by 500mg carbon felt vacuum drying treatment 6 hours at 70 DEG C, then soak
Bubble is in above-mentioned sense dough CNT solution, and soak time is 48 hours, does for 80 DEG C the most in an oven
Dry, and repeatedly soak dried 4 times.
In the present embodiment, it is thus achieved that each raw material of compound carbon felt be well combined, there is no CNT obscission,
And the correlated performance data of the present embodiment is as follows:
Recording barrier film internal resistance in vanadium redox battery under room temperature is 0.56 Ω/cm2, this ratio
The composite membrane surface resistance of preparation is less than former carbon felt (0.68 Ω/cm2), the battery performance in VRB is the most former
Carbon felt, adapts to the application requirement of VRB.
As it is shown in figure 1, equipped with the single VRB battery of modified carbon felt combination electrode material, charge and discharge process
In there is the highest coulombic efficiency, energy efficiency, through repeatedly circulating, its battery efficiency does not decay；Change
Property carbon felt in the concentrated sulfuric acid solution of VRB battery pentavalent vanadium can stable existence, there is good chemically stable
Property.So, this compound carbon felt can be good at adapting to vanadium cell system, its cheap price, good electricity
Pond performance can promote that the industrialization of vanadium cell produces.
Embodiment 2:
Difference from Example 1 is:
1, in the preparation of sense dough CNT, CNT quality becomes 400mg.
2, the same compound carbon felt of step preparation after using embodiment 1.
Recording barrier film internal resistance in vanadium redox battery under room temperature is 0.85 Ω/cm2, this ratio
The composite membrane surface resistance of preparation is higher than former carbon felt (0.68 Ω/cm2), the battery performance in VRB is poor with former carbon felt
Seldom, the application requirement of VRB is adapted to.CNT official energy dough degree prepared by this ratio is low, so proton
Conductivity has declined, and hydrophilicity has declined, and in battery charge and discharge process, voltage efficiency can drop
Low.
Embodiment 3
Difference from Example 1 is:
1, adding 20mg official in the preparation of sense dough CNT solution can dough CNT.
2, the same compound carbon felt of step preparation after using embodiment 1.
In preparation process, owing to sense dough CNT addition reduces, under the same conditions, compound electric
Extremely going up sense dough nano-carbon tube load amount to reduce, therefore this combination electrode proton conductivity can decline, and is less than
Embodiment 1.Therefore recording barrier film internal resistance in vanadium redox battery under room temperature is
0.62Ω/cm2, composite membrane surface resistance prepared by this ratio is less than former carbon felt (0.68 Ω/cm2), in VRB
Cell voltage efficiency is higher than former carbon felt, the basic application requirement adapting to VRB.But this ratio prepares composite carbon
In felt, sense dough nano-carbon tube load amount is relatively low, and long-time battery charging and discharging circulation rear stability declines, official
Can have partial exfoliation by dough CNT, therefore this ratio has much room for improvement.
Embodiment 4
Difference from Example 1 is:
1, adding 100mg official in the preparation of sense dough CNT solution can dough CNT.
2, the same compound carbon felt of step preparation after using embodiment 1.
Recording barrier film internal resistance in vanadium redox battery under room temperature is 0.86 Ω/cm2, this ratio
The composite membrane surface resistance of preparation is higher than former carbon felt (0.68 Ω/cm2), the cell voltage efficiency in VRB is less than former
Carbon felt.During main cause is the compound carbon felt of this ratio preparation, add relatively polyfunctional group CNT,
Can increase the reunion between carbon pipe, and cross-linking reaction occurs, the combination electrode of preparation will electrical conductivity decline,
Internal resistance increases.
Embodiment result shows, the present invention is with carbon felt as raw material, and by chemical graft process, preparation official can dough
CNT, utilizes Nafion as binding agent, official can be compound in carbon felt by dough CNT, preparation
Combination electrode material.Combination electrode prepared by the present invention has good electrical conductivity, hydrophilicity, electrochemistry
Performance, vanadium ion electricity is to advantages such as catalytic performance, chemical stability and single VRB battery performance are good.
Operation is simple for the preparation method of the present invention, low raw-material cost, it is easy to industrialization production and environment friend
The advantage such as good, can be widely used in vanadium redox battery field.
The above, the only present invention preferably detailed description of the invention, but protection scope of the present invention not office
Being limited to this, any those familiar with the art is in the technical scope that the invention discloses, according to this
The technical scheme of invention and inventive concept thereof in addition equivalent or change, all should contain the protection in the present invention
Within the scope of.
Claims (9)
1. high-performance is combined a preparation method for carbon felt, it is characterized in that, comprises the steps:
(1) CNT after dried is dissolved in strong acid solution, soak at room temperature certain time；
(2) CNT that strong acid in step (1) soaked is carried out sucking filtration process, the most repeatedly clean with deionized water；
(3) CNT of step (2) gained is put in 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；Described functional group carrier be p-aminobenzene sulfonic acid, para-amino benzoic acid, p-phenylenediamine, tetrabromoaniline, p-aminophenyl boric acid, p-aminophenyl phosphonic acids one or more；
(4) a certain amount of concentrated hydrochloric acid is added in step (3) gained solution, stir 2-5h；
(5) heating steps (4) gained solution, controlling temperature range is 30～100 DEG C, is subsequently adding sodium nitrite, the solution of preparation 0.05-2.5%, controls described temperature range between 30～90 DEG C, reacts 3-9h；
(6) filtration step (5) gained solution, is precipitated thing, then repeatedly cleans described precipitate with the ammonium sulfate that concentration is 0.2mol/L-1.5mol/L；
(7) deionized water cleaning step repeatedly (6) gained precipitate is utilized；
(8) by step (7) gained drying precipitate, sense dough CNT is obtained；
(9) being scattered in deionized water by the sense dough CNT of step (8) gained, preparation mass fraction is the dispersion liquid of 5%-35%；
(10) a certain amount of Nafion solution is added in step (9) gained dispersion liquid；
(11) dried carbon felt is immersed in the solution of step (10) gained, soaks 30min-60min；
(12) the carbon felt dried after step (11) being soaked.
A kind of high-performance the most according to claim 1 is combined the preparation method of carbon felt, it is characterized in that, repeats 3-6 step (11) and step (12).
A kind of high-performance the most according to claim 1 is combined the preparation method of carbon felt, it is characterized in that, in step (1), the temperature of drying nano carbon pipe is 60-100 DEG C.
A kind of high-performance the most according to claim 1 is combined the preparation method of carbon felt, it is characterized in that, in step (1), strong acid is the mixed liquor of concentrated sulphuric acid, concentrated nitric acid or concentrated sulphuric acid and concentrated nitric acid.
A kind of high-performance the most according to claim 1 is combined the preparation method of carbon felt, it is characterized in that, adding volume ratio shared by concentrated hydrochloric acid in step (4) is 1/20-1/5.
A kind of high-performance the most according to claim 1 is combined the preparation method of carbon felt, it is characterized in that, in step (8), the temperature range of dry sediment is 40～90 DEG C.
A kind of high-performance the most according to claim 1 is combined the preparation method of carbon felt, it is characterized in that, the temperature range being dried carbon felt in step (12) and step (11) is 40～100 DEG C.
A kind of high-performance the most according to claim 1 is combined the preparation method of carbon felt, it is characterized in that, the described Nafion solution mass fraction added in step (10) is 5%.
A kind of high-performance the most according to claim 1 is combined the preparation method of carbon felt, it is characterized in that, the described Nafion solution added in step (10) is 1-10ml.
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| 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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Inventor after: Jia Chuankun Inventor after: Liu Qi Inventor after: He Hao Inventor after: Wei Mingze Inventor after: Liu Yadong Inventor before: Liu Qi |
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