CN109950595A - Titania modified low-dimensional carbon material/chitosan proton exchange membrane and its preparation method and application - Google Patents
Titania modified low-dimensional carbon material/chitosan proton exchange membrane and its preparation method and application Download PDFInfo
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/50—Fuel cells
Abstract
The present embodiments relate to a kind of titania modified low-dimensional carbon material/chitosan proton exchange membranes and its preparation method and application.The titania modified low-dimensional carbon material/chitosan proton exchange membrane passes through the preparation method included the following steps and is made: using chitosan as matrix filmogen, using titania modified low-dimensional carbon material as the nanofiller in proton exchange membrane, titania modified low-dimensional carbon material/chitosan proton exchange membrane is prepared.Titania modified low-dimensional carbon material in the titania modified low-dimensional carbon material/chitosan proton exchange membrane can effectively improve oxidation stability, proton conductivity and the alcohol-rejecting ability of chitosan proton exchange membrane, can be applied to fuel cell.Preparation method is simple and fast, is suitable for industrialization.
Description
Technical field
The present invention relates to the technical field of proton exchange membrane more particularly to titania modified low-dimensional carbon material/chitosans
Proton exchange membrane and its preparation method and application.
Background technique
Since the 21th century, the shortage of fossil energy becomes the important problem for hindering human social development, therefore finds
The Land use systems for substituting fossil energy are the task of top priority.Chemical energy is converted into electricity by electrochemical principle by fuel cell
Can, therefore its efficiency is much higher than internal combustion engine, direct methanol fuel cell as a proton exchanging film fuel battery be it is a kind of very
Promising energy conversion device, chemical energy is effectively converted into electric energy by it.
The development of proton exchange membrane is the important branch of fuel cell technology progress, and wherein proton conductivity is proton exchange
The key characteristic of film has the proton exchange membrane based on chitosan in the prior art, but its oxidation stability is poor, proton conductivity
It is low.Although there is the proton for being used to improve proton exchange membrane for one-dimensional carbon nanotube, two-dimensional graphene oxide composite material to pass at present
The correlative study of conductance, but the oxidation stability of proton exchange membrane and proton conductivity still need to be further increased.
The information disclosed in the background technology section is intended only to increase the understanding to general background of the invention, without answering
When being considered as recognizing or imply that the information constitutes the prior art already known to those of ordinary skill in the art in any form.
Summary of the invention
Goal of the invention
It is scarce to solve that the proton exchange membrane oxidation stability based on chitosan is poor in the prior art, proton conductivity is low
It falls into, the purpose of the present invention is to provide a kind of titania modified low-dimensional carbon material/chitosan proton exchange membrane and its preparation sides
Method and application.Titania modified low-dimensional carbon material in the titania modified low-dimensional carbon material/chitosan proton exchange membrane
Oxidation stability, proton conductivity and the alcohol-rejecting ability that chitosan proton exchange membrane can be effectively improved, make it can be applied to fuel
Battery.Preparation method is simple and fast, is suitable for industrialization.
Solution
Purpose to realize the present invention, the embodiment of the invention provides a kind of titania modified low-dimensional carbon material/chitosans
The preparation method of proton exchange membrane comprising following steps:
Using chitosan as matrix filmogen, using titania modified low-dimensional carbon material as receiving in proton exchange membrane
Rice filler, prepares titania modified low-dimensional carbon material/chitosan proton exchange membrane.
Above-mentioned preparation method in one possible implementation, prepares titania modified low-dimensional carbon material/chitosan
When proton exchange membrane, also select sodium lignin sulfonate as additive；Optionally, the additive amount of the sodium lignin sulfonate is first
The 0.5-3% of shell element additive amount；Further it is optionally 2%.
In one possible implementation, the titania modified low-dimensional carbon material includes dioxy to above-mentioned preparation method
Change the modified zero dimension carbon material of titanium, titania modified one-dimensional carbon material, titania modified two-dimentional carbon material；Optionally, described
Titania modified low-dimensional carbon material includes titanium dioxide-carbon nanotube or titanium dioxide-graphene oxide；It is further optional
Ground, the titania modified low-dimensional carbon material include anatase titania-carbon nanotube or anatase titania-oxidation
Graphene.
In one possible implementation, the additive amount of the titanium dioxide-carbon nanotube is first to above-mentioned preparation method
The 0.5-10% of shell element additive amount, the additive amount of the titanium dioxide-graphene oxide are the 0.5-5% of chitin additive amount.
In one possible implementation, the titanium dioxide-carbon nanotube is to be coated with thereon to above-mentioned preparation method
The carbon nanotube of titanium dioxide.The preparation of the titanium dioxide-carbon nanotube the following steps are included: (1) by carbon nanotube, modification
Agent and water are modified carbon nanotube commonly through at least one of grinding, ultrasonic disperse or mechanical stirring mode, collect
Modified carbon nano-tube and drying, in which: the carbon nanotube includes carboxylic acid carbon nanotube, and the modifying agent includes lignin sulfonic acid
At least one of sodium, neopelex or oleoyl oxygroup ethanesulfonic acid sodium；(2) the modified carbon nano-tube dispersion after drying
In organic solvent, water is added and butyl titanate is hydrolyzed, wash, be centrifuged after the reaction was completed, products therefrom filters drying；
(3) high-temperature heat treatment under conditions of 300-600 DEG C of the product after drying.Hydrolysis and two steps of calcining synthesis two are utilized in this method
Titanium oxide-carbon nanotube, on the carbon nanotubes by anatase titanium dioxide cladding.
Above-mentioned preparation method in one possible implementation, the carboxylic acid carbon nanotube be outer tube diameter 10nm~
The multi wall or single wall carboxylic acid carbon nanotube of 20nm, 10 μm of length~30 μm, purity: >=98wt%.
In one possible implementation, the titanium dioxide-graphene oxide is negative is loaded with two to above-mentioned preparation method
The graphene oxide sheet of titanium oxide.The preparation of the titanium dioxide-graphene oxide is the following steps are included: titanium sulfate is placed in point
It mixes in the graphene oxide water solution dissipated, then mixed liquor is transferred in reaction kettle and reacts in a vacuum drying oven,
It washs after the reaction was completed, is dry.A step hydrothermal method synthesizing anatase titanium dioxide-graphene oxide is utilized in this method, it will
Anatase titanium dioxide is supported on stannic oxide/graphene nano on piece in situ.
Above-mentioned preparation method prepares titania modified low-dimensional in one possible implementation, by solution casting method
Carbon material/chitosan proton exchange membrane；Optionally, the solution casting method is the following steps are included: by titania modified low-dimensional
Carbon material obtains uniform dispersion liquid optionally further comprising sodium lignin sulfonate ultrasonic disperse is in aqueous solution；Glacial acetic acid is added
With chitosan in dispersion liquid, heating stirring forms uniform casting solution；It is poured into mold after casting solution is deaerated, is dried to film
Naturally it falls off；Gained film is immersed in cross-linking reagent dilute sulfuric acid and is crosslinked.
Above-mentioned preparation method in one possible implementation, concentration >=5% of cross-linking reagent dilute sulfuric acid, crosslinking time
≥24h。
In one possible implementation, the liner material of the reaction kettle is polytetrafluoroethylene (PTFE) to above-mentioned preparation method,
The enclosure material of the reaction kettle is carbon steel, stainless steel, high temperature resistant stainless steel, strong alkali-acid resistance stainless steel etc..
Above-mentioned preparation method in one possible implementation, when to carbon nano-tube modification, the processing method of grinding are as follows:
Hand lapping is carried out using one of agate mortar, ceramic mortar and aluminium oxide mortar；
When to carbon nano-tube modification, the processing method of ultrasonic disperse are as follows: handled using ultrasonic cleaner, processing side
Method is that control frequency is 30~45 kHz ultrasound 30 minutes；
When to carbon nano-tube modification, churned mechanically processing method are as follows: using in magnetic stirring apparatus or electric mixer
One kind, processing method are control 600 rev/min of revolving speed, are carried out 1~8 hour；
When modified carbon nano-tube after drying is dispersed in organic solvent, the decentralized processing of use are as follows: using at ultrasonic wave
One of reason, stir process, concussion processing, decentralized processing can be such that modified carbon nano-tube is evenly dispersed in organic solvent；
In solution casting method, when heating stirring forms casting solution, it is 60~80 DEG C that the heating stirring, which is in temperature,
Under the conditions of, it stirs 2~4 hours；
In solution casting method, the processing method of degassing are as follows: using ultrasonic degassing processing, Fruit storage, stand degassing
One kind of processing.
The embodiment of the invention also provides a kind of titania modified low-dimensional carbon material obtained by above-mentioned preparation method/
Chitosan proton exchange membrane.
The embodiment of the invention also provides a kind of titania modified low-dimensional carbon material obtained by above-mentioned preparation method/
The application of chitosan proton exchange membrane in a fuel cell.
Beneficial effect
(1) in the preparation method of the titania modified low-dimensional carbon material/chitosan proton exchange membrane of the embodiment of the present invention, lead to
It crosses and titania modified low-dimensional carbon material is added, make oxidation stability, proton conductivity and the alcohol-resistant performance of gained proton exchange membrane
It can all be significantly improved；Particularly with the addition of with excellent hydrophily and mechanical performance titanium dioxide-carbon nanotube and/or
Titanium dioxide-graphene oxide so that the oxidation stability of proton exchange membrane, proton conductivity and alcohol-rejecting ability have it is brighter
It is aobvious to improve.
(2) in the preparation method of the titania modified low-dimensional carbon material/chitosan proton exchange membrane of the embodiment of the present invention, lead to
The addition for crossing the sodium lignin sulfonate as filler introduces hydrophilic radical sulfonic group, the insertion of sodium lignin sulfonate micel
Into chitosan molecule chain network, according to Hopping mechanism, the process of proton transfer be between proton and hydrone hydrogen bond formed with
The process of fracture, the introducing of sulfonic group anionic group mean that proton can first rest on lignin sulfonic acid sodium molecule and jump again
It adjourns on hydrone nearby, lignin sulfonic acid sodium molecule helps proton transfer as the site that a proton jumps, and improves matter
Sub- conduction efficiency.The addition of lignin sulfonic acid sodium molecule simultaneously is also beneficial to improve alcohol-rejecting ability.
Detailed description of the invention
One or more embodiments are illustrated by the picture in corresponding attached drawing, these exemplary theorys
The bright restriction not constituted to embodiment.Dedicated word " exemplary " means " being used as example, embodiment or illustrative " herein.
Here as any embodiment illustrated by " exemplary " should not necessarily be construed as preferred or advantageous over other embodiments.
Fig. 1 a and Fig. 1 b are film cross section structure figure and the implementation of pure chitosan proton exchange membrane in the embodiment of the present invention 1 respectively
The film cross section structure figure of 3 proton exchange membrane of chitosan/titanium dioxide-graphene oxide in example 3.
Fig. 2 is the EDX figure (energy of 3 proton exchange membrane of chitosan/titanium dioxide-graphene oxide in the embodiment of the present invention 3
Chromatic dispersion quantity X-ray spectrum figure).
Fig. 3 is that anatase titania-graphene oxide TEM schemes (transmission electron microscope in the embodiment of the present invention 3
Figure).
Fig. 4 a be chitosan/titanium dioxide in the embodiment of the present invention 6-carbon nanotube proton exchange membrane proton conductivity with
Temperature variation, in which: CS represents chitosan, and TCNT represents titanium dioxide-carbon nanotube；Fig. 4 b is in the embodiment of the present invention 6
Chitosan/titanium dioxide-carbon nanotube/sodium lignin sulfonate proton exchange membrane proton conductivity varies with temperature figure, in which:
CS represents chitosan, and TCNT represents titanium dioxide-carbon nanotube, and SLS represents sodium lignin sulfonate.
Fig. 5 a is chitosan/titanium dioxide-graphene oxide methanol permeability figure in the embodiment of the present invention 7, in which: CS
Chitosan is represented, GOX represents graphene oxide, and TGOX represents anatase titania-graphene oxide；Fig. 5 b is of the invention real
Applying chitosan/titanium dioxide-graphene oxide in example 7/sodium lignin sulfonate methanol permeability figure, in which: CS represents chitosan,
TGOX represents anatase titania-graphene oxide, and SLS represents sodium lignin sulfonate.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described, it is clear that described embodiments are some of the embodiments of the present invention, rather than
Whole embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work premise
Under every other embodiment obtained, shall fall within the protection scope of the present invention.Unless otherwise explicitly stated, otherwise whole
In a specification and claims, it is to include that the term " include " or its transformations will be understood as
The element or component stated, and do not exclude other elements or other components.
In addition, in order to better illustrate the present invention, numerous details is given in specific embodiment below.
It will be appreciated by those skilled in the art that without certain details, the present invention equally be can be implemented.In some embodiments, right
It is not described in detail in raw material well known to those skilled in the art, element, method, means etc., in order to highlight master of the invention
Purport.
Deacetylation >=90.0% of chitosan used, average molecular weight are 70-80 ten thousand in following embodiment.
Carboxylic acid carbon nanotube used is outer tube diameter 10nm~20nm, 10 μm of length~30 μm, purity in following embodiment: >=
The multi wall carboxylic acid carbon nanotube of 98wt%.
The purity of sodium lignin sulfonate used is 80% in following embodiment.
Embodiment 1:
A kind of preparation method of pure chitosan proton exchange membrane, comprising the following steps:
It weighs 0.5g chitosan to be dispersed in the acetic acid solution of 50ml 2%, constant temperature stirs 2h at 70 DEG C, obtains casting film
Liquid.It will be poured into square dies after the degassing of finely dispersed casting solution, 60 DEG C of drying 5h immerse membrane material resulting after drying
It is crosslinked in 5% sulfuric acid solution, the acid of striping excess surface is washed with deionized water in crosslinking afterwards for 24 hours, obtains chitosan proton
Exchange membrane.
The oxidation stability of gained chitosan proton exchange membrane is measured.Measuring method is as follows: by what is be completely dried
Chitosan proton exchange membrane is placed in the Fenton reagent (3%H of 2ppm2O2Dissolve FeSO4, make FeSO4Concentration is 2ppm) in,
6h is kept the temperature under conditions of 50 DEG C and tests its mass loss, and mass loss is smaller, and oxidation stability is higher, and the results are shown in Table 1.
Embodiment 2:
(1) using hydrolysis and calcining two step synthesizing anatase titanium dioxide-carbon nanotube: the Carboxylation multi-wall carbon nano-tube of 0.1g
Pipe is mixed and added into deionized water grinding 1h with 0.4g sodium lignin sulfonate, and 100ml deionization is added into the product after grinding
Water and control frequency be 30 kHz ultrasonic disperse 30 minutes, control 600 rev/min mechanical stirring 1h of revolving speed.It will be resulting
Sulfonic acid carbon nano tube filters and the drying in 60 DEG C of convection ovens.Sulfonic acid carbon nano tube 0.1g after taking drying is dispersed in
In 100ml dehydrated alcohol, control frequency is 30 kHz ultrasound 30 minutes, 600 turns of revolving speed of addition 1ml deionized water control/every
Minute, stirring 15min are slowly added to 2ml butyl titanate later and control 600 rev/min of revolving speed, stirring 4h.By mixture
Be centrifuged 15min at 8000rpm, ethyl alcohol be added again with dispersion product after removing supernatant, and under the same conditions again from
The heart.Gained precipitating plus deionized water disperse and filter drying.Product after drying is heat-treated 1h at 500 DEG C in Muffle furnace, obtains
The carbon nanotube (referred to as titanium dioxide-carbon nanotube in following implementation) coated to anatase titania.
(2) 5 parts of 0.5g chitosan a kind of chitosan/titanium dioxide-carbon nanotube compound proton exchange membrane preparation: are weighed
It is dispersed in the acetic acid solution of 5 parts of 50ml 2% respectively, the above-mentioned titanium dioxide-carbon nanotube for being separately added into different quality makes it
Additive amount is 1%, 3%, 5%, 7% and the 9% of chitosan mass, and constant temperature stirs 2h at 70 DEG C after ultrasonic disperse 30min, will
It is poured into square dies after the finely dispersed casting solution degassing of gained titanium dioxide-carbon nanotube, 60 DEG C of vacuum drying 5h are dry
It is crosslinked in the sulfuric acid solution of composite membrane immersion 5% afterwards, the acid of striping excess surface is washed with deionized water in crosslinking afterwards for 24 hours.
According to the difference of the carbon nano tube-doped amount of titanium dioxide-, sample is respectively designated as chitosan/titanium dioxide-carbon nanotube 1, shell
Glycan/titanium dioxide-carbon nanotube 3, chitosan/titanium dioxide-carbon nanotube 5, chitosan/titanium dioxide-carbon nanotube 7,
Chitosan/titanium dioxide-carbon nanotube 9.Digital n after titanium dioxide-carbon nanotube represents the titanium dioxide-carbon nanometer being added
The additive amount of pipe is the n% (quality) of chitosan.
Gained chitosan/titanium dioxide-carbon nanotube compound proton exchange membrane oxidation stability is measured, measurement side
Method is same
Embodiment 1, the results are shown in Table 1.
Embodiment 3:
(1) one step hydro thermal method synthesizing anatase titanium dioxide-graphene oxide: the oxidation stone prepared using Hummers method
Black aqueous solution, measures 9.6ml graphene oxide water solution (wherein graphene oxide containing 14.8mg) and ultrasound is dispersed in it
It in 30.4ml deionized water, weighs 60mg titanium sulfate and is placed in scattered graphene oxide water solution and stir 15min, then will
Mixed liquor, which is transferred in reaction kettle to be placed in vacuum drying oven, reacts 4h under the conditions of 120 DEG C.Deionized water is used after the reaction was completed
Repeatedly washing centrifugation filters drying and grinding into powder with spare, as anatase titania loads graphene oxide to neutrality
(titanium dioxide-graphene oxide is referred to as in following embodiment).
(2) a kind of chitosan/titanium dioxide-graphene oxide compound proton exchange membrane preparation: 0.5g chitosan 5 is weighed
Part is dispersed in respectively in the acetic acid solution of 5 parts of 50ml 2%, is separately added into above-mentioned titanium dioxide-graphene oxide of different quality
Make 1%, 1.5%, 2%, 2.5% and the 3% of its additive amount chitosan mass, after ultrasonic disperse 30min at 70 DEG C constant temperature
2h is stirred, will be poured into square dies after the finely dispersed casting solution degassing of gained titanium dioxide-graphene oxide, 60 DEG C of drying
5h, it is dry after composite membrane immerse in 5% sulfuric acid solution and be crosslinked, it is more that film surface is washed with deionized water in crosslinking afterwards for 24 hours
Remaining acid.According to titanium dioxide-graphene oxide doped amount difference, sample is respectively designated as chitosan/titanium dioxide-oxidation
Graphene 1, chitosan/titanium dioxide-graphene oxide 1.5, chitosan/titanium dioxide-graphene oxide 2, chitosan/dioxy
Change titanium-graphene oxide 2.5, chitosan/titanium dioxide-graphene oxide 3.
In above-mentioned steps (2) if using different quality graphene oxide replacement of titanium dioxide-graphene oxide, make oxygen
Graphite alkene additive amount is 1%, 1.5%, 2%, 2.5% and the 3% of chitosan mass, the same above-mentioned steps of other steps (2), root
According to the difference of graphene oxide doped amount, sample is respectively designated as chitosan/oxidized graphene 1, chitosan/oxidized graphene
1.5, chitosan/oxidized graphene 2, chitosan/oxidized graphene 2.5, chitosan/oxidized graphene 3.
Digital n after above-mentioned titanium dioxide-graphene oxide represents the titanium dioxide-graphene oxide additive amount being added
It is the n% (quality) of chitosan, the additive amount that the digital m after graphene oxide represents the graphene oxide being added is chitosan
M% (quality).
It is compound to gained chitosan/titanium dioxide-graphene oxide compound proton exchange membrane and chitosan/oxidized graphene
The oxidation stability of proton exchange membrane is measured, and measuring method is with embodiment 1, and the results are shown in Table 1.
Chitosan/dioxy in the film cross section structure figure of pure chitosan proton exchange membrane and embodiment 3 in the embodiment of the present invention 1
The film cross section structure figure for changing 3 proton exchange membrane of titanium-graphene oxide is distinguished as illustrated in figs. 1A and ib, wherein Fig. 1 a pure chitosan
The film section of proton exchange membrane is uniform, fine and close, flawless, and Fig. 1 b chitosan/titanium dioxide -3 proton of graphene oxide
The film section of exchange membrane is in apparent sheet, and coarse is slightly significantly increased；Chitosan/titanium dioxide-in the embodiment of the present invention 3
The EDX of 1 proton exchange membrane of graphene oxide schemes to further demonstrate dioxy as shown in Fig. 2, there is the appearance of Ti element in Fig. 2
Change titanium-graphene oxide to act in glycan substrate；Anatase titania-graphene oxide TEM schemes such as in embodiment 3
Shown in Fig. 3, titanium dioxide nano-particle is clearly visible from Fig. 3 and is uniformly anchored on stannic oxide/graphene nano on piece.
Table 1
As shown in table 1, titanium dioxide-carbon nanotube, titanium dioxide-graphene oxide or graphene oxide is added facilitates
The mass loss of proton exchange membrane is reduced, and oxidation stability increases.Graphene oxide is compared in the addition of titanium dioxide-graphene oxide
Addition it is more effective, and compare graphene oxide addition, titanium dioxide-graphene oxide can also improve alcohol-rejecting ability etc. its
His performance, is characterized in embodiment 7.
Embodiment 4:
(1) using hydrolysis and calcining two step synthesizing anatase titanium dioxide-carbon nanotube: specific method is the same as embodiment 2；
(2) it a kind of preparation of chitosan/titanium dioxide-carbon nanotube/sodium lignin sulfonate compound proton exchange membrane: weighs
4 parts of 0.5g chitosan are dispersed in respectively in the acetic acid solution of 4 parts of 50ml 2%, are separately added into above-mentioned titanium dioxide-carbon nanotube
0.025g (i.e. titanium dioxide-carbon nanotube quality is the 5% of 0.5g chitosan) in every part of acetic acid solution, then be separately added into
(i.e. the quality of sodium lignin sulfonate is 0.5g chitosan to 0.005g, 0.0075g, 0.010g, 0.0125g sodium lignin sulfonate
1%, 1.5%, 2%, 2.5%) carry out after ultrasonic disperse 30min that constant temperature stirs 2h at 70 DEG C afterwards, by gained titanium dioxide-carbon
It is poured into square dies after the finely dispersed casting solution degassing of nanotube, sodium lignin sulfonate, 60 DEG C of vacuum drying 5h, after dry
Composite membrane immerse in 5% sulfuric acid solution and be crosslinked, the acid of striping excess surface is washed with deionized water in crosslinking afterwards for 24 hours.Root
According to the difference of sodium lignin sulfonate doping, sample is respectively designated as 5/ lignin sulfonic acid of chitosan/titanium dioxide-carbon nanotube
Sodium 1,5/ sodium lignin sulfonate 1.5 of chitosan/titanium dioxide-carbon nanotube, chitosan/titanium dioxide-carbon nanotube 5/ are wooden
Plain sodium sulfonate 2,5/ sodium lignin sulfonate 2.5 of chitosan/titanium dioxide-carbon nanotube.
It is shell that digital n after above-mentioned titanium dioxide-carbon nanotube, which represents the titanium dioxide-carbon nanotube additive amount being added,
The n% (quality) of glycan, it is chitosan that the digital m after sodium lignin sulfonate, which represents the additive amount for the sodium lignin sulfonate being added,
M% (quality).
To gained chitosan/titanium dioxide-carbon nanotube/sodium lignin sulfonate compound proton exchange membrane oxidation stability
It is measured, measuring method is with embodiment 1, and the results are shown in Table 2.The addition of sodium lignin sulfonate is to oxidation-stabilized in the system
Property to further enhance effect limited, but its addition can improve the proton conductivity of proton exchange membrane, as described in Example 6.
Table 2
Embodiment 5:
(1) one step hydro thermal method synthesizing anatase titanium dioxide-graphene oxide: specific method is the same as embodiment 3；
(2) a kind of preparation of chitosan/titanium dioxide-graphene oxide/sodium lignin sulfonate compound proton exchange membrane: claim
It takes 3 parts of 0.5g chitosan to be dispersed in the acetic acid solution of 3 parts of 50ml 2% respectively, is separately added into 3 parts of above-mentioned titanium dioxide-oxidations
Graphene makes titanium dioxide-graphene oxide quality be the 2% of 0.5g chitosan in acetic acid solution, add 0.005g,
0.01g, 0.015g sodium lignin sulfonate (i.e. the quality of sodium lignin sulfonate be 0.5g chitosan 1%, 2%, 3%) carry out afterwards
Constant temperature stirs 2h at 70 DEG C after ultrasonic disperse 30min, and gained titanium dioxide-graphene oxide, sodium lignin sulfonate are dispersed
It is poured into square dies after uniform casting solution degassing, 60 DEG C of drying 5h, the composite membrane after drying immerses in 5% sulfuric acid solution
It is crosslinked, the acid of striping excess surface is washed with deionized water in crosslinking afterwards for 24 hours.According to the difference of sodium lignin sulfonate doping,
Sample is respectively designated as 2/ sodium lignin sulfonate 1 of chitosan/titanium dioxide-graphene oxide, chitosan/titanium dioxide-oxidation
2/ sodium lignin sulfonate 2 of graphene, 2/ sodium lignin sulfonate 3 of chitosan/titanium dioxide-graphene oxide.
Digital n after above-mentioned titanium dioxide-graphene oxide represents the titanium dioxide-graphene oxide additive amount being added
It is the n% (quality) of chitosan, the additive amount that the digital m after sodium lignin sulfonate represents the sodium lignin sulfonate being added is that shell is poly-
The m% (quality) of sugar.
It is oxidation-stabilized to gained chitosan/titanium dioxide-graphene oxide/sodium lignin sulfonate compound proton exchange membrane
Property is measured, and measuring method is with embodiment 1, and the results are shown in Table 3.The addition of sodium lignin sulfonate makes oxidation stability into one
Step enhancing.
Table 3
Embodiment 6:
To 1 gained chitosan proton exchange membrane of embodiment, 2 gained chitosan/titanium dioxide of embodiment-carbon nanotube proton
4 gained chitosan/titanium dioxide of exchange membrane and embodiment-carbon nanotube/sodium lignin sulfonate proton exchange membrane proton conduction
Rate is assessed.
It is tested using proton conductivity of the AC impedence method to above-mentioned proton exchange membrane.The proton sufficiently to absorb water is handed over
The square that membrane sample is cut to 1 × 1cm is changed, two is sandwiched in and is connected between the stainless steel polar plate of binding post, use electrochemical workstation
Its impedance is analyzed.The impedance value that the high band of ac impedance spectroscopy fits is the resistance of film.Test condition are as follows: scanning frequency
Rate 100kHz to 0.1Hz, voltage amplitude 5mV.Its conductivity is calculated with formula σ=d/RA.Wherein, d is film thickness (cm), is 75
μm；R is resistance (Ω), is detected by ac impedance spectroscopy to it；A is film effective area (cm2), choose 1cm2；σ is proton
Conductivity (Scm-1)。
Proton conductivity increases after it can be seen that addition titanium dioxide-carbon nanotube in Fig. 4 a and Fig. 4 b, is added
Proton conductivity further increases after sodium lignin sulfonate, when titanium dioxide-carbon nanotube additive amount be chitosan 5%, wood
When quality sodium sulfonate additive amount is the 2% of chitosan, proton conductivity can improve about 40%.
Embodiment 7:
To the chitosan/oxidized graphene proton exchange membrane of 3 gained of embodiment, chitosan/titanium dioxide-graphene oxide matter
Proton exchange and embodiment 5 gained chitosan/titanium dioxide-graphene oxide/sodium lignin sulfonate proton exchange membrane resistance alcohol
Performance indicates that wherein methanol permeability is lower with methanol permeability, and alcohol-rejecting ability is better.
Methanol permeability is tested using diaphragm diffusion cell, be injected separately into the diffusion cell of two sides 200ml 3M methanol solution and
Distilled water, the fixed membrane sample to be measured in diffusion cell centre and sample can touch two sides liquid, interval 3h, 5h, 7h, and 9h is distilling
The sampling of water side is to be measured.Methanol concentration is measured by gas chromatograph in prepare liquid.
As shown in figure 5 a and 5b, chitosan/oxidized graphene proton exchange membrane, chitosan/titanium dioxide-oxidation are compared
The alcohol-rejecting ability of graphene proton exchange membrane improves, and alcohol-rejecting ability further increases after sodium lignin sulfonate is added.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. a kind of preparation method of titania modified low-dimensional carbon material/chitosan proton exchange membrane comprising following steps:
Using chitosan as matrix filmogen, filled out using titania modified low-dimensional carbon material as the nanometer in proton exchange membrane
Material, prepares titania modified low-dimensional carbon material/chitosan proton exchange membrane.
2. preparation method according to claim 1, it is characterised in that: it is poly- to prepare titania modified low-dimensional carbon material/shell
When saccharic proton exchange, sodium lignin sulfonate is additionally added as additive.
3. preparation method according to claim 1, it is characterised in that: the titania modified low-dimensional carbon material includes two
Titanium oxide is modified zero dimension carbon material, titania modified one-dimensional carbon material, titania modified two-dimentional carbon material；Optionally, institute
Stating titania modified low-dimensional carbon material includes titanium dioxide-carbon nanotube or titanium dioxide-graphene oxide.
4. preparation method according to claim 3, it is characterised in that: the titanium dioxide-carbon nanotube is to coat thereon
There is the carbon nanotube of titanium dioxide；Optionally, the preparation of the titanium dioxide-carbon nanotube is the following steps are included: (1) receives carbon
Mitron, modifying agent and water carry out carbon nanotube commonly through at least one of grinding, ultrasonic disperse or mechanical stirring mode
It is modified, collect modified carbon nano-tube and drying, in which: the carbon nanotube includes carboxylic acid carbon nanotube, and the modifying agent includes
At least one of sodium lignin sulfonate, neopelex or oleoyl oxygroup ethanesulfonic acid sodium；(2) carbon modified after drying
Nanotube disperses in organic solvent, water to be added and butyl titanate is hydrolyzed, and washs, is centrifuged, products therefrom after the reaction was completed
Filter drying；(3) high-temperature heat treatment under conditions of 300-600 DEG C of the product after drying.
5. preparation method according to claim 3, it is characterised in that: the titanium dioxide-graphene oxide, which is negative, to be loaded with
The graphene oxide sheet of titanium dioxide；Optionally, the preparation of the titanium dioxide-graphene oxide is the following steps are included: by sulphur
Sour titanium is placed in scattered graphene oxide water solution and mixes, and then mixed liquor is transferred in reaction kettle and is being dried in vacuo
It is reacted in case, washs after the reaction was completed, is dry.
6. the preparation method according to claim 4, it is characterised in that: the carboxylic acid carbon nanotube be outer tube diameter 10nm~
The multi wall or single wall carboxylic acid carbon nanotube of 20nm, 10 μm of length~30 μm, purity: >=98wt%.
7. preparation method according to claim 1, it is characterised in that: prepared by solution casting method titania modified low
Tie up carbon material/chitosan proton exchange membrane；Optionally, the solution casting method is the following steps are included: by titania modified low
It ties up carbon material ultrasonic disperse in aqueous solution, obtains uniform dispersion liquid；Glacial acetic acid and chitosan is added in dispersion liquid, heating
Stirring forms uniform casting solution；It is poured into mold after casting solution is deaerated, is dried to film and falls off naturally；Gained film is immersed in
It is crosslinked in cross-linking reagent dilute sulfuric acid.
8. preparation method according to claim 7, it is characterised in that: by titania modified low-dimensional carbon material ultrasonic disperse
When in aqueous solution, further include by sodium lignin sulfonate ultrasonic disperse in aqueous solution.
9. a kind of titania modified low-dimensional carbon material/shell obtained by preparation method described in one of claim 1-8 is poly-
Saccharic proton exchange.
10. titania modified low-dimensional carbon material/chitosan proton exchange membrane described in a kind of claim 9 is in a fuel cell
Using.
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