CN106099146A - A kind of modified halloysite nanotubes for PEM and preparation method thereof - Google Patents
A kind of modified halloysite nanotubes for PEM and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of modified halloysite nanotubes for PEM and preparation method thereof.First with dopamine hydrochloride, halloysite nanotubes is carried out Surface coating process, then introduces active halogen atom, then by ATRP reaction by the monomer glycerol polymerization with sulfonic acid group on halloysite nanotubes, obtain described modified halloysite nanotubes.The present invention by halloysite nanotubes glycerol polymerization with sulfonic acid group monomer introduce sulfonic acid group, modification halloysite nanotubes is adulterated with sulfonated polymer electrolyte, prepares the compound proton exchange membrane with high proton electrical conductivity and stable mechanical performance.
Description
Technical field
The invention belongs to the organically-modified technical field of inorganic nano-particle, particularly to a kind of changing for PEM
Property halloysite nanotubes and preparation method thereof.
Background technology
PEM is one of core component of fuel cell, is responsible for proton conducting and separates the dual work of anode and cathode
With, the operation conditions of fuel cell is played conclusive effect.And the perfluorosulfonic acid proton exchange film being widely used at present is to the greatest extent
Pipe has higher proton conductivity, but there is also fuel methanol and permeate serious problem from anode to negative electrode.
The inorganic nanoparticles that adulterates in PEM can make its alcohol-rejecting ability and mechanical stability obtain certain journey
The improvement of degree, but the proton conductivity of film can be reduced.
Summary of the invention
Not enough for prior art, the invention provides a kind of modified halloysite nanotubes for PEM and
Preparation method.
A kind of modified halloysite nanotubes for PEM, first enters halloysite nanotubes with dopamine hydrochloride
Row Surface coating processes, and then introduces active halogen atom, then is grafted poly-by ATRP reaction by the monomer with sulfonic acid group
Close on halloysite nanotubes, obtain described modified halloysite nanotubes.
The described monomer with sulfonic acid group is Sodium styrene sulfonate (NaSS) or 2-acrylamide-2-methyl propane sulfonic sodium
(AMPS)。
The preparation method of a kind of modified galapectite for PEM, comprises the following steps:
(1) in Tris-hydrochloride buffer, halloysite nanotubes, dopamine hydrochloride are added, ultrasonic mix homogeneously, then
Magnetic agitation reaction 4～24h, cleans, obtains the halloysite nanotubes D-HNTs that dopamine hydrochloride is modified after drying；
(2) under inert gas shielding, add oxolane, triethylamine, D-HNTs and initiator, magnetic agitation reaction 4～
24h, cleans, obtains the halloysite nanotubes Br-HNTs that active bromine is modified after drying；Wherein said initiator is alpha-brominated
Ester；
(3) under inert gas shielding add N-N dimethylformamide, deionized water, with sulfonic acid group monomer, urge
Agent, part and Br-HNTs, magnetic agitation reaction 4～96h, clean, obtain described modified halloysite nanotubes S-after drying
HNTs；Described catalyst is CuBr or CuBr and CuBr2Mixture；Described part is five methyl diethylentriamine or pregnancy
Base triethylene tetramine.
In step (1), the concentration of described Tris-hydrochloride buffer is 5～20mmol/L, with the KOH of 0.01mol/L or
NaOH solution regulation pH is 7～9；And/or
Dopamine hydrochloride concentration in reaction system is 4～20mmol/L；And/or
In reaction system, dopamine hydrochloride is 0.1～0.5mmol/ (g angstrom relative to the addition of halloysite nanotubes
Lip river stone nanotube).
In step (2), oxolane is (10～30) with the volume ratio of triethylamine: 1；And/or
In reaction system, the volume fraction of initiator is 5%～25%；And/or
In reaction system, the initiator addition relative to D-HNTs is 10～30mmol/ (g D-HNTs).
In step (3), it is (30～50) with the monomer of sulfonic acid group, catalyst, the mol ratio of part: (3～5): (1
～3)；And/or
It is 10～50mmol/ (g Br-HNTs) with the monomer of the sulfonic acid group addition relative to Br-HNTs.
In step (1), described cleaning is for using deionized water eccentric cleaning；And/or
In step (2) and (3), described cleaning be successively with acetone and methanol aqueous solution that volume fraction is 50% ultrasonic from
The heart cleans；And/or
In step (1), (2) and (3), described dry temperature is 30～50 DEG C.
A kind of compound proton exchange membrane prepared for the modified galapectite of PEM.
The preparation method of described compound proton exchange membrane comprises the following steps:
Modification halloysite nanotubes S-HNTs is evenly spread to make in deionized water dispersion liquid, by sulfonated polyether-ether-ketone
It is dissolved in N,N-dimethylacetamide formation solution, by dispersion liquid and solution mix homogeneously, casting film, wherein S-under room temperature
The weight/mass percentage composition of HNTs is 5wt%～20wt%；Film is dried at 60～100 DEG C 20～30h, then 80～100
It is vacuum dried 10～15h at DEG C, in 0.5～1.5mol/L dilute sulfuric acid, finally soaks the solvent of residual in 20～30h removing films,
Wash unnecessary sulphuric acid with water, prepare compound proton exchange membrane.
The invention have the benefit that
The present invention, will be changed with the monomer introducing sulfonic acid group of sulfonic acid group by glycerol polymerization on halloysite nanotubes
Property halloysite nanotubes and sulfonated polymer electrolyte adulterate, prepare and there is high proton electrical conductivity and stable mechanical performance
Compound proton exchange membrane.
Compound proton exchange membrane by the nano tube structure of galapectite as proton transmitting channel, the nanotube-shaped knot of galapectite
Structure can be effectively increased the water content in film, promotes proton transport；Sulfonic acid group can provide free proton, and has parent
Aqueous, can form hydrophilic region, promote proton transport further, and the proton conductivity of film is further enhanced, and especially exists
Under low relative humidity, proton conductivity has lifting greatly.Additionally, due to the existence of galapectite in film, suppression film is because inhaling effectively
Water rate raises the excessive expansion caused, and the dimensional stability of film is improved, and improves the service life of film.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention will be further described.It is emphasized that the description below is only
Exemplary rather than in order to limit the scope of the present invention and application thereof.
Embodiment 1
By molten for 0.5mmol Tris-hydrochloric acid in 50ml deionized water, it be adjusted to pH=8.5 with 0.01mol/L NaOH, add
Enter 2g HNTs and 0.5mmol dopamine hydrochloride, ultrasonic 30min, magneton stirring reaction 4h, use deionized water eccentric cleaning, 30
～at 50 DEG C, obtain D-HNTs after drying；
In 50ml there-necked flask, logical argon gets rid of steam, adds 20ml THF, 1ml triethylamine, 1.5g D-HNTs, 3ml
2-bromo-2-methyl-prop acylbromide (BIBB), magneton stirring reaction 8h, is the methanol aqueous solution of 50% by acetone and volume fraction successively
Ultrasonic eccentric cleaning, is dried to obtain Br-HNTs at 30～50 DEG C；
In 50ml there-necked flask, logical argon gets rid of air, adds 10ml N-N dimethylformamide (DMF), 10ml deionization
Water, 40mmol NaSS, 2mmol CuBr, 2mmol CuBr2, 2mmol hexamethyl triethylene tetramine, 1.5g Br-HNTs, magneton
Stirring reaction 24h, successively by acetone and the ultrasonic eccentric cleaning of methanol aqueous solution that volume fraction is 50%, is dried at 30～50 DEG C
Obtain NaSS graft modification halloysite nanotubes NaSS-HNTs.
Above-mentioned NaSS modification halloysite nanotubes is evenly spread to make in deionized water dispersion liquid, sulfonated polyether ether
Ketone is dissolved in N,N-dimethylacetamide formation solution, the most at room temperature dispersion liquid and solution is mixed, stirs, casting
Film forming, wherein, the content of NaSS modification halloysite nanotubes is 15wt%, and film is put into 80 DEG C of dry 24h in baking oven, then 80
12h it is vacuum dried at DEG C.The last 24h that soaks in sulfuric acid solution goes out the solvent of residual in striping, washes unnecessary sulphuric acid with water, system
Obtain compound proton exchange membrane.The proton conductivity of test compound PEM, result is as shown in table 1.
Embodiment 2
By molten for 0.5mmol Tris-hydrochloric acid in 50ml deionized water, it be adjusted to pH=8.5 with 0.01mol/L NaOH, depend on
Secondary addition 2g galapectite and 0.5mmol dopamine hydrochloride, ultrasonic 30min, magneton stirring reaction 10h, washing obtains after drying
D-HNTs；
In 50ml there-necked flask, logical argon gets rid of steam, adds 20ml THF, 1ml triethylamine, 1.5g D-HNTs, 3ml
BIBB, magneton stirring reaction 24h, washing is dried to obtain Br-HNTs；
In 50ml there-necked flask, logical argon gets rid of air, add 10ml DMF, 10ml deionized water, 40mmol NaSS,
2mmol CuBr、2mmol CuBr2, 2mmol hexamethyl triethylene tetramine, 1.5g Br-HNTs, magneton stirring reaction 48h, wash
Wash and be dried to obtain NaSS modification halloysite nanotubes NaSS-HNTs.
Being doped into PEM and test its proton conductivity by the halloysite nanotubes that above-mentioned NaSS is modified, result is such as
Shown in table 1.Film forming procedure is identical with in embodiment 1.
Embodiment 3
By molten for 0.5mmol Tris-hydrochloric acid in 50ml deionized water, being adjusted to pH with 0.01mol/L NaOH is 8.5, depends on
Secondary addition 2g galapectite and 0.5mmol dopamine hydrochloride, ultrasonic 30min, magneton stirring reaction 4h, washing obtains D-after drying
HNTs；
In 50ml there-necked flask, logical argon gets rid of steam, is sequentially added into 20ml THF, 1ml triethylamine, 1.5g D-
HNTs, 3ml BIBB, magneton stirring reaction 8h, washing is dried to obtain Br-HNTs；
In 50ml there-necked flask, logical argon gets rid of air, is sequentially added into 10ml DMF, 10ml deionized water, 40mmol
AMPS、2mmol CuBr、2mmol CuBr2, 2mmol hexamethyl triethylene tetramine, 1.5g Br-HNTs, magneton stirring reaction
24h, washing is dried to obtain AMPS modification halloysite nanotubes AMPS-HNTs.
Being doped into PEM and test its proton conductivity by the halloysite nanotubes that above-mentioned AMPS is modified, result is such as
Shown in table 1.Film forming procedure is with identical in embodiment 1.
Embodiment 4
By molten for 0.5mmol Tris-hydrochloric acid in 50ml deionized water, being adjusted to pH with 0.01mol/L NaOH is 8.5, depends on
Secondary addition 2g galapectite and 0.5mmol dopamine hydrochloride, ultrasonic 30min, magneton stirring reaction 10h, washing obtains after drying
D-HNTs；
Logical argon draining steam in 50ml there-necked flask, is sequentially added into 20ml THF, 1ml triethylamine, 1.5g D-HNTs,
3ml BIBB, magneton stirring reaction 24h, washing is dried to obtain Br-HNTs；
Logical argon air-discharging in 50ml there-necked flask, be sequentially added into 10ml DMF, 10ml deionized water, 40mmol AMPS,
2mmol CuBr、2mmol CuBr2, 2mmol hexamethyl triethylene tetramine, 1.5g Br-HNTs, magneton stirring reaction 48h, wash
Wash and be dried to obtain AMPS modification halloysite nanotubes AMPS-HNTs.
Being doped into PEM and test its proton conductivity by the halloysite nanotubes that above-mentioned AMPS is modified, result is such as
Shown in table 1.Film forming procedure is with identical in embodiment 1.
Comparative example 1
Sulfonated polyether-ether-ketone is dissolved in N,N-dimethylacetamide formation homogeneous solution, casting film, and 80 DEG C are dried
24h, is then vacuum dried 4h at 80 DEG C.Soaking in sulfuric acid solution one day and remove the solvent of residual in film, it is unnecessary to wash with water
Sulphuric acid.The proton conductivity of test film, result is as shown in table 1.
Comparative example 2
Non-modified halloysite nanotubes is evenly spread to make in deionized water dispersion liquid, sulfonated polyether-ether-ketone is molten
Solution is formed in N,N-dimethylacetamide, then by both the above mixed liquor mix homogeneously, casting film (halloysite nanotubes
Content be 15wt%), 80 DEG C of dry 24h, then at 80 DEG C be vacuum dried 4h.Sulfuric acid solution soaks one day and remove in film
The solvent of residual, washes unnecessary sulphuric acid with water.The proton conductivity of test film, result is as shown in table 1.
Table 1
Claims (9)
1. the modified halloysite nanotubes for PEM, it is characterised in that first with dopamine hydrochloride to an angstrom Lip river
Stone nanotube carries out Surface coating process, then introduces active halogen atom, then is reacted with sulfonic acid group by ATRP
Monomer glycerol polymerization, on halloysite nanotubes, obtains described modified halloysite nanotubes.
A kind of modified halloysite nanotubes for PEM, it is characterised in that described band
The monomer having sulfonic acid group is Sodium styrene sulfonate or 2-acrylamide-2-methyl propane sulfonic sodium.
3. the preparation method of a kind of modified galapectite for PEM described in claims 1 or 2, it is characterised in that
Comprise the following steps:
(1) in Tris-hydrochloride buffer, halloysite nanotubes, dopamine hydrochloride, ultrasonic mix homogeneously, then magnetic force are added
Stirring reaction 4～24h, cleans, obtains the halloysite nanotubes D-HNTs that dopamine hydrochloride is modified after drying；
(2) under inert gas shielding, oxolane, triethylamine, D-HNTs and initiator are added, magnetic agitation reaction 4～24h,
Clean, obtain the halloysite nanotubes Br-HNTs that active bromine is modified after drying；Wherein said initiator is alpha-brominated ester；
(3) under inert gas shielding, N-N dimethylformamide, deionized water, the monomer with sulfonic acid group, catalysis are added
Agent, part and Br-HNTs, magnetic agitation reaction 4～96h, clean, obtain described modified halloysite nanotubes S-after drying
HNTs；Described catalyst is CuBr or CuBr and CuBr2Mixture；Described part is five methyl diethylentriamine or pregnancy
Base triethylene tetramine.
4. according to the preparation method of the modified galapectite for PEM a kind of described in claims 3, it is characterised in that
In step (1), the concentration of described Tris-hydrochloride buffer is 5～20mmol/L, and KOH or NaOH solution with 0.01mol/L adjust
Joint pH is 7～9；And/or
Dopamine hydrochloride concentration in reaction system is 4～20mmol/L；And/or
In reaction system, dopamine hydrochloride is 0.1～0.5mmol/ (g galapectite relative to the addition of halloysite nanotubes
Nanotube).
5. according to the preparation method of the modified galapectite for PEM a kind of described in claims 3, it is characterised in that
In step (2), oxolane is (10～30) with the volume ratio of triethylamine: 1；And/or
In reaction system, the volume fraction of initiator is 5%～25%；And/or
In reaction system, the initiator addition relative to D-HNTs is 10～30mmol/ (g D-HNTs).
6. according to the preparation method of the modified galapectite for PEM a kind of described in claims 3, it is characterised in that
In step (3), it is (30～50) with the monomer of sulfonic acid group, catalyst, the mol ratio of part: (3～5): (1～3)；With/
Or
It is 10～50mmol/ (g Br-HNTs) with the monomer of the sulfonic acid group addition relative to Br-HNTs.
7. according to the preparation method of the modified galapectite for PEM a kind of described in claims 3, it is characterised in that
In step (1), described cleaning is for using deionized water eccentric cleaning；And/or
In step (2) and (3), described cleaning is ultrasonic centrifugal clear with acetone and the methanol aqueous solution that volume fraction is 50% successively
Wash；And/or
In step (1), (2) and (3), described dry temperature is 30～50 DEG C.
8. a kind of composite proton exchange prepared for the modified galapectite of PEM described in claims 1 or 2
Film.
The preparation method of a kind of PEM, it is characterised in that comprise the following steps:
Modification halloysite nanotubes S-HNTs is evenly spread to make in deionized water dispersion liquid, sulfonated polyether-ether-ketone is dissolved in
N,N-dimethylacetamide is formed solution, under room temperature by dispersion liquid and solution mix homogeneously, casting film, wherein S-HNTs
Weight/mass percentage composition is 5wt%～20wt%；Film is dried at 60～100 DEG C 20～30h, then true at 80～100 DEG C
Empty dry 10～15h, in 0.5～1.5mol/L dilute sulfuric acid, finally soak the solvent of residual in 20～30h removing films, wash with water
Remove unnecessary sulphuric acid, prepare described compound proton exchange membrane.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109351346A (en) * | 2018-11-14 | 2019-02-19 | 江苏科技大学 | A kind of preparation method and application of sulfonic acid type anion nano adsorber |
| CN109749115A (en) * | 2017-11-02 | 2019-05-14 | 中国石油化工股份有限公司 | A kind of hydrophilic polyurethane carrier and the preparation method and application thereof |
| CN110120539A (en) * | 2019-05-05 | 2019-08-13 | 华北电力大学 | A kind of preparation method and application of modified heteropoly acid nano material |
| CN113122205A (en) * | 2019-12-30 | 2021-07-16 | 中石化石油工程技术服务有限公司 | Sulfonated halloysite nanotube-based shale formation nano-micron plugging agent for drilling fluid and preparation method thereof |
| CN114192116A (en) * | 2021-11-05 | 2022-03-18 | 广州大学 | Modified halloysite composite material and application thereof |
| CN114883620A (en) * | 2022-07-11 | 2022-08-09 | 佛山市清极能源科技有限公司 | Proton exchange membrane and preparation method and application thereof |
| CN118610536A (en) * | 2024-08-08 | 2024-09-06 | 杭州德海艾科能源科技有限公司 | Proton exchange membrane for all-vanadium redox flow battery and preparation method thereof |
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| CN109749115A (en) * | 2017-11-02 | 2019-05-14 | 中国石油化工股份有限公司 | A kind of hydrophilic polyurethane carrier and the preparation method and application thereof |
| CN109351346A (en) * | 2018-11-14 | 2019-02-19 | 江苏科技大学 | A kind of preparation method and application of sulfonic acid type anion nano adsorber |
| CN110120539A (en) * | 2019-05-05 | 2019-08-13 | 华北电力大学 | A kind of preparation method and application of modified heteropoly acid nano material |
| CN113122205A (en) * | 2019-12-30 | 2021-07-16 | 中石化石油工程技术服务有限公司 | Sulfonated halloysite nanotube-based shale formation nano-micron plugging agent for drilling fluid and preparation method thereof |
| CN113122205B (en) * | 2019-12-30 | 2022-07-15 | 中石化石油工程技术服务有限公司 | Sulfonated halloysite nanotube-based shale formation nano-micron plugging agent for drilling fluid and preparation method thereof |
| CN114192116A (en) * | 2021-11-05 | 2022-03-18 | 广州大学 | Modified halloysite composite material and application thereof |
| CN114192116B (en) * | 2021-11-05 | 2024-03-19 | 广州大学 | Modified halloysite composite material and application thereof |
| CN114883620A (en) * | 2022-07-11 | 2022-08-09 | 佛山市清极能源科技有限公司 | Proton exchange membrane and preparation method and application thereof |
| CN118610536A (en) * | 2024-08-08 | 2024-09-06 | 杭州德海艾科能源科技有限公司 | Proton exchange membrane for all-vanadium redox flow battery and preparation method thereof |
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