CN101798178A - Medium-high temperature proton conductor material and preparation method thereof - Google Patents
Medium-high temperature proton conductor material and preparation method thereof Download PDFInfo
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- CN101798178A CN101798178A CN 201010135382 CN201010135382A CN101798178A CN 101798178 A CN101798178 A CN 101798178A CN 201010135382 CN201010135382 CN 201010135382 CN 201010135382 A CN201010135382 A CN 201010135382A CN 101798178 A CN101798178 A CN 101798178A
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Abstract
The invention relates to a medium-high temperature proton conductor material and a preparation method thereof in the material technical field. The components and the mole ratio of the medium-high temperature proton conductor material is that metallic oxide precursor, deionized water, organic solvent, inorganic acid and additive are 1 to 1-8 to 1-100 to 0-0.1 to 0-5. The preparation method comprises that the metallic oxide precursor, the deionized water, the organic solvent, the inorganic acid aqueous solution and the additive are mixed and made into sol, to which ionic liquid is added, mixed sol is obtained after strong stir, the sol is poured into a container or on a base plate, the sol is solidified and molded and gel is fabricated, the thermal processing is carried out on the gel, and the proton conductive material is fabricated. The proton conductivity of the proton conductive material obtained from the invention is above 200 degrees centigrade and can reach 10-2Scm-1 order. The proton conductive material can be applied to the fields of fuel cell, electrochemical sensor, super capacitor and the like.
Description
Technical field
What the present invention relates to is the proton conductor material in a kind of material technology field and preparation method thereof, specifically is a kind of at middle high-temperature proton-conductor material more than 200 ℃ and preparation method thereof.
Background technology
Solid-state proton-conducting material can be used as the electrolyte of fuel cell, chemical sensor and super capacitor etc. and uses, thereby is subjected to people's attention.Proton conductive polymer electrolytes mainly is the Nafion film, has higher proton conductivity and certain chemistry, mechanical stability, is widely used in low-temperature fuel cell.Yet the Nafion film costs an arm and a leg, thermostability is limited; When high temperature uses, can cause the functional group loss of grafting; Owing to be high fluoropolymer, the recycle of material and waste treatment difficulty are brought environmental pressure.Proton conduction unorganic glass and stupalith, preparation technology is simple, cost is low, and high low temperature all has processing property preferably, therefore is expected to become the substitute of polymer dielectric film.
Adopt sol-gel process, can prepare sintered glass and porous ceramic film material with proton conduction character, its proton conduction mechanism is, proton separates from the hole surface hydroxyl, form the cluster ion with the water of absorption,, carry out proton conduction by between hydroxyl and water molecules, jumping.Compare with the Nafion film, sintered glass, porous ceramics proton conductivity lower usually, this be the restriction its application a gordian technique difficult problem.
Through the prior art literature search is found that people such as Daiko are at " Microporous ﹠amp; Mesoporous Materiels " deliver " Pore size effect on proton transfer insol-gel porous silica " (hole dimension of proton conduction influence in the sol-gel porous silica) on (microporous mesoporous material 2004 the 69th phase the 149th page), reported the silica glass of 400 degree sintering processes, 50 ℃, during relative humidity 80%, proton conductivity is 2 * 10
-3Scm
-1People such as F.M.Colomer are at " Electrochemical ﹠amp; Solid-State Letters " deliver " Nanopore ceramic membranes as novel electrolytes for protonexchange membranes " (as the new electrolytical nanoporous ceramic membrane that is applied to proton exchange membrane) on (the solid-state wall bulletin of electrochemistry) (1999 the 2nd phase the 313rd page), the document discloses the TiO of 400 degree sintering processes
2And A
2O
3Ceramic membrane is under 80 ℃, humidity 81% and 92 ℃, humidity 81% condition, and proton conductivity is respectively 3.9 * 10
-3Scm
-1With 2 * 10
-3Scm
-1Add phosphorus containing components in glass, the pottery, introduce the POH group, can promote proton conduction.This be because, compare with groups such as SiOH, TiOH, AlOH, the POH functional group is more prone to ion characteristic, hole wall surface has more peracidity, makes that proton is easier to break away from and migration from oh group, thereby improves proton conductivity.
Find again by retrieval, people such as Nogami deliver " A sol-gel-derived class as a fuel cell electrolyte " (glass of the sol-gel preparation of the battery electrolyte that acts as a fuel) on " Advanced Materials " (advanced material) (2000 the 12 1370th page), reported the P of 700 degree sintering processes
2O
5-SiO
2Glass is when 50 ℃ and humidity 70%, and specific conductivity is 2.2 * 10
-2Scm
-1In addition, people such as Yamada deliver " A self-ordered; crystalline glass, mesoporous nanocompositewith high proton conductivity of 2x10 on " Journal of the American Chemical Society " (american chemical association will)
-2S cm
-1At intermediate temperature " (have 2x10 in middle temperature
-2S cm
-1The meso-porous nano synthetics from rule crystallization glass of high proton conductivity) (2005 the 127th phase the 13092nd page) disclose P
2O
5-TiO
2Pottery 160 ℃, specific conductivity is 1.6 * 10 during 100% humidity
-2Scm
-1In the above document, the high proton conductivity of disclosed glass and pottery all needs higher relative humidity.Therefore, its use temperature and humidity control all are restricted, and then influence its application in fuel cell.
Summary of the invention
The present invention is directed to the prior art above shortcomings, a kind of middle high-temperature proton-conductor material and preparation method thereof is provided.The present invention adopts sol-gel method to prepare in glass/ionic liquid high-temperature proton-conductor simple, the with low cost characteristics that have technology.After Overheating Treatment, the intensity of glass proton conductor improves greatly.Prepared ionic liquid/glass the proton conductor of the present invention can reach 10 still having high proton conductivity more than 200 ℃
-2More than the S/cm.
The present invention is achieved by the following technical solutions:
High-temperature proton-conductor material in the present invention relates to, its component and mol ratio are: metal oxide precursor, deionized water, organic solvent, mineral acid, additive are: 1: 1～8: 1～100: 0～0.1: 0～5; Metal oxide precursor refers to the compound of metal alkoxide or metal alkoxide; Organic solvent is meant: a kind of or its combination in methyl alcohol, ethanol or the propyl alcohol; Mineral acid is meant: a kind of or its combination in hydrochloric acid, sulfuric acid, the acetic acid; Additive is meant: tensio-active agent.
Described metal alkoxide comprises: methyl silicate, four titanium butoxide, four titanium propanolates, zirconium-n-propylate, tetrabutyl zirconate, aluminium butoxide, five butoxy niobiums, four butoxy tin; A kind of or its combination in methyltrimethoxy silane or the diethyl diethoxy silane.
Described phosphoric acid is meant: one or several in the product of phosphoric acid condensation.
Described additive is one or more in Brij56 (SIGMA-ALDRICH), Pluronic, F127 (BASF), the methyl ethyl diketone.
The present invention relates to aforesaid middle high-temperature proton-conductor preparation methods, may further comprise the steps:
The first step, with metal oxide precursor, deionized water, organic solvent, inorganic acid aqueous solution and additive through being mixed and made into colloidal sol, in colloidal sol, add ionic liquid then, stir back acquisition mixed sols through brute force.
Second step, be cast in colloidal sol in the container or on the substrate, the colloidal sol curing molding is made gelinite, then gelinite is heat-treated, and makes proton-conducting material.
Described ionic liquid is meant at standard atmosphere and depresses, is below 200 ℃ liquid ionic compound;
Described ionic liquid is not limited to the following ionic liquid of enumerating:
As: one or more in [dimethyl amine]/[trifluoromethanesulfonic acid] ionic liquid, [dimethyl amine]/[sulfuric acid] ionic liquid, [diethyl methylamine]/[trifluoromethanesulfonic acid] ionic liquid, [diethyl methylamine]/[sulfuric acid] ionic liquid, [diethyl methylamine]/[phosphoric acid] ionic liquid, [diethyl methylamine]/[phosphonic acids] ionic liquid etc.
Described metal oxide precursor and ion liquid mol ratio are 1: 0.1～10.
Described thermal treatment is meant: gelinite was remained in 100 ℃-300 ℃, the atmospheric environment of 0-40 5 minutes to 30 days.
The proton conductivity of the proton-conducting material that the present invention obtains can reach 10 more than 200 ℃
-2Scm
-1Magnitude.This proton-conducting material can be used for fields such as fuel cell, electrochemical sensor, super capacitor.
Description of drawings
Fig. 1 embodiment 1 preparation glass/proton conductivity of ionic liquid composite proton electro-conductive material under differing temps.
Embodiment
Below embodiments of the invention are elaborated, present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1:
Adopt sol-gel method to carry out material preparation: at first with tetraethoxy, deionized water and hydrochloric acid according to 1: 4: 4 * 10
-3Mol ratio was room temperature violent stirring 30 minutes.Then according to tetraethoxysilance: the molar percentage of [diethyl methylamine]/[trifluoromethanesulfonic acid] ionic liquid=3: 1, in solution, slowly add [diethyl methylamine]/[trifluoromethanesulfonic acid] ionic liquid, stirred 20 minutes.
The colloidal sol that obtains is poured in the culture dish, under room temperature environment, be converted into gel, make gelinite; The gelinite that obtains is placed heating container, under 1 atmospheric pressure,, obtain ionic liquid/glass composite material with middle high temperature proton conduction performance in 150 ℃ of insulations 30 hours.
Embodiment 2:
Adopt sol-gel method to carry out material preparation: at first with methyl silicate, deionized water and hydrochloric acid according to 1: 4: 4 * 10
-3Mol ratio was room temperature violent stirring 30 minutes.Then according to tetramethoxysilance: the molar percentage of [dimethyl amine]/[trifluoromethanesulfonic acid] ionic liquid=1: 0.1, in solution, slowly add [dimethyl amine]/[trifluoromethanesulfonic acid] ionic liquid, stirred 20 minutes.
The colloidal sol that obtains is poured in the culture dish, under room temperature environment, be converted into gel, make gelinite; The gelinite that obtains is placed heating container, under 1 atmospheric pressure,, obtain ionic liquid/glass composite material with middle high temperature proton conduction performance in 180 ℃ of insulations 10 hours.Gained ionic liquid/glass composite material performance is similar with embodiment 1.
Embodiment 3:
Adopt sol-gel method to carry out material preparation: at first with tetraethoxy, deionized water and hydrochloric acid according to 1: 4: 4 * 10
-3Mol ratio was room temperature violent stirring 30 minutes.Then according to tetraethoxysilance: the molar percentage of [diethyl methylamine]/[phosphoric acid] ionic liquid=1: 10, in solution, slowly add [diethyl methylamine]/[phosphoric acid] ionic liquids ionic liquids, stirred 20 minutes.
The colloidal sol that obtains is poured in the culture dish, under room temperature environment, be converted into gel, make gelinite; The gelinite that obtains is placed heating container, under 1 atmospheric pressure,, obtain ionic liquid/glass composite material with middle high temperature proton conduction performance in 200 ℃ of insulations 5 hours.Gained ionic liquid/glass composite material performance is similar with embodiment 1.
Embodiment 4:
Adopt sol-gel method to carry out material preparation: at first with tetraethoxy, deionized water, hydrochloric acid according to 1: 4: 4 * 10
-3Mol ratio was room temperature violent stirring 30 minutes.Then according to tetraethoxysilance: the molar percentage of [diethyl methylamine]/[phosphonic acids] ionic liquid=5: 1, in solution, slowly add [diethyl methylamine]/[phosphonic acids] ionic liquid, stirred 20 minutes.
The colloidal sol that obtains is poured in the culture dish, under room temperature environment, be converted into gel, make gelinite; The gelinite that obtains is placed heating container, under 1 atmospheric pressure,, obtain ionic liquid/glass composite material with middle high temperature proton conduction performance in 120 ℃ of insulations 15 hours.Gained ionic liquid/glass composite material performance is similar with embodiment 1.
Embodiment 5:
Adopt sol-gel method to carry out material preparation: at first with tetraethoxy, deionized water, hydrochloric acid according to 1: 10: 0.1 mol ratio room temperature violent stirring 30 minutes.Then according to tetraethoxysilance: the molar percentage of [dimethyl amine]/[sulfuric acid] ionic liquid=5: 1, in solution, slowly add [dimethyl amine]/[sulfuric acid] ionic liquid, stirred 20 minutes.
The colloidal sol that obtains is poured in the culture dish, under room temperature environment, be converted into gel, make gelinite; The gelinite that obtains is placed heating container, under 1 atmospheric pressure,, obtain ionic liquid/glass composite material with middle high temperature proton conduction performance in 120 ℃ of insulations 15 hours.Gained ionic liquid/glass composite material performance is similar with embodiment 1.
Embodiment 6:
Adopt sol-gel method to carry out material preparation: at first with tetraethoxy, deionized water, hydrochloric acid according to 1: 5: 0.1 mol ratio room temperature violent stirring 30 minutes.Then according to tetraethoxysilance: the molar percentage of [dimethyl amine]/[trifluoromethanesulfonic acid] ionic liquid=2: 1, in solution, slowly add [dimethyl amine]/[trifluoromethanesulfonic acid] ionic liquid, stirred 20 minutes.
The colloidal sol that obtains is poured in the culture dish, under room temperature environment, be converted into gel, make gelinite; The gelinite that obtains is placed heating container, under 1 atmospheric pressure,, obtain ionic liquid/glass composite material with middle high temperature proton conduction performance in 120 ℃ of insulations 15 hours.Gained ionic liquid/glass composite material performance is similar with embodiment 1.
Embodiment 7:
The 10g tetraethoxysilance is diluted in the 30g ethanol, adds 4g aqueous hydrochloric acid (0.1mol/l), stirs 1h at 60 ℃.Adding ethanol then is surfactant B rij 56 (SIGMA-ALDRICH) solution of solvent, room temperature continuously stirring 1h, then according to tetraethoxysilance: the molar percentage of [dimethyl amine]/[trifluoromethanesulfonic acid] ionic liquid=3: 1, in solution, slowly add [dimethyl amine]/[trifluoromethanesulfonic acid] ionic liquid, stirred 20 minutes.
The colloidal sol that obtains is poured in the culture dish, under room temperature environment, be converted into gel, make gelinite; The gelinite that obtains is placed heating container, under 1 atmospheric pressure,, obtain ionic liquid/glass composite material with middle high temperature proton conduction performance in 150 ℃ of insulations 15 hours.Gained ionic liquid/glass composite material performance is similar with embodiment 1.
Embodiment 8:
The colloidal sol preparation: the 10g tetraethoxysilance is diluted in the 30g methyl alcohol, add 4g aqueous hydrochloric acid (0.1mol/l), stir 1h at 60 ℃, then according to tetraethoxysilance: the molar percentage of [dimethyl amine]/[trifluoromethanesulfonic acid] ionic liquid=4: 1, in solution, slowly add [dimethyl amine]/[trifluoromethanesulfonic acid] ionic liquid, stirred 20 minutes.
The colloidal sol that obtains is poured in the culture dish, under room temperature environment, be converted into gel, make gelinite; The gelinite that obtains is placed heating container, under 1 atmospheric pressure,, obtain ionic liquid/glass composite material with middle high temperature proton conduction performance in 150 ℃ of insulations 15 hours.Gained ionic liquid/glass composite material performance is similar with embodiment 1.
Embodiment 9:
With tetrabutyl zirconate: methyl ethyl diketone: water: propyl alcohol: tensio-active agent Pluronic F127 (BASF)=1: 5: 5: 20: 0.01 ratio preparation colloidal sol.In proportion zirconium-n-butylate is diluted in the butanols, adds methyl ethyl diketone and water, at stirring at room 1h; Tensio-active agent Pluronic F127 is dissolved in the butanols of 5 times of volumes, at stirring at room 1h; With above-mentioned two kinds of solution mixing, room temperature continuously stirring 2h, then according to zirconium: the molar percentage of [diethyl methylamine]/[trifluoromethanesulfonic acid] ionic liquid=3: 1, in solution, slowly add [diethyl methylamine]/[trifluoromethanesulfonic acid] ionic liquid, stirred 20 minutes.
The colloidal sol that obtains is poured in the culture dish, under room temperature environment, be converted into gel, make gelinite; The gelinite that obtains is placed heating container, under 1 atmospheric pressure,, obtain ionic liquid/glass composite material with middle high temperature proton conduction performance in 150 ℃ of insulations 15 hours.Gained ionic liquid/glass composite material performance is similar with embodiment 1.
Embodiment 10:
According to four titanium propanolates: propyl alcohol: the ratio preparation colloidal sol of tensio-active agent=1: 20: 0.1.In proportion titanium isopropylate is diluted in the propyl alcohol; Tensio-active agent Pluronic F127 is dissolved in the propyl alcohol of 5 times of volumes simultaneously, at stirring at room 1h.With above-mentioned two kinds of solution mixing, room temperature continuously stirring 2h.Then according to titanium: the molar percentage of [dimethyl amine]/[trifluoromethanesulfonic acid] ionic liquid=4: 1, in solution, slowly add [dimethyl amine]/[trifluoromethanesulfonic acid] ionic liquid, stirred 20 minutes.
The colloidal sol that obtains is poured in the culture dish, under room temperature environment, be converted into gel, make gelinite; The gelinite that obtains is placed heating container, under 1 atmospheric pressure,, obtain ionic liquid/glass composite material with middle high temperature proton conduction performance in 150 ℃ of insulations 15 hours.Gained ionic liquid/glass composite material performance is similar with embodiment 1.
The foregoing description performance test:
The specific conductivity test of ionic liquid/glass composite proton electro-conductive material is a sputter gold electrode on sample, and the lead that connects sample is the Au lead.(voltage of alternating current is 10mV to specific conductivity for SI-1260, Solartron) test, and test is carried out in vacuum drying oven with the impedance spectrometer.Figure one is that the sample that obtains according to embodiment 1 is in the specific conductivity more than 100 ℃.The result shows that ionic liquid/glass composite proton electro-conductive material rises along with the rising of temperature in (more than 100 ℃) specific conductivity under the middle hot conditions.Specific conductivity can reach 10 in the time of 200 ℃
-2S/cm.
Present embodiment has obtained to have the ionic liquid/glass composite proton conductor of high proton electric conductivity by sol-gel method and thermal treatment process under middle hot conditions.Be with a wide range of applications, as in fields such as fuel cell, electrochemical sensor and super capacitors.
Claims (8)
1. high-temperature proton-conductor material in a kind, it is characterized in that its component and mol ratio are: metal oxide precursor, deionized water, organic solvent, mineral acid, additive are: 1: 1～8: 1～100: 0～0.1: 0～5; Metal oxide precursor refers to the compound of metal alkoxide or metal alkoxide; Organic solvent is meant: a kind of or its combination in methyl alcohol, ethanol or the propyl alcohol; Mineral acid is meant: a kind of or its combination in hydrochloric acid, sulfuric acid, the acetic acid; Additive is meant: tensio-active agent.
2. the preparation method of proton-conducting material according to claim 1, it is characterized in that described metal alkoxide comprises: methyl silicate, four titanium butoxide, four titanium propanolates, zirconium-n-propylate, tetrabutyl zirconate, aluminium butoxide, five butoxy niobiums, four butoxy tin; A kind of or its combination in methyltrimethoxy silane or the diethyl diethoxy silane.
3. the hydro-thermal treatment preparation method thereof of proton conductive composite according to claim 1 is characterized in that, described phosphoric acid is meant: one or several in the product of phosphoric acid condensation.
4. the preparation method of proton-conducting material according to claim 1 is characterized in that, described additive is one or more in Brij56, Pluronic, F127, the methyl ethyl diketone.
5. consistent middle high-temperature proton-conductor preparation methods according to claim 1 is characterized in that, may further comprise the steps:
The first step, with metal oxide precursor, deionized water, organic solvent, inorganic acid aqueous solution and additive through being mixed and made into colloidal sol, in colloidal sol, add ionic liquid then, stir back acquisition mixed sols through brute force;
Second step, be cast in colloidal sol in the container or on the substrate, the colloidal sol curing molding is made gelinite, then gelinite is heat-treated, and makes proton-conducting material.
6. high-temperature proton-conductor preparation methods in according to claim 5 is characterized in that, described ionic liquid is meant at standard atmosphere and depresses, is below 200 ℃ liquid ionic compound.
7. according to claim 5 or 6 described middle high-temperature proton-conductor preparation methods, it is characterized in that described ionic liquid is one or more in [dimethyl amine]/[trifluoromethanesulfonic acid] ionic liquid, [dimethyl amine]/[sulfuric acid] ionic liquid, [diethyl methylamine]/[trifluoromethanesulfonic acid] ionic liquid, [diethyl methylamine]/[sulfuric acid] ionic liquid, [diethyl methylamine]/[phosphoric acid] ionic liquid, [diethyl methylamine]/[phosphonic acids] ionic liquid etc.
8. high-temperature proton-conductor preparation methods in according to claim 4 is characterized in that described metal oxide precursor and ion liquid mol ratio are 1: 0.1～10.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172890A (en) * | 2013-01-24 | 2013-06-26 | 巨化集团技术中心 | Preparation method of organic/inorganic composite intermediate/high-temperature proton conductive membrane |
| CN109585889A (en) * | 2018-11-29 | 2019-04-05 | 江苏师范大学 | A kind of preparation method of ionic gel matrix proton exchange |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1927923A (en) * | 2006-09-06 | 2007-03-14 | 北京理工大学 | Ion liquid, non-aqueous liquid and polymer electrolyte material based on the same |
| CN101671120A (en) * | 2009-10-21 | 2010-03-17 | 上海交通大学 | Preparation method of proton conducting material |
-
2010
- 2010-03-30 CN CN 201010135382 patent/CN101798178A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1927923A (en) * | 2006-09-06 | 2007-03-14 | 北京理工大学 | Ion liquid, non-aqueous liquid and polymer electrolyte material based on the same |
| CN101671120A (en) * | 2009-10-21 | 2010-03-17 | 上海交通大学 | Preparation method of proton conducting material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172890A (en) * | 2013-01-24 | 2013-06-26 | 巨化集团技术中心 | Preparation method of organic/inorganic composite intermediate/high-temperature proton conductive membrane |
| CN109585889A (en) * | 2018-11-29 | 2019-04-05 | 江苏师范大学 | A kind of preparation method of ionic gel matrix proton exchange |
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Open date: 20100811 |