CN1385915A - Composite type proteon exchange film for high-temp. direct methanol fue cell and preparation process thereof - Google Patents
Composite type proteon exchange film for high-temp. direct methanol fue cell and preparation process thereof Download PDFInfo
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- CN1385915A CN1385915A CN02115184A CN02115184A CN1385915A CN 1385915 A CN1385915 A CN 1385915A CN 02115184 A CN02115184 A CN 02115184A CN 02115184 A CN02115184 A CN 02115184A CN 1385915 A CN1385915 A CN 1385915A
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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
- Y02E60/10—Energy storage using batteries
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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
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Abstract
This invention relates to electric chemical fuel battery technology, the raw material of the compound proton exchange film with millimicron micropore structure used in the high temperature direct, carbinol fuel battery is processed with PVDF and PVA added by mixed inorganic multi-element acid millimicron ceramic powder by doctoblade hot pressure, brie-coated, rolling process or imprenated methods. The carbinol permeability at 80-180 deg.c in smaller than Nafion film with good performance of cardinal resistance, available in the operation at high temperature (above 100deg.c) of direct carbinol fuel battery proton exchange film.
Description
Technical field
The present invention relates to electrochemical fuel cell technology, high temperature direct methanol fuel cell proton exchange membrane in more detail the invention still further relates to the preparation method of this film.
Background technology
The discharging of world today's fuel-engined vehicle tail gas has become one of main source of environmental pollution, and development is that the electric automobile of power source then is to reduce fuel combustion vehicle exhaust emissions amount with the electric energy, reduces the effective means of environmental pollution degree.Fuel cell with " zero discharge " feature then is to be hopeful to replace existing fuel engines to make the novel energy of car power source most.Among various dissimilar fuel cells, direct methanol fuel cell (DMFC) except having the general advantage of other fuel cell, have also that fuel source is rich and easy to get, low price, be easy to transportation and storage, battery structure is simple, volume and weight is little (be about hydrogen oxygen fuel cell 1/3) and advantage such as cost lower (be about hydrogen oxygen fuel cell 1/2).Therefore, direct methanol fuel cell (DMFC) system is that optimum is used as the removable electrical source of power that electric automobile or other portable set are used.Because it is quite slow that the employed fuel methanol of this fuel cell system carries out at the catalytic oxidation below 100 ℃, influenced the overall performance of system.Therefore, high temperature (more than 100 ℃) direct methanol fuel cell becomes the new trend of fuel cell development.Yet, have the Nafion film that in direct methanol fuel cell, uses now and not only have expensive problem, but also exist that high temperature proton conduction performance is poor, methyl alcohol to the permeability of film high and this two shortcoming problem such as increase also along with the rising of temperature, be unsuitable for being used in high temperature direct methanol fuel cell aspect.Therefore, how improving the high temperature proton conduction speed of proton exchange membrane, reduce the permeability of methyl alcohol under its high temperature, develop the novel proton exchange membranes of high-performance and low-cost, is a great technical barrier of exploitation high temperature direct methanol fuel cell.The researcher concentrates on the proton exchange membrane aspect with the research emphasis of this types of fuel cells at present one after another.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art part, proton conduction performance and features good methanol diffusion resistance under a kind of high temperature are provided, and price is lower than the price of commercially available Nafion film, can be applicable to the compoiste proton exchange film in the high temperature direct methanol fuel cell.
The present invention also provides the preparation method of above-mentioned high temperature direct methanol fuel cell with compoiste proton exchange film.
High temperature direct methanol fuel cell compoiste proton exchange film of the present invention is to be raw material with commercially available Kynoar or polyvinyl alcohol, and add the nano ceramic powder that is mixed with inorganic multivariate acid, by the compoiste proton exchange film with nanometer micropore structure of curtain coating pressure sintering, coating method, rolling process or cement-dipping method preparation;
Described inorganic multivariate acid is meant that general formula is A
3BM
12O
40NH
2O has anion cluster and is [BM
12O
40]
nThe compound of structure (Keggin structure), A=H wherein, B=Si, P, M=Mo, W; Inorganic multivariate acid is selected from silico-tungstic acid, phosphomolybdic acid, phosphotungstic acid or silicomolybdic acid etc.;
Described nano ceramic powder is meant the ceramic compound that is mixed with inorganic multivariate acid, and nano inorganic ceramic powders wherein is selected from tripoli, zircon or SiO 2 powder, grain diameter≤30nm.
Concrete preparation process of the present invention is as follows:
(1) in nano ceramic powder, adds the nothing that is equivalent to nano ceramic powder weight 5%～50%
The machine polyacid, stand-by after mixing;
(2) get the nothing that is mixed with of 100 parts by weight of polyvinylidene fluoride or polyvinyl alcohol and 15～70 weight portions
The nano ceramic powder of machine polyacid mixes gets the raw materials ready;
(3) Kynoar or polyvinyl alcohol are dissolved in conventional solvent and are mixed with Polymer Solution, and
In this Polymer Solution, add the nano ceramic powder that is mixed with inorganic multivariate acid, evenly shake
Swung 5～30 minutes, conventional solvent wherein be selected from N-methyl pyrrolidone, acetone or
Water;
(4) adopt the curtain coating pressure sintering, this mixed liquor be tiled in the glass culture dish surface, room temperature～
90 ℃ were heated 10～40 minutes, and at room temperature dry 0.5～20 hour then, with solvent
The formed film in dry back is torn from the culture dish surface, 100～170 ℃ of following hot pressing 3～
Got final product in 20 minutes; Perhaps adopt coating method, rolling process or cement-dipping method prepared film forming.
The present invention compares with technology with current material has following advantage:
1. the composite type proton with nanometer micropore structure that utilizes preparation method proposed by the invention to make is handed over
Change film proton conduction performance excellence at high temperature, its proton conduction speed is greater than the matter of Nafion film
Sub-conductivity.
2. utilize the prepared proton exchange membrane of the present invention to have the nanometer micropore structure, 80～180 ℃ of temperature ranges
Methanol permeability little than Nafion film, features good methanol diffusion resistance.With sample 1 is example, sees table 1 for details.
3. to prepare the preparation technology of proton exchange membrane simple in the present invention, and the film cost is lower than the Nafion film, is easy to produce
Industryization can promote the development of high temperature direct methanol fuel cell.
Embodiment
Embodiment 1
At particle diameter is to mix in the SiO 2 powder of 7.5nm to be equivalent to the phosphotungstic acid of SiO 2 powder weight 30%, mixes.Take by weighing 100 parts by weight of polyvinylidene fluoride and 60 weight portions and be mixed with the silicon dioxide of phosphotungstic acid, Kynoar is dissolved in the N-methyl pyrrolidone forms Polymer Solution, to wherein adding the silicon dioxide that contains 30% phosphotungstic acid, evenly vibrated 20 minutes with ultrasonic wave; This mixed solution is tiled in the culture dish surface, heated 20 minutes down at 80 ℃, dry 15 hours film forming got final product this film in 10 minutes in 160 ℃ of following hot pressing at last under the room temperature, and prepared film is a sample 1.With preceding elder generation film was soaked under 80 ℃ in the deionized water 3 hours.The high temperature methanol crossover of sample 1 and Nafion film relatively see table 1 for details.
Embodiment 2
In particle diameter is the SiO 2 powder of 7.5nm, mix the silico-tungstic acid that is equivalent to SiO 2 powder weight 45%, mix.Take by weighing 100 parts by weight of polyvinylidene fluoride and 60 weight portions and be mixed with the silicon dioxide of phosphotungstic acid, Kynoar is dissolved in the N-methyl pyrrolidone forms Polymer Solution, to wherein adding the silicon dioxide that contains 45% phosphotungstic acid, with supersonic oscillations 20 minutes; This mixed solution is tiled in the culture dish surface, heated 5 minutes down at 90 ℃, 15 hours film forming of drying at room temperature got final product this film in 10 minutes in 160 ℃ of following hot pressing at last.With preceding elder generation film was soaked under 80 ℃ in the deionized water 3 hours.
Embodiment 3
In particle diameter is the tripoli powder of 12nm, mix the phosphotungstic acid that is equivalent to tripoli powder weight 30%, mix.Take by weighing 100 parts by weight of polyvinylidene fluoride and 70 weight portions and be mixed with the tripoli powder of phosphotungstic acid, Kynoar is dissolved in the N-methyl pyrrolidone forms Polymer Solution, to wherein adding the tripoli that contains 30% phosphotungstic acid, with evenly vibration 10 minutes of ultrasonic wave; This mixed solution is tiled in the culture dish surface, heated 40 minutes down at 25 ℃, dry 24 hours film forming got final product this film in 3 minutes in 170 ℃ of following hot pressing at last under the room temperature.With preceding elder generation film was soaked under 80 ℃ in the deionized water 3 hours.
Embodiment 4
In particle diameter is the zircon powder of 12nm, mix the silico-tungstic acid that is equivalent to zircon powder weight 50%, mix.Take by weighing 100 parts by weight of polyvinylidene fluoride and 15 weight portions and be mixed with the zircon powder of silico-tungstic acid, Kynoar is dissolved in forms Polymer Solution in the acetone, to wherein adding the zircon powder that contains 50% silico-tungstic acid, with supersonic oscillations 30 minutes; This mixed solution is tiled in the culture dish surface, heated 5 minutes down at 90 ℃, dry 1 hour film forming got final product this film in 20 minutes in 100 ℃ of following hot pressing at last under the room temperature.With preceding elder generation film was soaked under 80 ℃ in the deionized water 3 hours.
Embodiment 5
In particle diameter is the tripoli powder of 12nm, mix the phosphotungstic acid that is equivalent to tripoli powder weight 5%, mix.Take by weighing 100 parts by weight of polyvinylidene fluoride and 40 weight portions and be mixed with the tripoli powder of phosphotungstic acid, Kynoar is dissolved in the N-methyl pyrrolidone forms Polymer Solution, to wherein adding the tripoli powder that contains 1% phosphotungstic acid, with supersonic oscillations 1 minute; This mixed solution is tiled in the culture dish surface, heated 20 minutes down at 70 ℃, dry 0.5 hour film forming got final product this film in 10 minutes in 160 ℃ of following hot pressing at last under the room temperature.With preceding elder generation film was soaked under 80 ℃ in the deionized water 3 hours.
Embodiment 6
In particle diameter is the tripoli powder of 7.5nm, mix the phosphotungstic acid that is equivalent to tripoli powder weight 45%, mix.Take by weighing 100 parts by weight of polyvinylidene fluoride and 70 weight portions and be mixed with the tripoli powder of phosphotungstic acid, Kynoar is dissolved in forms Polymer Solution in the acetone, to wherein adding the tripoli powder that contains 45% phosphotungstic acid, with supersonic oscillations 30 minutes; This mixed solution is tiled in the culture dish surface, heated 10 minutes down at 60 ℃, dry 20 hours film forming got final product this film in 20 minutes in 100 ℃ of following hot pressing at last under the room temperature.With preceding elder generation film was soaked under 80 ℃ in the deionized water 3 hours.
Embodiment 7
In particle diameter is the zircon powder of 12nm, mix the phosphotungstic acid that is equivalent to zircon powder weight 30%, mix.Take by weighing 100 parts by weight of polyvinylidene fluoride and 70 weight portions and be mixed with the zircon powder of phosphotungstic acid, Kynoar is dissolved in forms Polymer Solution in the acetone, to wherein adding the zircon powder that contains 30% phosphotungstic acid, with supersonic oscillations 30 minutes; This mixed solution is tiled in the culture dish surface, heated 40 minutes down at 50 ℃, dry 20 hours film forming got final product this film in 5 minutes in 170 ℃ of following hot pressing at last under the room temperature.With preceding elder generation film was soaked under 80 ℃ in the deionized water 3 hours.
Embodiment 8
In particle diameter is the zircon powder of 12nm, mix the phosphotungstic acid that is equivalent to zircon powder weight 30%, mix.It is even to take by weighing the polyvinyl alcohol of 100 weight portions and zircon powder that 70 weight portions are mixed with phosphotungstic acid, adopt rolling process, the adhesive polyethylene from high pressure process is added hot milling in calender complete to plasticizing, add flexibilizing agent rubber immediately, homogeneous mixes the back and adds minor amounts of lubricants and above-mentioned mixed material, mixing repeatedly, membrane, nylon net cloth on the film both sides cover, and through hydraulic press hot pressing, cooling back film forming.
Embodiment 9
In particle diameter is the SiO 2 powder of 7.5nm, mix the silico-tungstic acid that is equivalent to SiO 2 powder weight 45%, mix.Take by weighing the polyvinyl alcohol of 100 weight portions and the silicon dioxide that 60 weight portions are mixed with phosphotungstic acid, adopt coating method, with the polyvinyl alcohol heating for dissolving in water, to wherein adding the silicon dioxide that contains 45% phosphotungstic acid, supersonic oscillations 1 minute are mixed with slurries, be poured on the steel plate of completing glass cloth in advance, promote film liquid with glass bar, cover polyester film, squeeze residul liquid-removing with pressure roller, press steel plate, heat tracing is cooled to room temperature at last, promptly obtains required compoiste proton exchange film after peeling off polyester film.
Embodiment 10
In particle diameter is the tripoli powder of 7.5nm, mix the phosphotungstic acid that is equivalent to tripoli powder weight 45%, mix.Take by weighing the polyvinyl alcohol of 100 weight portions and the tripoli powder that 70 weight portions are mixed with phosphotungstic acid, adopt cement-dipping method, with the polyvinyl alcohol heating for dissolving in water, to wherein adding the tripoli powder that contains 45% phosphotungstic acid, with supersonic oscillations 30 minutes, be mixed into the slurries shape, after deaeration, it is coated with scrapes on the polyvinyl screen cloth, air-dry back film forming.
The comparison of the high temperature methanol permeability of table 1 proton exchange membrane of the present invention and Nafion film
| Temperature T (℃) | Methanol concentration (mol/L) | Methanol permeability (S -1cm 2×10 -6) | |
| Sample 1 | ??Nafion117 | ||
| ????80 | ????1.0 | ????1.2 | ???4.4 |
| ????110 | ????1.0 | ????2.0 | ???7.9 |
| ????130 | ????1.0 | ????2.4 | ???9.1 |
| ????160 | ????1.0 | ????3.7 | ???13.3 |
Claims (4)
1. a high temperature direct methanol fuel cell is characterized in that its proportioning and process conditions are as follows with the preparation method of compoiste proton exchange film:
(1) in nano ceramic powder, add the inorganic multivariate acid that is equivalent to nano ceramic powder weight 5%～50%, stand-by after mixing;
(2) get the nano ceramic powder that is mixed with inorganic multivariate acid of 100 parts by weight of polyvinylidene fluoride or polyvinyl alcohol and 15～70 weight portions, mix and get the raw materials ready;
(3) Kynoar or polyvinyl alcohol are dissolved in conventional solvent and are mixed with Polymer Solution, and in this Polymer Solution, add the nano ceramic powder be mixed with inorganic multivariate acid, evenly vibration is 5～30 minutes, and conventional solvent wherein is selected from N-methyl pyrrolidone, acetone or water;
(4) adopt the curtain coating pressure sintering, this mixed liquor is tiled in the glass culture dish surface, ℃ heating is 10～40 minutes in room temperature～90, and then drying at room temperature is 0.5～20 hour; The film that forms after the solvent seasoning is torn from the culture dish surface, 100～170 ℃ of following hot pressing 3～20 minutes; Perhaps adopt coating method, rolling process or cement-dipping method prepared film forming.
2. a kind of high temperature direct methanol fuel cell compoiste proton exchange film preparation method according to claim 1 is characterized in that:
Inorganic multivariate acid is meant that general formula is A
3BM
12O
40nH
2O has anion cluster and is [BM
12O
40]
nThe compound of structure (Keggin structure), A=H wherein, B=Si, P, M=Mo, W; Inorganic multivariate acid is selected from silico-tungstic acid, phosphomolybdic acid, phosphotungstic acid or silicomolybdic acid etc.;
Nano ceramic powder is selected from tripoli, zircon or SiO 2 powder, grain diameter≤30nm.
3. a kind of high temperature direct methanol fuel cell compoiste proton exchange film preparation method according to claim 1 is characterized in that:
(1) adding is equivalent to the phosphotungstic acid of SiO 2 powder weight 25～35% or the silico-tungstic acid that adding is equivalent to SiO 2 powder weight 40～50% in the SiO 2 powder of particle diameter 5～20nm, and is stand-by after mixing;
(2) SiO 2 powder that is mixed with phosphotungstic acid or silico-tungstic acid of getting 100 parts by weight of polyvinylidene fluoride or polyvinyl alcohol and 30～60 weight portions mixes and gets the raw materials ready;
(3) Kynoar or polyvinyl alcohol are dissolved in conventional solvent and are mixed with Polymer Solution, and in this Polymer Solution, add the SiO 2 powder be mixed with phosphotungstic acid or silico-tungstic acid, evenly vibrated 30 minutes with ultrasonic wave, conventional solvent wherein is selected from N-methyl pyrrolidone, acetone or water;
(4) mixed liquor is tiled in the glass culture dish surface, and 40～80 ℃ of heating 10～30 minutes, then drying at room temperature was 2～15 hours; The film that forms after the solvent seasoning is torn from the culture dish surface,, perhaps adopt coating method, rolling process or cement-dipping method prepared film forming 130 ℃～170 ℃ hot pressing 5～15 minutes.
4. the high temperature direct methanol fuel cell compoiste proton exchange film that adopts the described preparation method of claim 1～3 to make.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021151849A CN1202583C (en) | 2002-05-09 | 2002-05-09 | Composite type proteon exchange film for high-temp. direct methanol fue cell and preparation process thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021151849A CN1202583C (en) | 2002-05-09 | 2002-05-09 | Composite type proteon exchange film for high-temp. direct methanol fue cell and preparation process thereof |
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|---|---|
| CN1385915A true CN1385915A (en) | 2002-12-18 |
| CN1202583C CN1202583C (en) | 2005-05-18 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7115333B2 (en) * | 2003-02-07 | 2006-10-03 | Gas Technology Institute | High temperature composite proton exchange membranes |
| US8124294B2 (en) | 2006-10-04 | 2012-02-28 | Samsung Sdi Co., Ltd. | Polymer electrolyte membrane comprising inorganic nanoparticle bonded with proton-conducting group and solid acid, fuel cell including the same, and method of preparing the polymer electrolyte membrane |
| CN102714320A (en) * | 2010-01-25 | 2012-10-03 | 雷蒙特亚特特拉维夫大学有限公司 | Electrochemical systems and methods of operating same |
| CN102847449A (en) * | 2012-09-25 | 2013-01-02 | 内蒙古科技大学 | Preparation method of phosphotungstic acid/polyvinyl alcohol composite proton exchange membrane |
| CN104347886A (en) * | 2014-09-29 | 2015-02-11 | 成都新柯力化工科技有限公司 | Fuel cell ceramic proton exchange membrane material and use thereof |
| CN104681834A (en) * | 2015-02-05 | 2015-06-03 | 成都新柯力化工科技有限公司 | Keratin fuel battery proton exchange membrane and preparation method |
| CN104681833A (en) * | 2015-02-05 | 2015-06-03 | 成都新柯力化工科技有限公司 | Nano ceramic fiber tube fuel battery proton exchange membrane and preparation method |
| CN110433874A (en) * | 2019-09-06 | 2019-11-12 | 温州旭扬膜结构工程有限公司 | A kind of phosphotungstomolybdic acid-metal organic frame proton exchange membrane and its preparation method |
| CN113410496A (en) * | 2021-06-16 | 2021-09-17 | 东北大学秦皇岛分校 | All-solid-state trace water-containing low-temperature applicable proton exchange membrane and preparation method thereof |
-
2002
- 2002-05-09 CN CNB021151849A patent/CN1202583C/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7115333B2 (en) * | 2003-02-07 | 2006-10-03 | Gas Technology Institute | High temperature composite proton exchange membranes |
| US8124294B2 (en) | 2006-10-04 | 2012-02-28 | Samsung Sdi Co., Ltd. | Polymer electrolyte membrane comprising inorganic nanoparticle bonded with proton-conducting group and solid acid, fuel cell including the same, and method of preparing the polymer electrolyte membrane |
| CN102714320B (en) * | 2010-01-25 | 2015-07-15 | 雷蒙特亚特特拉维夫大学有限公司 | Electrochemical systems and methods of operating same |
| CN102714320A (en) * | 2010-01-25 | 2012-10-03 | 雷蒙特亚特特拉维夫大学有限公司 | Electrochemical systems and methods of operating same |
| CN102847449A (en) * | 2012-09-25 | 2013-01-02 | 内蒙古科技大学 | Preparation method of phosphotungstic acid/polyvinyl alcohol composite proton exchange membrane |
| CN102847449B (en) * | 2012-09-25 | 2014-12-10 | 内蒙古科技大学 | Preparation method of phosphotungstic acid/polyvinyl alcohol composite proton exchange membrane |
| CN104347886B (en) * | 2014-09-29 | 2017-02-15 | 成都新柯力化工科技有限公司 | Fuel cell ceramic proton exchange membrane material and use thereof |
| CN104347886A (en) * | 2014-09-29 | 2015-02-11 | 成都新柯力化工科技有限公司 | Fuel cell ceramic proton exchange membrane material and use thereof |
| CN104681833A (en) * | 2015-02-05 | 2015-06-03 | 成都新柯力化工科技有限公司 | Nano ceramic fiber tube fuel battery proton exchange membrane and preparation method |
| CN104681834A (en) * | 2015-02-05 | 2015-06-03 | 成都新柯力化工科技有限公司 | Keratin fuel battery proton exchange membrane and preparation method |
| CN104681833B (en) * | 2015-02-05 | 2017-02-22 | 成都新柯力化工科技有限公司 | Nano ceramic fiber tube fuel battery proton exchange membrane and preparation method |
| CN110433874A (en) * | 2019-09-06 | 2019-11-12 | 温州旭扬膜结构工程有限公司 | A kind of phosphotungstomolybdic acid-metal organic frame proton exchange membrane and its preparation method |
| CN113410496A (en) * | 2021-06-16 | 2021-09-17 | 东北大学秦皇岛分校 | All-solid-state trace water-containing low-temperature applicable proton exchange membrane and preparation method thereof |
| CN113410496B (en) * | 2021-06-16 | 2023-02-14 | 东北大学秦皇岛分校 | All-solid-state trace water-containing low-temperature applicable proton exchange membrane and preparation method thereof |
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|---|---|
| CN1202583C (en) | 2005-05-18 |
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Granted publication date: 20050518 |