DE19917813A1 - Membrane electrolyte, for a high temperature membrane fuel cell, comprises a self-dissociating compound chemically bonded to a base polymer - Google Patents
Membrane electrolyte, for a high temperature membrane fuel cell, comprises a self-dissociating compound chemically bonded to a base polymerInfo
- Publication number
- DE19917813A1 DE19917813A1 DE19917813A DE19917813A DE19917813A1 DE 19917813 A1 DE19917813 A1 DE 19917813A1 DE 19917813 A DE19917813 A DE 19917813A DE 19917813 A DE19917813 A DE 19917813A DE 19917813 A1 DE19917813 A1 DE 19917813A1
- Authority
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- Germany
- Prior art keywords
- self
- base polymer
- membrane
- fuel cell
- dissociating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 239000012528 membrane Substances 0.000 title claims abstract description 33
- 239000003792 electrolyte Substances 0.000 title claims abstract description 26
- 239000000446 fuel Substances 0.000 title claims abstract description 20
- 150000001875 compounds Chemical class 0.000 title claims abstract description 15
- 229920005601 base polymer Polymers 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 210000003608 fece Anatomy 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 13
- 239000004793 Polystyrene Substances 0.000 description 7
- 229920002223 polystyrene Polymers 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 3
- -1 phosphinic acid compound Chemical class 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003459 chloroalkylation reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 238000007082 phosphination reaction Methods 0.000 description 1
- 150000003008 phosphonic acid esters Chemical class 0.000 description 1
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0289—Means for holding the electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
Die Erfindung betrifft einen Membranelektrolyten für eine Hochtemperatur-Membran-(HTM)Brennstoffzelle und ein Verfahren zur Herstellung eines Membranelektrolyts. Der Membranelektrolyt umfaßt ein Basispolymer und eine eigendissoziierende Verbindung, die chemisch an das Basispolymer gebunden ist.The invention relates to a membrane electrolyte for a high-temperature membrane (HTM) fuel cell and a method for producing a membrane electrolyte. The membrane electrolyte comprises a base polymer and a self-dissociating compound which is chemically bound to the base polymer.
Description
Die Erfindung betrifft einen Membranelektrolyten für eine Hochtemperatur-Membran-(HTM)Brennstoffzelle und ein Verfahren zur Herstellung eines Membranelektrolyts.The invention relates to a membrane electrolyte for a High temperature membrane (HTM) fuel cell and process for the production of a membrane electrolyte.
Bekannt ist die Polymer-Elektrolyt-Membran-Brennstoffzelle, die als Membranelektrolyten ein Basispolymer hat, an dem [- SO3H]-Gruppen hängen. Die elektrolytische Leitung findet da bei über hydratisierte Protonen statt. Diese Membran braucht entsprechend flüssiges Wasser, d. h. unter Normaldruck Be triebstemperaturen unter 100°C, um die Protonenleitfähigkeit zu gewährleisten. Daraus ergibt sich das Problem, daß die einströmenden Prozeßgase bei Temperaturen oberhalb von ca. 65°C befeuchtet werden müssen.The polymer electrolyte membrane fuel cell is known, which has a base polymer as membrane electrolytes on which [- SO 3 H] groups are attached. The electrolytic conduction takes place with over-hydrated protons. Correspondingly, this membrane needs liquid water, ie operating temperatures below 100 ° C. under normal pressure, in order to ensure the proton conductivity. This leads to the problem that the inflowing process gases have to be humidified at temperatures above approx. 65 ° C.
Ein Ansatzpunkt, die Beschränkung der Betriebstemperatur auf zuheben, ist, daß anstelle der [-SO3H]-Gruppen enthaltenden Membran eine andere Membran (dabei kann es sich auch um eine Ionenaustauschermembran handeln) und/oder eine Matrix mit freier und/oder physikalisch gebundener Phosphorsäure und/oder einer anderen eigendissoziierenden bzw. autoprotoly tischen Verbindung als Membranelektrolyt einer Brennstoffzel le eingesetzt wird. Durch die Möglichkeit, diese Brennstoff zelle bei einer Betriebstemperatur < 100° einzusetzen, wird sie auch Hochtemperatur-Membran-Brennstoffzelle (HTM- Brennstoffzelle) genannt. Bei der Realisierung einer HTM- Brennstoffzelle mit z. B. freier Phosphorsäure tritt jedoch zumindest ein Problem auf, nämlich die Ausspülung des Membra nelektrolyten durch Produktwasser bei Temperaturen unter 100°C, also beim Starten der Brennstoffzellenanlage. Dies ist hauptsächlich ein Problem, wenn die Brennstoffzelle im Start/Stop Betrieb gefahren wird, also z. B. bei der mobilen Anwendung. Der durch die Ausspülung bedingte Elektrolytver lust kann zu Leistungseinbußen bis hin zum Funktionsausfall der Zelle führen. Der ausgespülte Membranelektrolyt verläßt beispielsweise mit dem Prozeßgasstrom die Zelle. Zum Erhalt der Funktionsfähigkeit der Zelle muß Membranelektrolyt nach dosiert werden.One starting point to lift the limitation of the operating temperature is that instead of the membrane containing the [-SO 3 H] groups, another membrane (this can also be an ion exchange membrane) and / or a matrix with free and / or physical bound phosphoric acid and / or another self-dissociating or autoprotolytic compound is used as the membrane electrolyte of a fuel cell. Due to the possibility of using this fuel cell at an operating temperature <100 °, it is also called high-temperature membrane fuel cell (HTM fuel cell). When realizing an HTM fuel cell with z. B. free phosphoric acid, however, at least one problem occurs, namely the flushing out of the membrane electrolyte by product water at temperatures below 100 ° C., that is when the fuel cell system is started. This is mainly a problem when the fuel cell is operated in the start / stop mode. B. in the mobile application. The electrolyte loss caused by the rinsing can lead to a loss of performance or even a functional failure of the cell. The flushed membrane electrolyte leaves the cell with the process gas stream, for example. To maintain the functionality of the cell, membrane electrolyte must be added.
Das Problem ist von der Phosphorsäurebrennstoffzelle PAFC (Phosphor Acid Fuel Cell) her bekannt, dort jedoch von unter geordneter Bedeutung, weil die PAFC vornehmlich stationär im ständigen Betrieb über einen längeren Zeitraum eingesetzt wird und der Großteil des Elektrolytverlustes, wie gesagt, während des Startens entsteht. An eine Anwendung der vorlie genden Erfindung bei mobilen wie bei stationären Anlagen ist gedacht.The problem is from the phosphoric acid fuel cell PAFC (Phosphoric Acid Fuel Cell) ago, but from there orderly importance, because the PAFC is mainly stationary in the permanent operation over a longer period of time and most of the electrolyte loss, as I said, occurs during startup. To an application of the present ing invention in mobile as in stationary systems thought.
Aufgabe der Erfindung ist, einen Membranelektrolyten zur Ver fügung zu stellen, der Phosphorsäure oder eine andere eigen dissoziierende bzw. autoprotolytische Verbindung enthält, die beim Hochfahren der Brennstoffzellenanlage nicht durch die Verdünnung mit Produktwasser einfach ausgespült wird.The object of the invention is a membrane electrolyte for Ver to provide, the phosphoric acid or another own contains dissociative or autoprotolytic compound which when starting up the fuel cell system not by the Dilution with product water is simply rinsed out.
Gegenstand der Erfindung ist ein Membranelektrolyt für eine HTM-Brennstoffzelle mit einem Basispolymer und zumindest ei ner eigendissoziierenden Verbindung als elektrolytisch akti ven Bestandteil, wobei die eigendissoziierende Verbindung chemisch an das Basispolymer gebunden ist.The invention relates to a membrane electrolyte for a HTM fuel cell with a base polymer and at least one ner self-dissociating compound as electrolytically active ven component, being the self-dissociating compound is chemically bound to the base polymer.
Außerdem ist Gegenstand der Erfindung ein Verfahren zur Her stellung eines Membranelektrolyten mit einem Basispolymer und zumindest einer chemisch gebundenen eigendissoziierenden Ver bindung, bei dem an das Basispolymer die eigendissoziierende Broenstedt-Säure chemisch gebunden wird und/oder ein Polymer aus einem Monomer gebildet wird, das eine eigendissoziierende Verbindung chemisch gebunden enthält.The invention also relates to a process for the preparation of position of a membrane electrolyte with a base polymer and at least one chemically bound self-dissociative ver bond, in which the self-dissociating to the base polymer Broenstedt acid is chemically bound and / or a polymer is formed from a monomer that is self-dissociating Compound contains chemically bound.
Bevorzugt wird die eigendissoziierende Verbindung über eine σ-(sigma)-Einfachbindung an das Basispolymer gebunden. The self-dissociating connection is preferred via a σ- (sigma) single bond bound to the base polymer.
Die Anbindung erfolgt bevorzugt über das Zentralatom der Bro enstedt-Säure oder über einen oder mehrere ihrer Liganden.The connection is preferably via the central atom of the Bro enstedt acid or via one or more of its ligands.
Als Basispolymere werden konventionelle oxidations- und tem peraturstabile Polymere eingesetzt, wie z. B. Polyetherketone, Polyethersulfone und/oder Polyimidazole.Conventional oxidation and tem Temperature-stable polymers used, such as. B. polyether ketones, Polyether sulfones and / or polyimidazoles.
Als eigendissoziierende bzw. autoprotolytische Verbindung wird bevorzugt eine Broenstedt-Säure eingesetzt. Bevorzugt wird Phosphinsäure, Phosphonsäure und Phosphorsäure verwen det. Als eigendissoziierend wird dabei die Eigenschaft einer Broenstedt-Säure, d. h. einer Protonensäure, bezeichnet, so wohl als Base als auch als Säure zu reagieren. Die verwende ten Broensted-Säuren können Protonen aufnehmen und abgeben.As a self-dissociating or autoprotolytic compound a Broenstedt acid is preferably used. Prefers will use phosphinic acid, phosphonic acid and phosphoric acid det. The property of one becomes self-dissociating Broenstedt acid, d. H. a protonic acid, so called to react probably as base as well as acid. The use Broensted acids can take up and release protons.
Die chemische Bindung der eigendissoziierenden Verbindung findet bevorzugt über eine sigma-Einfachbindung statt, sie kann aber genauso gut über eine beliebige andere chemisch Bindung erfolgen, solange diese Bindung gewährleistet, dass die eigendissoziierende Verbindung nicht durch das entstehen de flüssige Produktwasser verdünnt und ausgespült wird. Die Klassifizierung einer chemischen Bindung als beispielsweise "sigma-Einfachbindung" ist immer unvollständig, so dass keine vollständige Beschreibung vorliegt, wenn von einer σ- Einfachbindung z. B. bei der Bindung eines Phosphorsäurerestes an einen Phenylrest gesprochen wird. Deshalb kann die Art der Bindung hier nicht abgrenzend positiv beschrieben werden son dern nur, wie oben geschehen, über eine Abgrenzung zu einer rein physikalischen Bindung, bei der die Zugabe von flüssigem Lösungsmittel wie Produktwasser zur Ausspülung führt.The chemical bond of the self-dissociating compound takes place preferably via a sigma single bond, she but can just as well be chemical over any other Binding take place as long as this binding ensures that the self-dissociating connection does not arise from that de liquid product water is diluted and rinsed out. The Classification of a chemical bond as, for example "Sigma single binding" is always incomplete, so none Complete description is available if from a σ- Single bond z. B. in the binding of a phosphoric acid residue is spoken to a phenyl radical. Therefore, the type of Binding is not described positively here only, as has been done above, by delimitation to one purely physical bond, in which the addition of liquid Solvent such as product water leads to rinsing.
Denkbar sind beispielsweise ausser der Einfachbindung auch eine π-Bindung, eine Dreifachbindung, eine π-Donor-Akzeptor Bindung, eine Komplexbindung, eine ionogene Bindung und schließlich auch eine Protonen- oder sonstige -Brückenbin dung. In addition to single binding, for example, are also conceivable a π bond, a triple bond, a π donor acceptor Bond, a complex bond, an ionogenic bond and finally a proton or other bridge bin dung.
Im folgenden werden Beispiele zur Herstellung des Membrane lektrolyten gegeben:The following are examples of the manufacture of the membrane given electrolytes:
1. Phosphinierung von Polystyrol
Polystyrol wird zunächst in Gegenwart von Aluminiumtrichlorid
mit Phosphorsäuretrichlorid umgesetzt. Die entstandene
Dichlorphosinarylverbindung wird mit Wasser zur entsprechen
den Phosphinsäureverbindung hydrolisiert.
-[CHPh-CH2]n- + PCl3 → Zugabe von AlCl3 und Abspaltung von
HCl ergibt -[CH(Ph-PCl2)-CH2]n- → Hydrolyse ergibt
-[CH(Ph-PHO(OH))-CH2]n- "Phosphinat" oder "Phosphinsäure" an
Styrol gebunden.1. Phosphination of polystyrene
Polystyrene is first reacted with phosphoric acid trichloride in the presence of aluminum trichloride. The resulting dichlorophosinaryl compound is hydrolyzed with water to give the corresponding phosphinic acid compound.
- [CHPh-CH 2 ] n - + PCl 3 → addition of AlCl 3 and elimination of HCl gives - [CH (Ph-PCl 2 ) -CH 2 ] n - → hydrolysis gives - [CH (Ph-PHO (OH) ) -CH 2 ] n - "phosphinate" or "phosphinic acid" bound to styrene.
2. Phosphonierung von Polystyrol
Die nach Punkt 1 erhaltene Phosphinsäureverbindung wird mit
Salpetersäure und/oder KJ3 in Pyridin zur Polystyrolphosphon
säureverbindung umgesetzt.
-[CH(Ph-PHO(OH))-CH2]n- → Oxidation mit HNO3 ergibt
-[CH(Ph-PO (OH)2)-CH2]n-
"Phosphonsäure" an Polystyrol gebunden.2. Phosphonation of polystyrene
The phosphinic acid compound obtained according to point 1 is reacted with nitric acid and / or KJ 3 in pyridine to form the polystyrene phosphonic acid compound.
- [CH (Ph-PHO (OH)) - CH 2 ] n - → Oxidation with HNO 3 gives - [CH (Ph-PO (OH) 2 ) -CH 2 ] n - "phosphonic acid" bound to polystyrene.
3. Radikalische Polymerisation von Monomeren mit Phosphor säuregruppen ergibt auch den Membranelektrolyten.3. Radical polymerization of monomers with phosphorus Acid groups also result in the membrane electrolyte.
Ein denkbares Monomer dabei wäre das folgende:
A conceivable monomer would be the following:
CH2 = C(CH3)-CO-O-CH2-CH2-O-PO(OH)2 CH 2 = C (CH 3 ) -CO-O-CH 2 -CH 2 -O-PO (OH) 2
4. Chloralkylierung von Polystyrol und Umsetzung mit Trime
thoxyphosphin zum entsprechenden Phosphonsäureester der an
schließend hydrolisiert wird.
-[CHPh-CH2]n- + CH3OCH2Cl → Umsetzung nach Friedel-Craft er
gibt -[CH(PhCH2Cl)-CH2]n- → Umsetzung mit P(OCH3)3 ergibt
[CH(PhCH2PO(OCH3)2)-CH2]n-
→ Hydrolyse ergibt -[CH(Ph-CH2PO(OH)2)-CH2]n-
"Phosphonsäure" an Polystyrol gebunden.4. Chloroalkylation of polystyrene and reaction with trimethoxyphosphine to the corresponding phosphonic acid ester which is then hydrolyzed.
- [CHPh-CH 2 ] n - + CH 3 OCH 2 Cl → reaction according to Friedel-Craft results - [CH (PhCH 2 Cl) -CH 2 ] n - → reaction with P (OCH 3 ) 3 gives [CH ( PhCH 2 PO (OCH 3 ) 2 ) -CH 2 ] n - → hydrolysis gives - [CH (Ph-CH 2 PO (OH) 2 ) -CH 2 ] n - "phosphonic acid" bound to polystyrene.
Als Hochtemperatur-Membran-(HTM)-Brennstoffzelle wird jede Brennstoffzelle bezeichnet, die eine herkömmliche Elektrolyt- Membran und/oder die eine Membran als Matrix zur physikali schen und/oder chemischen Aufnahme des Elektrolyten als Kern stück enthält und deren Betriebstemperatur höher als die der herkömmlichen PEM-Brennstoffzelle ist, also höher als 80°C, bevorzugt höher als 100°C. Die maximale Betriebstemperatur liegt in etwa bei 220°C, bis 250°C. Die HTM-Brennstoffzelle hat einen Membranelektrolyten, der gute Leitfähigkeit auch im nicht-wässrigen Milieu bei den oben genannten Temperaturen besitzt.As a high temperature membrane (HTM) fuel cell, each Fuel cell, which is a conventional electrolyte Membrane and / or a membrane as a matrix for physi and / or chemical absorption of the electrolyte as the core piece contains and their operating temperature higher than that of conventional PEM fuel cell, i.e. higher than 80 ° C, preferably higher than 100 ° C. The maximum operating temperature is around 220 ° C to 250 ° C. The HTM fuel cell has a membrane electrolyte, which also has good conductivity non-aqueous environment at the above temperatures owns.
Claims (5)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19917813A DE19917813A1 (en) | 1999-04-20 | 1999-04-20 | Membrane electrolyte, for a high temperature membrane fuel cell, comprises a self-dissociating compound chemically bonded to a base polymer |
| PCT/DE2000/001229 WO2000063988A2 (en) | 1999-04-20 | 2000-04-19 | Membrane electrolyte for a high temperature membrane fuel cell and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19917813A DE19917813A1 (en) | 1999-04-20 | 1999-04-20 | Membrane electrolyte, for a high temperature membrane fuel cell, comprises a self-dissociating compound chemically bonded to a base polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE19917813A1 true DE19917813A1 (en) | 2000-10-26 |
Family
ID=7905194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19917813A Withdrawn DE19917813A1 (en) | 1999-04-20 | 1999-04-20 | Membrane electrolyte, for a high temperature membrane fuel cell, comprises a self-dissociating compound chemically bonded to a base polymer |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE19917813A1 (en) |
| WO (1) | WO2000063988A2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1056149A2 (en) * | 1999-05-27 | 2000-11-29 | Honda Giken Kogyo Kabushiki Kaisha | Fuel cell power generation system |
| WO2002036379A1 (en) * | 2000-10-30 | 2002-05-10 | Siemens Aktiengesellschaft | Fuel cell unit for a vehicle, in particular a motor vehicle |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1895612A4 (en) * | 2005-06-21 | 2012-05-30 | Dainippon Ink & Chemicals | FUEL CELL SEPARATOR, PROCESS FOR PRODUCING THE SAME, AND FUEL CELL |
| WO2008142570A2 (en) * | 2007-03-21 | 2008-11-27 | Advent Technologies | Proton conductors based on aromatic polyethers and their use as electrolytes in high temperature pem fuel cells |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5635039A (en) * | 1993-07-13 | 1997-06-03 | Lynntech, Inc. | Membrane with internal passages to permit fluid flow and an electrochemical cell containing the same |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5602185A (en) * | 1993-09-21 | 1997-02-11 | Ballard Power Systems Inc. | Substituted trifluorostyrene compositions |
| US5468574A (en) * | 1994-05-23 | 1995-11-21 | Dais Corporation | Fuel cell incorporating novel ion-conducting membrane |
| DE19535086B4 (en) * | 1995-09-21 | 2004-08-12 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Use of polymeric solid electrolytes and process for their production |
| JP3521579B2 (en) * | 1995-10-18 | 2004-04-19 | Ｊｓｒ株式会社 | Phosphate group-containing polymer |
| DE19632285A1 (en) * | 1996-08-09 | 1998-02-19 | Hoechst Ag | Proton conductor with a temperature resistance in a wide range and good proton conductivities |
| US5643689A (en) * | 1996-08-28 | 1997-07-01 | E.C.R.-Electro-Chemical Research Ltd. | Non-liquid proton conductors for use in electrochemical systems under ambient conditions |
-
1999
- 1999-04-20 DE DE19917813A patent/DE19917813A1/en not_active Withdrawn
-
2000
- 2000-04-19 WO PCT/DE2000/001229 patent/WO2000063988A2/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5635039A (en) * | 1993-07-13 | 1997-06-03 | Lynntech, Inc. | Membrane with internal passages to permit fluid flow and an electrochemical cell containing the same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1056149A2 (en) * | 1999-05-27 | 2000-11-29 | Honda Giken Kogyo Kabushiki Kaisha | Fuel cell power generation system |
| EP1056149A3 (en) * | 1999-05-27 | 2004-07-21 | Honda Giken Kogyo Kabushiki Kaisha | Fuel cell power generation system |
| WO2002036379A1 (en) * | 2000-10-30 | 2002-05-10 | Siemens Aktiengesellschaft | Fuel cell unit for a vehicle, in particular a motor vehicle |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2000063988A2 (en) | 2000-10-26 |
| WO2000063988A3 (en) | 2001-04-05 |
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