DE3110571A1 - Novel compounds which conduct hydrogen, their preparation and use - Google Patents
Novel compounds which conduct hydrogen, their preparation and useInfo
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- DE3110571A1 DE3110571A1 DE19813110571 DE3110571A DE3110571A1 DE 3110571 A1 DE3110571 A1 DE 3110571A1 DE 19813110571 DE19813110571 DE 19813110571 DE 3110571 A DE3110571 A DE 3110571A DE 3110571 A1 DE3110571 A1 DE 3110571A1
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/406—Cells and probes with solid electrolytes
- G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
- G01N27/4073—Composition or fabrication of the solid electrolyte
- G01N27/4074—Composition or fabrication of the solid electrolyte for detection of gases other than oxygen
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
- G02F1/1525—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material characterised by a particular ion transporting layer, e.g. electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/185—Cells with non-aqueous electrolyte with solid electrolyte with oxides, hydroxides or oxysalts as solid electrolytes
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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
Description
Neue Wasserstoff leitende Verbindungen, ihre Herstel- New hydrogen-conducting compounds, their production
lung und Verwendung Die Erfindung betrifft neue Verbindungen, die in fester Form Wasserstoff- oder Hydroniumleiter sind, ihre Herstellung und ihre Verwendung als Festkörperelektrolyte. development and use The invention relates to new compounds that in solid form are hydrogen or hydronium conductors, their production and their Use as a solid electrolyte.
Feste Wasserstoff- oder Hydroniumionenleiter sind seit langer Zeit Forschungsgegenstand, vor allem hinsichtlich ihrer Anwendung als Separatoren in Brennstoffzellen, H+-Detektoren, H2-Gas-Sensoren und elektrochromen Anzeigen.Solid hydrogen or hydronium ion conductors have been around for a long time Subject of research, especially with regard to their application as separators in Fuel cells, H + detectors, H2 gas sensors and electrochromic displays.
Dabei werden vor allem Substanzgruppen gesucht, die in Temperaturbereichen von 200 bis 3000C thermisch stabil sind.Above all, substance groups are sought that are in temperature ranges are thermally stable from 200 to 3000C.
Die bekanntesten Gruppen von H - bzw. H30+ H3O+-Ionenleitern sind: (a) HUO2PO4 . 41120 (HUP) #29o# = 4 x 10 3 (OHM-1CM-1) -1 -1 (b) H3OClO4 #298K - 3 x 1o##-4 (OHM-1CM-1) CM ) Diese beiden Substanzgruppen sind jedoch thermisch wenig stabil und zersetzen sich oberhalb 60°C. Dies schränkt ihre Brauchbarkeit stark ein.The best-known groups of H - or H30 + H3O + ion conductors are: (a) HUO2PO4. 41120 (HUP) # 29o # = 4 x 10 3 (OHM-1CM-1) -1 -1 (b) H3OClO4 # 298K - 3 x 1o ## - 4 (OHM-1CM-1) CM) However, these two substance groups are thermally little stable and decompose above 60 ° C. This severely limits their usefulness a.
Eine weitere Gruppe von bekannten H+ -bzw. H3O+-Leitern H30+ -Leitern basiert auf der Eigenschaft: von Na-ß'1-Aluminiumoxid als Ionenaustauscher zu wirken. So kann bei 300°C in konzen-+ trierter 112504 Na gegen 1130 ausgetauscht werden, wobei nach ca. 120 Stunden 70 % Na+ ersetzt sind. Die + 1130 -Leitfähigkeit bei Raumtemperatur wird mit kleiner als 5 x 10-5 (OHM 1CM 1) angegeben. Die thermische Zersetzung von H3 O+-ß"-Aluminiumoxid tritt oberhalb 1250C ein. NH4+/H3O+ -ß"-Aluminiumoxid entsteht, wenn man Naß"-Aluminiumoxid bei 2000C in eine NH4P03-Schmelze bringt.Another group of known H + or. H3O + ladders H30 + ladders is based on the property: of Na-ß'1-aluminum oxide to act as an ion exchanger. So at 300 ° C in concentrated 112504 Na can be exchanged for 1130, 70% Na + is replaced after approx. 120 hours. The + 1130 conductivity at Room temperature is given as less than 5 x 10-5 (OHM 1CM 1). The thermal Decomposition of H3 O + -ß "-alumina occurs above 1250C. NH4 + / H3O + -ß" -alumina occurs when wet "aluminum oxide is brought into an NH4P03 melt at 2000C.
Die entsprechende H+/H3O+-Leitfähigkeit wird mit 1 x lo (OHM -1CM -1) bei Raumtemperatur angegeben. Diese Verbindung ist jedoch oberhalb 2000C nicht stabil (Fast Ion Transport in Solids, 267-271, International Conference on Fast Ion Transport in Solids, Elektrode and Eiectrolytes, Lake Geneva, Wis., 1979).The corresponding H + / H3O + conductivity is 1 x lo (OHM -1CM -1) stated at room temperature. However, this connection is not above 2000C stable (Fast Ion Transport in Solids, 267-271, International Conference on Fast Ion Transport in Solids, Electrode and Eiectrolytes, Lake Geneva, Wis., 1979).
Der Erfindung liegt daher die Aufgabe zugrunde, Verbindungen zu schaffen, welche die Nachteile der oben erwähnten bekannten Verbindungen nicht aufweisen und auch noch bei Temperaturen bis mindestens 300°C ausreichend stabil sind, um als Protonen- bzw. Hydroniumionenleiter verwendbar zu sein.The invention is therefore based on the object of creating compounds which do not have the disadvantages of the above-mentioned known compounds and even at temperatures up to at least 300 ° C are sufficiently stable to be used as To be used proton or hydronium ion conductor.
Gelöst wird diese Aufgabe erfindungsgemäß durch neue Mischkristalle der allgemeinen Formel I worin Me ein einwertiges Metall, M ein Ubergangselement der IV. Gruppe des Periodensystems, Z ein Element der V. Gruppe des Periodensystems, w eine Zahl von o,1 bis 1 + x, x eine Zahl von o,ol bis 3 und y eine Zahl von o bis o,5 bedeuten.This object is achieved according to the invention by new mixed crystals of the general formula I where Me is a monovalent metal, M is a transition element of Group IV of the Periodic Table, Z is an element of Group V of the Periodic Table, w is a number from 0.1 to 1 + x, x is a number from 0.1 to 3 and y is a Number from o to o.5 mean.
Vorzugsweise ist Me aus der Gruppe der Alkalimetalle, insbesondere Natrium, Kalium oder/und Lithium. Vorzugsweise ist der Wert von x größer als o,1. Die Protonen- bzw. Hydroniumionenleitfähigkeit steigt mit zunehmendem Wert von w.Me is preferably from the group of alkali metals, in particular Sodium, potassium and / or lithium. The value of x is preferably greater than 0.1. The proton or hydronium ion conductivity increases as the value of w increases.
Die erfindungsgemäßen neuen Verbindungen liegen als Mischkristalle im Kristallfeld, definiert durch die quasibinären Schnitte MeZr2P3012 --- Me4Zr0,5Si309 und MeZr2P3012 Me4Zr1,5Si3O11, wobei Me teilweise durch H bzw. H30 ersetzt sein kann, vor.The new compounds according to the invention are in the form of mixed crystals in the crystal field, defined by the quasi-binary cuts MeZr2P3012 --- Me4Zr0.5Si309 and MeZr2P3012 Me4Zr1,5Si3O11, Me being partially replaced by H or H30 can, before.
Erfindungsgemäß erfolgt die Herstellung der neuen Verbindungen der allgemeinen Formel aus Verbindungen der allgemeinen Formel II durch Behandlung der letzteren in saurer wäßriger Lösung.According to the invention, the new compounds of the general formula are prepared from compounds of the general formula II by treating the latter in acidic aqueous solution.
Dabei werden Me+ -Ionen durch H+- bzw. H30+ ersetzt. Das Ausmaß des Austausches läßt sich leicht bestimmen, indem man die in die Lösung übergegangene Menge Me+-Ionen mißt.Me + ions are replaced by H + - or H30 +. The extent of the The exchange can easily be determined by looking at the one that has passed into the solution Measure the amount of Me + ions.
Um daher eine Verbindung der allgemeinen Formel I mit einem bestimmten gewünschten Wert von w zu erhalten, wird die Verbindung der Formel II so lange mit der sauren Lösung behandelt, bis der Me+-Gehalt der Lösung um den für w gewünschten molaren Wert angestiegen ist. Wegen des Austauschprozesses gibt w damit auch die H+- bzw. H30+-Konzentration im Festkörperelektrolyten an. Dies läßt sich mit den für die Bestimmung von Me üblichen analytischen Methoden verfolgen. Da ja gleichzeitig die Protonenkonzentration in der Lösung sinkt, mit anderen Worten der pH-Wert steigt, läßt sich das Ausmaß des Austausches auch durch pH-Wertbestimmung verfolgen Verbindungen der allgemeinen Formel II und ihre Herstellung sind in der deutschen Patentanmeldung der gleichen Anmelderin P 30 32 894.0 beschrieben. Die Herstellung erfolgt, indem die festen Ausgangskomponenten des Mischkristallssin den jeweils für eine bestimmte gewünschte Zusammensetzung erforderlichen molaren Anteilen in feinpulveriger Form gemischt und bei einer möglichst hohen Temperatur, jedoch unter Vermeidung des Auftretens einer flüssigen Phase, so lange calciniert werden, bis im Röntgendiagramm kein M02-Peak mehr erkennbar ist, wobei gegebenenfalls das Calcinieren ein- oder mehrfach unterbrochen wird, um das Material erneut fein zu vermahlen. M wird dabei vorzugsweise in Form von MO oder als metallorganische Verbindung eingesetzt.To therefore a compound of general formula I with a certain To obtain the desired value of w, the compound of formula II is so long with the acidic solution is treated until the Me + content of the solution is around that desired for w molar value has increased. Because of the exchange process, w also gives the H + or H30 + concentration in the solid electrolyte. This can be done with the follow the usual analytical methods for the determination of Me. Since at the same time the proton concentration in the solution decreases, in other words the pH increases, the extent of the exchange can also be followed by determining the pH of the compounds of the general formula II and their preparation are in the German patent application by the same applicant P 30 32 894.0. The production is done by the solid starting components of the mixed crystal are each for a certain desired composition required molar proportions in finely powdered form mixed and at the highest possible temperature, but avoiding the occurrence a liquid phase, are calcined until there is no MO2 peak in the X-ray diagram more can be seen, the calcining optionally being interrupted one or more times to finely grind the material again. M is preferably in the form used by MO or as an organometallic compound.
Die treibende Kraft für den Austausch von Me-Ion gegen Protonen kann zusätzlich durch ein äußerlich angelegtes elektrisches Feld verstärkt werden. Hierbei müssen Me blockierende Elektroden benutzt werden. Wenn Me Natrium bedeutet, sb ist eine geeignete Na+ blockierende Elektrode beispielsweise eine positive Platinelektrode in einer 112 -gesättigten sauren wassrigen Lösung.The driving force for the exchange of Me-Ion for protons can can also be reinforced by an externally applied electric field. Here Me blocking electrodes must be used. When Me means sodium, sb is a suitable Na + blocking electrode, for example a positive platinum electrode in a 112 -saturated acidic aqueous solution.
Wie ohne weiteres erkennbar ist, stellt die Austausch menge und Austauschrate von Me+ eine Funktion von x dar. As can be seen without further ado, the exchange quantity and exchange rate represent of Me + is a function of x.
Durch den pH-Wert der Lösung können Austauschmenge und Austauschgeschwindigkeit gesteuert werden. The amount and rate of exchange can be determined by the pH value of the solution being controlled.
Hat der Austausch von Ne den gewünschten Wert erreicht, so wird die gebildete unlösliche Verbindung der allgemeinen Formel I aus der Lösung abgetrennt, beispielsweise abfiltriert oder in sonstiger Weise entnommen. In der verbleibenden Lösung kann dann die Menge an ausgetauschtem Me+ beispielsweise durch Titration oder AAS (Atom-Absorptions-Spektroskopie) quantitativ bestimmt werden. If the exchange of Ne has reached the desired value, the formed insoluble compound of the general formula I separated from the solution, for example, filtered off or removed in any other way. In the remaining Solution can then determine the amount of exchanged Me +, for example by titration or AAS (atomic absorption spectroscopy) can be determined quantitatively.
Als saure wäßrige Lösungen kommen sowohl anorganische als auch organische Säuren in konzentrierter oder verdünnter Form in Betracht. Beispiele für geeignete Säuren sind Schwefelsäure, Salzsäure, Salpetersäure, Phosphorsäure aus der Reihe der Mineralsäuren, Essigsäure, Ameisensäure, Propionsäure und Oxalsäure aus der Reihe der organischen Säuren. Die Erfindung ist dabei mit beliebigen Säuren durchführbar, soweit sie Protonen bzw.Both inorganic and organic can be used as acidic aqueous solutions Acids in concentrated or diluted form are possible. Examples of suitable Acids are sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid out of the series the mineral acids, acetic acid, formic acid, propionic acid and oxalic acid from the Series of organic acids. The invention can be carried out with any acids, as far as they are protons or
Hydroniumionen liefern können und die Verbindung der Formel II bzw. I nicht zu lösen vermögen. Ob eine derartige Lösung, beispielsweise durch Komplexierung, auftritt, läßt sich leicht durch einen Vorversuch bestimmen, bei welchem festgestellt wird, ob in der Lösung P043- oder 4-Sioq -Gruppen auftreten oder nicht.Can supply hydronium ions and the compound of formula II or I am unable to solve. Whether such a solution, for example through complexation, occurs can easily be determined by a preliminary test in which it was found whether or not there are P043 or 4-Sioq groups in the solution.
Der Einbau von H+- bzw. H30+-Gruppen in das Kristallgitter von Verbindungen der allgemeinen Formel II bewirkt eine strukturelle Veränderung des Gitters <Intensitätsänderung der Reflexe, Anderung der Gitterkonstanten).Daher läßt sich mittels Röntgenpulver-Methoden die Umwandlung von Verbindungen der Formel II in erfindungsgemäße Verbindungen der Formel I verfolgen und kristallographisch einordne#n.The incorporation of H + or H30 + groups into the crystal lattice of compounds of the general formula II causes a structural change in the lattice <change in intensity of reflections, change in lattice constants) .Therefore, X-ray powder methods the conversion of compounds of the formula II into compounds according to the invention of Follow formula I and classify it crystallographically.
Wie bereits erwähnt, zeichnen sich die erfindungsgemäßen neuen Verbindungen durch gute thermische Beständigkeit und Leitfähigkeit für Protonen und Hydroniumionen aus.As already mentioned, the novel compounds according to the invention are notable due to good thermal resistance and conductivity for protons and hydronium ions the end.
So wurden bei erfindungsgemäßen Verbindungen bei Raumteniperatur Leitfähigkeiten im Bereich von 5 bis 20 ~ 10-7 (Ohm 1 cm 1), bei 3000C im Bereich von 1 bis 5 . 10-3 (Ohm 1 cm 13 gemessen. Aufgrund dieser hohen Leitfähigkeitswerte und der guten Temperaturbeständigkeit eignen sich die erfindungsgemäßen Verbindungen vorzüglich zur Verwendung als feste H bzw. H30+ leitende Elektrolyten (Separatoren) in elektrochemischen Zellen. Beispiele für geeignete elektrochemische Zellen sind Brennstoffzellen, ein Detektor zur Bestimmung von Ionenkonzentrationen in wäßrigen Lösungen, organischen Lösungen (z. B. pH-Meter) und Schmelzen, eine elektrochrom.e Anzeige, ein Separator in wasserstofferzeugenden Systemen bei niedrigen und hohen Temperaturen oder ein Wasserstoffgasreiniger (Ionensieb) bei niedrigen und hohen Temperaturen.In the case of compounds according to the invention, for example, conductivities were obtained at room temperature in the range of 5 to 20 ~ 10-7 (ohms 1 cm 1), at 3000C in the range of 1 to 5. 10-3 (Ohm 1 cm 13 measured. Because of these high conductivity values and the good The compounds according to the invention are eminently suitable for temperature resistance for use as solid H or H30 + conductive electrolytes (separators) in electrochemical Cells. Examples of suitable electrochemical cells are fuel cells, a Detector for the determination of ion concentrations in aqueous solutions, organic Solutions (e.g. pH meter) and melts, an electrochrom.e display, a separator in hydrogen generating systems at low and high temperatures or a Hydrogen gas cleaner (ion sieve) at low and high temperatures.
Besonders bevorzugt ist die Verwendung als fester Elektrolyt in einer elektrochemischen Zelle gemäß Anspruch 10 mit einer H+ bzw. H30 spendenden Elektrode.Use as a solid electrolyte in one is particularly preferred Electrochemical cell according to claim 10 with an H + or H30 donating electrode.
Die folgenden Beispiele erläutern die Erfindung weiter.The following examples further illustrate the invention.
Beispiele 1 bis 6 Die Herstellung von Pulvern gemäß der Formel Na1+xzr2-1/3x+ySixP3-x°12-2/3x+2y erfolgte wie in der Patentanmeldung P 30 32 894.0 beschrieben. Die Pulver mit verschiedenen Werten x wurde in einer schwefel sauren Lösung (pH=1, Volumen = 200 ml) ausgetauscht. Die Ergebnisse und die Leitfähigkeitsdaten sind in Tabelle 1 aufgeführt.Examples 1 to 6 The production of powders according to the formula Na1 + xzr2-1 / 3x + ySixP3-x ° 12-2 / 3x + 2y took place as described in patent application P 30 32 894.0. The powders with different Values x were exchanged in a sulfuric acid solution (pH = 1, volume = 200 ml). The results and the conductivity data are shown in Table 1.
Tabelle 1 Beispiel Symmetrie x y w Gewicht (g) End-pH #(l06 #1 cm@ ) 1 1,0 0,00 0,84 0,912 1,63 1,60 2 rhomboed. 1,2 0,00 0,95 1,052 1,68 0,84 3 1,5 0,00 1,21 0,987 1,73 1,30 4 1,8 0,00 1,35 0,925 1,75 1,40 5 monoclin. 2,0 0,00 1,49 0,951 1,80 1,00 6 2,C 0,16 1,51 0,978 1,80 1,30 Table 1 example symmetry x y w weight (g) final pH # (l06 # 1 cm @ ) 1 1.0 0.00 0.84 0.912 1.63 1.60 2 rhomboed. 1.2 0.00 0.95 1.052 1.68 0.84 3 1.5 0.00 1.21 0.987 1.73 1.30 4 1.8 0.00 1.35 0.925 1.75 1.40 5 monoclin. 2.0 0.00 1.49 0.951 1.80 1.00 6 2, C 0.16 1.51 0.978 1.80 1.30
Claims (11)
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DE19813110571 DE3110571A1 (en) | 1981-03-18 | 1981-03-18 | Novel compounds which conduct hydrogen, their preparation and use |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0156241A2 (en) * | 1984-03-13 | 1985-10-02 | Sharp Kabushiki Kaisha | Solid-state electrolytic battery |
US4724191A (en) * | 1985-06-28 | 1988-02-09 | Minister of Energy Mines & Resources | Bonded hydrogen conducting solid electrolytes |
DE3639802A1 (en) * | 1986-11-21 | 1988-05-26 | Battelle Institut E V | SENSOR FOR MONITORING HYDROGEN CONCENTRATIONS IN GASES |
EP0368181A1 (en) * | 1988-11-08 | 1990-05-16 | Joseph Dr. Lemoine | Material for conducting protons |
FR2660644A1 (en) * | 1990-04-06 | 1991-10-11 | Centre Nat Rech Scient | NOVEL COMPOUND OF THE K-NB-SI-O SYSTEM AND ITS DERIVATIVES, PROCESS FOR THEIR SYNTHESIS AND THEIR APPLICATIONS IN PARTICULAR IN OPTICS. |
EP1171384A2 (en) * | 1999-01-22 | 2002-01-16 | California Institute Of Technology | Proton conducting membrane using a solid acid |
US7416803B2 (en) | 1999-01-22 | 2008-08-26 | California Institute Of Technology | Solid acid electrolytes for electrochemical devices |
-
1981
- 1981-03-18 DE DE19813110571 patent/DE3110571A1/en not_active Withdrawn
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0156241A2 (en) * | 1984-03-13 | 1985-10-02 | Sharp Kabushiki Kaisha | Solid-state electrolytic battery |
EP0156241A3 (en) * | 1984-03-14 | 1987-04-01 | Sharp Kabushiki Kaisha | Solid-state electrolytic battery |
US4724191A (en) * | 1985-06-28 | 1988-02-09 | Minister of Energy Mines & Resources | Bonded hydrogen conducting solid electrolytes |
DE3639802A1 (en) * | 1986-11-21 | 1988-05-26 | Battelle Institut E V | SENSOR FOR MONITORING HYDROGEN CONCENTRATIONS IN GASES |
EP0268768A2 (en) * | 1986-11-21 | 1988-06-01 | Battelle-Institut e.V. | Sensor for monitoring hydrogen concentrations in gases |
EP0268768A3 (en) * | 1986-11-21 | 1989-08-23 | Battelle-Institut E.V. | Sensor for monitoring hydrogen concentrations in gases |
EP0368181A1 (en) * | 1988-11-08 | 1990-05-16 | Joseph Dr. Lemoine | Material for conducting protons |
FR2660644A1 (en) * | 1990-04-06 | 1991-10-11 | Centre Nat Rech Scient | NOVEL COMPOUND OF THE K-NB-SI-O SYSTEM AND ITS DERIVATIVES, PROCESS FOR THEIR SYNTHESIS AND THEIR APPLICATIONS IN PARTICULAR IN OPTICS. |
WO1991015426A1 (en) * | 1990-04-06 | 1991-10-17 | Centre National De La Recherche Scientifique | NEW COMPOUND OF THE K-Nb-Si-O SYSTEM AND ITS DERIVATIVES, PROCESS FOR SYNTHESISING THEM AND THEIR APPLICATIONS, IN PARTICULAR IN OPTICS |
EP1171384A2 (en) * | 1999-01-22 | 2002-01-16 | California Institute Of Technology | Proton conducting membrane using a solid acid |
US6468684B1 (en) * | 1999-01-22 | 2002-10-22 | California Institute Of Technology | Proton conducting membrane using a solid acid |
EP1171384A4 (en) * | 1999-01-22 | 2004-05-19 | California Inst Of Techn | Proton conducting membrane using a solid acid |
US7416803B2 (en) | 1999-01-22 | 2008-08-26 | California Institute Of Technology | Solid acid electrolytes for electrochemical devices |
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