EP0000785B1 - Elektrische Geräte mit einem mit Elektroden versehenen festen amorphen Material - Google Patents

Elektrische Geräte mit einem mit Elektroden versehenen festen amorphen Material Download PDF

Info

Publication number
EP0000785B1
EP0000785B1 EP78100638A EP78100638A EP0000785B1 EP 0000785 B1 EP0000785 B1 EP 0000785B1 EP 78100638 A EP78100638 A EP 78100638A EP 78100638 A EP78100638 A EP 78100638A EP 0000785 B1 EP0000785 B1 EP 0000785B1
Authority
EP
European Patent Office
Prior art keywords
electrodes
ion
percent
ions
ionic
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.)
Expired
Application number
EP78100638A
Other languages
English (en)
French (fr)
Other versions
EP0000785A3 (en
EP0000785A2 (de
Inventor
Alastair Malcolm Glass
Malcolm Ellis Lines
Kurt Nassau
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AT&T Corp
Original Assignee
Western Electric Co Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Western Electric Co Inc filed Critical Western Electric Co Inc
Publication of EP0000785A2 publication Critical patent/EP0000785A2/de
Publication of EP0000785A3 publication Critical patent/EP0000785A3/xx
Application granted granted Critical
Publication of EP0000785B1 publication Critical patent/EP0000785B1/de
Expired legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J5/00—Radiation pyrometry, e.g. infrared or optical thermometry
    • G01J5/10—Radiation pyrometry, e.g. infrared or optical thermometry using electric radiation detectors
    • G01J5/34—Radiation pyrometry, e.g. infrared or optical thermometry using electric radiation detectors using capacitors, e.g. pyroelectric capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • 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
    • 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

Definitions

  • the invention is concerned with electrical devices which depend for their operation on ionic motion. Such motion may be macroscopic involving movement of ions as between affixed electrodes or may be localized. Device uses include capacitors, electrolytic cells, and bolometers.
  • An emerging field of interest involves rigid electrical devices which depend for their function on some degree of ionic motion.
  • Motion may be macroscopic with ions moving between electrodes - a field of interest here involves solid electrolytic primary or secondary cells; motion may be extremely local (or macroscopic where block electrodes are used) with devices functioning on the basis of attendant dielectric constants.
  • dielectric constant may be strongly dependent upon frequency, as well as temperature or magnitude of applied electric field so that such devices may be utilized, as well, for critical measurement of such parameters.
  • the US patent 3 195 030 describes a capacitor which in its final fabricated form has a semicrystalline ceramic dielectricum between its electrodes.
  • the semicrystalline state is defined as a uniform dispersion of fine crystals in a glassy matrix.
  • the semicrystalline ceramics comprises, among others, niobates of sodium and potassium, and glass forming oxides of, among others, phosphorus, boron and silicon.
  • the capacitor is produced from an intermediate product which is in form of a fused and shaped glassy body of the mentioned composition with necessary electrodes being affixed thereto. Said intermediate product is subjected to a specific devitrification heat treatment, to convert the single-phase glassy body into its multi-phase semicrystalline state.
  • a series of glass compositions are found to manifest a degree of ionic motion which leads to their use in devices using either ionically blocking or conducting electrodes (e.g., capacitors or electrolytic cells).
  • Significant device characteristics are found in such glasses in which compositions are related to crystalline materials in which cations are coordinated within an oxygen octahedron.
  • Contemplated compositions are defined in claim 1, and are based on niobates and tantalates of lithium, potassium, and sodium with some modifications permitted. Retention and sometimes enhancement of device properties may result from deviation from crystalline stoichiometry - a phenomenon sometimes observed in crystalline materials. Since the ascribed mechanism is enhanced by voids in cation positions, departures from stoichiometry are largely in the direction of cation-lean compositions, although increase in cation content is also permitted.
  • compositions for the devices of the invention are amorphous in the traditional sense - i.e., no ordering for distances greater than about 10 nanometers (100 Angstrom units). As in other amorphous materials, departure from stoichiometry are more easily accommodated than in crystalline counterparts. Compositional ranges are considered to extend from compositions which are 50 atom percent cation deficient to those which are 20 atom percent cation rich. Nominal stoichiometric compositions based on crystalline materials are LiNbO a , LiTa0 3 , KNb0 3 , KTa0 3 , NaNb0 3 , and NaTa0 3 . Composition departures particularly by substitution of ions of valence values differing from that of nominal site occupant may be tolerated or even enhance properties. Mixtures of such compositions are permitted.
  • glass compositions contemplated for the devices of the invention do not require stabilization by network forming oxides, such as silica, but rather owe their existence to drastic heat treatment (quenching) during formation. Nevertheless, glass forming additives are sometimes utilized to expedite glass formation or even to stabilize the glass phase.
  • Materials for the devices of the invention have two characteristics in common: (a) all materials are amorphous in the sense that ordering, while detectable by state of the art electron microscopy does not exceed about 10 nanometers (100 Angstrom units), which is the approximate resolution limit for conventional X-ray diffraction; and (b) all compositions, broadly defined as lithium, potassium, or sodium niobates or tantalates or mixtures thereof, are of nominal compositions which, as stoichiometric and unmodified in the crystalline state, may result in octahedral coordination with an alkali metal cation within an oxygen octahedron.
  • Device properties are attributed to nominal compositions which are invariably of the form XZ'0 3 , where X is at least one alkali ion selected from the group consisting of Li, K, Na, and Z is at least one ion selected from the group consisting of Nb and Ta.
  • X is at least one alkali ion selected from the group consisting of Li, K, Na
  • Z is at least one ion selected from the group consisting of Nb and Ta.
  • a cation deviation from stoichiometry of from -50 atom percent to +20 atom percent is permitted, so resulting in the generalized formula X 0.5-1.2 Z 1.1-0.96 O 3' where X and Z are as above defined.
  • glass formers may expedite or stabilize glass phase.
  • P Z 0 5 , B 2 O 3 , Si0 2 , Ge0 2 generally in amounts of up to about 10 weight percent of total composition. Up to 20 ion percent - preferably up to 10 ion percent - of certain ions - may replace the alkali metal, as well as Nb or Ta.
  • the maxima, expressed in terms of percent for each cation in the AB0 3 composition applies to Mg 2+ and/or Ca2+ considered to substitute for Li, K and/or Na, as well as to Mo 4+ , Ti 4 ', Zr 4+ and/or W 4+ considered to substitute for Nb and/or Ta. Such substitution may induce vacancies and so increase conductivity.
  • Total compositional modification in other than addition of glass former (or other effective diluent) and disregarding simple departures from stoichiometry should not exceed about 10 weight percent, again based on total composition (including unintentional inclusions), since further modification may adversely affect the amorphous "structure" responsible for large values of ionic conductivity.
  • compositions are produced by simple quenching, a desire to produce certain configurations, perhaps thin films, may give rise to the desire to incorporate minor amounts of glass forming ingredients. Since such ingredients only dilute the essential device characteristics, addition is kept at a minimum. For most purposes, 10 weight percent addition is a realistic compromise to accomplish the desired objective while minimizing effect on device characteristics. So, addition of up to 10 weight percent of a silicate may both expedite formation and stabilize compositions. Silicon-containing glass formers may be added simply as silica or as silicates, again, desirably of any of the alkali metal ions Li, K, Na.
  • Glass formers e.g., Ge0 2 , P 2 0 5 , B 2 0 3 - may expedite formation and stabilization of the glass phase but may be non-preferred by reason of device property deterioration and difficulty of introduction in that order.
  • Device design considerations are interrelated with processing. Much of the study reported in this disclosure relates to measurements made on discrete devices. Devices of this nature are appropriately fabricated from samples made by roller quenching, splat cooling, etc. It has been indicated that an aspect of the invention considered of particular promise involves the extremely high dielectric constants attendant upon the same ionic motion responsible for high conductivity values. These very high values, which, in typical compositions tested at 1 kHz, range from 10 5 at temperatures of the order of 300 degrees C but still at a level as high as 150 at room temperature, present an alternative to the low dielectric constant thin film approach exemplified by the familiar tantalum oxide capacitor.
  • Sputtering techniques which depend on choice of source, i.e., vapor phase reactants, if any, as well as bias control effected through adjustment of such parameters as applied potential, use of floating electrodes, shaping electric fields, etc., are developed to a degree of sophistication as to enable the worker to realize desired layer characteristics.
  • Device electrodes blocking or conducting may be apnlied in a manner familiar to workers in the field of integrated circuits.
  • FIG. 1 is illustrative of a category of devices in accordance with the invention in which ionic motion is local - i.e., restricted to movement within the glassy material.
  • Devices of this category may serve a variety of uses.
  • the high capacitance values, characteristic of glass phase materials herein suggest construction of capacitors possibly by a technique compatible with silicon integrated circuit or other integrated or hybrid circuit fabrication.
  • dielectric characteristics are due to ionic motion - a temperature dependent phenomenon - capacitance and, in fact, all device characteristics of the invention, are also characterized by temperature dependence. This dependence may be tolerable in categories of circuits some of which may even be provided with close temperature control for other reasons.
  • temperature dependence for dielectric constant may be used to advantage, for example, serving as dielectric bolometer for measuring temperature (or for indirectly measuring any other condition which has the effect of altering temperature). Since typical circuitry depends upon elements themselves characterized by temperature dependence, inclusion of a device of the invention may serve to compensate such effect.
  • the device of FIG. 1 has a body 1 of an amorphous material as contemplated herein. Electrical connection is via leads 4 and 5 contacting electrodes 2 and 3, respectively.
  • electrodes 2 and 3 are "blocking" in that they do not show appreciable ionic conductivity. Suitable materials are electronic conductors, such as gold or aluminum, both of which lend themselves to ready fabrication.
  • FIG. 2 is illustrative of that class of devices in which at least some of the alkali ions traverse the glass-electrode interface. While alkali ion- deficient compositions are of general interest in all devices of the invention, it is in devices of this category in which such compositions are of particular interest.
  • the device depicted which may be regarded, for example, as a primary or secondary solid electrolytic cell comprises an amorphous body 20 of a composition herein, intimately contacted by a first alkali metal- containing electrode 21 and a second electrode 22, possibly of a transition metal chalcogenide. Examples of such chalcogenides presently under study are FeS x , NbSe, TiS 2 , VS 2 , and NbS 2 .
  • Electrodes rather than blocking, are ionic conductors. While alternatives are possible, it would be expected that electrode 21 and amorphous body (electrolyte) 20 would contain at least some alkali metal ions in common. Much work reported in the literature depends upon use of the high mobility of lithium; and it is expected that exemplary structures of the type depicted in FIG. 2 would make use of lithium- containing electrolyte and electrode material.
  • the structure of FIG. 2 is completed by electronic electrodes and leads 23, 24 and 25, 26.
  • FIG. 3 illustrates the temperature-dependent characteristics of typical compositions of materials for devices of the invention.
  • the particular coordinates chosen, logarithm of conductivity (in terms of the symbol a which may, for example, be in units of ohm- 1 cm- 1 ) on the ordinate, and reciprocal temperature (degrees Kelvin) on the abscissa conveniently result in a straight line plot which may reliably be extrapolated beyond the data for all temperatures in the amorphous phase.
  • the room temperature conductivity is approximately 10- 5 ohm-' cm- 1 . This value compares favorably with rigid ionic conductors, in general. While the slope of the plotted line is generally characteristic of ionic conductors, the absolute values of conductivity vary.
  • This temperature dependence of conductivity is a property of significance in devices exemplified by bolometers, as well as other devices in which varying values of conductivity/capacitance are useful for measurement purposes or to compensate for other temperature-dependent parameters.
  • the electrodes of which are, for example, essentially rionconductive for the alkaline metal ions, e.g. are metallic, to have a surface which is absorbing for the radiation to be detected, for instance IR radiation, in order to increase the device sensitivity against radiation.
  • FIG. 3 which is a measure of ionic flow, is properly considered for its broader implication - ionic movement, generally.
  • total charge accumulation - i.e., capacitance - is sufficiently related to conductivity - net ionic movement responsive to biasing - to permit use of the same data.
  • An additional use of devices of the invention also dependent upon localized movement - i.e., on charge accumulation - is dependent upon the pyroelectric effect either in biased material or in unbiased material which has previously been polarized. Charges so produced are temperature dependent primarily due to the temperature dependence of ionic motion. It has been noted that other device uses may also depend upon temperature dependence of ionic motion. Such devices generally use blocking electrodes (electrodes with large resistance to ionic conduction).
  • Material used in the following examples was prepared by roller quenching. Sintered material of the appropriate composition was powdered in a mortar and pestle to produce particles that would pass through a 120 mesh (125 micrometers) screen. Approximately 5 grams of powdered material was placed in an iridium crucible provided with a 10 mil (25.4 x 10- 3 centimeters) aperture, in the bottom surface. The crucible was covered with an apertured platinum lid which was then evacuated through the aperture to maintain a small vacuum of approximately 2 inches (5.1 centimetres) of water. Crucible and contents were then heated with a radio frequency heater, heated sufficiently to melt contents. To facilitate further processing, heating was actually carried out at a temperature somewhat in excess of melting (100 degrees C - 300 degrees C excess). The purpose of the vacuum is to prevent leakage of material during heating.
  • Flakes were inspected by X-ray diffraction, as well as differential thermal analysis, to result in a finding that there was no long-range ordering over dimensions as great as 10 nanometers (100 Angstrom units) and to indicate that the material was metastable (DTA exhibited exotherm).
  • electrodes were affixed to the flake specimens or portions thereof - electrodes were either blocking or ionically conducting, depending upon the nature of the experiment to be conducted. Details are set forth in the examples which follow. In each instance, a composition, as well as melt temperature actually utilized in its preparation, is listed.
  • Example. 9 is included as exemplary of a structure utilizing non-blocking electrodes. It will be noted that measured ionic conductivity is that expected from measurements conducted in the preceding examples.
  • Example 2 - LiTa0 3 - was measured at frequencies of 120H, 400H, and 1 kH to reveal dielectric constant dependence on this parameter.
  • the 100 degrees C dielectric constant was 7,000, 1,600, and 800, respectively.
  • Conductivity remained constant at a value of approximately 1.5 x 10 -6 ohm -2 cm -1 over this frequency range.
  • the dielectric constant of the specimen of Example 1 - LiNb0 3 - was measured at varying temperature to determine thermal response. Dielectric constant was found to vary at the fractional rate of 6 percent/degrees C over the entire temperature range from room temperature to 200 degrees C. For this configuration absorption of radiant energy results in a one degree temperature change per 5 microjoules absorption of radiant energy.
  • Example 1 A specimen of the composition and dimensions of that of Example 1 - LiNb0 3 - was provided with non-blocking electrodes of LiCI and the d.c. conductivity was measured. Measured values were approximately the same as the 1 kilohertz values set forth for Example 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Inorganic Chemistry (AREA)
  • Glass Compositions (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Claims (7)

1. Elektrisches Bauelement, das in seiner fertiggestellten Form ein Teil eines Materials und im Abstand voneinander gelegene Elektroden, die den Teil kontaktieren, aufweist, wobei das Material innerhalb eines Bereiches, der einen ununterbrochenen Weg zwischen den Elektroden definiert, amorph ist und der amorphe Zustand definiert ist durch eine fehlende Fernordnung über eine Entfernung von wenigstens 10 Nanometer (100 Angström), wie dieses durch Röntgenstrahlungsbeugung angegeben ist, dadurch gekennzeichnet, daß wenigstens 80 Gewichtsprozent des Materials eine Zusammensetzung umfaßt, die durch die stöchiometrische Formel X0,5-1,2Z1,1-0,96O3 dargestellt werden kann, worin X wenigstens eine Element ist, das von Li, Na und K ausgewählt ist, Z wenigstens ein Element ist, das von Nb und Ta ausgewählt ist, und O Sauerstoff ist und worin, gegebenenfalls, X ersetzt sein kann in einem Anteil von bis zu 20 lonenprozent durch wenigstens eine Ion, das von Mg2+ und Ca2+ ausgewählt ist, und Z ersetzt sein kann in einem Anteil von bis zu 20 lonenprozent durch wenigstens ein Ion, das aus Mo4+, Ti4+, Zr4+ und W4+ ausgewählt ist, und daß das Material gegebenenfalls bis zu 10 Gewichtsprozent von wenigstens einem Glasbildner, der von P2O5, P2O3, Si02 und Ge02 ausgewählt ist, enthalten kann.
2. Bauelement nach Anspruch 1, dadurch gekennzeichnet, daß X bis zu 10 lonenprozent wenigstens eines lons, das von Mg2+ und Ca2+ ausgewählt ist, enthält und Z bis zu 10 lonenprozent wenigstens eines lons, das von MO4+, Ti4+, Zr 4+ und W4+ ausgewählt ist, enthält.
3. Bauelement nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß X im wesentlichen aus Li besteht und Z im wesentlichen aus Nb besteht.
4. Bauelement nach Anspruch 1, 2 oder 3, mit Elektroden, die für X-Ionen im wesentlichen nichtleitend, z.B. metallisch sind, dadurch gekennzeichnet, daß eine Oberfläche vorgesehen ist, die für eine nachzuweisende Strahlung, beispielsweise eine im Infrarotwellenlängenbereich liegende Strahlung, absorbierend ist.
5. Bauelement nach einem der Ansprüche 1 bis 3, mit Elektroden, die für X-Ionen nichtsperrend sind, dadurch gekennzeichnet, daß die Elektroden von unterschiedlichem elektrochemischem Potential sind, wobei eine erste Elektrode als Quelle für X-Ionen wirkt und eine zweite Elektrode als eine Senke für X-Ionen wirkt, wodurch eine elektrisches Potential zwischen der ersten und zweiten Elektrode resultiert.
6. Bauelement nach Anspruch 5, dadurch gekennzeichnet, daß die erste Elektrode Lithium umfaßt.
7. Bauelement nach Anspruch 6, dadurch gekennzeichnet, daß die zweite Elektrode ein Chalkogenid umfaßt, das von NbSe2, VS2, TiS2 und FeS., mit x zwischen 1 und 3 liegend, ausgewählt ist.
EP78100638A 1977-08-15 1978-08-10 Elektrische Geräte mit einem mit Elektroden versehenen festen amorphen Material Expired EP0000785B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US824419 1977-08-15
US05/824,419 US4130694A (en) 1977-08-15 1977-08-15 Amorphous metal oxide material between electrodes of a cell

Publications (3)

Publication Number Publication Date
EP0000785A2 EP0000785A2 (de) 1979-02-21
EP0000785A3 EP0000785A3 (en) 1979-03-07
EP0000785B1 true EP0000785B1 (de) 1981-08-05

Family

ID=25241366

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100638A Expired EP0000785B1 (de) 1977-08-15 1978-08-10 Elektrische Geräte mit einem mit Elektroden versehenen festen amorphen Material

Country Status (5)

Country Link
US (1) US4130694A (de)
EP (1) EP0000785B1 (de)
JP (1) JPS5431550A (de)
CA (1) CA1100573A (de)
DE (1) DE2860902D1 (de)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0015229A1 (de) * 1979-02-21 1980-09-03 BIOTRONIK Mess- und Therapiegeräte GmbH & Co Ingenieurbüro Berlin Elektrode für einen künstlichen Herzschrittmacher
EP0051947A1 (de) * 1980-10-24 1982-05-19 RAYOVAC Corporation Feststoffelektrolyten für elektrochemische Zellen
EP0056852A1 (de) * 1981-01-26 1982-08-04 LGZ LANDIS & GYR ZUG AG Ladungszelle
EP0073877A1 (de) * 1981-08-29 1983-03-16 VARTA Batterie Aktiengesellschaft Galvanische Festkörperzelle mit ionen- und elektronenleitender Kathode, deren aktives Material aus Metallchloriden besteht
WO1984004206A1 (fr) * 1983-04-15 1984-10-25 Centre Nat Rech Scient Generateurs electrochimiques comportant une electrode positive et un electrolyte a base de materiaux vitreux
EP0386350A1 (de) * 1987-09-08 1990-09-12 Tufts University Ionenleitende Dünnschichtbekleidung
US5877228A (en) * 1995-02-22 1999-03-02 Dow Corning Toray Silicone Co., Ltd. Method for curing ultraviolet-curable silicone compositions

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4963741A (en) * 1987-06-22 1990-10-16 Molectron Detector, Inc. Large area pyroelectric joulemeter
KR100331271B1 (ko) 1999-07-01 2002-04-06 박종섭 ＴａＯＮ박막을 갖는 커패시터 제조방법
KR100335775B1 (ko) * 1999-06-25 2002-05-09 박종섭 반도체 소자의 캐패시터 제조 방법
KR100358066B1 (ko) 1999-06-25 2002-10-25 주식회사 하이닉스반도체 반도체 소자의 캐패시터 제조 방법
GB2355113B (en) 1999-06-25 2004-05-26 Hyundai Electronics Ind Method of manufacturing capacitor for semiconductor memory device
KR100328454B1 (ko) 1999-06-29 2002-03-16 박종섭 반도체 소자의 캐패시터 제조 방법
KR100327584B1 (ko) 1999-07-01 2002-03-14 박종섭 반도체소자의 고정전용량 커패시터 형성방법
KR100331270B1 (ko) 1999-07-01 2002-04-06 박종섭 ＴａＯＮ박막을 갖는 커패시터 제조방법
KR100305076B1 (ko) 1999-07-01 2001-11-01 박종섭 커패시터의 전하저장전극 형성방법
GB2358284B (en) 1999-07-02 2004-07-14 Hyundai Electronics Ind Method of manufacturing capacitor for semiconductor memory device
KR100371143B1 (ko) * 1999-12-29 2003-02-07 주식회사 하이닉스반도체 반도체장치의 고용량 커패시터 형성방법
DE10044451C1 (de) * 2000-09-08 2002-04-04 Epcos Ag Elektrode und Kondensator mit der Elektrode
US6994807B2 (en) * 2002-09-24 2006-02-07 Corning Incorporated Electrolytic perovskites
US9379414B2 (en) * 2014-02-21 2016-06-28 Panasonic Intellectual Property Management Co., Ltd. Entire solid lithium secondary battery
CN110794442B (zh) * 2019-10-31 2021-08-31 西北核技术研究院 一种用于测量高能x射线能量的高精度量热计及其制作方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3195030A (en) * 1964-06-26 1965-07-13 Corning Glass Works Glass and methods of devitrifying same and making a capacitor therefrom
US3781748A (en) * 1971-05-28 1973-12-25 Us Navy Chalcogenide glass bolometer
US3852077A (en) * 1972-04-05 1974-12-03 Owens Illinois Inc Glasses, glass-ceramics and process for making same
US4041220A (en) * 1972-08-18 1977-08-09 Agence Nationale De Valorisation De La Recherche (Anvar) Mixed conductors of graphite, processes for their preparation and their use, notably for the production of electrodes for electrochemical generators, and new electrochemical generators
US3980499A (en) * 1973-10-23 1976-09-14 E. I. Du Pont De Nemours And Company Device for use of lithium haloboracites as solid electrolytes
US3898605A (en) * 1974-06-19 1975-08-05 Us Navy Integrated optical bolometer for detection of infrared radiation
US4009092A (en) * 1976-02-27 1977-02-22 E. I. Du Pont De Nemours And Company Substituted lithium phosphates and solid electrolytes therefrom

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0015229A1 (de) * 1979-02-21 1980-09-03 BIOTRONIK Mess- und Therapiegeräte GmbH & Co Ingenieurbüro Berlin Elektrode für einen künstlichen Herzschrittmacher
EP0051947A1 (de) * 1980-10-24 1982-05-19 RAYOVAC Corporation Feststoffelektrolyten für elektrochemische Zellen
EP0056852A1 (de) * 1981-01-26 1982-08-04 LGZ LANDIS & GYR ZUG AG Ladungszelle
US4441138A (en) * 1981-01-26 1984-04-03 Lgz Landis & Gyr Zug A.G. Charge cell
EP0073877A1 (de) * 1981-08-29 1983-03-16 VARTA Batterie Aktiengesellschaft Galvanische Festkörperzelle mit ionen- und elektronenleitender Kathode, deren aktives Material aus Metallchloriden besteht
WO1984004206A1 (fr) * 1983-04-15 1984-10-25 Centre Nat Rech Scient Generateurs electrochimiques comportant une electrode positive et un electrolyte a base de materiaux vitreux
EP0386350A1 (de) * 1987-09-08 1990-09-12 Tufts University Ionenleitende Dünnschichtbekleidung
US5877228A (en) * 1995-02-22 1999-03-02 Dow Corning Toray Silicone Co., Ltd. Method for curing ultraviolet-curable silicone compositions

Also Published As

Publication number Publication date
US4130694A (en) 1978-12-19
CA1100573A (en) 1981-05-05
EP0000785A3 (en) 1979-03-07
JPS5431550A (en) 1979-03-08
EP0000785A2 (de) 1979-02-21
DE2860902D1 (en) 1981-11-05

Similar Documents

Publication Publication Date Title
EP0000785B1 (de) Elektrische Geräte mit einem mit Elektroden versehenen festen amorphen Material
Zhao et al. High dielectric constant in CaCu3Ti4O12 thin film prepared by pulsed laser deposition
Bandyopadhyay et al. Polaronic conduction and spectroscopy of borate glasses containing vanadium
Peddigari et al. Optical and microwave dielectric properties of phase pure (K0. 5Na0. 5) NbO3 thin films deposited by RF magnetron sputtering
Murugan et al. Lithium borate–strontium bismuth tantalate glass nanocomposite: a novel material for nonlinear optic and ferroelectric applications
Pengpat et al. Glass-ceramics containing ferroelectric bismuth germanate (Bi2GeO5)
Venkateswarlu et al. AC properties of laser ablated La-modified lead titanate thin films
Atyia et al. Influence of temperature and frequency on the AC conductivity and dielectric properties for Ge15Se60Bi25 amorphous films
Yang et al. Growth, microstructure, energy–storage and dielectric performances of chemical–solution NBT–based thin films: Effect of sodium nonstoichimometry
Jiang et al. Crystallization, microstructure and energy storage behavior of borate glass–ceramics
Pal et al. Electrical and optical properties of MoO3–TeO2 amorphous films prepared by PVD method
Al-Assiri et al. Study of nanostructural behavior and transport properties of BaTiO3 doped vanadate glasses and glass–ceramics dispersed with ferroelectric nanocrystals
Gautam et al. Synthesis, microstructure and dielectric properties of (Sr, Bi) TiO3 borosilicate glass-ceramics
Xie et al. Simultaneously ultra-low dielectric loss and rapid discharge time in Ta 2 O 5 doped niobate-based glass–ceramics
Rao et al. Impedance spectroscopy studies of K 0.5 Bi 0.5 TiO 3
Rao et al. Modulus spectroscopy of lead potassium titanium niobate (Pb 0.95 K 0.1 Ti 0.25 Nb 1.8 O 6) ceramics
Marple et al. Superionic conduction of silver in homogeneous chalcogenide glasses
El-Desoky et al. Electrical conductivity improvement of strontium titanate doped lead vanadate glasses by nanocrystallization
Xiao et al. Optimization of the dielectric properties and energy storage density in (K 2 O, SrO)–Nb 2 O 5–B 2 O 3–Al 2 O 3–SiO 2 glass–ceramics
Bourguiba et al. Colossal permittivity, impedance analysis, and optical properties in La 0.67 Ba 0.25 Ca 0.08 Mn 0.90 Ti 0.10 O 3 manganite
Varade et al. Excellent Electrocaloric and Energy Storage Capabilities in (Na0. 8K0. 2) 0.5 Bi0. 5TiO3 Ceramic
Bajpai et al. Pyroelectric properties of (Ba1-xCdx)(Zr0. 13Ti0. 87) O3 ferroelectric ceramics in polymorphic state
Čajko et al. Ag-doped As–S–Se chalcogenide glasses: a correlative study of structural and dielectrical properties
Bahgat Study of dielectric relaxation in Na-doped Bi–Pb–Sr–Ca–Cu–O glasses
Montedo et al. Effect of the crystalline layer on the electrical behaviour of 17.7 Li2O· 5.2 ZrO2· 68.1 SiO2· 9.0 Al2O3 glass ceramic monoliths

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Designated state(s): BE DE FR GB NL SE

AK Designated contracting states

Designated state(s): BE DE FR GB NL SE

17P Request for examination filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): BE DE FR GB NL SE

REF Corresponds to:

Ref document number: 2860902

Country of ref document: DE

Date of ref document: 19811105

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19840628

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19840630

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19840703

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19840831

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19840930

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19860301

GBPC Gb: european patent ceased through non-payment of renewal fee
NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19860430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19860501

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19860811

BERE Be: lapsed

Owner name: WESTERN ELECTRIC CY INC.

Effective date: 19860831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19881117

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19890831

EUG Se: european patent has lapsed

Ref document number: 78100638.2

Effective date: 19870812

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT