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WO1994015377A1 - Dispositif a pile a combustible a membrane d'echange de protons, et a plaques de separation pour le transfert de l'eau - Google Patents

Dispositif a pile a combustible a membrane d'echange de protons, et a plaques de separation pour le transfert de l'eau Download PDF

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Publication number
WO1994015377A1
WO1994015377A1 PCT/US1993/011559 US9311559W WO9415377A1 WO 1994015377 A1 WO1994015377 A1 WO 1994015377A1 US 9311559 W US9311559 W US 9311559W WO 9415377 A1 WO9415377 A1 WO 9415377A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
proton exchange
exchange membrane
porous plate
fuel cell
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.)
Ceased
Application number
PCT/US1993/011559
Other languages
English (en)
Inventor
Carl A. Reiser
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.)
UTC Power Corp
Original Assignee
International Fuel Cells Corp
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 International Fuel Cells Corp filed Critical International Fuel Cells Corp
Publication of WO1994015377A1 publication Critical patent/WO1994015377A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04291—Arrangements for managing water in solid electrolyte fuel cell systems
    • 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
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
    • 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
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0267—Collectors; Separators, e.g. bipolar separators; Interconnectors having heating or cooling means, e.g. heaters or coolant flow channels
    • 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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
    • 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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2465—Details of groupings of fuel cells
    • H01M8/2484—Details of groupings of fuel cells characterised by external manifolds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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

Definitions

  • the present invention relates to fuel cells in general, and more particularly to proton exchange membrane fuel cell devices and to water flow management and cooling systems therefor.
  • a gaseous fuel and an oxidizing gas are supplied to the anode electrode plate and to the cathode electrode plate, respectively, and distributed as uniformly as possible over the active surfaces of the respective electrode plates (that is, the electrode plate surfaces facing the proton exchange membrane and thus the respective electrodes or catalyst layers) , and that an electrochemical reaction takes place at and between such electrodes when the fuel cell device is in operation, with attendant formation of a product of the reaction between the fuel and oxygen (product water when the fuel is hydrogen) , release of thermal energy,
  • a fuel cell device of this type usually includes more than one fuel cell, typically a substantial number of such cells.
  • the individual fuel cells are arranged, usually electrically in series, in a stack.
  • the individual fuel cells are separated from one another by respective separator plates that are interposed between the adjacent cells. It is a normal practice to construct such separator plates as solid, that is, fluid impermeable, plates to avoid formation of a potentially explosive mixture as a result of direct mixing of the fuel gas with the oxidizing gas (oxygen or air) through the separator plate.
  • the removal of the entrained water from the anode side due to joint travel with the hydrogen ions through the membrane would dry out the membrane region facing the anode side of the fuel cell, unless measures are taken to replenish such anode side water.
  • a porous backing plate having a relatively substantial thickness and capable of accommodating and conducting fluids in its pores, and a separate relatively thin support plate that is juxtaposed with the associated catalyst layer and that is also porous.
  • the porosity of such backing and support plates is needed to provide not only for supply and substantially uniform distribution of the respective gaseous medium which flows through respective gas channels provided in the backing plate to and over the respective catalyst layer, but also for removal of the reaction product (water) from one of the catalyst layers and/or supply of water to the other of the catalyst layers.
  • Kunz in addition to using the porous cathode electrode for water removal from the cathode catalyst layer, to supply the needed replenishment water to the anode catalyst layer through the associated electrode plate which includes lands that are in contact with the anode catalyst layer so that the supplied water is able to cross the interface to the catalyst layer on the anode side.
  • This patent also mentions that the evaporation of water from at least one of the electrode plates into the respective gaseous medium in contact therewith provides for sufficient heat removal from the fuel cell.
  • Still another object of the present invention is to develop the proton exchange membrane fuel cell device of the above kind in such a manner as to be able to dispense with the otherwise existing need for using solid separator plates between the adjacent fuel ceil of the device.
  • a concomitant object of the present invention is to devise a proton exchange membrane device with a simpler and more efficient cooling system than heretofore used in similar fuel cell devices.
  • a proton exchange membrane fuel cell device with an internal water management and transfer system that includes a plurality of adjacently arranged proton exchange membrane assemblies.
  • Each of such assemblies includes a proton exchange membrane component having two oppositely facing major surfaces, and a pair or porous anode and a cathode catalyst layers each situated at a different one of the major surfaces of the proton exchange membrane substantially coextensively with the other.
  • a porous plate is interposed between and in contact with each two adjacent ones of the proton exchange membrane assemblies.
  • This porous plate has two major surfaces one of which faces the anode catalyst layer of one of the adjacent proton exchange membrane assemblies and the other of which faces the catalyst layer of the other of the adjacent proton exchange membrane assemblies and including a plurality of oxidant gas supply channels opening onto the one major surface and a plurality of fuel gas supply channel opening onto the other major surface of the porous plate.
  • the device further includes means for supplying oxidant gas into the oxidant gas supply channels and fuel gas into the fuel gas supply channels for distribution to the anode and cathode catalyst layers, respectively.
  • Figure 1 is a partially cross sectioned and partially front elevational view of a proton exchange membrane fuel cell device embodying the present invention, taken generally on line 1 - 1 of Figure 3;
  • Figure 2 is a somewhat simplified, partially broken away, front generally elevational view of the device of Fig. 1, taken on line 2 -2 of Figure 3;
  • Figure 3 is a cross sectional view through a fragment of the fuel cell of Figures l and 2 but showing only the region of the fuel cell proper at a somewhat enlarged different scale, as indicated by section line 3 - 3 in Figure 1.
  • the fuel cell device 10 includes a proton exchange fuel cell assembly 11, an oxidizing gas (oxygen or air) inlet manifold 12, an associated spent oxidizing gas outlet manifold 13, a fuel gas (hydrogen) inlet manifold 14, and an associated spent fuel outlet manifold 15.
  • oxidizing gas oxygen or air
  • spent oxidizing gas outlet manifold 13 a fuel gas (hydrogen) inlet manifold 14
  • spent fuel outlet manifold 15 an associated spent fuel outlet manifold 15.
  • the fuel outlet manifold 15 also serves as a water sump for collecting water that may drip or flow downwardly from the fuel cell assembly 11.
  • the manifolds 12 to 15 open in a sealed manner on respective peripheral portions or surfaces of the fuel cell assembly 11.
  • Figure 1 also shows that a cathode catalyst layer 22 is deposited or otherwise arranged on a major surface of a proton exchange membrane 21. As shown, the catalyst layer terminates short of the periphery of the membrane 21.
  • FIG. 3 of the drawing shows portions of two adjacent fuel cells 20 and 20' of the assembly 11. It may be seen there that, in addition to the cathode catalyst layer 22, the membrane 21 of the fuel cell 20 is similarly provided, at its other major surface, with an anode catalyst layer 23. Respective support plates 24 and 25 are arranged next to and are in area contact with the respective associated catalyst layers 22 and 23, respectively. The support plates 24 and 25 are porous to permit flow of the various gaseous media and water through the support plates 24 and 25. It should be apparent that, in accordance with the present invention, the fuel cell assembly 11 does not include any solid (water and gas impervious) separator plates between the adjacent cells 20 and 20'.
  • a porous hydrophilic plate 26 is situated at that location.
  • This plate 26, which is shown to be constituted by two separate partial plates 27 and 28 that are substantially identical in composition and structure and are preferably joined by lamination to give the plate 26 a unitary construction, performs several functions. For one, it serves to distribute the respective gaseous medium that is supplied from the respective manifold 12 or 14 (shown only in Figure l) in a known manner into respective oxidant and fuel gas channels 29 and 29', or 30 and 30', to and over the associated support plates 24 and 24' or 25 and 25' and through the pores of the same ultimately to and over the respective catalyst layers 22 and 22' or 23 and 23'.
  • the orientations of the hydrogen channels 30 and 30' have been changed in Figure 3 relative to the situation illustrated in Figure 1 by turning them through 90° about a horizontal axis located in the plane of Figure 3 of the drawing.
  • the plate 26 also must prevent the occurrence of direct contact and mixture of the reactant (oxidant and fuel) gases with one another through the plate 26. This gas separation function is achieved by making sure that seepage or flow of such reactants through the plate 26 is blocked by a barrier constituted by water contained in and completely filling the pores of the plate 26 at least at and all over the region of the parting plane between the partial plates 27 and 28.
  • At least that region of at least one of the partial plates 27 and 28 that is coextensive with the aforementioned parting plane not only is hydrophilic but also has a fine pore structure such that capillary forces cause water to completely fill such fine pores and thus block passage of gasses through this region.
  • water is supplied to this region, in an amount sufficient to keep its pores filled all over the area of the parting plane, through a horizontally extending distribution channel 32 and a multitude of vertically extending secondary channels 31.
  • the water to be used for this purpose is withdrawn from the water sump located at the bottom of the fuel exhaust manifold via a conduit 33 having a pump 34 interposed therein.
  • This water that is pumped by the pump 34 is discharged into a conduit 36 which leads to and communicates with a water inlet port 35 indicated in Figure 2 that, in turn, communicates with the distribution channel 32.
  • the distribution channel 32 distributes such water to all of the secondary distribution channels 31. As such water flows down through such channels 31, it penetrates into the fine pores of the aforementioned region and replenishes the water that may have been expelled or may have evaporated therefrom, thus continuously maintaining and restoring the integrity of the water barrier. This replenishment takes place continuously or frequently enough to prevent formation of any gas-conducting paths across such region and thus through the water barrier. Any excess water contained in the plate 26 eventually reaches the bottom of such plate 26, for instance, through the channels 31, and drips into or otherwise joins the water contained in the sump.
  • the plate 26 serves other purposes as well, namely that of removing water from the cathode support plate, such as 24' (and thus from the cathode catalyst layer 22' ) and wetting the region of the proton exchange membrane, such as 21, that faces the anode catalyst layer 23.
  • steps are taken to assure that the pressure of the oxidant gas slightly exceeds that prevailing at the region of the water barrier and thus in the water distribution channels 32 and 31. This is accomplished in any manner that is so well known that it need not be explained in detail here. Suffice it to say that it may involve the use of pressure-controllable pumps or controllable pressure regulators or valves arranged in the respective oxidant and water supply and/or discharge conduits or pipes.
  • the pressure differential existing between the cathode side of the respective fuel cell and the water barrier region propels the product and entrained water that has entered the pores of the plate 26 through the support plate 24' and that would otherwise tend to remain and accumulate there, toward the aforementioned parting plane.
  • the water present at the other side of the parting plane i.e. either the recirculated water or a mixture thereof with the product and entrained water
  • the water present at the other side of the parting plane i.e. either the recirculated water or a mixture thereof with the product and entrained water
  • the pressure in the water channels 31 and 32 is somewhat lower than fuel gas pressure to achieve the aforementioned through-plate water transfer at a rate commensurate with the demand for supplying replenishment water to the anode side of the membrane 21 or 21- due to the competition between the capillary forces and the pressure differential. This condition can once more be easily satisfied by again resorting to conventional measures such as those mentioned above.
  • the circulating water is then cooled in a non-illustrated water/ambient air heat exchanger to reduce its temperature before entering the distribution channel 32.
  • the structure, composition and operation of the various components of the fuel cell assembly 11 are so well known as not to need any elaboration. Suffice it to say that graphite is the material favored for the plates 26 and 26', particularly for its good electrical conductivity, rather high electrochemical stability, light weight, and relatively low cost. To be effective, it is advantageous for the stack or fuel cell assembly 11 to be operated or used in the orientation depicted in the drawing, that is, with the cells 20 and 20' arranged in a vertical orientation. However, by taking appropriate well-known measures, it would be possible to use the assembly 11 in other spatial orientations as well. It is also advantageous, albeit possibly not critical, that the fuel gas be externally manifolded and preferably pressurizable.
  • the bottom ends of the secondary water distribution channels 31 open into the manifold 15.
  • An alternative to this approach, which is also contemplated herein, is to form another horizontal channel at the bottom of the plate 26 and to collect the water reaching the same at the bottom corner(s) . At that point it could exit the assembly 11 stack directly into the manifold 15 or be directed to an external sump.

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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)

Abstract

Dispositif à pile à combustible à membrane d'échange de protons, pourvu d'un système de gestion et de transfert d'eau interne. Ce dispositif comprend une multiplicité d'ensembles membrane d'échange de protons adjacentes contenant une membrane (21, 21') d'échange de protons ainsi que deux couches de catalyseur anodique (23, 23') poreuses et deux couches de catalyseur cathodique (22, 22') poreuses, chacune placée sur une surface principale différente de la membrane de manière à s'étendre pratiquement sur la même longueur, ainsi qu'une plaque poreuse (26) placée entre chaque paire d'ensembles membrane adjacentes et en contact avec des dernières. Un gaz oxydant est introduit dans les conduits (29, 29') d'alimentation en gaz oxydant et un gaz combustible est introduit dans les conduits (30, 30') d'alimentation en gaz combustible de la plaque poreuse, ces gaz étant amenés, respectivement, vers les couches de catalyseur anodique et cathodique. Une couche hydrophobe est formée dans la zone hydrophobe située dans la plaque poreuse. La zone hydrophobe s'étend sur la même longueur que la plaque poreuse, et ses pores sont entièrement remplis d'eau afin d'empêcher tout contact entre les gaz oxydant et combustible à travers la plaque poreuse.
PCT/US1993/011559 1992-12-23 1993-12-01 Dispositif a pile a combustible a membrane d'echange de protons, et a plaques de separation pour le transfert de l'eau Ceased WO1994015377A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US99625892A 1992-12-23 1992-12-23
US07/996,258 1992-12-23

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WO1994015377A1 true WO1994015377A1 (fr) 1994-07-07

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5503944A (en) * 1995-06-30 1996-04-02 International Fuel Cells Corp. Water management system for solid polymer electrolyte fuel cell power plants
WO1997033331A1 (fr) * 1996-03-06 1997-09-12 Siemens Aktiengesellschaft Pile a combustible a humidification interne
US5942347A (en) * 1997-05-20 1999-08-24 Institute Of Gas Technology Proton exchange membrane fuel cell separator plate
DE19911016A1 (de) * 1999-03-12 2000-09-21 Daimler Chrysler Ag Brennstoffzellensystem mit kathodenseitigen Wasserabtrennmitteln
US6180273B1 (en) 1995-08-30 2001-01-30 Honda Giken Kogyo Kabushiki Kaisha Fuel cell with cooling medium circulation arrangement and method
DE10346594A1 (de) * 2003-10-07 2005-05-12 Daimler Chrysler Ag PEM-Brennstoffzelle mit Fluidräumen und weiteren, davon abgetrennten Räumen
USRE39556E1 (en) * 1997-11-20 2007-04-10 Relion, Inc. Fuel cell and method for controlling same
US7326480B2 (en) 2000-05-17 2008-02-05 Relion, Inc. Fuel cell power system and method of controlling a fuel cell power system
DE102010009584A1 (de) * 2010-02-26 2011-09-01 Schott Ag Chemisch vorgespanntes Glas

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2398392A1 (fr) * 1977-07-20 1979-02-16 Engelhard Min & Chem Systeme de pile a combustible utilisant des membranes d'echange d'ions et des plaques bipolaires
US4729932A (en) * 1986-10-08 1988-03-08 United Technologies Corporation Fuel cell with integrated cooling water/static water removal means
US4826741A (en) * 1987-06-02 1989-05-02 Ergenics Power Systems, Inc. Ion exchange fuel cell assembly with improved water and thermal management
US4855193A (en) * 1986-06-20 1989-08-08 United Technologies Corporation Bipolar fuel cell
AT389020B (de) * 1986-08-08 1989-10-10 Peter Dipl Ing Dr Schuetz Brennstoffzelle
EP0343679A1 (fr) * 1988-05-26 1989-11-29 International Fuel Cells Corporation Contrôle de l'évacuation de l'eau et de la chaleur d'une pile à combustible à polymère solide

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2398392A1 (fr) * 1977-07-20 1979-02-16 Engelhard Min & Chem Systeme de pile a combustible utilisant des membranes d'echange d'ions et des plaques bipolaires
US4855193A (en) * 1986-06-20 1989-08-08 United Technologies Corporation Bipolar fuel cell
AT389020B (de) * 1986-08-08 1989-10-10 Peter Dipl Ing Dr Schuetz Brennstoffzelle
US4729932A (en) * 1986-10-08 1988-03-08 United Technologies Corporation Fuel cell with integrated cooling water/static water removal means
US4826741A (en) * 1987-06-02 1989-05-02 Ergenics Power Systems, Inc. Ion exchange fuel cell assembly with improved water and thermal management
EP0343679A1 (fr) * 1988-05-26 1989-11-29 International Fuel Cells Corporation Contrôle de l'évacuation de l'eau et de la chaleur d'une pile à combustible à polymère solide

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ANDREI LEONIDA: "HYDROGEN/OXYGEN SPE ELECTROCHEMICAL DEVICES FOR ZERO-G APPLICATIONS", PROCEEDINGS OF THE EUROPEAN SPACE POWER CONFERENCE 2-6 OCTOBER 1989 MADRID; SPAIN, pages 227 - 231 *
K. STRASSER ET AL: "PEM FUEL CELLS FOR ENERGY STORAGE SYSTEMS", PROCEEDINGS OF THE 26TH INTERSOCIETY ENERGY CONVERSION ENGINEERING CONFERENCE VOLUME 3 4-9 AUGUST 1991 MASSACHUSETTS, pages 630 - 635 *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997002615A1 (fr) * 1995-06-30 1997-01-23 International Fuel Cells Corporation Systeme de gestion d'eau destine a des groupes energetiques a piles a combustible comprenant un electrolyte polymere solide
US5503944A (en) * 1995-06-30 1996-04-02 International Fuel Cells Corp. Water management system for solid polymer electrolyte fuel cell power plants
US6582844B2 (en) 1995-08-30 2003-06-24 Honda Giken Kogyo Kabushiki Kaisha Method of cooling a fuel cell
US6180273B1 (en) 1995-08-30 2001-01-30 Honda Giken Kogyo Kabushiki Kaisha Fuel cell with cooling medium circulation arrangement and method
WO1997033331A1 (fr) * 1996-03-06 1997-09-12 Siemens Aktiengesellschaft Pile a combustible a humidification interne
US5942347A (en) * 1997-05-20 1999-08-24 Institute Of Gas Technology Proton exchange membrane fuel cell separator plate
USRE39556E1 (en) * 1997-11-20 2007-04-10 Relion, Inc. Fuel cell and method for controlling same
DE19911016A1 (de) * 1999-03-12 2000-09-21 Daimler Chrysler Ag Brennstoffzellensystem mit kathodenseitigen Wasserabtrennmitteln
US6406810B1 (en) 1999-03-12 2002-06-18 Daimlerchrysler Ag Fuel cell system with cathode-side water separating devices
DE19911016C2 (de) * 1999-03-12 2001-07-26 Daimler Chrysler Ag Brennstoffzellensystem mit kathodenseitigen Wasserabtrennmitteln
US7326480B2 (en) 2000-05-17 2008-02-05 Relion, Inc. Fuel cell power system and method of controlling a fuel cell power system
DE10346594A1 (de) * 2003-10-07 2005-05-12 Daimler Chrysler Ag PEM-Brennstoffzelle mit Fluidräumen und weiteren, davon abgetrennten Räumen
DE102010009584A1 (de) * 2010-02-26 2011-09-01 Schott Ag Chemisch vorgespanntes Glas
DE102010009584B4 (de) * 2010-02-26 2015-01-08 Schott Ag Chemisch vorgespanntes Glas, Verfahren zu seiner Herstellung sowie Verwendung desselben
US10351471B2 (en) 2010-02-26 2019-07-16 Schott Ag Chemically tempered glass
US12017952B2 (en) 2010-02-26 2024-06-25 Schott Ag Chemically tempered glass

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