WO2012061965A1 - Electrolyte membrane, electrochemical device and solid oxide fuel cell - Google Patents

Electrolyte membrane, electrochemical device and solid oxide fuel cell Download PDF

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Publication number
WO2012061965A1
WO2012061965A1 PCT/CN2010/078493 CN2010078493W WO2012061965A1 WO 2012061965 A1 WO2012061965 A1 WO 2012061965A1 CN 2010078493 W CN2010078493 W CN 2010078493W WO 2012061965 A1 WO2012061965 A1 WO 2012061965A1
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WIPO (PCT)
Prior art keywords
electrolyte membrane
strength
layer
fuel cell
solid oxide
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PCT/CN2010/078493
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French (fr)
Chinese (zh)
Inventor
王蔚国
王建新
薛业建
李华民
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中国科学院宁波材料技术与工程研究所
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Priority to PCT/CN2010/078493 priority Critical patent/WO2012061965A1/en
Publication of WO2012061965A1 publication Critical patent/WO2012061965A1/en

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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
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • 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
    • H01M2300/0068—Solid electrolytes inorganic
    • 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

Definitions

  • the present invention relates to the field of electrochemical technology, and in particular to an electrolyte membrane and an electrochemical device including the electrolyte membrane. Background technique
  • the electrolyte membrane is a core component of an electrochemical device such as a solid oxide fuel cell (SOFC), an oxygen sensor, an oxygen pump, and a temperature sensor, and a major electrochemical reaction occurs in the electrolyte membrane.
  • SOFC solid oxide fuel cell
  • the solid oxide fuel cell is an energy conversion device for directly converting chemical energy into electrical energy, and has remarkable advantages such as high efficiency, no pollution, and all solid state, and has broad application prospects in many fields.
  • a solid oxide fuel cell power generation system generally consists of a plurality of battery stacks, each of which is assembled from dozens of single cells.
  • a solid oxide fuel cell comprises at least three functional layers of a cathode/electrolyte membrane/anode, wherein the anode or cathode is a porous layer, and the electrolyte membrane is a dense layer.
  • the electrolyte membrane is generally an oxygen ion conductor or a proton conductor, and has a thickness of generally 10 ⁇ m to 200 ⁇ m, and its conductivity has a characteristic of increasing rapidly with an increase in temperature.
  • the common material of the electrolyte membrane is zirconia, yttria and the like doped with one or more rare earth oxides, such as yttria-doped zirconia (YSZ), oxidized-resistant zirconia (ScSZ), Zirconium oxide doped with yttria (CeSZ), or zirconia ScCeSZ doped with yttria and yttria.
  • YSZ yttria-doped zirconia
  • ScSZ oxidized-resistant zirconia
  • CeSZ Zirconium oxide doped with yttria
  • CeSZ zirconia ScCeSZ doped with yttria and yttria.
  • the more doped rare earth oxides the more helpful it is to improve the electrical properties of the electrolyte membrane, but it will reduce the strength of the electrolyte membrane and increase the cost.
  • solid oxide fuel cells can be classified into two types: electrolyte support type and anode support type.
  • electrolyte support type an electrolyte membrane having a thickness of about 200 ⁇ m is usually used as a support. Since the ohmic internal resistance of the electrolyte-supported solid oxide fuel cell is large, the electrolytic performance of the conventional 8YSZ cannot be satisfied, and the extremely expensive lOSclCeSZ is required, which not only causes a high battery cost but also has a low overall strength. , also affects the overall performance of the battery.
  • the common feature of the above patents is that the performance of the single cell is improved by the improvement of the electrode, and the electrolyte used is a single material.
  • the main disadvantage of a single material electrolyte membrane is that it can only meet the strength requirements, or can only meet the electrical performance requirements, and can not make the electrolyte membrane meet the dual requirements of strength and electrical performance. Summary of the invention
  • the problem to be solved by the present invention is to provide an electrolyte membrane which, in comparison with the prior art, has good electrical properties and a good strength of 4 ⁇ .
  • the present invention provides an electrolyte membrane comprising at least one strength-enhancing electrolyte membrane layer and a high-ion conductivity electrolyte membrane layer, the strength-enhancing electrolyte membrane layer having a bending strength higher than 300 MPa, the high-ion conductance
  • the electrolyte membrane layer has an ionic conductivity of 800 ° C higher than 0.03 S/cm.
  • the strength enhancing electrolyte membrane layer and the high ion conductivity electrolyte membrane layer are alternately arranged.
  • the strength of the reinforced electrolyte membrane is doped layer is selected from the Y 2 ⁇ 6% mol 203, 203 of one kind or Sc CaO or more of Zr0 2.
  • the high-ion conducting electrolyte membrane layer is doped with one or more selected from the group consisting of Y 2 O 3 , Sc 2 0 3 , Ce0 2 , Yb 2 0 3 , Nd 2 03, Na 2 0 or Zr0 2 doped with La 2 0 3 and / or Gd Ce0 2 2 0 3; and doping amount of the high ion conductivity of the electrolyte separator layer of rare earth oxide is 7-21% mol "
  • the doping amount of the rare earth oxide in the high ion conductivity electrolyte membrane layer is 7.5 to 11.5% by mol.
  • the strength enhancing electrolyte membrane layer and the high ion conductive electrolyte membrane layer are thick The ratio is 1: 1 ⁇ 1: 4.
  • the electrolyte membrane has a thickness of 5 ⁇ ⁇ ! ⁇ 500 ⁇ ⁇ .
  • the invention also provides an electrochemical device comprising the electrolyte membrane of any of the above aspects.
  • the present invention also provides a solid oxide fuel cell, the solid oxide fuel cell comprising: an anode;
  • an electrolyte membrane according to any of the above aspects is disposed between the anode and the cathode.
  • the solid oxide fuel cell is an anode supported solid oxide fuel cell or a electrolyte supported solid oxide fuel cell.
  • the electrochemical device is an oxygen sensor.
  • the present invention provides an electrolyte membrane comprising a strength-enhancing electrolyte membrane layer and a high-ion conductivity electrolyte membrane layer.
  • the strength-enhancing electrolyte membrane layer can increase the strength of the electrolyte membrane
  • the high-ion conductive electrolyte membrane layer can increase the electrical properties of the electrolyte membrane, and thus the present invention provides an electrolyte membrane layer. It can meet the strength requirements and meet the electrical performance requirements.
  • Example 1 is a schematic structural view of an electrolyte membrane prepared in Example 1 of the present invention.
  • FIG. 2 is a schematic view showing the structure of a solid oxide fuel cell prepared in Example 4 of the present invention
  • FIG. 3 is a SEM microscopic topography of the electrolyte separator prepared in Example 3 of the present invention.
  • the present invention provides an electrolyte membrane for a solid oxide fuel cell, comprising: at least one strength-enhancing electrolyte membrane layer and a high-ion conductivity electrolyte membrane layer, wherein the strength-enhancing electrolyte membrane layer has a bending strength higher than 300 MPa,
  • the ionic conductivity of the high ion conductivity electrolyte membrane layer at 800 ° C is higher than 0.03 S / cm.
  • the strength-enhancing electrolyte membrane layer functions to increase the strength of the entire electrolyte membrane, and its bending strength is higher than 300 MPa, more preferably higher than 400 MPa, more preferably higher than 600 MPa, and still more preferably higher than 800 MPa.
  • Strength enhancing material preferably electrolyte membrane doped layer is 2 ⁇ 6% mol of the Y is selected from 203, 203 in one kind or Sc or more of CaO Zr0 2, preferably, the strength of the reinforced electrolyte membrane
  • the doping amount of the rare earth oxide in the layer is 2.5% mol to 5.5% mol, more preferably 2.8% mol to 5% mol.
  • strength of the reinforcing material of the electrolyte membrane layer may be doped 3molY 2 0 3 of Zr0 2 (3YSZ), 4YSZ, 5YSZ, 6YSZ, 3CaSZ, 4CaSZ, 5CaSZ, 6CaSZ, 3ScSZ, 4ScSZ, 5ScSZ, 6ScSZ the like, but not Limited to this.
  • the function of the high ion conductivity electrolyte membrane layer is to improve the electrical properties of the entire electrolyte membrane, and its ionic conductivity at 800 ° C is higher than 0.03 S / cm, more preferably higher than 0.04 S / cm, more preferably higher than 0.06 S/cm, more preferably higher than 0.1 S/cm.
  • Material high ion conductivity of the electrolyte membrane layer is preferably doped with Y 2 0 3, Sc 2 0 3, Ce0 2, Yb 2 0 3, Nd 2 03, 20 of one kind or more of Na or Zr0 2 doped with La 2 0 3 and / or Gd Ce0 2 2 0 3; and the doping amount of rare earth oxide high ion conductance electrolyte separator layer is preferably 7% mol -21% mol, more preferably 7.5% Mo is 11.5% mol, more preferably 8% mol to 10% mol. Specific examples may be 10SclCeSZ, 9Sc2CeSZ, 8Sc3CeSZ, lOLaCeZ, etc., but are not limited thereto.
  • a plurality of strength-enhancing electrolyte membrane layers and a plurality of high-ion conductivity electrolyte membrane layers may be included, and the thicknesses of the strength-enhancing electrolyte membrane layer and the high-ion conductivity electrolyte membrane layer may be the same or different.
  • a plurality of strength-enhancing electrolyte membrane layers and a plurality of high-ion conductivity electrolyte membrane layers may be alternately disposed.
  • a preferred arrangement is to alternately set the plurality of strength-enhancing dielectric diaphragm layers and the plurality of high-ion conductive dielectric membrane layers. And at the topmost layer and the bottommost layer are disposed as a high-ion electrically conductive medium diaphragm layer, that is, the strength-enhancing electrolyte layer is disposed in the middle of the high-ion-conducting electrolyte layer, at this time, the number of the high-ion-conducting electrolyte diaphragm layer is stronger than that of the electrolyte membrane layer The number is one more.
  • the thickness ratio of the strength-enhancing electrolyte membrane layer to the high-ion conductivity electrolyte membrane layer is preferably 1:1 to 1:4, more preferably 1:2 to 1:3.
  • the thickness of the strength-enhancing electrolyte membrane layer is preferably 5 ⁇ m to 100 ⁇ m, more preferably 10 ⁇ m to 80 ⁇ m, still more preferably 30 ⁇ m to 60 ⁇ m.
  • the present invention also provides a method of preparing the electrolyte membrane, comprising: a strength-enhancing electrolyte membrane
  • a strength-enhancing electrolyte membrane The layer strip and the high ion conductivity electrolyte membrane layer are laminated according to a preset manner and thickness, and the preset manner may be alternately stacked to enhance the strength of the electrolyte membrane layer strip and the high ion conductivity electrolyte membrane
  • pre-pressing is performed to obtain a pre-pressed piece.
  • the pressure in the case of applying the pre-pressure is not particularly limited, and is preferably 5 MPa to 20 MPa, and more preferably 8 MPa to 15 MPa.
  • the pre-pressing member can be placed in a vacuum bag for vacuum treatment, the residual gas in the pre-pressing member can be removed, and then the vacuum-treated pre-pressing member can be press-formed to obtain a molded part, which is preferably placed during press molding.
  • the press molding is carried out in an isostatic press, and the pressure at the time of press molding is preferably at least 25 MPa, more preferably 30 MPa to 200 MPa, still more preferably 50 MPa to 180 MPa, still more preferably 100 MPa to 150 MPa.
  • the molded article can be cut into a predetermined shape as needed, and then the cut molded article is sintered, and the sintering temperature is preferably 1300 ° C to 1500 ° C, more preferably 1350 ° C to 1450 °. C;
  • the sintering time it is preferably at least 30 min, more preferably at least 1 hour, still more preferably 4 hours to 8 hours.
  • the sintering environment it is preferably carried out under an air atmosphere.
  • the method for preparing the strength-enhancing electrolyte membrane layer strip or the high-ion-conducting electrolyte membrane layer strip can be prepared according to a method well known to those skilled in the art, and the specific example can be a casting method or the like, but Not limited to this.
  • the present invention also provides an electrochemical device in which the electrolyte membrane according to any of the above aspects is provided, and the electrochemical device is preferably a solid oxide fuel cell, an oxygen sensor, an oxygen pump, and a temperature sensor. However, it is not limited thereto, and is preferably a solid oxide fuel cell.
  • the invention also provides the use of the electrolyte membrane in an electrochemical device, which is preferably a solid oxide fuel cell, an oxygen sensor, an oxygen pump, a temperature sensor, but is not limited thereto, preferably a solid oxide fuel cell. .
  • the invention provides a solid oxide fuel cell, comprising:
  • An electrolyte membrane according to the above technical solution is disposed between the anode and the cathode.
  • the electrolyte membrane of the present invention can be used in an electrolyte supported solid oxide fuel cell, and can also be used in an anode supported solid oxide fuel cell.
  • the thickness of the electrolyte membrane is The degree is preferably from 100 ⁇ m to 400 ⁇ m, more preferably from 150 ⁇ m to 250 ⁇ m, still more preferably from 180 ⁇ m to 210 ⁇ m, and even more preferably 200 ⁇ .
  • the thickness of the electrolyte membrane is preferably less than 50 ⁇ m, more preferably 8 ⁇ m to 30 ⁇ m, still more preferably 8 ⁇ m ⁇ 15 ⁇ m.
  • the anode of the solid oxide fuel cell can be an anode well known to those skilled in the art.
  • the anode preferably includes an anode functional layer in contact with the electrolyte membrane and an anode support layer in contact with the anode functional layer, the anode functional layer functioning to provide a fuel electrochemical reaction region, preferably M-8YSZ, anode
  • the thickness of the functional layer is preferably ⁇ ⁇ ⁇ ! ⁇ 50 ⁇ ⁇ , preferably 15 ⁇ m to 40 ⁇ m, more preferably 20 ⁇ ⁇ to 35 ⁇ ⁇ .
  • the role of the anode support layer is to provide mechanical strength and anode current collection of the battery.
  • the preferred material is Ni-YSZ, and the doping amount of Y in Ni-YSZ is preferably between 2 and 8% mol; the thickness of the anode support layer. Preferably 100 ⁇ ⁇ ! ⁇ 400 ⁇ ⁇ , more preferably 150 ⁇ m to 350 ⁇ m.
  • the cathode can use a cathode material well known to those skilled in the art, including a cathode electrolyte compound which can provide ion conductivity and a cathode electron conductive material which can provide electron conductivity and catalytic activity.
  • the cathode electronically conductive material may include doped lanthanum manganite, doped barium ferrite, doped lanthanum cobalt sulphate, doped yttrium chromite, and manganate, ferrite, high cobalt acid A combination of a salt and a chromite.
  • the dopant of lanthanum manganite may be one or more of Sr, Ca, Mg, and Ba.
  • the cathode electrolyte compound may be doped zirconia such as ZrQ ⁇ YQ.QsO ⁇ or doped ruthenium dioxide such as Ceo.8Gdo.20L9 or the like.
  • lOSclCeSZ The method of preparing a casting thickness of about 50 ⁇ ⁇ containing 10mol% Sc 2 O 3 and the strip lmol Zr0 2% Ce0 2 (hereinafter, referred to lOSclCeSZ); a casting method having a thickness of about 50 ⁇ ⁇ of A Zr0 2 strip containing 3 mol% of Y 2 0 3 (hereinafter referred to as 3YSZ).
  • FIG. 1 three lOSclCeSZ strips 101 and two 3YSZ strips 102 are alternately stacked together, and a pressure of 8 MP is applied for pre-molding to obtain a pre-pressed piece; the pre-pressed part is placed in a vacuum bag. Vacuuming, and then isostatically pressing to obtain a molded article under a pressure of 50 MPa; sintering the molded article under an air atmosphere at 1450 ° C for 4 hours to obtain an electrolyte having a thickness of about 210 ⁇ m Diaphragm.
  • the electrolyte diaphragm was measured to have a flexural strength of 478 MPa at room temperature, and the conductivity of the electrolyte membrane measured at 800 ° C was 0.061 S/cm.
  • the method of preparing a casting thickness of about 40 ⁇ ⁇ containing 10mol% Sc 2 O 3 and the strip lmol Zr0 2% Ce0 2 (hereinafter, referred to lOSclCeSZ); a casting method having a thickness of about 20 ⁇ ⁇ of A Zr0 2 strip containing 5 mol% of Y 2 0 3 (hereinafter referred to as 5YSZ).
  • lOSclCeSZ strips and four 5YSZ strips were alternately stacked together, and a pre-pressing piece was obtained by pre-compression molding with a pressure of 15 MP; the pre-pressed part was placed in a vacuum bag to be evacuated, and then at a pressure of 150 MPa.
  • the molded article was obtained by isostatic pressing to obtain a molded article; the molded article was sintered under an air atmosphere at 1,450 ° C for 5 hours to obtain an electrolyte separator having a thickness of about 240 ⁇ m.
  • the flexural strength of the electrolyte membrane was measured at room temperature to be 456 MPa, and the conductivity of the electrolyte membrane measured at 800 ° C was 0.069 S/cm.
  • the method of preparing a casting thickness of about 40 ⁇ ⁇ containing 10mol% Sc 2 O 3 and the strip lmol Zr0 2% Ce0 2 (hereinafter, referred to lOSclCeSZ); a casting method having a thickness of about ⁇ ⁇ ⁇ of A Zr0 2 strip containing 6 mol% of Y 2 0 3 (hereinafter referred to as 6YSZ).
  • a pre-pressing piece was obtained by pre-compression molding with a pressure of 15 MP; the pre-pressed part was placed in a vacuum bag to be evacuated, and then subjected to a pressure of 50 MPa.
  • the molded article was obtained by isostatic pressing to obtain a molded article; the molded article was sintered under an air atmosphere at 1480 ° C for 5 hours to obtain an electrolyte separator having a thickness of about 250 ⁇ m.
  • the electrolyte diaphragm was measured to have a flexural strength of 433 MPa at room temperature, and the conductivity of the electrolyte membrane measured at 800 ° C was 0.074 S/cm.
  • Zr0 2 tape hereinafter referred 9Sc2CeSZ
  • CGO10 a casting method having a thickness of 15 ⁇ ⁇ containing 10mol% Gd 2 O 3 of the strip Ce0 2
  • One 9Sc2CeSZ strip and one CGO10 strip are alternately stacked together, and a pre-pressing piece is obtained by pre-compression molding by applying a pressure of 20MP; the pre-pressing piece is placed in a vacuum bag to be vacuumed, and then The molded article was obtained by isostatic pressing under a pressure of 100 MPa; the molded article was sintered under an air atmosphere at 1450 ° C for 5 hours to obtain an electrolyte separator having a thickness of about 25 ⁇ m.
  • the flexural strength of the electrolyte membrane was measured at room temperature to be 327 MPa, and the conductivity of the electrolyte membrane measured at 800 ° C was 0.011 S/cm.
  • a solid oxide fuel cell was prepared by using the electrolyte membrane 11 prepared in this example, in which Ni-2YSZ having a thickness of 300 ⁇ m was used as the anode supporting layer 201, and M-8YSZ having a thickness of 20 ⁇ m was used as The anode functional layer 202 is made of a sintered body of a thickness of 10 ( ⁇ 111 by 1 ⁇ .. ( ⁇ .40)..6.. 8 0 3 and Gd ⁇ CeiuO in a molar ratio of 1:1 as a cathode 12 Assembled into a solid oxide fuel cell.
  • the method of preparing a casting thickness of 40 ⁇ ⁇ containing 12mol% Sc 2 0 3 and the strip lmo Zr0 2% Ce0 2 (hereinafter, referred to 12SclCeSZ); a casting method having a thickness of ⁇ ⁇ ⁇ containing 4mol Zr0 2 strip of %Y 2 0 3 (hereinafter referred to as 4YSZ).
  • the flexural strength of the electrolyte membrane was measured at room temperature to be 473 MPa, and the conductivity of the electrolyte membrane measured at 800 ° C was 0.067 S/cm.
  • a Ce ⁇ GdojOw strip (hereinafter referred to as CGO10) having a thickness of about 40 ⁇ m was prepared by a casting method; a Zr0 2 strip containing 3 mol% of Y 2 0 3 having a thickness of 10 ⁇ m was prepared by casting ( Hereinafter referred to as 3YSZ).
  • a preloading member was obtained by applying a pressure of 20 MP to obtain a pre-pressing piece; the pre-pressing piece was placed in a vacuum bag to be evacuated, and then at a pressure of 150 MPa.
  • the molded article was obtained by isostatic pressing to obtain a molded article; the molded article was sintered under an air atmosphere at 1410 ° C for 5 hours to obtain an electrolyte separator having a thickness of about 200 ⁇ m.
  • the electrolyte membrane was measured to have a flexural strength of 437 MPa at room temperature, and the conductivity of the electrolyte membrane measured at 800 ° C was 0.073 S/cm.
  • a Zr0 2 strip containing 10 mol% of Sc 2 O 3 (hereinafter referred to as lOScSZ) having a thickness of about 100 ⁇ m was prepared by a casting method; a 3 mol% Y 2 0 having a thickness of 90 ⁇ m was prepared by a casting method.
  • 3YSZ 3 Zr0 2 strip
  • lOScSZ strips and one 3YSZ strip were alternately stacked together, and a pre-pressing piece was obtained by pre-compression molding by applying a pressure of 20MP; the pre-pressed part was placed in a vacuum bag to be evacuated, and then at a pressure of 150 MPa.
  • the molded article was obtained by isostatic pressing to obtain a molded article; the molded article was sintered under an air atmosphere at 1,450 ° C for 5 hours to obtain an electrolyte separator having a thickness of about 250 ⁇ m.
  • the SEM microstructure of the electrolyte membrane prepared in this example is shown in Fig. 3.
  • lOSclCeSZ strips Three lOSclCeSZ strips were stacked together, and a pre-pressing piece was obtained by pre-compression molding with a pressure of 15 MP; the pre-pressed part was placed in a vacuum bag to be vacuumed, and then isostatically pressed under a pressure of 100 MPa to obtain a molded part.
  • the molded article was sintered under an air atmosphere at 1430 ° C for 5 hours to obtain an electrolyte separator having a thickness of about 200 ⁇ m.
  • the electrolyte diaphragm was measured to have a flexural strength of 282 MPa at room temperature, and the conductivity of the electrolyte membrane measured at 800 ° C was 0.12 S/cm.
  • a Zr0 2 strip (hereinafter referred to as 4YSZ) containing 4 mol% of Y 2 0 3 having a thickness of about 60 ⁇ m was prepared by a casting method.
  • Two 4YSZ strips are stacked together, and a pre-pressing piece is obtained by pre-compression molding by applying a pressure of 10MP; the pre-pressing part is placed in a vacuum bag to be vacuumed, and then isostatically pressed under a pressure of 200 MPa to obtain a molded part.
  • the molded article was sintered under an air atmosphere at 1400 ° C for 8 hours to obtain an electrolyte membrane having a thickness of about ⁇ ⁇ .
  • the electrolyte diaphragm was measured to have a bending strength of 974 MPa at room temperature, and the conductivity of the electrolyte membrane measured at 800 ° C was 0.02 S/cm.
  • Electrolyte separator, electrochemical device and solid oxide fuel cell provided by the present invention
  • the description of the above embodiments is merely for assisting in understanding the method of the present invention and its core idea. It should be noted that those skilled in the art can make various modifications and changes to the present invention without departing from the spirit and scope of the invention.

Abstract

The present invention relates to an electrolyte membrane, an electrochemical device and a solid oxide fuel cell which comprise said electrolyte membrane. Said electrolyte membrane includes at least one strength reinforcing electrolyte membrane layer and at least one high ionic conductivity electrolyte membrane layer, wherein the bending strength of said strength reinforcing electrolyte membrane layer is more than 300MPa, and the ionic conductivity at 800℃ of said high ionic conductivity electrolyte membrane layer is more than 0.03 S/cm. The strength reinforcing electrolyte membrane layer can enhance the strength of the electrolyte membrane, and the high ionic conductivity electrolyte membrane layer can improve the electrical properties of the electrolyte membrane，thus the electrolyte membrane of the present invention can meet the requirements of strength and electrical property.

Description

一种电解质隔膜、 电化学装置和固体氧化物燃料电池 技术领域  Electrolyte diaphragm, electrochemical device and solid oxide fuel cell
本发明涉及电化学技术领域，具体涉及一种电解质隔膜以及包括所述电解 质隔膜的电化学装置。 背景技术  The present invention relates to the field of electrochemical technology, and in particular to an electrolyte membrane and an electrochemical device including the electrolyte membrane. Background technique
电解质隔膜是固体氧化物燃料电池（SOFC )、 氧传感器、 氧泵和温度传感 器等电化学装置的核心部件，在电解质隔膜中发生主要的电化学反应。在上述 电化学装置中，固体氧化物燃料电池是一种直接将化学能转化为电能的能量转 化装置， 具有高效率、 无污染、 全固态等显著优点， 在诸多领域有着广阔的应 用前景。  The electrolyte membrane is a core component of an electrochemical device such as a solid oxide fuel cell (SOFC), an oxygen sensor, an oxygen pump, and a temperature sensor, and a major electrochemical reaction occurs in the electrolyte membrane. In the above electrochemical device, the solid oxide fuel cell is an energy conversion device for directly converting chemical energy into electrical energy, and has remarkable advantages such as high efficiency, no pollution, and all solid state, and has broad application prospects in many fields.
固体氧化物燃料电池发电***一般由多个电池堆组成，每个电池堆由数十 片单电池组装而成。 通常， 固体氧化物燃料单电池至少包括阴极 /电解质隔膜 / 阳极三大功能层， 其中的阳极或阴极为多孔层， 电解质隔膜为致密层。 电解质 隔膜一般为氧离子导体或质子导体， 厚度一般为 10 μ ηι〜200 μ ηι, 其电导率具 有随温度升高而迅速升高的特性。 目前， 电解质隔膜的常用材质是掺杂一种或 多种稀土氧化物的氧化锆、 氧化铈等材料， 如掺杂氧化钇的氧化锆（YSZ )、 掺杂氧化抗的氧化锆 ( ScSZ )、 掺杂氧化铈的氧化锆 ( CeSZ )， 或同时掺杂氧 化钇和氧化铈的氧化锆 ScCeSZ等。 掺杂的稀土氧化物越多， 越有助于提高电 解质隔膜的电性能， 但是会降低电解质隔膜的强度， 而且还会增加成本， 例如 lOSclCeSZ的成本远高于 8YSZ的成本。  A solid oxide fuel cell power generation system generally consists of a plurality of battery stacks, each of which is assembled from dozens of single cells. Generally, a solid oxide fuel cell comprises at least three functional layers of a cathode/electrolyte membrane/anode, wherein the anode or cathode is a porous layer, and the electrolyte membrane is a dense layer. The electrolyte membrane is generally an oxygen ion conductor or a proton conductor, and has a thickness of generally 10 μm to 200 μm, and its conductivity has a characteristic of increasing rapidly with an increase in temperature. At present, the common material of the electrolyte membrane is zirconia, yttria and the like doped with one or more rare earth oxides, such as yttria-doped zirconia (YSZ), oxidized-resistant zirconia (ScSZ), Zirconium oxide doped with yttria (CeSZ), or zirconia ScCeSZ doped with yttria and yttria. The more doped rare earth oxides, the more helpful it is to improve the electrical properties of the electrolyte membrane, but it will reduce the strength of the electrolyte membrane and increase the cost. For example, the cost of lOSclCeSZ is much higher than the cost of 8YSZ.
按照结构的不同，固体氧化物燃料电池可以分为电解质支撑型和阳极支撑 型两种类型。 在电解质支撑型固体氧化物燃料电池中， 通常使用厚度为 200 μ m左右的电解质隔膜作为支撑体。由于电解质支撑型固体氧化物燃料电池的欧 姆性内阻较大， 因此普通的 8YSZ的电解性能不能满足要求， 需要使用价格极 为昂贵的 lOSclCeSZ, 这不但造成电池成本较高， 而且由于整体强度较低， 也 影响了电池整体的使用性能。  Depending on the structure, solid oxide fuel cells can be classified into two types: electrolyte support type and anode support type. In the electrolyte supported solid oxide fuel cell, an electrolyte membrane having a thickness of about 200 μm is usually used as a support. Since the ohmic internal resistance of the electrolyte-supported solid oxide fuel cell is large, the electrolytic performance of the conventional 8YSZ cannot be satisfied, and the extremely expensive lOSclCeSZ is required, which not only causes a high battery cost but also has a low overall strength. , also affects the overall performance of the battery.
为了改善固体氧化物燃料电池的使用性能，现有技术中已经公开了多种针 对固体氧化物燃料电池的改进方案。 如最近公布的美国专利申请 US20090136821中，在电池的阳极侧使用一种不连续的陶瓷层作为电池的骨架 支撑体， 电极功能层通过支撑体的不连续部位与电解质接触， 该专利通过将支 撑体与功能层区域相分离的方式提高了电池的性能。 在美国专利 US7767358 中，通过将阴阳极层的多孔骨架与电介质层一体成型的方式来制作电池， 其实 质是电解质与电极共同作为支撑体。 In order to improve the performance of the solid oxide fuel cell, various needles have been disclosed in the prior art. An improved solution for solid oxide fuel cells. In the recently published U.S. Patent Application No. US20090136821, a discontinuous ceramic layer is used as the skeleton support for the battery on the anode side of the battery, and the electrode functional layer is in contact with the electrolyte through the discontinuous portion of the support. The separation from the functional layer area improves the performance of the battery. In U.S. Patent No. 7,767,358, a battery is fabricated by integrally molding a porous skeleton of a cathode-anode layer with a dielectric layer, in which the electrolyte and the electrode together serve as a support.
上述专利所共同的特点是都通过对电极的改进来提高单电池的使用性能， 所使用的电解质均为单一材质。单一材质的电解质隔膜的主要缺点是要么只能 满足强度使用要求，要么只能满足电性能使用要求， 而无法使电解质隔膜兼顾 到强度和电性能的双重要求。 发明内容  The common feature of the above patents is that the performance of the single cell is improved by the improvement of the electrode, and the electrolyte used is a single material. The main disadvantage of a single material electrolyte membrane is that it can only meet the strength requirements, or can only meet the electrical performance requirements, and can not make the electrolyte membrane meet the dual requirements of strength and electrical performance. Summary of the invention
本发明要解决的问题在于提供一种电解质隔膜， 与现有技术相比， 本发明 提供的电解质隔膜在具有良好的电性能的同时， 还具有 4艮好的强度。  The problem to be solved by the present invention is to provide an electrolyte membrane which, in comparison with the prior art, has good electrical properties and a good strength of 4 Å.
为了解决以上技术问题， 本发明提供一种电解质隔膜， 包括至少一个强度 增强电解质隔膜层和一个高离子电导电解质隔膜层，所述强度增强电解质隔膜 层的弯曲强度高于 300MPa, 所述高离子电导电解质隔膜层 800°C的离子电导 率高于 0.03S/cm。  In order to solve the above technical problems, the present invention provides an electrolyte membrane comprising at least one strength-enhancing electrolyte membrane layer and a high-ion conductivity electrolyte membrane layer, the strength-enhancing electrolyte membrane layer having a bending strength higher than 300 MPa, the high-ion conductance The electrolyte membrane layer has an ionic conductivity of 800 ° C higher than 0.03 S/cm.
优选的， 所述强度增强电解质隔膜层和高离子电导电解质隔膜层交替排 列。  Preferably, the strength enhancing electrolyte membrane layer and the high ion conductivity electrolyte membrane layer are alternately arranged.
优选的， 所述强度增强电解质隔膜层是掺杂了 2〜6%mol选自 Y203、 CaO 或 Sc203中的一种或多种的 Zr02。 Preferably, the strength of the reinforced electrolyte membrane is doped layer is selected from the Y 2~6% mol 203, 203 of one kind or Sc CaO or more of Zr0 2.
优选的，所述高离子电导电解质隔膜层是掺杂了选自 Y203、 Sc203、 Ce02、 Yb203、 Nd203、 Na20中的一种或多种的 Zr02或是掺杂了 La203和 /或 Gd203 的 Ce02 ; 所述高离子电导电解质隔膜层中的稀土氧化物的掺杂量为 7-21%mol„ Preferably, the high-ion conducting electrolyte membrane layer is doped with one or more selected from the group consisting of Y 2 O 3 , Sc 2 0 3 , Ce0 2 , Yb 2 0 3 , Nd 2 03, Na 2 0 or Zr0 2 doped with La 2 0 3 and / or Gd Ce0 2 2 0 3; and doping amount of the high ion conductivity of the electrolyte separator layer of rare earth oxide is 7-21% mol "
优选的， 所述高离子电导电解质隔膜层中的稀土氧化物的掺杂量为 7.5〜11.5%mol。  Preferably, the doping amount of the rare earth oxide in the high ion conductivity electrolyte membrane layer is 7.5 to 11.5% by mol.
优选的，所述强度增强电解质隔膜层和所述高离子电导电解质隔膜层的厚 度比为 1 : 1〜1 :4。 Preferably, the strength enhancing electrolyte membrane layer and the high ion conductive electrolyte membrane layer are thick The ratio is 1: 1~1: 4.
优选的， 所述电解质隔膜的厚度为 5 μ η！〜 500 μ ηι。  Preferably, the electrolyte membrane has a thickness of 5 μ η! ~ 500 μ ηι.
本发明还提供一种电化学装置， 包括以上任一技术方案所述的电解质隔 膜。  The invention also provides an electrochemical device comprising the electrolyte membrane of any of the above aspects.
本发明还提供一种固体氧化物燃料电池， 所述固体氧化物燃料电池包括： 阳极；  The present invention also provides a solid oxide fuel cell, the solid oxide fuel cell comprising: an anode;
与所述阳极相对的阴极；  a cathode opposite the anode;
在所述阳极和阴极之间设置有以上任一技术方案所述的电解质隔膜。 优选的，所述固体氧化物燃料电池为阳极支撑型固体氧化物燃料电池或电 解质支撑型固体氧化物燃料电池。  An electrolyte membrane according to any of the above aspects is disposed between the anode and the cathode. Preferably, the solid oxide fuel cell is an anode supported solid oxide fuel cell or a electrolyte supported solid oxide fuel cell.
优选的， 所述电化学装置为氧传感器。  Preferably, the electrochemical device is an oxygen sensor.
本发明提供了一种电解质隔膜，包括强度增强电解质隔膜层和高离子电导 电解质隔膜层。 与现有技术相比， 本发明提供的电解质隔膜中， 强度增强电解 质隔膜层可以增加电解质隔膜的强度，而高离子导电电解质隔膜层可以增加电 解质隔膜的电性能， 因此本发明提供电解质隔膜层即能够满足强度要求， 又能 够满足电性能要求。 附图说明  The present invention provides an electrolyte membrane comprising a strength-enhancing electrolyte membrane layer and a high-ion conductivity electrolyte membrane layer. Compared with the prior art, in the electrolyte membrane provided by the present invention, the strength-enhancing electrolyte membrane layer can increase the strength of the electrolyte membrane, and the high-ion conductive electrolyte membrane layer can increase the electrical properties of the electrolyte membrane, and thus the present invention provides an electrolyte membrane layer. It can meet the strength requirements and meet the electrical performance requirements. DRAWINGS
图 1为本发明实施例 1制备的电解质隔膜的结构示意图；  1 is a schematic structural view of an electrolyte membrane prepared in Example 1 of the present invention;
图 2为本发明实施例 4制备的固体氧化物燃料电池结构示意图； 图 3为本发明实施例 3制备的电解质隔膜的 SEM微观形貌图。 具体实施方式  2 is a schematic view showing the structure of a solid oxide fuel cell prepared in Example 4 of the present invention; and FIG. 3 is a SEM microscopic topography of the electrolyte separator prepared in Example 3 of the present invention. detailed description
为了进一步了解本发明， 下面结合实施例对本发明优选实施方案进行描 述， 但是应当理解， 这些描述只是为进一步说明本发明的特征和优点， 而不是 对本发明权利要求的限制。  In order to further understand the invention, the preferred embodiments of the present invention are described in the accompanying drawings.
本发明提供的一种用于固体氧化物燃料电池的电解质隔膜， 包括： 至少一个强度增强电解质隔膜层和一个高离子电导电解质隔膜层，所述强 度增强电解质隔膜层的弯曲强度高于 3 OOMPa , 所述高离子电导电解质隔膜层 800°C的离子电导率高于 0.03S/cm。 本发明中， 强度增强电解质隔膜层的作用是提高整个电解质隔膜的强度， 其弯曲强度高于 300MPa, 更优选高于 400MPa、 更优选高于 600MPa, 更优选 高于 800MPa。 强度增强电解质隔膜层的材质优选为掺杂了 2〜6%mol 选自 Y203、 CaO或 Sc203中的一种或多种的 Zr02, 优选的， 所述强度增强电解质 隔膜层中的稀土氧化物的掺杂量为 2.5%mol〜5.5%mol , 更优选为 2.8%mol〜5%mol。 强度增强电解质隔膜层材质的具体例子可以为掺杂了 3molY203的 Zr02 ( 3YSZ )、 4YSZ、 5YSZ、 6YSZ、 3CaSZ、 4CaSZ、 5CaSZ、 6CaSZ、 3ScSZ、 4ScSZ、 5ScSZ、 6ScSZ等, 但不限于此。 The present invention provides an electrolyte membrane for a solid oxide fuel cell, comprising: at least one strength-enhancing electrolyte membrane layer and a high-ion conductivity electrolyte membrane layer, wherein the strength-enhancing electrolyte membrane layer has a bending strength higher than 300 MPa, The ionic conductivity of the high ion conductivity electrolyte membrane layer at 800 ° C is higher than 0.03 S / cm. In the present invention, the strength-enhancing electrolyte membrane layer functions to increase the strength of the entire electrolyte membrane, and its bending strength is higher than 300 MPa, more preferably higher than 400 MPa, more preferably higher than 600 MPa, and still more preferably higher than 800 MPa. Strength enhancing material preferably electrolyte membrane doped layer is 2~6% mol of the Y is selected from 203, 203 in one kind or Sc or more of CaO Zr0 2, preferably, the strength of the reinforced electrolyte membrane The doping amount of the rare earth oxide in the layer is 2.5% mol to 5.5% mol, more preferably 2.8% mol to 5% mol. Specific examples of the strength of the reinforcing material of the electrolyte membrane layer may be doped 3molY 2 0 3 of Zr0 2 (3YSZ), 4YSZ, 5YSZ, 6YSZ, 3CaSZ, 4CaSZ, 5CaSZ, 6CaSZ, 3ScSZ, 4ScSZ, 5ScSZ, 6ScSZ the like, but not Limited to this.
本发明中，高离子电导电解质隔膜层的作用是提高整个电解质隔膜的电性 能， 其在 800°C的离子电导率高于 0.03S/cm, 更优选高于 0.04S/cm, 更优选高 于 0.06S/cm, 更优选高于 0.1S/cm。 高离子电导电解质隔膜层的材质优选为掺 杂了 Y203、 Sc203、 Ce02、 Yb203、 Nd203、 Na20中的一种或多种的 Zr02或是 掺杂了 La203和 /或 Gd203的 Ce02; 所述高离子电导电解质隔膜层中的稀土氧 化物的掺杂量优选为 7%mol -21%mol, 更优选为 7.5%mo卜 11.5%mol, 更优选 为 8%mol 〜10%mol。 具体例子可以为 10SclCeSZ、 9Sc2CeSZ、 8Sc3CeSZ、 lOLaCeZ等， 但不限于此。 In the present invention, the function of the high ion conductivity electrolyte membrane layer is to improve the electrical properties of the entire electrolyte membrane, and its ionic conductivity at 800 ° C is higher than 0.03 S / cm, more preferably higher than 0.04 S / cm, more preferably higher than 0.06 S/cm, more preferably higher than 0.1 S/cm. Material high ion conductivity of the electrolyte membrane layer is preferably doped with Y 2 0 3, Sc 2 0 3, Ce0 2, Yb 2 0 3, Nd 2 03, 20 of one kind or more of Na or Zr0 2 doped with La 2 0 3 and / or Gd Ce0 2 2 0 3; and the doping amount of rare earth oxide high ion conductance electrolyte separator layer is preferably 7% mol -21% mol, more preferably 7.5% Mo is 11.5% mol, more preferably 8% mol to 10% mol. Specific examples may be 10SclCeSZ, 9Sc2CeSZ, 8Sc3CeSZ, lOLaCeZ, etc., but are not limited thereto.
按照本发明，在电解质隔膜中， 可以包括多个强度增强电解质隔膜层和多 个高离子电导电解质隔膜层，强度增强电解质隔膜层和高离子电导电解质隔膜 层的厚度可以相同， 也可以不同。 所述电解质隔膜中， 可以由多个强度增强电 解质隔膜层和多个高离子电导电解质隔膜层交替设置。  According to the present invention, in the electrolyte membrane, a plurality of strength-enhancing electrolyte membrane layers and a plurality of high-ion conductivity electrolyte membrane layers may be included, and the thicknesses of the strength-enhancing electrolyte membrane layer and the high-ion conductivity electrolyte membrane layer may be the same or different. In the electrolyte membrane, a plurality of strength-enhancing electrolyte membrane layers and a plurality of high-ion conductivity electrolyte membrane layers may be alternately disposed.
当包括多个强度增强电解质隔膜层和多个高离子电导电解质隔膜层时，优 选的设置方式是：将所述多个强度增强电介质隔膜层和所述多个高离子电导电 介质隔膜层交替设置， 且在最顶层和最底层设置为高离子电导电介质隔膜层， 即将所述强度增强电解质层设置在高离子电导电解质层中间， 此时， 高离子电 导电解质隔膜层的数量比强度增强电解质隔膜层的数量多 1个。  When a plurality of strength-enhancing electrolyte membrane layers and a plurality of high-ion conductivity electrolyte membrane layers are included, a preferred arrangement is to alternately set the plurality of strength-enhancing dielectric diaphragm layers and the plurality of high-ion conductive dielectric membrane layers. And at the topmost layer and the bottommost layer are disposed as a high-ion electrically conductive medium diaphragm layer, that is, the strength-enhancing electrolyte layer is disposed in the middle of the high-ion-conducting electrolyte layer, at this time, the number of the high-ion-conducting electrolyte diaphragm layer is stronger than that of the electrolyte membrane layer The number is one more.
按照本发明，所述强度增强电解质隔膜层与所述高离子电导电解质隔膜层 的厚度比优选为 1:1〜1:4, 更优选为 1:2〜1 :3。 强度增强电解质隔膜层的厚度优 选为 5 μ m〜100 μ m, 更优选为 10 μ m〜80 μ m, 更优选为 30 μ m〜60 μ m。  According to the invention, the thickness ratio of the strength-enhancing electrolyte membrane layer to the high-ion conductivity electrolyte membrane layer is preferably 1:1 to 1:4, more preferably 1:2 to 1:3. The thickness of the strength-enhancing electrolyte membrane layer is preferably 5 μm to 100 μm, more preferably 10 μm to 80 μm, still more preferably 30 μm to 60 μm.
本发明还提供所述电解质隔膜的制备方法， 包括： 将强度增强电解质隔膜 层带材和高离子电导电解质隔膜层带材根据预设的方式和厚度叠合在一起，预 设的方式可以为交替叠合在一起，将强度增强电解质隔膜层带材和高离子电导 电解质隔膜层带材叠合在一起后， 进行预压得到预压件。对于施加预压时的压 力， 本发明并无特别限制， 优选为 5MPa〜20MPa, 更优选为 8MPa〜15MPa。 The present invention also provides a method of preparing the electrolyte membrane, comprising: a strength-enhancing electrolyte membrane The layer strip and the high ion conductivity electrolyte membrane layer are laminated according to a preset manner and thickness, and the preset manner may be alternately stacked to enhance the strength of the electrolyte membrane layer strip and the high ion conductivity electrolyte membrane After the layers of the strips are stacked together, pre-pressing is performed to obtain a pre-pressed piece. The pressure in the case of applying the pre-pressure is not particularly limited, and is preferably 5 MPa to 20 MPa, and more preferably 8 MPa to 15 MPa.
按照本发明， 可以将预压件装入真空袋中进行抽真空处理，去除预压件中 的残留的气体， 然后再将真空处理后的预压件压制成型得到成型件，压制成型 时优选放置在等静压机中进行压制成型，对于压制成型时的压力，优选为至少 25MPa, 更优选为 30MPa〜200MPa, 更优选为 50MPa〜180MPa, 更优选为 100MPa〜150MPa。  According to the present invention, the pre-pressing member can be placed in a vacuum bag for vacuum treatment, the residual gas in the pre-pressing member can be removed, and then the vacuum-treated pre-pressing member can be press-formed to obtain a molded part, which is preferably placed during press molding. The press molding is carried out in an isostatic press, and the pressure at the time of press molding is preferably at least 25 MPa, more preferably 30 MPa to 200 MPa, still more preferably 50 MPa to 180 MPa, still more preferably 100 MPa to 150 MPa.
按照本发明， 可以根据需要将所述成型件切割成预定的形状， 然后将切割 后的成型件进行烧结， 对于烧结温度优选为 1300°C〜1500°C , 更优选为 1350 °C〜1450°C ; 对于烧结时间， 优选为至少 30min, 更优选为至少 1小时， 更优 选为 4小时〜 8小时。 对于烧结环境， 优选在空气气氛下进行。  According to the present invention, the molded article can be cut into a predetermined shape as needed, and then the cut molded article is sintered, and the sintering temperature is preferably 1300 ° C to 1500 ° C, more preferably 1350 ° C to 1450 °. C; For the sintering time, it is preferably at least 30 min, more preferably at least 1 hour, still more preferably 4 hours to 8 hours. For the sintering environment, it is preferably carried out under an air atmosphere.
按照本发明，对于所述强度增强电解质隔膜层带材或所述高离子电导电解 质隔膜层带材的制备方法， 可以按照本领域技术人员熟知的方法制备， 具体例 子可以为流延法等， 但不限于此。  According to the present invention, the method for preparing the strength-enhancing electrolyte membrane layer strip or the high-ion-conducting electrolyte membrane layer strip can be prepared according to a method well known to those skilled in the art, and the specific example can be a casting method or the like, but Not limited to this.
本发明还提供一种电化学装置，在所述电化学装置中设置有以上任意技术 方案所述的电解质隔膜， 所述电化学装置优选为固体氧化物燃料电池、氧传感 器、 氧泵、 温度传感器， 但不限于此， 优选为固体氧化物燃料电池。  The present invention also provides an electrochemical device in which the electrolyte membrane according to any of the above aspects is provided, and the electrochemical device is preferably a solid oxide fuel cell, an oxygen sensor, an oxygen pump, and a temperature sensor. However, it is not limited thereto, and is preferably a solid oxide fuel cell.
本发明还提供所述电解质隔膜在电化学装置中的应用，所述电化学装置优 选为固体氧化物燃料电池、 氧传感器、 氧泵、 温度传感器， 但不限于此， 优选 为固体氧化物燃料电池。  The invention also provides the use of the electrolyte membrane in an electrochemical device, which is preferably a solid oxide fuel cell, an oxygen sensor, an oxygen pump, a temperature sensor, but is not limited thereto, preferably a solid oxide fuel cell. .
本发明提供一种固体氧化物燃料电池， 包括：  The invention provides a solid oxide fuel cell, comprising:
阳极：  Anode:
与所述阳极相对应的阴极；  a cathode corresponding to the anode;
在所述阳极和阴极之间设置以上技术方案所述的电解质隔膜。  An electrolyte membrane according to the above technical solution is disposed between the anode and the cathode.
本发明所述的电解质隔膜可以用于电解质支撑型的固体氧化物燃料电池 中，也可以用于阳极支撑型的固体氧化物燃料电池中。 当将本发明提供的电解 质隔膜用于电解质支撑型的固体氧化物燃料电池中时， 对于电解质隔膜的厚 度，优选为 100 μ m〜400 μ m,更优选为 150 μ m〜250 μ m,更优选为 180 μ m〜210 μ ιη, 更优选为 200 μ ηι。 当将本发明提供的电解质隔膜用于阳极支撑型的固 体氧化物燃料电池中时， 对于电解质隔膜的厚度， 优选为小于 50 μ ιη, 更优选 为 8 μ m〜30 μ m, 更优选为 8 μ m〜15 μ m。 The electrolyte membrane of the present invention can be used in an electrolyte supported solid oxide fuel cell, and can also be used in an anode supported solid oxide fuel cell. When the electrolyte membrane provided by the present invention is used in an electrolyte-supported solid oxide fuel cell, the thickness of the electrolyte membrane is The degree is preferably from 100 μm to 400 μm, more preferably from 150 μm to 250 μm, still more preferably from 180 μm to 210 μm, and even more preferably 200 μηη. When the electrolyte membrane provided by the present invention is used in an anode-supported solid oxide fuel cell, the thickness of the electrolyte membrane is preferably less than 50 μm, more preferably 8 μm to 30 μm, still more preferably 8 μ m~15 μ m.
按照本发明 ,所述固体氧化物燃料电池的阳极可以为本领域技术人员熟知 的阳极。所述阳极优选包括与电解质隔膜接触的阳极功能层和与所述阳极功能 层接触的阳极支撑层， 所述阳极功能层的作用是提供燃料电化学反应区域，优 选的材料为 M-8YSZ, 阳极功能层的厚度优选为 ΙΟ μ η！〜 50 μ ιη, 优选为 15 μ m~40 μ m, 更优选为 20 μ ηι〜35 μ ηι。 阳极支撑层的作用是提供电池机械强度 和阳极集流， 优选的材料为 Ni-YSZ, 对于 Ni-YSZ中的 Y的掺杂量， 优选为 2〜8%mol之间； 阳极支撑层的厚度优选为 100 μ η！〜 400 μ ιη, 更优选为 150 μ m〜350 μ m。  According to the present invention, the anode of the solid oxide fuel cell can be an anode well known to those skilled in the art. The anode preferably includes an anode functional layer in contact with the electrolyte membrane and an anode support layer in contact with the anode functional layer, the anode functional layer functioning to provide a fuel electrochemical reaction region, preferably M-8YSZ, anode The thickness of the functional layer is preferably ΙΟ μ η! 〜 50 μ ιη, preferably 15 μm to 40 μm, more preferably 20 μ ηι to 35 μ ηι. The role of the anode support layer is to provide mechanical strength and anode current collection of the battery. The preferred material is Ni-YSZ, and the doping amount of Y in Ni-YSZ is preferably between 2 and 8% mol; the thickness of the anode support layer. Preferably 100 μ η! ~ 400 μ ιη, more preferably 150 μm to 350 μm.
按照本发明， 所述阴极可以使用本领域技术人员熟知的阴极材料， 包括可 提供离子导电性的阴极电解质化合物和可提供电子导电性和催化活性的阴极 电子导电材料。 阴极电子导电材料可包括掺杂的亚锰酸镧、 掺杂的铁酸镧、 掺 杂的高钴酸镧、 掺杂的亚铬酸镧， 以及亚锰酸盐、 铁酸盐、 高钴酸盐和亚铬酸 盐的组合物。 亚锰酸镧的掺杂剂可以为 Sr、 Ca、 Mg和 Ba中的一种或多种。 阴极电解质化合物可以为掺杂的氧化锆如 ZrQ^YQ.QsO^或者掺杂的二氧化铈 如 Ceo.8Gdo.20L9等。  According to the present invention, the cathode can use a cathode material well known to those skilled in the art, including a cathode electrolyte compound which can provide ion conductivity and a cathode electron conductive material which can provide electron conductivity and catalytic activity. The cathode electronically conductive material may include doped lanthanum manganite, doped barium ferrite, doped lanthanum cobalt sulphate, doped yttrium chromite, and manganate, ferrite, high cobalt acid A combination of a salt and a chromite. The dopant of lanthanum manganite may be one or more of Sr, Ca, Mg, and Ba. The cathode electrolyte compound may be doped zirconia such as ZrQ^YQ.QsO^ or doped ruthenium dioxide such as Ceo.8Gdo.20L9 or the like.
以下以具体实施例说明本发明的效果，但本发明的保护范围不受以下实施 例的限制。  The effects of the present invention are described below by way of specific examples, but the scope of the present invention is not limited by the following examples.
实施例 1  Example 1
采用流延的方法制备厚度约为 50 μ ιη的含 10mol%Sc2O3和 lmol%Ce02 的 Zr02带材（以下称为 lOSclCeSZ ); 采用流延的方法制备厚度约为 50 μ ιη 的含 3mol%Y203的 Zr02带材（以下称为 3YSZ )。 The method of preparing a casting thickness of about 50 μ ιη containing 10mol% Sc 2 O 3 and the strip lmol Zr0 2% Ce0 2 (hereinafter, referred to lOSclCeSZ); a casting method having a thickness of about 50 μ ιη of A Zr0 2 strip containing 3 mol% of Y 2 0 3 (hereinafter referred to as 3YSZ).
如图 1所示， 分别取 3个 lOSclCeSZ带材 101和 2个 3YSZ带材 102交 替叠合在一起， 施加 8MP的压力进行预压成型得到预压件； 将所述预压件装 入真空袋抽真空， 然后在 50MPa的压力下等静压成型得到成型件； 将所述成 型件在空气气氛下、 1450°C条件下烧结 4小时得到厚度约为 210 μ ιη的电解质 隔膜。 As shown in FIG. 1 , three lOSclCeSZ strips 101 and two 3YSZ strips 102 are alternately stacked together, and a pressure of 8 MP is applied for pre-molding to obtain a pre-pressed piece; the pre-pressed part is placed in a vacuum bag. Vacuuming, and then isostatically pressing to obtain a molded article under a pressure of 50 MPa; sintering the molded article under an air atmosphere at 1450 ° C for 4 hours to obtain an electrolyte having a thickness of about 210 μm Diaphragm.
室温下测量电解质隔膜弯曲强度为 478MPa, 800°C测量的电解质隔膜的 导电率为 0.061S/cm。  The electrolyte diaphragm was measured to have a flexural strength of 478 MPa at room temperature, and the conductivity of the electrolyte membrane measured at 800 ° C was 0.061 S/cm.
实施例 2  Example 2
采用流延的方法制备厚度约为 40 μ ιη的含 10mol%Sc2O3和 lmol%Ce02 的 Zr02带材（以下称为 lOSclCeSZ ); 采用流延的方法制备厚度约为 20 μ ιη 的含 5mol%Y203的 Zr02带材（以下称为 5YSZ )。 The method of preparing a casting thickness of about 40 μ ιη containing 10mol% Sc 2 O 3 and the strip lmol Zr0 2% Ce0 2 (hereinafter, referred to lOSclCeSZ); a casting method having a thickness of about 20 μ ιη of A Zr0 2 strip containing 5 mol% of Y 2 0 3 (hereinafter referred to as 5YSZ).
分别取 5个 lOSclCeSZ带材和 4个 5YSZ带材交替叠合在一起，施加 15MP 的压力进行预压成型得到预压件； 将所述预压件装入真空袋抽真空， 然后在 150MPa的压力下等静压成型得到成型件； 将所述成型件在空气气氛下、 1450 °C条件下烧结 5小时得到厚度约为 240 μ ιη的电解质隔膜。  Five lOSclCeSZ strips and four 5YSZ strips were alternately stacked together, and a pre-pressing piece was obtained by pre-compression molding with a pressure of 15 MP; the pre-pressed part was placed in a vacuum bag to be evacuated, and then at a pressure of 150 MPa. The molded article was obtained by isostatic pressing to obtain a molded article; the molded article was sintered under an air atmosphere at 1,450 ° C for 5 hours to obtain an electrolyte separator having a thickness of about 240 μm.
室温下测量电解质隔膜弯曲强度为 456MPa, 800°C测量的电解质隔膜的 导电率为 0.069S/cm。  The flexural strength of the electrolyte membrane was measured at room temperature to be 456 MPa, and the conductivity of the electrolyte membrane measured at 800 ° C was 0.069 S/cm.
实施例 3  Example 3
采用流延的方法制备厚度约为 40 μ ιη的含 10mol%Sc2O3和 lmol%Ce02 的 Zr02带材（以下称为 lOSclCeSZ ); 采用流延的方法制备厚度约为 ΙΟ μ ιη 的含 6mol%Y203的 Zr02带材（以下称为 6YSZ )。 The method of preparing a casting thickness of about 40 μ ιη containing 10mol% Sc 2 O 3 and the strip lmol Zr0 2% Ce0 2 (hereinafter, referred to lOSclCeSZ); a casting method having a thickness of about ΙΟ μ ιη of A Zr0 2 strip containing 6 mol% of Y 2 0 3 (hereinafter referred to as 6YSZ).
分别取 6个 lOSclCeSZ带材和 5个 6YSZ带材交替叠合在一起，施加 15MP 的压力进行预压成型得到预压件； 将所述预压件装入真空袋抽真空， 然后在 50MPa 的压力下等静压成型得到成型件； 将所述成型件在空气气氛下、 1480 °C条件下烧结 5小时得到厚度约为 250 μ ιη的电解质隔膜。  Six lOSclCeSZ strips and five 6YSZ strips were alternately stacked together, and a pre-pressing piece was obtained by pre-compression molding with a pressure of 15 MP; the pre-pressed part was placed in a vacuum bag to be evacuated, and then subjected to a pressure of 50 MPa. The molded article was obtained by isostatic pressing to obtain a molded article; the molded article was sintered under an air atmosphere at 1480 ° C for 5 hours to obtain an electrolyte separator having a thickness of about 250 μm.
室温下测量电解质隔膜弯曲强度为 433MPa, 800°C测量的电解质隔膜的 导电率为 0.074S/cm。  The electrolyte diaphragm was measured to have a flexural strength of 433 MPa at room temperature, and the conductivity of the electrolyte membrane measured at 800 ° C was 0.074 S/cm.
实施例 4  Example 4
采用流延的方法制备厚度为 15 μ ιη 的含 9mol%Sc203和 2mol%Ce02的The method of preparing a casting thickness of 15 μ ιη containing 9mol% Sc 2 0 3 and of 2mol% Ce0 2
Zr02带材（以下称为 9Sc2CeSZ ); 采用流延的方法制备厚度为 15 μ ιη 的含 10mol%Gd2O3的 Ce02带材（以下称为 CGO10 )。 Zr0 2 tape (hereinafter referred 9Sc2CeSZ); a casting method having a thickness of 15 μ ιη containing 10mol% Gd 2 O 3 of the strip Ce0 2 (hereinafter referred to CGO10).
分别取 1个 9Sc2CeSZ带材和 1个 CGO10带材交替叠合在一起，施加 20MP 的压力进行预压成型得到预压件； 将所述预压件装入真空袋抽真空， 然后在 lOOMPa的压力下等静压成型得到成型件； 将所述成型件在空气气氛下、 1450 °C条件下烧结 5小时得到厚度约为 25 μ ιη的电解质隔膜。 One 9Sc2CeSZ strip and one CGO10 strip are alternately stacked together, and a pre-pressing piece is obtained by pre-compression molding by applying a pressure of 20MP; the pre-pressing piece is placed in a vacuum bag to be vacuumed, and then The molded article was obtained by isostatic pressing under a pressure of 100 MPa; the molded article was sintered under an air atmosphere at 1450 ° C for 5 hours to obtain an electrolyte separator having a thickness of about 25 μm.
室温下测量电解质隔膜弯曲强度为 327MPa, 800°C测量的电解质隔膜的 导电率为 0.011S/cm。  The flexural strength of the electrolyte membrane was measured at room temperature to be 327 MPa, and the conductivity of the electrolyte membrane measured at 800 ° C was 0.011 S/cm.
如图 2所示， 以本例制备的电解质隔膜 11制备固体氧化物燃料电池， 其 中， 使用厚度为 300 μ m的 Ni-2YSZ作为阳极支撑层 201 , 使用厚度为 20 μ m 的 M-8YSZ作为阳极功能层 202,使用厚度为 10(^ 111的由1^。.(^。.40)。.^6。.803 和 Gd^CeiuO 按照 1 : 1的摩尔比混合烧结体作为阴极 12组装成固体氧化物 燃料电池。 As shown in Fig. 2, a solid oxide fuel cell was prepared by using the electrolyte membrane 11 prepared in this example, in which Ni-2YSZ having a thickness of 300 μm was used as the anode supporting layer 201, and M-8YSZ having a thickness of 20 μm was used as The anode functional layer 202 is made of a sintered body of a thickness of 10 (^111 by 1^.. ( ^.40)..6.. 8 0 3 and Gd^CeiuO in a molar ratio of 1:1 as a cathode 12 Assembled into a solid oxide fuel cell.
实施例 5  Example 5
采用流延的方法制备厚度为 40 μ ιη的含 12mol%Sc203和 lmo%Ce02的 Zr02带材（以下称为 12SclCeSZ ); 采用流延的方法制备厚度为 ΙΟ μ ιη的含 4mol%Y203的 Zr02带材（以下称为 4YSZ )。 The method of preparing a casting thickness of 40 μ ιη containing 12mol% Sc 2 0 3 and the strip lmo Zr0 2% Ce0 2 (hereinafter, referred to 12SclCeSZ); a casting method having a thickness of ΙΟ μ ιη containing 4mol Zr0 2 strip of %Y 2 0 3 (hereinafter referred to as 4YSZ).
分别取 5个 12SclCeSZ带材和 4个 4YSZ带材交替叠合在一起，施加 15MP 的压力进行预压成型得到预压件； 将所述预压件装入真空袋抽真空， 然后在 50MPa 的压力下等静压成型得到成型件； 将所述成型件在空气气氛下、 1480 °C条件下烧结 5小时得到厚度约为 200 μ ιη的电解质隔膜。  Five 12SclCeSZ strips and four 4YSZ strips were alternately stacked together, and a pre-pressing piece was obtained by pre-compression molding with a pressure of 15MP; the pre-pressed part was placed in a vacuum bag to be evacuated, and then subjected to a pressure of 50 MPa. The molded article was obtained by isostatic pressing to obtain a molded article; the molded article was sintered under an air atmosphere at 1480 ° C for 5 hours to obtain an electrolyte separator having a thickness of about 200 μm.
室温下测量电解质隔膜弯曲强度为 473MPa, 800°C测量的电解质隔膜的 导电率为 0.067S/cm。  The flexural strength of the electrolyte membrane was measured at room temperature to be 473 MPa, and the conductivity of the electrolyte membrane measured at 800 ° C was 0.067 S/cm.
实施例 6  Example 6
采用流延的方法制备厚度约为 40 μ ιη 的 Ce^GdojOw带材（以下称为 CGO10 );采用流延的方法制备厚度为 10 μ m的含 3mol%Y203的 Zr02带材（以 下称为 3YSZ )。 A Ce^GdojOw strip (hereinafter referred to as CGO10) having a thickness of about 40 μm was prepared by a casting method; a Zr0 2 strip containing 3 mol% of Y 2 0 3 having a thickness of 10 μm was prepared by casting ( Hereinafter referred to as 3YSZ).
分别取 5个 CGO10带材和 4个 3YSZ带材交替叠合在一起， 施加 20MP 的压力进行预压成型得到预压件； 将所述预压件装入真空袋抽真空， 然后在 150MPa的压力下等静压成型得到成型件； 将所述成型件在空气气氛下、 1410 °C条件下烧结 5小时得到厚度约为 200 μ ιη的电解质隔膜。  Five CGO10 strips and four 3YSZ strips were alternately stacked together, and a preloading member was obtained by applying a pressure of 20 MP to obtain a pre-pressing piece; the pre-pressing piece was placed in a vacuum bag to be evacuated, and then at a pressure of 150 MPa. The molded article was obtained by isostatic pressing to obtain a molded article; the molded article was sintered under an air atmosphere at 1410 ° C for 5 hours to obtain an electrolyte separator having a thickness of about 200 μm.
室温下测量电解质隔膜弯曲强度为 437MPa, 800°C测量的电解质隔膜的 导电率为 0.073S/cm。 实施例 7 The electrolyte membrane was measured to have a flexural strength of 437 MPa at room temperature, and the conductivity of the electrolyte membrane measured at 800 ° C was 0.073 S/cm. Example 7
采用流延的方法制备厚度约为 100 μ m的含 10mol%Sc2O3的 Zr02带材（以 下称为 lOScSZ ); 采用流延的方法制备厚度为 90 μ m的含 3mol%Y203的 Zr02 带材（以下称为 3YSZ )。 A Zr0 2 strip containing 10 mol% of Sc 2 O 3 (hereinafter referred to as lOScSZ) having a thickness of about 100 μm was prepared by a casting method; a 3 mol% Y 2 0 having a thickness of 90 μm was prepared by a casting method. 3 Zr0 2 strip (hereinafter referred to as 3YSZ).
分别取 2个 lOScSZ带材和 1个 3YSZ带材交替叠合在一起， 施加 20MP 的压力进行预压成型得到预压件； 将所述预压件装入真空袋抽真空， 然后在 150MPa的压力下等静压成型得到成型件； 将所述成型件在空气气氛下、 1450 °C条件下烧结 5小时得到厚度约为 250 μ ιη的电解质隔膜。  Two lOScSZ strips and one 3YSZ strip were alternately stacked together, and a pre-pressing piece was obtained by pre-compression molding by applying a pressure of 20MP; the pre-pressed part was placed in a vacuum bag to be evacuated, and then at a pressure of 150 MPa. The molded article was obtained by isostatic pressing to obtain a molded article; the molded article was sintered under an air atmosphere at 1,450 ° C for 5 hours to obtain an electrolyte separator having a thickness of about 250 μm.
本实施例制备的电解质隔膜的 SEM微观结构如图 3所示。  The SEM microstructure of the electrolyte membrane prepared in this example is shown in Fig. 3.
比较例 1  Comparative example 1
采用流延的方法制备厚度为 80 μ ιη的含 10mol%SC2O3和 lmol%Ce02的 Zr02带材（以下称为 10SclCeSZ )。 The method of preparing a casting thickness of 80 μ ιη containing 10mol% SC 2 O 3 and the strip lmol Zr0 2% Ce0 2 (hereinafter, referred to as 10SclCeSZ).
取 3个 lOSclCeSZ带材叠合在一起， 施加 15MP的压力进行预压成型得 到预压件； 将所述预压件装入真空袋抽真空， 然后在 lOOMPa的压力下等静压 成型得到成型件； 将所述成型件在空气气氛下、 1430°C条件下烧结 5小时得到 厚度约为 200 μ ιη的电解质隔膜。  Three lOSclCeSZ strips were stacked together, and a pre-pressing piece was obtained by pre-compression molding with a pressure of 15 MP; the pre-pressed part was placed in a vacuum bag to be vacuumed, and then isostatically pressed under a pressure of 100 MPa to obtain a molded part. The molded article was sintered under an air atmosphere at 1430 ° C for 5 hours to obtain an electrolyte separator having a thickness of about 200 μm.
室温下测量电解质隔膜弯曲强度为 282MPa, 800°C测量的电解质隔膜的 导电率为 0.12S/cm。  The electrolyte diaphragm was measured to have a flexural strength of 282 MPa at room temperature, and the conductivity of the electrolyte membrane measured at 800 ° C was 0.12 S/cm.
比较例 2  Comparative example 2
采用流延的方法制备厚度约为 60 μ m的含 4mol%Y203的 Zr02带材（以下 称为 4YSZ )。 A Zr0 2 strip (hereinafter referred to as 4YSZ) containing 4 mol% of Y 2 0 3 having a thickness of about 60 μm was prepared by a casting method.
取 2个 4YSZ带材叠合在一起，施加 10MP的压力进行预压成型得到预压 件； 将所述预压件装入真空袋抽真空， 然后在 200MPa的压力下等静压成型得 到成型件； 将所述成型件在空气气氛下、 1400°C条件下烧结 8小时得到厚度约 为 ΙΟΟ μ ιη的电解质隔膜。  Two 4YSZ strips are stacked together, and a pre-pressing piece is obtained by pre-compression molding by applying a pressure of 10MP; the pre-pressing part is placed in a vacuum bag to be vacuumed, and then isostatically pressed under a pressure of 200 MPa to obtain a molded part. The molded article was sintered under an air atmosphere at 1400 ° C for 8 hours to obtain an electrolyte membrane having a thickness of about ΙΟΟ μηη.
室温下测量电解质隔膜弯曲强度为 974MPa, 800°C测量的电解质隔膜的 导电率为 0.02S/cm。  The electrolyte diaphragm was measured to have a bending strength of 974 MPa at room temperature, and the conductivity of the electrolyte membrane measured at 800 ° C was 0.02 S/cm.
以上对本发明所提供的电解质隔膜、电化学装置以及固体氧化物燃料电池 述， 以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指 出， 对于本技术领域的普通技术人员来说， 在不脱离本发明原理的前提下， 还 可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的 保护范围内。 Electrolyte separator, electrochemical device and solid oxide fuel cell provided by the present invention The description of the above embodiments is merely for assisting in understanding the method of the present invention and its core idea. It should be noted that those skilled in the art can make various modifications and changes to the present invention without departing from the spirit and scope of the invention.

Claims

权 利 要 求 Rights request
1、 一种电解质隔膜， 其特征在于， 包括至少一个强度增强电解质隔膜层 和一个高离子电导电解质隔膜层，所述强度增强电解质隔膜层的弯曲强度高于 300MPa, 所述高离子电导电解质隔膜层 800°C的离子电导率高于 0.03S/cm。 What is claimed is: 1. An electrolyte membrane comprising: at least one strength-enhancing electrolyte membrane layer and a high-ion conductivity electrolyte membrane layer, said strength-enhancing electrolyte membrane layer having a bending strength higher than 300 MPa, said high-ion conductivity electrolyte membrane layer The ionic conductivity at 800 ° C is higher than 0.03 S / cm.
2、 根据权利要求 1所述的电解质隔膜， 其特征在于， 所述强度增强电解 质隔膜层和高离子电导电解质隔膜层交替排列。  The electrolyte membrane according to claim 1, wherein the strength-enhancing electrolyte membrane layer and the high-ion conductivity electrolyte membrane layer are alternately arranged.
3、 根据权利要求 2所述的电解质隔膜， 其特征在于， 所述强度增强电解 质隔膜层是掺杂了 2〜6%mol选自 Y203、 CaO或 Sc203中的一种或多种的 Zr02。 The electrolyte membrane according to claim 2, wherein the strength-enhancing electrolyte membrane layer is doped with 2 to 6% of one selected from the group consisting of Y 2 O 3 , CaO or Sc 2 0 3 or A variety of Zr0 2 .
4、 根据权利要求 3所述的电解质隔膜， 其特征在于， 所述高离子电导电 解质隔膜层是掺杂了选自 Y203、 Sc203、 Ce02、 Yb203、 Nd203、 Na20中的一 种或多种的 Zr02或或是掺杂了 La203和 /或 Gd203的 Ce02;所述高离子电导电 解质隔膜层中的稀土氧化物的掺杂量为 7-21%mol。 The electrolyte membrane according to claim 3, wherein the high ion conductivity electrolyte membrane layer is doped with Y 2 0 3 , Sc 2 0 3 , Ce0 2 , Yb 2 0 3 , Nd 2 03 a method of Na 2 0 or more doped or Zr0 2 or La 2 0 3 and Ce0 2 / or Gd 2 0 3; and the high ion conductivity of the electrolyte separator layer of rare earth oxides The doping amount is 7-21% by mol.
5、 根据权利要求 4所述的电解质隔膜， 其特征在于， 所述高离子电导电 解质隔膜层中的稀土氧化物的掺杂量为 7.5〜11.5%mol。  The electrolyte membrane according to claim 4, wherein a doping amount of the rare earth oxide in the high-ionic electroconductive solution membrane layer is 7.5 to 11.5% by mol.
6、 根据权利要求 1至 5任一项所述的电解质隔膜， 其特征在于， 所述强 度增强电解质隔膜层和所述高离子电导电解质隔膜层的厚度比为 1 : 1〜1 :4。  The electrolyte membrane according to any one of claims 1 to 5, wherein a thickness ratio of the strength-enhancing electrolyte membrane layer to the high-ion conductivity electrolyte membrane layer is 1:1 to 1:4.
7、 根据权利要求 1至 5任一项所述的电解质隔膜， 其特征在于， 所述电 解质隔膜的厚度为 5 μ m〜500 μ m。  The electrolyte membrane according to any one of claims 1 to 5, wherein the electrolyte membrane has a thickness of 5 μm to 500 μm.
8、 一种电化学装置， 其特征在于， 包括权利要求 1至 7任一项所述的电 解质隔膜。  An electrochemical device comprising the electrolyte membrane according to any one of claims 1 to 7.
9、 一种固体氧化物燃料电池， 所述固体氧化物燃料电池包括：  9. A solid oxide fuel cell, the solid oxide fuel cell comprising:
阳极；  Anode
与所述阳极相对的阴极；  a cathode opposite the anode;
在所述阳极和阴极之间设置有权利要求 1至 7任一项所述的电解质隔膜。 An electrolyte membrane according to any one of claims 1 to 7 is provided between the anode and the cathode.
10、 根据权利要求 9所述的电化学装置， 其特征在于， 所述固体氧化物燃 料电池为阳极支撑型固体氧化物燃料电池或电解质支撑型固体氧化物燃料电 池。 The electrochemical device according to claim 9, wherein the solid oxide fuel cell is an anode supported solid oxide fuel cell or an electrolyte supported solid oxide fuel cell.
11、 根据权利要求 8所述的电化学装置， 其特征在于， 所述电化学装置为 氧传感器。  The electrochemical device according to claim 8, wherein the electrochemical device is an oxygen sensor.
-μ -μ
PCT/CN2010/078493 2010-11-08 2010-11-08 Electrolyte membrane, electrochemical device and solid oxide fuel cell WO2012061965A1 (en)

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