TW201123589A - Solid oxide fuel cell and membrane electrode assembly used therein - Google Patents

Abstract

A membrane electrode assembly including a cathode, an anode and a dense electrolyte layer is provided. The material of the anode is cermet composite porous layer consisted of a metal and a ceramics. The metal includes nickel or Ni1-tCot, wherein 3% < t < 60%. The ceramics includes Ce1-wLn''wO2, Ln'' is selected from a group consisting of La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and combination thereof, wherein 3% < w < 40%. The material of the cathode is a material porous layer containing strontium or a material layer not containing strontium. The porous material layer containing strontium is selected from a group consisting of (La1-xSrx)(CoyFe1-y)O3, (Ba1-xSrx)(CoyFe1-y)O3, (Sm1-xSrx)CoO3, (Pr1-xSrx)CoO3, (Nd1-xSrx)CoO3, (Gd1-xSrx)CoO3, (Dy1-xSrx)CoO3, (La1-xSrx)MnO3 and combination thereof, wherein 3% < x < 60% and 0% ≤ y ≤ 100%. The material porous layer not containing strontium includes (Ln1-zKz)(CouFe1-u)O3, Ln(MouNi1-u)O3 or Ln(MouCo1-u)O3, wherein Ln is selected from a group consisting of La, Ce, Pr, Nd, Sm, Gd and combination thereof, 3% < z < 50% and 0% ≤ u ≤ 100%. The dense electrolyte layer, located between the cathode and the anode, is one of the solid solutions based on La2Mo2O9.

Description

201123589 0980096TW 33049twf.doc/n VI. Description of the Invention: [Technical Field] The present invention relates to a battery and is particularly related to a solid oxide fuel cell and a thin film electrode assembly for the same. [Prior Art] A solid oxide fuel cell (SQFC) is an energy source that uses hydrogen or a hydrogen-containing fuel to generate electric energy. Whether it is used in transportation or in rural areas, it has potential for development. The first-cina prototype (P-type) is a stable yttrium oxide (yttria s砸ized zirc〇 = as an electrolyte for conducting oxygen ions (〇2), which has a sufficiently high ion under C. Conductivity (4) Its ohmic impedance falls within an acceptable range, and it has sufficient commercial potential in the case of the 9-cell efficiencies. However, because of the higher temperature, it can be matched in the YSZ fuel cell. The selection of materials, especially the conductive metal connecting piece is expensive. The mainstream of the exhibition. Feng Zuo 4 has become a recent S0FC technology [invention] The present invention provides a thin film lightning fuel cell, which can be lower Temperature; operation; ^ can make the oxides provided by the present invention - a thin film electrode group, 201123589 0980096TW 33049twf.doc / n a wide range, and can greatly reduce the cost.

The present invention provides a solid state oxide fuel cell that can be operated at a degree. ', 'T4/JEL The present invention provides a solid oxide fuel cell. It can be used at a low cost. The Membrane Electrode Assembly (MEA) system includes an anode, a cathode and a cleavage layer. The material of the anode and the metallurgical layer constitute a boring layer of the lyon composite, and the metal includes = "CGt" wherein 3% &lt; t &lt; 6G% 'the Tao Jing including Ln" is selected from La, A group consisting of a combination of Pr, Nd, Pm, Sm, Eu, GdTb, HEr, Tm, Yb, Lu, and the like, and containing (4) materials ΪΓ 4 (%). The material of the cathode is a porous layer containing (four) material or a porous layer of material. The material of the porous layer containing the wrong material is selected from &1.χ8Γχ)(〇〇νρ6,ν)〇3. (Β&amp;1.χ8γχ)(〇ο,Ρο,υ)〇3, γΤΙ 〇3 ' (Pri-Sl^Co〇3 ' (Nd1.xSrx)Co〇3 , (^-xSr )C〇〇3 . (Dyi.xSrx)c〇〇3 . (Lai_xSrx)Mn〇3 a group, where .3% &lt;x&lt;6〇%,0./. 100%. The material of the porous layer of the material is selected from n, z)(C〇uFei u)〇3 ^ Ln (M〇uNi] u)〇3 . Ln(M〇uC〇Uu)〇 ,

Ln is selected from the mountain τ: a combination of La, Ce'Pr'Nd, Sm, Gd, and the like, and ginseng, wherein 3% &lt;z&lt;50%, 〇%^^1%. The dense electric contact is located between the cathode and the anode, and the dense electrolyte material comprises a solid solution of L2l^〇9, wherein L represents 80-100 mo 3 乂 and 0-20 mol% Selected from pr, Nd, Pm, Sm 201123589 uysuuyonV 33049twf.d〇c/n

a scale composed of a combination of Eu, Gd, Tb, Dy, H〇, 玢, K, Q, and, for example, a combination of M, (4), material (4), M, and the like, selected from v, w, Cr, and 0-50 At the same time, Ο indicates oxygen. The group consisting of and σ; according to an embodiment of the invention, the molar ratio of ± is 4: 6 to 7: 3. As described in the embodiment of the above-mentioned hybrid occupant, when the material of the cathode is a porous layer containing a faulty material, it further includes a diffusion barrier layer of the cathode and the upper barrier layer. The alkory includes (Ce)-running ice, Α中3〇/&lt;h&lt;, _ early layer material element or iron ride. t-transformation-like core steroid rare earth according to the embodiment of the invention, the above-mentioned thin film electrode The group further comprises an anode and a catalyst layer, such that the anode is interposed between the above-mentioned anode activation touches, and the above-mentioned anode active material layer is composed of a cerium oxide powder of a t-doped element. A solid oxide fuel cell comprising a single gas chamber, at least one membrane electrode assembly, and a mixed gas. The single gas chamber has an inlet and an outlet. The membrane electrode assembly is composed of a mixed metal powder. The fourth membrane electrode assembly comprises an anode, a cathode and a dense electrolyte layer. The material of the anode is a porous layer of ceramic gold and metal. The material of the cathode is It is a porous layer containing the wrong material or a porous layer of the material not recorded. The material of the porous layer containing the ruthenium material is selected from (La1.xSrx)(CoyFe1.y)〇3, (Ba,.xSrx)(CoyFe].y)03, (Sn^SrJCoCb, (pri_xSl.x) Cc)〇3,(NdixSi,x)c〇〇3, 201123589 0980096TW 33049twf.d〇c/n (Gd丨-xSrx)Co〇3, (Dyi xSl'x)c〇〇3, privately) a group consisting of 3 and the combination thereof, wherein 3% &lt;x&lt;60%, 〇%¥i〇〇%. The material f of the porous layer containing no material includes (Lni zKz) (CGuFei ^,

Ln(M〇uNil-u)〇3 or Ln(MouC〇I_u)03, wherein t Ln is selected from: ^, . a group consisting of a combination of Sm, Gd, and the like, wherein 3% &lt;z&lt;5〇%, 〇%^嶋. The dense electrolyte layer is located between the cathode and the anode, and the material of the dense electrolyte comprises a solid solution of L2M2〇9, wherein L represents 80-100 mol% of La and 0-20 mol% of lK* a group consisting of I>r, Nd, Pm, Sm, EU, Gd, Tb, Dy, =Er, K, Ca, Ba, Bi, Y, and the like; and 50-100% of M 〇 and (4) Mohr% are selected from the group consisting of:, W, Cr, and the like; and 〇 represents oxygen. The mixed gas includes a fuel and an oxidant which are incorporated into the single gas chamber described above. According to an embodiment of the present invention, the ratio of the above ceramics to the above metal mixing is 4:6-7:3. As described in the above, when the material of the cathode is the above-mentioned porous layer, the diffusion layer further includes a diffusion barrier layer (the diffusion barrier layer between the cathode and the dense electrode) The material includes iron ΐ?) 02, wherein 3% plus 40%, Ln, represents a rare earth element of the lanthanum or includes the above-mentioned solid oxide fuel cell to further activate the catalyst layer to make the anode Between the above-mentioned anode more catalyst layer and the upper rhombic electrolyte layer, the above-mentioned anode activation catalyst layer ^ 7 201123589 0980096TW 33049nvfdoc / n surface earth phase phase oxygen dumping_metal_powder mixing, the purity includes... Included is that the amount of air is less than 5% of the fuel cell anode and the cathode described above is in accordance with the embodiment of the invention, and the burner is % or more than 15% by mole. 3 and 2 = the above-mentioned _ oxides have been included in the collection, which is difficult to distinguish the periphery. Based on the above-described 'electrode group of the embodiment of the present invention, the sorrow oxide battery can be operated at a lower temperature. Scope of the film electrode group of the embodiment of the month, the selection of the material can be larger, and the cost can be greatly reduced. This is the operation of the _ 氡 _ _ _ _ _ _ _ _ _ _ _ _ The solid telluride fuel cell of the embodiment of the present invention can greatly reduce the cost. The above described features and advantages of the present invention will be more apparent from the following description. [Embodiment] FIG. 1A is a film electrode assembly according to an embodiment of the invention. Fig. 1B is another thin film electrode assembly which is shown in accordance with another embodiment of the present invention. '201123589 0980096TW 33049twf.d〇c/nb according to FIG. 1A 朗 iB, the film sets (Membmne Electrode Assembly, 〇Α) 1〇Α and 10B proposed in the embodiments of the present invention respectively include an anode 2G and a dense electrolyte layer 3G. And the cathode fairy. The dense electrolyte layer 3 is located between the cathode 4G and the anode 2G. = material f of dense electrolyte layer 30 includes in the middle of L2M2〇9 = 〇 〇 〇 耳 心 〇 〇 〇 = = = = = = = p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p , Mo;; a group of two gamma and combinations thereof; M represents M of 50_100 f ears/°. And (4) Moer% is selected from the group consisting of V, w, Cr and the enemy; and 0 generation _: ==3. 2高温9 of the high temperature phase ",: You P seems to be in the example, in the La position in La2M〇2〇9

nNd, Pln, Sm, Gd, Tb, Dy, Ho, Er]T are substituted. —, and Moer. /. , 兮3, &gt; /, etc. to replace 〇-5〇 cooling heat:: generation = main high temperature phase to reduce the rise of the junction ^ and 7 __ shape county over the porous anode 1 〇 ^ _ Reduce the ohmic core in the battery, the thickness range of which is between 1 and 3:9 is the ytterbium ion conductor. Although it has a high conductivity, it also has a unique problem in the evening, so ask...匕It is also a very polar component, at moderate temperature _, yin reduction 'and its heat _ is higher than; second = 201123589 u? 〇 ^? 〇i> V 33〇49twf.doc/n material and about 5-l〇 ppmK·], so the fuel cell with L2M2〇9 for electrolysis f needs to be designed to turn its battery function. In the present invention, the material of the anode 20 is a ceramic gold or composite porous layer formed of ceramics and metals. The molar ratio of ceramics to metal is 4:6 - 7.3. The porcelain is an oxygen ion conductor which includes doped cerium oxide (Cei_wLn''w〇2), wherein Ln, is selected from La, Pr, Nd, pm,

The group m%^^4〇% of the group of Sm Eu Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and the like. In the material of the anode, the price of Gd dGped Ce〇 2 (GDC) is the cheapest. The gold ^ includes Ni or Nil tC〇t, and the towel is 3% &lt; t &lt; 6 %. In an embodiment, when the anode junction frequency is prepared, because it is sintered in the air T, it is usually firstly mixed with nickel oxide 5 or 'nickel oxide and A Huaming, and then the oxygen is poured into the Jinlin before the battery= Riding an alloy. In the first operation, if the effect of nickel oxide reduction to metallic nickel is to use the fuel itself, then the anode activation catalyst layer 15 is placed or coated on the outer layer of the anode so that the anode β pole 20 is interposed between the anode activation contacts. Between the dielectric layer 15 and the dense electrolyte layer%. The anodic activation catalyst layer 15 is composed of an oxidized powder of doped rare earth elements and mixed with a nickel-nickel metal catalyst powder. When the fuel gas flows through the masculine first, 20 surface, the fuel gas (steamed) It is reduced by nickel metal catalyst to carbon monoxide and hydrogen, which in turn reduces the nickel oxide in the anode to metal and converts the anode into pottery. If the side of the anodic activation of the catalyst layer 25 is not employed, the formula must be such that the oxidation of the anode 20 is recorded as a hydrogen gas before the first operation, and the anode can be operated normally after it becomes a pottery. 201123589 0980096TW 33049t\vf.doc/n -, 1 bamboo porous layer or layer. The thickness of the cathode 40 layer is, for example, a material of 3 钇 枓 孔 孔 多孔 系 选自 选自 选自 选自 选自 选自 L L L L L L L L L L L L L L L L L L L L L L L L L L L L L L L L L L L L L L L L L 〇Γχ)(0°^^^〇3 ' /'丁..., wide a, x lx)Co°3 ' (Ργ,.χ8γχ)€ο〇3 ' (Nd1.xSrx)Co03 &gt; (Gdl.xSxx ) c〇〇2 , (D 〇ΜΓ 〇 〇 (LakSrJMnO; and its group Υ Χ Χ Χ x) 3, and the ethnic group formed by the mouth,

ΓΠΓΓΤΤν The material of the porous layer of the material without pin Ϊ = e "U) 〇 3, Ln (M〇uNil-u) 〇 3 or

Ln(M〇uC〇1-u)03 'Ln & from the group consisting of La, Ce, pr, Nd, Sm, (9) and the like, of which 3% &lt;z&lt;5〇%, 0% this 100%. When the material of the cathode 40 is a porous layer containing a wrong material, a diffusion barrier layer 45' is further included between the cathode 40 and the dense electrolyte layer 3G to prevent the high temperature process of the sintered body from causing a cathode cathode and a dense electrolyte. The diffusion reaction of layer 30, in turn, avoids ion interdiffusion and destroys the crystal structure. The composition of the diffusion barrier layer 45 is (Cei bLn, b) 〇 2, and 3% at &lt; 40% 'Ln' represents a lanthanum rare earth element or an iron element. The thickness of the diffusion barrier layer 45 is, for example, less than 1 μm. The porous layer of the germanium-free material does not have the concern of diffusion reaction, so that the diffusion barrier layer 45 is not required to separate the cathode 40 and the sensitive electrolyte layer 30. Therefore, such a porous cathode can be used without a barrier. Under the layer separation, directly over the electrolyte. The thin film electrode assembly 10 can be a self-supported membrane electrode set (self-supported ΜΕΑ) or an external support type of external-supported MEA. The self-support type may be, for example, a cathode-supported MEA of a cathode branch, an anode-supported MEA of an anode branch, or an anode-supported MEA of an anode branch or a thin electrode of an electrolyte branch. (e丨ectrolyte-supported MEA). The thin film electrode group of the external support type may be, for example, an interconnect-supported MEA or a porous substrate-supported MEA. Here, the control of the contained stomach means that it can provide the mechanical strength of the entire membrane electrode assembly, which is usually achieved by thickness. Further, the arrangement of the cathode 4 〇 and the anode 2 中 in the membrane electrode assembly iOA can be determined according to actual needs. In one embodiment, the cathode can be located on one side of the dense electrolyte layer 30 and the anode 2 can be located on the other side of the dense, qualitative layer 30. That is, the cathode 4 〇, the anode 2 〇 and the dense layer 30 are stacked, as shown in FIG. In another embodiment, the pattern of the cathode 40 and the anode 2G in the membrane electrode group _ is not pointed. Referring to Fig. 1B, the cathode cathode 40 and the anode Cm and cathode 4G patterns are located on the side of the dense electrolysis (4) door, and are respectively formed into fingers and intersect each other. It is also quite easy to refer to 40, anode 20 if connected to external circuit load. However, the configuration of the cathode-sensitive electrolyte layer 3G is not limited to the above. The thin-film T-electrode-designed thin-film electrode is the electrolyte support. The structure of the thin-film electrode group _ the structure of the ceramic 2, ii::, the electrolyte layer 3 〇 (plate) to support By way of example, the anode 20 and the cathode 40 are porous thin layers (diffusion resistance 12 201123589 0980096TW 33049t\vf.doc/n barrier layer 45 is also a porous thin layer) because of the thermal expansion of the l2M2〇9 dense electrolyte layer 30. The coefficient is higher than the anode 2〇 and the cathode 4〇 and the diffusion barrier layer 45, so the porosity of these thin layers 2〇, 4〇, 45 will be higher to reduce the effect of thermal stress, wherein the diffusion barrier layer The porosity of 45 must be appropriate in order to block the diffusion and not cause the thermal stress to be too high. An anode activation catalyst layer 15 is disposed on the anode 20 to facilitate the deamination of the original nickel oxide during the first time. The thickness of the anode 2 layer is 1〇_5〇. • For the forked cathode 4, if a tantalum-containing composition is used, there will be a two-layer structure, the lower layer is a diffusion barrier layer 45 having a thickness of less than 1 μm, and the upper layer is a tantalum-containing cathode 4〇 having a thickness of 10-50 μm. Without the ruthenium composition, there is only one layer of cathode with a thickness of 10-50 μπι. The plane distance between the anode 20 and the cathode 40 is 2.5-100 μm. In principle, the short distance will help to improve the battery efficiency, but the anode. If the distance between the 2 〇 and the cathode 'is too small, the difficulty in production will be increased. If the process capability is 5 pm, the plane distance between the anode 2 〇 and the cathode 4 缩小 can be reduced. The above-mentioned film electrode ·1〇Α or 10 Β can be exemplified by the following examples by any known method, however, it is not intended to limit the present invention. The GDC and NiO powder green bodies are sintered in a conventional ceramic powder process to form a porous structure as the anode 2G, and the thickness thereof is M _ . Thereafter, the L2M2〇9 loose electrolyte was coated by screen printing, spin coating or colloidal sedimentation, and its thickness was 2Q_6G (four). Thereafter, the screen thickness or thickness is less than 45 by screen printing or red box printing. Next, the thickness of the barrier layer 45 is about 2 (M〇_ cathode 4〇) by screen printing or spin coating on the diffusion layer 13 201123589 0980096TW 33049twf.doc/n. The oxide fuel cell can be divided into double Gas chamber and single gas chamber: The state oxide fuel cell is oxidized by TM burners. It is: at medium temperature, π = two = near-like heat _ used _ potential is the amount One of the key points of high oxygen ion transmission in the optimal temperature range, where the sulfhydryl group has a low oxygen partial pressure environment; in addition, the problem is, for example, oxidizing the above-mentioned _ electrode site of the present invention. The L2M2〇9 solid solution is used as the dense electrolyte layer 3QT1QB'. The operating temperature range is 5. The cathode of the plant is composed of the cathode 40 and the anode 20 at 2〇00 and is matched with §〇FC. This system is not suitable for single-chamber oxidation of the solid state of a single gas chamber of the fourth embodiment of the present invention: cyan with reference to Figure 2's single-chamber with a pre-air chamber 50, at least - thin:: make, 枓The battery 1 includes a single gas chamber 50 having a single ":", and a gas mixture 80. 52 is used to supply a mixed gas: With a single 1〇54. The inlet is used to extract the exhaust gas. The early milk is in the middle. The outlet 54 is 14 201123589 0980096TW 33049twf.doc/n The enamel electrode group can be thorn, ,, L i WOB, the shaft electrode of the material The group l〇A 戈" 4, , , ° ° will not be described here. The film electrode t 1 () Μ 3 single, or multiple parallel or series. In the figure only single = electrode group Κ) To the table *, but it is not limited to this = is set in the single gas chamber 50, in the %_• pole group 10 series τ 隹浔 membrane electrode group 10 of a room 50 inlet 52 ' another - The side is the outlet 54 of the single gas chamber 50, = early; the membrane electrode assembly 10 does not divide the single gas chamber 5 () into two gas chambers, and thus does not

A gas seal (Γ ―) is required to separate the fuel and oxidant streams that are required for use. By the way, in the outermost layer of the thin film electrode group 10, the outer circumference of the + + η π includes a current collecting WCun-ent collector 60, 7 〇. Current collectors 6〇, 7 are made of conductive materials such as silver, gold, and platinum. &quot;&quot; The mixed gas 80 includes the fuel and oxidant required for the battery. The materials include 曱9. The (four) of R can sigh natural gas, miscellaneous or some factory exhausts. Therefore, the application of S〇FC for simmering is very extensive. The oxidizing agent includes air. It is better to mix the fuel with the oxidized ❹m without burning and detonating. The upper limit of the combustion of methane and air is 15-17%. The content of formazan is less than .5 mol% or higher than 15%. In an embodiment, in the milk-rolling flow, the molar ratio of decane to oxygen is better than 丨: ,, so that the gas stream is rich in decane, and does not cause combustion to detonate. The molar ratio of oxygen is 2: j. The temperature of the mixed gas 8 可以 may be, for example, a temperature of 500-700 〇C. During the face-making process, a medium temperature air stream of mixed air and decane is introduced into the single gas chamber from the inlet 52 because the cathode 40 and the anode 20 are opposed to the gas flow 15 201123589 09S0096TW 33049Uvf.d〇c/„中气” The selectivity of methane can cause electricity to generate a potential difference, which in turn pushes the current through an external negative; St degree f completes the function of the battery. The battle of shellfish; work, and then the electric side of the solid oxide fuel invented by ice should be used for household fuel cells, work in the field = «reuse fuel cells. However, it == mask lwt〇/o^ ^ ^S|(P〇ly^ i ''s8 Λ '^^2 ball and alcohol solvent for wet ball grinding) 7 7 Γκ=93Κ for 12 hours to shift Digestion of diterpenes:

The test piece with a diameter of 55 is the J. The quality of the ship and the expansion: Service, and hold the temperature for 1 hour, in order to burn out the organic matter, and then the temperature of the sheep to raise the temperature to 1423~1523K and increase the price of the knife to the screen printing. ; Chapter v, Fe coated, 〇·6 r〇.4Co〇8Fe0.2〇3 cathode. After that, the screen printed on the square = the 2 body and the cathode, the screen is printed with silver glue as the electric collector 5 ^ and then the metal wire is adhered to the current collector, and the ceramic glue is used for the test. Chip. So far, the production of the s〇FC test piece is completed. ^ After, with methane: oxygen: 1 molar ratio, the total flow rate is 35 〇 3 can be used for electrical testing. The results are shown in Table 。. , this 1:7

o^tvallomw〇〇CV 16 201123589

UP0P'V-6SCC AU96°0860 Experimental Example 5 La1.3Dyo.2MO1 Wi〇9 ο ν〇0 inch MPD (mW/om2) 〇: OO Co 〇\ OCV (V) 0.94 .0.93 0.93 0.92 0.91 0.89 0.87 Experimental example 4 La1.sDyo.2M01.6Wo.4O9 ο ν〇0 inch MPD (mW/cm2) 〇CN OO 〇r—^ 119 OCV (V) 1 0.85 0.84 0.82 0.80 0.77 Experimental Example 3 Lai.sDy〇.2M〇2 〇9 ο ο MPD (mW/cm2) 13〇〇 inch i 4 132 122 OCV (V) 1 0.82 oo 0 Factory! 0.77 0.73 Experimental Example 2 Lai .8〇Υ〇.2Μ〇2〇9 0 Ό Ο inch MPD ί (mW/cm2) 卜b f1 &lt; 〇〇t* 4 on &lt; _〆00 1 — OCV (V) 〇〇〇1 0.79 1 1 0.78 0.77 0.76 Experimental Example 1 Lai3Dy〇.2M〇2〇9 ο To 0 MPD J (mW/cm2) CN CO OCV (V) Diphthene Experimental Example Electrolyte GDC: NiO g 823 848 CO 00 Os 00 923 948 973 201123589 0980096TW 33049twf.doc/n Experimental Example 2

The SOFC test piece was produced in the same manner as in Experimental Example 1, except that the weight of the *GDC and NiO powder was changed to 3.2 g and 4.8 g, that is, the weight ratio was 40:60. In addition, electrical tests were conducted at a plurality of temperatures, and the results are shown in Figures 3 and 4 and Table 1. The results show that as the temperature rises, the battery's MpD tends to rise. Under 8 dishes, the 0CV and maximum power density of the battery were 0.80V and 156mV/Cm2, respectively. At 898K, the battery has the highest maximum power density of 193 mV/cm2. This value shows that LDM as the electrolyte will perform better than YSZ. Experimental Example 3 An s〇FC test piece was produced in the same manner as in Experimental Example 1, except that the weight of the GDC and NiO powder was changed to 24 g and 56 g, i.e., the weight ratio was 30:70. The results of the electrical test are shown in Table 1. The results show that as the temperature rises, the MPD of the battery has a tendency to rise. At 823K, the 0CV and maximum power density of the battery are 〇 micro and 130mV/cm2, respectively. Experimental Example 4 An s〇FC test piece was produced in the same manner as in Experimental Example 2 except that the LauDywMoA electrolyte was changed to Lai 8Dy〇2M〇i 6w〇4〇9. The results of the electrical test are shown in Table 1. The results show that as the temperature rises, the MPD of the battery has a tendency to rise. Experimental Example 5 201123589 0980096TW 33〇49twf.doc/n The s〇FC test piece was produced in the same manner as in Experimental Example 2, but the results of changing the LauDyojMoA electrolyte to the electrical test are shown in Table 1. The result shows that as the temperature rises, the Mpr of the electricity pool has an increasing trend. Moreover, the MPD of the battery at 973K is still higher than 948K, and the electrolyte which represents tungsten doping has better resistance to reduction and has the ability to operate to a higher degree. ° '

As described above, the thin film electrode assembly of the embodiment of the present invention has a wide selection of materials that can be matched, so that a less expensive material can be used to greatly reduce the cost. The solid oxide fuel cell of the embodiment of the present invention can have excellent performance because the dense electrolyte layer of the thin film electrode assembly is matched with the extremely matched cathode and anode. The solid oxide fuel cell of the embodiment of the present invention can be operated at a medium temperature explosion of 7 GG ° Q. The use of the system and the general thermal energy device is gentle, and therefore, it is easy to combine with a general thermal energy device in application. The solid oxide fuel cell of the embodiment of the invention utilizes a single gas to no gas seal, is simple to manufacture, has low cost, and has mass production advantages. The solid oxide fuel cell of the embodiment of the present invention is widely used in a fuel cell, a fuel cell for a fuel cell, a combustion of a factory exhaust gas, or a fuel cell for burying a biogas incineration. Cup rff day τ material touch 34, Cai and turn to limit = month 'dumping (four) surgery leading the wealth has the spirit and scope of the invention _, when can make some changes and ^ not = 19 201123589 0980096TW 33049twf.doc/n invention The scope of protection is subject to the definition of the scope of the patent application. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1A is a diagram of a thin film electrode assembly according to an embodiment of the invention. 1B is another thin film electrode assembly according to another embodiment of the present invention. 2 is a single gas cell solid oxide fuel cell in accordance with an embodiment of the invention. Fig. 3 is a graph showing the relationship between voltage and current density of a solid oxide fuel cell of Experimental Example 2 of the present invention. Fig. 4 is a graph showing the relationship between the power density and the current density of the solid oxide fuel cell of Experimental Example 2 of the present invention. [Main component symbol description] 10, 10A, 10B: thin film electricity 45: diffusion barrier layer group 50: single gas chamber 15: anode activation catalyst layer 52: inlet 20: anode 54: outlet 30: dense electrolyte layer 60' 70: Current collection 40: Cathode 80: Mixed gas 20

Claims (1)

201123589 0980096TW 33049twf.doc/n VII. Application for patents: “Membrane Electrode Assembly (MEA), including. One Yang plant, JL more than 4彳,, 4, ±^ a A shell For the ceramic friend: the porous layer of the pottery-gold composite material of the metal structure, the winter genus includes the celLt package=1 or N11-tcot 'of which 3%&lt;t&lt;60%, Pm ewnw〇2 'Ln" It is selected from the group consisting of La, Pr, Nd, Sm, eu, Gd ^ 牮 如 人, Dy, Ho, Er, Tm, Yb, Lu and their combination. J - dangerous pole X <square group '3 %&lt;w&lt;40%; material porous layer, material is porous layer of recorded material or unrecorded (Lai_&amp;x) (^^ wrong material porous layer is selected from (Srn'-xSrx)C 〇〇ei'y)〇3, (Ba1.xSix)(CoyFe1.y)〇3, (Gd^xSrxX)C〇〇3 ' (Pl^-xsrx)C〇〇3 ' (Nd).xSrx)Co03 &gt; The combination of ^ (DykSl'x)C〇03, (Lai-xSrJMnO) and its current knowledge group '3〇/〇&lt;χ&lt;6〇%,〇%%; ^ni-zK2 (c〇p wrong material porous layer including Ln is selected from &quot;f)03, Ln(M〇uN')〇3 or Ln(M〇uC 〇Iu)〇3, the composition of the family, &amp;, (^, 朽, 、, 3111, 〇 (1 and its combination of the same 3% ^ ^ 0%, 〇% public ^ 100%; and a material cup desulfonating layer of the electrolyte, located between the cathode and the anode, the crucible comprising a solid solution of L2M2〇9, wherein from &amp;, 80-100% by mole of La and 0-20 The group consisting of Ca, Ba, Bi, Pm, Ru, G, Tb, Qiao, Ho, &amp; K, γ and the like; 21 201123589 09ϋϋϋ9δΙ W 33049twf.doc /n Six 卞7〇 Μ is selected from y, w, Cr, and in/or 〇, 5 〇 耳 % 〇 〇 〇 〇 。 。 。 。 。 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 Please refer to the patent "Wanwei. No.!" order that the ratio of the Tao and the Jinxue is 4: 6_Electrical Group, 3. For example, the material of the cathode is the material of the cathode. The inclusion portion has its expansion barrier between the cathode and the dense electrolyte layer: package = Representing the rare earth element of the lanthanum or 3% of her, Ln, μ, the thin film electrode set described in the first item of the patent range, the pole activation layer of the catalyst, such that the anode system is interposed between the anode and the electrolyte layer The anode activation catalyst layer is composed of rhenium as a rare earth (sumonized cyclamate mixed nickel metal contact powder). χ A solid oxide fuel cell comprising: a single gas chamber having an inlet and an outlet; a Membrane Electrode Assembly (MEA) is disposed in the single chamber, the membrane electrode assembly comprising: an anode which is made of ceramic and A porous layer of a pottery-gold composite material composed of metal 'this metal includes Ni or; ^, wherein 3〇/〇&lt;t&lt;60〇/〇,. The basal pottery includes Ln, which is selected from the group consisting of La, Pr, Nd ' Pm, Sm, Eu, Gd, Tb, Dy, Ho, Ει., Tm, Yb, Lu, and the like. , 3% &lt;w&lt;40%; 22 201123589 uvsuuyoTW 33049twf.d〇c/n One pole' is made of a porous layer containing a porous material or a porous layer of lithium-free material, wherein: Λ porous layer of interesting material It is selected from the group consisting of (4), (4), "calling", (ΡΠ) C°〇3, (Ndl.xSrx)C. 03, (rf 3, (DUrx) C 〇〇 3, (Lai_xSrx) Mn 〇 3 and its group a, which is 3% &lt; χ &lt; 6 〇 %, 〇 % rate ι 〇〇 % The porous layer of the ruthenium-free material includes (Lni-zKz)(C〇uFe^)〇3' Ln is selected from the group consisting of La, Ce, Pr, Nd, Sm Gd, and the like, Wherein 3% <z<5〇%, 0%&lt;u&lt;100〇/〇;, 'in the electrolyte layer, which is located between the cathode and the anode, the electrolyte material comprises a solid solution of L2M2o9, Wherein ... p L represents 80-100 mol. / ° La and 〇-20 mol%% Ca: Ba, rRNd, P'Sm, EU, Gd, Tb, Dy, H〇, Er, K, a 1. A group consisting of Y and its combination; Μ indicates that 50-100 mol% of Μ〇 and 〇5〇 are selected from the combination of V〇, /—, and Qi Q _^^ U Oxygen; and - a mixed gas 'which includes fuel and oxygen in the single gas chamber. , is from the inlet. 6. According to the scope of claim 5, the round &amp; Mix of ceramic fiber and metal molars C 23 201123589 uyeuuyoi W 3^049twf.doc/n 7· The solid oxide fuel cell according to claim 5, wherein when the material of the cathode is the porous layer of the cerium-containing material, the method further comprises a diffusion barrier layer between the cathode and the dense electrolyte layer. The material of the diffusion barrier layer is (Ce) bLn, b) 〇 2, of which 3% is 4%, and Ln represents lanthanum rare earth element or iron element. Battery 8 is complex, 2 please refer to the scope of claim 5 Solid oxide fuel ^ - anode activation catalyst layer, so that the anode is between the dense electric coffee, the oxidation of the element of the anode two powders - the end of the mixed nickel metal catalyst battery 9 The solid oxide fuel ι 5 5 〇枓 〇枓 5 , , , , 5 固态 固态 固态 固态 固态 固态 固态 固态 固态 固态 固态 固态 固态 固态 固态 固态 固态 固态 固态 固态 固态 固态Mol% or more than 15% Mo. The battery, which is more patented in the scope of the solid oxide fuel electrode described in item 5. The claws are collected by the genus, which are located at the anode and the yin 24 respectively.