TWI326933B - A novel synergistic process and recipe for fabrication of a high integrity membrane electrode assembly of solid oxide fuel cell - Google Patents

Description

1326933

* 1 P IX. Description of the Invention: [Technical Field of the Invention] The present invention provides an innovative procedure for modulating a flat-type SOFC-MEA related electrode from an original material, a finely tuned formulation, an anode and an electrolyte substrate slurry, and a blade forming process (Tape casting process) 'Making electrode substrate raw embryos. The embryonic layer is laminated (-η process). The high-integrated final green substrate is prepared by first forming a green substrate and then performing a high-pressure vacuum sintering process (Vucuum h〇t press system for VHPS). The raw substrate is subjected to a calcining/sintering process to produce an electrode substrate having mechanical strength, microstructural properties (porosity/gas permeability), twist, and size. With the screen printing / Sputtering coating / Spin coating / spray process, you can manufacture high-performance s〇 FC unit batteries. Its application to SOFC batteries provides excellent performance with high stability, durability and low degradation rate. The raw materials referred to herein are electrolytes such as YSZ/GDC/YDC/LSGM, and anode materials such as NiO + YSZ/GDC + NiO/YDC + NiO/LSGM + NiO. The cathode material is a variety of materials such as LSM/LSCF. But not limited to the above materials. • [Prior Art] SOFC has high performance conversion efficiency, low noise and low environmental pollution, high reliability and fuel multi-element, and has the potential to challenge the "internal combustion engine". Solve the problem of future energy shortages. Especially in the period when petrochemical energy is gradually depleted, hydrogen energy and coal gasification/liquefaction energy are gradually replaced, and s〇FC is the energy conversion equipment of the key. It will play the role of the era of innovation. The key objective of the production of the solid Oxide Fuel Cell-Membrane Electrode Assembly (SOFC-MEA) is the high operability of the MEA (High Perf〇). Rmance), durability (High 6 1326933 • <

Durability, High Stability, and Low Degradation Rate. A key condition for achieving the above goals is that the MEA uses Materials and Structure designs. The material content of the change and the structure of the MEA's characteristics of the MEA have also changed. In the material side-surface, the electrolyte is mainly composed of 8YSZ, which is suitable for insertion temperature, and varies depending on the structure of the substrate. The battery supported by the electrolyte (Electrolyte Supported Cell: ESC) has an operating temperature of 800 to 1000 °C. The thickness of the electrolyte layer substrate is about 150 to 300 μπι. It belongs to the first generation SOFC-MEA. Anode Supported Cell (ASC), • Its operating temperature is between 650 and 850 °C, and its electrolyte layer substrate thickness is around ι〇μηη, which belongs to SOFC-MEA of the second generation. NiO+8YSZ is the anode material for ASC/ESC. The thicknesses are 50-60 μm (ESC) and 500-1200 μm (ASC), respectively. The cathode materials are mainly LSM and LSCF, and their thickness is between 30 and 60 μπι. New electrolyte materials and cathode materials are being researched and developed in various research labs around the world. Looking forward to new materials, the operating temperature of SOFC-MEA will drop to 5〇〇~700°C. At that time, stack components of SOFC stacks such as interconnecting plates (Interc〇nnect〇r) can be replaced with metal materials. The material is not only easy to manufacture, but also has a mechanical/stabilization/financial long-term increase. It can also reduce the overall Cost Down's expansion of the competitiveness and penetration of the SOFC market, effectively creating a huge niche for the S〇FC industry. This technology development, in the field of universities and national research, focuses on material research and development, and hopes to invent advanced materials to reduce impedance, increase the conduction (I〇nicc〇nductivity) / electrical conductivity, and increase the power generation reliability of SOFC. There are many publications in Nature Science. Such as new electrolytes lsgm, YDC, LSGMC, lOScCeSZ with new cathode materials such as LSM / LSCF / LSF / LSC / lscm /BSCF / SSC. In the field of jl's emphasis on materials to enhance production technology and performance stability. Therefore, the materials used are mainly based on the characteristics of high performance and reliability. In conjunction with the process and structural design of the ergonomics 8 7 13 263 533, the mechanical/chemical stability, durability, and conversion rate of the unit cell (MEA) can be improved, and the S () FC wire ride can be achieved. The best product for the converter. National laboratories around the world have been investing in research and development for about 15 to 2 years, verifying that the function of s〇FC is correct and overcoming technical obstacles and industrial opportunities. Therefore, international companies cooperate with national laboratories to form joint ventures, and talent exchanges can be integrated or cooperated/such as ECN and InDEc and 乩匸汾^ in Europe.

IKTS with Karafol and Straxera with Webasto, NETL / SECA, EPFL and HT

CeranMX. The United States is supported by national laboratories such as PNNL and Simens Westinghouse, GE.

Six companies such as Ddphl commissioned research and development to verify the reliability and cost analysis and reduction of technology, and actively construct the SOFC industry. Among them, SOFC-MEA related materials have commercial products. As mentioned before, 8YSZ electrolytes, NiO+8YSZ anodes 'LSM / LSCF and LSF / LSC cathodes are the main products. As for the MEA process, it is the exclusive intellectual property of each company. It is rarely publicly disclosed and even reluctant to apply for a patent to avoid being harmed by the use or modification of patent content. However, the current SOFC-MEA production process is based on the blade forming technology to produce the electrode green embryo's re-lamination technology, adjusting the thickness and geometry of the green substrate, and after calcining/sintering, the electrode substrate or half cell is produced. The substrate (containing the electrolyte layer and the supporting electrode layer), and finally the cathode layer is placed on the half-cell substrate by a screen printing technique to complete the fabrication of the SOFC-MEA. The main disadvantage of sofc-mea thus obtained is that the mechanical strength is insufficient. 'Stability and durability (RedoxCycHng/Thermal Cycling) are not good. At the basic requirements of the cathode and anode requirements for porosity (for the gas-solid reaction mechanism), the mechanical strength is sacrificed. As a result, the subsequent stack failure of the battery stack package 8 1326933 failed. This shortcoming hindered the development of the perfect structure of s〇Fc and required an innovative solution. SUMMARY OF THE INVENTION The main purpose of this month is to propose a s〇FC M£a development material formulation (heart (4) and, supporting k innovation program to produce "highly integrated solid oxide fuel cell membrane electrode assembly (MEA) Or unit battery (referred to as HI-S0FOMEA or Hl_Unit Cell) je This HI SOFC MEA has the same mechanical strength and hardness, 2 can adjust the substrate porosity and air permeability 3 controllable #jMEA 夕 layer _ human material composition and microstructure Or sensitive density, 4 controllable (4) (10) a layer and layer thickness, 5 high sintered density, 6 high degree and durability characteristics. Since this item I SOFC MEA has the above-mentioned chicks, it can improve the output electrical density and fuel energy conversion of the battery. Rate. The most important feature is that it is suitable for the stacking and testing operation of the CellStack due to its high mechanical strength. It will not be vulnerable to cracks and lower the product due to the weakness of the Cell itself in the stack manufacturing process or test procedure. Reliability and yield. The inner valley of the present invention is mainly divided into a formula and a two-stage (electrode-containing embryo and electrode substrate) process, which are respectively described as follows: (1) Production of electrode substrate green embryo Liquid formula and production procedure: Recipe content Material type/name (a) Weight percentage range (%) Material work & points Description note (C) - Electrode material 1. 8YSZ (Electrolyte) 2. NiO/8YSZ (Anode) 50~ 86 (approximate value Q〇V(b)=68.0) &~86 (approximate value Q〇V(b)=68.0) Electrolyte 4 material "Sk material ~ electrolyte substrate / layer makes i(d) _Pole substrate/layer use~~--- The typical formulation of the electrode substrate of the present invention (Typicalrecipe) is shown in Table 1. Table 1 SOFC-MEA electrode substrate production paddle liquid formulation and modulation program 9 1326933 *, machine plus II. Organic solvent-dispersed sword plasticizer binder III, bismuth 3. MEK (Solvent 1) 12~22 (nearly accommodating value QOV(b)=16.0) Solvent to dissolve electrolyte material 4. EtOH (Solvent 2 5. TEA (Dispersant) 6. DBP (Plasticizer 1) 7. PEG (Plasticizer 2) 8. ηΰ (Polyvinylbutyra1) (Binder) 9. Graphite (Pore Former) 5~9 (nearly accommodating value Q〇V(b) ) = 8.0) 1~2 (approximate value Q〇V(b)=1.5) 0. 5-2.0 (nearly accommodating value Q〇V(b)=1.0) 0· 5~2· 0 (approximate Value Q〇V(b)=1.0) uuv iiLaia.iuia Q0V(b)=4 5) 1.1~10 wt% of the weight of the anode material Solvent dissolving the electrolyte material Dispersing the electrode material in the solvent to adjust the plasticity of the green embryo (high) / viscosity (low) / elastic coefficient (low) to mediate the plasticity of the embryo ( Low) / Viscosity (13⁄4) / Elasticity (High) / Breaking Strength (High) Bonding / bonding force is the porosity of the anode substrate and the gas can be other solvents. Solvents can be other dispersants. Other plasticizers can be used. Other plasticizers may be other pore formers _L___ 丨 body permeability _ . "·. Compound formula is listed in Table 1. b. : QOV=Quasi-〇ptimium Value. c. The type of additive you can use in combination with your needs. However, it is finally used in the blade forming process. The range of the range of l〇G~15G() cp' can be appropriately selected according to the thickness of the green body to be formed. “The solution material can be: GDC/YDC /SDC/LSGM, etc. ·. Other electric Lu main materials are divided into a. Electrode material containing electrolyte 8YSZ and anode material NiO+8YSZ, b · organic additive containing organic solvent (MEK, EtOH) 'dispersant (TEA)' plasticizer (DBP, PEG), combined with (viscosity, '°) agent (PVB), c. pore former (Pore former) (graphite Graphite). The composition of each material formula weight percentage is also listed in Table 1, other related compounds The molecular formula or composition is detailed in Table 2. Table 1 Main related compounds formula or composition table

Notes: Material type name abbreviated chemical formula (with representative composition) 1326933 YSZ (Y,0.)〇.〇8(Zr02)〇.92 ΜΕΚCH3COC2H5 EtOH C2H5OH TEA C6H15N〇3 DBP C16H22〇4__ PEG OH(C2H4〇 „H PVB Polyvinyl Butyral Chemical Formula (omitted) GDC Gd〇.2Ce〇.8〇i.9 YDC Υ〇.08^β〇.92〇3±δ LSGM La〇.8Sr〇.2Ga〇85Mg〇.i5〇 3±8 LSM La〇.8Sr〇.2Mn〇i LSCF Lao.6Sro.4COo.2F e〇.8〇3±5 LSC Lanthanum Strontium Cobaltite Chemical Formula (Omitted) LSF Lanthanum Strontium Ferrite Chemical Formula (Omitted) LSCM La〇.8Sr 〇.2Co〇.85Mg〇.!503±s For the electrolyte substrate/layer formulation, the approximate optimization of the weight composition is: 8YSZ (68 wt° / 〇) » MEK (17 wt ° / 〇) &gt EtOH (7 wt%) > TEA (1.5 wt%) > DBP (1.0 wt%) > PEG (1.0% by weight), 卩¥6 (4.5% by weight) 'Pore forming agent (0. Plus %) Since the electrolyte layer requires "zero gas permeability and 100% density", it is not necessary to use a pore former. As for the anode substrate/layer formulation, the near-optimal value is: Ni〇+ 8YSZ (68wt%) (where the weight ratio of NiO/8YSZ is 50/50 (approximate optimum value)), MEK (17 wt %), EtOH (7 wt%), TEA (1.5 wt%), DBP (1·0 wt%) 'PEG (1.0 wt%) 'PVB (4.5 wt%), pore former (graphite) (anode material weight 0_1~10 wt%). The amount of pore former can be adjusted according to the required void ratio of the anode substrate. The formula weight percentage range shown in Table 1 can be adjusted according to the material characteristics (particle size distribution and specific surface area, etc.). The goal of the adjustment is to create a high degree of uniformity, which is suitable for the molding process variables and product embryos (such as thickness / density / ease of operation) and high quality raw embryo products. The formulation electrode material and the pore forming are still pre-treated, and the main program is ball grinding! 326933 • ·. Mill (built-in zirconia grinding ball), grinding to electrode material powder particle size up to 200~300 nm . Further, it is ground together with the organic solvent and the dispersing agent in a ball mill for about 24 to 48 hours (or the grinding time may be reduced as appropriate) to achieve the purpose of homogenization. Finally, the plasticizer and the binder are added together and then grinded in the ball mill for another 24 to 48 hours (the grinding time can be increased or decreased as appropriate) to achieve complete homogenization and slurrying of the slurry. The thickness of the raw embryo is required to fine-tune the composition of the slurry and make a viscosity measurement and adjustment. The thickness of the raw embryo is 10~200 Jim, and the viscosity range of the slurry needs to be between 〇〇(M5〇〇cp (depending on the characteristics of the original powder, experience and technology, it is an indispensable tool for program optimization). The blade forming operation is smooth. The operation of the blade forming system, the reliable and skilled technology, and the operation of the blade forming machine are carried out to obtain the high quality green tape (Green Tape). : The raw embryos produced in the previous item (1) are sliced or punched (Punching/Bliing) into individual-sized single-layered embryos (abbreviated as raw embryos). The number of raw embryos is selected, and the superimposed overlap and The first section of the Luke gas "Lamination Process" (LP) can be used to produce a thickness of the electrode green substrate - A. The temperature and pressure of the hot laminate are 6 〇 ~ 100 〇 c and 2〇〇〇psi~ 5000 pSp The density of the raw substrate _A at this time is about 4% of the theoretical density of the ceramic oxide. The raw substrate-A is further subjected to the second stage of the vacuum thermo-hardening procedure (abbreviation) VHps)" to make a birth embryo substrate - B. The vacuum of this program is Ι〇·3~(1)·4 torrs, the pressure can be 丨68 xl〇5 psi (area=9cm2)~1.52xl〇4pSi (area=i〇〇cm2), the temperature is 5〇〇.〇.This raw substrate - The density of B can reach 70% of the theoretical density of the electrode ceramic oxide. This "two-stage vacuum hot laminate process" is defined as "innovative compound synergy production process" (N〇velSynergistic 12 1326933

Process) referred to as NSP. At the £ρ stage, the embryo is free to lay flat on the plate. The stage embryos are placed in a fixed-size model (4), and the relevant operations are carried out. (IV) Nsp process 1: The ultra-integrated substrate has a high integration property (High Integrity), and after the calcination/sintering process, the obtained electrode ceramic substrate has high integration characteristics and extremely high mechanical strength. It is then processed/produced by other electrode layers (such as cathode or electrolyte), such as ScreenPrinting, Sputtering Coating, Plasma Coating/Spraying, Spin Coating (Spin) Technology such as Coating) can be used to make cell batteries with unique features. High mechanical strength (suitable for battery pack packaging testing), high durability and stability. It is called "high-integration fuel electric electrode assembly unit". In addition, the amount of pore-forming agent used can be adjusted to modulate the inclusion and microstructure of the anode substrate to change the porosity between the layers to effectively increase the gas permeability and improve the energy conversion efficiency and output power density of the single 7C battery. Master the key manufacturing technologies of SOFC-j^A' to improve the precision specifications and excellent performance of products. [Embodiment] The present invention relates to a SOFC-MEA development material formulation and an associated manufacturing innovation program (see the first schematic diagram of the program for brief implementation) to produce a membrane electrode assembly (MEA) for a highly integrated solid oxide fuel cell. Or unit battery." Therefore, the main inventions include "a fine-grained and two-mesh substrate and electrode ceramic substrate fabrication process." The implementation methods are respectively described below. (1) Electrode substrate raw embryo preparation slurry formulation and production procedure. The invention comprises at least the following steps: Step 1: The self-made or purchased 8YSZ and Ni 〇 powder according to a certain weight ratio (Ni 〇 accounted for 35 65 65 wt% of M 〇 + 8 Ysz weight (its Q 〇 V value is 50 Milk%)) Mixing, co-located with cerium oxide grinding balls in a grinding jar (Jar) for grinding for 24 to 168 hours (or addition and subtraction time as needed) to achieve a highly uniform mixing of the powder. The uniformity can be judged by SEM for sample analysis 13 1326933, and the grinding time and rotation speed are increased if necessary. The average particle size of the powder is 300~5〇〇nm as the target value (larger or smaller particle size adjustment can be made as needed). The powder name of this item is Anode-P-b powder characteristic with particle size/specific surface area. /Equivalent (EDX-Mapping), all built standards check. This is the primary work of the slurry preparation of the electrode substrate. The main formula content is detailed in Table 1. See the primary intellectual property of the present invention. Step: The powder Anode-Ρ-Ι is taken out and placed in the oxidized wrong material tray, and then co-fired at a temperature of 12 〇 0~l6 〇 0 ° C for 2 to 8 hours (can be added or subtracted as needed). In the step 1 method, the ball mill is ground. The average particle size of the powder is in the range of 3 Å to 500 nm (or the particle size is adjusted as needed). At the same time with high uniformity. This powder is called Ajjode-Pd. To adjust the porosity of the final substrate, an appropriate amount of pore former (Poreformer: typical of Graphite) was added to the Anode-P-2. Repeat the grinding process for several hours (more than 24 hours), and the resulting powder is called Anode-P-3. Step 3: Weigh a certain amount of Anode-P-3 in 10 (TC dry and dry for several hours (more than 24 hours is better, remove moisture and water according to the formula 1), weigh a certain amount of organic solvent MEK, EtOH and dispersant TEA, all together in a grinding tank with zirconia grinding balls, grinding for several hours (more than 24 hours) to ensure homogenization of the whole system. This uniform solvent and dispersant The homogeneous liquid phase is called. Step 4: Add the dried powder Anode-P-3 to the SD solution and pick it up in liquid phase for several hours (more preferably for 48 hours) to make the powder and solvent/dispersant even. Dissolve / disperse into a mixed slurry, called SL-1. Step 5: According to the formula of Table 1, measure the quantitative plasticizer DBp, pEG and binding agent ργΒ, respectively, 1336933 into the slurry SL-1, and continue to liquid phase After grinding for several hours (about 48~72 hours), it is determined that the whole system is completely homogenized, and it becomes an anode substrate slurry suitable for the blade forming process, which is called SL-2. Measure and record the viscosity of sl-2 by viscometer and view it. Characteristics of SL-2 Step 6: Using fine-tuning technology, add appropriate amount of knots in stages Mixture, plasticizer to adjust the viscosity of SL-2 between 150~1500CP (QOV=200~500CP), this part of the deployment effect, relying on personal experience and technology / ability to decide trial and error (Zhuang ial and err〇r) operation Time and number of times. The final tape slurry is called SL-T. Step 7: The slurry slurry sl-T is processed by a Tape casting system to make a green tape. The width of the raw germ zone depends on the demand, roughly between 18 and 30 cm. The thickness of the single layer is between 1 〇 and 300 μm (the thickness of the single layer can be increased according to the requirements of the blade forming machine). Step 8: Cutting machine Or a fixed model punch that cuts the raw embryo strip into a single piece of embryonic band of a particular size and shape (usually square or round). The individual pieces are cut into individual pieces according to the specific thickness requirements. Feed the constant pressure laminator (named LM) as a lamination operation to produce a shaped green substrate (called GT-1). The laminator (called LP) pressure in this step is set to 2000~5000 psi. The temperature is between 50 and 100. (: Between GT-1 can be 100~1500μηι. The thickness of the substrate is Q〇V=600~1200μι η. The embryo density of GT1 is measured by Pychrometer. (2) Electrode ceramic substrate fabrication procedure: Step 1: The green embryo substrate (GT-1) (size 5x5cm2~15x15cm2 (or larger) thickness nearly 15 1326933 600 1200μηη ) placed in a 5 x 5 cm "suitable size mold, sent to the "vacuum hot pressing sintering system (referred to as VHPS) (detailed as shown in the second figure)" for vacuum (less than ΐχΐο-Ws) hot pressing (temperature < 50 (rc, pressure can be as high as i 68xi〇5psi (adjustable)). The high-density green germ substrate (referred to as GT-2) produced by this procedure has a green embryo density measured by Pychr〇meter up to 70% of the theoretical density of the ceramic oxide. Step 2: If necessary, the surface finish of GT_2 can be re-laminated by the LM machine. Such a procedure for enhancing the green germ substrate by interacting with the LM and VHPS systems will be referred to as the "ANovel Synergistic Process". This program finally produces a birth embryo substrate called GT-F. Step 3: The GTF is naturally pinched (sandwiched) on the zirconia substrate, placed in a high-temperature furnace (temperature can be up to 17 °C), which is oxidized and placed in a thick plate, for two-stage cyclic sintering. The first cycle temperature control is: room temperature - 20 (TC (4Hr) - 75 (η: (2Ηι〇 - 1250 (6Hr) - room temperature. And the second cycle temperature control: room temperature - 14 〇〇 t: (4Hr ) - room temperature. The temperature rise and fall rate of the two-stage cycle is kept at ^^c/min (preferably within 3 〇c/min). At the same time, an appropriate amount of air is supplied. The first cycle is calcined to remove all organic additives. Sintering, compact function, effective production of ceramic substrates. The completed electrode substrate is called AS-1, which must be characterized, including sintered density, mechanical strength, void ratio 'microstructure, etc.. AS-1 electrode plate High mechanical strength and flatness with appropriate porosity and gas permeability to meet the basic requirements of SOFC-MEA electrode structure. Step 4: Screen printing of AS-1 screen, difficult: Mine ), 1326933 Equipment and procedures such as SpinCoating or PlasmaSpray 'coating the appropriate thickness (<10μιη) of the best electrolyte (8YSZ) layer, and then sintering in a high temperature furnace (140 (TC) /4Hr), the temperature rise and fall rate is rc/min to make the semi-electricity of SOFC-MEA Pool. It is called AS-H. Step 5: Apply AS-H half-cell 'by grid printing technology, apply LSM (or LSCF and other materials) cathode layer on YSZ layer, the thickness is 30~50μπι (can be increased according to demand) Reduced. Then placed in a high temperature furnace for sintering (12 〇 (Tc / 3 ~ 4Hr), the temperature rise and fall rate are rC / min (best small Lu on 3 made the finished product called ASC-I this ASC-I for the anode support Battery (also known as ASC type SOFC-MEA) (detailed as the anode/substrate (NiO+YSZ) with multiple/functional layers as shown in the third figure). Through the above procedure, the SOFC battery of the anode support unit can be fabricated. It can be directly converted into electric power by hydrogen fuel, natural gas, hydrocarbon and other multi-fuels. The following is a detailed description of the embodiment of the invention: Example 1: Preparation of a high mechanical strength with suitable porosity (2〇 ~3〇v〇1%) s〇fc anode β substrate and unit cell This embodiment is to prepare a flat-type SOFC anode substrate with high mechanical strength and suitable porosity (20~30V〇1%) and continue to be S〇 FC unit battery finished product, tested for power supply and used for power generation. The preparation process includes (4). The first stage is Ni〇+ YSZ anode substrate raw pulp production paddle liquid formulation and production process total 8 steps, and (2) anode shouting substrate production process, a total of 5 steps 'described separately as follows: (1) NiO+8YSZ anode substrate green embryo production Slurry formulation and preparation procedure, including the following + 17 steps (as shown in the fourth figure): , 175 grams of cubic crystal structure of 8YSZ with an equal amount of oxidation recorded (ΝιΟ) (the average grain Mixing about 1 〇〇〇 nm), placed in a ball mill jar of oxidized (Zr〇2) grinding balls (about 250 g), and ground for about 168 hours to make NiO and

The sysz is completely mixed to form a highly uniform mixed powder. The uniformity can be SEM. σ analysis and judgment. If necessary, increase the grinding time and speed. Grinding

The average diameter of the dry powder is up to 3〇〇~5〇〇. This item is named after the powder. The powder characteristics include particle size/specific surface area/uniformity (EDX_Mapping), which are all documented. Less 2. The powder Anode-JM is taken out of the grinding jar, placed in a tray of oxidized material, and about gamma is carried out in the same furnace. c/4 hour co-firing procedure. After completion, repeat the steps of the grinding procedure' for another ball milling to make the powder particle size range from 300 to 500 nm with uniformity. This co-fired abrasive powder is called Anode-P-2. Add 3.5 grams of test rice, 'and/nano grade graphite powder to Anode-P-2, repeat grinding procedure 24

J wins above, ensuring high homogeneity of all powders, and the resulting powder is called Anode-P-3. Its total weight is 353 5 grams. Step 3: Take Anode-IM ++c on the [,. 353.5 grams, dried at about 100 c for more than 24 hours to remove moisture and moisture from the powder. Also referred to as solvent MEK78.1g, EtOH25.27g, and dispersant 8.05g, both together in the grinding tank with zirconia grinding ball (Zr02Ball), 々 24 hours or more 'to ensure system-wide homogenization . This solvent and dispersant is called a SD solution. The total weight of its SD solution was (1) 42 grams. Step 4: Add the powder after the dry preparation (4) to the SD solution, and grind the liquid in a liquid phase. The laminate of the U26933 is set at 2000~5000 psi and the temperature is set at 5〇~1〇〇. During the daytime, the embryos were measured by Pyehrometer (detailed in Figure 7). (2) The manufacturing procedure of the anode with the substrate, which comprises the following steps: Step 1. The raw substrate GT1 (the square size is (10)^ and 1〇xl〇cm2, and the thickness is 1200μπι) is divided into 5x5em>丨(4)(5)1 In the mold (the mold material is not recorded steel 'outer clock WC), it is sent to the "vacuum hot dust sintering system (VHPS)" for vacuum (pressure less than 1x10-3 t〇n*s) hot pressing (temperature < 500. 〇, the pressure can be up to h68Xl0 PS1 (adjustable) treatment. Through this procedure, a high-density raw germ substrate (called GT-2) is produced. The density of the raw embryo is measured by Pychr〇meter, which can reach 7〇% of the ceramic oxide. Theoretical density. Step 2 'Right is necessary' Beij GT_2 surface finishing can be re-laminated by LM machine. This procedure of LM and VHPS interaction to enhance the raw substrate is called "innovative compounding process" (A novel synefgistie p_ss). The final substrate of this secret is called GT_F〇GT·?; M, the required production and the size of the hot stamping die. Step 3. GT-F The yttria substrate is naturally pinched (sandwiched) and placed in oxidation High-temperature furnace for thick plate (temperature up to °C): Sintering in two-stage cycle. The first cycle temperature control is room temperature·>20(Τ〇(4HrS)+450°C (2hrs)+ 750 ° C (2 hr 〇 250 2250. (: (6 hrs)) room temperature. The second cycle temperature control is: room temperature + 14 〇〇 <> c (4 hrs) to temperature. Keep it at /min (preferably within 3 t/min). At the same time, apply a proper amount of air. The fabricated electrode substrate is called 20 1326933 AS-1 (see Figure 8). The characteristics of the forging are shown in Table 3. Table 2. Characteristics of the characteristics of the anode substrate Item Characteristics Analysis Value 1. Size LxWxH ( Thickness) = 50 mmx50 mmxlOOOO //m & lOOramxlOOmmxlOOowm 2. Shape flat type / high flatness 3. Mechanical strength a. 67. IMPa ( T=25〇C) 82.91MPa (T=700°C) 76.17Mpa High flatness (T=800°C) 4. Void ratio (T=25°C) a. Original product value=14. 534 % b. H2 reduction value = 26.1187 % 5. Air gas permeability (T = 25 ° C) The original product quality 1.14 x 10-4 l / psi-cm2-sec shows that the AS-1 anode substrate has high mechanical strength and surface flatness. With appropriate amount of porosity and gas permeation . Meet the SOFC-MEA anode structure requirements (detailed as shown in Figure 9 step 4: the anode substrate AS-1 with a mesh printing equipment and procedures, coating a layer of electrolyte (8YSZ material) thickness of about 1 〇 μπι, and then placed in 1700 The high temperature furnace performs a sintering process of 14〇〇Ό/4, and the temperature rise and fall rate is 1 to produce a half-cell of sofc-mea, called AS-H. Step 5: The AS-H half-cell is printed by mesh printing technology. The LSM cathode layer is coated on the 8YSZ electrolyte layer to a thickness of 40μm to form a full battery, called AS_WC. The AS WC is placed in a high temperature furnace to perform another sintering process (12〇〇〇c/37". The rate is 1 °C / min. You can make 8〇17(:_^8 finished product called AS CI (see the tenth figure for details), this is the complete anode supporting battery (also known as ASC type SOFC-MEA) The ASC-I is electrically tested by simple current collector (pr〇b〇stat SyStem) with an electrical power density of up to 32 mW/cm2 (test area = Ttcm2, temperature = 9 〇〇. 匚). 1326933 X 4 cm2 test, its electric power density is greater than loo mw/cm2 (temperature 840 °C). (Prototype MEA is not optimized for production) Brief Description: The first figure is the innovative integrated synergy production process of the high-integration solid oxide fuel cell membrane electrode assembly component (cell) of the present invention (ANovel Synergistic Process for Fabrication of a High Integrity Membrane Electrode Assembly of Solid Oxide Schematic diagram of a brief implementation of the fuel cell. The second diagram is a schematic diagram of the "Vacuum H〇t press System (VHPS)" in the procedure of the present invention. The third figure is a flat type solid oxide fuel cell. (pianarS〇FC) Anode Supported Cell (ASC) structure and physical diagram. The fourth figure is the SGFC_MEA electrode of the invention made of pulp touch and modulation program diagram. The fifth figure is a high integration electrode The solid image of the substrate embryo is made. The sixth figure is the solid map of the high-integration electrode substrate. The seventh figure is the high-integration electrode substrate. The eighth figure is the high-integrated electrode substrate. The ninth picture shows the microstructure and characteristic diagram of the highly integrated electrode substrate. The tenth figure is based on the highly integrated electrode substrate. S0FCMEA for forming the (unit cells) with FIG entity electrical performance test results of FIG. Main reference numerals 22 None DESCRIPTION

Claims (2)

1326933 X. Patent application scope: The production is complete. The method for preparing a membrane electrode assembly (age age) of a solid oxide fuel cell includes: (1) preparing a slurry formulation and a preparation procedure for producing an electrode substrate; and (7) preparing a slurry or an electrolyte substrate, the steps comprising: The preparation of the slurry preparation and preparation procedure of the electrode substrate raw embryo: a. Establishing the electrode/electrolyte substrate, the embryo preparation slurry formula and the Saki procedure (10) Convergence • In the table “) and preparing the relevant material powder, organic additive and Poreizer; one electrode table-SOFC-MEA formula content material type/name (a) 1. 8YSZ (Electrolyte) electrode substrate production pulp f 百分 percentage percentage range (%) 1〇~86 (nearly accommodating value Q〇V (b)=68.0) No-formulation and modulation test description note (C) Substrate/layer use (d) Material 2. N i 0/8 YSZ (Anode) 50~86 (nearly accommodating value Q〇V(b ) = 68.0) Anode material anode substrate / layer using organic additive organic solvent 3. MEK (Solvent 1) 12~22 (nearly accommodating value Q〇V (b) = 16.0) Solvent to dissolve electrolyte material can be other solvents 4. EtOH (Solvent 2) 5 to 9 (nearly optimised value QOV(b)=8.0) The medium to dissolve the electrolyte material can be other solvent dispersing agent 5. TEA (Dispersant) 1~2 (nearly accommodating value Q0V(b)=1.5) Dispersing electrode material in the solvent 1--- can be other dispersing agent plasticizer 6 DBP (Plasticizer 1) 0.5~2.0 (approximate value QOV(b)=1.0) Modification of the plasticity of the embryo (high) / viscosity (low) / elastic modulus (low) can be other plasticizers 7. PEG ( Plasticizer 2) 0. 5~2. 0 (nearly accommodating value QOV(b)=1.0) Modification of plasticity of plastic (low) / viscosity (high) / elastic modulus (high) / breaking strength (high) Other plasticizer bonding agent 8. PVB (Polyvinylbutyral) (Binder) 3~6 (nearly accommodating value Q0V(b)=4.5) The bonding strength/bonding force of electrolyte materials can be used for other bonding agents 23 1326933 9. Graphite (Pore Former) Anode material weight to adjust the porosity and gas permeability of the anode substrate b• According to the table-connotation ratio, the relevant shouting powder (anode substrate material is 8YSZ; electrolysis county woman _ 8YSZ) is placed in the grinding tank of Oxygen County for the first time to achieve the first homogenization of the whole powder material. Normalize the particle size; c. Place the b-step product in a high-temperature furnace for co-firing, perform solid-state homogenization, and after the furnace is discharged, perform the second oxidation of the county, and add the artificial pore agent at the same time. Achieve secondary homogenization of the whole powder material, and then dry to remove moisture and moisture to form a C-step product, called c powder; d. Add organic solvent MEK, Et0H and dispersant TEA to c In the step product, the grinding of the oxidized knot ball is performed to achieve homogenization, and the homogeneous liquid phase of the solvent and the dispersing agent developed in this step is called SD; and the product (SD) is added to the powder in the step c, and the execution is performed. The third oxidation recording of the grinding of the ball "to dissolve and disperse the powder and the solvent / dispersant into a mixed slurry is called e ~ ~ slurry; f. According to the table - connotation, the quantitative plasticizer DBP, PEG and The binder PVB is separately added to the e-slurry to perform the fourth oxygen Grinding the ball to determine the homogenization of the whole system, forming a f-step product, called f_substrate (which can be electrolyte or electrode slurry), measuring and recording the viscosity with a Viscosity Meter; 24 1326933 g. Using fine-tuning technology, adding a proper amount of binder and plasticizer in stages to adjust the viscosity of the f-substrate slurry, the substrate slurry is called g-to the knife slurry; h. g-scraper slurry to the knife forming machine (TapeCastingSystem) plus &, to make Green Tape, product specifications (thickness and width) of raw germ strip, can be adjusted as needed; i· cutting machine or fixed model punch A single-layer piece of embryonic band of a specific size and shape is cut into a single piece of shaped embryonic strips accurately stacked on the back, and fed into a laminating laminator (called LM) for lamination operation. Produce a sputum-type raw germ substrate (referred to as Gs) (which can be electrolyte or electrode type), and measure the characteristics of the raw germ substrate for program adjustment; (2) Electrode or electrolyte ceramic substrate fabrication procedure j. Will be the raw substrate of 1 v Wei, It is placed in a metal mold of the same size and sent to a vacuum hot pressing sintering system (VHPS for vacuum) (less than ixi().3t嶋) cold pressing or hot pressing (temperature < 5001, pressure can reach the core of the core Modulation)) Processing 'Develop a high-density green embryo substrate (referred to as Brain 3) and measure and record its density with her ^; GS's high integration of appearance and structure, can be further laminated by LM machine, planted with L1V [Interacting with the VHPS system to enhance the bio-matter substrate ((8) Program • 'Innovative compound efficiency program (AN〇vd do ah p_ss)), this. The most in the order is for the plant-level lining "Newcomb substrate". 1. The HIGS is fixed on the Wei-Taoman substrate with a natural sandwich (sandwich), 25 1326933 placed on the alumina as a thick plate. High-temperature furnace (temperature can be as high as 1700. The two-stage cycle program is used for sintering, the first cycle of calcination is to remove all organic additives and pore-forming agent, and the second cycle of sintering is to increase the density of the ceramic substrate, effectively producing the same & pottery substrate 'This step product is called HICS (High Integrity Ceramic Substrate); m. HICS screen printing, Sputtering Coating, Spin coating or plasma spraying (phsma plus Argument) and other equipment procedures, coating the electrolyte layer (if HICS is the anode ceramic substrate) or electric ring layer (if HICS is the electrolyte Tao competition substrate), and then placed in a high temperature furnace to perform the sintering process 'to produce SOFC-MEA Half of the battery (10) f CeU), called HC; η, HC half-cell, with screen printing / sputter / spin coating / plasma spray / slurry spray (Slurry Spray) film production technology, on the electrolyte layer A cathode layer such as lsm or LSCF is placed in a high-temperature furnace to perform a sintering process to obtain a "highly integrated solid oxide fuel cell membrane electrode assembly element (unit cell)) (SOFC-MEA (UnitCell)). The method for fabricating a membrane electrode assembly (S〇FC·leg) of a highly integrated solid oxide material battery according to the scope of the patent application, wherein the step of preparing the purple liquid solution of the electrode substrate raw embryo and the preparation procedure thereof The electrode/electrolyte substrate established by a is made of the product. The remaining order is as shown in Table-riding. The value of (8)v can be as shown in the table - but not limited to this value. The weight of the intestine accounts for Ni〇+ mz仏 26 2626933 Wt% 0 3. The method for fabricating a membrane electrode assembly (S0FC_MEA) of a highly integrated solid oxide fuel cell according to the scope of the patent application, wherein the electrode substrate is prepared into a slurry formulation and a preparation procedure thereof, and the steps thereof b The first ball milling time is 24~168 hours. 'The average particle size of the powder after grinding is 300~500nm. 〇4. According to the application, the high-integration _ oxide fuel cell membrane electrode assembly (SOTOMEA) is produced. square The towel electrode substrate is made into a slurry formulation and a preparation procedure thereof, and the high temperature co-firing temperature and time of the step c is 1200~16G (TC: with 2~8+) and the secondary ball grinding is intertwined and ground. The average target of the powder target is more than 24 hours and the period ~10 (10), and the addition of the ship type is a fine (Nuwei Weiwei) graphite powder, which is used to determine the porosity of the molded substrate in the future. 5. According to the method of applying the high-integration and oxide fuel cell membrane electrode assembly (SOFC) according to the application of the article, the electrode substrate and the slurry formulation and the preparation procedure thereof are The ball milling time of step d is more than one hour. 6. According to the application of the product of the high-integrated tantalum oxide fuel cell, the product of the high-integrated tantalum oxide fuel cell (9) FC iron), the T-square of the towel silk plate raw embryo production and its production procedure, the step e The third ball mill was ground for more than 48 hours. 7. According to the application, the method of making a highly integrated oxide fuel electrode 27 1326933 pool membrane electrode assembly (SOFC-MEA) is adopted, wherein the electrode substrate raw pulp preparation slurry formula and the preparation procedure thereof are the steps f The four ball milling time is 48 to 72 hours. & a method for fabricating a membrane electrode assembly (SOTC-MEA) of a highly integrated solid oxide fuel cell according to the scope of claim 1 of the patent application, wherein the electrode substrate is prepared into a slurry formulation and a preparation procedure thereof, and the step g is ideal f—The substrate liquid viscosity is between 150 and 1500 CP. 9. A method for producing a membrane electrode assembly (SOFC-MEA) of a high-integration solid oxide fuel 胄 池 ike according to the scope of claim 1, wherein the electrode substrate is prepared by using a slurry preparation method and a preparation procedure thereof, wherein the step The raw embryo tape product specification is between 18 and 30 cm, and the thickness is between 1 〇 and 3 〇〇 μιη. Η). A method for fabricating a membrane electrode assembly (SOFC-MEA) of a highly integrated solid oxide fuel cell according to the scope of claim 1 of the patent application, wherein the electrode substrate is used to prepare a poly liquid formulation and a preparation procedure thereof. The embryonic band shape is round or square, and the size is 5x5cm2~15x15 ^ 'Laminating machine operating temperature and pressure system φ 5〇~0: and 2_~5000 Psi' thickness of the molded raw embryonic substrate 600~1200μιη. η. The method for fabricating a membrane electrode assembly (SOFC-MEA) of a highly integrated solid oxide fuel cell according to the application of the patent item i, wherein the electrode or the electrolyte is in the process of making a substrate, the vacuum hot pressing of the step j Sintering system operating temperature and pressure system < 50 (TC and L68xH) 5 psi vacuum degree i 〇χΐ〇 · 3ι_, can also be 28 1326.933. Room pressure operation. .12. According to the method of the patent scope, the method for producing a highly integrated _ oxide fuel cell membrane electrode tilting (SQFC_MEA), the step of the step of the substrate The secondary lamination operation can be performed, but not limited to, a certain number of times. 13. According to the scope of the patent, please make a high-integration _ oxide fuel cell membrane electrode assembly (SOTOMEA) financial method, its electric discharge electrolyte Tao * * substrate production process, this step ,, the first - Cycle sintering procedure, warming program: room temperature today 20 (TC (4 hrs) ~> 45 (TC (2hrs) +75 (TC (21JS) + 125G ° C (6hrs) + room temperature, second cycle Sintering procedure, temperature control program: room temperature +1400 ° C (4 hrs) + room temperature, the temperature rise and fall rate of the two-stage sintering temperature cycle is l ° C / min ' but less than 3 ° (: / η ηη is preferred. R. The method for producing a membrane electrode assembly (SOFC-MEA) of a highly integrated solid oxide fuel cell according to the scope of the patent application 帛1, wherein the electrode or the electrolyte is used in the preparation process, the electrolyte layer in the step m Department 1〇μηι, its product sintering temperature control program: room temperature 14 〇 (TC / 4hrS room temperature, temperature rise and fall rate is l ° C / min, but preferably below 3 ° C / min. A method for fabricating a membrane electrode assembly (SOFC-MEA) of a highly integrated solid oxide fuel cell according to the first aspect of the patent application, wherein the electrode In the preparation process of the electrolyte ceramic substrate, in the step η, the thickness of the cathode layer material is LSM/LSCF and 30 to 50 μm, and the product temperature control program of the product is swarf to temperature 29 1326933 • > 1200 ° C / 3 hrs + room Temperature, the temperature rise and fall rate is l ° C / min, but preferably below 3 ° C / min. 30 1326933 T-06 ® disk is also tested for temperature: oo~socrc You are ϋ": 10013⁄4 Hz 200cc/mm Gasification gas: i[)W 〇2 200cc/mm Electric area: 7cm2 1000 § 800 E 600 400 Jp800 jV-800(_ jP-80〇(' jV-750(' JP-750C jV-70〇r jP-70〇r jv800 40 {2UJU/I Xin S ο ο ο ο 3 2 400 800 1200 Current Density ( mA/cm^ 1600 tenth figure 200