나노포러스구조를 구비하는 연료전지 촉매전극 제조방법 및 이에 의한 연료전지 촉매전극

In the present invention hereinafter with reference to the drawing to explain the preface is less than 1000. However the present invention refers to several different can be embodied in the form of, for example and not the confined within a the embodiment taught herein. The present invention is described in drawing and unambiguously account for when the dispensed portion that is independent, like part subjected to a similar drawing code is configured to receive through the entire specification.

The entire specification, any portion to other assistant "(connection, contact, coupled) connected" when, this "connected directly" as well as when, the other interposed therebetween intermediate comprises a unit when "indirectly connected". In addition any components that "comprising" when any portion, particularly the opposite substrate under the outside components without other components of the other number which is further switched to each other.

A term used in a particular embodiment to account for example specification only is used, the present invention intending to be define is endured. It is apparent that a single representation of the differently in order not providing language translators, comprising plurality of representation. In the specification, the term "comprising" or "having disclosed" specification of articles feature, number, step, operation, components, parts or specify a combination not present included, another aspect of one or more moveable number, step, operation, component, component or a combination of these is understood to presence of or additionally pre-times those possibility should not number.

For example products on the attached drawing of the present invention embodiment hereinafter detailed the on-sensors other.

First, cathode (cathode) comprising a fuel cell anode (anode) with membrane (Membrane) (20) child node catalyst layer nano gun [le[le] structure (10) forming a fuel cell catalyst electrode manufacturing method and it digs up, cow [tu[tu] catalyst layer described the on-sensors other.

Figure 1 shows a general outline of the present invention embodiment according to example child node catalyst layer membrane deposition also formed processes degrees and, for example according to Figure 2 of the present invention embodiment deposition chamber deposition at a mimetic process are disclosed.

To correspond, polymer electrolyte fuel cell (PEMFC) membrane (Membrane) (20) can be prepared.

Wherein, membrane (Membrane) (20) is a proton conducting big. Membrane (20) material is preferably a fluorine-based ionomer (Nafion) can be formed like a proton conducting how all of the materials can be used.

Second step, deposition chamber (100) due to the fact (20) can be fixed.

Third step, deposition chamber (100) can be made further.

Evacuation of process can be suitably performed using equipment which, thereof can require not necessarily form a complete vacuum.

Between the second and third steps, membrane (20) for evaporating a won (heat source) (30) is heat cutting desired locations having function of baffles (baffle) (40) can be provided.

Wherein, baffle (40) deposited particles (11) for movement of the plurality of it became other hole (hole) can be formed. At this time, the shape of the hole (hole) can be won or polygonal.

Baffle (baffle) (40) is, evaporation of deposition material when a semiconductor substrate on which a thermal energy is supplied by radiation or convection or conduction effectively transmitted through number billion, membrane (20) can be a low temperature of, membrane (20) can be minimize temperature increases occur in the surface.

The lamp material membrane (20) cooling unit (50) can be not cooled uniformly by, in this case child node catalyst layer (10) or it digs up, cow [tu[tu] catalyst layer generated can be non-uniform, a phenomenon baffle (40) prevented the launching the application disclosed.

In addition, the deposition particle (11) flow baffle (40) to number by the deposition chamber (100) and to minimize the depositing material deposited inner wall, the direction of movement of deposition material membrane (20) so as to be twisted when deposited.

The total hole area, baffle (40) of the whole area, 0. 70% hereinafter be a ratio of 1% or more. The total hole area of the baffle (40) the whole area 0. Is below 1%, the deposition particle (11) keep down and restrict the passage of the deposition efficiency are lower, the total hole area of the baffle (40) is greater than the whole area 70%, baffle (40) can be effect and thermal billion number.

Hole is, constant size can be formed, baffle (40) in a central portion of the inner space formed in the nozzle is so size changes gradually holds disapproval. In addition, hole is, constant and may be formed at regular intervals, so that the uniformity of deposition variation of different intervals along and disposed so as to be formed may be filled.

Baffle (40) is, at least one of two hereinafter 3 can be formed on the semiconductor substrate 1.

Baffle (40) has a thickness of, 0. 2 hereinafter 30 millimeter (mm) or more may be disclosed.

Baffle (40) has a thickness of, depending on the size of the hole or, in efficiency 0. 2 millimeter (mm) or more 30 millimeter (mm) hereinafter Cu2Se. Baffle (40) having a thickness of 0. 2 millimeter (mm) is below, baffle (40) the thermal billion number effect baffle (40) and may cause a decrease in the durability of, baffle (40) millimeter (mm) thickness of 30 greater than the, deposition particles (11) can be is considerably limited throughput.

The thickness in a range of, baffle (40) can be formed on the semiconductor substrate 3 at least one of the two 1 hereinafter, but several layers formed in the material is high efficiency number accepts the high thermal billion, billion number but the other layer is formed it is that expense material 670 is thermal energy, considering cost and efficiency can be selectively selecting material.

But, baffle (40) the plurality of layer in the form of the inner surface and each hole in a variety of divided, each divided area between deposition of nano-size particles (11) is deposited, deposition particles deposited in a hole (11) since the AC magnetic fields are, the deposition particle passing through hole (11) can be disturb a flow of. This phenomenon is baffle (40) is formed on the semiconductor substrate so that the at least one 4 when significant, baffle (40) is formed of two layer can be preferably 3 hereinafter.

Baffle (40) metal, alloy and ceramic material selected from the group consisting of one or more material can be formed.

Baffle (40) such that the number billion thermal energy at an elevated temperature, heat resistance material having low thermal conductivity and number bath 1308. Baffle (40) iron (Fe), titanium (Ti), molybdenum (Mo), cobalt (Co), nickel (Ni), tungsten (W), beryllium (Be), lead (Pb), tin (Sn), silicon (Si), chromium (Cr), zinc (Zn), copper (Cu), aluminum (Al) made of single metal and their alloy, or carbon steel, stainless steel, bronze, brass, beryllium - copper alloy, copper - aluminum alloy, cubic boron nitride (BN), aluminum oxide (Al₂ O₃ ) A high-refractive-alloy or oxide bath number can be disclosed. In addition, baffle (40) alumina, silicon nitride, silicon carbide, zirconia ceramic material such as their number bath using ceramic composite material can be disclosed.

Membrane (20) and an air baffle (40) and the distance between the, 0. 01 45 centimeter (cm) or more can be made hereinafter.

Membrane (20) and an air baffle (40) distance between, 0. 01 centimeter (cm) is below, membrane (20) and an air baffle (40) can be deposition process can be difficult to flag number description below, 45 centimeter (cm) is greater than, baffle (40) deposition material passed through the membrane (20) can be taken out of the chamber will not reach the vapor deposition can be lowered.

In this case, membrane (20) won pipe (30) between a plurality of baffle (40) be [e[e] it will do number are installed in the deposition process.

Membrane (20) won pipe (30) and the distance between the, 3 or more 100 centimeter (cm) hereinafter to be disclosed.

Membrane (20) for evaporating a won (30) distance between, 3 centimeter (cm) is below, membrane (20) number of magnets becoming a deposition efficiency are considerably reduced and, due to the high temperature child node catalyst layer (10) or it digs up, cow [tu[tu] catalyst layer portions can be difficult, the greater than 100 centimeter (cm), deposition efficiency are reduced levels of deposition thereof can not required.

Fourth step, vacuum deposition chamber (100) is in early pressure process gas into the process gas can.

Wherein, the pressure early, 0. 01 Torr or more implementation being 30 Torr hereinafter.

0 initial process pressure. 01 Torr is below, child node catalyst layer (10) formed in a dense or it digs up, cow [tu[tu] catalyst layerchild node catalyst layer (10) or there can be (pore) it digs up, in cow [tu[tu] catalyst layer pores is formed, is greater than 30 Torr, membrane (20) within a particle size and uniformity can be difficult to maintain. 30 Torr under the process pressure greater than the deposition particle (11) to the membrane (20) undergoing a collision too much until reaching's oldest.

Process gas can, and argon as inert gas (Ar), nitrogen (N₂ ), Helium (He), neon (Ne), krypton (Kr), xenon (Xe), radon (Rn) can be at least one selected gas. However, the deposition particle (11) on if not react with a limited gas does not.

Fifth step, membrane (20) can be set to a temperature of 50 °C hereinafter.

In this case, membrane (20) cooling unit (50) can be tightly secured. In this case membrane (20) can be kept at a constant temperature. In addition, the function for rotation, can be advantageously uniform deposition.

Order to enhance the membrane to nano gun [le[le] structure (20) to maintain a certain temperature of the need to flow tides. In the present invention membrane (20) -196 °C temperature of (liquid nitrogen vaporization point) or more can be isothermal holding temperature of 80 °C hereinafter. Membrane (20) than the temperature of -196 when disposed radially, with the use of helium or liquid received from the separate cooler to be used circular metal plate, membrane (20) when the temperature too high, so that energy of the deposited material reduced in more-than-necessary number under public affairs pores, particles and increases in size, nano in gun [le[le] structure operates simultaneously to be inside the pin is too dense. The preferably 50 °C hereinafter can be recommended to maintain isothermal. In addition, membrane (20) on, locally significantly if any temperature difference, membrane (20) is of a nano gun [le[le] structure local nonuniformity can occur, even if error positive temperature variation within that process inevitably on minus 5 °C manages, more preferably within plus minus 1 °C can be managing.

In an associate, deposition material (heat source) won evaporation container (30) forming a deposition temperature control can.

The deposition particle (11) is, platinum (Pt), palladium (Pd), cobalt (Co), gold (Au), is (Ag), copper (Cu), chromium (Cr), iron (Fe), manganese (Mn), nickel (Ni), titanium (Ti), zinc (Zn), lead (Pb), vanadium (V), aluminum (Al), molybdenum (Mo) be a selected from the group consisting of one or more metal particles.

In addition, the deposition particle (11) is, manganese (Mn), molybdenum (Mo), tungsten (W), tin (Sn), nickel (Ni), copper (Cu), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), cobalt (Co), zinc (Zn), is (Ag), gold (Au), platinum (Pt), iridium (Ir), ruthenium (Ru), lithium (Li), aluminum (Al), antimony (Sb), bismuth (Bi), magnesium (Mg), silicon (Si), indium (In), lead (Pb) and palladium (Pd) composed of oxide of the metal oxide particles of at least one selected from the group consisting be a.

The deposition particle (11) generation of, can be ten evaporation laws by sputtering or evaporation.

In seventh, an associate deposition particles produced in step (11) is anode direction membrane (20) child node catalyst layer surface (10) can be formed.

Wherein, anode direction membrane (20) child node catalyst layer surface (10) followed by a, child node catalyst layer (10) makes the duration of the process of the membrane surface it digs up, cow [tu[tu] catalyst layer cathode direction can be formed.

In child node catalyst layerseventh (10) during a it digs up, cow [tu[tu] catalyst layer or formed, deposition chamber (100) of process gas species, process pressure, membrane (20) temperature, membrane (20) won pipe (30) and the distance between the deposition particles (11) heating temperature of one or more deposition particles over time (11) varying the energy size, as a result child node catalyst layer (10) and it digs up, cow [tu[tu] catalyst layer in membrane (20) portion contiguous with uniform quality can be formed to have a relatively high density. (Hereinafter, child node catalyst layer (10) the density of the inner gradient the operating requirements, even it digs up, cow [tu[tu] catalyst layer can be force. And, child node catalyst layer (10) or in it digs up, cow [tu[tu] catalyst layer, membrane (20) for the portion of the adjacent inward direction and thickness direction, thereby forming in a thickness direction and vice versa are disclosed. Hereinafter, are the same.)

In the second process pressure seventh performed in time (gradually) progressively reducing or discretely (discretely), child node catalyst layer (10) within, child node catalyst layer relative density (10) can be reduced thickness thereby forming progressively or discretely. At this time, progressively (gradually) relative density (layer) without forming a reduction according to a separate layer continuously decreases from the components, discretely separate layer (layer) relative density (discretely) according reduction while form means that the can is reduced step by step.

Excitation relative density, child node catalyst layer (10) distribution density and, quantitative include bulk (bulk) density of child node catalyst layer contrast material (10) to a density of display can be. The description hereinafter are the same.

child node catalyst layer (10) in a direction in micro density, child node catalyst layer (10) child node catalyst layer in distribution density (10) thereby forming an thickness can be decrease. In this case, child node catalyst layer (10) in membrane (20) so that the free portion and closer nano gun [le[le] structure higher relative density, membrane (20) and child node catalyst layer (10) can be relatively enhance adhesion. And, child node catalyst layer (10) in membrane (20) distal from the lower portion of nano gun [le[le] structure and relative density, the child node catalyst layer (10) if most angle of relative density is lowest, child node catalyst layer (10) and an outer contact area can be maximize. The gate electrode is formed membrane (20) to child node catalyst layer (10) while stably with, child node catalyst layer (10) gas diffusion in can be widened.

child node catalyst layer (10) to implement uniform quality thickness thereby forming an decreasing density, deposition particles (11) progresses along and decreasing energy of deposition is necessary, in order along the same process pressure stepwise increasing over time can be required.

The deposition particle (11) of speed 0. 01 to 10 micrometers (micro m/min)/minutes implementation being.

The deposition particle (11) 0 deposition of speed. 01 micrometers/minutes (micro m/min) is below, too low productivity disadvantage which, is greater than 10 micrometers/minutes (micro m/min), which apply to the power input terminal of the renewable raw material for evaporating, so as nano gun [le[le] structure can be damaged.

Hereinafter, a fuel cell having an anode (anode) electrode substrate contained in the cathode (cathode) (60) child node catalyst layer nano gun [le[le] structure (10) forming a fuel cell catalyst electrode manufacturing method and it digs up, cow [tu[tu] catalyst layer described the on-sensors other.

Figure 3 shows a general outline of the present invention embodiment also that the catalyst layer is formed an electrode substrate according to example processes are disclosed.

To correspond, for polymer electrolyte fuel cell (PEMFC) electrode substrate (60) can be prepared.

Electrode substrate (60) includes a gas diffusion layer (gas diffusion layer: GDL) coated carbon paper or carbon cloth (carbon cloth) serves small layer activated carbon (carbon paper) can be means.

Second step, deposition chamber (100) to electrode substrate (60) can be fixed.

Third step, deposition chamber (100) can be made further.

Between the second and third steps, electrode substrate (60) evaporator for won (heat source) (30) is heat cutting desired locations having function of baffles (baffle) (40) can be provided.

Fourth step, vacuum deposition chamber (100) is in early pressure process gas into the process gas can.

Fifth step, electrode substrate (60) can be set to a temperature of 50 °C hereinafter.

In an associate, deposition material (heat source) won evaporation container (30) forming a deposition temperature control can.

In seventh, an associate deposition particles produced in step (11) is an electrode substrate for anode direction (60) child node catalyst layer surface (10) can be formed.

Wherein, an electrode substrate for anode direction (60) child node catalyst layer surface (10) followed by a, child node catalyst layer (10) makes an electrode substrate for the duration of the process the cathode direction (60) it digs up, cow [tu[tu] catalyst layer face can be formed.

In child node catalyst layerseventh (10) during a it digs up, cow [tu[tu] catalyst layer or formed, deposition chamber (100) of process gas species, process pressure, electrode substrate (60) temperature, electrode substrate (60) evaporator for won (30) and the distance between the deposition particles (11) heating temperature of one or more deposition particles over time (11) varying the energy size, as a result child node catalyst layer (10) and it digs up, cow [tu[tu] catalyst layer electrode substrate in (60) that is part adjacent uniform quality can be formed to have a relatively high density.

The operating requirements other than membrane (Membrane) (20) child node catalyst layer nano gun [le[le] structure (10) or it digs up, cow [tu[tu] catalyst layer electrode manufacturing method for forming fuel cell catalyst are the same document.

The first copper layer, of the present invention to explain relative to the electrode fuel cell catalyst less than 1000.

Fuel cell catalyst electrode child node catalyst layer (10) or it digs up, cow [tu[tu] catalyst layer, specific surface area (specific surface area) value 0. 1 to 600 m² Implementation being/g.

Specific surface area value 0. 1 m² /G is below, the too dense, such as thin film nanoporous 3 dimensional structure and high advantage disappears with disadvantage which, 600 m² Greater than the/g, ensuring stable binding between particles forming thin film nanoporous 3 dimensional structure is used, of forming porous layer can be endurance door number is generated.

child node catalyst layer (10) or it digs up, cow [tu[tu] catalyst layer, diameter 1. 0 to 100 nanometer (nm) in mesopores (mesopore) on diameter 0. 5 micrometers (micro m) or more (macropore) macropores can be simultaneously.

Of the present invention can be applied to a polymer electrolyte fuel cell (PEMFC) fuel cell catalyst electrode is.

Hereinafter, example embodiment based on the on-sensors other.

Example SEM Image according to Figure 4 of the present invention embodiment catalyst layer are disclosed.

[Embodiment example 1]

Palladium (Pd) deposition material selecting, [tyu[tyu] yarn of a Nafion membrane (20) from Milton. And, baffle (40) and membrane (20) and the distance between the 13. 2 cm is set to. In addition, according to the process pressure is 5Torr, process gas gas implanting argon (Ar), cooling (50) into a deposition temperature of 3 °C conducting. Deposition time is 120 minutes was. Said child node catalyst layer procedure such as (10) came into. Then, the same procedure it digs up, cow [tu[tu] catalyst layer weight percent.

As in Figure 4 the, said catalyst content such as deposition condition 1. 25 mg/cm² Have been measured, a uniform thickness distribution of nano gun [le[le] structure layer comprises three portions that were identified.

[Comparison example 1]

0. 1g (0. 1M) sodium hydroxide (NaOH) and 25 ml of ethylene glycol (Ethylene Glycol) agitating a solution is placed closes the number 1 yesterday. And, 0. 23g (0. 00084mol) palladium which is characterized hydrate {Pd (NO₃ )₂ , NH₂ O (n=2. 4)} and 25 ml of ethylene glycol (Ethylene Glycol) agitating solution number 2 is placed cap is generally attained. Then, 30 minutes agitating a solution number 1 number 2 solution is placed cap rounded number 3 solution yesterday. And, number 3 solution 0. 134g adding of carbon black, 160 °C temperature to the oligo, stirring time-gate 3. Then, a reference period number 3 solution heaters, number 3 solution 0. 1M sulfate (H₂ SO₄ ) Solution is placed, and pH3 acidic solution so as number 3, number 4 solution 24 time agitating yesterday. After this, number 4 into the ethanol solution been rapidly, centrifugal separator divides the cell beyond the periphery of the centrifuge (5000 rpm, 30 minutes) to, 40% Pd/C catalyst upon him. And, a Nafion membrane 2X2 cm (centimeter) 40% Pd/C catalyst obtained by applying a size comparison catalyst layer number 1 weight percent. The same procedure comparison catalyst layer number 1 number 2 comparison catalyst layer membrane surface not weight percent.

Figure 5 shows a variation example of the present invention embodiment which also current density according to cell voltage graph, Figure 6 of the present invention embodiment according to example current density graph indicating a change in the power mils are disclosed. 5 and also in Figure 6, and rectangular dot is displayed curve [embodiment example 1] on the top side by MEA prepared by the number associated with graph line and, being located at the side lower circular dot indicated by curve [comparison example 1] number associated with graph line MEA produced therewith are disclosed.

Current density and power density curve of Figure 6 current density - - cell voltage curve graph the graph of Figure 5, [embodiment example 1] and [comparison example 1] MEA prepared by the number by (Membrane and Electrode Assembly, membrane) by number for fuel cell test system (CNL Energy, Korea) for measuring MEA produced therewith have, using atmospheric air with hydrogen fuel cell, been operating in 80 °C.

As the 5 and also in Figure 6, [embodiment example 1] [comparison example 1] MEA prepared by the number by cell voltage of and power density and power density is high in comparison with his number by cell voltage of MEA produced therewith. The, [embodiment example 1] [comparison example 1] MEA prepared by the number by number by performance of T easy vector capable of better performance of MEA produced therewith.

In case that the description of the invention which is for example, of the present invention technical idea of the present invention is provided to a person with skill in the art or essential characteristics without changing other form may be understand easily outputted are disclosed. The exemplary embodiment described above are not limited to examples in all of which must not understood to 2000. For example, monolithic described embodiment in which the components may be dispersed, similarly dispersed described embodiment can be made of elements binding form.

The range of the present invention are represented by carry claim, claim meaning of the general outline of the form of the present invention evenly and items as well as some all changing or modified range should interpreted.