Process for separating electrode for membrane-electrode assembly of fuel cell and apparatus therefor
10749197 ยท 2020-08-18
Assignee
- Hyundai Motor Company (Seoul, KR)
- Kia Motors Corporation (Seoul, KR)
- Korea Advanced Institute Of Science And Technology (Daejeon, KR)
Inventors
- Bo Ki Hong (Seoul, KR)
- Byeong-Heon Jeong (Gyeonggi-do, KR)
- Taek-Soo KIM (Daejeon, KR)
- Jae-Han KIM (Daejeon, KR)
- Sanwi Kim (Gyeonggi-Do, KR)
Cpc classification
H01M4/8875
ELECTRICITY
Y02E60/50
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
H01M2250/20
ELECTRICITY
Y02T90/40
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
Abstract
Disclosed are a process for separating an electrode for membrane-electrode assemblies of fuel cells from the decal transfer film and an apparatus for separating the electrode. In particular, during the electrode separating process, only an electrode is separated from the decal transfer film on which the electrode is coated, without any damage, by a freezing method for freezing the specimen on the deionized water surface, and thus, wasting the expensive MEA is prevented. Thus, mechanical properties of the pristine electrode can be rapidly quantified in advance, and therefore, long term durability evaluation period during developing MEA having excellent durability is substantially reduced.
Claims
1. An apparatus for separating an electrode from a decal transfer film for membrane electrode assemblies (MEAs) of fuel cells, comprising: an electrode specimen which is formed by coating an electrode on a decal transfer film; a specimen tester comprising deionized water; a freezing device for freezing the deionized water in a state that the electrode specimen is soaked on the deionized water surface; and a thawing device that thaws the frozen deionized water by heating thereof, wherein the freezing device and the thawing device are incorporated in the same unit which is a freezing/thawing unit, and the electrode specimen floats on a surface of the deionized water.
2. The apparatus of claim 1 further comprising a film-removing device that removes the decal transfer film from the frozen electrode specimen.
3. The apparatus of claim 1, wherein the thawing device is configured to remove bubbles by boiling the deionized water through heating the deionized water before freezing the deionized water, and to thaw the frozen deionized water after freezing the deionized water.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The above and other features of the present invention will now be described in detail with reference to exemplary embodiments thereof illustrating the accompanying drawings which are given herein below by way of illustration only, and thus are not limitative of the present invention, and wherein:
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(10) It should be understood that the appended drawings are not necessarily to scale, presenting a somewhat simplified representation of various preferred features of the present invention as disclosed herein, including, for example, specific dimensions, orientations, locations, and shapes will be determined in part by the particular intended application and use environment.
(11) In the figures, reference numbers refer to the same or equivalent parts of the present invention throughout the several figures of the drawing.
DETAILED DESCRIPTION OF THE INVENTION
(12) Hereinafter reference will now be made in detail to various embodiments of the present invention, examples of which are illustrated in the accompanying drawings and described below. While the invention will be described in conjunction with exemplary embodiments, it will be understood that the present description is not intended to limit the invention to those exemplary embodiments. On the contrary, the invention is intended to cover the exemplary embodiments as well as various alternatives, modifications, equivalents and other embodiments; which may be included within the spirit and scope of the invention as defined by the appended claims.
(13) It is understood that the term vehicle or vehicular or other similar term as used herein is inclusive of motor vehicles in general such as passenger automobiles including sports utility vehicles (SUV), buses, trucks, various commercial vehicles, watercraft including a variety of boats and ships, aircraft, and the like, and includes hybrid vehicles, electric vehicles, plug-in hybrid electric vehicles, hydrogen-powered vehicles and other alternative fuel vehicles (e.g. fuels derived from resources other than petroleum). As referred to herein, a hybrid vehicle is a vehicle that has two or more sources of power, for example both gasoline-powered and electric-powered vehicles.
(14) The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms a, an and the are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms comprises and/or comprising, when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. As used herein, the term and/or includes any and all combinations of one or more of the associated listed items.
(15) Hereinafter, the present invention will be described in detail as various exemplary embodiments.
(16) Provided is a process and an apparatus for separating an electrode from the decal transfer film whose electrode is used for fuel cell MEA applications. In particular, only the electrode may be separated by floating the electrode coated on a decal transfer film on water, particularly on deionized water followed by freezing thereof. As such, the separated electrode may be used to quantify mechanical properties of the pristine electrode prior to being applied to fuel cell MEAs.
(17) According to exemplary embodiments of the present invention, only the electrode as a specimen for quantifying the mechanical properties thereof may be easily separated from the decal transfer film. The electrode specimen coated on the decal transfer film may be frozen on the surface of the deionized water, so as to make the interaction force between an ionomer in the electrode specimen and water molecule (the deionized water) greater than interaction force between the electrode and the decal transfer film. Since the pristine electrode may be easily separated from the decal transfer film without significant damage, the mechanical properties of the separated electrode may be quantified by direct measuring.
(18) The separation process of the electrode specimen may include a step of preparing the electrode specimen by coating an electrode onto the decal transfer film. The coated electrode may be a typically used material for fuel cell MEAs without limitation.
(19) For example, in the step of preparing the electrode specimen, an electrode specimen, in which an electrode is coated on a decal transfer film, may be manufactured by coating a catalyst ink onto the decal transfer film and by drying thereof. The catalyst ink may include a platinum catalyst supported on carbon (Pt/C), ionomer binder and solvent mixtures.
(20) Particularly, when the catalyst ink for the electrode specimen is manufactured, Pt/C catalyst which contains platinum in the amount from about 30 to about 50 wt % with respect to the total weight of a solid content of the Pt/C catalyst may be used. As used herein, the solid content of the Pt/C catalyst may be obtained by combining contents of the platinum and the carbon support. In other words, the platinum content in the Pt/C catalyst may be from about 30 to about 50 wt % with respect to the total weight of the solid content of the Pt/C catalyst (i.e. a sum of the platinum and the carbon support). Further, the amount of the ionomer binder in a solid phase electrode may be of about 20 to about 40 wt % with respect to the total weight of the solid content of the dried electrode. As used herein, the solid content of the dried electrode may be obtained by combining the Pt/C catalyst content and the ionomer binder content from the dried electrode. In other words, the ionomer content in the electrode may be from about 20 to about 40 wt % with respect to the total weight of the solid content of the dried electrode (i.e. a sum of the Pt/C catalyst and the ionomer binder). The ionomer binder may be, for example, used in the form of ionomer dispersion which contains the perfluorinated sulfonic acid (PFSA)-based Nafion ionomer in the amount from about 10 to about 30 wt % with respect to the total weight of the ionomer dispersion (i.e., a sum of ionomer binder and solvents in the dispersion). Moreover, the catalyst ink may be manufactured by mixing the Pt/C catalyst and the ionomer binder with solvent mixtures that may include deionized water and isopropyl alcohol, and by a stirring and sonicating thereof.
(21) The above catalyst ink may be coated on the decal transfer film and then fully dried to manufacture an electrode specimen. The platinum catalyst loading amount in the electrode formed on the decal transfer film may be from about 0.01 to about 1 mg-Pt/cm.sup.2, or particularly from about 0.05 to about 0.5 mg-Pt/cm.sup.2 after adjusting the amount of catalyst ink or coating thickness and drying the electrode specimen. If the catalyst loading is less than the predetermined amount, for example, less than about 0.01 mg-Pt/cm.sup.2, the electrode may not be evenly coated on the decal transfer film, and the electrode may be damaged or broken when separated. Meanwhile, when the catalyst loading is greater than the predetermined amount, for example, greater than about 1 mg-Pt/cm.sup.2, it may be economically disadvantageous.
(22) Accordingly, the platinum catalyst loading amount in the electrode may be from about 0.05 to about 0.4 mg-Pt/cm.sup.2, and the amount of the ionomer binder in the electrode may be of about 30 wt % with respect to the total weight of the solid content of the dried electrode when manufacturing the electrode specimen.
(23) The decal transfer film may be selected from the group consisting of polytetrafluoroethylene (PTFE), poly(ethylene terephthalate) (PET), poly(butylene terephthalate) (PBT), poly(trimethylene terephthalate) (PTT), poly(ethylene naphthalate) (PEN) and polyimide (PI), and those material may provide improved mechanical properties and excellent separability from an electrode when manufacturing an MEA by a hot press or a roll-lamination process. For example, the decal transfer film may be formed from poly(ethylene naphthalate) (PEN).
(24) The electrode specimen coated on the decal transfer film as described above may be soaked on the surface of water.
(25) Particularly, water used for soaking the specimen may be deionized water. When a general tap water used, the electrode may be damaged or broken and partly separated when separating, since impurities such as ions (mostly cations) in the tap water may weaken the interaction force between the water molecule and the electrode. Thus, after water and electrode are thawed, the electrode may fail to maintain its original shape, and then be destroyed into pieces. Further, when ionized water such as salt water is used, the electrode may not be properly separated from the decal transfer film because the interaction between ionomer in electrode and the water molecules in the salt water can be weakened substantially due to the contamination of ionomer by Na.sup.+ cations present in the salt water. In contrast, when deionized water is used, the electrode may be separated from the decal transfer film much evenly and homogeneously, and the shape of the electrode may be well maintained without any significant damage or deformation even after frozen water melts completely. Therefore, in the present invention, unless otherwise indicated, water refers to the deionized water.
(26) The deionized water may have the resistivity of about 10 M cm or greater at a temperature of about 25 C. If the resistivity value of the deionized water is less than about 10 M cm, the ionization degree may increase thereby contaminating the electrode.
(27) Further, in particular, the electrode specimen may be soaked in the deionized water by facing the electrode of the electrode specimen down toward the water, and facing the decal transfer film up. In other words, when the electrode specimen is soaked on the surface of the water by floating thereof, the electrode specimen may be soaked to almost the same level with the water surface, but the electrode may be positioned toward the water and then frozen, so as to easily separate the electrode from the decal transfer film without significant damage or deformation of the electrode. Indeed, the physical interaction force between the water and the electrode may increase by freezing, and such physical interaction force may become greater than the interaction force between the electrode and the decal transfer film. On the other hand, when the decal transfer film is positioned toward the water surface, the physical interaction force between the decal transfer film and water may be negligible and less than the interaction force between the decal transfer film and the electrode in the electrode specimen, such that the electrode may not be separated from the decal transfer film. In the soaking step of the electrode specimen on the water surface, when the electrode specimen is floated on the water surface, the water may be absorbed to the electrode.
(28) As mentioned above, after the electrode specimen is soaked in the deionized water, freezing step may be conducted. In the freezing step, a freezer (freezing device) may be used, and the proper amount of deionized water may be filled in the freezer (freezing device). Thus, freezing may be conducted by a general method known in the related arts without limitation. The freezing temperature may be the temperature enough to freeze the deionized water, i.e. subfreezing temperatures below 0 C., and the deionized water may be frozen for about 1 to about 6 hours, or particularly for about 2 to about 6 hours. When the decal transfer film is separated before the freezing is complete, the separation may fail.
(29) In particular, before the freezing step, a step of removing bubbles from the water, i.e., deionized water, may be additionally conducted.
(30) The bubbles or gases may be removed from the water by boiling the water. When the freezing is conducted after boiling the water, bubbles present in the water may be readily removed, and thus, the interaction force between the water and the electrode in the electrode specimen may be evenly and substantially maintained. Accordingly, damage of the electrode during the electrode separation process may be prevented. When the bubble-removing step is not conducted, substantial amount of bubbles may be contained in the water, thus the partial breakage or damage of the electrode may increase during the electrode separation process.
(31) After finishing up the freezing step, a step of removing the decal transfer film from the electrode specimen fixed on the frozen ice may be conducted.
(32) The decal transfer film may be removed by peeling off from the electrode specimen which is frozen in the deionized water. As such, the electrode may be easily separated by separating only the decal transfer film from the electrode specimen without electrode damage. For example, the electrode may be separated by hands, or if necessary, the decal transfer film also may be effectively removed by using a mechanical film detachment means or device.
(33) After removing the decal transfer film from the frozen electrode specimen, a step of separating only the electrode by thawing the frozen deionized water may be conducted.
(34) Since the decal transfer film is already removed from the electrode specimen and the frozen water is thawed, only the separated electrode may remain and float on the thawed water. Thus, the separated electrode may be preserved without any damage. Thawing may be conducted slowly, and may be conducted by using a common heating device without limitation. When the ice is thawed, only the electrode may be floated on the water as being separated from the decal transfer film, and thus the electrode may be easily kept as it is on the water surface. Accordingly, the separated electrode floating on water may be readily used as a specimen for measuring mechanical properties of the electrode and the like.
(35) According to various exemplary embodiments of the present invention, the electrode may be separated from the decal transfer film by using the separation method, the electrode separation may be easier and faster than the conventional electrode separation methods, and the quantification of mechanical properties of the electrode may be conducted economically and efficiently without any significant damage of the electrode. As discussed above, the decal transfer film may be removed from the electrode by freezing the electrode coated on the decal transfer film on the water surface, so as to make the interaction force between the ionomer in the electrode and the water greater than that between the electrode and the decal transfer film, and after the water is thawed, only the electrode floated on the water surface may be easily separated.
(36) Further, provided is an apparatus for separating an electrode which is suitable for using the above described electrode separation method. The electrode used in an MEA for fuel cell vehicles may contain a Pt/C catalyst and an ionomer binder, as generally used in the related arts. The ionomer binder used in the present invention may be perfluorinated sulfonic acid-based, and the ionomer having this molecular structure may form substantial interaction with liquid water as described by K. Jiao and X. Liin Progress in Energy and Combustion Science, 37, 221 (2011); and by E. L. Thompson, T. W. Capehart, T. J. Fuller, and J. Jorne, in J. Electrochem. Soc., 153, A2351 (2006)), entire contents of which are incorporated herein. Further, the electrode may have a porous structure, and therefore, when the electrode is directly in contact with the liquid water, the pores in the electrode may be filled with the water, and the water may be substantially bound to the ionomer binder. Accordingly, when the electrode directly in contact with the liquid water is frozen at the subfreezing temperature below 0 C. or freezing temperature thereof, the electrode and the water may bind strongly. At this time, the deionized water may be used for this separation process, since the electrode may be well separated from the decal transfer film when the interaction force between the electrode and the water becomes greater than that between the electrode and the decal transfer film. The interaction force between the electrode and deionized water may be made by the strong bonding formed between the sulfonic acid group in the ionomer and water molecule.
(37) As such, but not specifically bound to the theory, a process for independently separating an electrode from a decal transfer film by freezing water and an apparatus thereof may provide solutions to the problems associated with the related arts.
(38) An electrode separation apparatus for applying the electrode separation process according to the present invention will be described as an embodiment. As shown in
(39) The specimen tester may be used for separating the electrode frozen on the deionized water surface and may be any of glass, metal, plastic materials and the like. For example, a conventional petri dish may be used as the specimen tester. When the electrode-separating device by freezing is used, the electrode may contact the surface of the water (EOWS: Electrode On Water Surface), however a method of contacting the decal transfer film toward the water surface (FOWS: Film On Water Surface) should not be used, since the EOWS method may maintain the interaction force between the water and the electrode strong.
(40) After freezing, only the decal transfer film may be removed by peeling off from the electrode specimen frozen on the water surface, and the decal transfer film may be removed by using hands or tweezers. Further, the electrode separation apparatus may additionally have a film-removing means for safely removing of the decal transfer film. This film-removing means may have for example, a blade for detaching the decal transfer film without electrode damage.
(41) The freezing/thawing unit may further include a thawing device for thawing ice after the water is frozen. The thawing device may be constructed to raise temperature, and if necessary, it may be constructed to increase the temperature to boil the water before freezing. The thawing device may be used for boiling water by heating the water before freezing, and particularly, be also used for thawing the frozen ice after freezing. Further, freezing/thawing unit the also may be constructed to have both of the freezing and the heating devices.
(42) Accordingly, after removing the decal transfer film from the electrode specimen frozen in the freezing device only the electrode may remain on the frozen ice, and then the frozen ice may be thawed by using the thawing device, leaving only the separated electrode floating on the thawed water surface.
(43) The separated electrode may be applied to measure tensile properties of the electrode as being floated on the water, without taking the electrode from the water separately. For example, a dish containing the separated electrode may be transferred to a tensile tester, and the tensile properties of the electrode may be immediately measured as the electrode is floating on the water. As such, the electrode separation method and the separation apparatus according to the present invention may provide efficient way for measuring the mechanical properties of the electrode in a quantitative manner, without significant damage of the electrode.
(44) Accordingly, according to various exemplary embodiments of the present invention, a pristine electrode to be used for fuel cell MEAs may be easily separated from the decal transfer film on which the electrode is coated. By separating the pristine electrode from the decal transfer film but not from an MEA, an expensive MEA may not be destroyed or sated by separate the electrode directly from the MEA. Mechanical properties of the electrode may be rapidly quantified in advance, and therefore, long term durability evaluation period during developing MEA having improved durability may be substantially reduced.
(45) The following examples illustrate the invention and are not intended to limit the same.
(46) Example and Comparative Example
(47) A method for manufacturing an electrode sample coated on a decal transfer film is as follows.
(48) General
(49) A catalyst ink including a platinum catalyst supported on carbon (Pt/C), an ionomer binder, a solvent mixture and the like was prepared. The ionomer binder was used in the form of ionomer dispersion (Nafion D2021, DuPont, USA) which was composed of about 20 wt % of perfluorinated sulfonic acid (PFSA)-based Nafion ionomer with respect to the total weight of the ionomer dispersion (i.e., a sum of ionomer and solvents in the dispersion). An amount of about 70 wt % of Pt/C catalyst (HISPEC4000, 40 wt % Pt/C, Johnson Matthey, UK) with respect to the total weight of the solid content of the dried electrode was used as a catalyst. The Pt/C catalyst contains 40 wt % of platinum with respect to the total weight of a solid content of the Pt/C catalyst. The content of the ionomer binder in a solid phase electrode was adjusted to be about 30 wt % with respect to the total weight of the solid content of the dried electrode. Such Nafion ionomer binder and Pt/C catalyst were mixed together with a solvent mixture containing deionized water (Millipore Co., USA), isopropyl alcohol (Duksan Pure Chemicals, Korea) and the like as main ingredients, to obtain the catalyst ink, and then stirred in a mixer (WiseStir, Daihan Scientific Co., Korea) at room temperature for about 3 days. At this time, the catalyst ink was ultrasonicated total 8 times (based on 1 hour/time) using an ultrasonicator (3510E-DTH, Bransonic Ultrasonics Cor., USA) while stirring. After mixing was completed, the mixed catalyst ink was coated on a decal transfer film using a bar coater, and then fully dried in a dryer at a temperature of about 80 C. for about 2 hours. The amount of the catalyst ink and thickness were adjusted to make the Pt catalyst loading in the electrode coated on the decal transfer film to be of about 0.05 to 0.4 mg-Pt/cm.sup.2. At this time, a variety of polymer films such as polytetrafluoroethylene (PTFE), poly(ethylene terephthalate) (PET), poly(butylene terephthalate) (PBT), poly(trimethylene terephthalate) (PTT), poly(ethylene naphthalate) (PEN), polyimide (PI) and the like, which have excellent mechanical properties and excellent separability from an electrode when manufacturing an MEA by a hot press or a roll-lamination process, may be used as the decal transfer film, and in the present invention. For example, the PEN film was used.
(50) Example and Comparative Examples
(51) The electrode coated on the decal transfer film as described above was used as a specimen of Example and Comparative Example.
(52) Deionized water used for freezing the electrode may have resistivity of at least of about 10 M cm to maintain its purity, and herein, only deionized water having the resistivity of about 18 M cm or greater when freezing the electrode was used. Further, in order to remove bubbles which may disturb freezing and separation of the electrode in the deionized water, the deionized water was fully boiled at a temperature of boiling point or higher in advance, and then cooled down to room temperature, before using. When freezing the electrode on water surface, all the tests were conducted at a temperature of about 6 C., and the freezing time was maintained for at least about 2 hours.
(53) Effects of the differences in the contacting components (electrode vs. decal transfer film) on the deionized water surface on the electrode separation are shown in
(54)
(55) On the other hand,
(56) Effects of water type on the separation of the electrode are shown in
(57) Further, the effects of platinum catalyst loading on the separation of the electrode are illustrated in
(58) The effects of boiling of the deionized water on the separation of the electrode are shown in
(59) As a Comparative Example,
(60) As a Comparative Example,
(61) The detailed test results of Example and Comparative Example are summarized and listed in the following Table 1.
(62) TABLE-US-00001 TABLE 1 Electrode Pt Specimen Boiling Freezing Electrode Separating Loading Fixing Water Water Time Separation Classification Method (mg/cm.sup.2) Method Type or Not (hr) State Example1 Freezing 0.4 EOWS Deionized Yes 6 Method Water Example 2 Freezing 0.4 EOWS Deionized No 6 Method Water Example 3 Freezing 0.4 EOWS Deionized Yes 4 Method Water Example 4 Freezing 0.2 EOWS Deionized Yes 6 Method Water Example 5 Freezing 0.1 EOWS Deionized Yes 6 Method Water Example 6 Freezing 0.05 EOWS Deionized Yes 6 Method Water Comparative Hand 0.4 XX Example 1 Separation Comparative Copper 0.4 X Example 2 Plate Comparative Freezing 0.4 FOWS Deionized Yes 6 XX Example 3 Method Water Comparative Freezing 0.4 EOWS Tap Yes 6 XX Example 4 Method Water Comparative Freezing 0.4 EOWS Salt Yes 6 XX Example 5 Method Water
(63) In the results of electrode separation state shown in the above Table 1, the marks refers : very excellent, : excellent, x: partial damage, xx: complete damage or separation impossible, respectively. These are comprehensively evaluated results after each test was repeated several times.
(64) The process for separating an electrode according to various exemplary embodiments of the present invention may easily separate the electrode from the decal transfer film for fuel cell MEAs, thereby enabling rapid and easy quantification of mechanical properties of the electrode. Thus, long term durability evaluation period during developing MEA having excellent durability can be substantially reduced without breaking or wasting the expensive MEA.
(65) These techniques for separating an electrode and quantifying its mechanical properties described herein have never been tried before because an electrode was not separated without any damage or deformation. Accordingly, the present invention has an effect that the mechanical properties of the pristine electrode may be simply and economically quantified, compared to the conventional methods.
(66) The invention has been described in detail with reference to preferred embodiments thereof. However, it will be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.