Separator plate with periodic surface structures in the nanometer to micrometer range
12057608 ยท 2024-08-06
Assignee
Inventors
Cpc classification
B23K26/3584
PERFORMING OPERATIONS; TRANSPORTING
B23K2101/36
PERFORMING OPERATIONS; TRANSPORTING
Y02P70/50
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
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
H01M8/188
ELECTRICITY
International classification
Abstract
The present disclosure relates to a separator plate for an electrochemical system, wherein the separator plate has, at least in some regions, periodic surface structures with a mean spatial period of less than 10 ?m. The disclosure additionally relates to a method for producing a separator plate for an electrochemical system, comprising the steps: providing a separator plate; irradiating the separator plate by means of a pulsed laser, wherein a pulse duration of the laser pulses is less than 1 ns; and creating periodic surface structures on the separator plate by way of the laser radiation.
Claims
1. A separator plate for an electrochemical system, the separator plate comprising: a plurality of webs and channels formed between the webs; and at least in some regions, surface structures arranged periodically with a mean spatial period of less than 10 ?m, and the surface structures arranged on at least some sections of the webs and/or the surface structures arranged on at least some sections of rear webs, the rear webs formed on the surface of the separator plate opposite the channels.
2. The separator plate according to claim 1, wherein the surface structures comprise depressions which extend substantially parallel to one another.
3. The separator plate according to claim 2, wherein the depressions have: a depth of at least 8 nm and/or at most 0.5 ?m; and/or a width of at least 0.1 ?m and/or at most 2 ?m; and/or a period in one spatial direction of at least 0.3 ?m and/or at most 3 ?m.
4. The separator plate according to claim 1, wherein the separator plate is surface-treated by laser in the region of the surface structures.
5. The separator plate according to claim 1, wherein the surface structures are arranged periodically with respect to one another at least in one spatial direction.
6. The separator plate according to claim 1, wherein an oxygen content of a material of a surface of the separator plate is greater in the region of the surface structures than outside of the region of the surface structures.
7. The separator plate according to claim 1, wherein at least the regions provided with the surface structures are provided with a coating at least in some sections and the coating increases the electrical conductivity.
8. The separator plate according to claim 7, wherein the coating comprises one or more of the following substances or alloys thereof: electrically conductive oxides, carbon, electrically conductive carbon layers, noble metals, metals, metal nitrides, metal carbides, metal borides, metal silicides, and/or silicon carbide.
9. A bipolar plate comprising two separator plates according to claim 1, wherein the webs form a contact surface for bearing against a diffusion layer, and/or the rear webs form a contact surface for bearing against one another.
10. The bipolar plate according to claim 9, wherein an electrical resistance in the region of the contact surface between the webs and the gas diffusion layer and/or between the rear webs of the two separator plates is reduced by the surface structures.
11. The separator plate according to claim 1, wherein the surface structures reduce an electrical contact resistance of the separator plate.
12. The separator plate according to claim 1, wherein the separator plate does not have material bonds or welds within an electrochemically active region of the separator plate and the surface structures are arranged at a contact surface between the rear webs and another layer or plate of the electrochemical system.
Description
BRIEF DESCRIPTION OF THE FIGURES
(1) Exemplary embodiments of the separator plate, the bipolar plate and the electrochemical system are shown in the figures and will be explained in greater detail on the basis of the following description. In the figures:
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(25) Here and below, features which recur in different figures are denoted by the same or similar reference signs.
DETAILED DESCRIPTION
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(27) In alternative embodiments, the system 1 may also be configured as an electrolyser, electrochemical compressor or as a redox flow battery. Bipolar plates can also be used in these electrochemical systems. The structure of these bipolar plates may then correspond to the structure of the bipolar plates 2 explained in detail here, even though the media guided on or through the bipolar plates in the case of an electrolyser, in the case of an electrochemical compressor or in the case of a redox flow battery may differ from the media used for a fuel cell system. The same applies to the separator plates.
(28) The z-axis 7, together with an x-axis 8 and a y-axis 9, spans a right-handed Cartesian coordinate system. The bipolar plates 2 and separator plates 2a, 2b each define a plate plane, wherein the plate planes of the separator plates 2a, 2b are each oriented parallel to the x-y plane and thus perpendicular to the stacking direction or to the z-axis 7. The end plate 4 has a plurality of media ports 5, via which media can be supplied to the system 1 and via which media can be discharged from the system 1. These media that can be supplied to the system 1 and discharged from the system 1 may comprise for example fuels such as molecular hydrogen or methanol, reaction gases such as air or oxygen, reaction products such as water vapour or depleted fuels, or coolants such as water and/or glycol.
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(30) The single plates usually have through-openings, which are aligned with one another and form through-openings 11a-c of the bipolar plate 2. When a plurality of bipolar plates 2 are stacked, the through-openings 11a-c, 11a-c form media channels, which extend in the stacking direction 7 through the stack of the system 1 (see
(31) The first separator plates have, on the front side thereof facing towards the viewer of
(32) The structures of the active region 18 and the guide structures of the distribution region 20 and of the collection region 20 are each formed in one piece with the separator plates 2a and are integrally formed in the separator plates 2a, 2b, for example in a stamping, hydroforming or deep-drawing process. The same usually applies to the corresponding guide structures of the second separator plates 2b. The guide structures of the flow field 17 may comprise a plurality of webs 15 and optionally channels 16 formed between the webs 15 in the electrochemically active region 18, as well as a plurality of webs 35 and optionally channels 36 formed between the webs 35 in the distribution and collection region 20.
(33) Also shown in
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(35) A membrane composite 29 is arranged in each case between two adjacent bipolar plates 2 of the stack, each membrane composite having a membrane electrode 26 comprising an ionomer and at least one catalyst layer, gas diffusion layers 27 arranged on both sides of the membrane electrode 26, and reinforcing layers 28 arranged in some sections on both sides of the membrane electrode 26. The membrane electrode 26 and the reinforcing layers 28 together form the membrane electrode assembly (MEA) 10. Purely for the sake of clarity,
(36) In the region of the flow field 17, that is to say in the electrochemically active region 18 of the bipolar plates 2, the membrane composites 29 each comprise only the membrane electrode 26 and the gas diffusion layers 27 arranged on both sides of the membrane electrode. The membrane electrode 26 has a catalyst coating on both sides. In the region of the distribution or collection region 20, the membrane composites 29 each comprise only the two reinforcing layers 28, which are usually connected to one another. Only in the region corresponding to the transition region 21 of the separator plates 2 do each of the membrane composites 29 have a reinforced region 30, which in each case comprises the membrane electrode 26, the reinforcing layers 28 arranged on both sides of the membrane electrode 26, and the gas diffusion layers 27 arranged on both sides of the membrane electrode 26 and on both sides of the reinforcing layers 28. The reinforced region 30 of the membrane composite 29 typically forms an edge of the electrochemically active region of the membrane composite 29. Also in the transition region 21, the separator plates have webs 45 with channels 46 formed between the webs 45.
(37) The separator plates 2a, 2b usually contact one another in contact regions, which are formed by the rear sides of the depressions 16, 36, 46, and bear flat against one another there. To improve the electrical conductivity and/or to reduce the volume resistance in the active region 18 and optionally also in the transition region 21, the separator plates 2a, 2b are usually connected there by means of materially bonded connections, such as laser-welded joints 24. In the distribution region 20, on the other hand, laser-welded joints may be used to avoid local swelling of the channels, that is to say to clearly define the volumes available for the fluid flow. The laser-welded joints 24 are therefore provided for example in the flow field 17, in the electrochemically active region 18, in the transition region 21 and in the distribution region 20, or in the contact zones or contact regions thereof. In the x-direction for example (that is to say parallel to the cooling fluid flow direction), the welded joints 24 may form continuous welds or alternatively stitch welds, which each comprise a row of linear weld sections, for example spaced apart from one another.
(38) According to the present disclosure, the separator plate 2a, 2b has, at least in some regions, periodic surface structures 40 with a mean spatial period of less than 10 ?m. The surface structures 40 are thus arranged at periodic spacings. The periodic surface structures 40 are brought about on the surface of the separator plate 2a, 2b by irradiation by means of an ultra-short pulse laser. For example, one contiguous region or a number of contiguous regions of the separator plate 2a, 2b may have the periodic surface structures 40. The periodic surface structures 40 will be further explained below with reference to
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(40) The surface structures 40 may be present on one and/or both sides of the separator plate 2a, 2b, that is to say on the coolant side and/or on the reactant side/gas side.
(41) As can be seen from
(42) The surface structures 40 may extend for example in an undulating or linear manner along their longitudinal direction. One example of an undulating extension of the surface structures 40 is shown in
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(44) In
(45) Owing to the surface structures 40, the surface of the separator plate 2a, 2b has chemical, electrical and/or mechanical properties that differ from regions of the separator plate 2a, 2b with no surface structures 40. Due to the surface structures 40, for example, an oxygen content of the surface material of the separator plate 2a, 2b may be greater in the region of the periodic surface structures 40 than outside of the periodic surface structures 40.
(46) It has surprisingly been found that, despite the increased oxygen content, the electrical conductivity of the separator plate 2a, 2b in combination with a gas diffusion layer is greater in the region of the surface structures 40 than outside of the surface structures 40.
(47) The separator plate 2a, 2b may have at least one or more coatings. One such coating may be provided to increase the electrical conductivity and/or corrosion resistance of the separator plate 2a, 2b. The coating may take place across the entire surface. Alternatively, certain regions of the separator plate 2a, 2b are provided with a coating. In some embodiments, at least the regions that are provided with the periodic surface structures 40 are provided with the coating, for example with a coating that increases the electrical conductivity. The coating may be provided only in the region of the webs 15 and thus may be omitted in the region of the channels 16.
(48) The coating may for example contain one or more of the following substances or consist of one or more of said substances or alloys thereof: electrically conductive oxides, carbon, electrically conductive carbon layers, such as graphite, noble metals, such as Au, Ag or Pt, metals such as Ti or Cr, metal nitrides, for example TiN, CrN, Cr2N, metal carbides, metal borides, metal silicides and/or silicon carbide.
(49) A method for producing a separator plate for an electrochemical system will be disclosed below. The method is suitable for producing the separator plate 2a, 2b described above.
(50) The method is characterized by a laser treatment using a laser 100 shown in
(51) For embodiments of the method, a pulsed laser 100 is used, wherein each pulse has a pulse duration of less than 1 ns, less than 100 ps. The laser 100 may therefore be a picosecond laser (pulse duration shorter than 1 ns and greater than or equal to 1 ps) or a femtosecond laser (pulses shorter than 1 ps, shorter than 500 fs and/or greater than or equal to 30 fs). The laser 100 may generate linearly polarized laser radiation. A beam diameter or a smallest lateral size of the laser parallel to the surface of the separator plate 2a, 2b may be for example at least 20 ?m and/or at most 2 mm, in the example shown approximately 60 ?m. The wavelength ?, generated by the laser 100 is for example between 200 nm and 2000 nm, or between 400 nm and 1500 nm. Customary wavelengths are for example 700 to 1000 nm corresponding to a Ti:sapphire laser system; 1064 nm (fundamental wavelength) or 532 nm, 355 nm or 266 nm (frequency multiplication) corresponding to an Nd:YAG laser system. A fluence of the laser should be selected as a function of the material of the separator plate 2a, 2b and may be for example at least 0.1 and/or at most 10.0 J/cm2. The repetition rate of the laser may be for example at least 10 Hz, at least 1 kHz and/or at most 1000 kHz, or at most 20 kHz.
(52) Hoehm 2014 includes a detailed description of the interaction of laser radiation with material to create periodic surface structures 40, with advantageous combinations of laser parameters also being published in Hoehm 2014. For this reason, there is no need for a further description here.
(53) The method comprises at least the following steps: providing a separator plate 2a, 2b, irradiating the separator plate 2a, 2b by means of the pulsed laser 100, creating periodic surface structures 40 on the separator plate 2a, 2b by way of the laser radiation.
(54) For example, if only the region of the webs 16 or of the rear webs 19 is being treated, the laser beam may be guided parallel to the web direction or perpendicular to the web direction, or also at an angle differing therefrom. For example, when performing a laser surface treatment on the rear webs 19 of two separator plates 2a, 2b that are to be joined to form a bipolar plate 2, the laser may be guided for example in an identical, opposite or perpendicular manner in each case.
(55) The creation of said plurality of periodic surface structures 40 is already complete before the next laser pulse hits the surface of the separator plate 2a, 2b. For example, at least 10 or at least 20 surface structures, for example trench structures, may be created per laser pulse. The surface structures 40 are typically oriented perpendicular to the linear polarization direction of the incident laser radiation. The laser 100 may thus be directed onto a surface of the separator plate 2a, 2b in such a way that surface structures 40 that have a desired orientation are created. This applies for example to the core regions of the irradiated area. When the laser pulse hits the surface of the separator plate 2a, 2b, the incident laser radiation interferes with an electromagnetic surface wave in the surface material of the separator plate 2a, 2b that is generated by the laser pulse. The periodic surface structures 40 are formed as a result of this interaction.
(56) A mean spatial period Px of the surface structures 40 usually depends on the wavelength ? of the laser 100. For metals (metal sheet, stainless-steel sheet), the period P is approximately in the order of magnitude of the wavelength ?. By way of example, the mean spatial period P of the surface structures 40 is at least 2%, at least 5%, at least 20% and/or at most 200%, or at most 120% of the laser wavelength used.
(57) A single laser beam is in principle sufficient to create the surface structures 40. This laser beam can then scan the surface of the separator plate 2a, 2b that is to be treated. In this case, said plurality of periodic surface structures is created by each individual laser pulse within a spatial projection of the laser radiation onto the separator plate. The method can be accelerated if an interference pattern or diffraction pattern is formed by at least two laser beams and the surface is scanned with the interference pattern to create the surface structures 40. To this end, a linearly polarized laser beam of the laser 100 may be split by way of the beam splitter 106. The two linearly polarized partial beams thereby produced are then used to form the interference pattern. The interference pattern of the laser beams that is used serves only to enlarge the scanned surface area and has no direct influence on the periodicity of adjacent surface structures 40. The spatial period of the surface structures 40 thus differs from the spatial period of the interference pattern or diffraction pattern and is usually significantly smaller, for example 10 times smaller. However, comparative measurements have shown that, by means of this surface structuring applied in an accelerated way, the volume resistance cannot be reduced to the same extent as when using just one single laser beam. As an alternative or in addition, a line-type laser can also be used, with the laser line thereof having a width of at least 20 ?m in some embodiments.
(58) In some embodiments, at least the webs 15 and/or the rear webs 19 of the separator plate 2a, 2b are irradiated with the laser 100, as a result of which the surface structures 40 are formed on the webs 15 and/or on the rear webs 19. In this case, the webs 15 and/or rear webs 19 and/or the electrochemically active region 18 of the flow field 17 may be formed either before the laser treatment or after the laser treatment. In other words, the necessary steps of shaping the flat stainless-steel sheet to form the separator plate 2a, 2b, such as deep drawing or stamping, take place before or after the irradiation by means of the laser 100.
(59) A coating may be applied to the separator plate 2a, 2b, for example in order to increase the electrical conductivity of the separator plate 2a, 2b. The coating may have a thickness of at least 10 nm and/or at most 100 ?m, or of at least 50 nm and/or at most 50 ?m. For possible materials of the coating, reference is made to the materials above. For example, it is advantageous if the coating is applied to the surface structures 40. Depending on the type of coating, different coating processes are conceivable. For instance, the coating may take place by means of PVD, CVD or PA-CVD. Less technically demanding methods for applying the coating to the separator plate 2a, 2b include for example spraying, brush plating, screen printing, roller printing, stencil printing or metering processes. The coating may contain a thermoplastic or thermosetting binder for applying the coating to the separator plate in liquid form. If the coating takes place across the entire surface, the coating may in some sections be removed in a next step. To this end, the laser 100 or alternatively another laser can be used, which is configured to remove material of the coating.
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(62) The bipolar plates 2 of the electrochemical systems 1 of
(63) For instance, it can be seen in the electrochemical system 1 of
(64) The surface structures 40 discussed in this document may lead to a significant reduction in the electrical contact resistance and/or to a significant increase in the electrical conductivity, for example on the contact surfaces of the outer sides 22 of the bipolar plate 2, that is to say on the webs 15. A comparison of
(65) Due to this improvement in the electrical conductivity, if the surface structuring 40 is present on the surfaces where the separator plates 2a, 2b contact one another, that is to say on the rear webs 19, the laser-welded sections 24 in the contact zones on the coolant side of the separator plates 2a, 2b can be omitted. In one embodiment, therefore, the bipolar plate 2 may be free of materially bonded connections, such as laser-welded joints, within the flow field 17 or within the electrochemically active region 18 and in said contact zones of the two separator plates 2a, 2b on the coolant side, where the surface structures 40 are arranged, cf.
(66) In the electrochemical system 1 of
(67) As already indicated above, the bipolar plates 2 of
(68) It can also be seen in
(69) The periodic surface structures 40 may in each case be configured differently on the inner side 23 and outer side 22 by using different laser parameters. Likewise, regions of different surface structures 40 may be present on one side 22, 23, due to different laser parameters.
(70) Further comparative measurements have been carried out to demonstrate the effect that the position of the periodic surface structures 40 on the bipolar plate 2 has on the volume resistance.
(71) For two compressed separator plates 2a, 2b with no surface treatment and with no welded joints in the contact region of the separator plates, a volume resistance of 161 mOhm cm2 was measured.
(72) For two compressed separator plates 2a, 2b with no surface treatment and with welded joints 24 in the form of stitch welds in the contact region of the separator plates 2a, 2b, a volume resistance of 121 mOhm cm2 was measured, cf. the separator plates 2a, 2b of
(73) For two compressed separator plates 2a, 2b with surface treatment in the form of periodic surface structures 40 on the outer side 22 and with welded joints 24 in the form of stitch welds in the contact region of the separator plates, a volume resistance of 5.3 mOhm cm2 was measured, cf. the separator plates 2a, 2b of
(74) For two compressed separator plates 2a, 2b with surface treatment in the form of periodic surface structures 40 both on the outer side 22 and on the inner side 23 and with no welded joints in the contact region of the separator plates 2a, 2b, a volume resistance of 4.8 mOhm cm2 was measured, cf. the separator plates 2a, 2b of
(75) Based on a geometrically different separator plate type and with separator plates manufactured from a different stainless-steel batch, the following volume resistances were measured under comparable conditions for pairs of separator plates compressed together with gas diffusion layers: 6.1 mOhm cm2 for a separator plate pair provided with an LSFL surface structuring across the entire surface on both surfaces of the active region, compared to 6.6 mOhm cm2 for a separator plate pair connected by stitch welds and provided with an LSFL surface structuring across the entire surface only on the outer surface of the active region. For a separator plate pair with no laser surface structuring and with no stitch welds, a volume resistance of 74 mOhm cm2 is measured under otherwise identical conditions.
(76) It can be deduced from this that the effect of the surface treatment on the inner side leads to similar, in some cases even better, resistance values than the stitch welds 24.
(77) It should be noted that the separator plates 2a, 2b and bipolar plates 2 shown in
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(79) It will be appreciated that the configurations and routines disclosed herein are exemplary in nature, and that these specific embodiments are not to be considered in a limiting sense, because numerous variations are possible. Moreover, unless explicitly stated to the contrary, the terms first, second, third, and the like are not intended to denote any order, position, quantity, or importance, but rather are used merely as labels to distinguish one element from another. The subject matter of the present disclosure includes all novel and non-obvious combinations and sub-combinations of the various systems and configurations, and other features, functions, and/or properties disclosed herein.
(80) As used herein, the term approximately or substantially is construed to mean plus or minus five percent of the range unless otherwise specified.
(81) The following claims particularly point out certain combinations and sub-combinations regarded as novel and non-obvious. These claims may refer to an element or a first element or the equivalent thereof. Such claims should be understood to include incorporation of one or more such elements, neither requiring nor excluding two or more such elements. Other combinations and sub-combinations of the disclosed features, functions, elements, and/or properties may be claimed through amendment of the present claims or through presentation of new claims in this or a related application. Such claims, whether broader, narrower, equal, or different in scope to the original claims, also are regarded as included within the subject matter of the present disclosure.
LIST OF REFERENCE SIGNS
(82) 1 electrochemical system 2 bipolar plate 2a separator plate 2b separator plate 3 end plate 4 end plate 5 media port 7 z-direction 8 x-direction 9 y-direction 10 membrane electrode assembly (MEA) 11a through-opening 11b through-opening 11c through-opening 15 webs 16 channels 17 flow field 18 active region 19 rear webs 20 distribution or collection region 21 transition region 22 outer side of the bipolar plate 23 inner side of the bipolar plate 24 laser-welded joints 25 coating 26 membrane electrode 27 gas diffusion layer 28 reinforcing layer 29 membrane composite 30 reinforced region 35 webs of the distribution or collection region 36 channels of the distribution or collection region 40 surface structures 42 depression 44 elevation 45 webs of the transition region 46 channels of the transition region 100 laser system 101 laser head 102 first mirror 103 second mirror 104 V2 plate 105 polarizer 106 beam splitter 107 cap 108 lens b width t depth l length Px period in x-direction Py period in y-direction