CN117222294A - Thin film thermocouple and preparation method thereof, single cell, electric pile and proton exchange membrane fuel cell - Google Patents
Thin film thermocouple and preparation method thereof, single cell, electric pile and proton exchange membrane fuel cell Download PDFInfo
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Abstract
The application relates to the technical field of proton exchange membrane fuel cells, in particular to a thin film thermocouple, a preparation method thereof, a single cell, a galvanic pile and a proton exchange membrane fuel cell. The thin film thermocouple comprises a basal layer, a functional layer and a protective film layer which are sequentially laminated; the functional layer comprises an A functional area and a B functional area; the A functional area comprises an A bonding pad, an A lead and an A node which are integrally connected; the B functional area comprises a B bonding pad, a B lead and a B node which are integrally connected; the node B is partially coated with the node A, and the partial coating is formed by electroplating; and the protective film layer is provided with an A through hole and a B through hole which are respectively used for exposing the A bonding pad and the B bonding pad. According to the application, the node B partially coats the node A in an electroplating manner and is integrally connected with the node A, so that the use of conductive adhesive is avoided, and the reliability of the film thermocouple can be ensured.
Description
Technical Field
The application relates to the technical field of proton exchange membrane fuel cells, in particular to a thin film thermocouple, a preparation method thereof, a single cell, a galvanic pile and a proton exchange membrane fuel cell.
Background
The proton exchange membrane fuel cell system (simply called as a fuel cell system) is a very efficient hydrogen energy conversion device, and under the action of an electrocatalyst, chemical energy contained in hydrogen and oxygen can be directly converted into electric energy, and a product is only water. The whole conversion process is a mild electrochemical reaction process, is not limited by thermodynamic Carnot cycle, and has a theoretical energy conversion efficiency as high as 87%. Has extremely wide application prospect in various fields such as aerospace, submarines, land transportation, fixed power stations and the like.
The proton exchange membrane fuel cell system is a complex system with multiple parameters of gas-water-electricity-heat-force strong coupling, and comprises a galvanic pile, a hydrogen subsystem, an air subsystem, a cooling subsystem and a load control subsystem. The galvanic pile is a core place where the electrochemical reaction occurs, and is generally composed of tens or even hundreds of single cells, and each single cell is composed of a membrane electrode and a frame. The hydrogen is oxidized at the anode side of the membrane electrode, and the oxygen is reduced at the cathode side of the membrane electrode, so that chemical energy in the hydrogen and the oxygen is directly converted into electric energy. The internal temperature of the stack has an important influence on the operating state, the power generation efficiency, the reliability and the stability of the stack. Under ideal conditions, the temperature inside the electric pile is uniformly distributed, the temperatures of different positions of the membrane electrode are uniformly distributed, and the power generation capacity and the working state of different positions are completely consistent, so that the method is very beneficial to the control of a fuel cell system, the service life of key materials, the reliability and the durability of the system.
However, under the actual operation condition of the fuel cell, due to factors such as uneven gas distribution, uneven water content distribution, and local catalyst activity difference in the membrane electrode surface, uneven temperature distribution in the cell stack and at different positions of the membrane electrode are caused, the temperature distribution changes severely on a time scale, the distribution is uneven on a space scale, the performance attenuation and even structural damage of key materials of the membrane electrode are easily caused, and the durability and the operation stability of the membrane electrode and the cell stack are seriously affected. Therefore, on-line real-time monitoring is required to be carried out on each single-chip temperature distribution in the electric pile, when the temperature value at a certain position in the electric pile exceeds a safe temperature range, the system can timely take corresponding fault treatment measures or adjust the whole machine operation control strategy, thereby ensuring the normal operation of the membrane electrode, the electric pile and the whole fuel cell system, protecting the fuel cell and improving the durability of the system.
The existing internal temperature distribution test technology of the fuel cell is a thin film thermocouple technology, and a plurality of thin film thermocouples are implanted at different positions of a fuel cell stack, so that the temperature at different positions in the stack is monitored in real time. The preparation method of the existing film thermocouple comprises magnetron sputtering, vacuum evaporation and electroplating.
The specific preparation scheme of the magnetron sputtering and vacuum evaporation method is as follows: in cooperation with a mask process, a layer of metal film A is firstly plated on a flat substrate, then a layer of metal film B is plated on the upper surface of the metal film A, and the metal film A and the metal film B are overlapped at one end and separated at the other end, as shown in figure 1. Then, a protective film is covered on the upper surface, and the rest positions are covered except for the pad A and the pad B.
The specific preparation scheme of the electroplating method (namely the conductive adhesive method) is as follows: firstly, adhering a layer of metal film A on a flat substrate, and then, patterning the metal film A into a desired shape by using an etching method; then, a layer of metal film B is electroplated at one end by combining a mask process; then coating conductive adhesive on the upper surface of the metal film B to obtain a component 1 for later use; likewise, a metal film B is adhered on a flat substrate, and then patterned into a desired shape by an etching method to obtain a component 2; and (3) folding the assembly 2 and attaching the assembly 1 to obtain the film thermocouple, wherein the specific flow is shown in fig. 2.
However, the conventional vacuum evaporation method or magnetron sputtering method is not suitable for mass production of the film thermocouple, on one hand, because the vacuum thermal evaporation and magnetron sputtering equipment is expensive and huge in volume, and meanwhile, a large amount of metal targets are needed, so that the production cost is extremely high; on the other hand, the vacuum thermal evaporation and magnetron sputtering equipment has a narrow coating cavity volume, and the substrate material which can be put in at one time is limited, so that the production efficiency is low. Meanwhile, the interior of the coating cavity of the vacuum evaporation and magnetron sputtering equipment is at high temperature (more than 180 ℃) and vacuum environment, which limits the selection of coating substrate materials, and many substrate materials suitable for fuel cells cannot withstand high temperature and vacuum environment.
The electroplating method has low cost and is suitable for mass production, however, conductive glue is needed to be used for electrically connecting metals in the thin film thermocouple prepared by the electroplating method. In the production process, the component 2 needs to be folded and covered on the upper surface of the component 1 before the conductive adhesive is dried and cured, which results in that the conductive adhesive cannot be completely dried and is packaged into two layers of substrate films, and the conductive adhesive contains a large amount of organic solvents. When the temperature test is carried out, the organic solvent in the conductive adhesive volatilizes into gas along with the temperature rise, the pressure rises, and the substrate films at two sides are broken or bubbles are formed, so that the electrical connection is poor in contact, and the reliability of the film thermocouple is seriously affected.
In view of this, the present application has been made.
Disclosure of Invention
The first object of the present application is to provide a thin film thermocouple, in which the node B is partially covered with the node a by electroplating, so that the reliability of the thin film thermocouple can be ensured. The problem of use conductive adhesive to connect two subassemblies to lead to the thin film thermocouple reliability low among the prior art is solved.
The second object of the present application is to provide a method for manufacturing a thin film thermocouple, which has high reliability and low cost, and can be mass-produced.
The third object of the present application is to provide a single cell using the thin film thermocouple, by monitoring the temperature distribution of each single cell, when the temperature value at a certain position is found to exceed the safe temperature range, corresponding fault treatment measures can be adopted or the operation control strategy of the whole machine can be adjusted in time, so that the normal operation of the whole machine is ensured.
A fourth object of the present application is to provide a galvanic pile, which can ensure the normal operation of the galvanic pile using a single cell having the thin film thermocouple.
A fifth object of the present application is to provide a proton exchange membrane fuel cell which has good stability and durability and long service life.
In order to achieve the above object of the present application, the following technical solutions are specifically adopted:
the application provides a film thermocouple, which comprises a basal layer, a functional layer and a protective film layer which are sequentially laminated;
wherein the functional layer comprises an A functional area and a B functional area; the A functional area comprises an A bonding pad, an A lead and an A node which are integrally connected; the B functional area comprises a B bonding pad, a B lead and a B node which are integrally connected;
wherein the node B partially coats the node A, and the partial coating is formed by electroplating;
and the protective film layer is provided with an A through hole and a B through hole which are respectively used for exposing the A bonding pad and the B bonding pad.
The application further provides a preparation method of the film thermocouple, which comprises the following steps:
attaching an A film on one surface of a substrate, and performing patterning treatment on the A film to form an A bonding pad, an A lead, an A node, a preset lead and a preset bonding pad which are integrally connected;
after the A bonding pad and the A lead are completely covered by a mask, electroplating B films on the top surfaces and the side surfaces of the A node, the preset lead and the preset bonding pad respectively to form a B node which is partially covered by the A node, a B lead which is partially covered by the preset lead and a B bonding pad which is partially covered by the preset bonding pad, wherein the B node is integrally connected with the B lead and the B bonding pad to obtain a functional layer;
after the mask is removed, attaching a protective film on the surface of the functional layer, enabling the position of an A through hole on the protective film to correspond to the A bonding pad, and enabling the position of a B through hole on the protective film to correspond to the B bonding pad, so as to obtain a device;
and after the device is turned over for 180 degrees, removing the substrate on the surfaces of the preset lead and the preset bonding pad and the exposed preset lead and the preset bonding pad to form a groove, and filling the groove with glue to obtain the thin film thermocouple.
The application also provides a single cell which comprises the thin film thermocouple.
The application further provides a galvanic pile comprising the single cell.
The application also provides a proton exchange membrane fuel cell which comprises the electric pile.
Compared with the prior art, the application has the beneficial effects that:
(1) According to the film thermocouple provided by the application, the node B is partially coated with the node A by adopting an electroplating mode, and the connection is completed by using the conductive adhesive, so that the reliability of the film thermocouple is ensured.
(2) The film thermocouple provided by the application realizes the integral connection of the node B and the node A in an electroplating mode, has low production cost and can realize mass production.
(3) The preparation method of the film thermocouple provided by the application adopts an electroplating process, has high mass production efficiency and low cost, and can be used for more diversifying the optional substrate materials. The problems that the traditional vacuum thermal evaporation and magnetron sputtering technology is expensive in equipment and high in target cost due to the high-temperature vacuum environment and the narrow coating space and is not suitable for large-scale mass production of film thermocouples can be avoided.
(4) The preparation method of the film thermocouple solves the problem that the traditional electroplating process needs to electrically connect two metals by using the conductive adhesive, and avoids the problems of poor contact of the two metals and poor reliability of the thermocouple caused by the fact that the substrate and the protective film are broken or bubbles are formed between the substrate and the protective film due to volatilization and overflow of the organic solvent in the conductive adhesive in the temperature measuring process of the thermocouple.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present application, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a conventional magnetron sputtering and vacuum evaporation method for preparing a thin film thermocouple;
FIG. 2 is a schematic diagram of a conventional electroplating method for preparing a thin film thermocouple;
FIG. 3 is a schematic diagram showing an exploded structure of the thin film thermocouple provided by the present application;
FIG. 4 is a schematic diagram of a method for preparing a thin film thermocouple according to the present application;
fig. 5 is a schematic view of a partial structure of a single cell according to the present application;
FIG. 6 shows the results of temperature rise tests of thermocouples prepared in example 1 and comparative example 1 provided by the present application.
Detailed Description
The technical solution of the present application will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present application, and are intended to be illustrative of the present application only and should not be construed as limiting the scope of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In a first aspect, the present application provides a thin film thermocouple, as shown in fig. 3, comprising a base layer, a functional layer and a protective film layer, which are sequentially stacked.
The material used for the substrate layer comprises any conventional substrate material commonly used in the field, and can also be selected according to actual testing environment.
The thickness of the substrate can be any conventional thickness, and can be selected according to actual test requirements.
In some embodiments, the fuel cell stack has a high temperature, high humidity, high acidity, and oxygen-containing electrochemical environment inside, and thus materials are selected that can withstand such environments.
Wherein the functional layer comprises an A functional area and a B functional area.
The A functional area comprises an A bonding pad, an A wire and an A node which are integrally connected.
The B function area comprises a B bonding pad, a B wire and a B node which are integrally connected.
The node B partially coats the node A, wherein the partial coating is realized by electroplating.
It will be appreciated that after plating, the node B is integrally connected (or electrically connected) to the node a.
In some embodiments, the partial cladding is node B cladding on the top and sides of node a.
In some specific embodiments, an a pad, an a wire, an a node, a preset wire and a preset pad which are integrally connected are formed by attaching an a film and patterning the a film, and then B films are respectively electroplated on top surfaces (i.e., upper surfaces) and side surfaces of the a node, the preset wire and the preset pad to obtain a B node which is partially coated with the a node, a B wire which is partially coated with the preset wire and a B pad which is partially coated with the preset pad. That is, the B film formed by electroplating includes a node B, a B wire and a B pad integrally connected. It is understood that, the a pad, the a wire and the a node form an a functional area; the B bonding pad, the B lead and the B node form a B functional area; the A functional area and the B functional area form a functional layer.
And the protective film layer is provided with an A through hole and a B through hole which are respectively used for exposing the A bonding pad and the B bonding pad.
Two bonding pad holes are formed in the protective film layer, when the temperature changes, different thermoelectric voltages are generated between the node A and the node B, and the test temperature value can be obtained through conversion by collecting the potential difference between the bonding pad A and the bonding pad B.
In order to solve the problem that in the prior art, the conductive adhesive is used for connecting two components so as to cause low reliability of the film thermocouple, the node B is partially coated with the node A by adopting an electroplating mode, the connection is completed by using the conductive adhesive, the problem that the organic solvent in the conductive adhesive volatilizes into gas along with the temperature rise, the pressure rise causes the rupture of the substrate films at two sides or the formation of bubbles so as to cause poor electrical connection contact is avoided, and the reliability of the film thermocouple is further ensured.
And the integrated connection of the node B and the node A is realized by adopting an electroplating mode, so that the production cost is low, the batch production can be realized, and the technical problems that the traditional vacuum evaporation method or the magnetron sputtering method is not suitable for the batch production of the film thermocouple, the production cost is high, the production efficiency is low, the selection of a film coating substrate material is limited and the like are solved.
It is understood that the materials of the a functional region and the B functional region may be any conventional or common materials in the art, such as metals, and the present application is not limited thereto.
The size, shape and material of the above-mentioned base layer, bonding pad, wire, node, protective film layer, etc. may be any conventional size, shape and material, and the application is not limited thereto.
In some embodiments, to achieve the performance of the thermocouple, the material of the a functional region and the B functional region are different.
In some specific embodiments, in order to further comprehensively consider the performance such as stability, reliability and sensitivity of the thin film thermocouple, the material of the functional layer is optimized, wherein the materials of the functional region a and the functional region B may be, for example, platinum-rhodium 30-platinum-rhodium 6, platinum-rhodium 10-platinum, nickel-chromium-nickel-silicon, nickel-chromium-nickel-copper, iron-copper-nickel, copper-nickel, etc., but not limited thereto, and other unshaped thermocouple materials may be used.
In some specific embodiments, in order to consider the response characteristics of the thin film thermocouple, the materials of the A functional area and the B functional area are in a thin film form, the thinner the thickness is, the better the flexibility is, and the smaller the heat capacity is, the better the dynamic response characteristics of the thermocouple for measuring temperature are.
In some embodiments, to further improve reliability and stability of the thin film thermocouple, the size of the a via is smaller than the size of the a pad, and the size of the B via is smaller than the size of the B pad.
In a second aspect, the present application provides a method for preparing the high-reliability thin film thermocouple, which is a back surface material reduction method, as shown in fig. 4, and specifically includes the following steps:
attaching an A film on one surface of a substrate (namely a basal layer), and carrying out patterning treatment on the A film to form an A bonding pad, an A wire, an A node, a preset wire and a preset bonding pad which are integrally connected. The A bonding pad, the A lead and the A node form an A functional area.
It can be understood that the materials of the A bonding pad, the A wire, the A node, the preset wire and the preset bonding pad are all A.
In some embodiments, a metal a film is applied with glue to the upper surface of the flat substrate, as shown in fig. 4 (a), without bubbles and wrinkles. Then, by combining with mask design, the metal A film is subjected to patterning treatment by adopting an etching process to obtain a required shape, and as shown in fig. 4 (b), the patterned metal A film comprises the following parts: the device comprises an A bonding pad, an A wire, an A node, a preset wire and a preset bonding pad.
Further, as shown in fig. 4 (c), after the a-pad and the a-wire are completely covered by a mask, a layer of B film is electroplated on the top surface and the side surface (i.e., the upper surface and the periphery) of the a-node, the preset wire and the preset pad, respectively, to form a B-node partially covering the a-node and connected therewith, a B-wire partially covering the preset wire and connected therewith, and a B-pad partially covering the preset pad and connected therewith. Wherein the node B is integrally connected with the B wire and the B pad as shown in fig. 4 (d). Wherein the B pad, the B wire, and the B node constitute a B functional area. The A functional area and the B functional area form a functional layer. Thus obtaining the functional layer.
It is understood that the materials of the node B, the B wire and the B pad are B.
And after the mask is removed, attaching a protective film on the surface of the functional layer by using glue, enabling the position of an A through hole on the protective film to correspond to the A bonding pad, and enabling the position of a B through hole on the protective film to correspond to the B bonding pad, so as to form a protective film layer, thereby obtaining the device, as shown in fig. 4 (e).
In some specific embodiments, the sizes of the through holes A and the through holes B are slightly smaller than those of the bonding pads A and the bonding pads B respectively, so that the peripheries of the bonding pads are protected, and the reliability and the stability of the film thermocouple are improved.
After the device is turned 180 ° (even if the base layer is turned upward) along the direction perpendicular to the connection line between the a-pad and the B-pad, the base on the surface of the preset wire and the preset pad is removed (e.g., cut off), the preset wire and the preset pad are exposed from the back, and the exposed preset wire and preset pad are further etched and removed by etching (without excessively removing the B-pad and the B-wire), so as to form a groove, as shown in fig. 4 (f).
In some specific embodiments, the concentration and etching time of the etching solution are controlled to completely eliminate the exposed preset wire and preset pad, but not excessively eliminate the B pad and the B wire, which is a mature technology in the art, and the present application will not be repeated.
The grooves are then filled with glue, preferably in the same plane as the substrate, as shown in fig. 4 (g). And turning the device 180 degrees along the direction perpendicular to the connecting line of the bonding pads A and B, thus obtaining the high-reliability thin film thermocouple, as shown in fig. 4 (h).
The grooves are filled with glue, so that the B bonding pad and the B lead can be prevented from being corroded and failed due to contact with the water sample environment, namely, the glue is filled for packaging protection, and the reliability and durability of the film thermocouple can be improved.
The application provides a high-reliability and high-flexibility ultrathin thermocouple prepared by adopting a back material reduction electroplating process, which can solve the problems that the traditional vacuum thermal evaporation and magnetron sputtering technology is not suitable for large-scale mass production of film thermocouples due to the high-temperature vacuum environment and narrow film coating space, expensive equipment and high target material cost. The application adopts the electroplating process, has high mass production efficiency and low cost, and can select more diversified substrate materials.
In addition, according to the back material reduction scheme provided by the application, the other metal is directly grown and electroplated on the surface of one metal, and the two metals are directly electrically connected, so that the problem that the two metals are required to be electrically connected by conductive adhesive in the traditional electroplating process is solved, and the problems that the substrate and the protective film are broken or bubbles are formed between the substrate and the protective film due to volatilization and overflow of an organic solvent in the conductive adhesive in the temperature measurement process of the thermocouple, so that poor contact of the two metals and poor reliability of the thermocouple are caused are avoided.
In addition, the preparation method has the advantages of low cost, easiness in realizing mass production, improvement of reliability and stability of the film thermocouple and the like.
In some embodiments, the a film is attached to the surface of the substrate using an adhesive.
It will be appreciated that any adhesive material commonly used in the art may be used for the glue.
In some embodiments, the patterning is accomplished by mask etching.
In some specific embodiments, the substrate on the surface of the preset wire and the preset pad is removed by cutting.
In some specific embodiments, the preset wire and the preset pad are removed by etching.
In a third aspect, the present application provides a cell comprising a thin film thermocouple as described above.
In some specific embodiments, the thin film thermocouple provided by the application can be used to place the thin film thermocouple in the frame of the fuel cell and deep into the active region of the membrane electrode, so as to obtain the temperature distribution of different positions of the active region of the membrane electrode, as shown in fig. 5.
It is understood that the arrangement specification (2×5) and the number of the thin film thermocouples are merely illustrative of the technical scheme, and any arrangement specification and number may be set according to actual test requirements.
In a fourth aspect, the present application provides a galvanic pile comprising a cell as described above.
The stack is the core site where the electrochemical reactions described above occur, and in some embodiments the stack includes a plurality of cells as described above.
The stack internal temperature has a substantial effect on the operating state of the stack, the power generation efficiency, the reliability and the stability. By arranging the single cell with the thin film thermocouple, the temperature of different positions in the electric pile can be monitored in real time, and the reliability, the durability and the service life of the proton exchange membrane fuel cell system are further improved.
In a fifth aspect, the present application provides a proton exchange membrane fuel cell comprising a stack as described above.
In some embodiments, the proton exchange membrane fuel cell further comprises a hydrogen subsystem, an air subsystem, a cooling subsystem, and a load control subsystem.
The proton exchange membrane fuel cell provided by the application has good stability and durability and long service life.
Embodiments of the present application will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The preparation method of the thin film thermocouple provided by the embodiment comprises the following steps:
a layer of metal A (pure copper, thickness 5 μm) film is adhered on the upper surface of a flat substrate (polyethylene naphthalate, thickness 20 μm) by using glue (polyacrylic acid glue, glue layer thickness 5 μm), and no bubbles and wrinkles are generated; and then combining with mask design, carrying out patterning treatment on the metal A film by adopting an etching process to obtain a required shape, wherein the patterned metal A film comprises an A bonding pad, an A lead, an A node, a preset lead and a preset bonding pad which are integrally connected.
Then, completely covering the A bonding pad and the A wire by using a mask (polyimide, thickness is 50 μm), and electroplating a layer of metal B film (copper-nickel alloy, thickness is 5 μm) on the upper surface and the periphery of the A node, the upper surface and the periphery of the preset wire and the upper surface and the periphery of the preset bonding pad respectively by adopting an electroplating process; forming a node B which is partially coated with the node A and is integrally connected with the node A, a wire B which is partially coated with a preset wire and is integrally connected with the preset wire, and a pad B which is partially coated with a preset pad and is integrally connected with the preset pad, wherein the node B, the wire B and the pad B are integrally connected. Thus obtaining the functional layer.
And after removing the mask, adhering a layer of protective film (polyethylene naphthalate, thickness of 20 μm) on the upper surface of the obtained functional layer by using glue, and enabling the position of an A through hole on the protective film to correspond to an A bonding pad and the position of a B through hole on the protective film to correspond to a B bonding pad, wherein the size of the A through hole is smaller than that of the A bonding pad, and the size of the B through hole is smaller than that of the B bonding pad, so as to obtain the device.
And turning the device 180 degrees to enable the substrate to face upwards, cutting off substrate materials on the surfaces of the preset wires and the preset bonding pads, exposing the preset wires and the preset bonding pads, and removing the exposed preset wires and the exposed preset bonding pads by etching without excessively removing the B bonding pads and the B wires to form grooves.
And then filling the grooves with glue, specifically filling the grooves into the same plane with the substrate, and turning over the device for 180 degrees to obtain the high-reliability film thermocouple.
The thin film thermocouple manufactured by the embodiment comprises a basal layer, a functional layer and a protective film layer which are sequentially laminated; wherein the functional layer comprises an A functional area and a B functional area; the A functional area comprises an A bonding pad, an A lead and an A node which are integrally connected; the B functional area comprises a B bonding pad, a B lead and a B node which are integrally connected; and the node B partially coats the node A, and the node B is integrally connected with the node A. And the protective film layer is also provided with an A through hole and a B through hole which are respectively used for exposing the A bonding pad and the B bonding pad.
Example 2
The preparation method of the thin film thermocouple provided by the embodiment comprises the following steps:
a layer of metal A (nickel-chromium alloy, thickness 10 μm) film is adhered on the upper surface of a flat substrate (polyimide, thickness 15 μm) by using adhesive (pressure sensitive adhesive, thickness 5 μm), and no bubbles and wrinkles are generated; and then combining with mask design, carrying out patterning treatment on the metal A film by adopting an etching process to obtain a required shape, wherein the patterned metal A film comprises an A bonding pad, an A lead, an A node, a preset lead and a preset bonding pad which are integrally connected.
Then, completely covering the A bonding pad and the A wire by using a mask (polyimide, thickness is 50 μm), and electroplating a layer of metal B film (nickel-silicon alloy, thickness is 10 μm) on the upper surface and the periphery of the A node, the upper surface and the periphery of the preset wire and the upper surface and the periphery of the preset bonding pad respectively by adopting an electroplating process; forming a node B which is partially coated with the node A and is integrally connected with the node A, a wire B which is partially coated with a preset wire and is integrally connected with the preset wire, and a pad B which is partially coated with a preset pad and is integrally connected with the preset pad, wherein the node B, the wire B and the pad B are integrally connected. Thus obtaining the functional layer.
And after removing the mask, adhering a layer of protective film (polyimide, thickness of 15 μm) on the upper surface of the obtained functional layer by using glue, and enabling the position of an A through hole on the protective film to correspond to the A bonding pad and the position of a B through hole on the protective film to correspond to the B bonding pad, wherein the size of the A through hole is smaller than that of the A bonding pad, and the size of the B through hole is smaller than that of the B bonding pad, so as to obtain the device.
And turning the device 180 degrees to enable the substrate to face upwards, cutting off substrate materials on the surfaces of the preset wires and the preset bonding pads, exposing the preset wires and the preset bonding pads, and removing the exposed preset wires and the exposed preset bonding pads by etching without excessively removing the B bonding pads and the B wires to form grooves.
And then filling the grooves with glue, specifically filling the grooves into the same plane with the substrate, and turning over the device for 180 degrees to obtain the high-reliability film thermocouple.
The thin film thermocouple manufactured by the embodiment comprises a basal layer, a functional layer and a protective film layer which are sequentially laminated; wherein the functional layer comprises an A functional area and a B functional area; the A functional area comprises an A bonding pad, an A lead and an A node which are integrally connected; the B functional area comprises a B bonding pad, a B lead and a B node which are integrally connected; and the node B partially coats the node A, and the node B is integrally connected with the node A. And the protective film layer is also provided with an A through hole and a B through hole which are respectively used for exposing the A bonding pad and the B bonding pad.
Example 3
The preparation method of the thin film thermocouple provided by the embodiment comprises the following steps:
a layer of metal A (nickel-chromium alloy, thickness 15 μm) film is adhered on the upper surface of a flat substrate (polyimide, thickness 15 μm) by using glue (thermosensitive glue, glue layer thickness 5 μm), and no bubbles and wrinkles are generated; and then combining with mask design, carrying out patterning treatment on the metal A film by adopting an etching process to obtain a required shape, wherein the patterned metal A film comprises an A bonding pad, an A lead, an A node, a preset lead and a preset bonding pad which are integrally connected.
Then, completely covering the A bonding pad and the A wire by using a mask (polyimide, thickness is 50 μm), and electroplating a layer of metal B film (copper-nickel alloy, thickness is 15 μm) on the upper surface and the periphery of the A node, the upper surface and the periphery of the preset wire and the upper surface and the periphery of the preset bonding pad respectively by adopting an electroplating process; forming a node B which is partially coated with the node A and is integrally connected with the node A, a wire B which is partially coated with a preset wire and is integrally connected with the preset wire, and a pad B which is partially coated with a preset pad and is integrally connected with the preset pad, wherein the node B, the wire B and the pad B are integrally connected. Thus obtaining the functional layer.
And after removing the mask, adhering a layer of protective film (polyimide, thickness of 15 μm) on the upper surface of the obtained functional layer by using glue, and enabling the position of an A through hole on the protective film to correspond to the A bonding pad and the position of a B through hole on the protective film to correspond to the B bonding pad, wherein the size of the A through hole is smaller than that of the A bonding pad, and the size of the B through hole is smaller than that of the B bonding pad, so as to obtain the device.
And turning the device 180 degrees to enable the substrate to face upwards, cutting off substrate materials on the surfaces of the preset wires and the preset bonding pads, exposing the preset wires and the preset bonding pads, and removing the exposed preset wires and the exposed preset bonding pads by etching without excessively removing the B bonding pads and the B wires to form grooves.
And then filling the grooves with glue, specifically filling the grooves into the same plane with the substrate, and turning over the device for 180 degrees to obtain the high-reliability film thermocouple.
The thin film thermocouple manufactured by the embodiment comprises a basal layer, a functional layer and a protective film layer which are sequentially laminated; wherein the functional layer comprises an A functional area and a B functional area; the A functional area comprises an A bonding pad, an A lead and an A node which are integrally connected; the B functional area comprises a B bonding pad, a B lead and a B node which are integrally connected; and the node B partially coats the node A, and the node B is integrally connected with the node A. And the protective film layer is also provided with an A through hole and a B through hole which are respectively used for exposing the A bonding pad and the B bonding pad.
Comparative example 1
The method for preparing the film thermocouple by the conductive adhesive method is shown in fig. 2, and comprises the following steps:
firstly, a layer of metal film A is adhered on a flat substrate, and then the metal film A is subjected to patterning treatment by an etching method to obtain a required shape. And then, a layer of metal film B is electroplated at one end by combining a mask process, and glue is coated on the upper surface of the metal film B to obtain the assembly 1 for later use. Similarly, a metal film B is bonded to a flat substrate, and then patterned by etching to a desired shape to obtain the component 2. And (3) folding the assembly 2, attaching the assembly 2 to the assembly 1, and bonding the assembly 2 and the assembly 1 to obtain the film thermocouple.
The materials and thicknesses of the substrate, the adhesive, the metal a and the metal B used in this comparative example were the same as those of example 1.
Experimental example
The thin film thermocouple prepared by the electroplating method of example 1 and the thin film thermocouple prepared by the conductive adhesive method of comparative example 1 were simultaneously placed in an oil bath for temperature rise test, and the test results are shown in fig. 6.
The test shows that when the temperature is higher than 110 ℃, the thin film thermocouple prepared by adopting the conductive adhesive method (namely the comparative example 1) shows that the temperature value cliff drops to zero, which indicates that the thermocouple has broken circuit failure. And the thin film thermocouple prepared by the electroplating method (namely, the embodiment 1) does not have failure phenomenon.
While the application has been illustrated and described with reference to specific embodiments, it is to be understood that the above embodiments are merely illustrative of the technical aspects of the application and not restrictive thereof; those of ordinary skill in the art will appreciate that: modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some or all of the technical features thereof, without departing from the spirit and scope of the present application; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions; it is therefore intended to cover in the appended claims all such alternatives and modifications as fall within the scope of the application.
Claims (10)
1. A thin film thermocouple is characterized by comprising a basal layer, a functional layer and a protective film layer which are sequentially laminated;
wherein the functional layer comprises an A functional area and a B functional area; the A functional area comprises an A bonding pad, an A lead and an A node which are integrally connected; the B functional area comprises a B bonding pad, a B lead and a B node which are integrally connected;
wherein the node B partially coats the node A, and the partial coating is formed by electroplating;
and the protective film layer is provided with an A through hole and a B through hole which are respectively used for exposing the A bonding pad and the B bonding pad.
2. The thin film thermocouple of claim 1, wherein the a-functional region and the B-functional region are of different materials.
3. The thin film thermocouple of claim 1, wherein the a via has a size smaller than the a pad and the B via has a size smaller than the B pad.
4. A method of manufacturing a thin film thermocouple according to any one of claims 1 to 3, comprising the steps of:
attaching an A film on one surface of a substrate, and performing patterning treatment on the A film to form an A bonding pad, an A lead, an A node, a preset lead and a preset bonding pad which are integrally connected;
after the A bonding pad and the A lead are completely covered by a mask, electroplating B films on the top surfaces and the side surfaces of the A node, the preset lead and the preset bonding pad respectively to form a B node which is partially covered by the A node, a B lead which is partially covered by the preset lead and a B bonding pad which is partially covered by the preset bonding pad, wherein the B node is integrally connected with the B lead and the B bonding pad to obtain a functional layer;
after the mask is removed, attaching a protective film on the surface of the functional layer, enabling the position of an A through hole on the protective film to correspond to the A bonding pad, and enabling the position of a B through hole on the protective film to correspond to the B bonding pad, so as to obtain a device;
and after the device is turned over for 180 degrees, removing the substrate on the surfaces of the preset lead and the preset bonding pad and the exposed preset lead and the preset bonding pad to form a groove, and filling the groove with glue to obtain the thin film thermocouple.
5. The method of manufacturing a thin film thermocouple of claim 4, wherein the a thin film is attached to the surface of the substrate using a glue.
6. The method of manufacturing a thin film thermocouple of claim 4, wherein the patterning is accomplished by mask etching.
7. The method for manufacturing a thin film thermocouple according to claim 4, wherein the base on the surfaces of the preset wire and the preset pad is removed by cutting;
and/or removing the preset wire and the preset bonding pad in an etching mode.
8. A single cell comprising the thin film thermocouple of any one of claims 1 to 3.
9. A stack comprising the single cell of claim 8.
10. A proton exchange membrane fuel cell comprising the stack of claim 9.
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| CN202311245600.XA CN117222294A (en) | 2023-09-25 | 2023-09-25 | Thin film thermocouple and preparation method thereof, single cell, electric pile and proton exchange membrane fuel cell |
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