All-solid-state thin film fuel cell and manufacturing method thereof

Abstract

An all-solid-state thin-film fuel cell and a method for making the same belong to the field of fuel cells. The method for making the same includes: providing a combination, processing the combination so that the filler is removed to form a fuel flow channel including a first groove and a second groove. The combination includes a first current collecting layer, a first electrode layer, an electrolyte layer, a second electrode and a second current collecting layer which are stacked in sequence, and the first current collecting layer has a first groove facing the first electrode layer, and the second current collecting layer has a second groove facing the second electrode layer. The first groove and the second groove are both filled with fillers that can be removed. The fuel cell in the example is an all-solid-state thin-film battery, the thickness of which can reach micrometers or even nanometers, thereby improving the volume energy density, enabling the fuel cell to be miniaturized and developed into a micro fuel cell.

Description

Technical Field

[0001] The present application relates to the field of fuel cells, and in particular, to an all-solid-state thin film fuel cell and a method for manufacturing the same. Background Art

[0002] A fuel cell is a device that uses the chemical reaction of hydrogen and oxygen to generate electricity, and uses the electron conversion brought about by the redox reaction in the chemical reaction to generate current. The entire power generation process of the fuel cell does not involve the combustion of fuel, and does not follow the Carnot cycle of the second law of thermodynamics. Therefore, the energy conversion efficiency is very high - generally 40-60% - and the fuel cell is a very efficient clean energy power generation device.

[0003] Traditional fuel cells, especially solid fuel cells, mainly use metal oxides and ceramic materials as the electrodes and electrolyte components. Therefore, this type of solid fuel cell is often produced through ceramic technology and its production line. However, due to the limitations of the ceramic technology itself, it is difficult to produce and manufacture smaller, thinner, and more finely structured solid fuel cells, especially micron or even nanometer-level fuel cells, using ceramic technology.

[0004] With the development of fuel cells towards miniaturization, especially the limitation of space size and the increase in the requirement for volume energy density, there is an increasing need to reduce the dimensions of fuel cells and produce fuel cells at the micron or even nano level.

[0005] The information disclosed in this background technology section is only intended to deepen the understanding of the overall background technology of the present application, and should not be regarded as acknowledging or suggesting in any form that the information constitutes the prior art already known to those skilled in the art. Summary of the invention

[0006] In order to improve or even solve at least one problem in the prior art, the present application proposes an all-solid-state thin film fuel cell and a method for manufacturing the same.

[0007] This application is implemented as follows:

[0008] In a first aspect, an example of the present application provides a method for manufacturing an all-solid-state thin film fuel cell.

[0009] The preparation method comprises:

[0010] Providing a combination, the combination comprising a first current collecting layer, a first electrode layer, an electrolyte layer, a second electrode layer and a second current collecting layer which are stacked in sequence;

[0011] The first current collecting layer has a first groove facing the first electrode layer, the second current collecting layer has a second groove facing the second electrode layer, and both the first groove and the second groove are filled with fillers that can be removed;

[0012] Processing the assembly causes the filler to be removed to form a fuel flow passage including a first groove and a second groove.

[0013] Fuel cells need to be supplied with fuel so that energy can be released through the chemical reaction (redox) of the fuel, which is then converted into electrical energy to supply power to electrical devices. In the prior art, in order to make all-solid-state fuel cells, the thickness of the structure is often lost, resulting in a lower energy density.

[0014] Generally, in the related art, the manufacture of fuel cells requires reserving a fuel supply channel and preventing it from being blocked. The various structures that constitute the fuel cell need to be prepared separately and then laminated through appropriate processes, making it difficult to further reduce its thickness. In addition, the specifications, sizes and performances of fuel cells produced from different batches vary greatly.

[0015] In the present application, the manufacturing method is improved. Before manufacturing the fuel supply channel, the overall structure of the fuel is first formed, and then the fuel supply channel is opened by post-processing, thereby obtaining a fully solid-state thin-film fuel cell. By forming the fuel supply channel in post-processing, the inconvenience of pre-reserving the channel for various processing processes can be avoided, and the thickness of the fuel cell can be significantly reduced by coordinating the processes.

[0016] In combination with the first aspect, in a first possible implementation manner of the first aspect of the present application, the first current collecting layer and the second current collecting layer are manufactured by an etching process or a deposition process.

[0017] The etching process and deposition process can use or borrow various equipment and processes in the semiconductor manufacturing process. Therefore, better product quality and higher efficiency can be obtained through mature processes.

[0018] For different structural layers in a fuel cell, different processes can be selected according to their functional requirements and the difficulty of the process in order to achieve better process effects.

[0019] For example, the first electrode layer, the second electrode layer and the electrolyte layer are manufactured by a deposition process.

[0020] For example, the deposition process includes sputtering deposition or pulsed laser deposition.

[0021] In combination with the first aspect, in some optional examples of the second possible implementation manner of the first aspect of the present application, the first current collecting layer is made of a first material, and the first current collecting layer is obtained in the following manner:

[0022] Forming a patterned first mask on a base layer formed of a first material, and forming a first groove by etching the base layer;

[0023] The first groove is filled with a filler.

[0024] The first current collecting layer is manufactured by masking, etching and setting a filler, so as to achieve a more refined process operation, so as to obtain a thinner thickness and a corresponding first groove.

[0025] In order to obtain a thinner thickness, the base layer can be thinned later.

[0026] Based on the needs of subsequent operations, the method for manufacturing the first current collecting layer may also include: removing the first mask after etching the base layer to form the first groove and before filling the first groove with a filler; or removing the first mask after filling the first groove with a filler.

[0027] In combination with the second possible implementation manner of the first aspect, in some optional examples of the third possible implementation manner of the first aspect of the present application, the second current collecting layer is made of a second material, and the second current collecting layer is obtained in the following manner:

[0028] forming a removal layer at the second electrode using a filler;

[0029] forming a patterned second mask on the removal layer, forming a second groove by etching the removal layer, and removing the mask;

[0030] The second groove is filled with a second material in a manner of covering the removed layer.

[0031] Similar to the above, the mask and etching combined process can achieve the adjustment of finer structures, thereby achieving a thickness reduction effect.

[0032] In combination with the first aspect, in some optional examples of the fourth possible implementation of the first aspect of the present application, the assembly includes a third electrode, and the third electrode stack is disposed on the second current collecting layer;

[0033] The second current collecting layer has a third groove away from the second electrode layer, and the third groove is occupied by a filler.

[0034] In order to integrate more batteries and provide higher power, more battery structures can be set. For this reason, without damaging the processed assembly and without causing an increase in thickness when the fuel cell is subsequently manufactured, a third groove is formed in the second current collecting layer to facilitate subsequent processing to form a fuel supply channel, thereby ensuring that the stacked structure of multiple fuel cells has good electrical performance.

[0035] In combination with the first aspect, in some optional examples of the fifth possible implementation of the first aspect of the present application, the method of processing the assembly to remove the filler includes:

[0036] The assembly is heated to cause the filler to disappear by combustion or vaporization.

[0037] By heating the assembly, not only can the filler be removed to form a fuel supply channel, but the layers in the formed fuel cell can also be assembled more tightly and firmly without the need for the assistance of other connection and matching methods.

[0038] Depending on the filler, there are different options for the heating method, such as the heating temperature, time, etc. For example, the method of heating the assembly includes: heating the assembly by a gradient temperature increase method until the filler disappears.

[0039] After the filler is removed, of course, the cooling method can also be selected to avoid problems such as cracking due to rapid cooling. Therefore, optionally, after the filler disappears, the assembly is cooled by gradient cooling.

[0040] Based on the convenience of filling operation in the groove and appropriate requirements for heat treatment, optionally, the filler is a colloid, and the colloid includes polystyrene.

[0041] In a second aspect, examples of the present application provide an all-solid-state membrane fuel cell.

[0042] The all-solid-state thin film fuel cell includes a first unit cell.

[0043] The first single cell includes a first current collecting plate, an anode plate, an electrolyte plate, a cathode plate layer and a second current collecting plate which are stacked in sequence.

[0044] The first current collecting plate and the second current collecting plate are made of semiconductor silicon material, and the anode plate, the electrolyte plate and the cathode plate are made of ceramic material;

[0045] The first current collecting plate is provided with a first groove facing the anode plate, and the second current collecting plate is provided with a second groove facing the cathode plate, and the first groove and the second groove are configured to transport fuel;

[0046] The thickness of the all-solid-state thin film fuel cell in the stacking direction reaches the micrometer scale or nanometer scale.

[0047] The above fuel cells are based on silicon materials and combined with ceramic materials, and can be processed and manufactured by semiconductor process methods, so that a thin-film-level all-solid-state battery can be obtained. In this way, based on the same thickness of the fuel cell, the fuel cell in this application can integrate more batteries to obtain a higher volume energy density.

[0048] In conjunction with the second aspect, in some optional examples of the first possible implementation of the second aspect of the present application, the thickness of the anode plate in the stacking direction is 10 to 100 microns;

[0049] Alternatively, the thickness of the electrolyte sheet in the stacking direction is 5 to 30 microns;

[0050] Alternatively, the thickness of the cathode plate in the stacking direction is 10 to 100 microns;

[0051] Alternatively, the thickness of the first current collecting plate in the stacking direction is 50 to 200 microns;

[0052] Alternatively, the thickness of the second current collecting plate in the stacking direction is 50-200 microns.

[0053] Although the thickness of a single battery can be limited to the micrometer or nanometer scale, the structure of each layer inside the battery can also be selectively adjusted to make corresponding changes according to the different functions of each layer in order to improve the performance of the battery.

[0054] In combination with the second aspect or the first possible implementation manner of the second aspect, in some optional examples of the second possible implementation manner of the first aspect of the present application, the anode plate is made of a mixture of nickel oxide and yttrium-doped zirconium oxide;

[0055] Alternatively, the electrolyte plates are made of yttrium-doped zirconium oxide;

[0056] Alternatively, the cathode plate layer is made of rare earth-based perovskite composite oxide, wherein the rare earth-based perovskite composite oxide includes lanthanum, strontium and manganese ternary composite oxide.

[0057] Ceramic-based electrolyte plates and electrode plates used as battery functional layers have good electrical performance, and the material cost is low and easy to obtain.

[0058] In combination with the second aspect, in some optional examples of the third possible implementation of the second aspect of the present application, the second current collecting plate has a third groove away from the second groove;

[0059] The all-solid-state thin film fuel cell comprises at least one second single cell stacked on the first single cell, each of the at least one second single cell comprises a second anode plate, a second electrolyte plate, a second cathode plate layer and a third current collecting plate, the third current collecting plate having a fourth groove arranged facing the second cathode;

[0060] Two adjacent second cells are stacked in a manner that the third current collecting plate contacts the second anode plate, and the third current collecting plate sandwiched between the second cathode and the second anode is provided with a fifth groove, which is arranged away from the fourth groove.

[0061] Based on the need for higher energy density, more batteries can be integrated. Based on the structural characteristics of the above-mentioned current collector, it can be conveniently formed into a multiple battery stacking structure by adding other structural layers, so that more batteries can be integrated in a thinner thickness.

[0062] In the above implementation process, the method for manufacturing an all-solid-state thin-film fuel cell provided in the embodiment of the present application separates the formation process of the fuel supply channel from the formation of each structural layer of the battery. That is, each structural layer is first stacked and formed, and then the fuel supply channel is formed by processing the aforementioned structure, so that the two steps will not adversely affect and restrict each other, so that the method can be implemented by selecting and combining a process that is easy to form a microstructure and a thin layer to manufacture a fuel cell.

[0063] Most of the fuel cells on the market and in research now are liquid electrolyte fuel cells. Therefore, traditional fuel cells with liquid electrolytes cannot achieve such micro-nano structures, and it is difficult to develop miniaturization such as micron or even nanometer levels. The process proposed in the example of this application can achieve a micro-nano structure of all-solid-state thin film fuel cells. BRIEF DESCRIPTION OF THE DRAWINGS

[0064] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for use in the embodiments will be briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present application and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without paying creative work.

[0065] Figure 1 A schematic diagram of the structure of the combination proposed in the embodiment of the present application;

[0066] Figure 2 Shown based on Figure 1 A schematic diagram of the structure of the all-solid-state membrane fuel cell of the assembly shown;

[0067] Figure 3 A schematic diagram of the structure of another all-solid-state thin film fuel cell in an embodiment of the present application is shown;

[0068] Figure 4 A schematic diagram of the structure of another all-solid-state thin film fuel cell in an embodiment of the present application is shown;

[0069] Figure 5 Shows Figure 1 A schematic diagram of a process for manufacturing a first current collecting layer in a manufacturing process of the assembly;

[0070] Figure 6 Shown by Figure 5A schematic diagram of the process of manufacturing the first electrode layer, the electrolyte layer, the second electrode layer and the removal layer from the first current collecting layer;

[0071] Figure 7 Shown in Figure 5 Based on this, a flow chart of the assembly is produced.

[0072] Icons: 100-assembly; 101-first current collecting layer; 102-first electrode layer; 103-electrolyte layer; 104-second electrode layer; 105-second current collecting layer; 106-filler; 107-first groove; 108-second groove; 109-fuel flow channel; 110-third groove; 111-second anode plate; 112-second electrolyte plate; 113-second cathode plate; 114-third current collecting plate; 115-second single cell; 201-base layer; 202-removal layer; 203-first mask; 204-second mask. DETAILED DESCRIPTION

[0073] In this application, the embodiments, implementation methods and features of this application can be combined with each other without contradiction or conflict. In this application, conventional equipment, devices, components, etc. can be purchased commercially or made according to the contents disclosed in this application. In this application, in order to highlight the key points of this application, some conventional operations and equipment, devices, and components are omitted or simply described.

[0074] Fuel cells have unique advantages and are therefore a very promising device for converting electric energy. They have high energy conversion efficiency and generate electricity at a relatively low environmental cost. As an electrical device, battery life is a key concern. Therefore, people certainly expect fuel cells to provide sufficient electricity. Based on this demand, efforts have been made to develop fuel cells with high energy density.

[0075] Currently, the usual approach is to stack multiple batteries in parallel or series, but this approach will obviously increase the size of the fuel cell, greatly reducing its portability and storage. Therefore, the advantages brought by a longer battery life cannot cover the disadvantages brought by it.

[0076] In view of this, providing a solution for high volumetric energy density and compressed thickness of fuel cells becomes a challenge.

[0077] After research, the inventor believes that one of the main crux of the problem is that the limitations of existing solid-state fuel cells are mainly due to their process conditions. One of the problems is that in the relevant technology, fuel cells are often made using ceramic processes, which makes it difficult to further compress their thickness. And the existing fuel cell process is often inseparable from the ceramic process.

[0078] In view of the above problems, the inventor has proposed a method to circumvent the above problems. One of the improvements of the method is to separate the formation process of the fuel supply channel of the fuel cell from the formation process of each structural layer in the fuel cell. In the example, each structural layer of the fuel cell is formed first, and then processed to form the fuel supply channel. In this way, the formation process of each structural layer in the fuel cell can be made thinner, and there is no need to consider the formation process of the fuel supply channel, thereby better solving the above problems.

[0079] The fuel cell in the examples of the present application is a fully solid structure and forms a stacked structure / layered structure. Therefore, each of its structural layers is also solid. Further, the fuel cell is also a thin film battery. In other words, the thickness of the battery is relatively thin and can meet the special battery thickness requirements. Therefore, in some examples, the fuel cell can be referred to as a fully solid thin film fuel cell.

[0080] As an exemplary illustration, the thickness of the fuel cell can be limited to the micrometer level or even the nanometer level. Such a thickness is usually not easy to achieve for existing fuel cells. However, it should be understood that although the process proposed in the examples of this application can be used to make batteries with thinner structures, the method can also be used to make thicker fuel cells.

[0081] In addition, using the method given in the examples of this application, a single-layer all-solid-state thin film fuel cell can be made. Of course, this method can also be used to make multi-layer all-solid-state thin film fuel cells, such as two layers, two layers, four layers, or even more layers. It should be pointed out that the "single layer" / "two layers" mentioned here refers to the number of cells with the main structural layer of the fuel cell contained in the battery. Subsequently, the batteries mentioned in this way may be referred to as single cells. Therefore, a single-layer fuel cell may refer to a first single cell; a two-layer fuel cell may refer to two single cells, such as a first single cell and a second single cell.

[0082] If you only need to make a single or single-layer all-solid-state thin-film fuel cell, the structure is as follows Figure 2 , which uses Figure 1 After the structure is sintered, the filler is removed. If multiple layers are to be made, all the monomers can be stacked layer by layer (technically, this can be achieved through deposition in the semiconductor process), and after the stacked structure is completed, the filler is removed by unified sintering. Here we only take a 2-layer all-solid-state thin film fuel cell as an example. In fact, you can also make a third, fourth, etc. multi-layer all-solid-state thin film fuel cell containing 3 or even more monomers.

[0083] In general, the method in the example can be combined with thin film technology to produce core components of solid fuel cells such as positive electrodes, negative electrodes and electrolytes. In addition, by combining thin film and etching processes, bipolar plate components with groove structures can be effectively combined with electrodes to form a complete full battery structure.

[0084] In existing traditional fuel cells, the grooved part is called a bipolar plate, which is generally a steel plate or a graphite plate. The groove structure is etched on it by chemical corrosion. Then the prepared bipolar plate is buckled on the positive and negative electrodes of the battery to form a real single fuel cell. Therefore, the preparation method and process are completely different from the thin film fuel cell described in the example of this application. Because traditional fuel cells are thick, the bipolar plate and the positive and negative electrodes of the battery can be prepared separately.

[0085] However, as the thin film fuel cell that is desired and achievable in the examples of this application, the thickness of its electrode material is only micrometers or even nanometers, so the inventor proposes to use the material of the bipolar plate as a substrate or base plate, first etch a groove structure on this base plate, and all processes are built on this base plate step by step. Secondly, because the chemical corrosion method cannot achieve controllable micrometer or even nanometer level etching, the reactive ion beam etching method can be used. In industry, the reactive particle beam etching method can be used to achieve controllable micrometer or even nanometer level microstructures.

[0086] The following is a more detailed description of the method in the example.

[0087] The method for manufacturing the all-solid-state thin film fuel cell in the example mainly includes step S101 and step S102 mentioned below, as well as some optional steps that may be mentioned later.

[0088] Step S101: providing an assembly 100.

[0089] The assembly 100 has a basic structure of a fuel cell in principle. In addition, from the perspective of process implementation, combined with thin film technology, refer to Figure 1 The assembly 100 includes a first current collecting layer 101, a first electrode layer 102, an electrolyte layer 103, a second electrode layer 104 and a second current collecting layer 105 which are stacked in sequence.

[0090] From the material level, each of the above structural layers can be made of ceramic materials, which can be adjusted according to actual selection needs. For example, the first electrode layer 102 is made of a composition of nickel oxide and yttrium-doped zirconium oxide. The second electrode layer 104 can be made of rare earth-based perovskite composite oxide. Among them, the rare earth-based perovskite composite oxide includes lanthanum strontium manganese ternary composite oxide. The electrolyte plate can be made of yttrium-doped zirconium oxide.

[0091] See also Figure 1 and Figure 2 The first current collecting layer 101 has a first groove 107 facing the first electrode layer 102, and the second current collecting layer 105 has a second groove 108 facing the second electrode layer 104, and the first groove 107 and the second groove 108 are both filled with a removable filler 106 so that the filler 106 can be removed in the subsequent step S102.

[0092] For the first current collecting layer 101 and the second current collecting layer 105, both can be made of the same material (based on the convenience of process operation, and of course both can also be made of different materials). As the name implies, the first current collecting layer 101 / the second current collecting layer 105 has the ability to collect current and therefore has a corresponding structure. It can collect the current generated by the active substances (fuel redox reaction) of the battery and form a macroscopic current for external output. Therefore, in order to improve or improve the ability to collect charges, the two current collecting layers can usually be in full contact with the active substances, and the internal resistance should be as small as possible. Based on such considerations, the current collecting layer can be made of silicon material used in semiconductor processes. The inventor believes that the conductivity of silicon materials (such as semiconductor silicon) can just meet the functionality of fuel cell power collection.

[0093] For ease of understanding, the first current collecting layer 101 and the second current collecting layer 105 can be shown in a similar structure in a lithium ion battery. In a lithium ion battery, this often means a metal foil, such as a copper foil, an aluminum foil, etc. In the present application, alternatively, the current collecting layer as mentioned above can be a silicon film.

[0094] Structurally, each of the above structural layers can have different thicknesses, which can be adjusted according to actual selection needs. For example, the thickness of the first electrode layer 102 in the stacking direction is 10 to 100 microns; the thickness of the second electrode layer 104 in the stacking direction is 10 to 100 microns; the thickness of the electrolyte layer 103 in the stacking direction is 5 to 30 microns; the thickness of the first current collector layer 101 in the stacking direction is 50 to 200 microns; the thickness of the second current collector layer 105 in the stacking direction is 50 to 200 microns. Although, here, the thickness of each structural layer (which is essentially also a functional layer) is given, it is not intended to limit the above thickness to be necessary. On the contrary, each structural layer can have different thicknesses, and generally a larger thickness is easy to implement, while a smaller thickness may often require more delicate and harsh conditions to achieve. For example, as mentioned above, micron and even nanometer scale control can be achieved by selecting a thin film process in a semiconductor process. However, it should be pointed out that for all-solid-state thin-film fuel cells with micron or even nanometer microstructures, in addition to using semiconductor processes, it is also necessary to combine the above-mentioned subsequent processing (such as step S102 mentioned below) to obtain the processing method for the fuel supply channel.

[0095] In terms of process, there are many possible options for the process of each structural layer in the assembly 100. But generally speaking, the first current collecting layer 101 and the second current collecting layer 105 can be made by an etching process or a deposition process. Generally, when the first current collecting layer 101 is made by an etching process, the second current collecting layer 105 can usually be made by a deposition process, and vice versa. The first electrode layer 102, the second electrode and the electrolyte layer 103 are made by a deposition process. Among them, the deposition process includes sputtering deposition or pulsed laser deposition. Based on this explanation, it can be known that the assembly 100 is mainly made by combining additive and subtractive methods.

[0096] As an example, the first current collecting layer 101 is obtained by:

[0097] First step, refer to Figure 5 A patterned first mask 203 is formed on the base layer 201 made of the first material used to form the first current collecting layer 101. For example, through a semiconductor process, a mask is covered on the upper surface of the silicon substrate, and the mask has a pattern in the form of holes, through holes, through grooves, etc.

[0098] Step 2: Refer to Figure 5, the first groove 107 is formed by etching the base layer / base layer 201. The pattern therein will constitute a part of the fuel supply channel. For example, the base layer is etched by a laser through the holes of the mask plate, so that the substrate is burned by a high-energy beam and part of the material is removed to form a channel. Obviously, the first mask 203 can maintain its own stability under etching conditions (such as laser irradiation), that is, it will not be ablated by high-energy laser. Therefore, it can be considered that the first mask 203 is a non-transparent material of the etching condition, and the etching condition can only penetrate the first mask 203 in the patterned area (such as the groove) and irradiate the base layer 201. In addition, in order to avoid the pattern etched on the base layer 201 being different from the desired shape, the etching condition is expected to be irradiated vertically on the mask plate so as to achieve the "transfer" of the pattern on the first mask 203 to the base layer 201.

[0099] The third step is to fill the first groove 107 with a filler 106, see Figure 6 .

[0100] The filler 106 may be made of various substances that are easy to remove and will not adversely affect the substrate due to the removal of the filler 106. Alternatively, the filler 106 may be made of a substance that is easy to remove by heating.

[0101] Since the base layer 201 may be provided in a relatively thicker state (which can play a supporting role) when initially provided, after performing the above first to third steps, the base layer 201 may be processed, i.e., thinned. This means that when the base layer 201 can provide a supporting role in a relatively thinner state, the step of thinning the base layer 201 may not be performed.

[0102] Further, based on the need to subsequently fabricate other structural layers on the first current collecting layer 101, the first mask 203 may be removed. The timing of removing the mask may be, for example, after etching the base layer to form the first groove 107 and before filling the first groove 107 with the filler 106; or, after filling the first groove 107 with the filler 106, the first mask 203 may be removed. Since the first mask 203 does not need to be specifically fixed to the surface of the base layer 201, its removal is also easy to achieve.

[0103] In accordance with the manufacturing method of the first current collecting layer 101, the second current collecting plate can be made of the second material. Correspondingly, the second current collecting layer 105 can be obtained by the following method (see Figure 7 ):

[0104] First, the removal layer 202 is formed on the second electrode layer 104 using the filler material. Usually, the removal layer 202 can be formed by coating the filler material by scraping, etc., but based on special thickness requirements, it may be necessary to take other methods to process the filler so that it covers the second electrode with a thinner thickness.

[0105] Next, a patterned second mask 204 is formed on the removal layer 202 , the removal layer 202 is etched to form a second groove, and the mask is removed.

[0106] Similar to the above-mentioned production of the first current collecting layer 101, the second mask 204 is an opaque body of the etching conditions. The etching conditions only contact the second electrode through the structures such as through holes and through grooves of the second mask 204, and cause ablation and other effects and influences on the second electrode. The second mask 204 can be made of the same material as the first mask 203, but its graphic shape, specifications / size can be different from the first mask 203. For example, the graphic structure of the first mask 203 can be a plurality of narrow strip grooves arranged at equal intervals in a first size; the graphic structure of the second mask 204 can be a plurality of narrow strip grooves arranged at equal intervals in a second size (different from the first size, such as greater than or less than). Of course, other layout methods can also be used, for example, the plurality of narrow strip grooves of the first mask 203 are arranged in a first direction, and the plurality of narrow strip grooves of the second mask 204 are arranged in a second direction (perpendicular to the first direction).

[0107] The second mask 204 is removed by etching, so that the removed layer on the second electrode after the filler material is removed has the same patterned structure as the second mask 204 .

[0108] Next, the second material is filled into the second groove in a manner of covering the removed layer 202 .

[0109] Through the previous step, the removal layer 202 is formed with a groove, namely, the second groove 108. Therefore, the second groove 108 is filled by filling the second material into the second groove 108. Further based on the needs of charge transfer and battery packaging, the second material may cover the entire removal layer 202. Therefore, the second material not only has a portion located in the second groove 108, but also has a region on the surface of the removal layer 202 and covers the removal layer 202 where the second groove 108 is not provided.

[0110] When the second current collecting layer 105 is made as described above, it is mainly through forming a removal layer 202 composed of a complete filler 106, then partially removing it, and then filling it with the material (second material) for making the second current collecting layer 105. In other examples, a graphical removal layer 202 with grooves can also be directly made. For example, a mask is covered on the second electrode, and then the filler 106 material is covered on the mask by a method such as brushing. The mask can be a complementary mask of the second mask 204 (that is, both are made of the same sheet, the holes of one are used to etch and remove the filler 106 material, and the holes of the other are used to form the filler 106 material).

[0111] As a further embodiment, in other examples of the present application, in order to integrate more fuel cell structures, the assembly 100 may also include a third electrode, and the third electrode stack is placed in the second current collector 105. In such an example, the second current collector 105 is usually made and used in the form of a bipolar plate (fuel can be transmitted through channels on both sides in the thickness direction), so the second current collector 105 has a third groove 110 away from the second electrode layer 104, and the third groove 110 is occupied by the filler 106. In this way, in further other examples, electrodes, electrolytes, electrodes and current collector layer structures similar to the first electrode layer 102, the electrolyte layer 103, the second electrode layer 104 and the second current collector 105 can be formed later. In this way, such a fuel cell can be equivalent to a series structure of two batteries. In other words, the method for making the assembly 100 may also include the steps of making electrodes, electrolytes, electrodes and current collector layer structures.

[0112] The first mask 203 and the second mask 204 (which may be a photomask) mentioned above may be made of various mask materials in existing semiconductor processes, and are not particularly limited in this application. In order to understand the mask more clearly, in the example, for example, metal, glass (such as quartz glass, borosilicate glass), etc. may be selected to make the mask. The mask may be a structure with a rectangular cross-section, which may have a plurality of holes and grooves for subsequent production of a fuel supply channel.

[0113] Step S102 : Processing the assembly 100 so that the filler 106 is removed to form a fuel flow channel 109 including a first groove 107 and a second groove 108 .

[0114] There are many possible options for processing the assembly 100, which are determined according to the properties of the filler 106 and the properties of the various structural layers in the assembly 100. For example, in an optional example, when the filler 106 can be removed by heat treatment, and the heat treatment is not sufficient to damage the various structural layers (such as the first current collecting layer 101, etc.), the assembly 100 can be heated. Therefore, the method of processing the assembly 100 to remove the filler 106 includes: heating the assembly 100 so that the filler 106 disappears by burning or gasification.

[0115] In some of the aforementioned examples, the first current collecting layer 101 and the second current collecting layer 105 are both made of silicon materials, while the first electrode layer 102, the second electrode layer 104 and the electrolyte layer 103 are made of ceramic materials. When the filler 106 is a colloid with polystyrene, the assembly 100 can be heated. The heating temperature can be 1000°C and the heating time can be 2 hours to heat and volatilize the colloid. The filler 106 can also be other polymer materials such as polypropylene, polyethylene and other resin materials. This can be understood as the assembly 100 is processed by a sintering process, the filler 106 is removed, and the various structural layers of the ceramic material are tightly combined and strengthened.

[0116] Corresponding to the heating treatment scheme, the heating method can be more finely controlled. For example, the method of heating the assembly 100 includes: heating the assembly 100 by a gradient temperature increase until the filler 106 disappears. By selecting the heating method, it may be easier to remove a certain filler 106 material, while ensuring that other structural layers in the assembly 100 are more firmly combined.

[0117] Furthermore, after heating, it is cooled based on the needs of testing and use. Therefore, after the filler 106 disappears, the assembly 100 can be cooled by a gradient cooling method so that the assembly 100 does not have cracks, etc. Of course, the heat treatment of the assembly 100 can be directly placed in a container (such as a furnace) at 1000°C for direct heating, and then air-cooled or furnace-cooled.

[0118] In addition to the above-mentioned heat treatment, the filler 106 may also be removed by chemical reaction, for example, by causing it to disappear by reaction under light or by other chemical reactions. However, considering that the various structural layers in the assembly 100 will be more firmly bonded by heat treatment, if the filler 106 cannot be removed by appropriate temperature (it still cannot be removed above the temperature at which the various structural layers are damaged by high temperature), the assembly 100 may be heat treated first to bond the various structural layers, and then the filler 106 may be removed by treating it in a corresponding manner.

[0119] The above describes the removal of the filler 106 by heat treatment, chemical reaction, etc., but it does not exclude the removal of the filler 106 by mechanical means. For example, the filler 106 can be made of magnetic material, and when it needs to be removed, the filler 106 can be removed by adsorption such as a magnet. Alternatively, a very small probe (smaller than the width of the first groove 107 and the second groove 108) is used to remove the filler 106 by puncture, squeezing, dragging, etc.

[0120] Alternatively, the filler 106 may be removed by a combination of chemical reaction and mechanical treatment. For example, the filler 106 may be changed by chemical reaction so that the contact between the filler 106 and the groove (such as the first groove 107 and the second groove 108) is reduced or even loosened, so that the filler 106 can be removed by various appropriate mechanical methods.

[0121] In addition, the first electrode and the second electrode described above may be a cathode and an anode, respectively, or may be an anode and a cathode, respectively.

[0122] Corresponding to the above-mentioned process method, an all-solid-state thin film fuel cell was obtained in the example.

[0123] In one embodiment, the all-solid-state thin film fuel cell can be substantially a first single cell. Its thickness (stack direction) reaches micrometer scale or nanometer scale. The first single cell includes a first current collector plate, an anode plate, an electrolyte plate, a cathode plate layer and a second current collector plate which are stacked in sequence.

[0124] The first current collecting plate is provided with a first groove facing the anode plate, and the second current collecting plate is provided with a second groove facing the cathode plate. The first groove and the second groove are configured to transport fuel.

[0125] The first current collecting plate and the second current collecting plate are made of semiconductor silicon material, and the anode plate (such as zinc oxide / ZnO+yttrium stabilized zirconium oxide / YSZ), the electrolyte plate (such as YSZ) and the cathode plate (such as LaSrMnO x / lanthanum strontium manganese oxide or lanthanum strontium manganate) is made of ceramic material. The anode plate can be made of a combination of nickel oxide and yttrium-doped zirconium oxide; or, the electrolyte plate is made of yttrium-doped zirconium oxide; or, the cathode plate layer is made of rare earth-based perovskite composite oxide, wherein the rare earth-based perovskite composite oxide includes lanthanum strontium manganese ternary composite oxide.

[0126] As for the thickness of the first single cell, the following effects can be achieved through reasonable selection of the above-mentioned processes: the thickness of the anode plate in the stacking direction is 10 to 100 microns; or, the thickness of the electrolyte plate in the stacking direction is 5 to 30 microns; or, the thickness of the cathode plate in the stacking direction is 10 to 100 microns; or, the thickness of the first current collecting plate in the stacking direction is 50 to 200 microns; or, the thickness of the second current collecting plate in the stacking direction is 50 to 200 microns.

[0127] Further, in other examples, the all-solid-state thin film fuel cell may include two single cell structures, such as the aforementioned first single cell and the second single cell 115 (see Figure 4 ). The first single cell and the second single cell 115 can be integrated at the micrometer and nanometer scale in a similar manner to the series connection. Of course, in other examples, the all-solid-state thin film fuel cell can also include three or four or five or more single cells integrated into one. The following will be described by taking the battery composed of the first single cell and the second single cell 115 (hereinafter referred to as a double-layer battery) as an example.

[0128] The double-layer battery includes a stacked first single cell and a second single cell 115. For a multi-layer battery, it will include a plurality of second single cells 115.

[0129] In the double-layer battery, the first single cell can be adaptively adjusted as follows so that it cooperates with the second single cell 115. For example, the second current collecting plate of the first single cell has a third groove away from the second groove (in other words, the second current collecting plate has grooves distributed on two surfaces / top surface and bottom surface in the thickness direction - the second groove and the third groove).

[0130] For two layers of cells in the multi-layer battery, it includes a second cell 115 stacked on the first cell. The second cell 115 includes a second anode plate 111, a second electrolyte plate 112, a second cathode plate 113 and a third current collector 114, wherein the third current collector 114 has a fourth groove arranged facing the second cathode. Figure 3 The structure shown is provided as a front layer of a two-layer and above three-layer fuel cell structure, upon which the complete cell structure is subsequently formed. Figure 3 In the figure, the structure shown in the figure includes a layer of single cells and a structural layer formed thereon. Among them, a layer of single cells is composed of a first current collecting layer 101 to a second current collecting layer 105 (having two upper and lower grooves); and the "structural layer formed thereon" includes a second anode 111. Although Figure 3It is shown that each current collecting layer has holes (such as the first groove 107, etc.), however, for a complete all-solid-state thin film fuel cell with an expected number of layers (such as 1, 2, 3, etc.), the holes are formed by sintering to remove the filler in the holes after all the structural layers / functional layers are stacked.

[0131] For three or more layers of batteries in a multi-layer battery, two adjacent second single batteries 115 are stacked in such a way that the third current collecting plate 114 and the second anode plate 111 are in contact, and the third current collecting plate 114 clamped between the second cathode and the second anode is provided with a fifth groove, which is arranged away from the fourth groove.

[0132] For example, as a more understandable explanation, when the number of second single cells 115 is one, the second single cell 115 is combined with the second current collecting plate of the first single cell with the second anode plate 111, and the third groove of the second current collecting plate faces the second anode plate 111 of the second single cell 115, and the third current collecting plate 114 of the second single cell has a fourth groove set facing the second cathode plate 113 of the second single cell.

[0133] When the number of the second single cells 115 is two and they are respectively recorded as the first bottom cell and the first top cell, the first bottom cell and the first top cell are stacked with the second anode plate 111 contacting the third current collecting plate 114, and the third current collecting plate 114 contacting the first bottom cell is provided with a fifth groove opposite to the third groove.

[0134] When the number of second single cells 115 is more than three, two adjacent second single cells 115 are stacked with the second anode plate 111 in contact with the third current collecting plate 114, and the second single cell 115 in contact with the first battery among all the second single cells 115 is defined as the bottom battery, the outermost second single cell 115 is defined as the top battery, and the second single cell 115 located between the bottom battery and the top battery is defined as the middle battery.

[0135] The processes in some of the above examples and the fuel cells manufactured thereby have at least the following advantages.

[0136] (1) The thickness of all-solid-state thin film fuel cells can be reduced to micrometers or even nanometers. (2) The above process can produce single-layer, double-layer, and multi-layer all-solid-state thin film fuel cells. (3) The positive electrode, negative electrode, and electrolyte are produced by combining thin film technology. In addition, by combining thin film and etching technology, the bipolar plate components with groove structures are effectively combined with the electrodes to form a complete full battery structure. (4) The above process is an integrated manufacturing process, and the entire all-solid-state thin film fuel cell is integrated in a set of organically combined manufacturing processes. (5) The process flow can draw on semiconductor technology and combine ceramic materials and ceramic sintering technology.

[0137] The above description is only the preferred embodiment of the present application and is not intended to limit the present application. For those skilled in the art, the present application may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for manufacturing an all-solid-state thin film fuel cell, characterized in that: The production method comprises: Providing a combination, the combination comprising a first current collecting layer, a first electrode layer, an electrolyte layer, a second electrode layer and a second current collecting layer which are stacked in sequence; The first current collector layer has a first groove facing the first electrode layer, the second current collector layer has a second groove facing the second electrode layer, and the first groove and the second groove are both filled with removable fillers; the first electrode layer, the second electrode layer and the electrolyte layer are manufactured by a deposition process; processing the assembly so that the filler is removed to form a fuel flow passage including the first groove and the second groove; The method of treating the assembly so that the filler is removed comprises: Heating the assembly so that the filler disappears by burning or gasification; The filler is a colloid, and the colloid includes polystyrene.

2. The method for manufacturing an all-solid-state thin film fuel cell according to claim 1, characterized in that: The first current collecting layer and the second current collecting layer are manufactured by using an etching process or a deposition process.

3. The method for manufacturing an all-solid-state thin film fuel cell according to claim 1, characterized in that: The deposition process includes sputtering deposition or pulsed laser deposition.

4. The method for manufacturing an all-solid-state thin film fuel cell according to claim 1, characterized in that: The first current collecting layer is made of a first material, and the first current collecting layer is obtained by the following method: forming a patterned first mask on a base layer formed of the first material, and forming a first groove by etching the base layer; The first groove is filled with the filler.

5. The method for manufacturing an all-solid-state thin film fuel cell according to claim 4, characterized in that: The base layer is thinned.

6. The method for manufacturing an all-solid-state thin film fuel cell according to claim 5, characterized in that: The first current collecting layer is obtained by: removing the first mask after etching the base layer to form a first groove and before filling the first groove with the filler; or removing the first mask after filling the first groove with the filler.

7. The method for manufacturing an all-solid-state thin film fuel cell according to claim 6, characterized in that: The second current collecting layer is made of a second material, and the second current collecting layer is obtained by the following method: forming a removal layer at the second electrode using the filler; forming a patterned second mask on the removal layer, forming a second groove by etching the removal layer, and removing the mask; The second groove is filled with a second material in a manner of covering the removal layer.

8. The method for manufacturing an all-solid-state thin film fuel cell according to claim 1, characterized in that: The assembly includes a third electrode, and the third electrode stack is disposed on the second current collecting layer; The second current collecting layer has a third groove facing away from the second electrode layer, and the third groove is occupied by the filler.

9. The method for manufacturing an all-solid-state thin film fuel cell according to claim 1, characterized in that: The method of heating the assembly includes: heating the assembly by a gradient temperature increase method until the filler disappears.

10. The method for manufacturing an all-solid-state thin film fuel cell according to claim 9, characterized in that: After the filler disappears, the assembly is cooled by a gradient cooling method.

11. An all-solid-state thin film fuel cell manufactured according to the manufacturing method according to any one of claims 1 to 10, characterized in that: comprising a first single battery; The first single cell comprises a first current collecting plate, an anode plate, an electrolyte plate, a cathode plate layer and a second current collecting plate which are stacked in sequence, wherein the first current collecting plate and the second current collecting plate are made of semiconductor silicon material, and the anode plate, the electrolyte plate and the cathode plate are made of ceramic material; The first current collecting plate is provided with a first groove facing the anode plate, and the second current collecting plate is provided with a second groove facing the cathode plate, and the first groove and the second groove are configured to transport fuel; The thickness of the all-solid-state thin film fuel cell in the stacking direction reaches micrometer scale or nanometer scale.

12. The all-solid-state thin film fuel cell according to claim 11, characterized in that: The thickness of the anode plate in the stacking direction is 10 to 100 microns; Alternatively, the electrolyte sheet has a thickness in the stacking direction of 5 to 30 microns; Alternatively, the thickness of the cathode plate in the stacking direction is 10 to 100 microns; Alternatively, the thickness of the first current collecting plate in the stacking direction is 50 to 200 microns; Alternatively, the thickness of the second current collecting plate in the stacking direction is 50-200 microns.

13. The all-solid-state thin film fuel cell according to claim 11 or 12, characterized in that: The anode plate is made of a mixture of nickel oxide and yttrium-doped zirconium oxide; Alternatively, the electrolyte plate is made of yttrium-doped zirconium oxide; Alternatively, the cathode plate layer is made of rare earth-based perovskite composite oxide, wherein the rare earth-based perovskite composite oxide includes lanthanum, strontium and manganese ternary composite oxide.

14. The all-solid-state thin film fuel cell according to claim 11, characterized in that: The second current collecting plate has a third groove facing away from the second groove; The all-solid-state thin film fuel cell comprises at least one second unit cell stacked on the first unit cell, each of the at least one second unit cell comprises a second anode plate, a second electrolyte plate, a second cathode plate layer and a third current collector, the third current collector having a fourth groove arranged facing the second cathode; Two adjacent second single cells are stacked in a manner that the third current collecting plate contacts the second anode plate, and the third current collecting plate sandwiched between the second cathode and the second anode is provided with a fifth groove, which is arranged away from the fourth groove.

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