CN107039658B - Method for low-cost batch production of metal polar plates - Google Patents
Method for low-cost batch production of metal polar plates Download PDFInfo
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- CN107039658B CN107039658B CN201710134283.2A CN201710134283A CN107039658B CN 107039658 B CN107039658 B CN 107039658B CN 201710134283 A CN201710134283 A CN 201710134283A CN 107039658 B CN107039658 B CN 107039658B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention relates to a method for producing metal pole plates in batches at low cost, which comprises the following steps: (1) taking a metal plate to be processed for surface pretreatment; (2) printing the anti-corrosion layer ink on the metal plate which is obtained in the step (1) and is cleaned, and drying; (3) covering the metal plate with a graphic film with a designed processing pattern, and exposing and developing the ink of the anti-corrosion layer on the metal plate to expose the part to be etched; (4) processing the part to be etched by using an etching solution to etch a corresponding pattern; (5) removing the ink of the anti-corrosion layer, and drying to obtain the metal polar plate processed at one time; (6) and (5) repeating the steps (2) to (5) for 0 time or more than 1 time to obtain the final product metal pole plate. Compared with the prior art, the metal polar plate processed by the method has the advantages of high processing precision, smooth surface, almost no residual stress, short development period, low cost and the like.
Description
Technical Field
The invention relates to development and manufacture of metal plates of a flow battery and a fuel battery, in particular to a method for producing the metal plates in batches at low cost.
Background
Flow batteries, fuel cells and other power generation devices requiring fluid participation each include positive and negative electrode materials, an electrolyte membrane, and a plate for supplying reactant and coolant fluids. The cost, performance and durability of the plates greatly affect the commercial promotion and application of flow batteries and fuel cells.
The flow battery can be divided into various types such as all vanadium, all chromium, all iron, titanium-iron, chromium-iron, vanadium-cerium, vanadium-bromine and the like according to different valence element systems, but all the types need to be charged and discharged through electrochemical reaction by respectively introducing solutions containing anions and cations with different valence states into a positive electrode and a negative electrode through a flow channel on a polar plate. The positive/negative electrode pair of the flow battery has the advantages of large potential difference, good reversibility, small side reaction, high and stable solubility, easy preparation, low price, environmental friendliness and small corrosivity. If the manufacturing cost of key materials and components such as ion exchange membranes, polar plates and the like can be greatly reduced, the method has wide application prospect in the field of energy storage, and is very suitable for large-scale development and utilization of renewable energy sources such as wind energy, solar energy, tidal energy and the like. The method has important significance in the aspects of popularization and application of new energy and stable power supply.
Fuel cells also include various types of Direct Methanol Fuel Cells (DMFCs), hydrogen/air (oxygen) fuel cells (PEFCs), Solid Oxide Fuel Cells (SOFCs), Molten Carbonate Fuel Cells (MCFCs), Phosphoric Acid Fuel Cells (PAFCs), and the like. The fuel cell takes air or pure oxygen as an oxidant and takes methanol, hydrogen, methane, hydrazine and the like as fuels, and electrochemical reactions respectively occur at the anode and the cathode of the cell, so that electric energy is obtained. Due to the advantages of high energy conversion efficiency, cleanness, no pollution, high power density and the like, the PEMFC-based mobile power supply, power generation devices, various power stations and vehicle engines are developed by paying more and more attention from governments, energy enterprises and automobile manufacturers.
Flow batteries and fuel cells also require that the plates be fed with liquid or gaseous reactants, and in some low temperature fuel cells it is also necessary to feed a cooling medium. As an important component of flow batteries and fuel cells, the plates account for more than 60% of their weight, and the overall stack costs more than 30%. Therefore, reducing the cost of the plate is of far-reaching significance to the commercial promotion and application of the flow battery and the fuel battery.
The functions of the polar plate are mainly as follows: (1) collecting the current generated by the reaction and conducting it from the anode of one cell to the cathode of the next cell; (2) separating the oxidant and the reductant and uniformly distributing the reactants on the surfaces of the anode and the cathode; (3) discharging the resultant product; (4) if necessary, introducing a cooling medium to ensure that the temperature of the electric pile is stable and is uniformly distributed; (5) separate and support each set of electrolyte and catalyst in a flow cell or fuel cell.
To meet the above requirements, the plates of flow batteries and fuel cells must have the following requirements: (1) high conductivity to conduct electrons more efficiently; (2) good sealing performance to block reaction substances between adjacent single cells; (3) corrosion resistance; (4) better bending strength and compressive strength; (5) low manufacturing cost. Therefore, the research progress of the polar plate has a significant effect on improving the specific power density of the power generation device and reducing the manufacturing cost thereof, and has an important influence on the industrialization of the whole flow battery and the fuel cell, so that research on the material and the processing technology of the polar plate becomes a hot spot at home and abroad.
The bipolar plate materials of the plates can be roughly classified into the following types: pure graphite materials, polymer/conductive filler composites, carbon/carbon composites, metallic materials, and the like. Graphite has excellent conductivity and corrosion resistance, but pure graphite materials are high in cost, brittle and difficult to process, so that large-scale application of the pure graphite materials is limited.
Since metals have the characteristics of good conductivity, high electrochemical activity, excellent mechanical properties and the like, metals are conventionally used as electrode materials. The metal material capable of being used as the bipolar plate of the flow battery and the fuel battery comprises the following components: gold, lead, titanium-based platinum, stainless steel, aluminum, and nickel-based alloys, and the like.
Since the distribution of cathode and anode reactants and the voltage drop have a large influence on the battery, these two factors become important considerations in the design and processing of the plate flow channels. Generally, the flow passages can be divided into the following four forms: single serpentine flow channels, parallel flow channels, multiple serpentine flow channels, composite flow channels, and the like. The pressure drop of the snake-shaped flow passage is large, and the fluid dispersibility is good. The pressure drop of the parallel flow channels is smaller, but the fluid dispersibility is not as good as that of the serpentine flow channels. The advantages of the multi-snake-shaped flow passage and the composite flow passage can be combined.
The conventional metal plate forming process includes rolling, stamping, and the like. The rolling and stamping process can realize the rolling forming and continuous manufacturing of the polar plate flow channel, the production efficiency is higher, the development cost of the die can be reduced during mass production, and the comprehensive manufacturing cost is reduced. However, when the roller is rolled, the contact area becomes small, the pressure is uneven, and the deformation of the plate surface is inevitable; the accuracy of the roll manufacture can affect the final plate forming accuracy.
The stamping forming process relies on one or more stamping operations of a flat die to form the sheet metal. The sheet metal stamping and forming production efficiency is high, the automation is convenient to realize, and the cost can be obviously reduced in batch production, so that the sheet metal stamping and forming production method is concerned by extensive researchers.
The rolling and stamping forming process has other disadvantages besides high requirements on the precision of the die and high manufacturing cost, such as: the front and the back are concave-convex symmetrical and cannot be independently designed; the method is not suitable for processing a flow channel with a complex design; the through hole needs secondary processing and cannot be formed at one time; uneven stress distribution and easy surface deformation, which causes inconvenience to the subsequent corrosion resistance treatment of the dense surface, the manufacture and the assembly of the sealing element, and the like.
On the other hand, the forming of the metal plate belongs to the micro-forming technology field, the ductility of the metal is extremely large when rolling and stamping are adopted, the deformation area range is extremely wide, and the size details of deformation are relatively small but the number is large. Therefore, when finite element simulation and design of the whole plate forming are carried out, a large number of grids need to be divided, and the situation that simulation cannot be carried out often takes a long time. Before the sheet material is processed, much work needs to be carried out on the aspects of selection of a modeling scheme, optimization of process parameters, design of a forming die and the like, so that high die development cost is caused. Therefore, it can be said that, at present, the social demand for new energy is urgent, and the time and economic cost for developing the high metal plate mold become a bottleneck restricting the development of the flow battery and the fuel cell.
In view of the limitations of the above two processes, it is very necessary to develop a simple and efficient metal plate forming process with low development and manufacturing cost.
Disclosure of Invention
The present invention is directed to overcoming the above-mentioned drawbacks of the prior art and providing a method for mass producing metal plates at low cost.
The purpose of the invention can be realized by the following technical scheme:
a method of low cost mass production of metal plates comprising the steps of:
(1) taking a metal plate to be processed for surface pretreatment;
(2) printing the anti-corrosion layer ink on the metal plate which is obtained in the step (1) and is cleaned, and drying;
(3) covering the metal plate with a graphic film with a designed processing pattern, and exposing and developing the ink of the anti-corrosion layer on the metal plate to expose the part to be etched;
(4) processing the part to be etched by using an etching solution to etch a corresponding pattern;
(5) removing the ink of the anti-corrosion layer, and drying to obtain the metal polar plate processed at one time;
(6) and (5) repeating the steps (2) to (5) for 0 time or more than 1 time to obtain the final product metal pole plate.
In a preferred embodiment, the metal plate is made of aluminum, stainless steel, nickel or titanium.
As a preferred embodiment, the process of pretreating the metal plate in the step (1) comprises brushing the plate, degreasing, removing scale, washing with water and drying, wherein the removing scale is selected from one of tumbling, vibrating, shot blasting, polishing, chemical polishing or mechanical polishing.
In a preferred embodiment, the ink for the anti-corrosion layer in step (2) is screen-printed on the metal plate, wherein the environment for screen-printing is a clean and dust-free space, and the screen is a single screen with 100-200 meshes, and the material of the single screen is stainless steel, nylon or polyester.
As a preferred embodiment, the etching solution in step (4) is an alkaline etching solution or an acidic etching solution, wherein the alkaline etching solution uses sodium hydroxide as a main etchant, and the main etchant of the acidic etching solution is one or more of hydrochloric acid, nitric acid, phosphoric acid, hydrofluoric acid, ferric trichloride, chromic acid, sulfuric acid, oxalic acid, and acetic acid.
As a more preferable embodiment, the etching solution in the step (4) is an acidic etching solution, and the formula of the acidic etching solution is 65 g/L g of hydrochloric acid, 190 g/L g of nitric acid, 135 g/L g of ammonium nitrate, 80 g/L g of phosphoric acid and the balance of deionized water.
As a preferred embodiment, the etching mode in the step (4) is vertical etching, the residence time of the etching solution on the metal plate is 5-15min, and the temperature during etching is 45-55 ℃. In order to ensure the etching depth and reduce side corrosion, vertical etching can be adopted, so that the etching solution is uniformly distributed on the surface of the metal plate, and the flow rate of the etching solution is consistent everywhere.
In a preferred embodiment, after removing the ink of the anti-corrosion layer in the step (5), the substrate is baked at 50 to 150 ℃ for 0.5 to 2 hours. After etching, the resist ink needs to be removed. For alkali-resistant ink, removing with dilute sulfuric acid solution; for acid resistant inks, sodium hydroxide solution is used for removal.
As a preferred embodiment, the groove depth of the plate flow channel on the processed metal plate is more than 0.4mm, and the groove depth is as follows: the groove width is 0.7-0.9: 1. In order to reduce the flow resistance of the fuel, oxidant, cooling medium and other fluids in the electrochemical reaction process, the etched plate flow channel must be deep enough, and the groove depth is generally more than 0.4 mm. At the same time, in order to ensure a good contact area, a sufficient groove width must also be ensured. Therefore, the ratio of the groove depth to the width needs to be controlled within a reasonable range, and the groove depth is generally required to be: the groove width is 0.7-0.9: 1.
in the preferred embodiment, the etching width of the etching resist ink lines on the graphic film in step (3) is reserved with the etching width compensation, the etching rate of the etching process is required to be kept at an extremely low level, the etching process is shown in fig. 4, the smaller the etching width is, the higher the accuracy of the processed flow channel is, the more important the etching width is, the more important the control of the etching process of the metal plate, the etching width is, as shown in fig. 4, the metal plate is marked with 8, the etching resist is marked with 9, if the etching depth is h and the etching width is a, the side etching factor F is calculated as a/h, if the etching conditions such as the etching solution formula, the flow rate and the temperature and the etching factor F are fixed, the etching width is completely determined by the etching depth of the metal plate, the etching depth is increased, the etching amount is increased as much as possible, the etching amount of the etching solution is increased as much as possible, and if the etching condition of the etching width of the etching channel is increased, the etching width compensation is required, the etching width compensation is optimized, the etching width is increased, the etching width is, the most important the etching width is, the etching width is reduced, the formula is, the formula of the etching width compensation is, the etching width is increased, the formula of the etching width is, the etching width is1Of lines of the resist layerWidth L2The amplification compensation is performed, and the value can be calculated by the following formula:
L2＝L1+h×F×2。
compared with the prior art, the method adopts a processing method of photochemical etching, combines the processes of mechanical drawing, silk-screen printing, exposure, development, chemical etching and the like to manufacture the metal pole plate, and is different from the processes of rolling and punch forming, the method forms a common channel, a positioning hole and a flow channel by the corrosion action of an etching solution on a metal substrate, thereby abandoning any mechanical processing process which can possibly generate deformation and internal stress, so the development period is short, the manufacturing cost is extremely low no matter in large batch or small batch, a front flow channel and a back flow channel can be independently designed, the processing precision is high, the surface is smooth, and residual stress is hardly generated; the fast development and low-cost manufacture of the flow battery and the fuel battery pole plate can be realized.
Drawings
FIG. 1 is a flow chart of the process of the present invention;
FIG. 2 is a side cross-sectional view of a metal plate;
FIG. 3 is a schematic view of a ridge and a groove of a metal plate;
FIG. 4 is a schematic diagram of the occurrence of side etching in the process of machining a metal plate.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
The embodiment provides an example of a metal bipolar plate processing process for processing a bipolar plate which is provided with air on one side and cooling water on the other side in a hydrogen/air proton exchange membrane fuel cell stack. It will be appreciated by those skilled in the art that the present invention can be used in other types of fuel cells and various flow batteries in addition to hydrogen/air proton exchange membrane fuel cells; besides 304 stainless steel, the stainless steel can also be used for various types of stainless steel and various metals such as nickel, aluminum, titanium and the like and alloys thereof.
The resist ink in the following examples was acid-resistant mask ink.
Fig. 1 is a flow chart of a processing technique of a metal plate according to the present invention, and according to structures such as a common channel, a positioning hole, and a runner etched on the metal plate, a twice etching processing method can be adopted, that is, a through hole structure such as the common channel and the positioning hole is processed first, and then the runner is processed, which specifically includes the following steps:
(1) surface treatment of metal sheets
Placing a 304 stainless steel plate on a pretreatment production line, performing processes of plate brushing, degreasing, descaling, water washing and the like according to steps, and finally drying for 5 minutes in a drying oven at 110 ℃ until the stainless steel plate is completely dried.
(2) First screen printing
Printing acid-resistant mask ink on the stainless steel plate with the surface-treated monofilament nylon net by using a 150-mesh monofilament nylon net, and then baking the stainless steel plate in an oven at 150 ℃ for 30 minutes until the stainless steel plate is completely dried;
(3) first exposure
Covering a transparent film with through hole patterns such as a shared channel, a positioning hole and the like on a stainless steel plate by using a prepared transparent film, and exposing the printing ink in an exposure machine. The ink in the light-transmitting part of the film is exposed, and the rest is shielded.
(4) First development
The exposed stainless steel plate is soaked in a developing solution, and after 10 minutes, the parts of the through holes needing to be etched are exposed, and the parts which do not need to be etched are protected by the unexposed ink (namely, an anti-corrosion layer).
(5) First etching
In the vertical etching machine, etching solution is adopted to etch the corresponding through hole of the metal plate. During the etching process, the running speed of the etching machine is adjusted to be 1 m/min, the temperature is 50 +/-5 ℃, and the injection pressure is controlled to be 3 bar. Etching time was 15 minutes to obtain the desired vias.
The main formula of the etching solution is 65 g/L g of hydrochloric acid, 190 g/L g of nitric acid, 135 g/L g of ammonium nitrate, 80 g/L g of phosphoric acid and the balance of deionized water.
(6) First removing the corrosion-resistant layer
And removing the ink of the anti-corrosion layer by using a 20% NaOH aqueous solution, and drying.
(7) Second screen printing
Similarly, printing acid-resistant mask ink on a stainless steel plate with etched through holes by adopting a 150-mesh monofilament nylon net, and then baking for 30 minutes in an oven at 150 ℃ until the printing is completely dried;
(8) second exposure
Covering the transparent film with the flow field and other patterns on the stainless steel plate, and exposing the printing ink.
(9) Second development
And soaking the exposed stainless steel plate in a developing solution for 10 minutes to expose the flow channel to be etched.
(10) Second etching
In the vertical etching machine, the same process parameters and etching solution as those in the first etching are used to etch corresponding flow channels (as shown in fig. 2, it can be seen that the formed metal plate includes a ridge a1, a ridge b2, a flow channel a2, a flow channel b4, a sealing groove 5, a through hole a6, a through hole b7, etc.). The etching time was 8 minutes.
(11) Second removal of the corrosion protection layer
And removing the ink of the anti-corrosion layer by using a 20% NaOH aqueous solution, and drying.
(12) Drying by baking
And (3) placing the etched and formed stainless steel plate in an oven, baking for 30 minutes at 150 ℃ until the stainless steel plate is completely dried, and removing hydrogen which may enter a metal lattice.
As shown in FIG. 3, the stainless steel plate obtained by etching had a thickness of 1.0. + -. 0.01 mm. The air side runner groove depth is 0.5 plus or minus 0.05mm, the groove width is 0.6 plus or minus 0.05mm, and the ridge width is 0.5 plus or minus 0.05 mm. The depth of the water side runner groove is 0.3 +/-0.05 mm, the groove width is 1.5 +/-0.05 mm, and the ridge width is 1.0 +/-0.05 mm. The air side etch rate was measured to be 0.20 and the water side 0.33.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (1)
1. A method for low-cost mass production of metal plates is characterized by comprising the following steps:
(1) taking a metal plate to be processed for surface pretreatment;
(2) printing the anti-corrosion layer ink on the metal plate which is obtained in the step (1) and is cleaned, and drying;
(3) covering the metal plate with a graphic film with a designed processing pattern, and exposing and developing the ink of the anti-corrosion layer on the metal plate to expose the part to be etched;
(4) processing the part to be etched by using an etching solution to etch a corresponding pattern;
(5) removing the ink of the anti-corrosion layer, and drying to obtain the metal polar plate processed at one time;
(6) repeating the steps (2) to (5) for 0 time or more than 1 time to obtain a final product, namely the metal pole plate;
the etching solution in the step (4) is an acidic etching solution, and the formula of the acidic etching solution comprises 65 g/L g of hydrochloric acid, 190 g/L g of nitric acid, 135 g/L g of ammonium nitrate, 80 g/L g of phosphoric acid and the balance of deionized water;
the etching mode in the step (4) is vertical etching, the retention time of the etching solution on the metal plate is 5-15min, and the temperature during etching is 45-55 ℃;
the groove depth of the polar plate runner on the processed metal polar plate is more than 0.4mm, and the groove depth is as follows: the groove width is 0.7-0.9: 1;
the metal plate is made of aluminum, stainless steel, nickel or titanium;
the metal plate pretreatment process in the step (1) comprises plate brushing, degreasing, descaling, water washing and drying, wherein the descaling is one of roller burnishing, vibration polishing, shot blasting, polishing, chemical polishing or mechanical polishing;
the ink of the anti-corrosion layer in the step (2) is printed on the metal plate by screen printing, wherein the environment of the screen printing is a clean dust-free space, and the screen is a single screen with the mesh number of 100 and 200 meshes and is made of stainless steel, nylon or polyester;
after removing the ink of the anti-corrosion layer in the step (5), baking for 0.5-2 hours at 50-150 ℃;
and (4) reserving an anti-corrosion width compensation for the lines of the anti-corrosion layer ink on the graphic film in the step (3).
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| CN110507229A (en) * | 2019-08-18 | 2019-11-29 | 应伟明 | A kind of manufacturing method and composite ganoine defrosting chopping board of composite ganoine defrosting chopping board |
| CN112349924B (en) * | 2020-09-21 | 2022-03-18 | 中国科学院大连化学物理研究所 | Etching processing method of conductive partition plate with gas-liquid distribution flow field |
| CN112680730A (en) * | 2020-12-01 | 2021-04-20 | 上海易慧机电科技有限公司 | Stainless steel product mark etching method |
| CN113140654A (en) * | 2021-03-31 | 2021-07-20 | 扬州工业职业技术学院 | Preparation method of solar cell metal base |
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| CN102747367A (en) * | 2011-02-15 | 2012-10-24 | 三星电子株式会社 | Non-halogenated etchant and method of manufacturing a display substrate using the non-halogenated etchant |
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| CN103374725A (en) * | 2013-06-27 | 2013-10-30 | 天长市京发铝业有限公司 | Chemical etching process of aluminum plate |
| CN104233302A (en) * | 2014-09-15 | 2014-12-24 | 南通万德科技有限公司 | Etching liquid and application thereof |
| CN105295923A (en) * | 2015-11-25 | 2016-02-03 | 江阴江化微电子材料股份有限公司 | High generation tablet personal computer ITO etching solution |
| CN105970225A (en) * | 2016-07-01 | 2016-09-28 | 苏州博洋化学股份有限公司 | Aluminum etching agent and preparation method thereof |
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