CN107039658A - A kind of method of low cost batch production metal polar plate - Google Patents
A kind of method of low cost batch production metal polar plate Download PDFInfo
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- CN107039658A CN107039658A CN201710134283.2A CN201710134283A CN107039658A CN 107039658 A CN107039658 A CN 107039658A CN 201710134283 A CN201710134283 A CN 201710134283A CN 107039658 A CN107039658 A CN 107039658A
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The present invention relates to a kind of method of low cost batch production metal polar plate, comprise the following steps：(1) metallic plate to be processed is taken to carry out surface preparation；(2) lumarith ink is printed to what step (1) was obtained and handled on clean metallic plate, and dried；(3) take the figure film for designing processing graphic pattern to cover metallic plate, the lumarith ink on metallic plate is exposed and developed, expose the part of needs etching；(4) part for needing to etch is processed using etching solution, etches respective graphical；(5) take off except lumarith ink, drying, that is, the metal polar plate processed at one time；(6) repeat step (2)~step (5) 0 times or more than 1 time, that is, obtain final products metal polar plate.Compared with prior art, the metal polar plate machining accuracy height of the invention processed, almost surfacing, no residual stress, the construction cycle are short, and cost is low.
Description
Technical field
It is low more particularly, to one kind the present invention relates to the exploitation and manufacture of a kind of flow battery and fuel battery metal pole plate
The method that costs in mass produces metal polar plate.
Background technology
The TRT that flow battery, fuel cell etc. need fluid to participate in includes positive and negative pole material, electrolyte membrance
With supply reactive material and the pole plate of coolant fluid.Cost, performance and the durability of pole plate greatly affect flow battery
Commercialization with fuel cell is promoted and application.
Flow battery press valence variation element system difference, can be divided into as full vanadium, Quan Ge, Quan Tie, titanium-iron, chromium-iron, vanadium-
Cerium, and the polytype such as vanadium-bromine, but be required to by the way that the solution of the zwitterion comprising different valence state is passed through on pole plate
Runner introduces positive pole and negative pole respectively, occurs electrochemical reaction and carries out discharge and recharge.Flow battery positive/negative electricity is big to potential difference,
Good reversibility, side reaction is small, and solubility is high and stably, it is easy to prepare, cheap, environment-friendly, corrosivity is small.If can be big
Width reduces the manufacturing cost of the critical material such as amberplex and pole plate and part, and it will have wide application in energy storage field
Prospect, is very suitable for scale development and the utilization of the regenerative resources such as large-scale wind energy, solar energy, tide energy.In new energy
Popularization and application, realize in terms of stable power-supplying possess significance.
Fuel cell includes DMFC (DMFC), hydrogen/sky (oxygen) fuel cell (PEFC), solid oxidation again
The polytypes such as thing fuel cell (SOFC), molten carbonate fuel cell (MCFC), phosphoric acid fuel cell (PAFC).Fuel electricity
Pond is using air or pure oxygen as oxidant, using methanol, hydrogen, methane and hydrazine etc. as fuel, respectively in the positive pole of battery and negative
Electrochemical reaction occurs for pole, so as to obtain electric energy.The advantages of because of its energy conversion efficiency height, cleanliness without any pollution, high power density,
Increasingly paid attention to by national governments, energy enterprise and automobile manufacturing company, numerous and confused portable power source of the exploitation based on PEMFC,
TRT, various types of power stations and vehicular engine.
Flow battery and fuel cell need also exist for pole plate and import liquid or gaseous reactive material, in some low temp fuels
Also need to import cooling medium in battery.As flow battery and the important composition part of fuel cell, pole plate occupies it and surpassed
Cross 60% weight, and whole pile more than 30% cost.Therefore, the cost of reduction pole plate is for flow battery and fuel
The commercialization promotion and application of battery also have far-reaching significance.
The function of pole plate mainly has：(1) collect the electric current of reaction generation and be transmitted to it from the anode of a monocell
The negative electrode of next monocell；(2) separate Oxidizing and Reducing Agents, and reactant is uniformly distributed in positive pole and negative terminal surface；
(3) discharge generation product；(4) if it is necessary, introducing cooling medium, it is ensured that the temperature stabilization of pile, and it is evenly distributed；(5) divide
Every and support each group electrolyte and catalyst in flow battery or fuel cell.
In order to reach above-mentioned requirements, the pole plate of flow battery and fuel cell must have claimed below：(1) high conduction
Property, more effectively to conduct electronics；(2) good sealing, to obstruct the reactive material between adjacent single cells；(3) anti-corruption
Corrosion；(4) preferable bending strength and compression strength；(5) low manufacturing cost.Therefore, the progress of pole plate is for lifting
The specific power density of TRT, notable, the industrialization to whole flow battery and fuel cell that reduces the effect of its manufacturing cost
All there is material impact, this to turn into focus both domestic and external on the material of pole plate and the research of processing technology.
The material bipolar plate material of pole plate is broadly divided into following several classes：Pure graphite material, polymer/conductive filler are combined
Material, carbon/carbon compound material, metal material etc..Graphite has excellent electric conductivity and corrosion resistance, but pure graphite material is in itself
Cost is higher, and its matter is crisp, and difficulty of processing is big, and which has limited its large-scale application.
Because the conductive good, electro-chemical activity of metal is high, good mechanical performance the features such as, traditionally common metal is made
For electrode material.It can include as the bipolar plates metal material of flow battery and fuel cell：It is gold, lead, titanium, titanium-based platinum, stainless
Steel, al and ni based alloy etc..
Because the influence to battery of distribution and pressure drop of anode and cathode reactant is larger, the two factors turn into polar plate flow passage
Design and processing when important consideration.Usually, runner can be divided into following four form：Single channel serpentine flow path, concurrent flow
Road, multichannel serpentine flow path is combined runner etc..The pressure drop of serpentine flow path is big, and the dispersiveness of fluid is preferably.The pressure drop of parallel fluid channels compared with
It is small, but the dispersiveness of fluid does not have serpentine flow path good.Many serpentine flow paths and compound runner then can in summary both advantages.
Traditional sheet metal forming processing technology includes roll-in, punching press etc..Roll-in and Sheet Metal Forming Technology can realize polar plate flow passage
Rolling formation, continuous manufacture, production efficiency is higher, and can make thinner mould development cost during production in enormous quantities, the comprehensive manufacture of reduction
Cost.But during roll-in, contact area diminishes, pressure is uneven, and punching shear can be produced unavoidably；The accuracy of manufacture of roller can shadow
Ring the last forming accuracy of pole plate.
Punch forming process is then formed dependent on one or many punching press metal sheets of tabular mould.Sheet-metal press working into
Shape production efficiency is high, is easy to implement automation, batch production can significantly reduce cost, therefore be paid close attention to by numerous researchers.
Roll-in is with punch forming process except mould and die accuracy requires high, and manufacturing cost is high outer, also there are other weak points,
Such as：Positive and negative is concavo-convex symmetrical, it is impossible to independent design；It is unsuitable for the runner processing of somewhat complex design；Through hole needs secondary operation, it is impossible to
One-shot forming；Stress distribution is uneven, and surface is yielding, and to follow-up close surface corrosion stability processing, seal makes and assembling is caused
Inconvenience etc..
On the other hand, the shaping of metal polar plate belongs to microsecond delay technology category, using the extension of metal when roll-in and punching press
Property greatly, deformed region scope is extremely wide, and the dimensional details of deformation are comparatively small but quantity is again more.So carry out whole pole plate into
, it is necessary to divide substantial amounts of grid when the finite element modelling and design of shape, generally require to take a long time or even appearance can not mould
The situation of plan.Before sheet fabrication is carried out, the side such as the selection of modeling scheme, the optimization of technological parameter, design of shaping dies
Face also has many needs of work to carry out, and this has resulted in high mould development cost.It therefore, it can say so, in society
For demand urgent today increasingly of new energy, the time of high metal plate mold exploitation and financial cost, as restriction
The big bottleneck that flow battery develops with fuel cell.
In view of the limitation of above two technique, pole is necessary a kind of low exploitation of exploitation and manufacturing cost, simple, efficient
Metal polar plate forming technology.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of low cost batch is raw
The method for producing metal polar plate.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of method of low cost batch production metal polar plate, comprises the following steps：
(1) metallic plate to be processed is taken to carry out surface preparation；
(2) lumarith ink is printed to what step (1) was obtained and handled on clean metallic plate, and dried；
(3) take the figure film for designing processing graphic pattern to cover metallic plate, the lumarith ink on metallic plate is exposed
Light and development, expose the part of needs etching；
(4) part for needing to etch is processed using etching solution, etches respective graphical；
(5) take off except lumarith ink, drying, that is, the metal polar plate processed at one time；
(6) repeat step (2)~step (5) 0 times or more than 1 time, that is, obtain final products metal polar plate.
As preferred embodiment, the material of described metallic plate is aluminium, stainless steel, nickel or titanium.
As preferred embodiment, in step (1) metallic plate pre-process technique include brush board, degreasing, descale,
Wash and dry, wherein, descale from a kind of in tumbling, the light that shakes, shot-peening, polishing, chemical polishing or mechanical polishing.
As preferred embodiment, lumarith ink is used and is screen printed onto on metallic plate in step (2), wherein, silk
The environment of wire mark brush be clean dustless space, silk screen be mesh number 100-200 mesh monofilament net, its material be stainless steel, nylon or
Polyester.
As preferred embodiment, the etching solution described in step (4) is alkaline etching liquid or acidic etching liquid, its
In, described alkaline etching liquid is using sodium hydroxide as main etchant, and the main etchant of described acidic etching liquid is hydrochloric acid, nitre
One or more in acid, phosphoric acid, hydrofluoric acid, ferric trichloride, chromic acid, sulfuric acid, oxalic acid, acetic acid.
As further preferred embodiment, the etching solution described in step (4) is acidic etching liquid, and its formula is：Salt
Sour 65g/L, nitric acid 190g/L, ammonium nitrate 135g/L, phosphoric acid 80g/L, remaining is deionized water.
As preferred embodiment, the mode of etching is vertical etching in step (4), and etching solution is on a metal plate
Residence time is 5-15min, and temperature during etching is 45-55 DEG C.To ensure the depth of etching, side corrosion is reduced, can be used
Vertical etching, makes etching solution be evenly distributed in metal sheet surface, flow velocity is consistent everywhere.
As preferred embodiment, taken off in step (5) except after lumarith ink, toast 0.5 at 50 DEG C~150 DEG C~
2 hours.After etching, in addition it is also necessary to remove the protective layer ink of corrosion protection.For alkali resistance ink, removed using dilution heat of sulfuric acid；It is right
In acid resistance ink, then removed using sodium hydroxide solution.
As preferred embodiment, the groove depth for the polar plate flow passage processed on obtained metal polar plate in more than 0.4mm, and
Groove depth：Groove width=0.7~0.9:1.In order to reduce the stream of the fluids such as fuel in electrochemical reaction process, oxidant and cooling medium
Dynamic resistance, etching obtained polar plate flow passage must be deep enough, and general groove depth will reach more than 0.4mm.At the same time, in order to ensure
Good contact area, it is necessary to ensure enough groove widths.Therefore groove depth and the ratio of width need to control in rational model
Enclose, typically require groove depth：Groove width=0.7~0.9：1.
As preferred embodiment, it is wide that the lines of the lumarith ink in step (3) on figure film are reserved with corrosion protection
Degree compensation.Side rate of corrosion in etching process is also required to be maintained at extremely low level, and lateral etching process is as shown in Figure 4.Lateral erosion width
Smaller, then the precision for processing obtained runner is higher.Therefore, lateral erosion width is to need priority control in metal polar plate process
A factor.The formula of lateral erosion width and etching solution, flow velocity, the spray regime of etching machine, the concentration of main etching solution, operation
The etching condition such as temperature and use time has direct relation.The relation of lateral erosion width and depth is as shown in figure 4, mark metal pole
Plate is 8, and lumarith is marked as 9.If being h by the etch depth tested, lateral erosion width is a, then can calculate lateral erosion
Factor F=a/h.If when the etching conditions such as above-mentioned etching solution formula, flow velocity and temperature and etching factor F fixations, lateral erosion is wide
Degree then depends entirely on the etch depth of metallic plate；Etch depth is deeper, and side etching quantity also can be bigger.Conversely, want ensure compared with
In the case of high etch depth and runner (or ridge) width, lateral erosion factor F must be just reduced as far as possible, it is various that this is accomplished by adjustment
Etching condition, most important of which is that the formula of optimization etching solution.On the other hand, it can shift to an earlier date in lumarith in etching
Compensation is made on line thickness.Such as want a width of L of ridge for obtaining etching1, then the width L of lumarith lines2It must be amplified
Compensation, its value can be calculated by following formula and obtained：
L2=L1+h×F×2。
Compared with prior art, the present invention using photochemical etching processing method, with reference to mechanical drawing, silk-screen, exposure,
Development and the process such as chemical etching, manufacture metal polar plate, and unlike roll-in and punch forming process, the present invention is by losing
Etching solution forms common-use tunnel, positioning hole and runner to the corrosiveness of metal base, thus give up there may be deformation with it is interior
Any mechanical processing process of stress, no matter therefore the construction cycle it is short, high-volume or small lot manufacturing cost it is all extremely low, positive and negative
Surface current road can be with independent design, machining accuracy height, almost surfacing, no residual stress；Flow battery and fuel can be achieved
The quick exploitation of battery pole plates is manufactured with low cost.
Brief description of the drawings
Fig. 1 is processing process figure of the invention；
Fig. 2 is the side sectional view of metal polar plate；
Fig. 3 is the ridge and groove schematic diagram of metal polar plate；
Fig. 4 is that schematic diagram occurs for metal polar plate processing processing lateral erosion.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
For side blowing air in hydrogen/sky proton exchange film fuel cell electric piling, side leads to adding for the bipolar plates of cooling water
Work, present embodiments provides a kind of example of metal double polar plates process.It will be understood by those skilled in the art that the present invention is removed
It can be used for outside hydrogen/sky Proton Exchange Membrane Fuel Cells, moreover it can be used to other types of fuel cell and various flow batteries；Remove
It is used for outside 304 stainless steels, can be also used for various metals and its alloys such as other various types of stainless steels and nickel, aluminium, titanium.
Lumarith ink in following embodiments uses acid resistance mask ink.
Fig. 1 is the processing process figure of metal polar plate of the present invention, shared logical according to what is etched on metal polar plate
The structures such as road, positioning hole and runner, can first process the through hole knot such as common-use tunnel and positioning hole using etching and processing method twice
Structure, reprocesses runner, it specifically includes following steps：
(1) metal sheet surface is handled
304 stainless steel plates are placed on Pretreatment Line, brush board, degreasing is carried out by step, descales, the work such as washes
Sequence, finally dries 5 minutes to whole dryings in drying box at 110 DEG C.
(2) first time silk-screen printing
With 150 mesh filament nylon nets, acid resistance mask ink is printed into the stainless steel plate to surface treatment upper, then
Baking 30 minutes is to being completely dried at 150 DEG C of baking oven；
(3) expose for the first time
Covered using the well prepared in advance, transparent film with through-hole patterns such as common-use tunnel, positioning holes in stainless steel plate
On, ink is exposed in exposure machine.The ink of film light transmission part is exposed, and remainder is then shielded.
(4) develop for the first time
Stainless steel plate after ink is exposed is immersed in developer solution, after 10 minutes, that is, manifesting needs each of etching
Throughhole portions, the part without etching was not exposed the ink (i.e. lumarith) of light and protected.
(5) etch for the first time
In vertical etching machine, corresponding metallic plate through hole is etched using etching solution.In etching process, regulation erosion
Quarter, the speed of service of machine was 1 m/min, and 50 ± 5 DEG C of temperature sprays Stress control in 3bar.Etching period 15 minutes, needed for obtaining
Each through hole.
The main formula of this etching solution is as follows：Hydrochloric acid 65g/L, nitric acid 190g/L, ammonium nitrate 135g/L, phosphoric acid 80g/L, its
Remaining is deionized water.
(6) take off for the first time except lumarith
Lumarith ink is removed with the 20%NaOH aqueous solution, and is dried.
(7) second of silk-screen printing
Similarly, using 150 mesh filament nylon nets, acid resistance mask ink is printed to the stainless steel for having etched through hole
On plate, then at 150 DEG C of baking oven baking 30 minutes to being completely dried；
(8) second of exposure
Transparent film with patterns such as flow fields is covered on stainless steel, ink is exposed.
(9) second development
Stainless steel plate after ink is exposed is immersed in developer solution, after 10 minutes, that is, manifests the stream for needing to etch
Road.
(10) second of etching
In vertical etching machine, using with first time etching technological parameter and etching solution, etch corresponding stream
Road is (as shown in Figure 2, it is seen that the metal polar plate of shaping includes ridge a1, ridge b2, runner a2, runner b4, seal groove 5, through hole a6 and led to
Hole b7 etc.).Etching period 8 minutes.
(11) take off for the second time except lumarith
Lumarith ink is removed with the 20%NaOH aqueous solution, and is dried.
(12) dry
The stainless steel plate of etch-forming is placed in baking oven, 30 minutes are toasted at 150 DEG C to being completely dried, and exclude metal
In lattice possibly into hydrogen.
As shown in figure 3, the stainless steel plate that etching is obtained, thickness is 1.0 ± 0.01mm.Air side runner groove depth 0.5 ±
0.05mm, 0.6 ± 0.05mm of groove width, the wide 0.5 ± 0.05mm of ridge.Water side runner 0.3 ± 0.05mm of groove depth, groove width 1.5 ±
0.05mm, the wide 1.0 ± 0.05mm of ridge.Through measurement, its air lateral erosion rate is 0.20, and water side is 0.33.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using invention.
Person skilled in the art obviously can easily make various modifications to these embodiments, and described herein general
Principle is applied in other embodiment without passing through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability
Field technique personnel are according to the announcement of the present invention, and not departing from improvement and modification that scope made all should be the present invention's
Within protection domain.
Claims (10)
1. a kind of method of low cost batch production metal polar plate, it is characterised in that comprise the following steps：
(1) metallic plate to be processed is taken to carry out surface preparation；
(2) lumarith ink is printed to what step (1) was obtained and handled on clean metallic plate, and dried；
(3) take design processing graphic pattern figure film cover metallic plate, the lumarith ink on metallic plate is exposed and
Development, exposes the part of needs etching；
(4) part for needing to etch is processed using etching solution, etches respective graphical；
(5) take off except lumarith ink, drying, that is, the metal polar plate processed at one time；
(6) repeat step (2)~step (5) 0 times or more than 1 time, that is, obtain final products metal polar plate.
2. a kind of method of low cost batch production metal polar plate according to claim 1, it is characterised in that described gold
The material for belonging to plate is aluminium, stainless steel, nickel or titanium.
3. a kind of method of low cost batch production metal polar plate according to claim 1, it is characterised in that step (1)
The technique of middle metallic plate pretreatment includes brush board, degreasing, descales, washes and dry, wherein, the selection tumbling that descales,
Shake a kind of in light, shot-peening, polishing, chemical polishing or mechanical polishing.
4. a kind of method of low cost batch production metal polar plate according to claim 1, it is characterised in that step (2)
Middle lumarith ink is used and is screen printed onto on metallic plate, wherein, the environment of silk-screen printing is clean dustless space, and silk screen is mesh
The monofilament net of number 100-200 mesh, its material is stainless steel, nylon or polyester.
5. a kind of method of low cost batch production metal polar plate according to claim 1, it is characterised in that step (4)
Described in etching solution be alkaline etching liquid or acidic etching liquid, wherein, described alkaline etching liquid is based on sodium hydroxide
Etchant, the main etchant of described acidic etching liquid is hydrochloric acid, nitric acid, phosphoric acid, hydrofluoric acid, ferric trichloride, chromic acid, sulfuric acid,
One or more in oxalic acid, acetic acid.
6. a kind of method of low cost batch production metal polar plate according to claim 5, it is characterised in that step (4)
Described in etching solution be acidic etching liquid, its formula is：Hydrochloric acid 65g/L, nitric acid 190g/L, ammonium nitrate 135g/L, phosphoric acid
80g/L, remaining is deionized water.
7. a kind of method of low cost batch production metal polar plate according to claim 1, it is characterised in that step (4)
The mode of middle etching is vertical etching, and the residence time of etching solution on a metal plate is 5-15min, and temperature during etching is
45-55℃。
8. a kind of method of low cost batch production metal polar plate according to claim 1, it is characterised in that step (5)
In take off except after lumarith ink, toasted 0.5~2 hour at 50 DEG C~150 DEG C.
9. the method for a kind of low cost batch production metal polar plate according to claim 1, it is characterised in that processing is obtained
Metal polar plate on polar plate flow passage groove depth in more than 0.4mm, and groove depth：Groove width=0.7~0.9:1.
10. a kind of method of low cost batch production metal polar plate according to claim 1, it is characterised in that step (3)
The lines of lumarith ink on middle figure film are reserved with corrosion protection width compensation.
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| CN112349924A (en) * | 2020-09-21 | 2021-02-09 | 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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