CN101043078A - Composite dual-electrode plates preparation method of minisize directly connecting methanol fuel battery - Google Patents
Composite dual-electrode plates preparation method of minisize directly connecting methanol fuel battery Download PDFInfo
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- CN101043078A CN101043078A CNA2007100177938A CN200710017793A CN101043078A CN 101043078 A CN101043078 A CN 101043078A CN A2007100177938 A CNA2007100177938 A CN A2007100177938A CN 200710017793 A CN200710017793 A CN 200710017793A CN 101043078 A CN101043078 A CN 101043078A
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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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- 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
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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract
The invention discloses a clad plate preparation method of micro methanol battery, the modified polymethyl methacryate is the basis materials, the high conductivity copper is conductive layer, and the nickel is as the anti-corrosion protective material. Adopting non-siliceous composite preparation technology, firstly producing the master mask and silicon rubber soft mould; then adopting the craft of 'inverse autogram' to stamp the micro channel of flow field on the modified polymethyl methacryate whose substrate is glass; then depositing the copper on surface of micro channel with craft of plating, a layer of nickel is plated on the substrate of the copper, then the composite deposite is nitration surface modified treatment; at last, after eliminating the glass substrate, producing the imports and exports of the reactants and resultant by laser micromachining. The polymer/copper nickel base clad plate possesses advantages that the weight is light, the volume is small, performance is well, cost is low, and it fits for batch size production.
Description
Technical field
The invention belongs to the micro fuel cell technical field, that the composite dual-electrode plates preparation method that relates to a kind of micro direct methanol fuel battery (μ DMFC), the Ni-based composite dual-electrode plates of μ DMFC polymer/copper of this method preparation have is in light weight, volume is little, performance good, cost of manufacture is low, can be fit to making in enormous quantities.
Background technology
Along with wireless telecommunications system and all kinds of portable type electronic product (as mobile phone, notebook computer, digital machine, PDA, MP4 etc.) continue to bring out and the improving constantly of performance, increasing to the demand of high-energy, minicell.And traditional NI-G, ni-mh and lithium ion battery have been difficult to adapt to the requirement of these production developments.In addition, minicell is integrated on the same chip as the part of whole M EMS system, for microsensor, microactrator, microprocessor etc. in the system provide independent power supply, the fast development of other functional unit relatively and in the MEMS system, the research of minicell is backward relatively, has become the bottleneck that restriction MEMS deeply develops.Therefore, need the research and development of carrying out minicell badly.Minicell mainly contains in the world at present: micro zinc-nickel battery, miniature solid electrolyte lithium battery, miniature solar battery, miniature thermoelectric cell and micro fuel cell and miniature isotope battery etc.Minicell with respect to other kinds, micro direct methanol fuel battery (MicroDirectMethanolFuelCell, be called for short MDMFC or μ DMFC) (reach 60%～80% with its energy conversion efficiency height, be not subjected to " Carnot cycle " restriction), specific energy height (specific energy and volumetric specific energy reach 6000Wh/kg and 4800Wh/L respectively), (product mainly is water and amounts of carbon dioxide in environmental protection, and noise is little), startup is rapid, in light weight, volume is little, advantages of simple structure and simple, has become the optimal selection of current minicell and little energy.But, the commercialization and the marketization of micro direct methanol fuel battery at present still faces many technical barriers and challenge, such as the methanol crossover problem of proton exchange membrane, seek the electrode material of non-precious metal, further improve its specific energy and specific power, fail safe, low cost and new structural material and little processing and preparing technology etc. efficiently.Wherein bipolar plates and preparation method thereof is at first to need one of key technology that solves cheaply.Bipolar plates (collector plate, flow-field plate) is one of critical component of μ DMFC, and it has following function and characteristics: (1) distributes fuel and the oxidant in the battery; (2) collect the conveying electric current; (3) each battery in the separate batteries heap; (4) get rid of battery and produce heat; (5) support membrane electrode; (6) even distributing gas on entire electrode.Performance, volume, life-span, cost (accounting for 30%) and the lightweight (accounting for 60-80%) of μ DMFC played a part very important, therefore, reduce cost of bipolar plates and improve its performance and have extremely important meaning for the industrialization of μ DMFC.
The subject matter that bipolar plates is made is at raw-material selection and moulding process.The used material of conventional direct methanol fuel cell bipolar plates mainly contains three classes: the metallic plate of pure graphite cake of atresia or carbon plate, surface modification or alloy sheets, composite panel (carbon/polymer composites and carbon/carbon composite).Its forming method mainly contains: compression molding, punch forming, injection moulding, extrude-injection moulding, precast body moulding, " SlurryMoulding " and machining etc.Existing micro fuel cell reactant miniflow field generally is made up of a series of little raceway grooves of arranging according to certain rule, and the degree of depth of little raceway groove, width dimensions have reached sub-micron to tens micron number magnitude.After the flow field structure form is determined, for improving the specific power and the energy conversion efficiency of fuel cell, the microminiaturization of design forward and the densification direction of bipolar plates raceway groove develop, result of study shows: under the situation of identical percent opening, groove dimensions more little (can realize sufficient reaction), battery performance is good more.The feature width of μ DMFC is generally 1 μ m-300 μ m, be in the scope of microfabrication, the bipolar plates that the preparation technology of conventional bipolar plates can't make μ DMFC, the main at present fine processes such as little Milling Process, MEMS, Laser Micro-Machining that adopt.Little milling and laser micro-machining technology all are the microminiaturizations of traditional process technology, can process precision tens microns micro-structural.The figure micro-structural that designs can be transferred to base material and get on, and can process the figure of different depth.Their machinable materials are comparatively extensive.But working (machining) efficiency is lower, the production cost height.But be suitable for processing the minisize mould that is used to prepare bipolar plates.Adopt the bipolar plates of MEMS prepared μ DMFC to become common recognition gradually in recent years.Adopt MEMS technology (photoetching, wet etching, plasma etching, LPCVD, sputter, body/surperficial little processing etc.) preparation silicon-base miniature fuel to be proved to be a kind of effective preparation method.Therefore, the bipolar plates of μ DMFC mainly is based on silica-based at present, and preparation technology adopts the MEMS technology.The preparation of the bipolar plates of existing bibliographical information only is a process procedure during whole μ DMFC makes.The MEMS preparation method of silica-based bipolar plates has many advantages: 1) with the favorable compatibility of IC technology; 2) effectively reduce the characteristic size of micro fuel cell; 3) improve battery performance, improved volumetric specific power; 4) be fit to batch making etc.But, make silica-based bipolar plates method based on MEMS technology, the deficiency of its maximum is that cost of manufacture height, efficient are low, can't realize the preparation of very three-dimensional little raceway groove.In addition, compare with existing rectangle, trapezoidal or triangular channels cross sectional shape, shaped form cross section ditch passage double pole plate has more performance, shaped form cross section raceway groove is a kind of large-area three-dimensional micro-structural, the traditional micro-fabrication technology that grows up based on microelectric technique generally can only form two-dimension plane structure or accurate three-dimensional microstructures, be difficult to process true three-dimensional microstructures, low-cost production's large-area three-dimensional micro-structural remains technological difficulties.And, compare with the bipolar plates of silica-based μ DMFC, be that the μ DMFC bipolar plates of matrix has more performance with the polymer: 1) preparation easily; 2) good adhesiveness; 3) reduce the resistance of proton exchange membrane and electrode; 4) need not silicon substrate is carried out etching, simplified technology; 5) reduced cost of manufacture.Thereby, press for exploitation new μ DMFC bipolar plates and low-cost preparation method thereof, the present invention proposes the Ni-based composite dual-electrode plates of a kind of new polymers/copper for this reason, and develops the compound preparation technology of a kind of non-silicon, realizes the low cost preparation of micro direct methanol fuel battery with bipolar plates.
Summary of the invention
The objective of the invention is to, a kind of μ of being used for DMFC NEW TYPE OF COMPOSITE bipolar plates and low-cost technology of preparing thereof are provided.For this reason, the present invention proposes a kind of new Ni-based composite dual-electrode plates of μ DMFC polymer/copper, and a kind of non-silicon produced with combination technology proposed, this technology combines the advantage of micro-embossing (a kind of low cost, large tracts of land, high efficiency, accurate micro-nano structure replica technology) and microplating, and by the copper nickel coating being carried out nitrided surface modification processing, improve the corrosion resistance of composite dual-electrode plates, reduced contact resistance.Realize the low-cost preparation of the Ni-based composite dual-electrode plates of μ DMFC polymer/copper.This novel Ni-based composite bipolar plate structure of μ DMFC polymer/copper and preparation method thereof, have in light weight, volume is little, performance good, cost of manufacture is low, be fit to advantage of making in enormous quantities, for μ DMFC provides a kind of composite dual-electrode plates and low-cost preparation technology thereof.
To achieve these goals, the present invention takes following technical solution:
A kind of composite dual-electrode plates preparation method of micro direct methanol fuel battery, it is characterized in that, this method is a basis material with the polymethyl methacrylate of the modification that is spin-coated on the glass substrate substrate, the deposition combarloy is a conductive layer on matrix, as anticorrosive protective material, adopt the composite dual-electrode plates of non-silicon produced with combination prepared micro direct methanol fuel battery at conductive layer microplating nickel or Cr or Ni-50Cr alloy;
Described non-silicon produced with combination technology is at first to carry out the making of mastering and silicon rubber soft mold; Adopt " contrary impression " technology on the modified poly (methyl methacrylate) that with glass is substrate, to impress out little raceway groove in flow field subsequently; Utilize microplating technology plated metal copper on little channel surface then, in the substrate of electro-coppering, continue to electroplate the thin bright nickel layer of one deck, and after the plating reprocessing is finished, again the copper nickel composite deposite is carried out the nitrided surface modification and handle; At last, behind the removal glass substrate, make the import and export of reactant and product by Laser Micro-Machining.
Imprint lithography (IL) is a kind of brand-new nano graph clone method that the Zhou Yu by scientist's Princeton of Chinese origin university at first proposed in nineteen ninety-five, it adopts traditional little replica mechanism of machine die to replace comprising the traditional complicated optical lithography of optics, chemistry and photochemical reaction mechanism, avoided special exposure electron gun, high accuracy lens system, utmost point short wavelength lenses system and resist resolution are subjected to the restriction and the requirement of light half-wavelength effect, the minimum feature size of impression can reach 6nm at present.Imprint lithography (IL) is than existing projection lithography and other photoetching of future generation (NGL) technology, have characteristics such as high resolution, Ultra Low Cost (internal authority mechanism assesses the imprint lithography (IL) of equal production technique than the low at least order of magnitude of traditional optical projection lithography) and high production rate, be included into 2005 editions international semiconductor blueprint (ITRS), and come ITRS blueprint 16nm node.
Making nine parts that the basic craft course based on micro-embossing and the Ni-based composite dual-electrode plates of the compound preparation μ of the non-silicon of microplating DMFC polymer/copper that the present invention proposes is imported and exported by the contrary imprinting moulding of making, substrate preliminary treatment, the making of substrate alignment mark, sputtering seed layer, little raceway groove, electroplating deposition copper and mickel, copper nickel composite deposite nitrided surface modification processing, reactant and the product of mastering, silicon rubber soft mold are formed.Specifically may further comprise the steps:
1) mastering
The shape and size in flow field are the cores of design bipolar plates, and reasonably the flow field should guarantee that electrode all can obtain sufficient reactant supply everywhere, guarantees the discharge of reaction product water simultaneously again.According to the results of optimum design of bipolar plate flow field, make mother matrix.Mastering is the generation phase of the little feature of bipolar plate flow field, adopts electron-beam direct writing and little electroforming to make mother matrix.Though this manufacture method cost is higher, a secondary mother matrix can be used multiple times makes the silicon rubber soft mold.
2) making of silicon rubber soft mold
It is to be used for shifted the first time of the little feature in flow field that silicon rubber (PDMS) soft mold is made, and little channel features on the mother matrix is transferred to the silicon rubber soft mold that is used for micro-embossing technology, and mould adopts quartz material to make substrate, and silicon rubber is as mold materials.
3) substrate preliminary treatment
Get quartz glass substrate as the substrate of making composite dual-electrode plates, adopt nitrogen current and method for suppersonic cleaning that quartz glass substrate is cleaned, remove greasy dirt, the quartz glass substrate after the cleaning toasted 3 hours in 180 ℃ of baking ovens;
4) the quartz glass substrate alignment mark is made
In imprint lithography (IL) technology, owing to carry out overlay alignment and pattern stitching, so must make the pattern (Mark) that is used to aim on the impressing mould.Mark only is used for aiming in moulding process, does not participate in the transfer moulding process of pattern, so Mark and pattern transition range must be on two planes.
Adopt low-pressure chemical vapor deposition method, at quartz glass substrate surface deposition one deck chromium; Adopt rotation to be coated with shop one deck positive photoresist at chromium surface subsequently; Evenly be coated with spread photoresist after, expose, develop; At last, adopt reactive ion etching that unnecessary Cr is got rid of, and sputter one deck Al
2O
3Transparent protective film repeatedly is used with the protection figure;
5) sputtering seed layer
In micro direct methanol fuel battery, electrochemical reaction occurs in the surface of bipolar plate flow field, and the electronics of generation is collected by polar board surface and is transmitted to external circuit, and the surface, flow field of bipolar plates must have conductivity.And the substrate of finishing the feature pattern transfer belongs to nonconducting organic material, therefore need be to the processing of substrate plate conduction.Therefore, before micro-embossing technology, the thick Cr/Cu plating seed layer of the about 100nm of sputter one deck on substrate at first.
6) the contrary imprinting moulding of little raceway groove
The polymethyl methacrylate of cast modification in the die cavity of silicon rubber soft mold, and levelling surface, the organic photo-curing material of silicon rubber soft mold and levelling processing back is pressed to quartz glass, fully behind the photocuring, the demoulding, produce little raceway groove (a kind of " contrary impression " technology) of bipolar plates, finish the making of little channel features;
7) electroplating deposition copper and mickel on basis material
Selected the copper nickel composite deposite as the bipolar plates metal conducting layer, at first utilize microplating technology on prepared little channel surface, to deposit 100 μ m thickness copper metal conducting layers, continue to electroplate the bright nickel coating of 25 μ m thereon as substrate then as anticorrosive protective coating.
Though the standard electrode potential height of copper (+0.337V) belong to the corrosion resistance material, because copper coating is in being applied to anode of fuel cell the time, the carbon dioxide CO that can discharge with water and reaction
2Have an effect, surface corrosion generates verdigris (basic copper carbonate), thereby has influence on the performance and the useful life of battery.Therefore, need carry out corrosion-resistant treatments to copper.When electronickelling (or Cr) layer was tested in fuel cell, because the corrosion resistance that the protection of surface passivation layer shows obviously will be higher than copper, and the resistivity of nickel was 6.8 * 10
-8Ω m is the resistivity 1.75 * 10 of copper
-8Nearly 3.9 times of Ω m, but the cost of nickel coating is higher than copper coating also far away.Therefore, this process using continues to electroplate the method for the composite galvanized coating of thin protectiveness nickel dam of one deck in the substrate of electro-coppering.In addition, because the material constant of copper and mickel can be found the close (copper: 17.7 * 10 of the thermal coefficient of expansion of copper, nickel
-6℃
-1Nickel: 17.9 * 10
-6℃
-1), this thermal deformation meeting that makes composite galvanized coating produce under the situation of variations in temperature is very little, can ignore its influence.
8) modification of copper nickel composite deposite nitrided surface is handled
In order to reduce the bipolar plates contact resistance, improve the performance of μ DMFC, the copper nickel composite deposite is carried out the nitrided surface modification handle.Nitriding can improve the corrosion resistance of steamalloy, and contact resistance further reduces after the nitriding modification, can improve the performance of μ DMFC.Though it is more satisfactory proton exchange membrane (PEMFC) bipolar plate material that people such as Brady and Davies result of study shows the Ni-50Cr of nitriding modification, more have superiority aspect useful life at raising battery performance, prolongation pole plate, but for entering commercial market μ DMFC's, employing is low-cost, conductivity coating high, that corrosion resistance is good is more practical, therefore, the present invention adopts this kind technology.
9) remove glass substrate;
10) making of the import and export of reactant and product
Make the import and export of reactant and product by Laser Micro-Machining.
This novel Ni-based composite bipolar plate structure of μ DMFC polymer/copper and non-silicon composite preparation process thereof of the present invention, have in light weight, volume is little, performance good, cost of manufacture is low, be fit to advantage of making in enormous quantities.
Description of drawings
Fig. 1 is the non-silicon produced with combination of the Ni-based composite dual-electrode plates of μ DMFC polymer/copper of the present invention technology path figure.
Fig. 2 is that employing electron-beam direct writing of the present invention has three-dimensional microstructures feature (little raceway groove of bipolar plates) mother matrix schematic diagram in conjunction with little electroforming process making.
Fig. 3 adopts electron-beam direct writing to be deposited on SiO on the glass substrate in conjunction with deep etching
2Layer is made the principle schematic of mother matrix.
Fig. 4 is the structure chart of impression soft mold profile of the present invention.
Fig. 5 is a silicon rubber soft mold manufacture craft flow chart of the present invention.
Fig. 6 is the making schematic diagram of impressing mould alignment mark Mark of the present invention.
Fig. 7 is that employing of the present invention " soft mold " and " contrary impression " technology are made the imprinting moulding schematic diagram of the little raceway groove of large-area three-dimensional on the polymethyl methacrylate of modification.
The present invention is described in further detail according to embodiment that technical scheme of the present invention provides below in conjunction with accompanying drawing and inventor.
Embodiment
The composite dual-electrode plates preparation method of micro direct methanol fuel battery of the present invention; polymethyl methacrylate with the modification that is spin-coated on glass substrate is a basis material; the deposition combarloy is a conductive layer on matrix; as anticorrosive protective material, adopt the composite dual-electrode plates of non-silicon produced with combination prepared micro direct methanol fuel battery at conductive layer microplating nickel or Cr or Ni-50Cr alloy.Its preparation method adopts a kind of new non-silicon produced with combination technology, this process synthesis the advantage of micro-embossing and microplating depositing operation, and handle by the copper nickel coating being carried out the nitrided surface modification, improve the corrosion resistance of composite dual-electrode plates, reduced contact resistance.
The non-silicon produced with combination technology path of the Ni-based composite dual-electrode plates of micro direct methanol fuel battery polymer/copper comprises referring to Fig. 1: 1. mastering; 2. the making of silicon rubber soft mold; 3. substrate preliminary treatment; 4. the substrate alignment mark is made; 5. sputtering seed layer; 6. the contrary imprinting moulding of little raceway groove; 7. electroplating deposition copper and mickel; 8. the modification of coating nitrided surface is handled; 9. remove glass substrate; 10. the making of the import and export of reactant and product.
(1) mastering
Use the e-beam direct write lithography system, follow an exposure scanpath to continuously change the ability of its exposure dose owing to it has, thereby can on electric lithography glue, obtain the continually varying exposure depth.Utilize this characteristic, can on electric lithography glue, form the micro-nano structure of 3D shape.Because need usually to adopt a secondary mother matrix, make a plurality of silicon rubber soft molds.Therefore, mastering becomes metal die, adopts little electroforming process for this reason, and precise electrotyping goes out to comprise the metal die (the present invention adopts the electroforming metal nickel) of Field Characteristics micro-structural on hard system back lining materials.
Fig. 2 has sub-micron three-dimensional microstructures feature (the little raceway groove of bipolar plates) mother matrix to make principle schematic: a figure has to follow an exposure scanpath to continuously change the electron beam lithography of its exposure depth, and the exposure area in the electric lithography colloid is trapezoidal sidewall micro-structural; B figure is the electric lithography glue deep submicron 3-D micro-structural after development removes glue; C figure is accurate little electroforming, and metal deposition in the micro-structural of electric lithography glue, is formed transoid sub-micron micro-structural mould; D figure combines mould with metal-backed, to increase mother matrix rigidity.
Fig. 3 is deposited on SiO on the glass substrate by etching
2Layer is made the principle schematic of mother matrix.A figure is at glass deposition one deck ito thin film, adopts PECVD deposition SiO subsequently
2, its thickness determines according to prepared microstructure graph; B figure is at SiO
2Last rotation is coated with the shop electron beam resist, and adopts electron beam lithography to make microstructure graph, the microstructure graph on the back electron beam resist that develops; C figure is etching SiO
2The microstructure graph of Xing Chenging thereon.
(2) making of silicon rubber (PDMS) soft mold
The used mould of micro-embossing can be divided into soft mold and hard mold according to material hardness.The surface energy height of hard mold material, close with resist surface energy after solidifying, stick together easily, be difficult for the demoulding.Must influence impression efficient greatly at the mould surface spraying release agent in actual use.And, also stick together easily even sprayed release agent.The demoulding for the large-area three-dimensional micro-structural is particularly difficult.In addition because the parallelism error and the flatness tolerance issues that exist between silicon chip surface and the hard mold surface, cause between hard mold and the silicon chip surface to contact effect relatively poor, also limited the effective area of pattern conversion simultaneously.Soft mold is compared with hard mold, its sharpest edges are that mold materials has certain elasticity, can be good at adapting to flatness tolerance and depth of parallelism error problem between mould and the silicon chip, can increase the imprinting area area, improve impression efficient, satisfy the requirement of large-area micro-imprinting seal technology.But the elasticity of soft mold has also been introduced the problem on deformation in the moulding process, the failure that this distortion can cause pattern to shift equally.Because the loaded load in the impression loading procedure must be accurately controlled in the pattern distortion that die deformation causes, cause loading procedure complicated in order to control and to eliminate.By contrasting various correlative factors, find that soft mold is compared with hard mold has following advantage: the resist curing and demolding is easy in imprint lithography (IL) technology that adopts the ultraviolet light polymerization resist; It is big that the single pattern shifts area.Because little raceway groove of μ DMFC bipolar plates is a kind of large-area three-dimensional features of microstructures, takes all factors into consideration various factors, the suitable soft mold that adopts.Existing soft mold material mainly contains PDMS, photosensitive resin and PMMA, comprehensive relatively they the ultraviolet light permeability, with various characteristics such as resist adhesive, choose PDMS (silicon rubber) as the impressing mould material, because silastic material does not possess mechanical hardness, therefore must use a kind of hard material as support, so impressing mould is by elastic mould and quartzy the composition.Quartz can guarantee that as stiffener whole impressing mould has bearing strength and ultraviolet light transmission, and grating is Mold Making and chromatography alignment mark, and elastic mould and quartz are fixed together by bonding.In the Mold Making process, the casting of elastic mould and with the bonding of quartz be one step completed, therefore guaranteed the surperficial opposing parallel of quartzy stiffener surface and elastic mould.Fig. 4 is the structure chart of the soft impressing mould profile of silicon rubber used of the present invention.
After definite mold materials is silicon rubber, in order to reach the optimal mechanical physical property of silicon rubber, and eliminate the defective that silicon rubber is unfavorable for little replica technology, need the relevant parameter in the strict control Mold Making technological process.Fig. 5 is a silicon rubber soft mold manufacture craft flow chart.It mainly may further comprise the steps:
1. quartzy backing is made.When making impressing mould, at first to make quartzy backing, quartz glass is carried out surface correct grinding and polishing.
2. aim at the making of Mark.In imprint lithography (IL) technology, owing to carry out overlay alignment and pattern stitching, so must make the pattern (Mark) that is used to aim on the impressing mould.Mark only is used for aiming in moulding process, does not participate in the transfer moulding process of pattern, so Mark and pattern transition range must be on two planes.Owing in imprint process, will guarantee Mark and the relative position that is transferred pattern, when making mould pattern transition range, must therefore make aligning Mark earlier with Mark as alignment mark, its process is as shown in Figure 6.A is a quartz glass among the figure.B is for adopting low-pressure chemical vapor deposition (LPCVD) at quartz surfaces deposition one deck chromium (Cr), and thickness is 600nm.C is coated with shop one deck positive photoresist for adopt rotation to be coated with the shop method on the Cr surface.D is the resist exposure developing process.E gets rid of unnecessary Cr etching for adopting the RIE etching method, aims at the Mark etching to this and finishes.
3. prepare burden.PDMS monomer and curing agent carry out proportioning, mixing and stirring at 10: 1 by mass ratio.
4. cast molding.The batching for preparing is cast on the master mold.
5. vacuumize.Vacuumize and have two effects: get rid of and mix back PDMS material internal bubble and vacuum assisted resin infusion.Getting vacuum degree is 213 * 10
-2Pa promptly can guarantee the replica quality of silicon rubber and the uniformity after the silicon rubber curing;
6. heated at constant temperature.Main effect is to improve the lower monomer energy of curing activity among the PDMS, makes it participate in curing reaction, guarantees the PDMS full solidification.Parameters of curing is: T=40 ℃, and t=45h, the δ after the curing=017 ‰;
7. the demoulding.Mould after solidifying is separated from the pattern mother matrix, finish the manufacturing process of whole soft mold.
(3) substrate preliminary treatment
Adopt nitrogen current and ultrasonic cleaning technology to carry out the cleaning of quartz glass substrate, clean the back and in 180 ℃ of baking ovens, toasted 3 hours.
(4) the substrate alignment mark is made
The manufacturing process of substrate alignment mark: at first adopt low-pressure chemical vapor deposition (LPCVD) method at quartz glass surface deposition 600nm chromium layer; Adopt rotation to be coated with shop one deck positive photoresist on the Cr surface subsequently; Evenly be coated with spread photoresist after, expose, develop; At last, adopt reactive ion etching that unnecessary Cr is got rid of, and sputter one deck Al
2O
3Transparent protective film repeatedly is used with the protection figure.
(5) sputtering seed layer
At the thick Cr/Cu plating seed layer of the about 100nm of glass substrate sputter one deck.
(6) the contrary imprinting moulding of little raceway groove
By adopting " soft mold " and " contrary impression " technology to realize the imprinting moulding of the little raceway groove of large-area three-dimensional on organic photo-curing material, the micro-embossing method is the method for forming Micro-Nano structure of a kind of high efficiency, large tracts of land, low cost, high resolution.Wherein " just impress " comparatively ripe, the various nanostructures that can realize small size, the following characteristic dimension of 10nm are shaped, and at MEMS, little/as to receive and obtained application in the opto-electronic device manufacturing, the producer of also existing in the world some production nano-imprinting apparatus and hot padding equipment.Therefore, adopt micro-embossing to make and press micron order, can satisfy its required resolution completely to the micron order micro-structural.But because little raceway groove of μ DMFC bipolar plates is a kind of large-area three-dimensional features of microstructures, if adopt traditional " just impressing " technology, the big force of impression that need apply mould causes the distortion of the impression pattern that the distortion of elastic mould causes on the one hand easily; On the other hand, adhere to easily, cause resist curing and demolding difficulty, the difficulty of having aggravated the demoulding for three-dimensional microstructures more." contrary impression " technology substrate microstructure is shaped and depends on the adhesive transfer of organic photo-curing material of patternization to base material, but not " just impressing " relies on the forced shaping of mould to material like that, therefore the force of impression that contrary impression needs is very little, thereby has reduced the stress deformation of base material and mould.This guarantees the precision of the impression of big face on the one hand, reduces the possibility that sticks together on the other hand, compares with " just impressing " technology, and the demoulding is more prone to.
Fig. 7 is that the present invention adopts " soft mold " and " contrary impression " technology to make the imprinting moulding schematic diagram of the little raceway groove of large-area three-dimensional at the polymethyl methacrylate of modification.A is for to be coated with one deck release agent at the silicon rubber soft mold among the figure.B is the organic photo-curing material of polymethyl methacrylate of a kind of modification of cast in the die cavity of silicon rubber soft mold, and the levelling surface exists.C is the plating seed layer Cr/Cu in the glass substrate sputter, and the organic photo-curing material of silicon rubber soft mold and levelling processing back is pressed to quartz glass.D shines from substrate back for utilizing ultraviolet light, the exposure curing molding.After E is abundant photocuring, the demoulding (because glass substrate has different surface energies with silicon rubber mould, the polymethyl methacrylate of modification is on glass substrate).F is the little raceway groove that forms on the polymethyl methacrylate of modification after the demoulding.
(7) microplating deposition copper and mickel
Selected the copper nickel composite deposite as the bipolar plates metal conducting layer, at first utilize microplating technology on prepared little channel surface, to deposit 100 μ m thickness copper metal conducting layers, continue to electroplate the bright nickel coating of 25 μ m thereon as substrate then as anticorrosive protective coating.
The prescription of selecting acid copper plating solution to electroplate as copper.Selecting in the acid copper plating solution to use copper-bath, the main component in the solution is sulfuric acid and copper sulphate.Because sulfate is higher with respect to the current efficiency of other acid copper-plating salt such as borofluoride, iodate, composition is simple and the tolerant easy adjustment of opereating specification.Acid copper sulfate electroplating formula and process conditions:
Copper sulphate CuSO
450g/L
Sulfuric acid H2SO
450g/L
Current density 10mA/cm
2
30 ℃ of electroplating temperatures
Alr mode is slight
Select the prescription of Watts nickel-plating liquid commonly used in the industry,, add the normal dissolving that nickel chloride guarantees anode with the main component of nickelous sulfate as electrolyte.This plating bath safeguards that easily simple to operate, deposition velocity is fast, and coating stress is little.Concrete experimental formula and process conditions are as follows:
Nickelous sulfate NiSO
47H
2O 240g/L
Nickel chloride NiCl
26H
2O 20g/L
Boric acid H
3BO
320g/L
Lauryl sodium sulfate 0.05g/L
PH value 3.5
30 ℃-50 ℃ of working temperatures
Current density 1A/cm
2-2.5A/cm
2
The alr mode middling speed stirs
(8) modification of coating nitrided surface is handled
Adopt surface carburization technology that coating surface is carried out modification and handle, reduce contact resistance, increase corrosion stability.
(9) remove glass substrate
(10) making of the import and export of reactant and product
Make the import and export of reactant and product by Laser Micro-Machining.
The Ni-based composite dual-electrode plates of new polymers/copper that the present invention proposes is a basis material with the polymethyl methacrylate of modification, the combarloy that deposits on basis material is a conductive layer, microplating nickel or Cr or Ni-50Cr alloy are as anticorrosive protective material on conductive layer, except adopting with nickel as the anticorrosive protective material, the one, can also select with Cr as anticorrosive protective material; The 2nd, select with the Ni-50Cr alloy as anticorrosive protective material.Proof Ni-50Cr alloy better effects if in experiment, but its cost is higher.
Use technology of the present invention to make μ DMFC bipolar plates, the method for mastering has multiple, and the electron-beam direct writing of recommending except the present invention adds little electroforming process and prepares mother matrix; The 2nd, electron-beam direct writing adds reactive ion etching process; The 3rd, adopt little stereolithography; The 4th, the gray scale photoetching; The 5th, on glass substrate, carry out the soft etching of wet method.
Using electron-beam direct writing to make motherboard has two kinds of technologies, and a kind of method is: at first adopt direct electronic beam to write on the little raceway groove that forms 3D shape on the electric lithography glue, subsequently by little electroforming process plated metal (as nickel), make metal die as motherboard.Second method is: at first at glass deposition one deck ito thin film, and continue to adopt PECVD deposition one deck SiO on ITO
2, its thickness determines according to prepared microstructure graph; Subsequently, at SiO
2Last rotation is coated with the shop electron beam resist, and adopts electron beam lithography to make microstructure graph, and the acquisition microstructure graph of back on electron beam resist develops; At last, etching SiO
2The three-dimensional microstructures figure of Xing Chenging thereon.
The mother matrix that the present invention makes can be used multiple times makes the silicon rubber soft mold.
The present invention is to the processing of substrate conduction, except adopting the present invention at first the thick Cr/Cu plating seed layer of the about 100nm of substrate brush plating one deck, can also before the microplating depositing operation, adopt electroless deposition one deck 1 μ m with interior thin metal layer, as the metal level of electroplating technology.
To produce the cost of making in enormous quantities and shorten the production cycle in order to reduce, can only adopt this technology single-piece to make the miniflow field, and many modes of processing simultaneously that adopt are handled in the making of the import and export of reactant and product and the modification of coating nitrided surface.
Claims (6)
1. the composite dual-electrode plates preparation method of a micro direct methanol fuel battery, it is characterized in that, this method is a basis material with the polymethyl methacrylate of the modification that is spin-coated on quartz glass substrate, the deposition combarloy is a conductive layer on matrix, as anticorrosive protective material, adopt the composite dual-electrode plates of non-silicon produced with combination prepared micro direct methanol fuel battery at conductive layer microplating nickel or Cr or Ni-50Cr alloy;
Described non-silicon produced with combination technology is 1. to add little electroforming process with e-beam direct write lithography and prepare mother matrix; 2. turn over system silicon rubber soft mold by vacuum-assisted cast silicon rubber; 3. be substrate with the quartz glass, it is carried out surface preparation and conductionization processing; 4. the polymethyl methacrylate of a kind of modification of cast in the die cavity of silicon rubber soft mold, and levelling surface; 5. the polymethyl methacrylate of silicon rubber soft mold and levelling being handled post-modification is pressed to quartz glass, and fully behind the photocuring, little raceway groove of bipolar plates is produced in the demoulding; 6. on prepared little channel surface, deposit high-conductive metal copper with microplating technology; 7. in the substrate of electro-coppering, continue to electroplate the thin anticorrosive protectiveness bright nickel layer of one deck; 8. electroplate and again the copper nickel composite deposite is carried out nitrided surface modification processing after reprocessing is finished; 9. remove glass substrate; 10. make the import and export of reactant and product by Laser Micro-Machining.
2. the method for claim 1 is characterized in that, described non-silicon is compound preparation technology specifically may further comprise the steps:
1. mastering
According to the results of optimum design of bipolar plate flow field, adopt electron-beam direct writing and little electrocasting method precise electrotyping on hard system back lining materials to go out to comprise the metal die of little raceway groove of bipolar plates;
2. the soft impressing mould of silicon rubber is made
The soft impressing mould of silicon rubber is used for the little raceway groove three-dimensional microstructures feature transfer on the mother matrix to silicon rubber, and prepared silicon rubber mould is used for micro-embossing, and the soft impressing mould of silicon rubber adopts quartz material to make substrate, and silicon rubber is as mold materials;
3. the substrate of composite dual-electrode plates is handled
A. get quartz glass substrate as the substrate of making composite dual-electrode plates, adopt nitrogen current and method for suppersonic cleaning that quartz glass substrate is cleaned, remove greasy dirt, the quartz glass substrate after the cleaning toasted 3 hours in 180 ℃ of baking ovens;
B. adopt low-pressure chemical vapor deposition method, at quartz glass substrate surface deposition one deck chromium; Adopt rotation to be coated with shop one deck positive photoresist at chromium surface subsequently; Evenly be coated with spread photoresist after, expose, develop; At last, adopt reactive ion etching that unnecessary Cr is got rid of, and sputter one deck Al
2O
3Transparent protective film repeatedly is used with the protection figure;
C. sputter one deck Cr/Cu plating seed layer on the quartz glass substrate surface, the conduction processing;
4. the contrary imprinting moulding of little raceway groove
The polymethyl methacrylate of cast modification in the die cavity of silicon rubber soft mold, and levelling surface are pressed to quartz glass with the organic photo-curing material of silicon rubber soft mold and levelling processing back, fully behind the photocuring, little raceway groove of bipolar plates is produced in the demoulding, finishes the making of little channel features;
5. electroplating deposition copper nickel composite deposite
Utilize microplating technology on prepared flow field micro-structure surface, to deposit 100 μ m thickness copper metal conducting layers, and in the substrate of electro-coppering, continue to electroplate the bright nickel coating of 25 μ m as anticorrosive protective coating;
6. composite deposite surface modification treatment
In order to reduce the bipolar plates contact resistance, improve the performance of micro direct methanol fuel battery, the copper nickel composite deposite is carried out the nitrided surface modification handle;
7. remove glass substrate
8. make the import and export of reactant and product at last by Laser Micro-Machining.
3. the method for claim 1 is characterized in that, the soft impressing mould of described silicon rubber is made according to the following steps:
1. quartzy backing is made: at first will make quartzy backing when making impressing mould, quartz glass is carried out surface correct grinding and polishing;
2. aim at the making of pattern: on impressing mould, make the pattern that is used to aim at; Pattern of aiming at and pattern transition range are on two planes;
3. the batching: rubber monomer and curing agent carry out proportioning, mixing and stirring at 10: 1 by mass ratio;
4. cast molding: the batching that will prepare is cast on the master mold;
5. vacuumize: the silicon rubber that is cast on the master mold is vacuumized, and vacuum degree is 213 * 10
-2Pa gets rid of the silicon rubber air entrapment, with the replica quality of assurance silicon rubber and the uniformity after the silicon rubber curing;
6. heated at constant temperature, curing: parameters of curing is: 40 ℃ of temperature, and the time is 45h;
7. the demoulding: the mould after will solidifying separates from the pattern mother matrix, can finish the making of whole soft mold.
4. method as claimed in claim 2 is characterized in that, the method for described mastering adopts electron-beam direct writing to add reactive ion etching process; Perhaps adopt little stereolithography technology; Perhaps adopt the gray-level light carving technology; Perhaps on glass substrate, carry out the soft etching of wet method.
5. the method for claim 1 is characterized in that, using electron-beam direct writing to add reactive ion etching process making motherboard has two kinds of processes:
First method is: at first adopt direct electronic beam to write on the little raceway groove that forms 3D shape on the electric lithography glue, subsequently by little electroforming process plated metal, make metal die as motherboard;
Second method is: at first at glass deposition one deck ito thin film, and continue to adopt PECVD deposition one deck SiO on ITO
2, its thickness determines according to prepared microstructure graph; Subsequently, at SiO
2Last rotation is coated with the shop electron beam resist, and adopts electron beam lithography to make microstructure graph, and the acquisition microstructure graph of back on electron beam resist develops; At last, etching SiO
2The three-dimensional microstructures figure of Xing Chenging thereon.
6. the method for claim 1 is characterized in that, to the processing of quartz glass substrate conduction, is before the microplating depositing operation, adopts electroless deposition one deck 1 μ m with interior thin metal layer, as the metal level of electroplating technology.
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