CN105789664A - Three-electrode solid electrolyte electrochemical reactor - Google Patents
Three-electrode solid electrolyte electrochemical reactor Download PDFInfo
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- CN105789664A CN105789664A CN201610128451.2A CN201610128451A CN105789664A CN 105789664 A CN105789664 A CN 105789664A CN 201610128451 A CN201610128451 A CN 201610128451A CN 105789664 A CN105789664 A CN 105789664A
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- H01M8/00—Fuel cells; Manufacture thereof
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Abstract
The invention provides a three-electrode solid electrolyte electrochemical reactor, which comprises a membrane electrode assembly, a flow field plate, a sealing gasket and a reference electrode, wherein the membrane electrode assembly comprises an active area and an inactive area capable of generating electrochemical reaction; the inactive area is located on the periphery of the active area; the inactive area is an exposed area of a solid electrolyte membrane; the flow field plate comprises a cathode flow field plate and an anode flow field plate; the membrane electrode assembly is clamped between the cathode flow field plate and the anode flow field plate; the sealing gasket is arranged between the membrane electrode assembly and the flow field plate and is located in the inactive area of the membrane electrode assembly; an access point of the reference electrode is arranged outside the sealing gasket; and ion connection is kept with the inactive area through an electrolyte solution or under an assist of the solid electrolyte membrane. The electrochemical reactor provided by the invention can start or cancel monitoring by the reference electrode at any time, does not affect the working states of an anode and a cathode and does not affect the structure and the air-tightness of the reactor.
Description
Technical field
The present invention relates to electrochemical field, be specifically related to three electrode solid electrolyte electrochemical reactors.
Background technology
Solid state electrochemical reactors (includes battery and electrolyzer) and is the energy conversion device of a kind of compact conformation.Its core function unit includes three parts such as negative electrode, anode and solid electrolyte film, and anode and cathode catalyst and film generally use with three-in-one form (i.e. membrane electrode assembly 8 complex).In order to evaluate and optimize negative electrode and the respective contribution of anode, in order to prevent anode and cathode overload, corrosion or other damages, in reactor work process, except the potential difference (reactor voltage) between monitoring anode and cathode, also need monitoring negative electrode and the respective current potential of anode real-time and accurately.This needs to introduce in the reactor reference electrode, that is builds three-electrode system in the reactor.
The difficult point that structure three-electrode system runs in solid state electrochemical reactor is in that reactor compact structure and thin film thickness.In order to evade this point, practice often adopts two electrode systems.Namely directly using one of them electrode of anode and cathode as reference electrode, carried out the current potential of grappling reference electrode by logical hydrogen, electrochemistry liberation of hydrogen or other modes.Although this two electrode system simple structures, easy to operate, but it is only capable of the current potential of one electrode of monitoring, and monitoring is staggered the time, easy distortion (state that not the two poles of the earth work simultaneously of monitoring).
The matter of utmost importance building three-electrode system is to select suitable reference electrode.Practice can include standard hydrogen electrode, all kinds of dynamic electrode, air electrode and various commercially available electrode (such as calomel electrode, hydrargyrum/Mercurous sulfate electrode etc.) as the example of reference electrode.The definition of standard hydrogen electrode current potential clearly, but is installed and uses inconvenience, is also vulnerable to the impact of the toxicity species of absorption.Although air electrode is easy to use, but current potential definition is indefinite, is only capable of doing coarse estimation.And dynamic electric has potential drifting and the problem of long-time stability aspect.By contrast, how all kinds of commercial reference electrodes better as indicating electrode, but can access and become crucial.
The Second Problem building three-electrode system determines that the on-position of reference electrode.This is actually relevant with the size of the reference electrode selected and kind.What in practice, use was more is inserted in the middle of the cross section of film by very thin tinsel, or adopts two membranes, and tinsel is sandwiched therebetween, as dynamic reference electrode.These schemes can the current potential of monitor in real time working electrode, but the current potential of the current potential of working electrode and reference electrode easily influences each other, and affects sealing and the internal resistance of reactor, and/or the installation of reference electrode is had significantly high technology requirement.
Summary of the invention
The present invention provides a kind of three electrode solid electrolyte electrochemical reactors, including: membrane electrode assembly, including active region and inactive area that electrochemical reaction can occur, described inactive area is positioned at the periphery of described active region, and described non-active region is the exposed region of solid electrolyte film；Flow-field plate, including cathode flow field plate plate and anode flow field board, described membrane electrode assembly is located between described cathode flow field plate and anode flow field board；Sealing gasket, is arranged between described membrane electrode assembly and described flow-field plate, is positioned at the inactive area of described membrane electrode assembly；And reference electrode, the access point of described reference electrode is arranged at outside described sealing gasket.
Wherein, described electrochemical reactor is provided with reference electrode installing hole at the access point place of described reference electrode, exposes the solid electrolyte film at described access point place；Described electrochemical reactor also includes reference electrode tube, described reference electrode tube one end contacts with the solid electrolyte film at described access point place, electrolyte solution is filled in described reference electrode tube, described electrolyte solution directly contacts and no leakage with the solid electrolyte film at described access point place, and described reference electrode is installed in described reference electrode tube.If being inserted directly into reference electrode inconvenience, it is possible to use a salt bridge and reference electrode is introduced, insert in the electrolyte solution in reference electrode tube by one end of salt bridge, the other end then insert one be contained with electrolyte solution, the container of reference electrode be installed in.
Wherein, the exposed part of described solid electrolyte film includes extending to the outside film long-tail formed of described reactor to one direction of described electrochemical reactor with long line or strip, and afterbody and the described reference electrode of described film long-tail are installed in the container filling electrolyte solution.Epitaxial form is used to access the cutting of film long-tail pair film, the preparation of membrane electrode assembly and install all inconvenient, and cause waste economically, grafting form can be adopted: when cutting film and prepare membrane electrode assembly for this, a little exposed part is only retained outside the seal area of membrane electrode assembly, additionally cut the film long-tail of long line or strip simultaneously, when membrane electrode assembly is installed, the exposed part of the solid electrolyte film being laminated to described electrochemical reactor is formed.
Wherein, the access point of described reference electrode is arranged at cathode plane or anode surface.
Wherein, the access point of described reference electrode is an access or face access.
Wherein, described reference electrode is the electrode that any applicable electromotive force is stable, for instance commercially available calomel electrode, hydrargyrum/Mercurous sulfate electrode, hydrargyrum/mercuric oxide electrode, silver/silver chloride electrode etc..
Wherein, described electrochemical reactor is battery or electrolyzer.
The present invention also provides for a kind of battery pile including above-mentioned electrochemical reactor.
The present invention also provides for a kind of electrolyzer heap including above-mentioned electrochemical reactor.
It is convenient that the solid state electrochemical reactors of the present invention has mounting, commissioning and maintenance, can in real time, accurately, stability monitoring, can start or cancel monitoring at any time, and not affect the duty at negative and positive the two poles of the earth, do not affect the structure of reactor and the advantage of sealing.The solid state electrochemical reactors of the present invention, it is also possible to pile for battery pile and electrolyzer, it is achieved the monitoring to monolithic arbitrary in pile and arbitrary electrode.
Accompanying drawing explanation
Its example embodiment being described in detail by referring to accompanying drawing, the above-mentioned and further feature of the present invention and advantage will be apparent from.
Fig. 1 solid state electrochemical reactors structure；
Potential distribution and reference electrode access point position in Fig. 2 film cross section；
The first reference electrode access way of Fig. 3；
Fig. 4 the second reference electrode access way；
Fig. 5 thickness flow-field plate, keep flat, the first reference electrode access way of direct plugging-in single pellet reactor；
Fig. 6 same battery battery steady-state polarization under hydrogen-oxygen proton exchange membrane fuel cell operational mode and DMFC operational mode and anode and cathode steady-state polarization；
Fig. 7 CO2Electrolyzer linear voltage when electroreduction prepares carbon monoxide scans the polarization curve of polarization curve and anode and cathode；
The thin flow-field plate of Fig. 8, keep flat, the first reference electrode access way of direct plugging-in single pellet reactor；
Fig. 9 keeps flat, the first reference electrode access way of salt bridge type single pellet reactor；
Figure 10 is sidelong, the first reference electrode access way of salt bridge type single pellet reactor；
Figure 11 is sidelong, the second reference electrode access way of film long-tail extended pattern single pellet reactor；
Figure 12 keeps flat, the second reference electrode access way of film long-tail extended pattern single pellet reactor；
The second reference electrode access way of Figure 13 film long-tail grafting-type single pellet reactor；And
Reference electrode access way in Figure 14 pile.
Wherein, description of reference numerals is as follows:
1 cathode fluid import 2 cathode fluid outlet
3 negative electrode clamping plate 4 cathode insulation plates
5 cathode collector plate 6 cathode flow field plates
7 cathode side membrane electrode assembly sealing gasket 8 membrane electrode assemblies
9 anode-side membrane electrode assembly sealing gasket 10 anode flow field boards
11 anode current collector plate 12 anodized insulation plates
13 anode clamp 14 anode fluid imports
15 anode fluids export 16 bolts hole
17 anode support 18 anode micro porous layer
19 anode catalyst layer 20 solid electrolyte films
21 cathode catalyst layer 22 cathode micro porous layer
23 cathode support layers 24 membrane electrode assembly active regions
25 membrane electrode assembly seal area 26 reference electrode access points
27 film equipotential region 28 equipotential lines
29 electric current line 30 reacting fluid manhole appendixs
31 membrane electrode assembly sealing gasket 32 film exposed parts
33 reference electrodes access sealing gasket 34 reference electrode tube
35 reference electrode 36 electrolyte solutions
37 reference electrode installing hole 38 film long-tails
39 salt bridge 40 electrolyte solution containers
41 bipolar plates
Battery steady-state polarization under 42 Proton Exchange Membrane Fuel Cells operational modes
Negative electrode steady-state polarization under 43 Proton Exchange Membrane Fuel Cells operational modes
Anodic steady polarization curve under 44 Proton Exchange Membrane Fuel Cells operational modes
Battery steady-state polarization under 45 DMFC operational modes
Negative electrode steady-state polarization under 46 DMFC operational modes
Anodic steady polarization curve under 47 DMFC operational modes
48CO2Electroreduction prepares the linear voltage scanning polarization curve of carbon monoxide electrolyzer
49CO2Electroreduction prepares the cathodic polarization response under the scanning of carbon monoxide electrolyzer linear voltage
50CO2Electroreduction prepares the anode polarization response under the scanning of carbon monoxide electrolyzer linear voltage
Detailed description of the invention
It is described more fully with example embodiment referring now to accompanying drawing.But, example embodiment can be implemented in a variety of forms, and is not understood as limited to embodiment set forth herein；On the contrary, it is provided that these embodiments make the present invention will fully and completely, and the design of example embodiment is conveyed to those skilled in the art all sidedly.In the drawings, in order to clearly, exaggerate the thickness of region and layer.Accompanying drawing labelling identical in the drawings represents same or similar structure, thus will omit their detailed description.
As it is shown in figure 1, monolithic solid electrolyte electrochemical reactor is made up of basic structure and supplementary structure.Basic structure includes cathode flow field plate 6, membrane electrode assembly 8 and anode flow field board 10.Cathode plane on membrane electrode assembly 8 and anode surface are except outside having corresponding catalyst layer 21,19, it is also possible to have microporous layers 22,18, supporting layer 23,17 etc.；Catalyst layer 21 on membrane electrode assembly 8 cathode plane, microporous layers 22 and supporting layer 23 etc. together constitute negative electrode with cathode flow field plate 6, and catalyst layer 19 on membrane electrode assembly 8 another side, microporous layers 18 and supporting layer 17 then constitute anode with anode flow field board 10.Anode and cathode flow-field plate 6,10 is made by inertia electronic conductive material, and one mask has chute so that reaction-ure fluid is distributed to whole conversion zone (being called active region 24, refer to the region with negative electrode or anode catalyst).Supplementary structure includes negative electrode clamping plate 3, cathode insulation plate 4, cathode collector plate 5, anode clamp 13, anodized insulation plate 12 and anode current collector plate 11 etc..Bolt is utilized to clamp base structure and supplementary structure by modes such as bolts hole 16；All having the duct (be collectively referred to as reacting fluid and import and export 1,2,14,15) that anode and cathode fluid passes in and out in anode and cathode flow-field plate 6,10 and supplementary structure element, the chute on these ducts and anode and cathode has been joined together to form the passage of anode and cathode fluid flowing；Channel seal pad is all had, to prevent fluid from leaking between the respective auxiliary element of anode and cathode and between the respective collector plate 5,11 of anode and cathode and flow-field plate 6,10；In the periphery of active region 24, between cathode flow field plate 6 and membrane electrode assembly 8 and between anode flow field board 10 and membrane electrode assembly 8, all there is sealing gasket 7,9, to prevent the leakage of anode and cathode fluid or to be mutually mixed.
The on-position of reference electrode is located at outside membrane electrode assembly active region 24 by the present invention, and meanwhile, in order to not affect the sealing of reactor, access point continues outer shifting, is located at the moon or the outside of anode film electrode assemblie sealing gasket 7,9.For the convenience installed and use, access point can be located at the either side of film, it is not necessary to filament inserts cross section.When being located away from 24 edge, membrane electrode assembly active region of access point, the current potential of access point still can be equal to the current potential of active region 24 inner membrance kernel of section.nullAdler(S.B.Adler,B.T.Henderson,M.A.Wilson,D.M.TaylorandR.E.Richards,Solid-state ionics (SolidStateIonics) 134 (2000) 35-42.S.B.Adler,J. electrochemistry (Electrochem) .Soc.149 (2002) E166-E172.) result of study show，As shown in Figure 2，As long as the distance between access point 26 and edge, active region 24 is more than three times of film thickness，The equipotential region 27 (including cathode plane and the anode surface of film) that then access point 26 has been put on film on exposed region (being not covered with catalyst layer)，The current potential in this region is equal to the current potential (Fig. 2 shows the Potential distribution represented in film under duty and the electric charge mobile route represented with electric current line 29 with equipotential line 28) of active region 24 inner membrance kernel of section.Because the thickness of the solid electrolyte film used under normal circumstances is mostly at a few tenths of a mm, so access point 26 from edge, active region 24 distance need not too away from namely can reach requirement, be typically near membrane electrode assembly sealing gasket 31 (including cathode side membrane electrode assembly sealing gasket 7 and anode-side membrane electrode assembly sealing gasket 9) the outer width of more than two millimeters (sealing gasket generally have).Due to the existence of the outer equipotential region 27 in active region 24, reference electrode access point 26 is possible not only to be geometric point, it is also possible to be geometric surface.According to determined reference electrode access point 26 position, the present invention provides two kinds of reference electrode access waies: the first is extrapolation reference electrode tube 34, and the second is buildup film long-tail 38.
The first access way needs the size of extension reactor, so as to insert reference electrode tube 34, as shown in Figure 3.Optional one in anode and cathode after expansion, in its clamping plate, insulation board, collector plate 5,11, punch in the position corresponding to reference electrode access point 26 in flow-field plate, and wherein the diameter in the hole on other elements of the boring ratio in flow-field plate wants big, it is possible to hold the elastic rubber plug that a centre is porose；Simultaneously in the corresponding position of the flow-field plate of another electrode, making a call to a blind hole near the side of film, this blind hole can hold an elastic rubber plug (be collectively referred to as reference electrode with the elastic rubber plug of offside and access sealing gasket) not having hole；When after reactor installation, the hole beaten constitutes a duct (being called reference electrode installing hole 37), at this moment inserting a glass tubing or plastic tube 34 from reactor is outside, the pipe inserted tightly is waled by rubber stopper, and two rubber stoppers are tightly clamped exposed film；Now, pipe injects electrolyte solution, electrolyte solution is directly contacted and no leakage with film, then by reference electrode 35, (reference electrode can be the electrode that any electromotive force is stable, such as commercially available saturated calomel electrode, hydrargyrum/Mercurous sulfate electrode, hydrargyrum/mercuric oxide electrode, silver/silver chloride electrode etc.) it is inserted directly in electrolyte solution, so far, reference electrode access 35 completes.If it is inconvenient to be inserted directly into reference electrode 35, also can use a salt bridge 39 to be introduced by reference electrode 35: one end of salt bridge 39 inserted in the electrolyte solution in reference electrode tube 34, the other end then insert one be contained with electrolyte solution, be inserted with container 40 or the vessel of reference electrode in.
The second access way requires to extend to reactor outside by exposed film (reference electrode access point position place) outside sealing gasket to a direction with the form of line or bar, and the long line of extension or strip form a film long-tail, as shown in Figure 4.In order to prevent film long-tail 38 from contacting with the flow-field plate of anode and cathode, it is both needed in the film both sides of reference electrode on-position arrange an elastic rubber gasket (be also collectively referred to as reference electrode and access sealing gasket 33).The afterbody of film long-tail 38 is inserted into one be contained with electrolyte solution, be inserted with the container of reference electrode 35 in, now, reference electrode 35 has accessed.Use epitaxial form to access film long-tail 38 and to the cutting of film, the preparation of membrane electrode assembly 8 and install all inconvenient, and cause waste economically, grafting form can be adopted: when cutting film and prepare membrane electrode assembly 8 for this, a little exposed part 32 is only retained outside the seal area of membrane electrode assembly 8, additionally cut film long-tail 38 simultaneously, when membrane electrode assembly 8 is installed, the exposed part 32 of the film on the head of long-tail 38 and membrane electrode assembly 8 is overlapped together.
Two kinds of access waies are all made by liquid electrolyte and achieve solid electrolyte film and be connected with the ion of reference electrode, it is therefore desirable to select suitable reactor place orientation or be aided with other measures as the case may be.Under the first access way, the reference electrode installing hole of setting is easy to adopt straight reference electrode tube to hold liquid electrolyte；If the placement orientation of reactor causes reference electrode installing hole not erect, then should adopt the reference electrode tube of bending；When using the reference electrode tube of bending, need to prevent from being mixed into bubble blocking ion channels when injecting electrolyte solution.The second access way receptible reactor place orientation and the pliability of film about: be only capable of selective membrane long-tail obliquely or vertically reactor placement orientation down when film pliability is poor, so that the end of film long-tail can touch the electrolyte solution being inserted with reference electrode；If film can hang naturally, or film bar appropriateness can be made to bend by fixing external force, then can accept more reactor and place orientation.
The first access way is installed and uses relatively simple, is especially easy to the disassembly and assembly repeatedly of reactor.It is commonly used for the single electrochemical reactor that flow-field plate is thicker, but the flow-field plate of thickness is not the essential condition using the first access way.Because its premise is with rubber, reference electrode tube to be sealed against electrolyte solution to contact with flow-field plate (electrode), so, the segment thickness of clamping plate or collector plate can also be used, so as to hold the rubber sealing reference electrode tube when flow-field plate thickness is relatively low.Comparatively speaking, the second access way scope of application is wider, is possible not only to be applicable to single electrochemical reactor, it is possible to be applicable to the pile being made up of multiple single electrochemical reactors, and the thickness of no matter flow-field plate.The second access way simple installation, but slightly numerous on using: need to control and keep the impedance of film long-tail.The adjustment of film long-tail impedance should be determined according to the specific nature of solid electrolyte: as, when using copolymer solid electrolyte, the part that the napkin with certain humidity or cloth coating film long-tail can be used to be in outside flow-field plate, answers coating plastic thin film to prevent water evaporation outside napkin or cloth；When using ceramic-like solid electrolyte, the temperature of the part that available temperature controller and heater assist control film long-tail are in outside flow-field plate.
Embodiment 1
As it is shown in figure 1, monolithic solid electrolyte electrochemical reactor is made up of basic structure and supplementary structure.Basic structure includes cathode flow field plate 6, membrane electrode assembly 8 and anode flow field board 10.Cathode plane on membrane electrode assembly 8 and anode surface are except outside having corresponding catalyst layer 21,19, it is also possible to have microporous layers 22,18, supporting layer 23,17 etc.；Catalyst layer 21 on membrane electrode assembly 8 cathode plane, microporous layers 22 and supporting layer 23 etc. together constitute negative electrode with cathode flow field plate 6, and another side catalyst layer 19, microporous layers 18 and supporting layer 17 etc. then constitute anode with anode flow field board 10.Anode and cathode flow-field plate 6,10 is made by inertia electronic conductive material, and one mask has chute so that reaction-ure fluid is distributed to whole conversion zone.Supplementary structure includes negative electrode clamping plate 3, cathode insulation plate 4, cathode collector plate 5, anode clamp 13, anodized insulation plate 12 and anode current collector plate 11 etc..Base structure and supplementary structure are clamped together by modes such as bolts；All having the duct (being collectively referred to as reacting fluid manhole appendix 30) that anode and cathode fluid passes in and out in anode and cathode flow-field plate 6,10 and supplementary structure element, the chute on these ducts and anode and cathode has been joined together to form the passage of anode and cathode fluid flowing；Channel seal pad is all had, to prevent fluid from leaking between the respective auxiliary element of anode and cathode and between the respective collector plate 5,11 of anode and cathode and flow-field plate 6,10；In the periphery of active region 24, between cathode flow field plate 6 and membrane electrode assembly 8 and between anode flow field board 10 and membrane electrode assembly 8, all there is sealing gasket 7,9, to prevent the leakage of anode and cathode fluid or to be mutually mixed.
In order to access reference electrode 35, it is necessary to the size of extension reactor, to hold a reference electrode tube 34.As shown in Figure 5, reactor keeps flat, near the outside of membrane electrode assembly 8 sealing gasket, corresponding position punching in the clamping plate 3 of negative electrode after expansion, insulation board 4, collector plate 5, flow-field plate 6, wherein the diameter in the hole on other elements of boring ratio in flow-field plate 6 wants big, it is possible to hold the elastic rubber plug that a centre is porose；Simultaneously in the corresponding position of the flow-field plate 10 of another electrode, making a call to a blind hole near the side of film, this blind hole can hold an elastic rubber plug (be collectively referred to as reference electrode with the elastic rubber plug of offside and access sealing gasket 33) not having hole；When after reactor installation, the hole beaten constitutes a duct (reference electrode installing hole 37), at this moment being inserted vertically into a straight glass tubing or plastic tube outside reactor, the pipe inserted tightly is waled by rubber stopper, and two rubber stoppers are tightly clamped exposed film；Now, pipe injects electrolyte solution so that electrolyte solution directly contacts and no leakage with film, is then inserted directly in electrolyte solution by commercial reference electrode 35, and so far, reference electrode 35 has accessed.
During three-electrode system work, anode and cathode and reference electrode are connected on potentiostat respectively or other are about on the equipotential line joint of instrument, potential difference between anode and cathode is the pond pressure of battery or electrolyzer, potential difference between negative electrode and reference electrode is the electrode potential of negative electrode, the electrode potential that potential difference is anode of anode and reference electrode.Fig. 6 gives the same monocell of application PEM three-electrode system measurement result under hydrogen-oxygen proton exchange membrane fuel cell and two kinds of operational modes of DMFC and (includes battery steady-state polarization 42,45 and the steady-state polarization 43 of anode and cathode, 44,46,47).When three-electrode system runs, reference electrode is saturated calomel electrode (SCE), and electrolyte solution is saturated potassium sulfate solution.Fig. 7 gives the three-electrode system measurement result (including the linear sweep voltametry polarization curve 48 of electrolyzer and the polarization response 49,50 of anode and cathode) that the electrolyzer of an application PEM generates carbon monoxide at electroreduction carbon dioxide.
Two electrode systems are only capable of the polarization behavior of monitoring electrolyzer or battery, three-electrode system then also can monitor the polarization behavior of anode and cathode simultaneously, and the three-electrode system constructed by the present invention is when monitoring the polarization behavior of anode and cathode, the access of reference electrode does not affect the duty of anode and cathode.In Fig. 6, the cell polarization curves of hydrogen-oxygen proton exchange membrane fuel cell is also the result of the cathode performance using two electrode systems mensuration DMFCs, obviously, if it will be inaccurate for evaluating the cathode performance under DMFC operational mode by this measurement result.Under two electrode systems, Methanol Anode is changed to hydrogen anode and is used as reference electrode, not only change the duty of anode, also have changed the duty of negative electrode simultaneously.
Three-electrode system constructed by the present invention employs liquid electrolyte solution, but there is junctionpotential between liquid electrolyte and solid electrolyte, and this junctionpotential is included among the anode and cathode current potential measured.It is to say, the electrode potential measured is without respect to reference electrode, but relative to the complex potential of junctionpotential and reference electrode current potential.According to mensuration, when liquid electrolyte is saturated potassium sulfate solution, solid electrolyte be PEM, reference electrode is composite reference electrode potential during saturated calomel electrode is 0.182V (25 DEG C), when liquid electrolyte is 1mol L-1During sulfuric acid solution, composite reference electrode potential becomes 0.238V (25 DEG C).The result provided in figure 6 and figure 7 has all had contemplated that this combination electrode current potential, and has been converted in order to relative to standard hydrogen electrode current potential (NHE).
Embodiment 2
As shown in Figure 8, when flow-field plate is insufficient to thickness, for instance less than 4mm, it is possible to use the collector plate 5 even segment thickness of clamping plate 3 to place reference electrode sealing gasket 33.Other structures are with embodiment 1.For being shown more clearly by the access of reference electrode 35, figure eliminates a part for reactor, lower same.
Embodiment 3
Sometimes for reducing the propagation of electrochemical reactor, thinner reference electrode tube 34 or reference electrode installing hole 37 must maybe be used, thus causing reference electrode 35 can not be inserted directly into reference electrode tube 34.Dielectric film can be realized by means of salt bridge 39 in the case to be connected with the ion of reference electrode 35, as shown in Figure 9.Other structures are with embodiment 2 or embodiment 3.
Embodiment 4
Sometimes the placement location of reactor causes straight reference electrode tube 34 can not meet requirement, as shown in Figure 10, can use the reference electrode tube 34 of bending.Other structures are with embodiment 1,2 and 3.
Embodiment 5
As shown in figure 11, in electrochemical reactor with the form of line or bar by exposed at sealing gasket 7, film (reference electrode access point 26 position) outside 9 extends to outside reactor to a direction, the long line of extension or strip form a film long-tail 38, by the afterbody of film long-tail 38 vertically or tilt to be inserted into down one be contained with electrolyte solution, be inserted with the container 40 of reference electrode 35 in, now, reference electrode 35 has accessed.In order to prevent the flow-field plate 11,5 of film long-tail 38 and anode and cathode from contacting, being both needed in the film both sides of reference electrode 35 on-position, a reference electrode is set and accesses sealing gasket 33.
Before using reference electrode 35, need to control and keep the impedance of film long-tail 38.The adjustment of film long-tail 38 impedance should be determined according to the specific nature of solid electrolyte: as, when using Nafion copolymer solid electrolyte, the part that the napkin with certain humidity or cloth coating film long-tail 38 can be used to be in outside flow-field plate, answers coating plastic thin film to prevent water evaporation outside napkin or cloth；When using ceramic-like solid electrolyte, the temperature of the part that available temperature controller and heater assist control film long-tail 38 are in outside flow-field plate 5,11.
The circuit of reference electrode 35 connects identical with embodiment 1 with use.
Embodiment 6
As shown in figure 12, can naturally hang if film is pliable and tough, or when film bar appropriateness can be made to bend by external force, then can keep flat (relative to membrane plane) by homologation reaction device 40.Other structures are with embodiment 5.
Embodiment 7
As shown in figure 13, it is possible to adopt grafting form to use film long-tail 38.When cutting film and preparing membrane electrode assembly 8, a little exposed part 32 is only retained outside the seal area of membrane electrode assembly 8, additionally cut film long-tail 38 simultaneously, when membrane electrode assembly 8 is installed, the film exposed part 32 on the head of long-tail 38 and membrane electrode assembly 8 is overlapped together.Other structures are with embodiment 5 or 6.
Embodiment 8
As shown in figure 14, in embodiment 5,6,7, the access of reference electrode 35 also apply be applicable in pile, and each film long-tail 38 can be arranged on identical position, it is possible to is arranged on different positions.Pile is made up of multiple single electrochemical reactors, except clamping plate 3,13, insulation board 4,12, collector plate 5, outside 11, inside is made up of the two of two ends flow-field plate 6,10, middle multiple bipolar plates 41 (one side is anode flow field board 10, and another side is cathode flow field plate 6) and membrane electrode assembly 8.Bipolar plates 41, end flow-field plate 6,10 and membrane electrode assembly 8 interphase distribution.The input and output material mode of pile is incomplete same with single reactor, but the access way of film long-tail 38 is identical.In order to highlight the emphasis of the present invention, the input and output material form within not shown pile.
Certainly; the present invention also can have other various embodiments; when without departing substantially from present invention spirit and essence thereof; those of ordinary skill in the art are when can make various corresponding change and deformation according to the present invention, but these change accordingly and deformation all should belong to the scope of the claims appended by the present invention.
Claims (9)
1. a three electrode solid electrolyte electrochemical reactor, including:
Flow-field plate, including cathode flow field plate plate and anode flow field board, described membrane electrode assembly is located between described cathode flow field plate and anode flow field board；
Membrane electrode assembly, including active region and inactive area that electrochemical reaction can occur, described inactive area is positioned at the periphery of described active region, and described non-active region is the exposed region of solid electrolyte film；
Sealing gasket, is arranged between described membrane electrode assembly and described flow-field plate, is positioned at the inactive area of described membrane electrode assembly；With
Reference electrode, it is characterised in that the access point of described reference electrode is arranged at outside described sealing gasket.
2. three electrode solid electrolyte electrochemical reactors according to claim 1, it is characterised in that described electrochemical reactor is provided with reference electrode installing hole at the access point place of described reference electrode, exposes the solid electrolyte film at described access point place；
Described electrochemical reactor also includes reference electrode tube, described reference electrode tube one end contacts with the solid electrolyte film at described access point place, electrolyte solution is filled in described reference electrode tube, described electrolyte solution directly contacts and no leakage with the solid electrolyte film at described access point place, and described reference electrode is installed in described reference electrode tube.
3. three electrode solid electrolyte electrochemical reactors according to claim 1, it is characterised in that described electrochemical reactor is provided with reference electrode installing hole at the access point place of described reference electrode, exposes the solid electrolyte film at described access point place；
Described electrochemical reactor also includes reference electrode tube, described reference electrode tube one end contacts with the solid electrolyte film at described access point place, filling electrolyte solution in described reference electrode tube, described electrolyte solution directly contacts and no leakage with the solid electrolyte film at described access point place；
Described reference electrode is installed in the container filling electrolyte solution, and salt bridge connects described reference electrode tube and described container.
4. three electrode solid electrolyte electrochemical reactors according to claim 1, it is characterized in that, the exposed part of described solid electrolyte film includes extending to the outside film long-tail formed of described reactor to one direction of described electrochemical reactor with long line or strip, and afterbody and the described reference electrode of described film long-tail are installed in the container filling electrolyte solution.
5. three electrode solid electrolyte electrochemical reactors according to claim 4, it is characterised in that the exposed part of the solid electrolyte film that described film long-tail is laminated to described electrochemical reactor by the solid electrolyte film cutting growth line or strip is formed.
6. three electrode solid electrolyte electrochemical reactors according to claim 1, it is characterised in that the access point of described reference electrode is arranged at cathode plane or anode surface.
7. three electrode solid electrolyte electrochemical reactors according to claim 1, it is characterised in that described electrochemical reactor is battery or electrolyzer.
8. a battery pile, it is characterised in that include the arbitrary described electrochemical reactor of claim 1-7.
9. an electrolyzer heap, including the arbitrary described electrochemical reactor of claim 1-7.
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