CN102478536B - External reference electrode determination method for SPE water electrolytic bath - Google Patents
External reference electrode determination method for SPE water electrolytic bath Download PDFInfo
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- CN102478536B CN102478536B CN201010563766.2A CN201010563766A CN102478536B CN 102478536 B CN102478536 B CN 102478536B CN 201010563766 A CN201010563766 A CN 201010563766A CN 102478536 B CN102478536 B CN 102478536B
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Abstract
The invention relates to an external reference electrode measurement method for a SPE water electrolytic bath. A proton exchange membrane in the SPE water electrolytic bath is extended, and the proton exchange membrane and the external reference electrode are immersed in an electrolyte solution to communicate the external reference electrode with cathode and anode of the electrolytic bath so as to form a three-electrode system. Thus, the cathode and anode electrode potential is determined. The invention has advantages of simple structure, convenient operation, high measurement precision and good stability. By the adoption of the external reference electrode during the operation of the SPE water electrolytic bath, the change of the cathode and anode electrode potential of the electrolytic bath is monitored at real time, thus providing important online basis for the performance degradation mechanism of the SPE water electrolytic bath.
Description
Technical field
The present invention relates to solid polymer electrolyte (SPE) water electrolysis field, be specially a kind of method of the additional contrast electrode for on-line measurement SPE water electrolytic cell anode and cathode electrode potential.
Background technology
SPE water electrolysis is to take solid polymer as electrolytical water electrolysis technology, and its working current density can be up to 1～3Acm
-2, and have that electrolytic efficiency is high, device volume is little, generate the advantages such as hydrogen purity high (99.999%) and environmentally safe, be considered to the most promising water electrolysis technology.
When research SPE water electrolytic cell, while especially studying performance kill mechanism and catalyst performance, often need anode and cathode electrode potential separately to measure.In bibliographical information, use the contrast electrodes such as reversible hydrogen electrode (RHE), microtubule hydrogen electrode or dynamic hydrogen electrode (DHE) that anode and cathode electrode potential is separately measured.The preparation of RHE is that PEM in membrane electrode MEA is extended, and the black catalyzer of PEM top spraying Pt extending.During test, to the black catalyzer of Pt place, pass into hydrogen and form RHE contrast electrode.Microtubule hydrogen electrode comprises microtubule, the black catalyzer of Pt and platinum filament.Polymer dielectric is made microtubule, and the potpourri of the black catalyzer of Pt and Nafion is injected to microtubule, and platinum filament is put into microtubule as collector, to passing into hydrogen in microtubule, can be used as microtubule hydrogen electrode contrast electrode.The preparation of DHE is comparatively complicated.First get two platinum filaments, every platinum filament two ends are exposed 1mm remainder and are coated with PTFE.Platinum black, Nafion solution and isopropanol mixture are coated in to one end of two platinum filaments.After room temperature is dried, one end 1mm hot pressing apart that two platinum filaments are scribbled to potpourri is in the middle of two Nafion films.One of two platinum filament as conduct of hydrogen-precipitating electrode to electrode.In addition, also need in use constant-current supply (9V dry cell) and trimmable resistance device (0-1M Ω) to make steady current (μ A level) by DHE, with the hydrogen that guarantees to separate out, cover hydrogen-precipitating electrode.Several contrast electrodes exist preparation comparatively complicated above, and cost is higher, and the problem such as inconvenient operation.
Summary of the invention
In order to overcome SPE water electrolytic cell contrast electrode complex structure, cost is higher, use platinum filament and hydrogen, and the problem such as inconvenient operation, the object of the invention is to provide for measuring SPE water electrolytic cell anode and cathode electrode potential a kind of preparation simply, easy to operate additional contrast electrode preparation method.
For achieving the above object, technical scheme of the present invention is:
A kind of method for the additional contrast electrode of SPE water electrolytic cell, comprise SPE water electrolytic cell, SPE water electrolytic cell comprises overlay film Catalytic Layer (CCM), anode and cathode diffusion layer and end plate, end plate outside is extended in one end of PEM in CCM, the PEM extending out extend in an electrolyte solution storage tank, PEM is immersed in electrolyte solution, in electrolyte solution in storage tank, be provided with contrast electrode, contrast electrode immerses in electrolyte solution and is communicated with SPE water electrolytic cell anode and cathode by PEM, forms additional contrast electrode.
In described SPE water electrolytic cell CCM, PEM extends to end plate outside, and the PEM both sides outside electrolytic cell, all without Catalytic Layer, are solid polymer dielectric film.
Described electrolyte solution is acid solution, as the H of 0.1-2M
2sO
4solution;
Described contrast electrode is mercurous chloride electrode, mercury-mercurous sulfate electrode or silver-silver chloride electrode.
In contrast electrode and SPE water electrolytic cell, the PEM of CCM is communicated with by electrolyte solution, forms three-electrode system, thereby anode and cathode electrode potential is measured.
The present invention has following characteristics:
(1) the present invention is simple in structure, easy to operate, reduces noble metal and uses, and cost is low.
(2) the present invention can measure SPE water electrolytic cell anode and cathode electromotive force quickly and accurately, can measure in real time anode and cathode electromotive force in electrolytic cell operational process.
(3) the present invention extends to PEM in CCM outside SPE water electrolytic cell, and electrolytic process and measuring process can not cause phase mutual interference.
Measuring accuracy of the present invention is high, good stability.In SPE water electrolytic cell operational process, adopt this kind of additional contrast electrode, can realize the Real-Time Monitoring of electrolytic cell anode and cathode potential change, for inquiring into SPE water electrolytic cell performance degradation mechanism, provide important online foundation.
Accompanying drawing explanation
In Fig. 1, a is water electrolytic cell CCM schematic diagram, and b is additional contrast electrode schematic diagram.(1) PEM, (2) Catalytic Layer, (3) SPE water electrolytic cell, (4) contrast electrode, (5) electrolyte solution.
Fig. 2 is contrast electrode stability.
Fig. 3 is SPE water electrolytic cell, anode and cathode polarization curve.
Fig. 4 is 0.002M Na
+ionic soil solution affects SPE water electrolytic cell.
Fig. 5 is variable concentrations Na
+ionic soil affects SPE water electrolytic cell.
Embodiment
Below in conjunction with accompanying drawing, the present invention will be further described.
CCM of the present invention is comprised of Catalytic Layer and PEM, PEM 1 is that PEM in CCM is extended as shown in Figure 1a, when assembling electrolytic cell, PEM 1 is extended to outside the end plate of electrolytic cell 3, and the PEM 1 equal catalyst-free in both sides.
Be the additional contrast electrode schematic diagram of the present invention as shown in Figure 1 b, in SPE water electrolytic cell, PEM 1 immerses the electrolyte solution 5 (H of 0.1-2M
2sO
4solution; ), contrast electrode 4 immerses electrolyte solution and is communicated with the additional contrast electrode of formation with SPE water electrolytic cell anode and cathode, thereby anode and cathode electrode potential is measured.
Adopt Nafion 115 film preparation CCM, anode catalyst load amount is 2mg/cm
2, cathod catalyst Pt/C load amount is 1mg/cm
2.Under 140 ℃, 1MPa, hot pressing obtains membrane electrode.In membrane electrode both sides, add respectively Anodic and cathode diffusion layer and end plate assembling monocell, electrolytic cell useful area 5cm
2.By shown in Fig. 1 b, form additional contrast electrode, the H that electrolyte solution is 0.5M
2sO
4, contrast electrode is saturated calomel electrode (SCE).To SPE water electrolytic cell anode, pass into deionized water, flow velocity 5ml/min, makes electrolytic cell keep 60 ℃; Then to negative electrode, pass into 0.1M Pa H
2, flow velocity 20ml/min.Contrast electrode and negative electrode form primary element, because negative electrode is used Pt/C catalyzer, pass into hydrogen after negative electrode as standard hydrogen electrode, the electromotive force that records primary element is contrast electrode electromotive force.Figure 2 shows that the stability of saturated calomel electrode.As can be seen from the figure contrast electrode measuring accuracy is high, and 0.241V compares with standard saturated calomel electrode electromotive force, and measuring error is in 7mV; Contrast electrode stability is high, 0.236 ± 0.002V.Saturated calomel electrode solution temperature of living in is room temperature (20 ℃), and in test process, affected by electrolytic cell temperature little for contrast electrode electromotive force stability.
The preparation of MEA and the assembling of electrolytic cell are identical with example 1.By forming shown in Fig. 1 b after additional contrast electrode, to SPE water electrolytic cell anode, pass into deionized water, flow velocity 5ml/min, makes electrolytic cell keep 60 ℃; Electrolytic cell making alive test polarization curve is measured anode and cathode electrode potential simultaneously.Fig. 3 is SPE water electrolytic cell harmonizing yinyang utmost point polarization curve, and as can be seen from the figure, in institute's test specification, the polarization of electrolytic cell is mainly from anode polarization, and cathodic polarization is along with current density increases and increases.
The preparation of MEA and the assembling of electrolytic cell are identical with example 1.By forming shown in Fig. 1 b after additional contrast electrode, to SPE water electrolytic cell anode, pass into deionized water, flow velocity 5ml/min, makes electrolytic cell keep 60 ℃; Electrolytic cell anode and cathode is connected additional power source, constant current 500mA/cm
2electrolysis deionized water, writing time, decomposition voltage harmonizing yinyang electrode potential.After electrolysis 1 hour, anode passes into concentration 0.002M Na
+pollute writing time, decomposition voltage harmonizing yinyang electrode potential.Fig. 4 is that SPE water electrolytic cell is at 0.002M Na
+electrolytic cell voltage harmonizing yinyang electrode potential change curve before and after polluting.Before polluting as we can see from the figure, electrolytic cell voltage harmonizing yinyang electrode potential does not change; Na
+after polluting, electrolytic cell voltage and anode potential raise, and cathode potential does not change within a very long time, then slow decreasing; Along with continuing to raise, the aggravation decomposition voltage polluting finally keeps constant; Anode potential declines after being elevated to peak, final anode electromotive force held stationary; When anode potential declines, cathode potential sharply declines, and finally keeps stable.
The preparation of MEA and the assembling of electrolytic cell are identical with example 1.By forming shown in Fig. 1 b after additional contrast electrode, to SPE water electrolytic cell anode, pass into deionized water, flow velocity 5ml/min, makes electrolytic cell keep 60 ℃; Electrolytic cell anode and cathode is connected additional power source, constant current 500mA/cm
2electrolysis deionized water.After electrolysis 1 hour, anode passes into variable concentrations Na
+ionic soil, writing time, decomposition voltage harmonizing yinyang electrode potential, as shown in Figure 5.Na
+ion concentration is higher, and electrolytic cell voltage is higher, and rate of voltage rise is faster, and cathodic polarization is more serious, and anode electrode electromotive force is more or less the same after stablizing.
Claims (1)
1. for a method for the additional contrast electrode of the anode and cathode electrode potential of on-line measurement SPE water electrolytic cell, comprise SPE water electrolytic cell, SPE water electrolytic cell comprises overlay film Catalytic Layer (CCM), anode and cathode diffusion layer and end plate, it is characterized in that:
End plate outside is extended in one end of PEM in overlay film Catalytic Layer (CCM), the PEM extending out extend in an electrolyte solution storage tank, PEM is immersed in electrolyte solution, in electrolyte solution in storage tank, be provided with contrast electrode, contrast electrode immerses in electrolyte solution and is communicated with SPE water electrolytic cell anode and cathode by PEM, forms additional contrast electrode;
In the overlay film Catalytic Layer (CCM) of described SPE water electrolytic cell, PEM extends to end plate outside, and the PEM both sides outside electrolytic cell, all without Catalytic Layer, are solid polymer dielectric film;
Described electrolyte solution is acid solution;
Described electrolyte solution is the H of 0.1-2M
2sO
4solution.
2 methods according to claim 1, is characterized in that: described contrast electrode is mercurous chloride electrode, mercury-mercurous sulfate electrode or silver-silver chloride electrode.
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