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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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 12
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 17
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical group Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000009792 diffusion process Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims description 2
- 229910000371 mercury(I) sulfate Inorganic materials 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 abstract description 13
- 239000012528 membrane Substances 0.000 abstract description 5
- 238000012544 monitoring process Methods 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 51
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 23
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 9
- 102000029749 Microtubule Human genes 0.000 description 8
- 108091022875 Microtubule Proteins 0.000 description 8
- 210000004688 microtubule Anatomy 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
- 230000010287 polarization Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229920000557 Nafion® Polymers 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
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Abstract
本发明涉及一种用于SPE水电解池外加参比电极的方法，延长SPE水电解池中质子交换膜，将质子交换膜和外部参比电极浸入电解质溶液使外部参比电极与电解池的阴阳极连通构成三电极体系，从而对阴阳极电极电势进行测定。本发明结构简单，操作方便，测量精度高，稳定性好。在SPE水电解池运行过程中采用此种外加参比电极，可实现电解池阴阳极电势变化的实时监测，为探讨SPE水电解池性能衰减机理提供重要的在线依据。The invention relates to a method for adding a reference electrode to an SPE water electrolysis cell, prolonging the proton exchange membrane in the SPE water electrolysis cell, immersing the proton exchange membrane and the external reference electrode in the electrolyte solution to make the external reference electrode and the positive and negative electrodes of the electrolytic cell The poles are connected to form a three-electrode system, so that the potential of the cathode and anode electrodes can be measured. The invention has the advantages of simple structure, convenient operation, high measuring precision and good stability. Using this additional reference electrode during the operation of the SPE water electrolysis cell can realize real-time monitoring of the potential change of the cathode and anode of the electrolysis cell, and provide an important online basis for exploring the performance attenuation mechanism of the SPE water electrolysis cell.
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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| CN108226781A (en) * | 2016-12-10 | 2018-06-29 | 中国科学院大连化学物理研究所 | Single-cell electrodes potential measurement method in proton or anion-exchange membrane fuel cells pile |
| CN115786949B (en) * | 2022-12-30 | 2024-09-24 | 田文颖 | Electrolytic tank with double in-situ reference electrodes and application |
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| CN101008087B (en) * | 2006-01-25 | 2010-08-04 | 中国科学院大连化学物理研究所 | A kind of preparation method of membrane electrode for solid polymer electrolyte water electrolysis |
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