CN102478536A - 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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- CN102478536A CN102478536A CN2010105637662A CN201010563766A CN102478536A CN 102478536 A CN102478536 A CN 102478536A CN 2010105637662 A CN2010105637662 A CN 2010105637662A CN 201010563766 A CN201010563766 A CN 201010563766A CN 102478536 A CN102478536 A CN 102478536A
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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 that adds contrast electrode that is used for on-line measurement SPE water electrolytic cell anode and cathode electrode potential.
Background technology
The SPE water electrolysis is to be electrolytical water electrolysis technology with solid polymer, and its working current density can be up to 1～3Acm
-2, and have electrolytic efficiency height, device volume little, generate 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, when especially studying performance degradation mechanism and catalyst performance, often need the anode and cathode electrode potential separately be measured.Use reversible hydrogen electrode (RHE), microtubule hydrogen electrode or dynamic hydrogen electrode contrast electrodes such as (DHE) that the anode and cathode electrode potential is separately measured in the bibliographical information.The preparation of RHE is that PEM among the membrane electrode MEA is prolonged, and the black catalyzer of PEM top spraying Pt that is prolonging.Feed hydrogen to the black catalyzer place of Pt during test and constitute the RHE contrast electrode.The microtubule hydrogen electrode comprises microtubule, the black catalyzer of Pt and platinum filament.Polymer dielectric is made microtubule, and with the potpourri injection microtubule of black catalyzer of Pt and Nafion, platinum filament is put into microtubule as collector, in microtubule, feeds hydrogen and can be used as microtubule hydrogen electrode contrast electrode.The preparation of DHE is comparatively complicated.At first get two platinum filaments, every platinum filament two ends are exposed the 1mm remainder and are coated with PTFE.Platinum black, Nafion solution and isopropanol mixture are coated in an end of two platinum filaments.After room temperature is dried, the end that two platinum filaments are scribbled potpourri at a distance of 1mm hot pressing in the middle of two Nafion films.One of two platinum filament as conduct of hydrogen-precipitating electrode to electrode.In addition, also need constant-current supply (9V dry cell) and trimmable resistance device (0-1M Ω) to make steady current (μ A level) in use, cover hydrogen-precipitating electrode with the hydrogen that guarantees to separate out through DHE.More than several kinds of reference electrodes exist preparation comparatively complicated, cost is higher, and 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 problem such as inconvenient operation, the objective of the invention is to provides a kind of preparation simply to measuring SPE water electrolytic cell anode and cathode electrode potential, the easy to operate contrast electrode preparation method that adds.
For realizing above-mentioned purpose, technical scheme of the present invention is:
A kind of SPE of being used for water electrolytic cell adds the method for contrast electrode; Comprise the SPE water electrolytic cell; The SPE water electrolytic cell comprises overlay film Catalytic Layer (CCM), anode and cathode diffusion layer and end plate, and an end of the PEM among the CCM extends the end plate outside, prolongs the PEM that comes out and extend in the electrolyte solution storage tank; PEM is immersed in the electrolyte solution; Be provided with contrast electrode in the electrolyte solution in storage tank, contrast electrode immerses in the electrolyte solution and is communicated with SPE water electrolytic cell anode and cathode through PEM, constitutes to add contrast electrode.
PEM extends to the end plate outside among the said SPE water electrolytic cell CCM, and being in the outer PEM both sides of electrolytic cell does not all have Catalytic Layer, is solid polymer dielectric film.
Said electrolyte solution is an acid solution, like the H of 0.1-2M
2SO
4Solution;
Said contrast electrode is mercurous chloride electrode, mercury-mercurous sulfate electrode or silver-silver chloride electrode.
The PEM of CCM is communicated with through electrolyte solution in contrast electrode and the SPE water electrolytic cell, constitutes three-electrode system, thereby the anode and cathode electrode potential is measured.
The present invention has following characteristics:
(1) the present invention is simple in structure, and is 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 anode and cathode electromotive force in the electrolytic cell operational process in real time.
(3) the present invention extends to PEM among the CCM outside the SPE water electrolytic cell, and electrolytic process can not cause mutual interference mutually with measuring process.
Measuring accuracy of the present invention is high, good stability.In SPE water electrolytic cell operational process, adopt this kind to add contrast electrode, can realize the real-time monitoring of electrolytic cell anode and cathode potential change, important online foundation is provided for inquiring into SPE water electrolytic cell performance degradation mechanism.
Description of drawings
A is a water electrolytic cell CCM synoptic diagram among Fig. 1, and b is for adding the contrast electrode synoptic diagram.(1) PEM, (2) Catalytic Layer, (3) SPE water electrolytic cell, (4) contrast electrode, (5) electrolyte solution.
Fig. 2 is a contrast electrode stability.
Fig. 3 is SPE water electrolytic cell, anode and cathode polarization curve.
Fig. 4 is 0.002M Na
+Ionic soil solution influences the SPE water electrolytic cell.
Fig. 5 is variable concentrations Na
+Ionic soil influences the SPE water electrolytic cell.
Embodiment
Below in conjunction with accompanying drawing the present invention is further specified.
CCM according to the invention is made up of Catalytic Layer and PEM; PEM 1 is that PEM among the CCM is prolonged shown in Fig. 1 a; When the assembling electrolytic cell, PEM 1 is extended to outside the end plate of electrolytic cell 3, and the equal catalyst-free in PEM 1 both sides.
Be that the present invention adds the contrast electrode synoptic diagram shown in Fig. 1 b, PEM 1 immerses the electrolyte solution 5 (H of 0.1-2M in the SPE water electrolytic cell
2SO
4Solution; ), contrast electrode 4 immersion electrolyte solutions are communicated with formation and add contrast electrode with SPE water electrolytic cell anode and cathode, thereby the 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
2Hot pressing gets membrane electrode under 140 ℃, 1MPa.Add anode and cathode diffusion layer and end plate assembling monocell respectively in the membrane electrode both sides, electrolytic cell useful area 5cm
2Add contrast electrode by constituting shown in Fig. 1 b, electrolyte solution is the H of 0.5M
2SO
4, contrast electrode is saturated calomel electrode (SCE).Feed deionized water to SPE water electrolytic cell anode, flow velocity 5ml/min makes electrolytic cell keep 60 ℃; Feed 0.1M Pa H to negative electrode then
2, flow velocity 20ml/min.Contrast electrode and negative electrode are formed primary element, because negative electrode uses the Pt/C catalyzer, negative electrode is as standard hydrogen electrode behind the feeding hydrogen, and the electromotive force that records primary element is the contrast electrode electromotive force.Shown in Figure 2 is the stability of saturated calomel electrode.As can be seen from the figure the 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 contrast electrode electromotive force stability receives electrolytic cell temperature effect little in the test process.
The preparation of MEA is identical with instance 1 with the assembling of electrolytic cell.By constitute shown in Fig. 1 b add contrast electrode after, feed deionized water to SPE water electrolytic cell anode, flow velocity 5ml/min makes electrolytic cell keep 60 ℃; Electrolytic cell making alive test polarization curve is measured the anode and cathode electrode potential simultaneously.Fig. 3 is a SPE water electrolytic cell harmonizing yinyang utmost point polarization curve, and as can be seen from the figure, the polarization of electrolytic cell is mainly from anode polarization in institute's test specification, and cathodic polarization increases and increases along with current density.
The preparation of MEA is identical with instance 1 with the assembling of electrolytic cell.By constitute shown in Fig. 1 b add contrast electrode after, feed deionized water to SPE water electrolytic cell anode, flow velocity 5ml/min makes electrolytic cell keep 60 ℃; The electrolytic cell anode and cathode is connected additional power source, constant current 500mA/cm
2The electrolysis deionized water, writing time, decomposition voltage harmonizing yinyang electrode potential.After the electrolysis 1 hour, anode feeds concentration 0.002M Na
+Pollute writing time, decomposition voltage harmonizing yinyang electrode potential.Fig. 4 is that the SPE water electrolytic cell is at 0.002M Na
+Electrolytic cell voltage harmonizing yinyang electrode potential change curve before and after polluting.Can see that from figure polluting preceding electrolytic cell voltage harmonizing yinyang electrode potential does not change; Na
+Pollute back electrolytic cell voltage and anode potential and raise, cathode potential did not change in a very long time, then slowly descended; Along with continuing to raise, the aggravation decomposition voltage that pollutes keeps constant at last; Anode potential descends after being elevated to peak, final anode electromotive force held stationary; Cathode potential sharply descends when anode potential descends, and keeps stable at last.
Embodiment 4
The preparation of MEA is identical with instance 1 with the assembling of electrolytic cell.By constitute shown in Fig. 1 b add contrast electrode after, feed deionized water to SPE water electrolytic cell anode, flow velocity 5ml/min makes electrolytic cell keep 60 ℃; The electrolytic cell anode and cathode is connected additional power source, constant current 500mA/cm
2The electrolysis deionized water.After the electrolysis 1 hour, anode feeds variable concentrations Na
+Ionic soil, writing time, decomposition voltage harmonizing yinyang electrode potential are seen shown in Figure 5.Na
+Ion concentration is high more, and electrolytic cell voltage is high more, and rate of voltage rise is fast more, and cathodic polarization is serious more, and the anode electrode electromotive force is more or less the same after stablizing.
Claims (5)
1. one kind is used for the method that the SPE water electrolytic cell adds contrast electrode, comprises the SPE water electrolytic cell, and the SPE water electrolytic cell comprises overlay film Catalytic Layer (CCM), anode and cathode diffusion layer and end plate, it is characterized in that:
One end of the PEM among the CCM extends the end plate outside; Prolonging the PEM that comes out extend in the electrolyte solution storage tank; PEM is immersed in the electrolyte solution; Be provided with contrast electrode in the electrolyte solution in storage tank, contrast electrode immerses in the electrolyte solution and is communicated with SPE water electrolytic cell anode and cathode through PEM, constitutes to add contrast electrode.
2. method according to claim 1 is characterized in that: PEM extends to the end plate outside among the said SPE water electrolytic cell CCM, and being in the outer PEM both sides of electrolytic cell does not all have Catalytic Layer, is solid polymer dielectric film.
3. method according to claim 1 is characterized in that: said electrolyte solution is an acid solution.
4. method according to claim 3 is characterized in that: said electrolyte solution is the H of 0.1-2M
2SO
4Solution.
5. method according to claim 1 is characterized in that: said contrast electrode is mercurous chloride electrode, mercury-mercurous sulfate electrode or silver-silver chloride electrode.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106596686A (en) * | 2016-10-24 | 2017-04-26 | 中国科学院长春应用化学研究所 | Evaluation device and evaluation method an electrocatalyst property used for a solid polymer electrolyte fuel cell and water electrolysis |
| 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 |
Citations (4)
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| CN2650146Y (en) * | 2003-05-02 | 2004-10-20 | 保定金风帆蓄电池有限公司 | Electrode potential measuring and treating device |
| CN101008087A (en) * | 2006-01-25 | 2007-08-01 | 中国科学院大连化学物理研究所 | Preparation method of film electrode for solid polymer electrolyte water electrolysis |
| CN101816088A (en) * | 2007-06-29 | 2010-08-25 | 凸版印刷株式会社 | Membrane electrode assembly, process for producing membrane electrode assembly, and solid polymer electrolyte fuel cell |
| CN101855773A (en) * | 2007-09-14 | 2010-10-06 | A123系统公司 | Lithium rechargable battery with the reference electrode that is used for state of health monitoring |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2650146Y (en) * | 2003-05-02 | 2004-10-20 | 保定金风帆蓄电池有限公司 | Electrode potential measuring and treating device |
| CN101008087A (en) * | 2006-01-25 | 2007-08-01 | 中国科学院大连化学物理研究所 | Preparation method of film electrode for solid polymer electrolyte water electrolysis |
| CN101816088A (en) * | 2007-06-29 | 2010-08-25 | 凸版印刷株式会社 | Membrane electrode assembly, process for producing membrane electrode assembly, and solid polymer electrolyte fuel cell |
| CN101855773A (en) * | 2007-09-14 | 2010-10-06 | A123系统公司 | Lithium rechargable battery with the reference electrode that is used for state of health monitoring |
Non-Patent Citations (1)
| Title |
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| 梁栋 等: "质子交换膜燃料电池燃烧饥饿现象", 《电源技术》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106596686A (en) * | 2016-10-24 | 2017-04-26 | 中国科学院长春应用化学研究所 | Evaluation device and evaluation method an electrocatalyst property used for a solid polymer electrolyte fuel cell and water electrolysis |
| CN106596686B (en) * | 2016-10-24 | 2018-10-26 | 中国科学院长春应用化学研究所 | A kind of evaluating apparatus and evaluation method for solid polymer electrolyte fuel cell and water electrolysis elctro-catalyst performance |
| 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 |
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| CN102478536B (en) | 2014-03-19 |
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