Photoelectrochemical Cell with the CdSe Photoanode

Photoelectrochemical Cell with the CdSe Photoanode | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Photoelectrochemical Cell with the CdSe Photoanode Sergii Chivikov, Igor Rusetskyі, Andrii Davydov, Youzheng Wu, and 2 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7897765/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 12 Jan, 2026 Read the published version in Monatshefte für Chemie - Chemical Monthly → Version 1 posted 4 You are reading this latest preprint version Abstract A variant of a reversible photoelectrochemical system. A CdSe photoanode is used, with the electrolyte in the anode compartment based on the K 3 [Fe(CN) 6 ]/K 4 [Fe(CN) 6 ] redox system. In the cathode compartment, a redox system based on sulfur polysulfides is used. Open-circuit voltage is up to 0.90 V, short-circuit current density for the illuminated surface of the photoanode is up to 5 mA/cm². There is problem of K 3 [Fe(CN) 6 ] Photodegradation. Another variant of Photoelectrochemical redox flow battery is prepoused. Chalcogenides Photodegradation Electrochemistry Inorganic polymers Figures Figure 1 Figure 2 Introduction The use of renewable energy sources is one of the ways to provide electricity. A serious drawback of electricity sources that convert solar radiation energy is the need to use accumulators or other energy sources to continuously supply energy to consumers. Electrochemical solar energy converters capable of storing energy are being developed. In work [ 1 ], a system based on a CdS/CdSe photoelectrode combined with a vanadium redox flow cell is described. The optimized CdS/CdSe photoelectrode showed an open-circuit voltage of 0.67 V and a short-circuit photocurrent of 1.4 mA/cm². Vanadium electrolyte solution containing 1.6 M vanadium in 2M H 2 SO 4 was used. The long-term stability of photoanodes is limited because the acidic nature of the electrolyte. A reversible photoelectrochemical system was described by us in [ 2 ]. Such a system, under the influence of solar radiation, is capable of generating and storing electrical energy similar to a battery. The stored energy can be used in the absence of illumination or during peak consumption when the energy obtained from light conversion is insufficient. The ability to reversibly store energy is a significant advantage. Nevertheless, the efficiency of light-to-energy conversion turned out to be low. The open-circuit voltage is 0.4 V, and the short-circuit current is 1.4 mA/cm². CdSe was used as the material for the photoanode. This system became the basis for further development, so we will describe it in more detail. The reversibility of the system is obtained by introducing a third electrode into the anode part of the cell. The third electrode is needed because the reduction reaction does not occur on photoelectrodes based on cadmium chalcogenides. The CdSe-photoelectrode and the third electrode were placed in the anode compartment filled with a polysulfide electrolyte (KOH, Na 2 S / Na 2 S x ). The anode and cathode chambers are separated by an ion-exchange membrane. A hydrogen-absorbing electrode was placed in the cathode chamber with an alkaline solution. The third electrode is Cu 2 S-electrode. An overview article on Solar Rechargeable Batteries and materials used in them is presented [ 3 ]. The goal of further work is to improve the characteristics of the reversible photoelectrochemical system was described in [ 2 ]. Results and Discussion The low efficiency of light energy conversion in the system in [2] is due to the low photopotential of the CdSe photoanode in the polysulfide solution. As shown in work [4], the change in the photoanode potential under the influence of light is significantly higher if the electrolyte contains Hexacyano ferrate(III), K 3 [Fe(CN) 6 ]. This result was obtained for photoanodes based on CdS, electrolyte was Na 2 SO 4 . Our tests for an anode based on CdSe and an alkaline electrolyte with the addition of K 3 [Fe(CN) 6 ]/K 4 [Fe(CN) 6 ] showed similar results. In the first stage, a change in the potential of the CdSe photoanode under the action of sunlight up to 0.82 V ( E L ) was obtained. An electrolyte with the composition 1M KOH, 0.14M K 4 [Fe(CN) 6 ]·3H 2 O, 0.16M K 3 [Fe(CN) 6 ] was used. A nickel plate served as the third electrode electrode. To allow for energy storage, it was necessary to select a cathode with a potential above -0.4 V. The cathode potential ( E C ) was determined from the condition: E L > E A – E C , E A – potential of anode. The cathode chosen was a system that was used in the original version in the anode compartment—an alkaline solution of sodium polysulfides. This electrode showed a potential close to the required value. Moreover, polysulfides are a series of compounds (S 2 2- , S 3 2- …), and accordingly, a range of potential values ( E 0 ,V -0.506, -0.478, -0.441) [5]. It was assumed that electrochemical treatment would make it possible to adjust the cathode potential to the required value. The selected electrode was available and showed good results in terms of reversibility and stability. As a result, the cell was connected as a reversible photoelectrochemical system. A discharge current of 3 mA was applied. The cell discharged at voltages of 0.65-0.7 V in the absence of photoanode illumination. Under photoanode illumination, an increase in the electrode voltage up to 0.7 V and higher was observed (at a discharge current of 3 mA). The result has demonstrated possibility significantly increase the operating voltage of a reversible photoelectrochemical cell. The active surface area of the photoanode was 15 cm². Accordingly, the current density for the photoanode was 0.2 mA/cm². Subsequently, the cell was left under sunlight. Approximately a month later, it was found that the cell had lost its functionality. Carbonization of the electrolyte occurred (the experimental cell did not have good seals), and the characteristics of the photoanode significantly decreased. The goal of further work was to determine the characteristics of the CdSe photoanode (stability, photopotential, photocurrent density) in an electrolyte based on K 3 [Fe(CN) 6 ]/K 4 [Fe(CN) 6 ]. The same cell was used, but it was connected in a two-electrode configuration. In the first stage, the second electrode was a foam nickel plate. The concentration ratio of the electrolyte components was changed: 0.02M K 3 [Fe(CN) 6 ]; 0.2M K 4 [Fe(CN) 6 ]·3H 2 O; 0.25M NaOH . A smaller photoanode (2 × 1 cm) was used. In some tests, the photoanode was partially immersed in the electrolyte. Immediately after assembly, the cell showed high characteristics. The photoanode current density was approximately 2 mA/cm² at a voltage of 0.7 V. The open-circuit voltage reached up to 0.9 V. A day later, the characteristics declined (see Fig. 1). The curves are given for electrodes partially immersed in the electrolyte. It was found that if the nickel electrode is not immersed in the electrolyte during storage, the cell characteristics are preserved. The reason for the decrease in cell performance during storage in the presence of nickel foam is the loss of K 3 [Fe(CN) 6 ] in the electrolyte. Adding the appropriate amount of K 3 [Fe(CN) 6 ] to the electrolyte restored the original cell characteristics. Subsequently, the nickel foam electrode was replaced with an electrode based on carbon-graphite fabric. Rapid degradation of the cell characteristics during storage with the electrolyte was not observed. The load characteristics of the photoelectrochemical cell with a CdSe photoanode and an electrolyte based on K 3 [Fe(CN) 6 ]/K 4 [Fe(CN) 6 ] are illustrated in (Fig. 2), with the photoanode area being ~2.5 cm². Considering the area of the photoanode, at a current density of 1.2 mA/cm² the cell voltage is about 0.8 V. At a current density of 2 mA/cm², the cell voltage is about 0.7 V. When the current increased to 7 mA, the cell voltage dropped to zero. Measurements carried out on a cell with an additional reference electrode showed that the change in the photoanode potential when switching the current from 5 mA to 7 mA corresponds to the change in potential when switching the current from 3 mA to 5 mA. The drop in cell voltage to zero is determined by the cathode reaching its limiting current. It can be noted that the ratio of components K 3 [Fe(CN) 6 ]/K 4 [Fe(CN) 6 ] of approximately 1:10 favors the reaction occurring at the photoanode and hinders the reaction at the cathode. The low cathode limiting current is a consequence of the low concentration of K 3 [Fe(CN) 6 ] in the electrolyte. The choice of a low concentration of K 3 [Fe(CN) 6 ] and a high concentration of K 4 [Fe(CN) 6 ] is associated with the need to reduce the electrode potential of K 3 [Fe(CN) 6 ]/K 4 [Fe(CN) 6 ]. A high positive potential of K 3 [Fe(CN) 6 ]/K 4 [Fe(CN) 6 ] leads to electrolyte instability and possibly to the instability of the CdSe photoanode. For example, in concentrated alkali, water decomposition with oxygen evolution can occur. In addition, the K 3 [Fe(CN) 6 ] solution has an intense color, which leads to light absorption and a decrease in photovoltage and photocurrent [4]. Overall, the CdSe photoanode remained in the selected electrolyte for 2 months without losing functionality. The time spent under intense illumination during this period was up to 10 hours. The electrolyte was changed multiple times during this period. The electrolyte, when kept in the dark, showed stability for months. However, when illuminated in the cell, the electrolyte decomposes, forming a precipitate on the walls of the cell. Regarding the stability of K 3 [Fe(CN) 6 ] solutions, there is a lot of research, for example [6]. Conclusion The use of the redox pair K 3 [Fe(CN) 6 ]/K 4 [Fe(CN) 6 ] in the electrolyte for the CdSe photoanode allowed the photopotential and the voltage of the photoelectrochemical cell to more than double to 0.9 V. The problem of photodegradation of K 3 [Fe(CN) 6 ] remains unresolved. The current density of the photoanode also significantly increased to 5 mA/cm². A solution for the cathode of the photoelectrochemical cell with an increased operating voltage is proposed. The performance of a reversible photoelectrochemical cell has been tested. As a development of the results, one can propose a system based on a CdS/CdSe photoelectrode combined with a redox flow cell. The components of the redox flow cell are K 3 [Fe(CN) 6 ]/K 4 [Fe(CN) 6 ]// Na 2 S X / Na 2 S Y . Experimental A galvanostatic method was used for testing the photoelectrochemical cell. Most of the results were obtained using a two-electrode setup. In some cases, a three-electrode configuration with an AgCl reference electrode was used. The galvanostat was of our own design. The photoelectrochemical cell was assembled from the same elements as the original version described in [2]. The electrodes were obtained using the same technologies. The same photoanodes were used. The third electrode (Cu 2 S electrode) of the photoelectrochemical cell from work [2] became the cathode in the new version of the cell. A polysulfide solution of the same composition was used in the cathode compartment. As the third electrode in the first stage, a nickel or nickel foam plate was used. Later, the nickel electrode was replaced with a carbon-graphite cloth electrode. The third electrode is located in the anode compartment. The construction of the photoelectrochemical cell housing remained unchanged and was also 3D printed. The anode and cathode chambers are separated by an ion-exchange membrane. In the first stage, the electrolyte used in the anode compartment was: 1M KOH , 0.14M K 4 [Fe(CN) 6 ]·3H 2 O , 0.16M K 3 [Fe(CN) 6 ] . Later, the electrolyte composition was changed to 0.02M K 3 [Fe(CN) 6 ]; 0.2M K 4 [Fe(CN) 6 ]·3H 2 O; 0.25M NaOH . After assembling the cell was connected to a galvanostat via the cathode and third electrode and subjected to prolonged cycling in the range of 0.8...0.4 V. In the initial cycles, a small capacity was observed, which limited the initial cycling current to 60 µA. During cycling, the charge-discharge capacity increased from cycle to cycle. This allowed the current to be increased to 1 mA and more. This result can be explained by the accumulation of polysulfide of the corresponding composition in the cathode compartment. Declarations Competing interest The authors have no competing interest to declare that are relevant to the content of this article. References Azevedo J, Seipp T, Burfeind J, Sousa C, Bentien A, Araújo JP, Mendes A (2016) Nano Energy 22:396 Chivikov SV, Rusetskyi IA, Fomanyuk SS, Danilov MO, Smilyk VO, Kolbasov GY (2022) Journal of Physics:Conference Series 2382 Hongmin L, Xinran G, Yitao L, Hua KL, Shi Xue Dou, Zhongchao B, Nana W (2024) Adv. Energy Mater. 14:2402381 DOI: 10.1002/aenm.202402381 Demidenko IV (2022) Elektronnaya Obrabotka Materialov 58(3):78 Suhotin AM (1981) Handbook on electrochemistry, Chemistry, Leningrad, p146 Maowei H, Abigail PW, Jian L, Qianshun W, Leo TL (2023) Adv. Energy Mater., 13, 2203762 DOI: 10.1002/aenm.202203762 Cite Share Download PDF Status: Published Journal Publication published 12 Jan, 2026 Read the published version in Monatshefte für Chemie - Chemical Monthly → Version 1 posted Reviewers agreed at journal 29 Oct, 2025 Reviewers invited by journal 24 Oct, 2025 Editor assigned by journal 23 Oct, 2025 First submitted to journal 22 Oct, 2025 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-7897765","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":534400075,"identity":"c7078dc1-dae2-488b-851f-939bd46646a4","order_by":0,"name":"Sergii 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2","display":"","copyAsset":false,"role":"figure","size":15100,"visible":true,"origin":"","legend":"\u003cp\u003eCurrent 1mA ; 3mA ; 5mA ; 7mA\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-7897765/v1/2ff22f56d15f3d61cd8439e3.png"},{"id":100614784,"identity":"be9e9156-2184-4d56-8950-cd55e6247e27","added_by":"auto","created_at":"2026-01-19 17:25:02","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":314072,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-7897765/v1/6574ec02-f028-4651-8982-b6ed070de96a.pdf"}],"financialInterests":"","formattedTitle":"Photoelectrochemical Cell with the CdSe Photoanode","fulltext":[{"header":"Introduction","content":"\u003cp\u003eThe use of renewable energy sources is one of the ways to provide electricity. A serious drawback of electricity sources that convert solar radiation energy is the need to use accumulators or other energy sources to continuously supply energy to consumers. Electrochemical solar energy converters capable of storing energy are being developed. In work [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e], a system based on a CdS/CdSe photoelectrode combined with a vanadium redox flow cell is described. The optimized CdS/CdSe photoelectrode showed an open-circuit voltage of 0.67 V and a short-circuit photocurrent of 1.4 mA/cm\u0026sup2;. Vanadium electrolyte solution containing 1.6 M vanadium in 2M H\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e was used. The long-term stability of photoanodes is limited because the acidic nature of the electrolyte.\u003c/p\u003e\u003cp\u003eA reversible photoelectrochemical system was described by us in [\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e]. Such a system, under the influence of solar radiation, is capable of generating and storing electrical energy similar to a battery. The stored energy can be used in the absence of illumination or during peak consumption when the energy obtained from light conversion is insufficient. The ability to reversibly store energy is a significant advantage. Nevertheless, the efficiency of light-to-energy conversion turned out to be low. The open-circuit voltage is 0.4 V, and the short-circuit current is 1.4 mA/cm\u0026sup2;. CdSe was used as the material for the photoanode.\u003c/p\u003e\u003cp\u003eThis system became the basis for further development, so we will describe it in more detail. The reversibility of the system is obtained by introducing a third electrode into the anode part of the cell. The third electrode is needed because the reduction reaction does not occur on photoelectrodes based on cadmium chalcogenides. The CdSe-photoelectrode and the third electrode were placed in the anode compartment filled with a polysulfide electrolyte (KOH, Na\u003csub\u003e2\u003c/sub\u003eS / Na\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003ex\u003c/sub\u003e). The anode and cathode chambers are separated by an ion-exchange membrane. A hydrogen-absorbing electrode was placed in the cathode chamber with an alkaline solution. The third electrode is Cu\u003csub\u003e2\u003c/sub\u003eS-electrode.\u003c/p\u003e\u003cp\u003eAn overview article on Solar Rechargeable Batteries and materials used in them is presented [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e].\u003c/p\u003e\u003cp\u003eThe goal of further work is to improve the characteristics of the reversible photoelectrochemical system was described in [\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e].\u003c/p\u003e"},{"header":"Results and Discussion","content":"\u003cp\u003eThe low efficiency of light energy conversion in the system in [2] is due to the low photopotential of the CdSe photoanode in the polysulfide solution. As shown in work [4], the change in the photoanode potential under the influence of light is significantly higher if the electrolyte \u0026nbsp; contains Hexacyano ferrate(III), K\u003csub\u003e3\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]. This result was obtained for photoanodes based on CdS, electrolyte was Na\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e. Our tests for an anode based on CdSe and an alkaline electrolyte with the addition of K\u003csub\u003e3\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]/K\u003csub\u003e4\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e] showed similar results.\u0026nbsp;In the first stage, a change in the potential of the CdSe photoanode under the action of sunlight up to 0.82 V (\u003cem\u003eE\u003csub\u003eL\u003c/sub\u003e\u003c/em\u003e) was obtained. An electrolyte with the composition 1M KOH, 0.14M\u0026nbsp;K\u003csub\u003e4\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]\u0026middot;3H\u003csub\u003e2\u003c/sub\u003eO, 0.16M \u0026nbsp;K\u003csub\u003e3\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]\u0026nbsp;was used. A nickel plate served as the third electrode electrode. To allow for energy storage, it was necessary to select a cathode with a potential above -0.4 V. The cathode potential (\u003cem\u003eE\u003csub\u003eC\u003c/sub\u003e\u003c/em\u003e) was determined from the condition:\u003cem\u003e\u0026nbsp;E\u003csub\u003eL\u003c/sub\u003e \u0026gt; E\u003csub\u003eA\u003c/sub\u003e \u0026ndash; E\u003csub\u003eC\u003c/sub\u003e\u003c/em\u003e , \u003cem\u003eE\u003csub\u003eA\u003c/sub\u003e\u003c/em\u003e \u0026ndash; potential of anode. \u0026nbsp; The cathode chosen was a system that was used in the original version in the anode compartment\u0026mdash;an alkaline solution of sodium polysulfides. This electrode showed a potential close to the required value. Moreover, polysulfides are a series of compounds (S\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e2-\u003c/sup\u003e, S\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e2-\u003c/sup\u003e \u0026hellip;), and accordingly, a range of potential values (\u003cem\u003eE\u003csup\u003e0\u003c/sup\u003e,V\u003c/em\u003e -0.506, -0.478, -0.441) [5]. It was assumed that electrochemical treatment would make it possible to adjust the cathode potential to the required value. The selected electrode was available and showed good results in terms of reversibility and stability.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;As a result, the cell was connected as a reversible photoelectrochemical system. A discharge current of 3 mA was applied. The cell discharged at voltages of 0.65-0.7 V in the absence of photoanode illumination. Under photoanode illumination, an increase in the electrode voltage up to 0.7 V and higher was observed (at a discharge current of 3 mA). The result has demonstrated possibility significantly increase the operating voltage of a reversible photoelectrochemical cell.\u003c/p\u003e\n\u003cp\u003eThe active surface area of the photoanode was 15 cm\u0026sup2;. Accordingly, the current density for the photoanode was 0.2 mA/cm\u0026sup2;. Subsequently, the cell was left under sunlight. Approximately a month later, it was found that the cell had lost its functionality. Carbonization of the electrolyte occurred (the experimental cell did not have good seals), and the characteristics of the photoanode significantly decreased.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe goal of further work was to determine the characteristics of the CdSe photoanode (stability, photopotential, photocurrent density) in an electrolyte based on\u0026nbsp;K\u003csub\u003e3\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]/K\u003csub\u003e4\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]. The same cell was used, but it was connected in a two-electrode configuration. In the first stage, the second electrode was a foam nickel plate.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;The concentration ratio of the electrolyte components was changed: 0.02M K\u003csub\u003e3\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]; 0.2M\u0026nbsp;K\u003csub\u003e4\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]\u0026middot;3H\u003csub\u003e2\u003c/sub\u003eO; 0.25M NaOH . A smaller photoanode (2 \u0026times; 1 cm) was used. In some tests, the photoanode was partially immersed in the electrolyte.\u003c/p\u003e\n\u003cp\u003eImmediately after assembly, the cell showed high characteristics. The photoanode current density was approximately 2 mA/cm\u0026sup2; at a voltage of 0.7 V. The open-circuit voltage reached up to 0.9 V. A day later, the characteristics declined (see Fig. 1). The curves are given for electrodes partially immersed in the electrolyte.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eIt was found that if the nickel electrode is not immersed in the electrolyte during storage, the cell characteristics are preserved. The reason for the decrease in cell performance during storage in the presence of nickel foam is the loss of\u0026nbsp;K\u003csub\u003e3\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]\u0026nbsp;in the electrolyte. Adding the appropriate amount of\u0026nbsp;K\u003csub\u003e3\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]\u0026nbsp;to the electrolyte restored the original cell characteristics.\u003c/p\u003e\n\u003cp\u003eSubsequently, the nickel foam electrode was replaced with an electrode based on carbon-graphite fabric. Rapid degradation of the cell characteristics during storage with the electrolyte was not observed.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe load characteristics of the photoelectrochemical cell with a CdSe photoanode and an electrolyte based on\u0026nbsp;K\u003csub\u003e3\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]/K\u003csub\u003e4\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e] are illustrated in (Fig. 2), with the photoanode area being ~2.5 cm\u0026sup2;.\u003c/p\u003e\n\u003cp\u003eConsidering the area of the photoanode, at a current density of 1.2 mA/cm\u0026sup2; the cell voltage is about 0.8 V. At a current density of 2 mA/cm\u0026sup2;, the cell voltage is about 0.7 V. When the current increased to 7 mA, the cell voltage dropped to zero. Measurements carried out on a cell with an additional reference electrode showed that the change in the photoanode potential when switching the current from 5 mA to 7 mA corresponds to the change in potential when switching the current from 3 mA to 5 mA. The drop in cell voltage to zero is determined by the cathode reaching its limiting current. It can be noted that the ratio of components\u0026nbsp;K\u003csub\u003e3\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]/K\u003csub\u003e4\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]\u0026nbsp;of approximately 1:10 favors the reaction occurring at the photoanode and hinders the reaction at the cathode. The low cathode limiting current is a consequence of the low concentration of\u0026nbsp;K\u003csub\u003e3\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]\u0026nbsp;in the electrolyte.\u003c/p\u003e\n\u003cp\u003eThe choice of a low concentration of\u0026nbsp;K\u003csub\u003e3\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]\u0026nbsp;and a high concentration of\u0026nbsp;K\u003csub\u003e4\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]\u0026nbsp;is associated with the need to reduce the electrode potential of\u0026nbsp;K\u003csub\u003e3\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]/K\u003csub\u003e4\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]. A high positive potential of\u0026nbsp;K\u003csub\u003e3\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]/K\u003csub\u003e4\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]\u0026nbsp;leads to electrolyte instability and possibly to the instability of the CdSe photoanode. For example, in concentrated alkali, water decomposition with oxygen evolution can occur. In addition, the\u0026nbsp;K\u003csub\u003e3\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]\u0026nbsp;solution has an intense color, which leads to light absorption and a decrease in photovoltage and photocurrent [4].\u003c/p\u003e\n\u003cp\u003eOverall, the CdSe photoanode remained in the selected electrolyte for 2 months without losing functionality. The time spent under intense illumination during this period was up to 10 hours. The electrolyte was changed multiple times during this period. The electrolyte, when kept in the dark, showed stability for months. However, when illuminated in the cell, the electrolyte decomposes, forming a precipitate on the walls of the cell. Regarding the stability of\u0026nbsp;K\u003csub\u003e3\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e] solutions, there is a lot of research, for example [6].\u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eThe use of the redox pair\u0026nbsp;K\u003csub\u003e3\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]/K\u003csub\u003e4\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]\u0026nbsp;in the electrolyte for the CdSe photoanode allowed the photopotential and the voltage of the photoelectrochemical cell to more than double to 0.9 V. The problem of photodegradation of\u0026nbsp;K\u003csub\u003e3\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]\u0026nbsp;remains unresolved. The current density of the photoanode also significantly increased to 5 mA/cm\u0026sup2;. A solution for the cathode of the photoelectrochemical cell with an increased operating voltage is proposed. The performance of a reversible photoelectrochemical cell has been tested.\u003c/p\u003e\n\u003cp\u003eAs a development of the results, one can propose a system based on a CdS/CdSe photoelectrode combined with a redox flow cell. The components of the redox flow cell are K\u003csub\u003e3\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]/K\u003csub\u003e4\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]// Na\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003eX\u003c/sub\u003e / Na\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003eY\u003c/sub\u003e.\u003c/p\u003e"},{"header":"Experimental","content":"\u003cp\u003eA galvanostatic method was used for testing the photoelectrochemical cell. Most of the results were obtained using a two-electrode setup. In some cases, a three-electrode configuration with an AgCl reference electrode was used. The galvanostat was of our own design.\u003c/p\u003e\n\u003cp\u003eThe photoelectrochemical cell was assembled from the same elements as the original version described in [2]. The electrodes were obtained using the same technologies. The same photoanodes were used. The third electrode (Cu\u003csub\u003e2\u003c/sub\u003eS electrode) of the photoelectrochemical cell from work [2] became the cathode in the new version of the cell. A polysulfide solution of the same composition was used in the cathode compartment. As the third electrode in the first stage, a nickel or nickel foam plate was used. Later, the nickel electrode was replaced with a carbon-graphite cloth electrode. The third electrode is located in the anode compartment. The construction of the photoelectrochemical cell housing remained unchanged and was also 3D printed. The anode and cathode chambers are separated by an ion-exchange membrane. In the first stage, the electrolyte used in the anode compartment was: 1M KOH , 0.14M\u0026nbsp;K\u003csub\u003e4\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]\u0026middot;3H\u003csub\u003e2\u003c/sub\u003eO\u0026nbsp;, 0.16M\u0026nbsp;K\u003csub\u003e3\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]\u0026nbsp;. Later, the electrolyte composition was changed to 0.02M\u0026nbsp;K\u003csub\u003e3\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]; 0.2M\u0026nbsp;K\u003csub\u003e4\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]\u0026middot;3H\u003csub\u003e2\u003c/sub\u003eO; 0.25M NaOH .\u003c/p\u003e\n\u003cp\u003eAfter assembling the cell was connected to a galvanostat via the cathode and third electrode and subjected to prolonged cycling in the range of 0.8...0.4 V. In the initial cycles, a small capacity was observed, which limited the initial cycling current to 60 \u0026micro;A. During cycling, the charge-discharge capacity increased from cycle to cycle. This allowed the current to be increased to 1 mA and more. This result can be explained by the accumulation of polysulfide of the corresponding composition in the cathode compartment.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eCompeting interest\u003c/h2\u003e\n\u003cp\u003e\u0026nbsp;The authors have no competing interest to declare that are relevant to the content of this article.\u003c/p\u003e\n\u003cp\u003e\u003cbr\u003e\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eAzevedo J, Seipp T, Burfeind J, Sousa C, Bentien A, Ara\u0026uacute;jo JP, Mendes A (2016) Nano Energy 22:396\u003c/li\u003e\n\u003cli\u003eChivikov SV, Rusetskyi IA, Fomanyuk SS, Danilov MO, Smilyk VO, Kolbasov GY (2022) Journal of Physics:Conference Series 2382\u003c/li\u003e\n\u003cli\u003eHongmin L, Xinran G, Yitao L, Hua KL, Shi Xue Dou, Zhongchao B, Nana W (2024) Adv. Energy Mater. 14:2402381 DOI: 10.1002/aenm.202402381\u003c/li\u003e\n\u003cli\u003eDemidenko IV (2022) Elektronnaya Obrabotka Materialov 58(3):78\u003c/li\u003e\n\u003cli\u003eSuhotin AM (1981) Handbook on electrochemistry, Chemistry, Leningrad, p146\u003c/li\u003e\n\u003cli\u003eMaowei H, Abigail PW, Jian L, Qianshun W, Leo TL (2023) Adv. Energy Mater., 13, 2203762 DOI: 10.1002/aenm.202203762\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"monatshefte-fur-chemie-chemical-monthly","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"mccm","sideBox":"Learn more about [Monatshefte für Chemie - Chemical Monthly](https://www.springer.com/journal/706)","snPcode":"706","submissionUrl":"https://www.editorialmanager.com/mccm/","title":"Monatshefte für Chemie - Chemical Monthly","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Chalcogenides, Photodegradation, Electrochemistry, Inorganic polymers ","lastPublishedDoi":"10.21203/rs.3.rs-7897765/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-7897765/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eA variant of a reversible photoelectrochemical system. A CdSe photoanode is used, with the electrolyte in the anode compartment based on the K\u003csub\u003e3\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e]/K\u003csub\u003e4\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e] redox system. In the cathode compartment, a redox system based on sulfur polysulfides is used. Open-circuit voltage is up to 0.90 V, short-circuit current density for the illuminated surface of the photoanode is up to 5 mA/cm\u0026sup2;. There is problem of K\u003csub\u003e3\u003c/sub\u003e[Fe(CN)\u003csub\u003e6\u003c/sub\u003e] Photodegradation. Another variant of Photoelectrochemical redox flow battery is prepoused.\u003c/p\u003e","manuscriptTitle":"Photoelectrochemical Cell with the CdSe Photoanode","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-11-05 10:27:44","doi":"10.21203/rs.3.rs-7897765/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"reviewerAgreed","content":"","date":"2025-10-29T13:09:24+00:00","index":0,"fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-10-24T08:58:32+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-10-23T07:28:32+00:00","index":"","fulltext":""},{"type":"submitted","content":"Monatshefte für Chemie - Chemical Monthly","date":"2025-10-22T20:32:26+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"monatshefte-fur-chemie-chemical-monthly","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"mccm","sideBox":"Learn more about [Monatshefte für Chemie - Chemical Monthly](https://www.springer.com/journal/706)","snPcode":"706","submissionUrl":"https://www.editorialmanager.com/mccm/","title":"Monatshefte für Chemie - Chemical Monthly","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"39f46b82-34ff-476e-a600-2aadac676b0b","owner":[],"postedDate":"November 5th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2026-01-19T16:48:52+00:00","versionOfRecord":{"articleIdentity":"rs-7897765","link":"https://doi.org/10.1007/s00706-025-03430-5","journal":{"identity":"monatshefte-fur-chemie-chemical-monthly","isVorOnly":false,"title":"Monatshefte für Chemie - Chemical Monthly"},"publishedOn":"2026-01-12 16:30:17","publishedOnDateReadable":"January 12th, 2026"},"versionCreatedAt":"2025-11-05 10:27:44","video":"","vorDoi":"10.1007/s00706-025-03430-5","vorDoiUrl":"https://doi.org/10.1007/s00706-025-03430-5","workflowStages":[]},"version":"v1","identity":"rs-7897765","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-7897765","identity":"rs-7897765","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}