H2Evolution from Water on Modified Cu2ZnSnS4Photoelectrode under Solar Light

Yokoyama, Daisuke; Minegishi, Tsutomu; Jimbo, Kazuo; Hisatomi, Takashi; Ma, Guijun; Katayama, Masao; Kubota, Jun; Katagiri, Hironori; Domen, Kazunari

doi:10.1143/apex.3.101202

Cited by 165 publications

(143 citation statements)

References 16 publications

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“…[19,30,[46][47][48] The volume of the CBD solution was 50 mL, and it contained 14 wt% of ammonia (Wako), 25 × 10 −3 m of Cd(CH 3 COO) 2 , (Kanto, 98.0%), and 0.375 m of SC(NH 2 ) 2 (Kanto, 98.0%). During the deposition period of 14 min, the bath temperature was gradually increased from room temperature to typically 326 K over the span of about 8 min.…”

Section: Methodsmentioning

confidence: 99%

A Novel Photocathode Material for Sunlight‐Driven Overall Water Splitting: Solid Solution of ZnSe and Cu(In,Ga)Se₂

Kaneko

Minegishi

Nakabayashi

et al. 2016

Adv Funct Materials

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109

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content; a similar effect has been found for other material systems. [21][22][23] As shown in Scheme 1, for a solid solution of ZnSe and CIGS, the VBM is expected to be deeper than that for CIGS, and the absorption edge longer than that for ZnSe. In this work, we investigated the PEC properties of (ZnSe) x (CIGS) 1-x thin-film photocathodes. The VBM was 0.25 V deeper than that for CIGS, and the onset potential was 0.89 V RHE , which is 0.17 V higher than that for CIGS. This higher onset potential allows PEC cells to be fabricated with a variety of photoanodes without the need for an external bias voltage. [24][25][26][27] Moreover, (ZnSe) 0.85 (CIGS) 0.15 contains much less of the rare metals indium and gallium. Therefore, (ZnSe) 0.85 (CIGS) 0.15 offers advantages over CIGS from the viewpoint of large-scale applications.Using a (ZnSe) 0.85 (CIGS) 0.15 photocathode with a BiVO 4 photoanode, [28] PEC overall water splitting without the need for an external bias voltage was demonstrated. The two-electrode cell produced stoichiometric amounts of H 2 and O 2 under simulated sunlight. The maximum STH was 0.91%, which is one of the highest values reported for a PEC cell containing a photoanode and a photocathode. [4] Results and Discussion PEC Properties of (ZnSe) 0.85 (CIGS) 0.15 PhotocathodesCurrent density versus potential curves for Pt and Pt/CdS modified (ZnSe) 0.85 (CIGS) 0.15 photocathodes are shown in Figure 1a. This composition was found to produce the largest photocurrent at 0.5 V RHE , as discussed in the next section.Whereas the photocathode modified by Pt alone showed a small cathodic photoresponse, the photocathode modified with both Pt and CdS exhibited a large photocurrent density of 6.5 mA cm −2 at 0 V RHE with a relatively high onset potential of 0.81 V RHE , which was defined as a cathodic photocurrent density of 0.05 mA cm −2 . It has been reported that an n-type CdS layer enhances the degree of charge separation by forming a p-n junction at the solid-liquid interface with the underlying p-type layer, which leads to a larger photocurrent and a higher onset potential because of the change in the band alignment. [29,30] As shown in Figure S1 (Supporting Information), the Pt/CdS/(ZnSe) 0.85 (CIGS) 0.15 photocathode showed no decay in the photocurrent at 0.1 V RHE over a period of more than 1 h. Such stable hydrogen evolution from water is similar to that reported for photocathodes based on chalcopyrites. [30][31][32] The incident photon to current conversion efficiency (IPCE) spectrum shown in Figure 1b indicates that the absorption edge is located around 900 nm. Despite the relatively high fraction of ZnSe, whose absorption edge is about 460 nm, the absorption edge for (ZnSe) 0.85 (CIGS) 0.15 is close to that for CIGS (≈1100 nm). Thus, due to its bandgap and onset potential, (ZnSe) 0.85 (CIGS) 0.15 is the promising material for sunlightdriven hydrogen production from water.Furthermore, insertion of 3-nm-thick Mo and Ti layers between the Pt and CdS improves the photocurrent around the onset potentia...

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Section: Methodsmentioning

confidence: 99%

A Novel Photocathode Material for Sunlight‐Driven Overall Water Splitting: Solid Solution of ZnSe and Cu(In,Ga)Se₂

Kaneko

Minegishi

Nakabayashi

et al. 2016

Adv Funct Materials

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109

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“…These studies suggest that TiO 2 operates as a robust protective layer preventing the direct contact of the chalcopyrite/CdS with the electrolyte. [ 15,73 ] Additionally, its deeper valence band is believed to induce a larger electrostatic repulsion of holes from the surface, therefore reducing surface recombination. [ 74 ] However, despite the benefi cial effects of TiO 2 , it is not an especially active catalyst for the water reduction reaction.…”

Section: Overlayersmentioning

confidence: 99%

A Bottom‐Up Approach toward All‐Solution‐Processed High‐Efficiency Cu(In,Ga)S₂ Photocathodes for Solar Water Splitting

Guijarro

Prévot

et al. 2016

Advanced Energy Materials

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The development of solution‐processable routes to prepare efficient photoelectrodes for water splitting is highly desirable to reduce manufacturing costs. Recently, sulfide chalcopyrites (Cu(In,Ga)S2) have attracted attention as photocathodes for hydrogen evolution owing to their outstanding optoelectronic properties and their band gap—wider than their selenide counterparts—which can potentially increase the attainable photovoltage. A straightforward and all‐solution‐processable approach for the fabrication of highly efficient photocathodes based on Cu(In,Ga)S2 is reported for the first time. It is demonstrated that semiconductor nanocrystals can be successfully employed as building blocks to prepare phase‐pure microcrystalline thin films by incorporating different additives (Sb, Bi, Mg) that promote the coalescence of the nanocrystals during annealing. Importantly, the grain size is directly correlated to improved charge transport for Sb and Bi additives, but it is shown that secondary effects can be detrimental to performance even with large grains (for Mg). For optimized electrodes, the sequential deposition of thin layers of n‐type CdS and TiO2 by solution‐based methods, and platinum as an electrocatalyst, leads to stable photocurrents saturating at 8.0 mA cm–2 and onsetting at ≈0.6 V versus RHE under AM 1.5G illumination for CuInS2 films. Electrodes prepared by our method rival the state‐of‐the‐art performance for these materials.

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“…It also should be noted that p-type Cu2ZnSnS4, which has a kesterite structure, has been investigated as a photocathode, and shows photocurrent values comparable to those of chalcopyrite materials [50][51][52]. This material is attractive in that it is made of Earth-abundant and low-toxicity elements.…”

Section: Hydrogen Evolution From Water Using Copper Chalcopyrite Photmentioning

confidence: 99%

Chalcopyrite Thin Film Materials for Photoelectrochemical Hydrogen Evolution from Water under Sunlight

2015

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Abstract:Copper chalcopyrite is a promising candidate for a photocathode material for photoelectrochemical (PEC) water splitting because of its high half-cell solar-to-hydrogen conversion efficiency (HC-STH), relatively simple and low-cost preparation process, and chemical stability. This paper reviews recent advances in copper chalcopyrite photocathodes. The PEC properties of copper chalcopyrite photocathodes have improved fairly rapidly: HC-STH values of 0.25% and 8.5% in 2012 and 2015, respectively. On the other hand, the onset potential remains insufficient, owing to the shallow valence band maximum mainly consisting of Cu 3d orbitals. In order to improve the onset potential, we explored substituting Cu for Ag and investigate the PEC properties of silver gallium selenide (AGSe) thin film photocathodes for varying compositions, film growth atmospheres, and surfaces. The modified AGSe photocathodes showed a higher onset potential than copper chalcopyrite photocathodes. It was demonstrated that element substitution of copper chalcopyrite can help to achieve more efficient PEC water splitting.

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H₂Evolution from Water on Modified Cu₂ZnSnS₄Photoelectrode under Solar Light

Cited by 165 publications

References 16 publications

A Novel Photocathode Material for Sunlight‐Driven Overall Water Splitting: Solid Solution of ZnSe and Cu(In,Ga)Se₂

A Novel Photocathode Material for Sunlight‐Driven Overall Water Splitting: Solid Solution of ZnSe and Cu(In,Ga)Se₂

A Bottom‐Up Approach toward All‐Solution‐Processed High‐Efficiency Cu(In,Ga)S₂ Photocathodes for Solar Water Splitting

Chalcopyrite Thin Film Materials for Photoelectrochemical Hydrogen Evolution from Water under Sunlight

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H2Evolution from Water on Modified Cu2ZnSnS4Photoelectrode under Solar Light

Cited by 165 publications

References 16 publications

A Novel Photocathode Material for Sunlight‐Driven Overall Water Splitting: Solid Solution of ZnSe and Cu(In,Ga)Se2

A Novel Photocathode Material for Sunlight‐Driven Overall Water Splitting: Solid Solution of ZnSe and Cu(In,Ga)Se2

A Bottom‐Up Approach toward All‐Solution‐Processed High‐Efficiency Cu(In,Ga)S2 Photocathodes for Solar Water Splitting

Chalcopyrite Thin Film Materials for Photoelectrochemical Hydrogen Evolution from Water under Sunlight

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H₂Evolution from Water on Modified Cu₂ZnSnS₄Photoelectrode under Solar Light

A Novel Photocathode Material for Sunlight‐Driven Overall Water Splitting: Solid Solution of ZnSe and Cu(In,Ga)Se₂

A Novel Photocathode Material for Sunlight‐Driven Overall Water Splitting: Solid Solution of ZnSe and Cu(In,Ga)Se₂

A Bottom‐Up Approach toward All‐Solution‐Processed High‐Efficiency Cu(In,Ga)S₂ Photocathodes for Solar Water Splitting