Single‐Step Spray Printing of Symmetric All‐Organic Solid‐State Batteries Based on Porous Textile Dye Electrodes

A symmetric solid‐state battery based on organic porous electrodes is fabricated using scalable spray‐printing. The active electrode material is based on a textile dye (disperse blue 134 anthraquinone) and is capable of forming divalent cations and anions in oxidation and reduction processes. The resulting molecule can be used in both negative and positive electrode reactions. After spray printing an inter‐connected pore honeycomb electrode, a solid‐state electrolyte (σ_Li: × 10^?4 S cm^?1) based on a polymeric ionic liquid is spray‐printed as a second layer and infiltrated through the porous electrodes. A symmetric all‐organic battery is then formed with the addition of another identical set of electrode and electrolyte layers. Both density functional theory calculations and charge‐discharge profiles show that the potentials for the negative and positive electrode reactions are amongst the lowest (≈2.0 V vs Li) and the highest (≈3.5 V vs Li), respectively, for quinone‐type molecules. Over the C‐rate range 0.2 to 5 C, the battery has a discharge cell voltage of more than 1 V even up to 250 charge‐discharge cycles and capacities are in the range 50–80 mA h g^?1 at 0.5 C.     

A Stable Graphitic,Nanocarbon‐Encapsulated,Cobalt‐Rich Core–Shell Electrocatalyst as an Oxygen Electrode in a Water Electrolyzer

The oxygen electrode plays a vital role in the successful commercialization of renewable energy technologies, such as fuel cells and water electrolyzers. In this study, the Prussian blue analogue‐derived nitrogen‐doped nanocarbon (NC) layer‐trapped, cobalt‐rich, core–shell nanostructured electrocatalysts (core–shell Co@NC) are reported. The electrode exhibits an improved oxygen evolution activity and stability compared to that of the commercial noble electrodes. The core–shell Co@NC‐loaded nickel foam exhibits a lower overpotential of 330 mV than that of IrO₂ on nickel foam at 10 mA cm^?2 and has a durability of over 400 h. The commercial Pt/C cathode‐assisted, core–shell Co@NC–anode water electrolyzer delivers 10 mA cm^?2 at a cell voltage of 1.59 V, which is 70 mV lower than that of the IrO₂–anode water electrolyzer. Over the long‐term chronopotentiometry durability testing, the IrO₂–anode water electrolyzer shows a cell voltage loss of 230 mV (14%) at 95 h, but the loss of the core–shell Co@NC–anode electrolyzer is only 60 mV (4%) even after 350 h cell‐operation. The findings indicate that the Prussian blue analogue is a class of inorganic nanoporous materials that can be used to derive metal‐rich, core–shell electrocatalysts with enriched active centers.     

Highly Efficient Sunlight‐Driven Seawater Splitting in a Photoelectrochemical Cell with Chlorine Evolved at Nanostructured WO3 Photoanode and Hydrogen Stored as Hydride within Metallic Cathode

A seawater splitting photoelectrochemical cell featuring a nanostructured tungsten trioxide photoanode that exhibits very high and stable photocurrents producing chlorine with average 70% Faradaic efficiency is described. Fabrication of the WO₃ electrodes on fluorine‐doped tin oxide substrates involves a simple solution‐based method and sequential layer‐by‐layer deposition with a progressively adjusted amount of structure‐directing agent in the precursor and a two‐step annealing. Such a procedure allows tailoring of thick, highly porous, structurally stable WO₃ films with a large internal photoactive surface area optimizing utilization of visible light wavelengths by the photoanode. With the application of an anodic potential of 0.76 V versus Ag/AgCl reference electrode (0.4 V below the thermodynamic Cl₂/Cl^? potential) in synthetic seawater, the designed WO₃ photoanodes irradiated with simulated 1 sun AM 1.5G light reach currents exceeding 4.5 mA cm^?2. Photocurrents close to 5 mA cm^?2 are attained in the case of fresh water splitting using 1 m methane–sulfonic acid supporting electrolyte with oxygen evolved at the WO₃ photoanode. The amount of formed hydrogen is determined by discharging the palladium sheet electrode employed as a cathode. Collection of hydrogen in the form of a hydride opens, more generally, the prospect of subsequently using such materials as anodes in batteries employing oxygen reduction cathodes.     

Electroless Plating of Highly Efficient Bifunctional Boride‐Based Electrodes toward Practical Overall Water Splitting

Exploring highly‐efficient and low‐cost electrodes for both hydrogen and oxygen evolution reaction (HER and OER) is of primary importance to economical water splitting. Herein, a series of novel and robust bifunctional boride‐based electrodes are successfully fabricated using a versatile Et₂NHBH₃‐involved electroless plating (EP) approach via deposition of nonprecious boride‐based catalysts on various substrates. Owing to the unique binder‐free porous nodule structure induced by the hydrogen release EP reaction, most of the nonprecious boride‐based electrodes are highly efficient for overall water splitting. As a distinctive example, the Co‐B/Ni electrode can afford 10 mA cm^?2 at overpotentials of only 70 mV for HER and 140 mV for OER, and can also survive at large current density of 1000 mA cm^?2 for over 20 h without performance degradation in 1.0 m KOH. Several boride‐based two‐electrode electrolyzers can achieve 10 mA cm^?2 at low voltages of around 1.4 V. Moreover, the facile EP approach is economically viable for flexible and large size electrode production.     

Stable Seamless Interfaces and Rapid Ionic Conductivity of Ca–CeO2/LiTFSI/PEO Composite Electrolyte for High‐Rate and High‐Voltage All‐Solid‐State Battery

Stable and seamless interfaces among solid components in all‐solid‐state batteries (ASSBs) are crucial for high ionic conductivity and high rate performance. This can be achieved by the combination of functional inorganic material and flexible polymer solid electrolyte. In this work, a flexible all‐solid‐state composite electrolyte is synthesized based on oxygen‐vacancy‐rich Ca‐doped CeO₂ (Ca–CeO₂) nanotube, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and poly(ethylene oxide) (PEO), namely Ca–CeO₂/LiTFSI/PEO. Ca–CeO₂ nanotubes play a key role in enhancing the ionic conductivity and mechanical strength while the PEO offers flexibility and assures the stable seamless contact between the solid electrolyte and the electrodes in ASSBs. The as‐prepared electrolyte exhibits high ionic conductivity of 1.3 × 10^?4 S cm^?1 at 60 °C, a high lithium ion transference number of 0.453, and high‐voltage stability. More importantly, various electrochemical characterizations and density functional theory (DFT) calculations reveal that Ca–CeO₂ helps dissociate LiTFSI, produce free Li ions, and therefore enhance ionic conductivity. The ASSBs based on the as‐prepared Ca–CeO₂/LiTFSI/PEO composite electrolyte deliver high‐rate capability and high‐voltage stability.     

Yolk–Shell NiS2 Nanoparticle‐Embedded Carbon Fibers for Flexible Fiber‐Shaped Sodium Battery

Fiber‐shaped rechargeable batteries hold promise as the next‐generation energy storage devices for wearable electronics. However, their application is severely hindered by the difficulty in fabrication of robust fiber‐like electrodes with promising electrochemical performance. Herein, yolk–shell NiS₂ nanoparticles embedded in porous carbon fibers (NiS₂?PCF) are successfully fabricated and developed as high‐performance fiber electrodes for sodium storage. Benefiting from the robust embedded structure, 3D porous and conductive carbon network, and yolk–shell NiS₂ nanoparticles, the as‐prepared NiS₂?PCF fiber electrode achieves a high reversible capacity of about 679 mA h g^?1 at 0.1 C, outstanding rate capability (245 mA h g^?1 at 10 C), and ultrastable cycle performance with 76% capacity retention over 5000 cycles at 5 C. Notably, a flexible fiber‐shaped sodium battery is assembled, and high reversible capacity is kept at different bending states. This work offers a new electrode‐design paradigm toward novel carbon fiber electrodes embedded with transition metal oxides/sulfides/phosphides for application in flexible energy storage devices.     

Achieving Ultrahigh Energy Densities of Supercapacitors with Porous Titanium Carbide/Boron‐Doped Diamond Composite Electrodes

The energy densities of most supercapacitors (SCs) are low, hindering their practical applications. To construct SCs with ultrahigh energy densities, a porous titanium carbide (TiC)/boron‐doped diamond (BDD) composite electrode is synthesized on a titanium plate that is pretreated using a plasma electrolytic oxidation (PEO) technique. The porous and nanometer‐thick TiO₂ layer formed during PEO process prevents the formation of brittle titanium hydride and enhances the BDD growth during chemical vapor deposition processes. Meanwhile, the in situ conversion of TiO₂ into TiC is achieved. Combination of this capacitor electrode with soluble redox electrolytes leads to the fabrication of high‐performance SCs in both aqueous and organic solutions. In 0.05 m Fe(CN)₆^3?/4? + 1 m Na₂SO₄ aqueous solution, the capacitance is as high as 46.3 mF cm^?2 at a current density of 1 mA cm^?2; this capacitance remains 92% of its initial value even after 10 000 charge/discharge cycles; the energy density is up to 47.4 Wh kg^?1 at a power density of 2236 W kg^?1. The performance of constructed SCs is superior to most available SCs and some electrochemical energy storage devices like batteries. Such a porous capacitor electrode is thus promising for the construction of high‐performance SCs for practical applications.     

High‐Energy Density Li‐Ion Capacitor with Layered SnS2/Reduced Graphene Oxide Anode and BCN Nanosheet Cathode

Lithium‐ion capacitors (LICs) with capacitor‐type cathodes and battery‐type anodes are considered a promising next‐generation advanced energy storages system that meet the requirements of high energy density and power density. However, the mismatch of charge‐storage capacity and electrode kinetics between positive and negative electrodes remains a challenge. Herein, layered SnS₂/reduced graphene oxide (RGO) nanocomposites are developed for negative electrodes and a 2D B/N codoped carbon (BCN) nanosheet is designed for the positive electrode. The SnS₂/RGO derived from SnS₂‐bonded RGO of high conductivity exhibits a capacity of 1198 mA h g^?1 at 100 mA g^?1. Boron and nitrogen atoms in BCN are found to promote adsorption of anions, which enhance the pseudocapacitive contribution as well as expanding the voltage of LICs. A quantitative kinetics analysis indicates that the SnS₂/RGO electrodes with a dominating capacitive mechanism and a diminished intercalation process, benefit the kinetic balance between the two electrodes. With this particular structure, the LIC is able to operate at the highest operating voltage for these devices recorded to date (4.5 V), exhibiting an energy density of 149.5 W h kg^?1, a power density of 35 kW kg^?1, and a capacity retention ratio of 90% after 10 000 cycles.     

Interface‐Engineered All‐Solid‐State Li‐Ion Batteries Based on Garnet‐Type Fast Li+ Conductors

All‐solid‐state Li‐ion batteries based on Li₇La₃Zr₂O₁₂ (LLZO) garnet structures require novel electrode assembly strategies to guarantee a proper Li⁺ transfer at the electrode–electrolyte interfaces. Here, first stable cell performances are reported for Li‐garnet, c‐Li_6.25Al_0.25La₃Zr₂O₁₂, all‐solid‐state batteries running safely with a full ceramics setup, exemplified with the anode material Li₄Ti₅O₁₂. Novel strategies to design an enhanced Li⁺ transfer at the electrode–electrolyte interface using an interface‐engineered all‐solid‐state battery cell based on a porous garnet electrolyte interface structure, in which the electrode material is intimately embedded, are presented. The results presented here show for the first time that all‐solid‐state Li‐ion batteries with LLZO electrolytes can be reversibly charge–discharge cycled also in the low potential ranges (≈1.5 V) for combinations with a ceramic anode material. Through a model experiment, the interface between the electrode and electrolyte constituents is systematically modified revealing that the interface engineering helps to improve delivered capacities and cycling properties of the all‐solid‐state Li‐ion batteries based on garnet‐type cubic LLZO structures.     

Copper–Nickel Nitride Nanosheets as Efficient Bifunctional Catalysts for Hydrazine‐Assisted Electrolytic Hydrogen Production

Electrocatalytic water splitting is one of the sustainable and promising strategies to generate hydrogen fuel but still remains a great challenge because of the sluggish anodic oxygen evolution reaction (OER). A very effective approach to dramatically decrease the input cell voltage of water electrolysis is to replace the anodic OER with hydrazine oxidation reaction (HzOR) due to its lower thermodynamic oxidation potential. Therefore, developing the low‐cost and efficient HzOR catalysts, coupled with the cathodic hydrogen evolution reaction (HER), is tremendously important for energy‐saving electrolytic hydrogen production. Herein, a new‐type of copper–nickel nitride (Cu₁Ni₂‐N) with rich Cu₄N/Ni₃N interface is rationally constructed on carbon fiber cloth. The 3D electrode exhibits extraordinary HER performance with an overpotential of 71.4 mV at 10 mA cm^?2 in 1.0 m KOH, simultaneously delivering an ultralow potential of 0.5 mV at 10 mA cm^?2 for HzOR in a 1.0 m KOH/0.5 m hydrazine electrolyte. Moreover, the electrolytic cell utilizing the synthesized Cu₁Ni₂‐N electrode as both the cathode and anode display a cell voltage of 0.24 V at 10 mA cm^?2 with an excellent stability over 75 h. The present work develops the promising copper–nickel‐based nitride as a bifunctional electrocatalyst through hydrazine‐assistance for energy‐saving electrolytic hydrogen production.     

Cellular Toxicity of TiO2 Nanoparticles in Anatase and Rutile Crystal Phase

Titanium dioxide nanoparticles are massively produced and widely used in daily life, which has posed potential risk to human health. However, the molecular mechanism of TiO₂ nanoparticles (NPs) with different crystal phases is not clear. In this study, the characterization of two crystalline phases of TiO₂ NPs is evaluated by transmission electron microscopy and X-ray absorption fine structure spectrum; an interaction of these TiO₂ NPs with HaCaT cells is studied in vitro using transmission electron microscopy, chemical precipitation method, and X-ray absorption fine structure spectrometry. The coordination and surface properties indicate that only the anatase–TiO₂ NPs allow spontaneous reactive oxygen species (ROS) generation, but rutile–TiO₂ NPs do not after dispersion. The interaction between TiO₂ NPs and cellular components might also generate ROS for both anatase–TiO₂ NPs and rutile–TiO₂ NPs. The ROS generation could lead to cellular toxicity if the level of ROS production overwhelms the antioxidant defense of the cell or induces the mitochondrial apoptotic mechanisms. Furthermore, Ti had a direct combination with some protein or DNA after NPs enter the cell, which could also lead to cellular toxicity.     

Light‐Induced Activation of Adaptive Junction for Efficient Solar‐Driven Oxygen Evolution: In Situ Unraveling the Interfacial Metal–Silicon Junction

The integration of surface metal catalysts with semiconductor absorbers to produce photocatalytic devices is an attractive method for achieving high‐efficiency solar‐induced water splitting. However, once combined with a photoanode, detailed discussions of the light‐induced processes on metal/semiconductor junction remain largely inadequate. Here, by employing in situ X‐ray scattering/diffraction and absorption spectroscopy, the generation of a photoinduced adaptive structure is discovered at the interfacial metal–semiconductor (M–S) junction between a state‐of‐the‐art porous silicon wire and nickel electrocatalyst, where oxygen evolution occurs under illumination. The adaptive layer in M–S junction through the light‐induced activation can enhance the voltage by 247 mV (to reach a photocurrent density of 10 mA cm^?2) with regard to the fresh photoanode, and increase the photocurrent density by six times at the potential of 1.23 V versus reversible reference electrode (RHE). This photoinduced adaptive layer offers a new perspective regarding the catalytic behavior of catalysts, especially for the photocatalytic water splitting of the system, and acting as a key aspect in the development of highly efficient photoelectrodes.     

General Controlled Sulfidation toward Achieving Novel Nanosheet‐Built Porous Square‐FeCo2S4‐Tube Arrays for High‐Performance Asymmetric All‐Solid‐State Pseudocapacitors

A significant advance toward the design and fabrication of a novel hierarchical supercapacitor electrode consisting of FeCo₂S₄‐tubes with well‐defined square cross‐section and intersecting nanosheets built porous shells on a 3D porous Ni backbone via controlled sulfidation is reported. This general method allows template‐free synthesis of metal sulfides tubular structures with polygonal cross‐sections and also fine control over the nanostructure leading to both maximized porosity and saturation sulfidation. New insights into concentration and time dependent sulfidation reaction kinetics are proposed. The FeCo₂S₄ electrode achieves a specific capacitance reaching 2411 F g^‐1 at 5 mA cm^‐2 and good rate capability, which are superior over those for nanotube arrays of other ternary transition metal sulfides. This is attributed to rich redox reactions, the highly porous but robust architecture as well as high electrical conductivity. Especially such porous shells effectively avoid “dead volume”, thus improve the utilization ratio of the electrode material. Asymmetric solid‐state device applying the FeCo₂S₄ as positive electrode and N‐doped graphene hydrogel film as negative electrode has a high cell voltage of 1.6 V and thus delivers considerably higher energy density of 76.1 W h kg^‐1 (at 755 W kg^‐1) than those reported for similar devices.     

Manipulation of microparticles for construction of array patterns by negative dielectrophoresis using multilayered array and grid electrodes

In this study, a useful method was developed to fabricate array patterns of microparticles not on electrode surfaces, but on arbitrary surfaces, using negative‐dielectrophoresis (n‐DEP). First, electrodes were designed and electric field simulations were performed to manipulate microparticles toward target areas. Based on the simulation results, multilayered array and grid (MLAG) electrodes, consisting of array electrodes surrounded by insulated regions and a grid electrode, were fabricated for the formation of localized, non‐uniform electric fields. The MLAG electrode was mounted to a target substrate in a face‐to‐face configuration with a spacer. When an AC voltage (4.60 V_rms and 1 MHz) was applied to the MLAG electrode, array patterns of 6 and 20 µm diameter microparticles were rapidly fabricated on the target substrate with ease. The results suggest that MLAG electrodes can be widely applied for the fabrication of biochips including cell arrays. Biotechnol. Bioeng. 2009; 104: 709–718 © 2009 Wiley Periodicals, Inc.     

Polymer‐in‐“Quasi‐Ionic Liquid” Electrolytes for High‐Voltage Lithium Metal Batteries

Due to the limited oxidation stability (<4 V) of ether oxygen in its polymer structure, polyethylene oxide (PEO)‐based polymer electrolytes are not compatible with high‐voltage (>4 V) cathodes, thus hinder further increases in the energy density of lithium (Li) metal batteries (LMBs). Here, a new type of polymer‐in‐“quasi‐ionic liquid” electrolyte is designed, which reduces the electron density on ethereal oxygens in PEO and ether solvent molecules, induces the formation of stable interfacial layers on both surfaces of the LiNi_1/3Mn_1/3Co_1/3O₂ (NMC) cathode and the Li metal anode in Li||NMC batteries, and results in a capacity retention of 88.4%, 86.7%, and 79.2% after 300 cycles with a charge cutoff voltage of 4.2, 4.3, and 4.4 V for the LMBs, respectively. Therefore, the use of “quasi‐ionic liquids” is a promising approach to design new polymer electrolytes for high‐voltage and high‐specific‐energy LMBs.     

All Pseudocapacitive MXene‐RuO2 Asymmetric Supercapacitors

2D transition metal carbides and nitrides, known as MXenes, are an emerging class of 2D materials with a wide spectrum of potential applications, in particular in electrochemical energy storage. The hydrophilicity of MXenes combined with their metallic conductivity and surface redox reactions is the key for high‐rate pseudocapacitive energy storage in MXene electrodes. However, symmetric MXene supercapacitors have a limited voltage window of around 0.6 V due to possible oxidation at high anodic potentials. In this study, the fact that titanium carbide MXene (Ti₃C₂T_x) can operate at negative potentials in acidic electrolyte is exploited, to design an all‐pseudocapacitive asymmetric device by combining it with a ruthenium oxide (RuO₂) positive electrode. This asymmetric device operates at a voltage window of 1.5 V, which is about two times wider than the operating voltage window of symmetric MXene supercapacitors, and is the widest voltage window reported to date for MXene‐based supercapacitors. The complementary working potential windows of MXene and RuO₂, along with proton‐induced pseudocapacitance, significantly enhance the device performance. As a result, the asymmetric devices can deliver an energy density of 37 µW h cm^?2 at a power density of 40 mW cm^?2, with 86% capacitance retention after 20 000 charge–discharge cycles. These results show that pseudocapacitive negative MXene electrodes can potentially replace carbon‐based materials in asymmetric electrochemical capacitors, leading to an increased energy density.     

A Large‐Scale Graphene–Bimetal Film Electrode with an Ultrahigh Mass Catalytic Activity for Durable Water Splitting

The practical industralization of water splitting needs high‐efficient and cost‐effective catalytic electrodes. A versatile and scalable solution‐processing method to prepare such a catalytic electrode with high flexibility and conductivity is introduced. This preparation method is applicable for a wide variety of metal species and takes graphene sheets as metal carriers and film‐forming agents, resulting in 100% utilization of raw materials. The obtained graphene–bimetal film has excellent comprehensive performance with high areal activity and superior turnover frequency at a low mass loading of 0.05 mg cm^?2, as well as a record‐high mass activity for oxygen or hydrogen evolution. The assembled two‐electrode configuration can be used in a practical full water splitting system, requiring a cell voltage of 1.58 or 1.50 V at 30 or 70 °C to afford a current density of 10 mA cm^?2; it also exhibits a long‐term durability over 200 h, superior to most of the reported systems for the same purpose. This work provides a new platform for large‐scale and high‐yield production of electrocatalysts and also uncovers the design principles of catalytic electrodes with high mass activity toward industralization.     

Controlled Growth of NiMoO4 Nanosheet and Nanorod Arrays on Various Conductive Substrates as Advanced Electrodes for Asymmetric Supercapacitors

Hierarchical NiMoO₄ architectures assembled from well‐aligned uniform nanosheets or nanorods are successfully grown on various conductive substrates using a facile and effective general approach. Importantly, the nanostructures of NiMoO₄ can be easily controlled to be nanosheets or nanorods by using different solvents. By virtue of their intriguing structure features, NiMoO₄ nanosheets as integrated additive‐free electrodes for supercapacitors manifest higher Faradaic capacitance than NiMoO₄ nanorods. Moreover, an asymmetric supercapacitor (ASC) is constructed using the as‐prepared NiMoO₄ nanosheets as the positive electrode and activated carbon (AC) as the negative electrode. The optimized ASC with an extended operating voltage range of 0–1.7 V displays excellent electrochemical performance with a high energy density of 60.9 Wh kg^?1 at a power density of 850 W kg^?1 in addition to superior rate capability. Furthermore, the NiMoO₄//AC ASC device exhibits remarkable cycling stability with 85.7% specific capacitance retention after 10 000 cycles. The results show that these NiMoO₄‐based nanostructures are promising for high‐energy supercapacitors.     

Facile Synthesis of 3D MnO2–Graphene and Carbon Nanotube–Graphene Composite Networks for High‐Performance,Flexible, All‐Solid‐State Asymmetric Supercapacitors

The integration of graphene nanosheets on the macroscopic level using a self‐assembly method has been recognized as one of the most effective strategies to realize the practical applications of graphene materials. Here, a facile and scalable method is developed to synthesis two types of graphene‐based networks, manganese dioxide (MnO₂)–graphene foam and carbon nanotube (CNT)–graphene foam, by solution casting and subsequent electrochemical methods. Their practical applications in flexible all‐solid‐state asymmetric supercapacitors are explored. The proposed method facilitates the structural integration of graphene foam and the electroactive material and offers several advantages including simplicity, efficiency, low‐temperature, and low‐cost. The as‐prepared MnO₂–graphene and CNT–graphene electrodes exhibit high specific capacitances and rate capability. By using polymer gel electrolytes, a flexible all‐solid‐state asymmetric supercapacitor was synthesized with MnO₂–graphene foam as the positive electrode and CNT‐graphene as the negative electrode. The asymmetric supercapacitors can be cycled reversibly in a high‐voltage region of 0 to 1.8 V and exhibit high energy density, remarkable rate capability, reasonable cycling performance, and excellent flexibility.     

Efficient and Stable TiO2:Pt–Cu(In,Ga)Se2 Composite Photoelectrodes for Visible Light Driven Hydrogen Evolution

Novel thin film composite photocathodes based on device‐grade Cu(In,Ga)Se₂ chalcopyrite thin film absorbers and transparent conductive oxide Pt‐implemented TiO₂ layers on top are presented for an efficient and stable solar‐driven hydrogen evolution. Thin films of phase‐pure anatase TiO₂ are implemented with varying Pt‐concentrations in order to optimize simultaneously i) conductivity of the films, ii) electrocatalytic activity, and iii) light‐guidance toward the chalcopyrite. Thereby, high incident‐photon‐to‐current‐efficiencies of more than 80% can be achieved over the full visible light range. In acidic electrolyte (pH 0.3), the most efficient Pt‐implemented TiO₂–Cu(In,Ga)Se₂ composite electrodes reveal i) photocurrent densities up to 38 mA cm^?2 in the saturation region (?0.4 V RHE, reversible hydrogen electrode), ii) 15 mA cm^?2 at the thermodynamic potential for H₂‐evolution (0 V RHE), and iii) an anodic onset potential shift for the hydrogen evolution (+0.23 V RHE). It is shown that the gradual increase of the Pt‐concentration within the TiO₂ layers passes through an efficiency‐ and stability‐maximum of the device (5 vol% of Pt precursor solution). At this maximum, optimized light‐incoupling into the device‐grade chalcopyrite light‐absorber as well as electron conductance properties within the surface layer are achieved while no degradation are observed over more than 24 h of operation.