Oxygen Vacancy Creation,Drift, and Aggregation in TiO2‐Based Resistive Switches at Low Temperature and Voltage

Transmission electron microscopy with in situ biasing has been performed on TiN/single‐crystal rutile TiO₂/Pt resistive switching structures. Three elementary processes essential for switching: i) creation of oxygen vacancies by electrochemical reactions at low temperatures (<150 °C), ii) their drift in the electric field, and iii) their coalescence into planar faults (and dissociation from them) have been documented. The faults have a form of vacancy discs in {110} and {121} planes, are bound by partial dislocation loops, and are identical to Wadsley defects observed in nonstoichiometric TiO₂ annealed at high temperatures. The faults can be regarded as a precursor to the formation of oxygen‐deficient Magnéli phases, but 3D secondary phase inclusions have not been detected. Together, the observations shed light on the behavior of oxygen vacancies in relatively low electric fields and temperatures, suggesting that, in addition to the rather accepted notion of oxygen vacancy motion during the writing processes in resistive switching devices, such motion may occur even during reading, and may be accompanied by significant oxygen vacancy creation at modest device excitation levels.     

Blending Layered Cathode with Olivine: An Economic Strategy for Enhancing the Structural and Thermal Stability of 4.65 V LiCoO2

The intrinsic poor structural and thermal stability of high-voltage layered cathodes are aggravated as the charging depth increases, which severely threatens the cycle life and safety of the battery. Herein, without modifying the high-voltage layered cathode itself, a simple and economic blending strategy is introduced, and an olivine-LiCoO₂ blended cathode featuring superior comprehensive performance (energy, power, cycle-life, and safety) at 4.65 V is fabricated. The strong bonding affinity at the olivine/LiCoO₂ contact interface suppresses lattice O₂ release of LiCoO₂, thus significantly improving the structural and thermal stability at high delithiation states. Meanwhile, by contacting with high-electron-conductivity LiCoO₂, the redox activity of olivine is further activated. Therefore, a stable operation of both olivine-LiCoO₂ and olivine-LiNi_0.8Co_0.1Mn_0.1O₂ blended cathode is achieved under harsh cycling conditions (high voltage or elevated temperature) and long-life pouch-cell (91.6% capacity retention after 1000 cycles) is harvested, demonstrating the feasibility and universality of this economic blending strategy on heterogenous cathode candidates.     

Self‐Standing Porous LiCoO2 Nanosheet Arrays as 3D Cathodes for Flexible Li‐Ion Batteries

Self‐standing electrodes are the key to realize flexible Li‐ion batteries. However, fabrication of self‐standing cathodes is still a major challenge. In this work, porous LiCoO₂ nanosheet arrays are grown on Au‐coated stainless steel (Au/SS) substrates via a facile “hydrothermal lithiation” method using Co₃O₄ nanosheet arrays as the template followed by quick annealing in air. The binder‐free and self‐standing LiCoO₂ nanosheet arrays represent the 3D cathode and exhibit superior rate capability and cycling stability. In specific, the LiCoO₂ nanosheet array electrode can deliver a high reversible capacity of 104.6 mA h g^?1 at 10 C rate and achieve a capacity retention of 81.8% at 0.1 C rate after 1000 cycles. By coupling with Li₄Ti₅O₁₂ nanosheet arrays as anode, an all‐nanosheet array based LiCoO₂//Li₄Ti₅O₁₂ flexible Li‐ion battery is constructed. Benefiting from the 3D nanoarchitectures for both cathode and anode, the flexible LiCoO₂//Li₄Ti₅O₁₂ battery can deliver large specific reversible capacities of 130.7 mA h g^?1 at 0.1 C rate and 85.3 mA h g^?1 at 10 C rate (based on the weight of cathode material). The full cell device also exhibits good cycling stability with 80.5% capacity retention after 1000 cycles at 0.1 C rate, making it promising for the application in flexible Li‐ion batteries.     

Heterostructured Nanocube‐Shaped Binary Sulfide (SnCo)S2 Interlaced with S‐Doped Graphene as a High‐Performance Anode for Advanced Na+ Batteries

Heterostructuring electrodes with multiple electroactive and inactive supporting components to simultaneously satisfy electrochemical and structural requirements has recently been identified as a viable pathway to achieve high‐capacity and durable sodium‐ion batteries (SIBs). Here, a new design of heterostructured SIB anode is reported consisting of double metal‐sulfide (SnCo)S₂ nanocubes interlaced with 2D sulfur‐doped graphene (SG) nanosheets. The heterostructured (SnCo)S₂/SG nanocubes exhibit an excellent rate capability (469 mAh g^?1 at 10.0 A g^?1) and durability (5000 cycles, 487 mAh g^?1 at 5.0 A g^?1, 92.6% capacity retention). In situ X‐ray diffraction reveals that the (SnCo)S₂/SG anode undergoes a six‐stage Na⁺ storage mechanism of combined intercalation, conversion, and alloying reactions. The first‐principle density functional theory calculations suggest high concentration of p–n heterojunctions at SnS₂/CoS₂ interfaces responsible for the high rate performance, while in situ transmission electron microscopy unveils that the interlacing and elastic SG nanosheets play a key role in extending the cycle life.     

Platinum‐Coated Hollow Graphene Nanocages as Cathode Used in Lithium‐Oxygen Batteries

One of the formidable challenges facing aprotic lithium‐oxygen (Li‐O₂) batteries is the high charge overpotential, which induces the formation of byproducts, loss in efficiency, and poor cycling performance. Herein, the synthesis of the ultrasmall Pt‐coated hollow graphene nanocages as cathode in Li‐O₂ batteries is reported. The charge voltage plateau can reduce to 3.2 V at the current density of 100 mA g^?1, even maintain below 3.5 V when the current density increased to 500 mA g^?1. The unique hollow graphene nanocages matrix can not only provide numerous nanoscale tri‐phase regions as active sites for efficient oxygen reduction, but also offer sufficient amount of mesoscale pores for rapid oxygen diffusion. Furthermore, with strong atomic‐level oxygen absorption into its subsurface, ultrasmall Pt catalytically serves as the nucleation site for Li₂O₂ growth. The Li₂O₂ is subsequently induced into a favorable form with small size and amorphous state, decomposed more easily during recharge. Meanwhile, the conductive hollow graphene substrate can enhance the catalytic activity of noble metal Pt catalysts due to the graphene‐metal interfacial interaction. Benefiting from the above synergistic effects between the hollow graphene nanocages and the nanosized Pt catalysts, the ultrasmall Pt‐decorated graphene nanocage cathode exhibits enhanced electrochemical performances.     

Process Pathway Controlled Evolution of Phase and Van‐der‐Waals Epitaxy in In/In2O3 on Graphene Heterostructures

Many applications of 2D materials require deposition of non‐2D metals and metal‐oxides onto the 2D materials. Little is however known about the mechanisms of such non‐2D/2D interfacing, particularly at the atomic scale. Here, atomically resolved scanning transmission electron microscopy (STEM) is used to follow the entire physical vapor deposition (PVD) cycle of application‐relevant non‐2D In/In₂O₃ nanostructures on graphene. First, a “quasi‐in‐situ” approach with indium being in situ evaporated onto graphene in oxygen‐/water‐free ultra‐high‐vacuum (UHV) is employed, followed by STEM imaging without vacuum break and then repeated controlled ambient air exposures and reloading into STEM. This allows stepwise monitoring of the oxidation of specific In particles toward In₂O₃ on graphene. This is then compared with conventional, scalable ex situ In PVD onto graphene in high vacuum (HV) with significant residual oxygen/water traces. The data shows that the process pathway difference of oxygen/water feeding between UHV/ambient and HV fabrication drastically impacts not only non‐2D In/In₂O₃ phase evolution but also In₂O₃/graphene out‐of‐plane texture and in‐plane rotational van‐der‐Waals epitaxy. Since non‐2D/2D heterostructures' properties are intimately linked to their structure and since influences like oxygen/water traces are often hard to control in scalable fabrication, this is a key finding for non‐2D/2D integration process design.     

Hierarchical Engineering of Porous P2‐Na2/3Ni1/3Mn2/3O2 Nanofibers Assembled by Nanoparticles Enables Superior Sodium‐Ion Storage Cathodes

Layered transition metal oxides (TMOs) are appealing cathode candidates for sodium‐ion batteries (SIBs) by virtue of their facile 2D Na⁺ diffusion paths and high theoretical capacities but suffer from poor cycling stability. Herein, taking P2‐type Na_2/3Ni_1/3Mn_2/3O₂ as an example, it is demonstrated that the hierarchical engineering of porous nanofibers assembled by nanoparticles can effectively boost the reaction kinetics and stabilize the structure. The P2‐Na_2/3Ni_1/3Mn_2/3O₂ nanofibers exhibit exceptional rate capability (166.7 mA h g^?1 at 0.1 C with 73.4 mA h g^?1 at 20 C) and significantly improved cycle life (≈81% capacity retention after 500 cycles) as cathode materials for SIBs. The highly reversible structure evolution and Ni/Mn valence change during sodium insertion/extraction are verified by in operando X‐ray diffraction and ex situ X‐ray photoelectron spectroscopy, respectively. The facilitated electrode process kinetics are demonstrated by an additional study using the electrochemical measurements and density functional theory computations. More impressively, the prototype Na‐ion full battery built with a Na_2/3Ni_1/3Mn_2/3O₂ nanofibers cathode and hard carbon anode delivers a promising energy density of 212.5 Wh kg^?1. The concept of designing a fibrous framework composed of small nanograins offers a new and generally applicable strategy for enhancing the Na‐storage performance of layered TMO cathode materials.     

Carbon Nanotube‐Encapsulated Noble Metal Nanoparticle Hybrid as a Cathode Material for Li‐Oxygen Batteries

Although Li‐oxygen batteries offer extremely high theoretical specific energy, their practical application still faces critical challenges. One of the main obstacles is the high charge overpotential caused by sluggish kinetics of charge transfer that is closely related to the morphology of discharge products and their distribution on the cathode. Here, a series of noble metal nanoparticles (Pd, Pt, Ru and Au) are encapsulated inside end‐opened carbon nanotubes (CNTs) by wet impregnation followed by thermal annealing. The resultant cathode materials exhibit a dramatic reduction of charge overpotentials compared to their counterparts with nanoparticles supported on CNT surface. Notably, the charge overpotential can be as low as 0.3 V when CNT‐encapsulated Pd nanoparticles are used on the cathode. The cathode also shows good stability during discharge–charge cycling. Density functional theory (DFT) calculations reveal that encapsulation of “guest” noble metal nanoparticles in “host” CNTs is able to strengthen the electron density on CNT surfaces, and to avoid the regional enrichment of electron density caused by the direct exposure of nanoparticles on CNT surface. These unique properties ensure the uniform coverage of Li₂O₂ nanocrystals on CNT surfaces instead of localized distribution of Li₂O₂ aggregation, thus providing efficient charge transfer for the decomposition of Li₂O₂.     

Probing the Self‐Boosting Catalysis of LiCoO2 in Li–O2 Battery with Multiple In Situ/Operando Techniques

Designing high‐activity catalysts and revealing the in‐depth structure–property relationship is particularly important for Li–O₂ batteries. Herein, the self‐boosting catalysis of LiCoO₂ as an electrocatalyst for Li–O₂ batteries and the investigation of its self‐adjustment mechanism using in situ X‐ray absorption spectroscopy and other operando characterization techniques is reported. The intercalation/extraction of Li⁺ in LiCoO₂ not only induces the change in Co valence and modulates the electronic/crystal structure but also tunes the surface disorder degree, lattice strain, and local symmetry, which all affect the catalysis activity. In a discharge, highly ordered LiCoO₂ acts as a catalyst to boost oxygen reduction reaction. During charging, the initial extraction of Li⁺ from LiCoO₂ induces Li/oxygen vacancy and Co⁴⁺, which deforms CoO₆ octahedron as well as lowers the symmetry, and accordingly promotes oxygen evolution reaction. This article offers insights into tuning the activity of catalysts for Li–O₂ batteries with the intercalation/extraction of alkali metal ions in traditional cathodes.     

A New rGO‐Overcoated Sb2Se3 Nanorods Anode for Na+ Battery: In Situ X‐Ray Diffraction Study on a Live Sodiation/Desodiation Process

Sodium ion batteries (SIBs) are a promising alternative to lithium ion batteries for a broader range of energy storage applications in the future. However, the development of high‐performance anode materials is a bottleneck of SIBs advancement. In this work, Sb₂Se₃ nanorods uniformly wrapped by reduced graphene oxide (rGO) as a promising anode material for SIBs are reported. The results show that such Sb₂Se₃/rGO hybrid anode yields a high reversible mass‐specific energy capacity of 682, 448, and 386 mAh g^?1 at a rate of 0.1, 1.0, and 2.0 A g^?1, respectively, and sustains at least 500 stable cycles at a rate of 1.0 A g^?1 with an average mass‐specific energy capacity of 417 mAh g^?1 and capacity retention of 90.2%. In situ X‐ray diffraction study on a live SIB cell reveals that the observed high performance is a result of the combined Na⁺ intercalation, conversion reaction between Na⁺ and Se, and alloying reaction between Na⁺ and Sb. The presence of rGO also plays a key role in achieving high rate capacity and cycle stability by providing good electrical conductivity, tolerant accommodation to volume change, and strong electron interactions to the base Sb₂Se₃ anode.     

Understanding the Origin of Li2MnO3 Activation in Li‐Rich Cathode Materials for Lithium‐Ion Batteries

Li‐rich layered cathode materials have been considered as a family of promising high‐energy density cathode materials for next generation lithium‐ion batteries (LIBs). However, although activation of the Li₂MnO₃ phase is known to play an essential role in providing superior capacity, the mechanism of activation of the Li₂MnO₃ phase in Li‐rich cathode materials is still not fully understood. In this work, an interesting Li‐rich cathode material Li_1.87Mn_0.94Ni_0.19O₃ is reported where the Li₂MnO₃ phase activation process can be effectively controlled due to the relatively low level of Ni doping. Such a unique feature offers the possibility of investigating the detailed activation mechanism by examining the intermediate states and phases of the Li₂MnO₃ during the controlled activation process. Combining powerful synchrotron in situ X‐ray diffraction analysis and observations using advanced scanning transmission electron microscopy equipped with a high angle annular dark field detector, it has been revealed that the subreaction of O₂ generation may feature a much faster kinetics than the transition metal diffusion during the Li₂MnO₃ activation process, indicating that the latter plays a crucial role in determining the Li₂MnO₃ activation rate and leading to the unusual stepwise capacity increase over charging cycles.     

Template‐Assisted Formation of Rattle‐type V2O5 Hollow Microspheres with Enhanced Lithium Storage Properties

In this work, rattle‐type ball‐in‐ball V₂O₅ hollow microspheres are controllably synthesized with the assistance of carbon colloidal spheres as hard templates. Carbon spheres@vanadium‐precursor (CS@V) core–shell composite microspheres are first prepared through a one‐step solvothermal method. The composition of solvent for the solvothermal synthesis has great influence on the morphology and structure of the vanadium‐precursor shells. V₂O₅ hollow microspheres with various shell architectures can be obtained after removing the carbon microspheres by calcination in air. Moreover, the interior hollow shell can be tailored by varying the temperature ramping rate and calcination temperature. The rattle‐type V₂O₅ hollow microspheres are evaluated as a cathode material for lithium‐ion batteries, which manifest high specific discharge capacity, good cycling stability and rate capability.     

A Novel Moisture‐Insensitive and Low‐Corrosivity Ionic Liquid Electrolyte for Rechargeable Aluminum Batteries

Rechargeable aluminum batteries (RABs) are extensively developed due to their cost‐effectiveness, eco‐friendliness, and low flammability and the earth abundance of their electrode materials. However, the commonly used RAB ionic liquid (IL) electrolyte is highly moisture‐sensitive and corrosive. To address these problems, a 4‐ethylpyridine/AlCl₃ IL is proposed. The effects of the AlCl₃ to 4‐ethylpyridine molar ratio on the electrode charge–discharge properties are systematically examined. A maximum graphite capacity of 95 mAh g^?1 is obtained at 25 mA g^?1. After 1000 charge–discharge cycles, ≈85% of the initial capacity can be retained. In situ synchrotron X‐ray diffraction is employed to examine the electrode reaction mechanism. In addition, low corrosion rates of Al, Cu, Ni, and carbon‐fiber paper electrodes are confirmed in the 4‐ethylpyridine/AlCl₃ IL. When opened to the ambient atmosphere, the measured capacity of the graphite cathode is only slightly lower than that found in a N₂‐filled glove box; moreover, the capacity retention upon 100 cycles is as high as 75%. The results clearly indicate the great potential of this electrolyte for practical RAB applications.     

Highly Surface‐Wrinkled and N‐Doped CNTs Anchored on Metal Wire: A Novel Fiber‐Shaped Cathode toward High‐Performance Flexible Li–CO2 Batteries

Li–CO₂ batteries are regarded as a promising candidate for the next‐generation high‐performance electrochemical energy storage system owing to their ultrahigh theoretical energy density and environmentally friendly CO₂ fixation ability. Until now, the majority of reported catalysts for Li–CO₂ batteries are in the powder state. Thus, the air electrodes are produced in 2D rigid bulk structure and their electrochemical properties are negatively influenced by binder. The nondeformable feature and unsatisfactory performance of the cathode have already become the main obstacles that hinder Li–CO₂ batteries toward ubiquity for wearable electronics. In this work, for the first time, a flexible hybrid fiber is reported comprising highly surface‐wrinkled and N‐doped carbon nanotube (CNT) networks anchored on metal wire as the cathode integrated with high performance and high flexibility for fiber‐shaped Li–CO₂ battery. It exhibits a large discharge capacity as high as 9292.3 mAh g^?1, an improved cycling performance of 45 cycles, and a decent rate capability. A quasi‐solid‐state flexible fiber‐shaped Li–CO₂ battery is constructed to illustrate the advantages on mechanical flexibility of this fiber‐shaped cathode. Experiments and theoretical simulations prove that those doped pyridinic nitrogen atoms play a critical role in facilitating the kinetics of CO₂ reduction and evolution reaction, thereby enabling distinctly enhanced electrochemical performance.     

2D Heterostructure Membranes with Sunlight‐Driven Self‐Cleaning Ability for Highly Efficient Oil–Water Separation

Introducing solar energy into membrane filtration to decrease energy and chemicals consumption represents a promising direction in membrane fields. In this study, a kind of 0D/2D heterojunction is fabricated by depositing biomineralized titanium dioxide (TiO₂) nanoparticles with delaminated graphitic carbon nitride (g‐C₃N₄) nanosheets, and subsequently a kind of 2D heterostructure membrane is fabricated via intercalating g‐C₃N₄@TiO₂ heterojunctions into adjacent graphene oxide (GO) nanosheets by a vacuum‐assisted self‐assembly process. Due to the enlarged interlayer spacing of GO nanosheets, the initial permeation flux of GO/g‐C₃N₄@TiO₂ membrane reaches to 4536 Lm^?2 h^?1 bar^?1, which is more than 40‐fold of GO membranes (101 Lm^?2 h^?1 bar^?1) when utilized for oil/water separation. To solve the sharp permeation flux decline, arising from the adsorption of oil droplets, the a sunlight‐driven self‐cleaning process is followed, maintaining a flux recovery ratio of more than 95% after ten cycles of filtration experiment. The high permeation flux and excellent sunlight‐driven flux recovery of these heterostructure membranes manifest their attractive potential application in water purification.     

Thermogelling,ABC Triblock Copolymer Platform for Resorbable Hydrogels with Tunable,Degradation‐Mediated Drug Release

Clinical application of injectable, thermoresponsive hydrogels is hindered by lack of degradability and controlled drug release. To overcome these challenges, a family of thermoresponsive, ABC triblock polymer‐based hydrogels has been engineered to degrade and release drug cargo through either oxidative or hydrolytic/enzymatic mechanisms dictated by the “A” block composition. Three ABC triblock copolymers are synthesized with varying “A” blocks, including oxidation‐sensitive poly(propylene sulfide), slow hydrolytically/enzymatically degradable poly(ε‐caprolactone), and fast hydrolytically/enzymatically degradable poly(d ,l ‐lactide‐co‐glycolide), forming the respective formulations PPS₁₃₅‐b‐PDMA₁₅₂‐b‐PNIPAAM₂₂₅ (PDN), PCL₈₅‐b‐PDMA₁₅₀‐b‐PNIPAAM₁₅₀ (CDN), and PLGA₆₀‐b‐PDMA₁₄₈‐b‐PNIPAAM₁₅₂ (LGDN). For all three polymers, hydrophilic poly(N,N‐dimethylacrylamide) and thermally responsive poly(N‐isopropylacrylamide) comprise the “B” and “C” blocks, respectively. These copolymers form micelles in aqueous solutions at ambient temperature that can be preloaded with small molecule drugs. These solutions quickly transition into hydrogels upon heating to 37 °C, forming a supra‐assembly of physically crosslinked, drug‐loaded micelles. PDN hydrogels are selectively degraded under oxidative conditions while CDN and LGDN hydrogels are inert to oxidation but show differential rates of hydrolytic/enzymatic decomposition. All three hydrogels are cytocompatible in vitro and in vivo, and drug‐loaded hydrogels demonstrate differential release kinetics in vivo corresponding with their specific degradation mechanism. These collective data highlight the potential cell and drug delivery use of this tunable class of ABC triblock polymer thermogels.     

Pyrolysis of Self‐Assembled Iron Porphyrin on Carbon Black as Core/Shell Structured Electrocatalysts for Highly Efficient Oxygen Reduction in Both Alkaline and Acidic Medium

A simple carbonization of evaporation‐induced self‐assembled iron(III) porphyrin (FeP) layers uniformly coated on carbon black, leading to an unprecedented core/shell structured nonprecious metal electrocatalysts (NPMEs) composed of N‐doped graphene‐like layers uniformly coated on carbon is reported. The thickness of graphene‐like shell can be readily adjusted up to about 6.6 nm by varying the amount of FeP loaded on carbon. Interestingly, the obtained NPME exhibits one of the highest oxygen reduction reaction (ORR) activity in both alkaline (half‐wave potential of 0.87 V vs reversible hydrogen electrode‐RHE) and acidic (half‐wave potential of 0.75 V vs RHE) medium. In particular, the core/shell structured NPME demonstrates a remarkable durability in acidic conditions superior to that of commercial Pt/C, which likely comes from the exposure of inner active sites after the outermost layer is consumed. Furthermore, the core/shell NPME displays direct 4e and indirect 4e process toward ORR in alkaline and acidic medium, respectively. This study points out a new avenue for the design of high‐performance NPMEs in both alkaline and acidic media, which may have potential applications in polymer electrolyte membrane fuel cells (PEMFCs), metal‐air batteries, and electrolyzers.     

Plasmonic Au/TiO2‐Dumbbell‐On‐Film Nanocavities for High‐Efficiency Hot‐Carrier Generation and Extraction

Plasmon‐induced hot carriers have vast potential for light‐triggered high‐efficiency carrier generation and extraction, which can overcome the optical band gap limit of conventional semiconductor‐based optoelectronic devices. Here, it is demonstrated that Au/TiO₂ dumbbell nanostructures assembled on a thin Au film serve as an efficient optical absorber and a hot‐carrier generator in the visible region. Upon excitation of localized surface plasmons in such coupled particle‐on‐film nanocavities, the energetic conduction electrons in Au can be injected over the Au/TiO₂ Schottky barrier and migrated to TiO₂, participating in the chemical reaction occurring at the TiO₂ surface. Compared with the same dumbbell nanostructures on an indium tin oxide (ITO) film, such nanocavities exhibit remarkable enhancement in both photocurrent amplitude and reaction rate that arise from increased light absorption and near‐field amplification in the presence of the Au film. The incident‐wavelength‐dependent photocurrent and reaction rate measurements jointly reveal that Au‐film‐mediated near‐field localization facilitates more efficient electron–hole separation and transport in the dumbbells and also promotes strong d‐band optical transitions in the Au film for generation of extra hot electrons. Such nanocavities provide a new plasmonic platform for effective photoexcitation and extraction of hot carriers and also better understanding of their fundamental science and technological implications in solar energy harvesting.     

Enhanced Sb2Se3 solar cell performance through theory‐guided defect control

Defects present in the absorber layer largely dictate photovoltaic device performance. Recently, a binary photovoltaic material, Sb₂Se₃, has drawn much attention due to its low‐cost and nontoxic constituents and rapid performance promotion. So far, however, the intrinsic defects of Sb₂Se₃ remain elusive. Here, through a combined theoretical and experimental investigation, we revealed that shallow acceptors, Se_Sb antisites, are the dominant defects in Sb₂Se₃ produced in an Se‐rich environment, where deep donors, Sb_Se and V_Se, dominate in Sb₂Se₃ produced in an Se‐poor environment. We further constructed a superstrate CdS/Sb₂Se₃ thin‐film solar cell achieving 5.76% efficiency through in situ Se compensation during Sb₂Se₃ evaporation and through careful optimization of absorber layer thickness. The understanding of intrinsic defects in Sb₂Se₃ film and the demonstrated success of in situ Se compensation strategy pave the way for further efficiency improvement of this very promising photovoltaic technology. Copyright © 2017 John Wiley & Sons, Ltd.