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Chemical self-recharging zinc ion batteries (ZIBs), which are capable of auto-recharging in ambient air, are promising in self-powered battery systems. Nevertheless, the exclusive reliance on chemical energy from oxygen for ZIBs charging often would bring some obstacles in charging efficiency. Herein, we develop photo-assisted chemical self-recharging aqueous ZIBs with a heterojunction of MoS 2 /SnO 2 cathode, which are favorable to enhancing both the charging and discharging efficiency as well as the chemical self-charging capabilities under illumination. The photo-assisted process promotes the electron transfer from MoS 2 /SnO 2 to oxygen, accelerating the occurrence of the oxidation reaction during chemical self-charging. Furthermore, the electrons within the MoS 2 /SnO 2 cathode exhibit a low transfer impedance under illumination, which is beneficial to reducing the migration barrier of Zn 2+ within the cathode and thereby facilitating the uniform inserting of Zn 2+ into MoS 2 /SnO 2 cathode during discharging. This photo-assisted chemical self-recharging mechanism enables ZIBs to attain a maximum self-charging potential of 0.95 V within 3 hours, a considerable self-charging capacity of 202.5 mAh g -1 and excellent cycling performance in a self-charging mode. This work not only provides a route for optimizing chemical self-charging energy storage, but also broadens the potential application of aqueous ZIBs., (© 2024 Wiley-VCH GmbH.)

Photo-assisted Zn-air batteries can accelerate the kinetics of oxygen reduction and oxygen evolution reactions (ORR/OER); however, challenges such as rapid charge carrier recombination and continuous electrolyte evaporation remain. Herein, for the first time, piezoelectric catalysis is introduced in a photo-assisted Zn-air battery to improve carrier separation capability and accelerate the ORR/OER kinetics of the photoelectric cathode. The designed microhelical catalyst exploits simple harmonic vibrations to regenerate the built-in electric field continuously. Specifically, in the presence of the low-frequency kinetic energy that occurs during water flow, the piezoelectric-photocoupling catalyst of poly(vinylidene fluoride-co-trifluoroethylene)@ferric oxide(Fe@P(V-T)) is periodically deformed, generating a constant reconfiguration of the built-in electric field that separates photogenerated electrons and holes continuously. Further, on exposure to microvibrations, the gap between the charge and discharge potentials of the Fe@P(V-T)-based photo-assisted Zn-air battery is reduced by 1.7 times compared to that without piezoelectric assistance, indicating that piezoelectric catalysis is highly effective for enhancing photocatalytic efficiency. This study provides a thorough understanding of coupling piezoelectric polarization and photo-assisted strategy in the field of energy storage and opens a fresh perspective for the investigation of multi-field coupling-assisted Zn-air batteries., (© 2024 Wiley‐VCH GmbH.)

Piezocatalysis is considered to be a favorable catalytic technology by utilizing external mechanical stimulation to promote the specific redox reactions. The application of piezocatalysis in batteries is promising but faces formidable challenges. Herein, the operation principles of piezocatalysis were successfully demonstrated by constructing solid-state Li-Se and Li-S battery models with interfacial stress accumulation. Lead zirconate titanate with an ultra-high piezoelectric coefficient was applied as the piezoelectric catalyst. The uniformity of the dipole orientation in materials was essential for achieving piezocatalysis in batteries. The accumulated high-stress converts to piezopotential for catalyzing most reaction processes in batteries, while the rapid stress change prevents the internal charge reorganization, ensuring continuous efficient catalysis. The internal stress change alters the internal polarisation strength, driving excess screening charge to participate in the electrochemical reaction. Under piezocatalysis, solid-state Li-Se batteries exhibited a initial discharge capacity of 670.9 mAh g -1 (99.4 % of the theoretical value) at 0.1 C, and Li-S batteries showed a capacity of 1463 mAh g -1 at 0.2 C, which was still maintained up to 1084 mAh g -1 at an elevated rate of 0.5 C. This piezocatalysis strategy provides a strong theoretical basis and design specification for enhancing Li-Se and Li-S battery reaction kinetics., (© 2024 Wiley-VCH GmbH.)

The lack of stable solid-state electrolytes (SSEs) with high-ionic conductivity and the rational design of electrode/electrolyte interfaces remains challenging for solid-state lithium batteries. Here, for the first time, a high-performance solid-state lithium-oxygen (Li-O 2 ) battery is developed based on the Li-ion-conducted hydrogen-bonded organic framework (LHOF) electrolyte and the HOF-DAT@CNT composite cathode. Benefiting from the abundant dynamic hydrogen bonding network in the backbone of LHOF-DAT SSEs, fast Li + ion transport (2.2×10 -4  S cm -1 ), a high Li + transference number (0.88), and a wide electrochemical window of 5.05 V are achieved. Symmetric batteries constructed with LHOF-DAT SSEs exhibit a stably cycled duration of over 1400 h with uniform deposition, which mainly stems from the jumping sites that promote a uniformly high rate of Li + flux and the hydrogen-bonding network structure that can relieve the structural changes during Li + transport. LHOF-DAT SSEs-based Li-O 2 batteries exhibit high specific capacity (10335 mAh g -1 ), and stable cycling life up to 150 cycles. Moreover, the solid-state lithium metal battery with LHOF-DAT SSEs endow good rate capability (129.6 mAh g -1 at 0.5 C), long-term discharge/charge stability (210 cycles). The design of LHOF-DAT SSEs opens an avenue for the development of novel SSEs-based solid-state lithium batteries., (© 2024 Wiley-VCH GmbH.)

Uncontrollable interfacial side reactions generated from common aqueous electrolytes, just like the hydrogen evolution reaction (HER) and dendrite growth, have severely prevented the practical application of zinc-ion batteries (ZIBs). Solid-state ZIBs are considered to be an efficient strategy by adopting high-quality solid-state electrolytes (SSEs). Here, by confining deep eutectic electrolyte (DEE) into the nanochannels of metal-organic framework (MOF)-PCN-222, a stable DEE@PCN-222 SSE with internal Zn 2+ transport channels was obtained. A distinctive ion-transport network composed of DEE and PCN-222 in the interior of DEE@PCN-222 realizes the efficient Zn 2+ conduction, contributing to high ionic conductivity of 3.13×10 -4  S cm -1 at room temperature, low activation energy of 0.12 eV, and a high Zn 2+ transference number of 0.74. Furthermore, experimental and theoretical investigations demonstrate that DEE@PCN-222 with its unique channel structure could homogeneously regulate the Zn 2+ distribution and effectively alleviate the side reactions. Highly reversible Zn plating/stripping performance of 2476 h can be realized by the SSE. The solid-state ZIBs show a specific capacity of 306 mAh g -1 and display cycling stability of 517 cycles. This unique design concept provides a new perspective in realizing the high-safety and high-performance ZIBs., (© 2024 Wiley-VCH GmbH.)

Solid-state lithium-oxygen (Li-O 2 ) batteries have been widely recognized as one of the candidates for the next-generation of energy storage batteries. However, the development of solid-state Li-O 2 batteries has been hindered by the lack of solid-state electrolyte (SSE) with high ionic conductivity at room temperature, high Li + transference number, and the high stability to air. Herein, the organic molecular porous solid cucurbit[7]uril (CB[7]) with one-dimensional (1D) ion migration channels is developed as the SSE for solid-state Li-O 2 batteries. Taking advantage of the 1D ion migration channel for Li + conduction, CB[7] SSE achieves high ionic conductivity (2.45 × 10 -4 S cm -1 at 25 °C). Moreover, the noncovalent interactions facilitated the immobilization of anions, realizing a high Li + transference number (t Li + = 0.81) and Li + uniform distribution. The CB[7] SSE also shows a wide electrochemical stability window of 0-4.65 V and high thermal stability and chemical stability, as well as realizes stable Li + plating/stripping (more than 1000 h at 0.3 mA cm -2 ). As a result, the CB[7] SSE endows solid-state Li-O 2 batteries with superior rate capability and long-term discharge/charge stability (up to 500 h). This design strategy of CB[7] SSE paves the way for stable and efficient solid-state Li-O 2 batteries toward practical applications., (© 2024 Wiley‐VCH GmbH.)

Li-CO 2 batteries have received significant attention owing to their advantages of combining greenhouse gas utilization and energy storage. However, the high kinetic barrier between gaseous CO 2 and the Li 2 CO 3 product leads to a low operating voltage (<2.5 V) and poor energy efficiency. In addition, the reversibility of Li 2 CO 3 has always been questioned owing to the introduction of more decomposition paths caused by its higher charging plateau. Here, a novel "trinity" Li-CO 2 battery system was developed by synergizing CO 2 , soluble redox mediator (2,2,6,6-tetramethylpiperidoxyl, as TEM RM), and reduced graphene oxide electrode to enable selective conversion of CO 2 to Li 2 C 2 O 4 . The designed Li-CO 2 battery exhibited an output plateau reaching up to 2.97 V, higher than the equilibrium potential of 2.80 V for Li 2 CO 3 , and an ultrahigh round-trip efficiency of 97.1 %. The superior performance of Li-CO 2 batteries is attributed to the TEM RM-mediated preferential growth mechanism of Li 2 C 2 O 4 , which enhances the reaction kinetics and rechargeability. Such a unique design enables batteries to cope with sudden CO 2 -deficient environments, which provides an avenue for the rationally design of CO 2 conversion reactions and a feasible guide for next-generation Li-CO 2 batteries., (© 2024 Wiley‐VCH GmbH.)

Applying solar energy into energy storage battery systems is challenging in achieving green and sustainable development, however, the efficient progress of photo-assisted metal-air batteries is restricted by the rapid recombination of photogenerated electrons and holes upon the photocathode. Herein, a 1D-ordered MoS 2 nanotube (MoS 2 -ONT) with confined mass transfer can be used to extend the lifetime of photogenerated carriers, which is capable of overcoming the challenge of rapid recombination of electron and holes. The tubular confined space cannot only promote the orderly separation and migration of charge carriers but also realize the accumulation of charge and the rapid activation of oxygen molecules. The concave surface of MoS 2 -ONT can improve the carrier separation ability and prolong the carrier lifetime. Meanwhile, the ordered tubular confined space can effectively realize the rapid transfer of charge, ion, and oxygen. Under light irradiation, a fast oxygen reduction reaction kinetics of 70 mW cm -2 for photo-assisted Zn-air battery is achieved, which is the highest value reported for photo-assisted Zn-air batteries. Significantly, the photo-assisted Li-O 2 battery based on MoS 2 -ONT also shows superior rate capability and other exciting battery performance. This work shows the universality of the confined carrier separation strategy in photo-assisted metal-air batteries., (© 2023 Wiley‐VCH GmbH.)

Li-N 2 batteries have received widespread attention for their potential to integrate N 2 fixation, energy storage, and conversion. However, because of the low activity and poor stability of cathode catalysts, the electrochemical performance of Li-N 2 batteries is suboptimal, and their electrochemical reversibility has rarely been proven. In this study, a novel bifunctional photo-assisted Li-N 2 battery system was established by employing a plasmonic Au nanoparticles (NPs)-modified defective carbon nitride (Au-N v -C 3 N 4 ) photocathode. The Au-N v -C 3 N 4 exhibits strong light-harvesting, N 2 adsorption, and N 2 activation abilities, and the photogenerated electrons and hot electrons are remarkably beneficial for accelerating the discharge and charge reaction kinetics. These advantages enable the photo-assisted Li-N 2 battery to achieve a low overpotential of 1.32 V, which is the lowest overpotential reported to date, as well as superior rate capability and prolonged cycle stability (≈500 h). Remarkably, a combination of theoretical and experimental results demonstrates the high reversibility of the photo-assisted Li-N 2 battery. The proposed novel strategy for developing efficient cathode catalysts and fabricating photo-assisted battery systems breaks through the overpotential bottleneck of Li-N 2 batteries, providing important insights into the mechanism underlying N 2 fixation and storage., (© 2024 Wiley-VCH GmbH.)

The use of light-assisted cathode is regarded as an effective approach to reduce the overpotential of lithium carbon dioxide (Li - CO 2 ) batteries. However, the inefficient electron-hole separation and the complex discharge-charge reactions hamper the efficiency of CO 2 photocatalytic reaction in battery. Herein, a highly reversible force-assisted Li - CO 2 battery has been established for the first time by employing a Bi 0.5 Na 0.5 TiO 3 nanorods piezoelectric cathode. The high-energy electron and holes generated by the piezoelectric cathode with ultrasonic force can effectively enhance the carbon dioxide reduction reaction (CDRR) and carbon dioxide evolution reaction (CDER) kinetics, thereby reducing the overpotentials during the discharge-charge processes. Moreover, the morphology of the discharge product (Li 2 CO 3 ) can be modified via the dense surface electrons of the piezoelectric cathode, resulting in the promoted decomposition kinetics of Li 2 CO 3 in charging progress. Thus, the force-assisted Li - CO 2 battery with the unique piezoelectric cathode can adjust the output and input energy by ultrasonic wave, and provides an ultra-low charging platform of 3.52 V, and exhibits excellent cycle stability (a charging platform of 3.42 V after 100 h cycles). The investigation of the force-assisted process described herein provides significant insights to solve overpotential in the Li - CO 2 batteries system., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Reticular chemistry effectively yields porous structures with distinct topological lattices for a broad range of applications. Polyhedral oligomeric silsesquioxane (POSS)-based octatopic building blocks with a rare O h symmetric configuration and attracting inorganic features have great potential for creating three-dimensional (3D) covalent organic frameworks (COFs) with new topologies. However, the intrinsic flexibility and intensive motion of cubane-type POSS molecules make the construction of 3D regular frameworks challenging. Herein, by fastening three or four POSS cores with per aromatic rigid linker from rational steric directions, we successfully developed serial crystalline 3D COFs with unpresented "the" and scu topologies. Both the experimental and theoretical results proved the formation of target 3D POSS-based COFs. The resultant hybrid networks with designable chemical skeletons and high surface areas maintain the superiorities of both the inorganic and organic components, such as their high compatibility with inorganic salts, abundant periodic electroactive sites, excellent thermal stability, and open multilevel nanochannels. Consequently, the polycubane COFs could serve as outstanding solid electrolytes with a high ionic conductivity of 1.23 × 10 -4 S cm -1 and a lithium-ion transference number of 0.86 at room temperature. This work offers a pathway to generate ordered lattices with multiconnected flexible cube motifs and enrich the topologies of 3D COFs for potential applications.

Solid-state lithium (Li) batteries promise both high energy density and safety while existing solid-state electrolytes (SSEs) fail to satisfy the rigorous requirements of battery operations. Herein, novel polyoxometalate SSEs, Li 3 PW 12 O 40 and Li 3 PMo 12 O 40 , are synthesized, which exhibit excellent interfacial compatibility with electrodes and chemical stability, overcoming the limitations of conventional SSEs. A high ionic conductivity of 0.89 mS cm -1 and a low activation energy of 0.23 eV are obtained due to the optimized three-dimensional Li + migration network of Li 3 PW 12 O 40 . Li 3 PW 12 O 40 exhibits a wide window of electrochemical stability that can both accommodate the Li anode and high-voltage cathodes. As a result, all-solid-state Li metal batteries fabricated with Li/Li 3 PW 12 O 40 /LiNi 0.5 Co 0.2 Mn 0.3 O 2 display a stable cycling up to 100 cycles with a cutoff voltage of 4.35 V and an areal capacity of more than 4 mAh cm -2 , as well as a cost-competitive SSEs price of $5.68 kg -1 . Moreover, Li 3 PMo 12 O 40 homologous to Li 3 PW 12 O 40 was obtained via isomorphous substitution, which formed a low-resistance interface with Li 3 PW 12 O 40 . Applications of Li 3 PW 12 O 40 and Li 3 PMo 12 O 40 in Li-air batteries further demonstrate that long cycle life (650 cycles) can be achieved. This strategy provides a facile, low-cost strategy to construct efficient and scalable solid polyoxometalate electrolytes for high-energy solid-state Li metal batteries., (© 2023 Wiley-VCH GmbH.)

Aprotic lithium-oxygen (Li-O 2 ) batteries are considered to be a promising alternative option to lithium-ion batteries for high gravimetric energy storage devices. However, the sluggish electrochemical kinetics, the passivation, and the structural damage to the cathode caused by the solid discharge products have greatly hindered the practical application of Li-O 2 batteries. Herein, the nonsolid-state discharge products of the off-stoichiometric Li 1- x O 2 in the electrolyte solutions are achieved by iridium (Ir) single-atom-based porous organic polymers (termed as Ir/AP-POP) as a homogeneous, soluble electrocatalyst for Li-O 2 batteries. In particular, the numerous atomic active sites act as the main nucleation sites of O 2 -related discharge reactions, which are favorable to interacting with O 2 - /LiO 2 intermediates in the electrolyte solutions, owing to the highly similar lattice-matching effect between the in situ-formed Ir 3 Li and LiO 2 , achieving a nonsolid LiO 2 as the final discharge product in the electrolyte solutions for Li-O 2 batteries. Consequently, the Li-O 2 battery with a soluble Ir/AP-POP electrocatalyst exhibits an ultrahigh discharge capacity of 12.8 mAh, an ultralow overpotential of 0.03 V, and a long cyclic life of 700 h with the carbon cloth cathode. The manipulation of nonsolid discharge products in aprotic Li-O 2 batteries breaks the traditional growth mode of Li 2 O 2 , bringing Li-O 2 batteries closer to being a viable technology.

All-solid-state batteries with a high energy density and safety are desirable candidates for next-generation energy storage applications. However, conventional solid electrolytes for all-solid-state batteries encounter limitations such as poor ionic conduction, interfacial compatibility, instability, and high cost. Herein, taking advantage of the ingenious capability of zeolite to incorporate functional guests in its void space, we present an innovative ionic activation strategy based on the "guest wrench" mechanism, by introducing a pair of cation and anion of LiTFSI-based guest species (GS) into the supercage of the LiX zeolite, to fabricate a zeolite membrane (ZM)-based solid electrolyte (GS-ZM) with high Li ionic conduction and interfacial compatibility. The restriction of zeolite frameworks toward the framework-associated Li ions is significantly reduced through the dynamic coordination of Li ions with the "oxygen wrench" of TFSI - at room temperature as shown by experiments and Car-Parrinello molecular dynamics simulations. Consequently, the GS-ZM shows an ∼100% increase in ionic conductivity compared with ZM and an outstanding Li + transference number of 0.97. Remarkably, leveraging the superior ionic conduction of GS-ZM with the favorable interface structure between GS-ZM and electrodes, the assembled all-solid-state Li-ion and Li-air batteries based on GS-ZM exhibit the best-level electrochemical performance much superior to batteries based on liquid electrolytes: a capacity retention of 99.3% after 800 cycles at 1 C for all-solid-state Li-ion batteries and a cycle life of 909 cycles at 500 mA g -1 for all-solid-state Li-air batteries. The mechanistic discovery of a "guest wrench" in zeolite will significantly enhance the adaptability of zeolite-based electrolytes in a variety of all-solid-state energy storage systems with high performance, high safety, and low cost.

Rechargeable lithium-oxygen (Li-O 2 ) batteries with high theoretical energy density are considered as promising candidates for portable electronic devices and electric vehicles, whereas their commercial application is hindered due to poor cyclic stability caused by the sluggish kinetics and cathode passivation. Herein, the intrinsic stress originated from the growth and decomposition of the discharge product (lithium peroxide, Li 2 O 2 ) is employed as a microscopic pressure resource to induce the built-in electric field, further improving the reaction kinetics and interfacial Lithium ion (Li + ) transport during cycling. Piezopotential caused by the intrinsic stress-strain of solid Li 2 O 2 is capable of providing the driving force for the separation and transport of carriers, enhancing the Li + transfer, and thus improving the redox reaction kinetics of Li-O 2 batteries. Combined with a variety of in situ characterizations, the catalytic mechanism of barium titanate (BTO), a typical piezoelectric material, was systematically investigated, and the effect of stress-strain transformation on the electrochemical reaction kinetics and Li + interface transport for the Li-O 2 batteries is clearly established. The findings provide deep insight into the surface coupling strategy between intrinsic stress and electric fields to regulate the electrochemical reaction kinetics behavior and enhance the interfacial Li + transport for battery system., (© 2023 Wiley-VCH GmbH.)

Solid-state electrolytes (SSEs) with high ionic conductivity and superior stability are considered to be a key technology for the safe operation of solid-state lithium batteries. However, current SSEs are incapable of meeting the requirements for practical solid-state lithium batteries. Here we report a general strategy for achieving high-performance SSEs by engineering polymers of intrinsic microporosity (PIMs). Taking advantage of the interconnected ion pathways generated from the ionizable groups, high ionic conductivity (1.06×10 -3  S cm -1 at 25 °C) is achieved for the PIMs-based SSEs. The mechanically strong (50.0 MPa) and non-flammable SSEs combine the two superiorities of outstanding Li + conductivity and electrochemical stability, which can restrain the dendrite growth and prevent Li symmetric batteries from short-circuiting even after more than 2200 h cycling. Benefiting from the rational design of SSEs, PIMs-based SSEs Li-metal batteries can achieve good cycling performance and superior feasibility in a series of withstand abuse tests including bending, cutting, and penetration. Moreover, the PIMs-based SSEs endow high specific capacity (11307 mAh g -1 ) and long-term discharge/charge stability (247 cycles) for solid-state Li-O 2 batteries. The PIMs-based SSEs present a powerful strategy for enabling safe operation of high-energy solid-state batteries., (© 2023 Wiley-VCH GmbH.)

The demand for high-energy sustainable rechargeable batteries has motivated the development of lithium-oxygen (Li-O 2 ) batteries. However, the inherent safety issues of liquid electrolytes and the sluggish reaction kinetics of existing cathodes remain fundamental challenges. Herein, we demonstrate a promising photo-assisted solid-state Li-O 2 battery based on metal-organic framework-derived mixed ionic/electronic conductors, which simultaneously serve as the solid-state electrolytes (SSEs) and the cathode. The mixed conductors could effectively harvest ultraviolet-visible light to generate numerous photoelectrons and holes, which is favorable to participate in the electrochemical reaction, contributing to greatly improved reaction kinetics. According to the study on conduction behavior, we discover that the mixed conductors as SSEs possess outstanding Li + conductivity (1.52 × 10 -4 S cm -1 at 25 °C) and superior chemical/electrochemical stability (especially toward H 2 O, O 2 - , etc.). Application of mixed ionic electronic conductors in photo-assisted solid-state Li-O 2 batteries further reveals that a high energy efficiency (94.2%) and a long life (320 cycles) can be achieved with a simultaneous design of SSEs and cathodes. The achievements present the widespread universality in accelerating the development of safe and high-performance solid-state batteries.

The design of highly efficient electrocatalysts is a promising strategy to improve the electrochemical kinetics of Li-CO 2 batteries. However, electrocatalysts usually aim to reduce the energetic barrier for the corresponding electrochemical reactions; little attention has been given to modulating the kinetics that directly determine the local concentration of reaction molecules surrounding catalysts. Herein, we present a systematic study on the role of Li + reunion on the improvement of reaction kinetics in Li-CO 2 batteries with a Cu cone cathode. Specifically, this local, geometry-driven tip effect can enrich the local electron concentration to facilitate Li + ions diffusion from the bulk electrolyte to the surface of catalyst, leading to boosted catalytic performance. Further studies demonstrate that Cu(II/I) as a solid redox mediator dominates the reversible bulk redox reactions in a Cu cone cathode, which acts as an electron-hole transfer agent and permits the efficient reduction and oxidation of solid Li 2 CO 3 , contributing to an accessible theoretical discharge voltage, low charge potential below 3.2 V, impressive rate capability, and a long cycling stability (333 days) for Li-CO 2 batteries. The exploitation of the sharp-tip enhancement effect and dynamic creation of catalytic active sites is expected to become routine practice in future mechanistic studies for metal-air batteries.

At present, photoassisted Li-air batteries are considered to be an effective approach to overcome the sluggish reaction kinetics of the Li-air batteries. And, the organic liquid electrolyte is generally adopted by the current conventional photoassisted Li-air batteries. However, the superior catalytic activity of photoassisted cathode would in turn fasten the degradation of the organic liquid electrolyte, leading to limited battery cycling life. Herein, we tame the above limitation of the traditional liquid electrolyte system for Li-CO 2 batteries by constructing a photoassisted all-solid-state Li-CO 2 battery with an integrated bilayer Au@TiO 2 /Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP)/LAGP (ATLL) framework, which can essentially improve battery stability. Taking advantage of photoelectric and photothermal effects, the Au@TiO 2 /LAGP layer enables the acceleration of the slow kinetics of the carbon dioxide reduction reaction and evolution reaction processes. The LAGP layer could resolve the problem of liquid electrolyte decomposition under illumination. The integrated double-layer LAGP framework endows the direct transportation of heat and Li + in the entire system. The photoassisted all-solid-state Li-CO 2 battery achieves an ultralow polarization of 0.25 V with illumination, as well as a high round-trip efficiency of 92.4%. Even at an extremely low temperature of -73 °C, the battery can still deliver a small polarization of 0.6 V by converting solar energy into heat to achieve self-heating. This study is not limited to the Li-air batteries but can also be applied to other battery systems, constituting a significant step toward the practical application of all-solid-state photoassisted Li-air batteries.

Photoassisted electrochemical reaction is regarded as an effective approach to reduce the overpotential of lithium-oxygen (Li-O 2 ) batteries. However, the achievement of both broadband absorption and long term battery cycling stability are still a formidable challenge. Herein, an oxygen vacancy-mediated fast kinetics for a photoassisted Li-O 2 system is developed with a silver/bismuth molybdate (Ag/Bi 2 MoO 6 ) hybrid cathode. The cathode can offer both double advantages for light absorption covering UV to visible region and excellent electrochemical activity for O 2 . Upon discharging, the photoexcited electrons from Ag nanoplate based on the localized surface plasmon resonance (LSPR) are injected into the oxygen vacancy in Bi 2 MoO 6 . The fast oxygen reaction kinetics generate the amorphous Li 2 O 2 , and the discharge plateau is improved to 3.05 V. Upon charging, the photoexcited holes are capable to decompose amorphous Li 2 O 2 promptly, yielding a very low charge plateau of 3.25 V. A first cycle round-trip efficiency is 93.8% and retention of 70% over 500 h, which is the longest cycle life ever reported in photoassisted Li-O 2 batteries. This work offers a general and reliable strategy for boosting the electrochemical kinetics by tailoring the crystalline of Li 2 O 2 with wide-band light., (© 2022 Wiley-VCH GmbH.)

The photoassisted lithium-oxygen (Li-O 2 ) system has emerged as an important direction for future development by effectively reducing the large overpotential in Li-O 2 batteries. However, the advancement is greatly hindered by the rapidly recombined photoexcited electrons and holes upon the discharging and charging processes. Herein, a breakthrough is made in overcoming these challenges by developing a new magnetic and optical field multi-assisted Li-O 2 battery with 3D porous NiO nanosheets on the Ni foam (NiO/FNi) as a photoelectrode. Under illumination, the photogenerated electrons and holes of the NiO/FNi photoelectrode play a key role in reducing the overpotential during discharging and charging, respectively. By introducing the external magnetic field, the Lorentz force acts oppositely on the photogenerated electrons and holes, thereby suppressing the recombination of charge carriers. The magnetic and optical field multi-assisted Li-O 2 battery achieves an ultralow charge potential of 2.73 V, a high energy efficiency of 96.7%, and good cycling stability. This external magnetic and optical field multi-assisted technology paves a new way of developing high-performance Li-O 2 batteries and other energy storage systems., (© 2021 Wiley-VCH GmbH.)

Metal halide perovskite quantum dots, with high light-absorption coefficients and tunable electronic properties, have been widely studied as optoelectronic materials, but their applications in photocatalysis are hindered by their insufficient stability because of the oxidation and agglomeration under light, heat, and atmospheric conditions. To address this challenge, herein, we encapsulated CsPbBr 3 nanocrystals into a stable iron-based metal-organic framework (MOF) with mesoporous cages (∼5.5 and 4.2 nm) via a sequential deposition route to obtain a perovskite-MOF composite material, CsPbBr 3 @PCN-333(Fe), in which CsPbBr 3 nanocrystals were stabilized from aggregation or leaching by the confinement effect of MOF cages. The monodispersed CsPbBr 3 nanocrystals (4-5 nm) within the MOF lattice were directly observed by transmission electron microscopy and corresponding mapping analysis and further confirmed by powder X-ray diffraction, infrared spectroscopy, and N 2 adsorption characterizations. Density functional theory calculations further suggested a significant interfacial charge transfer from CsPbBr 3 quantum dots to PCN-333(Fe), which is ideal for photocatalysis. The CsPbBr 3 @PCN-333(Fe) composite exhibited excellent and stable oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalytic activities in aprotic systems. Furthermore, CsPbBr 3 @PCN-333(Fe) composite worked as the synergistic photocathode in the photoassisted Li-O 2 battery, where CsPbBr 3 and PCN-333(Fe) acted as optical antennas and ORR/OER catalytic sites, respectively. The CsPbBr 3 @PCN-333(Fe) photocathode showed lower overpotential and better cycling stability compared to CsPbBr 3 nanocrystals or PCN-333(Fe), highlighting the synergy between CsPbBr 3 and PCN-333(Fe) in the composite.

Directly converting and storing abundant solar energy in next-generation energy storage devices is of central importance to build a sustainable society. Herein, a new prototype of a light-promoted rechargeable and flexible Li-CO 2 battery with a TiO 2 /carbon cloth (CC) cathode is reported for the direct utilization of solar energy to promote the kinetics of the carbon dioxide reduction reaction and carbon dioxide evolution reaction (CO 2 ER). Under illumination, photoelectrons are generated in the conduction band of TiO 2 /CC, followed by the enhancing diffusion of electrons and lithium ions during the discharge process. The photoelectrons on the cathode surface can regulate the morphology of the discharge product Li 2 CO 3 , contributing to boosting the kinetics of the subsequent CO 2 ER process. In the reverse charge process, photogenerated holes can favor the decomposition of Li 2 CO 3 , leading to a negative charge potential of 2.88 V without increased polarization over ≈60 h of cycling. Owing to an ultralow overpotential of 0.06 V between the discharge and charge process, an ultrahigh energy efficiency of 97.9% is attained under illumination. The introduction of a light-promoted flexible Li-CO 2 battery can pave the way toward developing the use of solar energy to address the charging overpotential of conventional Li-CO 2 batteries., (© 2021 Wiley-VCH GmbH.)

Although the lithium-oxygen (Li-O 2 ) battery brings hope for the improvement of high-energy rechargeable batteries, the sluggish oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) kinetics become the major stumbling block. Herein, the incorporation of a plasmonic silver cathode as an advanced strategy to promote ORR and OER kinetics due to strong local surface plasmon resonance (LSPR) is introduced. Chronoamperometry results revealed that the highly energetic electrons and holes excited by LSPR of silver nanostructure facilitated ORR and OER kinetics ascribe to the emission of hot carriers in femtosecond time scale. Furthermore, a relatively rare discharge voltage 3.1 V is obtained, correspondingly, the charge plateau also decline to 3.3 V, the energy efficiency of Li-O 2 battery by a 23% increase in comparison with a commercial 5% Pt/C catalyst (discharge and charge plateau of 2.75 and 3.61 V). Additionally, the improvement in the efficient charge transfer manner result in a reversible spherical Li 2 O 2 which further improve the ORR and OER kinetics. The LSPR strategy represents a critical step toward developing fast kinetics and high energy efficiency Li-O 2 batteries.

A photoinduced flexible Li-CO 2 battery with well-designed, hierarchical porous, and free-standing In 2 S 3 @CNT/SS (ICS) as a bifunctional photoelectrode to accelerate both the CO 2 reduction and evolution reactions (CDRR and CDER) is presented. The photoinduced Li-CO 2 battery achieved a record-high discharge voltage of 3.14 V, surpassing the thermodynamic limit of 2.80 V, and an ultra-low charge voltage of 3.20 V, achieving a round trip efficiency of 98.1 %, which is the highest value ever reported (<80 %) so far. These excellent properties can be ascribed to the hierarchical porous and free-standing structure of ICS, as well as the key role of photogenerated electrons and holes during discharging and charging processes. A mechanism is proposed for pre-activating CO 2 by reducing In 3+ to In + under light illumination. The mechanism of the bifunctional light-assisted process provides insight into photoinduced Li-CO 2 batteries and contributes to resolving the major setbacks of the system., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Lithium-oxygen batteries with ultrahigh energy density have received considerable attention as of the future energy storage technologies. The development of effective electrocatalysts and a corresponding working mechanism during cycling are critically important for lithium-oxygen batteries. Here, a single cobalt atom electrocatalyst is synthesized for lithium-oxygen batteries by a polymer encapsulation strategy. The isolated moieties of single atom catalysts can effectively regulate the distribution of active sites to form micrometre-sized flower-like lithium peroxide and promote the decomposition of lithium peroxide by a one-electron pathway. The battery with single cobalt atoms can operate with high round-trip efficiency (86.2%) and long-term stability (218 days), which is superior to a commercial 5 wt% platinum/carbon catalyst. We reveal that the synergy between a single atom and the support endows the catalyst with excellent stability and durability. The promising results provide insights into the design of highly efficient catalysts for lithium-oxygen batteries and greatly expand the scope of future investigation.

A number of inherent and thorny obstacles still stand in the way of the practical application of Li-O 2 batteries, which require development of an advanced lithium anode and O 2 cathode. Herein, the strategy of a symmetrical Li-O 2 battery is presented. Specifically, Cu nanoneedle arrays with a nanoengineered Au coating are grown directly on a Cu foam substrate (Au/Cu@FCu), which can act as both the anode backbone and the cathode in a Li-O 2 battery. The excellent conductivity, high porosity, large specific surface, and superior lithiophilicity as well as high catalytic activity of the Au/Cu@FCu electrodes can simultaneously regulate the deposition behavior of the lithium metal in the anode and catalyze the formation/decomposition of Li 2 O 2 in the cathode. As a result, the Li uniformly deposited on the Au/Cu@FCu anode without Li dendrites, showing a high Coulombic efficiency over 96% and a long and stable cycle lifetime over 970 h. At the same time, the Au/Cu@FCu cathode demonstrates extremely low overpotentials (0.64 V) and a much higher specific capacity of 27 270 mAh g -1 compared to the Li-O 2 batteries with a carbon-free cathode reported to date. Moreover, the "ebb and flow" phenomenon of the anode and cathode morphology is also observed in the Li-O 2 battery.

The design of a nanoporous cathode for Li-O2 batteries that can achieve high chemical stability and superior electrochemical performance remains a formidable challenge. A novel approach for the fabrication of nanoengineered PdNi alloys directly coated onto Ni nonwoven fabric (PdNi/NiNF) obtained through electrospinning has been proposed. On the basis of the contributions of the porous structure, the prepared metal-based cathodes can exhibit high chemical and mechanical stabilities, high catalytic activity, and high conductivity. In this design, the major side reactions were excluded when compared with popularly used carbon cathodes, and excellent cycling stability (266 cycles) could be achieved. The proposed cathode exhibited a high discharge capacity of 15 700 mA h g-1 at 500 mA g-1, which was 5 times higher than those reported for carbon-free cathodes.

The rapid and effective formation and decomposition of Li 2 O 2 during cycling is crucial to solve the problems associated with the practical limitation of lithium-oxygen (Li-O 2 ) batteries. In this work, a highly dispersed electrocatalyst with Ru nanoclusters inside the special organic molecular cage (RuNCs@RCC3) through a reverse double-solvent method for Li-O 2 batteries has been proposed for the first time. This RuNCs@RCC3 shows an effective catalyst enabling reversible formation and decomposition of the Li 2 O 2 at the interface between the Li 2 O 2 and the liquid electrolyte, rather than the sluggish solid-solid interface reactions on commonly used solid catalysts. As a result, the Li-O 2 cells with RuNCs@RCC3 show enhanced electrochemical performance, including low overpotential (310 mV at a current density of 100 mA g -1 ), high specific capacity (15,068 mAh g -1 ), good rate capability (1,800 mAh g -1 at a current density of 2.8 A g -1 ), and especially superior cycle stability up to 470 cycles., (Copyright © 2019 The Authors. Published by Elsevier Inc. All rights reserved.)

With the rising development of flexible and wearable electronics, corresponding flexible energy storage devices with high energy density are required to provide a sustainable energy supply. Theoretically, rechargeable flexible Li-O 2 batteries can provide high specific energy density; however, there are only a few reports on the construction of flexible Li-O 2 batteries. Conventional flexible Li-O 2 batteries possess a loose battery structure, which prevents flexibility and stability. The low mechanical strength of the gas diffusion layer and anode also lead to a flexible Li-O 2 battery with poor mechanical properties. All these attributes limit their practical applications. Herein, the authors develop an integrated flexible Li-O 2 battery based on a high-fatigue-resistance anode and a novel flexible stretchable gas diffusion layer. Owing to the synergistic effect of the stable electrocatalytic activity and hierarchical 3D interconnected network structure of the free-standing cathode, the obtained flexible Li-O 2 batteries exhibit superior electrochemical performance, including a high specific capacity, an excellent rate capability, and exceptional cycle stability. Furthermore, benefitting from the above advantages, the as-fabricated flexible batteries can realize excellent mechanical and electrochemical stability. Even after a thousand cycles of the bending process, the flexible Li-O 2 battery can still possess a stable open-circuit voltage, a high specific capacity, and a durable cycle performance., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The successful development of Li-O 2 battery technology depends on resolving the issue of cathode corrosion by the discharge product (Li 2 O 2 ) and/or by the intermediates (LiO 2 ) generated during cell cycling. As an important step toward this goal, we report for the first time the nanoporous Ni with a nanoengineered AuNi alloy surface directly attached to Ni foam as a new all-metal cathode system. Compared with other noncarbonaceous cathodes, the Li-O 2 cell with an all-metal cathode is capable of operation with ultrahigh specific capacity (22,551 mAh g -1 at a current density of 1.0 A g -1 ) and long-term life (286 cycles). Furthermore, compared with the popularly used carbon cathode, the new all-metal cathode is advantageous because it does not show measurable reactivity toward Li 2 O 2 and/or LiO 2 . As a result, extensive cyclability (40 cycles) with 87.7% Li 2 O 2 formation and decomposition was obtained. These superior properties are explained by the enhanced solvation-mediated formation of the discharge products as well as the tailored properties of the all-metal cathode, including intrinsic chemical stability, high specific surface area, highly porous structure, high conductivity, and superior mechanical stability.

To achieve a high reversibility and long cycle life for Li-O 2 battery system, the stable tissue-directed/reinforced bifunctional separator/protection film (TBF) is in situ fabricated on the surface of metallic lithium anode. It is shown that a Li-O 2 cell composed of the TBF-modified lithium anodes exhibits an excellent anodic reversibility (300 cycles) and effectively improved cathodic long lifetime (106 cycles). The improvement is attributed to the ability of the TBF, which has chemical, electrochemical, and mechanical stability, to effectively prevent direct contact between the surface of the lithium anode and the highly reactive reduced oxygen species (Li 2 O 2 or its intermediate LiO 2 ) in cell. It is believed that the protection strategy describes here can be easily extended to other next-generation high energy density batteries using metal as anode including Li-S and Na-O 2 batteries., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

An ultrathin, lightweight, and wearable Li-O 2 battery with a novel segmented structure is first fabricated by employing a "break up the whole into parts" strategy. Superior battery performance including low overpotential, high specific capacity, good rate capability, excellent cycle stability, and high gravimetric/volumetric energy density (294.68 Wh kg -1 /274.06 Wh L -1 ) is successfully achieved even under repeatedly various deformation., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The "nonsticky" surface of a highly stable RuO 2 /carbon nanotube cathode enhances the formation and decomposition of cathode surface-induced, solvation-mediated, micrometer-sized discharge products Li 2 O 2 in Li-O 2 batteries and thus significantly improves the specific capacity, overpotentials, and cycle life. These findings contribute to a new understanding how the cathode surface controls Li-O 2 electrochemistry., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Inspired by the favorable structure and shape of golden-toad eggs, a self-standing macroporous active carbon fiber electrode is designed and fabricated via a facile and scalable strategy. After being decorated with ruthenium oxide, it endows Li-O2 batteries with superior electrochemical performances., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A novel cable-type water-survivable flexible Li-O2 battery is developed with a hydrophobic and free standing gel polymer electrolyte. Superior battery performances are successfully achieved under mechanical twisting, bending, and even immersed in water conditions, showing the high promise to power next-generation versatile flexible electronics., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A flexible freestanding air cathode inspired by traditional Chinese calligraphy art is built. When this novel electrode is employed as both a new concept cathode and current collector, to replace conventional rigid and bulky counterparts, a highly flexible and foldable Li-O2 battery with excellent mechanical strength and superior electrochemical performance is obtained., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

An artificial while very stable solid electrolyte interphase film is formed on lithium metal using an electrochemical strategy. When this protected Li anode is first used in a Li-O2 battery, the film formed on the anode can effectively suppress the parasitic reactions on the Li anode/electrolyte interface and significantly enhance the cycling stability of the Li-O2 battery., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Although flexible power sources are crucial for the realization next-generation flexible electronics, their application in such devices is hindered by their low theoretical energy density. Rechargeable lithium-oxygen (Li-O2) batteries can provide extremely high specific energies, while the conventional Li-O2 battery is bulky, inflexible and limited by the absence of effective components and an adjustable cell configuration. Here we show that a flexible Li-O2 battery can be fabricated using unique TiO2 nanowire arrays grown onto carbon textiles (NAs/CT) as a free-standing cathode and that superior electrochemical performances can be obtained even under stringent bending and twisting conditions. Furthermore, the TiO2 NAs/CT cathode features excellent recoverability, which significantly extends the cycle life of the Li-O2 battery and lowers its life cycle cost.

With the development of renewable energy and electrified transportation, electrochemical energy storage will be more important in the future than it has ever been in the past. Although lithium-ion batteries (LIBs) are traditionally considered to be the most likeliest candidate thanks to their relatively long cycle life and high energy efficiency, their limited energy density as well as cost are still causing a bottleneck for their long-term application. Alternatively, metal-air batteries have been proposed as a very promising large-scale electricity storage technology with the replacement of the intercalation reaction mechanism by the catalytic redox reaction of a light weight metal-oxygen couple. Generally, based on the electrolyte, these metal-air batteries can be divided into aqueous and nonaqueous systems, corresponding to two typical batteries of Zn-air and Li-air, respectively. The prominent feature of both batteries are their extremely high theoretical energy density, especially for nonaqueous Li-air batteries, which far exceeds the best that can be achieved with LIBs. In this review, we focus on the major obstacle of sluggish kinetics of the cathode in both batteries, and summarize the fundamentals and recent advances related to the oxygen catalyst materials. According to the electrolyte, the aqueous and nonaqueous electrocatalytic mechanisms of the oxygen reduction and evolution reactions are discussed. Subsequently, seven groups of oxygen catalysts, which have played catalytic roles in both systems, are selectively reviewed, including transition metal oxides (single-metal oxides and mixed-metal oxides), functional carbon materials (nanostructured carbons and doped carbons), metal oxide-nanocarbon hybrid materials, metal-nitrogen complexes (non-pyrolyzed and pyrolyzed), transition metal nitrides, conductive polymers, and precious metals (alloys). Nonaqueous systems have the advantages of energy density and rechargeability over aqueous systems and have gradually become the research focus of metal-air batteries. However, there are considerable challenges beyond catalysts from aqueous to nonaqueous electrolytes, which are also discussed in this review. Finally, several future research directions are proposed based on the results achieved in this field, with emphasis on nonaqueous Li-air batteries.

Supercapacitors, as one of alternative energy devices, have been characterized by the rapid rate of charging and discharging, and high power density. But they are now challenged to achieve their potential energy density that is related to specific capacitance. Thus it is extremely important to make such materials with high specific capacitances. In this report, we have gained homogenous Ni(OH)2 on graphene by efficiently using of a facile and effective electrostatic induced stretch growth method. The electrostatic interaction triggers advantageous change in morphology and the ordered stacking of Ni(OH)2 nanosheets on graphene also enhances the crystallization of Ni(OH)2. When the as-prepared Ni(OH)2/graphene composite is applied to supercapacitors, they show superior electrochemical properties including high specific capacitance (1503 F g(-1) at 2 mV s(-1)) and excellent cycling stability up to 6000 cycles even at a high scan rate of 50 mV s(-1).

Lithium-oxygen batteries are an attractive technology for electrical energy storage because of their exceptionally high-energy density; however, battery applications still suffer from low rate capability, poor cycle stability and a shortage of stable electrolytes. Here we report design and synthesis of a free-standing honeycomb-like palladium-modified hollow spherical carbon deposited onto carbon paper, as a cathode for a lithium-oxygen battery. The battery is capable of operation with high-rate (5,900 mAh g ⁻¹ at a current density of 1.5 A g⁻¹) and long-term (100 cycles at a current density of 300 mA g⁻¹ and a specific capacity limit of 1,000 mAh g⁻¹). These properties are explained by the tailored deposition and morphology of the discharge products as well as the alleviated electrolyte decomposition compared with the conventional carbon cathodes. The encouraging performance also offers hope to design more advanced cathode architectures for lithium-oxygen batteries.

A tetramethylene sulfone based electrolyte was used in rechargeable Li-O(2) batteries for the first time. Without a catalyst, superior battery performances were successfully obtained, and desired lithium peroxide (Li(2)O(2)) dominates the discharge product.

A dimethyl sulfoxide (DMSO) based electrolyte is first proposed for rechargeable lithium-O(2) (Li-O(2)) batteries. Superior battery performances, including high discharge capacity and low charge potential, are successfully obtained.