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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.)

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.)

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.)

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.)

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.)

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.)

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.)