A highly reversible force-assisted Li - CO2 battery based on piezoelectric effect of Bi0.5Na0.5TiO3 nanorods.

The use of light-assisted cathode is regarded as an effective approach to reduce the overpotential of lithium carbon dioxide (Li - CO2) batteries. However, the inefficient electron-hole separation and the complex discharge-charge reactions hamper the efficiency of CO2 photocatalytic reaction in battery. Herein, a highly reversible force-assisted Li - CO2 battery has been established for the first time by employing a Bi0.5Na0.5TiO3 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 (Li2CO3) can be modified via the dense surface electrons of the piezoelectric cathode, resulting in the promoted decomposition kinetics of Li2CO3 in charging progress. Thus, the force-assisted Li - CO2 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 - CO2 batteries system.

Enabling High-Performance All-Solid-State Batteries via Guest Wrench in Zeolite Strategy.

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.

All-Solid-State Photo-Assisted Li-CO2 Battery Working at an Ultra-Wide Operation Temperature.

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-CO2 batteries by constructing a photoassisted all-solid-state Li-CO2 battery with an integrated bilayer Au@TiO2/Li1.5Al0.5Ge1.5(PO4)3 (LAGP)/LAGP (ATLL) framework, which can essentially improve battery stability. Taking advantage of photoelectric and photothermal effects, the Au@TiO2/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-CO2 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.

Oxygen Vacancy-Mediated Growth of Amorphous Discharge Products toward an Ultrawide Band Light-Assisted Li-O2 Batteries.

Photoassisted electrochemical reaction is regarded as an effective approach to reduce the overpotential of lithium-oxygen (Li-O2 ) 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-O2 system is developed with a silver/bismuth molybdate (Ag/Bi2 MoO6 ) hybrid cathode. The cathode can offer both double advantages for light absorption covering UV to visible region and excellent electrochemical activity for O2 . Upon discharging, the photoexcited electrons from Ag nanoplate based on the localized surface plasmon resonance (LSPR) are injected into the oxygen vacancy in Bi2 MoO6 . The fast oxygen reaction kinetics generate the amorphous Li2 O2 , and the discharge plateau is improved to 3.05 V. Upon charging, the photoexcited holes are capable to decompose amorphous Li2 O2 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-O2 batteries. This work offers a general and reliable strategy for boosting the electrochemical kinetics by tailoring the crystalline of Li2 O2 with wide-band light.

Magnetic and Optical Field Multi-Assisted Li-O2 Batteries with Ultrahigh Energy Efficiency and Cycle Stability.

The photoassisted lithium-oxygen (Li-O2 ) system has emerged as an important direction for future development by effectively reducing the large overpotential in Li-O2 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-O2 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-O2 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-O2 batteries and other energy storage systems.

In Situ Fabrication of Cuprous Selenide Electrode via Selenization of Copper Current Collector for High-Efficiency Potassium-Ion and Sodium-Ion Storage.

Selenium-based materials are considered as desirable candidates for potassium-ion and sodium-ion storage. Herein, an in situ fabrication method is developed to prepare an integrated cuprous selenide electrode by means of directly chemical selenization of the copper current collector with commercial selenium powder. Interestingly, only the electrolyte of 1 m potassium hexafluorophosphate dissolved in 1,2-dimethoxyethane with higher highest occupied molecular orbital energy and lower desolvation energy facilitates the formation of polyselenide intermediates and the further selenization of the copper current collector. Benefiting from the unique thin-film-like nanosheet morphology and the robust structural stability of the integrated electrode, the volume change and the loss of selenide species could be effectively restrained. Therefore, high performance is achieved in both potassium-ion batteries (462 mA h g-1 at 2 A g-1 for 300 cycles) and sodium-ion batteries (775 mA h g-1 at 2 A g-1 for 4000 cycles). The facile fabrication strategy paves a new direction for the design and preparation of high-performance electrodes.

Joint Enhancement in the Electrochemical Reversibility and Cycle Lives for Copper Sulfide for Sodium- and Potassium-Ion Storage via Selenium Substitution.

Transition metal sulfides have received considerable interest as the anodes for sodium-ion (SIBs) and potassium-ion batteries (PIBs) owing to their high theoretical capacity and suitable working potential. However, they suffer from poor electrochemical reversibility and limited cycle lives. Herein, we design and synthesize a Se-substituted CuS material, which demonstrates superior electrochemical properties for both potassium and sodium storage because of the enhanced electronic conductivity, lowered diffusion barrier, and shortened diffusion pathway. The anode delivers a specific capacity of 374 mA h g-1 at a current density of 5 A g-1 in SIBs and 341 mA h g-1 at 2 A g-1 in PIBs and nearly 100% capacity retention over 2000 cycles (SIBs) and 600 cycles (PIBs), respectively. Moreover, a combined measurement including X-ray diffraction, Raman, and transmission electron microscopy reveals an interesting discharge product of Na2S0.8Se0.2, which could accelerate the conversion reaction and enhance the electrochemical reversibility.

A Renewable Light-Promoted Flexible Li-CO2 Battery with Ultrahigh Energy Efficiency of 97.9.

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-CO2 battery with a TiO2 /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 (CO2 ER). Under illumination, photoelectrons are generated in the conduction band of TiO2 /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 Li2 CO3 , contributing to boosting the kinetics of the subsequent CO2 ER process. In the reverse charge process, photogenerated holes can favor the decomposition of Li2 CO3 , 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-CO2 battery can pave the way toward developing the use of solar energy to address the charging overpotential of conventional Li-CO2 batteries.

Driving Oxygen Electrochemistry in Lithium-Oxygen Battery by Local Surface Plasmon Resonance.

Although the lithium-oxygen (Li-O2) 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-O2 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 Li2O2 which further improve the ORR and OER kinetics. The LSPR strategy represents a critical step toward developing fast kinetics and high energy efficiency Li-O2 batteries.

A highly stable and flexible zeolite electrolyte solid-state Li-air battery.

Solid-state lithium (Li)-air batteries are recognized as a next-generation solution for energy storage to address the safety and electrochemical stability issues that are encountered in liquid battery systems1-4. However, conventional solid electrolytes are unsuitable for use in solid-state Li-air systems owing to their instability towards lithium metal and/or air, as well as the difficulty in constructing low-resistance interfaces5. Here we present an integrated solid-state Li-air battery that contains an ultrathin, high-ion-conductive lithium-ion-exchanged zeolite X (LiX) membrane as the sole solid electrolyte. This electrolyte is integrated with cast lithium as the anode and carbon nanotubes as the cathode using an in situ assembly strategy. Owing to the intrinsic chemical stability of the zeolite, degeneration of the electrolyte from the effects of lithium or air is effectively suppressed. The battery has a capacity of 12,020 milliamp hours per gram of carbon nanotubes, and has a cycle life of 149 cycles at a current density of 500 milliamps per gram and at a capacity of 1,000 milliamp hours per gram. This cycle life is greater than those of batteries based on lithium aluminium germanium phosphate (12 cycles) and organic electrolytes (102 cycles) under the same conditions. The electrochemical performance, flexibility and stability of zeolite-based Li-air batteries confer practical applicability that could extend to other energy-storage systems, such as Li-ion, Na-air and Na-ion batteries.

Boosting potassium-storage performance via the functional design of a heterostructured Bi2S3@RGO composite.

Potassium-ion batteries (PIBs) are considered a promising alternative to lithium-ion batteries (LIBs) for next-generation energy storage due to the abundance and competitive cost of potassium resources. However, the excavation and the development of proper electrodes for PIBs are still confronted with great challenges. Herein, a self-assembled bismuth sulfide microsphere wrapped with reduced graphene oxide was fabricated to form a heterostructured Bi2S3@RGO composite via a visible-light-assisted method and served as the anode for PIBs. The as-prepared Bi2S3@RGO composite presented a high reversible specific capacity of 538 mA h g-1 at 0.2 A g-1 and superior rate capability of 237 mA h g-1 at a high current density of 2 A g-1 after 300 cycles. In particular, the high capacity could be ascribed to the synergistic effect of the conversion and alloying reactions during the electrochemical processes, which was validated by ex situ X-ray diffraction. The fabrication of a unique heterostructure combining the self-assembled Bi2S3 microspheres and flexible RGO boosted the facile charge transfer, leading to the enhanced cyclic stability and rate performance.

A Bifunctional Photo-Assisted Li-O2 Battery Based on a Hierarchical Heterostructured Cathode.

Photo-assisted charging is considered an effective approach to reducing the overpotential in lithium-oxygen (Li-O2 ) batteries. However, the utilization of photoenergy during the discharge process in a Li-O2 system has been rarely reported, and the functional mechanism of such a process remains unclear. Herein, a novel bifunctional photo-assisted Li-O2 system is established by employing a hierarchical TiO2 -Fe2 O3 heterojunction, in which the photo-generated electrons and holes play key roles in reducing the overpotential in the discharging and charging processes, respectively. Moreover, the morphology of the discharge product (Li2 O2 ) can be modified via the dense surface electrons of the cathode under illumination, resulting in promoted decomposition kinetics of Li2 O2 during the charging progress. Accordingly, the output and input energies of the battery can be tuned by illumination, giving an ultralow overpotential of 0.19 V between the charge and discharge plateaus with excellent cyclic stability (retaining a round-trip efficiency of ≈86% after 100 cycles). The investigation of the bifunctional photo-assisted process presented here provides significant insight into the mechanism of the photo-assisted Li-O2 battery and addresses the overpotential bottleneck in this system.

Porous Materials Applied in Nonaqueous Li-O2 Batteries: Status and Perspectives.

Porous materials possessing high surface area, large pore volume, tunable pore structure, superior tailorability, and dimensional effect have been widely applied as components of lithium-oxygen (Li-O2 ) batteries. Herein, the theoretical foundation of the porous materials applied in Li-O2 batteries is provided, based on the present understanding of the battery mechanism and the challenges and advantageous qualities of porous materials. Furthermore, recent progress in porous materials applied as the cathode, anode, separator, and electrolyte in Li-O2 batteries is summarized, together with corresponding approaches to address the critical issues that remain at present. Particular emphasis is placed on the importance of the correlation between the function-orientated design of porous materials and key challenges of Li-O2 batteries in accelerating oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) kinetics, improving the electrode stability, controlling lithium deposition, suppressing the shuttle effect of the dissolved redox mediators, and alleviating electrolyte decomposition. Finally, the rational design and innovative directions of porous materials are provided for their development and application in Li-O2 battery systems.

Light/Electricity Energy Conversion and Storage for a Hierarchical Porous In2 S3 @CNT/SS Cathode towards a Flexible Li-CO2 Battery.

A photoinduced flexible Li-CO2 battery with well-designed, hierarchical porous, and free-standing In2 S3 @CNT/SS (ICS) as a bifunctional photoelectrode to accelerate both the CO2 reduction and evolution reactions (CDRR and CDER) is presented. The photoinduced Li-CO2 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 CO2 by reducing In3+ to In+ under light illumination. The mechanism of the bifunctional light-assisted process provides insight into photoinduced Li-CO2 batteries and contributes to resolving the major setbacks of the system.

Graphene oxide wrapped Cu3V2O7(OH)2 · 2H2O nanocomposite with enhanced electrochemical performance for lithium-ion storage.

Transition metal oxides (TMOs) are widely accepted as one of the alternatives for the graphite anode in lithium-ion batteries (LIBs) owing to the high specific capacity and facile synthesis of nanoscale materials facilitating fast ionic transfer. However, the lower electronic conductivity always impedes the application of TMOs. Herein, we report a graphene oxide wrapped layer-structured Cu3V2O7(OH)2 · 2H2O nanocomposite (CVO/GO) synthesized via an in situ co-precipitation method. It is corroborated that the introduction of GO not only provides more active sites for lithium-ion storage, but also improves the charge transfer rate of the electrode, issuing an enhanced electrochemical performance. As expected, the CVO/GO nanocomposite exhibits an ultrahigh specific capacity of 870 mA h g-1 at 0.1 A g-1 compared with CVO nanoparticles. Even at a high current density of 5 A g-1, a specific capacity of 158 mA h g-1 could be achieved for the CVO/GO nanocomposite.

Ti3C2T x MXene decorated with Sb nanoparticles as anodes material for sodium-ion batteries.

A large family of two-dimensional (2D) transition metal carbides, MXene, has demonstrated potential applications for electrochemical energy storage. 2D MXene sheets may buffer large volume changes and form a 3D conductive network to facilitate the electronic transfer of working electrodes. However, multilayer Ti3C2T x material could only deliver a moderate capacity in sodium ion battery cells, below the requirement of commercial applications. Herein, we decorated multilayer MXene (Ti3C2T x ) with Sb nanoparticles (NPs) via a facile solution-phase method, in which Sb NPs with a diameter of about 5-10 nm are absorbed on the surface of MXene layers by the electrostatic attraction action. The hybrid material Ti3C2T x @Sb-0.5 delivers a higher reversible capacity of 200 mA h g-1 at 0.1 A g-1 than that of pure Ti3C2T x (90 mA h g-1), and shows a much better capacity retention of nearly 98% after 500 cycles compared with Sb NPs. Also, it achieves superior rate performance (remaining a capacity of 127 mA h g-1 at 2 A g-1) and excellent long-term stability (a capacity retention of almost 92.3% after 8000 cycles). These results indicate that Ti3C2T x @Sb-0.5 possess a potential for high-performance sodium ion batteries anodes.

Cu3 V2 O8 Nanoparticles as Intercalation-Type Anode Material for Lithium-Ion Batteries.

Cu3 V2 O8 nanoparticles with particle sizes of 40-50 nm have been prepared by the co-precipitation method. The Cu3 V2 O8 electrode delivers a discharge capacity of 462 mA h g(-1) for the first 10 cycles and then the specific capacity, surprisingly, increases to 773 mA h g(-1) after 50 cycles, possibly as a result of extra lithium interfacial storage through the reversible formation/decomposition of a solid electrolyte interface (SEI) film. In addition, the electrode shows good rate capability with discharge capacities of 218 mA h g(-1) under current densities of 1000 mA g(-1) . Moreover, the lithium storage mechanism for Cu3 V2 O8 nanoparticles is explained on the basis of ex situ X-ray diffraction data and high-resolution transmission electron microscopy analyses at different charge/discharge depths. It was evidenced that Cu3 V2 O8 decomposes into copper metal and Li3 VO4 on being initially discharged to 0.01 V, and the Li3 VO4 is then likely to act as the host for lithium ions in subsequent cycles by means of the intercalation mechanism. Such an "in situ" compositing phenomenon during the electrochemical processes is novel and provides a very useful insight into the design of new anode materials for application in lithium-ion batteries.

NASICON-Structured NaTi2(PO4)3@C Nanocomposite as the Low Operation-Voltage Anode Material for High-Performance Sodium-Ion Batteries.

NASICON-type structured NaTi2(PO4)3 (NTP) has attracted wide attention as a promising anode material for sodium-ion batteries (SIBs), whereas it still suffer from poor rate capability and cycle stability due to the low electronic conductivity. Herein, the architecture, NTP nanoparticles embedded in the mesoporous carbon matrix, is designed and realized by a facile sol-gel method. Different than the commonly employed potentials of 1.5-3.0 V, the Na(+) storage performance is examined at low operation voltages between 0.01 and 3.0 V. The electrode demonstrates an improved capacity of 208 mAh g(-1), one of the highest capacities in the state-of-the-art titanium-based anode materials. Besides the high working plateau at 2.1 V, another one is observed at approximately 0.4 V for the first time due to further reduction of Ti(3+) to Ti(2+). Remarkably, the anode exhibits superior rate capability, whose capacity and corresponding capacity retention reach 56 mAh g(-1) and 68%, respectively, over 10000 cycles under the high current density of 20 C rate (4 A g(-1)). Worthy of note is that the electrode shows negligible capacity loss as the current densities increase from 50 to 100 C, which enables NTP@C nanocomposite as the prospective anode of SIBs with ultrahigh power density.

P2-NaCo(0.5)Mn(0.5)O2 as a Positive Electrode Material for Sodium-Ion Batteries.

As a promising positive electrode material for sodium-ion batteries (SIBs), layered sodium oxides have attracted considerable attention in recent years. In this work, stoichiometric P2-phase NaCo(0.5)Mn(0.5)O2 was prepared through the conventional solid-state reaction, and its structural and physical properties were studied in terms of XRD, XPS, and magnetic susceptibility. Furthermore, the P2-NaCo(0.5)Mn(0.5)O2 electrode delivered a discharge capacity of 124.3 mA h g(-1) and almost 100% initial coulombic efficiency over the potential window of 1.5-4.15 V. It also showed good cycle stability, with a reversible capacity and capacity retention reaching approximately 85 mA h g(-1) and 99%, respectively, at the 5 C rate after 100 cycles. Additionally, cyclic voltammetry and ex situ XRD were employed to explain the electrochemical behavior at the different electrochemical stages. Owing to the applicable performances, P2-NaCo(0.5)Mn(0.5)O2 can be considered as a potential positive electrode material for SIBs.

Preparation and Electrochemical Properties of Tin-Iron-Carbon Nanocomposite as the Anode of Lithium-Ion Batteries.

Tin-iron-carbon nanocomposite is successfully prepared by a sol-gel method followed by a chemical vapor deposition (CVD) process with acetylene gas as the carbon source. The structural properties, morphology, and electrochemical performances of the nanocomposite are comprehensively studied in comparison with those properties of tin-carbon and iron-carbon nanocomposites. Sheet-like carbon architecture and different carbon contents are induced thanks to the catalytic effect of iron during CVD. Among three nanocomposites, tin-iron-carbon demonstrates the highest reversible capacity of 800 mA h g(-1) with 96.9% capacity retention after 50 cycles. It also exhibits the best rate capability with a discharge capacity of 420 mA h g(-1) at a current density of 1000 mA g(-1). This enhanced performance is strongly related to the carbon morphology and content, which can not only accommodate the large volume change, but also improve the electronic conductivity of the nanocomposite. Hence, the tin-iron-carbon nanocomposite is expected to be a promising anode for lithium-ion batteries.