Lithium and sodium metal batteries are considered as promising next‐generation energy storage devices due to their ultrahigh energy densities. The high reactivity of alkali metal toward organic ...solvents and salts results in side reactions, which further lead to undesirable electrolyte depletion, cell failure, and evolution of flammable gas. Herein, first‐principles calculations and in situ optical microscopy are used to study the mechanism of organic electrolyte decomposition and gas evolution on a sodium metal anode. Once complexed with sodium ions, solvent molecules show a reduced LUMO, which facilitates the electrolyte decomposition and gas evolution. Such a general mechanism is also applicable to lithium and other metal anodes. We uncover the critical role of ion–solvent complexation for the stability of alkali metal anodes, reveal the mechanism of electrolyte gassing, and provide a mechanistic guidance to electrolyte and lithium/sodium anode design for safe rechargeable batteries.
Safe rechargeable batteries: Ion–solvent complexes in alkali metal batteries have been studied by first‐principles calculations and in situ optical microscopy. The ion–solvent complexes have low LUMOs and are readily reduced on an alkali metal anode. A general mechanism for organic electrolyte decomposition and gas evolution was discovered.
The lifespan of high‐energy‐density lithium metal batteries (LMBs) is hindered by heterogeneous solid electrolyte interphase (SEI). The rational design of electrolytes is strongly considered to ...obtain uniform SEI in working batteries. Herein, a modification of nitrate ion (NO3−) is proposed and validated to improve the homogeneity of the SEI in practical LMBs. NO3− is connected to an ether‐based moiety to form isosorbide dinitrate (ISDN) to break the resonance structure of NO3− and improve the reducibility. The decomposition of non‐resonant −NO3 in ISDN enriches SEI with abundant LiNxOy and induces uniform lithium deposition. Lithium–sulfur batteries with ISDN additives deliver a capacity retention of 83.7 % for 100 cycles compared with rapid decay with LiNO3 after 55 cycles. Moreover, lithium–sulfur pouch cells with ISDN additives provide a specific energy of 319 Wh kg−1 and undergo 20 cycles. This work provides a realistic reference in designing additives to modify the SEI for stabilizing LMBs.
The modification of NO3− is achieved by connecting NO3− to an ether‐based moiety. The broken resonance structure of −NO3 improves its reducibility compared with NO3−. The decomposition of −NO3 forms a LiNxOy‐rich solid electrolyte interphase (SEI) and induces uniform Li deposition.
Lithium‐metal electrodes have undergone a comprehensive renaissance to meet the requirements of high‐energy‐density batteries due to their lowest electrode potential and the very high theoretical ...capacity. Unfortunately, the unstable interface between lithium and nonaqueous electrolyte induces dendritic Li and low Coulombic efficiency during repeated Li plating/stripping, which is one of the huge obstacles toward practical lithium‐metal batteries. Here, a composite mixed ionic/electronic conductor interphase (MCI) is formed on the surface of Li by in situ chemical reactions of a copper‐fluoride‐based solution and Li metal at room temperature. The as‐obtained MCI film acts like the armor of a soldier to protect the Li‐metal anode by its prioritized lithium storage, high ionic conductivity, and high Young's modulus. The armored MCI can effectively suppress Li‐dendrite growth and work effectively in LiNi0.5Co0.2Mn0.3O2/Li cells. The armored MCI presents fresh insights into the formation and regulation of the stable electrode–electrolyte interface and an effective strategy to protect Li‐metal anodes in working Li‐metal batteries.
A composite mixed ionic/electronic conductor interphase (MCI) is formed on the surface of lithium by in situ chemical reactions of copper‐fluoride‐based solution and Li metal at room temperature. The as‐obtained MCI film acts like the armor of a soldier to protect the Li‐metal anode by its prioritized lithium storage, high ionic conductivity, and high Young's modulus.
Safe and rechargeable lithium metal batteries have been difficult to achieve because of the formation of lithium dendrites. Herein an emerging electrolyte based on a simple solvation strategy is ...proposed for highly stable lithium metal anodes in both coin and pouch cells. Fluoroethylene carbonate (FEC) and lithium nitrate (LiNO3) were concurrently introduced into an electrolyte, thus altering the solvation sheath of lithium ions, and forming a uniform solid electrolyte interphase (SEI), with an abundance of LiF and LiNxOy on a working lithium metal anode with dendrite‐free lithium deposition. Ultrahigh Coulombic efficiency (99.96 %) and long lifespans (1000 cycles) were achieved when the FEC/LiNO3 electrolyte was applied in working batteries. The solvation chemistry of electrolyte was further explored by molecular dynamics simulations and first‐principles calculations. This work provides insight into understanding the critical role of the solvation of lithium ions in forming the SEI and delivering an effective route to optimize electrolytes for safe lithium metal batteries.
Not dead ′Li′: Fluoroethylene carbonate (FEC) and lithium nitrate (LiNO3) were concurrently introduced into an electrolyte, thus altering the solvation sheath of lithium ions and forming a uniform solid electrolyte interphase (SEI). An abundance of LiF and LiNxOy is formed on the working lithium metal anode and contributes to dendrite‐free lithium deposition.
Bifunctional electrocatalysis for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) constitutes the bottleneck of various sustainable energy devices and systems like rechargeable ...metal–air batteries. Emerging catalyst materials are strongly requested toward superior electrocatalytic activities and practical applications. In this study, transition metal hydroxysulfides are presented as bifunctional OER/ORR electrocatalysts for Zn–air batteries. By simply immersing Co‐based hydroxide precursor into solution with high‐concentration S2−, transition metal hydroxides convert to hydroxysulfides with excellent morphology preservation at room temperature. The as‐obtained Co‐based metal hydroxysulfides are with high intrinsic reactivity and electrical conductivity. The electron structure of the active sites is adjusted by anion modulation. The potential for 10 mA cm−2 OER current density is 1.588 V versus reversible hydrogen electrode (RHE), and the ORR half‐wave potential is 0.721 V versus RHE, with a potential gap of 0.867 V for bifunctional oxygen electrocatalysis. The Co3FeS1.5(OH)6 hydroxysulfides are employed in the air electrode for a rechargeable Zn–air battery with a small overpotential of 0.86 V at 20.0 mA cm−2, a high specific capacity of 898 mAh g−1, and a long cycling life, which is much better than Pt and Ir‐based electrocatalyst in Zn–air batteries.
Transition metal hydroxysulfides are proposed as bifunctional electrocatalysts in working Zn–air batteries with high oxygen evolution reaction/oxygen reduction reaction reactivities, high power densities, large capacities, and extraordinary stabilities. These transition metal hydroxysulfides are fabricated through a novel room‐temperature sulfurization strategy, which opens new doors to materials innovation of transition metal (hydro/oxy)sulfides and their practical applications in hetero/electrocatalysis, energy storage, and healthcare applications.
Lithium (Li)‐metal batteries promise energy density beyond 400 Wh kg−1, while their practical operation at an extreme temperature below −30 °C suffers severe capacity deterioration. Such battery ...failure highly relates to the remarkably increased kinetic barrier of interfacial processes, including interfacial desolvation, ion transportation, and charge transfer. In this work, the interfacial kinetics in three prototypical electrolytes are quantitatively probed by three‐electrode electrochemical techniques and molecular dynamics simulations. Desolvation as the limiting step of interfacial processes is validated to dominate the cell impedance and capacity at low temperature. 1,3‐Dioxolane‐based electrolyte with tamed solvent–solute interaction facilitates fast desolvation, enabling the practical Li|LiNi0.5Co0.2Mn0.3O2 cells at −40 °C to retain 66% of room‐temperature capacity and withstand remarkably fast charging rate (0.3 C). The barrier of desolvation dictated by solvent–solute interaction environments is quantitatively uncovered. Regulating the solvent–solute interaction by low‐affinity solvents emerges as a promising solution to low‐temperature batteries.
Desolvation is validated as the predominant contributor to energy loss at low temperatures, largely overwhelming the contributions from other interfacial ion transportation processes. A rational and original design by taming solvent–solute interaction with low‐affinity solvents like 1,3‐dioxolane is proposed to enable high capacity and durable operation of practical lithium‐metal batteries at −40 °C.
Metasurfaces have enabled a plethora of emerging functions within an ultrathin dimension, paving way towards flat and highly integrated photonic devices. Despite the rapid progress in this area, ...simultaneous realization of reconfigurability, high efficiency, and full control over the phase and amplitude of scattered light is posing a great challenge. Here, we try to tackle this challenge by introducing the concept of a reprogrammable hologram based on 1-bit coding metasurfaces. The state of each unit cell of the coding metasurface can be switched between '1' and '0' by electrically controlling the loaded diodes. Our proof-of-concept experiments show that multiple desired holographic images can be realized in real time with only a single coding metasurface. The proposed reprogrammable hologram may be a key in enabling future intelligent devices with reconfigurable and programmable functionalities that may lead to advances in a variety of applications such as microscopy, display, security, data storage, and information processing.Realizing metasurfaces with reconfigurability, high efficiency, and control over phase and amplitude is a challenge. Here, Li et al. introduce a reprogrammable hologram based on a 1-bit coding metasurface, where the state of each unit cell of the coding metasurface can be switched electrically.
The challenges of developing neuromorphic vision systems inspired by the human eye come not only from how to recreate the flexibility, sophistication, and adaptability of animal systems, but also how ...to do so with computational efficiency and elegance. Similar to biological systems, these neuromorphic circuits integrate functions of image sensing, memory and processing into the device, and process continuous analog brightness signal in real-time. High-integration, flexibility and ultra-sensitivity are essential for practical artificial vision systems that attempt to emulate biological processing. Here, we present a flexible optoelectronic sensor array of 1024 pixels using a combination of carbon nanotubes and perovskite quantum dots as active materials for an efficient neuromorphic vision system. The device has an extraordinary sensitivity to light with a responsivity of 5.1 × 10
A/W and a specific detectivity of 2 × 10
Jones, and demonstrates neuromorphic reinforcement learning by training the sensor array with a weak light pulse of 1 μW/cm
.
The construction of active sites with intrinsic oxygen evolution reaction (OER) is of great significance to overcome the limited efficiency of abundant sustainable energy devices such as fuel cells, ...rechargeable metal–air batteries, and in water splitting. Anionic regulation of electrocatalysts by modulating the electronic structure of active sites significantly promotes OER performance. To prove the concept, NiFeS electrocatalysts are fabricated with gradual variation of atomic ratio of S:O. With the rise of S content, the overpotential for water oxidation exhibits a volcano plot under anionic regulation. The optimized NiFeS‐2 electrocatalyst under anionic regulation possesses the lowest OER overpotential of 286 mV at 10 mA cm−2 and the fastest kinetics being 56.3 mV dec−1 to date. The anionic regulation methodology not only serves as an effective strategy to construct superb OER electrocatalysts, but also enlightens a new point of view for the in‐depth understanding of electrocatalysis at the electronic and atomic level.
Anionic regulation of NiFe (oxy)sulfide electrocatalysts by modulating the electronic structure of oxygen evolution reaction (OER) active sites significantly promotes the water oxidation performance. Antagonistic S/O anions polarize the NiFe active sites, rendering the OER reactivity dependent on the anionic composition. The as‐obtained electrocatalyst exhibits superb OER performance with an ultralow overpotential of 286 mV at an OER current density of 10.0 mA cm−2.
The performance of rechargeable lithium (Li) batteries is highly correlated with the structure of solid electrolyte interphase (SEI). The properties of a working anode are vital factors in ...determining the structure of SEI; however, the correspondingly poor understanding hinders the rational regulation of SEI. Herein, the electrode potential and anode material, two critical properties of an anode, in dictating the structural evolution of SEI were investigated theoretically and experimentally. The anode potential is identified as a crucial role in dictating the SEI structure. The anode potential determines the reduction products in the electrolyte, ultimately giving rise to the mosaic and bilayer SEI structure at high and low potential, respectively. In contrast, the anode material does not cause a significant change in the SEI structure. This work discloses the crucial role of electrode potential in dictating SEI structure and provides rational guidance to regulate SEI structure.
The role of electrode potential and anode material, two critical properties of a working anode, in dictating the structural evolution of solid electrolyte interphase (SEI) was investigated theoretically and experimentally, which provides rational guidance to regulate SEI structure.
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