A trinity strategy enabled by iodine-loaded nitrogen-boron-doped carbon protective layer for dendrite-free zinc-ion batteries.

Although aqueous zinc ion batteries (AZIBs) have the merits of environmental friendliness, high safety and theoretical capacity, the slow kinetics associated with zinc deposition and unavoidable interfacial corrosion have seriously affected the commercialization of aqueous zinc ion batteries. In this work, an ingenious "trinity" design is proposed by applying a porous hydrophilic carbon-loaded iodine coating to the zinc metal surface (INBC@Zn), which simultaneously acts as an artificial protective layer, electrolyte additive and anode curvature regulator, so as to reduce the nucleation overpotential of Zn and promote the preferential deposition of (002) planes to some extent. With this synergistic effect, INBC@Zn exhibits high reversibility and strong side reaction inhibition. As a result, INBC@Zn shows high symmetric cycling stability up to 4500 h at 1 mA cm-2. An ultra-long cycle stability of 1500 cycles with high Coulombic efficiency (99.8 %) is achieved in the asymmetric cell. In addition, the INBC@Zn//NVO full cells exhibit impressive capacity retention (96 % after 1000 cycles at 3 A/g). Importantly, the designed pouch cell demonstrates stable performance and shows certain prospects for application. This work provides a facile and instructive approach toward the development of high-performance AZIBs.

A corrosion inhibiting layer to tackle the irreversible lithium loss in lithium metal batteries.

Reactive negative electrodes like lithium (Li) suffer serious chemical and electrochemical corrosion by electrolytes during battery storage and operation, resulting in rapidly deteriorated cyclability and short lifespans of batteries. Li corrosion supposedly relates to the features of solid-electrolyte-interphase (SEI). Herein, we quantitatively monitor the Li corrosion and SEI progression (e.g., dissolution, reformation) in typical electrolytes through devised electrochemical tools and cryo-electron microscopy. The continuous Li corrosion is validated to be positively correlated with SEI dissolution. More importantly, an anti-corrosion and interface-stabilizing artificial passivation layer comprising low-solubility polymer and metal fluoride is designed. Prolonged operations of Li symmetric cells and Li | |LiFePO4 cells with reduced Li corrosion by ~74% are achieved (0.66 versus 2.5 µAh h-1). The success can further be extended to ampere-hour-scale pouch cells. This work uncovers the SEI dissolution and its correlation with Li corrosion, enabling the durable operation of Li metal batteries by reducing the Li loss.

Stabilizing Li4SnS4 Electrolyte from Interface to Bulk Phase with a Gradient Lithium Iodide/Polymer Layer in Lithium Metal Batteries.

Sulfide electrolytes promise superior ion conduction in all-solid-state lithium (Li) metal batteries, while suffering harsh hurdles including interior dendrite growth and instability against Li and moist air. A prerequisite for solving such issues is to uncover the nature of the Li/sulfide interface. Herein, air-stable Li4SnS4 (LSS) as a prototypical sulfide electrolyte is selected to visualize the dynamic evolution and failure of the Li/sulfide interface by cryo-electron microscopy. The interfacial parasitic reaction (2Li + 2Li4SnS4 = 5Li2S + Sn2S3) is validated by direct detection of randomly distributed Li2S and Sn2S3 crystals. A bifunctional buffering layer is consequently introduced by self-diffusion of halide into LSS. Both the interface and the grain boundaries in LSS have been stabilized, eliminating the growing path of Li dendrites. The buffering layer enables the durability of Li symmetric cell (1500 h) and high-capacity retention of the LiFePO4 full-cell (95%). This work provides new insights into the hierarchical design of sulfide electrolytes.

Biomass-Derived Anion-Anchoring Nano-CaCO3 Coating for Regulating Ion Transport on Li Metal Surface.

The free transport of anions in a Li metal battery can cause multiple issues, including a high anion transference number, space charge, and concentration polarization, eventually leading to uncontrolled dendrite formation and decreased performance. Herein, we report an anion-anchoring nano-CaCO3 (NC) coating derived from eggshell biowaste for stabilizing Li metal anodes. As the adsorption of local TFSI- anions onto the NC adsorbent can undermine the anion concentration gradient and promote rapid Li-ion diffusion, it can effectively inhibit the proliferation of Li dendrites assisted by the NC coating. Consequently, Li/Cu cells with NC@Cu electrode can achieve a high Coulombic efficiency of ∼98.4% for more than 420 cycles and can even reach ∼99.1% at an ultrahigh areal capacity of 20 mAh cm-2. In particular, full cells with NC/Li@Cu electrodes show a stable lifespan of over 240 cycles with an average efficiency of ∼99.8% at a low N/P ratio of ∼3.3.

Self-assembled monolayers direct a LiF-rich interphase toward long-life lithium metal batteries.

High-energy density lithium (Li) metal batteries (LMBs) are promising for energy storage applications but suffer from uncontrollable electrolyte degradation and the consequently formed unstable solid-electrolyte interphase (SEI). In this study, we designed self-assembled monolayers (SAMs) with high-density and long-range-ordered polar carboxyl groups linked to an aluminum oxide-coated separator to provide strong dipole moments, thus offering excess electrons to accelerate the degradation dynamics of carbon-fluorine bond cleavage in Li bis(trifluoromethanesulfonyl)imide. Hence, an SEI with enriched lithium fluoride (LiF) nanocrystals is generated, facilitating rapid Li+ transfer and suppressing dendritic Li growth. In particular, the SAMs endow the full cells with substantially enhanced cyclability under high cathode loading, limited Li excess, and lean electrolyte conditions. As such, our work extends the long-established SAMs technology into a platform to control electrolyte degradation and SEI formation toward LMBs with ultralong life spans.

Soybean Protein Fiber Enabled Controllable Li Deposition and a LiF-Nanocrystal-Enriched Interface for Stable Li Metal Batteries.

The proliferation of lithium (Li) dendrites stemming from uncontrollable Li deposition seriously limits the practical application of Li metal batteries. The regulation of uniform Li deposition is thus a prerequisite for promoting a stable Li metal anode. Herein, a commercial lithiophilic skeleton of soybean protein fiber (SPF) is introduced to homogenize the Li-ion flux and induce the biomimetic Li growth behavior. Especially, the SPF can promote the formation of a LiF-nanocrystal-enriched interface upon cycling, resulting in low interfacial impedance and rapid charge transfer kinetics. Finally, the SPF-mediated Li metal anode can achieve high Coulombic efficiency of 98.7% more than 550 cycles and a long-term lifespan over 3400 h (∼8500 cycles) in symmetric tests. Furthermore, the practical pouch cell modified with SPF can maintain superior electrochemical performance over 170 cycles under a low N/P ratio and high mass loading of the cathode.

Undervalued Roles of Binder in Modulating Solid Electrolyte Interphase Formation of Silicon-Based Anode Materials.

The use of silicon (Si) for lithium (Li) storage has the significant merits of an ultrahigh theoretical specific capacity and a low working platform, potentially enabling a high-energy-density Li-ion battery (LIB). However, the Si itself undergoes a huge volume variation (>300%) upon the lithiation/delithiation process, which inevitably causes material pulverization and electrode cracking as well as ceaselessly repairs the solid electrolyte interphase (SEI), eventually resulting in a rapid capacity decay of the Si anode. Presently, using a robust binder has been well-recognized as an effective solution, which is generally explained by its robust mechanical properties that enable the electrode integrity of the Si anode during the repeated cycling process. Comparatively, the roles of the binder in modulating the chemical composition and the spatial distribution of the Si-based SEI layer are overlooked. This review will specifically provide an overview of the correlation between the binder species and SEI properties. The binder species have a critical role of inducing a robust SEI layer by selectively allowing the electrolyte salt and the solvent to connect the Si surface in the initial discharging process. Finally, we conclude by providing the perspective of the binder design based on interfacial chemistries and new characterization techniques.

Reclaiming Inactive Lithium with a Triiodide/Iodide Redox Couple for Practical Lithium Metal Batteries.

High-energy-density lithium (Li) metal batteries suffer from a short lifespan owing to apparently ceaseless inactive Li accumulation, which is accompanied by the consumption of electrolyte and active Li reservoir, seriously deteriorating the cyclability of batteries. Herein, a triiodide/iodide (I3 - /I- ) redox couple initiated by stannic iodide (SnI4 ) is demonstrated to reclaim inactive Li. The reduction of I3 - converts inactive Li into soluble LiI, which then diffuses to the cathode side. The oxidation of LiI by the delithiated cathode transforms cathode into the lithiation state and regenerates I3 - , reclaiming Li ion from inactive Li. The regenerated I3 - engages the further redox reactions. Furthermore, the formation of Sn mitigates the corrosion of I3 - on active Li reservoir sacrificially. In working Li | LiNi0.5 Co0.2 Mn0.3 O2 batteries, the accumulated inactive Li is significantly reclaimed by the reversible I3 - /I- redox couple, improving the lifespan of batteries by twice. This work initiates a creative solution to reclaim inactive Li for prolonging the lifespan of practical Li metal batteries.

In Situ Construction of a LiF-Enriched Interface for Stable All-Solid-State Batteries and its Origin Revealed by Cryo-TEM.

The application of solid polymer electrolytes (SPEs) is still inherently limited by the unstable lithium (Li)/electrolyte interface, despite the advantages of security, flexibility, and workability of SPEs. Herein, the Li/electrolyte interface is modified by introducing Li2 S additive to harvest stable all-solid-state lithium metal batteries (LMBs). Cryo-transmission electron microscopy (cryo-TEM) results demonstrate a mosaic interface between poly(ethylene oxide) (PEO) electrolytes and Li metal anodes, in which abundant crystalline grains of Li, Li2 O, LiOH, and Li2 CO3 are randomly distributed. Besides, cryo-TEM visualization, combined with molecular dynamics simulations, reveals that the introduction of Li2 S accelerates the decomposition of N(CF3 SO2 )2 - and consequently promotes the formation of abundant LiF nanocrystals in the Li/PEO interface. The generated LiF is further verified to inhibit the breakage of CO bonds in the polymer chains and prevents the continuous interface reaction between Li and PEO. Therefore, the all-solid-state LMBs with the LiF-enriched interface exhibit improved cycling capability and stability in a cell configuration with an ultralong lifespan over 1800 h. This work is believed to open up a new avenue for rational design of high-performance all-solid-state LMBs.

Biomacromolecules enabled dendrite-free lithium metal battery and its origin revealed by cryo-electron microscopy.

Metallic lithium anodes are highly promising for revolutionizing current rechargeable batteries because of their ultrahigh energy density. However, the application of lithium metal batteries is considerably impeded by lithium dendrite growth. Here, a biomacromolecule matrix obtained from the natural membrane of eggshell is introduced to control lithium growth and the mechanism is motivated by how living organisms regulate the orientation of inorganic crystals in biomineralization. Specifically, cryo-electron microscopy is utilized to probe the structure of lithium at the atomic level. The dendrites growing along the preferred < 111 > crystallographic orientation are greatly suppressed in the presence of the biomacromolecule. Furthermore, the naturally soluble chemical species in the biomacromolecules can participate in the formation of solid electrolyte interphase upon cycling, thus effectively homogenizing the lithium deposition. The lithium anodes employing bioinspired design exhibit enhanced cycling capability. This work sheds light on identifying substantial challenges in lithium anodes for developing advanced batteries.

Synthesis of Diverse Green Carbon Nanomaterials through Fully Utilizing Biomass Carbon Source Assisted by KOH.

With multiple properties, green carbon nanomaterials with high specific surface area have become extensively attractive as energy storage devices with environmental-friendly features. The primary synthesis attempts were based on alkalis activation, which, however, faced the dilemma of low utilization rate of carbon sources. Herein, the green carbon with ultrahigh surface area (up to 3560 m2/g) was prepared by the KOH-assisted biomass carbonization. Moreover, the redundant K2O steam and CxHy flow were further utilized; as a result, the carbon materials with a wide range of morphological diversity were collected on the Cu foam. Accordingly, we carried out density functional theory simulations to reveal the mechanism of O-adatom-promoted CH4 dissociation over the Cu surface for carbon formation. The electrodes of electrochemical capacitor fabricated by carbon synthesis possess a 170% higher specific capacitance compared with commercial carbon electrodes. As such, this strategy might be promising in developing hierarchical carbons along with sufficient carbon sources for broadening their potential applications.

Mg2B2O5 Nanowire Enabled Multifunctional Solid-State Electrolytes with High Ionic Conductivity, Excellent Mechanical Properties, and Flame-Retardant Performance.

High ionic conductivity, satisfactory mechanical properties, and wide electrochemical windows are crucial factors for composite electrolytes employed in solid-state lithium-ion batteries (SSLIBs). Based on these considerations, we fabricate Mg2B2O5 nanowire enabled poly(ethylene oxide) (PEO)-based solid-state electrolytes (SSEs). Notably, these SSEs have enhanced ionic conductivity and a large electrochemical window. The elevated ionic conductivity is attributed to the improved motion of PEO chains and the increased Li migrating pathway on the interface between Mg2B2O5 and PEO-LiTFSI. Moreover, the interaction between Mg2B2O5 and -SO2- in TFSI- anions could also benefit the improvement of conductivity. In addition, the SSEs containing Mg2B2O5 nanowires exhibit improved the mechanical properties and flame-retardant performance, which are all superior to the pristine PEO-LiTFSI electrolyte. When these multifunctional SSEs are paired with LiFePO4 cathodes and lithium metal anodes, the SSLIBs show better rate performance and higher cyclic capacity of 150, 106, and 50 mAh g-1 under 0.2 C at 50, 40, and 30 °C. This strategy of employing Mg2B2O5 nanowires provides the design guidelines of assembling multifunctional SSLIBs with high ionic conductivity, excellent mechanical properties, and flame-retardant performance at the same time.

Enhancing Catalyzed Decomposition of Na2CO3 with Co2MnO x Nanowire-Decorated Carbon Fibers for Advanced Na-CO2 Batteries.

The metal-CO2 batteries, especially Na-CO2, batteries come into sight owing to their high energy density, ability for CO2 capture, and the abundance of sodium resource. Besides the sluggish electrochemical reactions at the gas cathodes and the instability of the electrolyte at a high voltage, the final discharge product Na2CO3 is a solid and poor conductor of electricity, which may cause the high overpotential and poor cycle performance for the Na-CO2 batteries. The promotion of decomposition of Na2CO3 should be an efficient strategy to enhance the electrochemical performance. Here, we design a facile Na2CO3 activation experiment to screen the efficient cathode catalyst for the Na-CO2 batteries. It is found that the Co2MnO x nanowire-decorated carbon fibers (CMO@CF) can promote the Na2CO3 decomposition at the lowest voltage among all these metal oxide-decorated carbon fiber structures. After assembling the Na-CO2 batteries, the electrodes based on CMO@CF show lower overpotential and better cycling performance compared with the electrodes based on pristine carbon fibers and other metal oxide-modified carbon fibers. We believe this catalyst screening method and the freestanding structure of the CMO@CF electrode may provide an important reference for the development of advanced Na-CO2 batteries.

Solid-State Lithium-Sulfur Batteries Operated at 37 °C with Composites of Nanostructured Li7La3Zr2O12/Carbon Foam and Polymer.

An all solid-state lithium-ion battery with high energy density and high safety is a promising solution for a next-generation energy storage system. High interface resistance of the electrodes and poor ion conductivity of solid-state electrolytes are two main challenges for solid-state batteries, which require operation at elevated temperatures of 60-90 °C. Herein, we report the facile synthesis of Al3+/Nb5+ codoped cubic Li7La3Zr2O12 (LLZO) nanoparticles and LLZO nanoparticle-decorated porous carbon foam (LLZO@C) by the one-step Pechini sol-gel method. The LLZO nanoparticle-filled poly(ethylene oxide) electrolyte shows improved conductivity compared with filler-free samples. The sulfur composite cathode based on LLZO@C can deliver an attractive specific capacity of >900 mAh g-1 at the human body temperature 37 °C and a high capacity of 1210 and 1556 mAh g-1 at 50 and 70 °C, respectively. In addition, the solid-state Li-S batteries exhibit high Coulombic efficiency and show remarkably stable cycling performance.