A locally solvent-tethered polymer electrolyte for long-life lithium metal batteries.

Solid polymer electrolytes exhibit enhanced Li+ conductivity when plasticized with highly dielectric solvents such as N,N-dimethylformamide (DMF). However, the application of DMF-containing electrolytes in solid-state batteries is hindered by poor cycle life caused by continuous DMF degradation at the anode surface and the resulting unstable solid-electrolyte interphase. Here we report a composite polymer electrolyte with a rationally designed Hofmann-DMF coordination complex to address this issue. DMF is engineered on Hofmann frameworks as tethered ligands to construct a locally DMF-rich interface which promotes Li+ conduction through a ligand-assisted transport mechanism. A high ionic conductivity of 6.5 × 10-4 S cm-1 is achieved at room temperature. We demonstrate that the composite electrolyte effectively reduces the free shuttling and subsequent decomposition of DMF. The locally solvent-tethered electrolyte cycles stably for over 6000 h at 0.1 mA cm-2 in Li | |Li symmetric cell. When paired with sulfurized polyacrylonitrile cathodes, the full cell exhibits a prolonged cycle life of 1000 cycles at 1 C. This work will facilitate the development of practical polymer-based electrolytes with high ionic conductivity and long cycle life.

Achieving Stable Lithium Anodes through Leveraging Inevitable Stress Variations via Adaptive Piezoelectric Effect.

Unleashing the potential of lithium-metal anodes in practical applications is hindered by the inherent stress-related challenges arising from their limitless volume expansion, leading to mechanical failures such as electrode cracking, solid electrolyte interphase damage, and dendritic growth. Despite the various protective strategies to "combat" stress in lithium-metal anodes, they fail to address the intrinsic issue fundamentally. Here, a unique strategy is proposed that leverages the stress generated during the battery cycling via the piezoelectric effect, transforming to the adaptive built-in electric field to accelerate lithium-ion migration, homogenize the lithium deposition, and alleviate the stress concentration. The mechanism of the piezoelectric effect in modulating electro-chemomechanical field evolution is further validated and decoupled through finite element method simulations. Inspired by this strategy, a high sensitivity, fast responsive, and strength adaptability polymer piezoelectric is used to demonstrate the feasibility and the corresponding protected lithium-metal anode shows cycling stability over 6000 h under a current density of 10 mA cm-2 and extending life in a variety of coin and pouch cell systems. This work effectively tackles the stress-related issues and decoupling the electro-chemomechanical field evolution also contributes to developing more stable lithium anodes for future research.

Unraveling the Coupling Effect between Cathode and Anode toward Practical Lithium-Sulfur Batteries.

The localized reaction heterogeneity of the sulfur cathode and the uneven Li deposition on the Li anode are intractable issues for lithium-sulfur (Li-S) batteries under practical operation. Despite impressive progress in separately optimizing the sulfur cathode or Li anode, a comprehensive understanding of the highly coupled relationship between the cathode and anode is still lacking. In this work, inspired by the Butler-Volmer equation, a binary descriptor (IBD ) assisting the rational structural design of sulfur cathode by simultaneously considering the mass-transport index (Imass ) and the charge-transfer index (Icharge ) is identified, and subsequently the relationship between IBD and the morphological evolution of Li anode is established. Guided by the IBD , a scalable electrode providing interpenetrated flow channels for efficient mass/charge transfer, full utilization of active sulfur, and mechanically elastic support for aggressive electrochemical reactions under practical conditions is reported. These characteristics induce a homogenous distribution of local current densities and reduced reaction heterogeneity on both sides of the cathode and anode. Impressive energy density of 318 Wh kg-1 and 473 Wh L-1 in an Ah-level pouch cell can be achieved by the design concept. This work offers a promising paradigm for unlocking the interaction between cathode and anode and designing high-energy practical Li-S batteries.

Energy Band Engineering Guided Design of Bidirectional Catalyst for Reversible Li-CO2 Batteries.

Li-CO2 batteries arouse great interest in the context of carbon neutralization, but their practicability is severely hindered by the sluggish CO2 redox reaction kinetics at the cathode, which brings about formidable challenges such as high overpotential and low Coulombic efficiency. For the complex multi-electron transfer process, the design of catalysts at the molecular or atomic level and the understanding of the relationship between electron state and performance are essential for the CO2 redox. However, little attention is paid to it. In this work, using Co3 S4 as a model system, density functional theory (DFT) calculations reveal that the adjusted d-band and p-band centers of Co3 S4 with the introduction of Cu and sulfur vacancies are hybridized between CO2 and Li species, respectively, which is conducive to the adsorption of reactants and the decomposition of Li2 CO3 , and the experimental results further verify the effectiveness of energy band engineering. As a result, a highly efficient bidirectional catalyst is produced and shows an ultra-small voltage gap of 0.73 V and marvelous Coulombic efficiency of 92.6%, surpassing those of previous catalysts under similar conditions. This work presents an effective catalyst design and affords new insight into the high-performance cathode catalyst materials for Li-CO2 batteries.

Band Structure Engineering and Orbital Orientation Control Constructing Dual Active Sites for Efficient Sulfur Redox Reaction.

The kinetics difference among multistep electrochemical processes leads to the accumulation of soluble polysulfides and thus shuttle effect in lithium-sulfur (Li-S) batteries. While the interaction between catalysts and representative species has been reported, the root of the kinetics difference, interaction change among redox reactions, remains unclear, which significantly impedes the catalysts design for Li-S batteries. Here, this work deciphers the interaction change among electrocatalytic sulfur reactions, using tungsten disulfide (WS2 ) a model system to demonstrate the efficiency of modifying electrocatalytic selectivity via dual-coordination design. Band structure engineering and orbital orientation control are combined to guide the design of WS2 with boron dopants and sulfur vacancies (B-WS2- x ), accurately modulating interaction with lithium and sulfur sites in polysulfide species for relatively higher interaction with short-chain polysulfides. The modified interaction trend is experimentally confirmed by distinguishing the kinetics of each electrochemical reaction step, indicating the effectiveness of the designed strategy. An Ah-level pouch cell with B-WS2- x delivers a gravimetric energy density of up to 417.6 Wh kg-1 with a low electrolyte/sulfur ratio of 3.6 µL mg-1 and negative/positive ratio of 1.2. This work presents a dual-coordination strategy for advancing evolutionarily catalytic activity, offering a rational strategy to develop effective catalysts for practical Li-S batteries.

Regulating the Spin State Configuration in Bimetallic Phosphorus Trisulfides for Promoting Sulfur Redox Kinetics.

Lithium-sulfur (Li-S) batteries suffer from sluggish kinetics due to the poor conductivity of sulfur cathodes and polysulfide shutting. Current studies on sulfur redox catalysis mainly focus on the adsorption and catalytic conversion of lithium polysulfides but ignore the modulation of the electronic structure of the catalysts which involves spin-related charge transfer and orbital interactions. In this work, bimetallic phosphorus trisulfides embedded in Prussian blue analogue-derived nitrogen-doped hollow carbon nanocubes (FeCoPS3/NCs) were elaborately synthesized as a host to reveal the relationship between the catalytic activity and the spin state configuration for Li-S batteries. Orbital spin splitting in FeCoPS3 drives the electronic structure transition from low-spin to high-spin states, generating more unpaired electrons on the 3d orbit. Specifically, the nondegenerate orbitals involved in the high-spin configuration of FeCoPS3 result in the upshift of energy levels, generating more active electronic states. Such tailored electronic structure increases the charge transfer, influences the d-band center, and further modifies the adsorption energy with lithium polysulfides and the potential reaction pathways. Consequently, the cell with FeCoPS3/NC host exhibits an ultralow capacity decay of 0.037% per cycle over 1000 cycles. This study proposed a general strategy for sculpting geometric configurations to enable spin and orbital topology regulation in Li-S battery catalysts.

Uncoordinated chemistry enables highly conductive and stable electrolyte/filler interfaces for solid-state lithium-sulfur batteries.

Composite-polymer-electrolytes (CPEs) embedded with advanced filler materials offer great promise for fast and preferential Li+ conduction. The filler surface chemistry determines the interaction with electrolyte molecules and thus critically regulates the Li+ behaviors at the interfaces. Herein, we probe into the role of electrolyte/filler interfaces (EFI) in CPEs and promote Li+ conduction by introducing an unsaturated coordination Prussian blue analog (UCPBA) filler. Combining scanning transmission X-ray microscope stack imaging studies and first-principle calculations, fast Li+ conduction is revealed only achievable at a chemically stable EFI, which can be established by the unsaturated Co-O coordination in UCPBA to circumvent the side reactions. Moreover, the as-exposed Lewis-acid metal centers in UCPBA efficiently attract the Lewis-base anions of Li salts, which facilitates the Li+ disassociation and enhances its transference number (tLi+). Attributed to these superiorities, the obtained CPEs realize high room-temperature ionic conductivity up to 0.36 mS cm-1 and tLi+ of 0.6, enabling an excellent cyclability of lithium metal electrodes over 4,000 h as well as remarkable capacity retention of 97.6% over 180 cycles at 0.5 C for solid-state lithium-sulfur batteries. This work highlights the crucial role of EFI chemistry in developing highly conductive CPEs and high-performance solid-state batteries.