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All‐solid‐state Li‐metal batteries (ASLMBs) represent a significant breakthrough in the quest to overcome limitations associated with traditional Li‐ion batteries, particularly in energy density and safety aspects. However, widespread implementation is stymied due to a lack of profound understanding of the complex mechano‐electro‐chemical behavior of Li metal in the ASLMBs. Herein, operando neutron imaging and X‐ray computed tomography (XCT) are leveraged to nondestructively visualize Li behaviors within ASLMBs. This approach offers real‐time observations of Li evolutions, both pre‐ and post‐ occurrence of a “soft short”. The coordination of 2D neutron radiography and 3D neutron tomography enables charting of the terrain of Li metal deformation operando. Concurrently, XCT offers a 3D insight into the internal structure of the battery following a “soft short”. Despite the manifestation of a “soft short”, the persistence of Faradaic processes is observed. To study the elusive “soft short” , phase field modeling is coupled with electrochemistry and solid mechanics theory. The research unravels how external pressure curbs dendrite growth, potentially leading to dendrite fractures and thus uncovering the origins of both “soft” and “hard” shorts in ASLMBs. Furthermore, by harnessing finite element modeling, it dive deeper into the mechanical deformation and the fluidity of Li metal.

The utilization of silicon anodes in all‐solid‐state lithium batteries provides good prospects for facilitating high energy density. However, the compatibility of sulfide solid‐state electrolytes (SEs) with Si and carbon is often questioned due to potential decomposition. Herein, operando X‐ray absorption near‐edge structure (XANES) spectroscopy, ex situ scanning electron microscopy (SEM), and ex situ X‐ray nanotomography (XnT) are utilized to investigate the chemistry and structure evolution of nano‐Si composite anodes. Results from XANES demonstrate a partial decomposition of SEs during the first lithiation stage, which is intensified by the presence of carbon. Nevertheless, the performances of first three cycles in Si–SE–C are stable, which proves that the generated media is ionically conductive. XnT and SEM results show that the addition of SEs and carbon improves the structural stability of the anode, with fewer pores and voids. A chemo‐elasto‐plastic model reveals that SEs and carbon buffer the volume expansion of Si, thus enhancing mechanical stability. The balance between the pros and cons of SEs and carbon in enhancing reaction kinetics and structural stability enables the Si composite anode to demonstrate the highest Si utilization with higher specific capacities and a better rate than pure Si and Si composite anodes with only SEs.

Due to its outstanding safety and high energy density, all‐solid‐state lithium‐sulfur batteries (ASLSBs) are considered as a potential future energy storage technology. The electrochemical reaction pathway in ASLSBs with inorganic solid‐state electrolytes is different from Li‐S batteries with liquid electrolytes, but the mechanism remains unclear. By combining operando Raman spectroscopy and ex situ X‐ray absorption spectroscopy, we investigated the reaction mechanism of sulfur (S₈) in ASLSBs. Our results revealed that no Li₂S_8,Li₂S_6,and Li₂S₄were formed, yet Li₂S₂was detected. Furthermore, first‐principles structural calculations were employed to disclose the formation energy of solid state Li₂S_n(1≤n≤8), in which Li₂S₂was a metastable phase, consistent with experimental observations. Meanwhile, partial S₈and Li₂S₂remained at the full lithiation stage, suggesting incomplete reaction due to sluggish reaction kinetics in ASLSBs.

Porous carbon plays a significant role in all‐solid‐state lithium‐sulfur batteries (ASSLSBs) to enhance the electronic conductivity of sulfur. However, the conventional porous carbon used in cell with liquid electrolyte exhibits low efficiency in ASSLSBs because the immobile solid electrolyte (SE) cannot reach sulfur confined in the deep pores. The structure and distribution of pores in carbon highly impact the electrochemical performance of ASSLSBs. Herein, a N‐doped carbon fiber with micropores located only at the surface with an ultrahigh surface area of 1519 m² g^–1is designed. As the porous layer is only on the surface, the sulfur hosted in the pores can effectively contact SE; meanwhile the dense core provides excellent electrical conductivity. Therefore, this structurally designed carbon fiber enhances both electron and ion accessibilities, promotes charge transfer, and thus dramatically improves the reaction kinetic in the ASSLSBs and boosts sulfur utilization. Compared to the vapor grown carbon fibers, the ASSLSBs using PAN‐derived porous carbon fibers exhibit three times enhancement in the initial capacity of 1166 mAh g^–1at C/20. An exceedingly cycling stability of 710 mAh g^–1is maintained after 220 cycles at C/10, and satisfactory rate capability of 889 mAh g^–1at C/2 is achieved.

Current sulfide solid‐state electrolyte (SE) membranes utilized in all‐solid‐state lithium batteries (ASLBs) have a high thickness (0.5–1.0 mm) and low ion conductance (<25 mS), which limit the cell‐level energy and power densities. Based on ethyl cellulose's unique amphipathic molecular structure, superior thermal stability, and excellent binding capability, this work fabricates a freestanding SE membrane with an ultralow thickness of 47 µm. With ethyl cellulose as an effective disperser and a binder, the Li₆PS₅Cl is uniformly dispersed in toluene and possesses superior film formability. In addition, an ultralow areal resistance of 4.32 Ω cm⁻²and a remarkable ion conductance of 291 mS (one order higher than the state‐of‐the‐art sulfide SE membrane) are achieved. The ASLBs assembled with this SE membrane deliver cell‐level high gravimetric and volumetric energy densities of 175 Wh kg⁻¹and 675 Wh L⁻¹, individually.

Sulfide solid‐state electrolytes have remarkable ionic conductivity and low mechanical stiffness but suffer from relatively narrow electrochemical and chemical stability with electrodes. Therefore, pairing sulfide electrolytes with the proper cathode is crucial in developing stable all‐solid‐state Li batteries (ASLBs). Herein, one type of thioantimonate ion conductor, Li_6+xGe_xSb_1−xS₅I, with different compositions is systematically synthesized and studied, among these compositions, an outstanding ionic conductivity of 1.6 mS cm⁻¹is achieved with Li_6.6Ge_0.6Sb_0.4S₅I. To improve the energy density and advance the interface compatibility, a metal sulfide FeS₂cathode with a high theoretical capacity (894 mAh g⁻¹) and excellent compatibility with sulfide electrolytes is coupled with Li_6.6Ge_0.6Sb_0.4S₅I in ASLBs without additional interface engineering. The structural stabilities of Li_6.6Ge_0.6Sb_0.4S₅I and FeS₂during cycling are characterized by operando energy dispersive X‐ray diffraction, which allows rapid collection of structural data without redesigning or disassembling the sealed cells and risking contamination by air. The electrochemical stability is assessed, and a safe operating voltage window ranging from 0.7≈2.4 V (vs. In–Li) is confirmed. Due to the solid confinement in the ASLBs, the Fe⁰aggregation and polysulfides shuttle effects are well addressed. The ASLBs exhibit an outstanding initial capacity of 715 mAh g⁻¹at C/10 and are stable for 220 cycles with a high capacity retention of 84.5% at room temperature.