Lithium (Li) metal anodes have regained intensive interest in recent years due to the ever-increasing demand for next-generation high energy battery technologies. Li metal, unfortunately, suffers from poor cycling stability and low efficiency as well as from the formation of dangerous Li dendrites, raising safety concerns. Utilizing solid-state electrolytes (SSEs) to prevent Li dendrite growth provides a promising approach to tackle the challenge. However, recent studies indicate that Li dendrites easily form at high current densities, which calls for full investigation of the fundamental mechanisms of Li dendrite formation within SSEs. Herein, the origin and evolution of Li dendrite growth through SSEs have been studied and compared by using Li 6.1 Ga 0.3 La 3 Zr 2 O 12 (LLZO) and NASICON-type Li 2 O–Al 2 O 3 –P 2 O 5 –TiO 2 –GeO 2 (LATP) pellets as the separators. We discover that a solid electrolyte interphase (SEI)-like interfacial layer between Li and SSE plays a critical role in alleviating the growth of dendritic Li, providing new insights into the interface between SSE and Li metal to enable future all solid-state batteries.
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Recent Advances in Conduction Mechanisms, Synthesis Methods, and Improvement Strategies for Li 1+ x Al x Ti 2− x (PO 4 ) 3 Solid Electrolyte for All‐Solid‐State Lithium Batteries
With the increasing use of Li batteries for storage, their safety issues and energy densities are attracting considerable attention. Recently, replacing liquid organic electrolytes with solid‐state electrolytes (SSE) has been hailed as the key to developing safe and high‐energy‐density Li batteries. In particular, Li1+
- Award ID(s):
- 2124775
- NSF-PAR ID:
- 10393615
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Energy Materials
- Volume:
- 13
- Issue:
- 4
- ISSN:
- 1614-6832
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract All‐solid‐state lithium‐sulfur batteries (ASSLSBs) based on sulfide solid‐state electrolytes (SSEs) provide prospectively high energy density and safety. However, the low conductivity and sluggish reaction kinetic of sulfur cathode limit its commercialization. The use of carbon additives can improve the electrical conductivity but accelerates the decomposition of SSEs. Herein, a highly conductive carbon fiber decorated with hybrid 1T/2H MoS2nanosheets is designed. The high chemical and electrochemical compatibility among MoS2and sulfide SSE can greatly improve the stability of the cathode and therefore maintain pristine interfaces. The uniform distribution of electrical‐conductive metallic 1T MoS2on carbon fiber benefits the electron transfer between carbon and sulfur. Meanwhile, the layered structure of MoS2can be intercalated by a large amount of Li ions facilitating ionic and electronic conductivity. In consequence, the charge transfer and reaction kinetics are greatly enhanced, and the decomposition of SSEs is successfully relieved. As a result, the ASSLSB delivers an ultrahigh initial discharge and charge capacity of 1456 and 1470 mAh g−1at 0.05 C individually with ultrahigh coulombic efficiency and maintains high capacity retention of 78% after 220 cycles. The batteries also obtain a remarkable rate performance of 1069 mAh g−1at 1 C.
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All-solid-state batteries (ASSBs) have garnered increasing attention due to the enhanced safety, featuring nonflammable solid electrolytes as well as the potential to achieve high energy density. 1 The advancement of the ASSBs is expected to provide, arguably, the most straightforward path towards practical, high-energy, and rechargeable batteries based on metallic anodes. 1 However, the sluggish ion transmission at the cathode-electrolyte (solid/solid) interface would result in the high resistant at the contact and limit the practical implementation of these all solid-state materials in real world batteries. 2 Several methods were suggested to enhance the kinetic condition of the ion migration between the cathode and the solid electrolyte (SE). 3 A composite strategy that mixes active materials and SEs for the cathode is a general way to decrease the ion transmission barrier at the cathode-electrolyte interface. 3 The active material concentration in the cathode is reduced as much as the SE portion increases by which the energy density of the ASSB is restricted. In addition, the mixing approach generally accompanies lattice mismatches between the cathode active materials and the SE, thus providing only limited improvements, which is imputed by random contacts between the cathode active materials and the SE during the mixing process. Implementing high-pressure for the electrode and electrolyte of ASSB in the assembling process has been verified is a but effective way to boost the ion transmission ability between the cathode active materials and the SE by decreasing the grain boundary impedance. Whereas the short-circuit of the battery would be induced by the mechanical deformation of the electrolyte under high pressure. 4 Herein, we demonstrate a novel way to address the ion transmission problem at the cathode-electrolyte interface in ASSBs. Starting from the cathode configuration, the finite element method (FEM) was employed to evaluate the current concentration and the distribution of the space charge layer at the cathode-electrolyte interface. Hierarchical three-dimensional (HTD) structures are found to have a higher Li + transfer number (t Li+ ), fewer free anions, and the weaker space-charge layer at the cathode-electrolyte interface in the resulting FEM simulation. To take advantage of the HTD structure, stereolithography is adopted as a manufacturing technique and single-crystalline Ni-rich (SCN) materials are selected as the active materials. Next, the manufactured HTD cathode is sintered at 600 °C in an N 2 atmosphere for the carbonization of the resin, which induces sufficient electronic conductivity for the cathode. Then, the gel-like Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 (LATP) precursor is synthesized and filled into the voids of the HTD structure cathode sufficiently. And the filled HTD structure cathodes are sintered at 900 °C to achieve the crystallization of the LATP gel. Scanning transmission electron microscopy (STEM) is used to unveil the morphology of the cathode-electrolyte interface between the sintered HTD cathode and the in-situ generated electrolyte (LATP). A transient phase has been found generated at the interface and matched with both lattices of the SCN and the SE, accelerating the transmission of the Li-ions, which is further verified by density functional theory calculations. In addition, Electron Energy Loss Spectroscopy demonstrates the preserved interface between HTD cathode and SEs. Atomic force microscopy is employed to measure the potential image of the cross-sectional interface by the peak force tapping mode. The average potential of modified samples is lower than the sample that mix SCN and SEs simply in the 2D planar structure, which confirms a weakened space charge layer by the enhanced contact capability as well as the ion transmission ability. To see if the demonstrated method is universally applicable, LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) is selected as the cathode active material and manufactured in the same way as the SCN. The HTD cathode based on NCM811 exhibits higher electrochemical performance compared with the reference sample based on the 2D planar mixing-type cathode. We believe such a demonstrated universal strategy provides a new guideline to engineer the cathode/electrolyte interface by revolutionizing electrode structures that can be applicable to all-solid-state batteries. Figure 1. Schematic of comparing of traditional 2D planar cathode and HTD cathode in ASSB Tikekar, M. D. , et al. , Nature Energy (2016) 1 (9), 16114 Banerjee, A. , et al. , Chem Rev (2020) 120 (14), 6878 Chen, R. , et al. , Chem Rev (2020) 120 (14), 6820 Cheng, X. , et al. , Advanced Energy Materials (2018) 8 (7) Figure 1more » « less
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Abstract Solid‐state electrolytes (SEs) with high anodic (oxidation) stability are essential for achieving all‐solid‐state Li‐ion batteries (ASSLIBs) operating at high voltages. Until now, halide‐based SEs have been one of the most promising candidates due to their compatibility with cathodes and high ionic conductivity. However, the developed chloride and bromide SEs still show limited electrochemical stability that is inadequate for ultrahigh voltage operations. Herein, this challenge is addressed by designing a dual‐halogen Li‐ion conductor: Li3InCl4.8F1.2. F is demonstrated to selectively occupy a specific lattice site in a solid superionic conductor (Li3InCl6) to form a new dual‐halogen solid electrolyte (DHSE). With the incorporation of F, the Li3InCl4.8F1.2DHSE becomes dense and maintains a room‐temperature ionic conductivity over 10−4S cm−1. Moreover, the Li3InCl4.8F1.2DHSE exhibits a practical anodic limit over 6 V (vs Li/Li+), which can enable high‐voltage ASSLIBs with decent cycling. Spectroscopic, computational, and electrochemical characterizations are combined to identify a rich F‐containing passivating cathode‐electrolyte interface (CEI) generated in situ, thus expanding the electrochemical window of Li3InCl4.8F1.2DHSE and preventing the detrimental interfacial reactions at the cathode. This work provides a new design strategy for the fast Li‐ion conductors with high oxidation stability and shows great potential to high‐voltage ASSLIBs.
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Abstract 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, Li6+
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