Showing papers on "Ionic conductivity published in 2021"
TL;DR: The required properties of the sulfide electrolytes, such as the electrochemical stabilities of the electrolytes and the compatible electrode/electrolyte interfaces are highlighted, and the opportunities for sulfide-based ASSLBs are discussed.
Abstract: All-solid-state lithium batteries (ASSLBs) are considered as the next generation electrochemical energy storage devices because of their high safety and energy density, simple packaging, and wide operable temperature range. The critical component in ASSLBs is the solid-state electrolyte. Among all solid-state electrolytes, the sulfide electrolytes have the highest ionic conductivity and favorable interface compatibility with sulfur-based cathodes. The ionic conductivity of sulfide electrolytes is comparable with or even higher than that of the commercial organic liquid electrolytes. However, several critical challenges for sulfide electrolytes still remain to be solved, including their narrow electrochemical stability window, the unstable interface between the electrolyte and the electrodes, as well as lithium dendrite formation in the electrolytes. Herein, the emerging sulfide electrolytes and preparation methods are reviewed. In particular, the required properties of the sulfide electrolytes, such as the electrochemical stabilities of the electrolytes and the compatible electrode/electrolyte interfaces are highlighted. The opportunities for sulfide-based ASSLBs are also discussed.
293 citations
TL;DR: In this article, the authors proposed a method for achieving high performance solid polymer ion conductors by engineering of molecular channels, which enables fast transport of Li+ ions along the polymer chains.
Abstract: Although solid-state lithium (Li)-metal batteries promise both high energy density and safety, existing solid ion conductors fail to satisfy the rigorous requirements of battery operations. Inorganic ion conductors allow fast ion transport, but their rigid and brittle nature prevents good interfacial contact with electrodes. Conversely, polymer ion conductors that are Li-metal-stable usually provide better interfacial compatibility and mechanical tolerance, but typically suffer from inferior ionic conductivity owing to the coupling of the ion transport with the motion of the polymer chains1–3. Here we report a general strategy for achieving high-performance solid polymer ion conductors by engineering of molecular channels. Through the coordination of copper ions (Cu2+) with one-dimensional cellulose nanofibrils, we show that the opening of molecular channels within the normally ion-insulating cellulose enables rapid transport of Li+ ions along the polymer chains. In addition to high Li+ conductivity (1.5 × 10−3 siemens per centimetre at room temperature along the molecular chain direction), the Cu2+-coordinated cellulose ion conductor also exhibits a high transference number (0.78, compared with 0.2–0.5 in other polymers2) and a wide window of electrochemical stability (0–4.5 volts) that can accommodate both the Li-metal anode and high-voltage cathodes. This one-dimensional ion conductor also allows ion percolation in thick LiFePO4 solid-state cathodes for application in batteries with a high energy density. Furthermore, we have verified the universality of this molecular-channel engineering approach with other polymers and cations, achieving similarly high conductivities, with implications that could go beyond safe, high-performance solid-state batteries. By coordinating copper ions with the oxygen-containing groups of cellulose nanofibrils, the molecular spacing in the nanofibrils is increased, allowing fast transport of lithium ions and offering hopes for solid-state batteries.
172 citations
157 citations
TL;DR: A poly(vinylidene fluoride-co-hexafluoropropylene)-based polymer-in-salt solid electrolyte (PISSE) with high room-temperature ionic conductivity presents high performance close to that with liquid electrolyte, which also exhibits robust flexibility and brilliant safety under abuse tests.
Abstract: Solid-state lithium batteries (SSLBs) are promising owing to enhanced safety and high energy density but plagued by the relatively low ionic conductivity of solid-state electrolytes and large electrolyte-electrode interfacial resistance. Herein, we design a poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP)-based polymer-in-salt solid electrolyte (PISSE) with high room-temperature ionic conductivity (1.24×10-4 S cm-1 ) and construct a model integrated TiO2 /Li SSLB with 3D fully infiltration of solid electrolyte. With forming aggregated ion clusters, unique ionic channels are generated in the PISSE, providing much faster Li+ transport than common polymer electrolytes. The integrated device achieves maximized interfacial contact and electrochemical and mechanical stability, with performance close to liquid electrolyte. A pouch cell made of 2 SSLB units in series shows high voltage plateau (3.7 V) and volumetric energy density comparable to many commercial thin-film batteries.
146 citations
137 citations
TL;DR: In this article, Mg(ClO4)2 is demonstrated to be an effective additive in the poly(ethylene oxide) (PEO)-based composite electrolyte to regulate Li+ ion transport and manipulate the Li metal/electrolyte interfacial performance.
Abstract: The application of flexible, robust, and low-cost solid polymer electrolytes in next-generation all-solid-state lithium metal batteries has been hindered by the low room-temperature ionic conductivity of these electrolytes and the small critical current density of the batteries. Both issues stem from the low mobility of Li+ ions in the polymer and the fast lithium dendrite growth at the Li metal/electrolyte interface. Herein, Mg(ClO4)2 is demonstrated to be an effective additive in the poly(ethylene oxide) (PEO)-based composite electrolyte to regulate Li+ ion transport and manipulate the Li metal/electrolyte interfacial performance. By combining experimental and computational studies, we show that Mg2+ ions are immobile in a PEO host due to coordination with ether oxygen and anions of lithium salts, which enhances the mobility of Li+ ions; more importantly, an in-situ formed Li+-conducting Li2MgCl4/LiF interfacial layer homogenizes the Li+ flux during plating and increases the critical current density up to a record 2 mA cm-2. Each of these factors contributes to the assembly of competitive all-solid-state Li/Li, LiFePO4/Li, and LiNi0.8Mn0.1Co0.1O2/Li cells, demonstrating the importance of surface chemistry and interfacial engineering in the design of all-solid-state Li metal batteries for high-current-density applications.
132 citations
TL;DR: Owing to high ionic conductivity and good oxidation stability, halide‐based solid electrolytes regain interest for application in solid‐state batteries but cannot be used against Li, but may be promising candidates as cathode electrolytes.
Abstract: Owing to high ionic conductivity and good oxidation stability, halide-based solid electrolytes regain interest for application in solid-state batteries. While stability at the cathode interface seems to be given, the stability against the lithium metal anode has not been explored yet. Herein, the formation of a reaction layer between Li3 InCl6 (Li3 YCl6 ) and lithium is studied by sputter deposition of lithium metal and subsequent in situ X-ray photoelectron spectroscopy as well as by impedance spectroscopy. The interface is thermodynamically unstable and results in a continuously growing interphase resistance. Additionally, the interface between Li3 InCl6 and Li6 PS5 Cl is characterized by impedance spectroscopy to discern whether a combined use as cathode electrolyte and separator electrolyte, respectively, might enable long-term stable and low impedance operation. In fact, oxidation stable halide-based lithium superionic conductors cannot be used against Li, but may be promising candidates as cathode electrolytes.
113 citations
112 citations
TL;DR: In this paper, the effects of the molecular structure of ionic liquids on ionic conductivity, Li+ ion transference number, electrochemical stability window, and lithium metal anode/electrolyte interface, as well as the application of the ionic liquid in Li-high voltage cathode batteries, Li-O2 batteries and Li-S batteries are discussed.
99 citations
TL;DR: In this article, a uniform conjugated polymer nanocoating formed on the surface of ceramic oxide particles builds pathways for Li+ conduction between adjacent particles in the unsintered ceramics.
Abstract: Li+-conductive ceramic oxide electrolytes, such as garnet-structured Li7La3Zr2O12, have been considered as promising candidates for realizing the next-generation solid-state Li-metal batteries with high energy density. Practically, the ceramic pellets sintered at elevated temperatures are often provided with high stiffness yet low fracture toughness, making them too brittle for the manufacture of thin-film electrolytes and strain-involved operation of solid-state batteries. The ceramic powder, though provided with ductility, does not yield satisfactorily high Li+ conductivity due to poor ion conduction at the boundaries of ceramic particles. Here we show, with solid-state nuclear magnetic resonance, that a uniform conjugated polymer nanocoating formed on the surface of ceramic oxide particles builds pathways for Li+ conduction between adjacent particles in the unsintered ceramics. A tape-casted thin-film electrolyte (thickness: <10 μm), prepared from the polymer-coated ceramic particles, exhibits sufficient ionic conductivity, a high Li+ transference number, and a broad electrochemical window to enable stable cycling of symmetric Li/Li cells and all-solid-state rechargeable Li-metal cells.
99 citations
TL;DR: In this paper, an eutectic 7.6m ZnCl2 aqueous electrolyte with 0.05m SnCl2 additive was used to overcome Zn dendritic growth and low-temperature performance.
Abstract: Aqueous Zn batteries promise high energy density but suffer from Zn dendritic growth and poor low-temperature performance. Here, we overcome both challenges by using an eutectic 7.6 m ZnCl2 aqueous electrolyte with 0.05 m SnCl2 additive, which in situ forms a zincophilic/zincophobic Sn/Zn5 (OH)8 Cl2 ⋅H2 O bilayer interphase and enables low temperature operation. Zincophilic Sn decreases Zn plating/stripping overpotential and promotes uniform Zn plating, while zincophobic Zn5 (OH)8 Cl2 ⋅H2 O top-layer suppresses Zn dendrite growth. The eutectic electrolyte has a high ionic conductivity of ≈0.8 mS cm-1 even at -70 °C due to the distortion of hydrogen bond network by solvated Zn2+ and Cl- . The eutectic electrolyte enables Zn∥Ti half-cell a high Coulombic efficiency (CE) of >99.7 % for 200 cycles and Zn∥Zn cell steady charge/discharge for 500 h with a low overpotential of 8 mV at 3 mA cm-2 . Practically, Zn∥VOPO4 batteries maintain >95 % capacity with a CE of >99.9 % for 200 cycles at -50 °C, and retain ≈30 % capacity at -70 °C of that at 20 °C.
TL;DR: In this paper, a 30 μm sulfide SE membrane with ultrahigh room temperature conductivity of 8.4 mS cm-1 is realized by mechanized manufacturing technologies using highly conductive Li5.4PS4.4Cl1.6 SE powder.
Abstract: All-solid-state lithium batteries (ASSLBs) employing Li-metal anode, sulfide solid electrolyte (SE) can deliver high energy density with high safety. The thick SE separator and its low ionic conductivity are two major challenges. Herein, a 30 μm sulfide SE membrane with ultrahigh room temperature conductivity of 8.4 mS cm-1 is realized by mechanized manufacturing technologies using highly conductive Li5.4PS4.4Cl1.6 SE powder. Moreover, a 400 nm magnetron sputtered Al2O3 interlayer is introduced into the SE/Li interface to improve the anodic stability, which suppresses the short circuit in Li/Li symmetric cells. Combining these merits, ASSLBs with LiNi0.5Co0.2Mn0.3O2 as the cathode exhibit a stable cyclic performance, delivering a discharge specific capacity of 135.3 mAh g-1 (1.4 mAh cm-2) with a retention of 80.2% after 150 cycles and an average Coulombic efficiency over 99.5%. The high ionic conductivity SE membrane and interface design principle show promising feasible strategies for practical high performance ASSLBs.
TL;DR: In this paper, a chemically stable ceramic-polymer-anchored solvent composite electrolyte with high ionic conductivity was proposed, which enabled the solid-state NCM811/Li batteries to stably cycle for 1500 times.
Abstract: The severe interfacial side reactions of polymer electrolyte with LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode and lithium (Li) metal anode become huge challenge to restrict ultra-stable cycling performance of solid-state NCM811/Li batteries. Herein, we propose a chemically stable ceramic-polymer-anchored solvent composite electrolyte with high ionic conductivity of 6.0×10-4 S cm-1, which enables the solid-state NCM811/Li batteries to stably cycle for 1500 times. The Li1.4Al0.4Ti1.6(PO4)3 nanowires (LNs) can tightly anchor the essential N, N-dimethylformamide (DMF) in poly(vinylidene fluoride) (PVDF), which greatly enhances its electrochemical stability and suppresses the side reactions. We clearly identify the ceramic-polymer-liquid multiple ion transport mechanism of the LNs-PVDF-DMF composite electrolyte by tracking the 6Li and 7Li substitution behavior via solid-state nuclear magnetic resonance, which endow homogeneous and efficient ions flux and uniform lithium depositions. The stable interface chemistry and efficient ion transport of LNs-PVDF-DMF contribute to superior performances of the solid-state batteries at wide temperature range of -20~60 oC.
TL;DR: Li10GeP2S12 (LGPS) has a high ionic conductivity and compatibility with sulfur cathodes; however, the instability of LGPS against Li and Li dendrite growth still remains unsolved.
Abstract: Li10GeP2S12 (LGPS) has a high ionic conductivity and compatibility with sulfur cathodes; however, the instability of LGPS against Li and Li dendrite growth still remains unsolved Here, we solved t
TL;DR: Li2ZrCl6 as discussed by the authors is a cost-effective and humidity-tolerant chloride solid electrolyte, which has a room-temperature all-solid-state cell with a stable specific capacity of about 150 mAh g/1 for 200 cycles at 200mA g/g/1.
Abstract: Li-ion-conducting chloride solid electrolytes receive considerable attention due to their physicochemical characteristics such as high ionic conductivity, deformability and oxidative stability. However, the raw materials are expensive, and large-scale use of this class of inorganic superionic conductors seems unlikely. Here, a cost-effective chloride solid electrolyte, Li2ZrCl6, is reported. Its raw materials are several orders of magnitude cheaper than those for the state-of-the-art chloride solid electrolytes, but high ionic conductivity (0.81 mS cm–1 at room temperature), deformability, and compatibility with 4V-class cathodes are still simultaneously achieved in Li2ZrCl6. Moreover, Li2ZrCl6 demonstrates a humidity tolerance with no sign of moisture uptake or conductivity degradation after exposure to an atmosphere with 5% relative humidity. By combining Li2ZrCl6 with the Li-In anode and the single-crystal LiNi0.8Mn0.1Co0.1O2 cathode, we report a room-temperature all-solid-state cell with a stable specific capacity of about 150 mAh g–1 for 200 cycles at 200 mA g–1. Stable inorganic solid electrolytes are instrumental in developing high-voltage Li metal batteries. Here, the authors present the synthesis and electrochemical energy storage properties of a cost-effective and humidity-tolerant chloride solid electrolyte.
TL;DR: In this article, the potential of chitosan as a biopolymer laden with NaI salt is explored and applied as solid polymer electrolyte for dye sensitised solar cells.
TL;DR: Li2S6-integrated composite electrolyte has excellent cyclability and a high critical current density of 0.9 mA cm-2 at 40 °C.
Abstract: The integration of Li2 S6 within a poly(ethylene oxide) (PEO)-based polymer electrolyte is demonstrated to improve the polymer electrolyte's ionic conductivity because the strong interplay between O2- (PEO) and Li+ from Li2 S6 reduces the crystalline volume within the PEO. The Li/electrolyte interface is stabilized by the in situ formation of an ultra-thin Li2 S/Li2 S2 layer via the reaction between Li2 S6 and lithium metal, which increases the ionic transport at the interface and suppresses lithium dendrite growth. A symmetric Li/Li cell with the Li2 S6 -integrated composite electrolyte has excellent cyclability and a high critical current density of 0.9 mA cm-2 at 40 °C. Impressive electrochemical performance is demonstrated with all-solid-state Li/LiFePO4 and high-voltage Li/LiNi0.8 Mn0.1 Co0.1 O2 cells at 40 °C.
TL;DR: In this article, a relaxor ferroelectric (RFE) polymer of poly(vinylidene fluoride-co-trifluoroethylene,co-chlorotrifluorethylene) [P(VDF-TrFE-CTFE)] is investigated as a matrix of SPEs.
Abstract: The extremely low room-temperature ionic conductivity of solid-state polymer electrolytes (SPEs) ranging from 10−7 to 10−5 S cm−1 seriously restricts their practical application in solid-state lithium metal batteries (LMBs). Herein, a unique relaxor ferroelectric (RFE) polymer of poly(vinylidene fluoride-co-trifluoroethylene-co-chlorotrifluoroethylene) [P(VDF-TrFE-CTFE)] is first investigated as a matrix of SPEs. We find that the P(VDF-TrFE-CTFE) with an ultrahigh dielectric constant (er) of 44 presents a stronger solvation ability towards lithium ions, which promotes the dissociation of LiN(SO2CF3)2 to form more free charge carriers and enhances their mobility compared to the conventional PVDF with a low er of 9. The P(VDF-TrFE-CTFE) based SPEs show a much higher ionic conductivity of 3.10 × 10−4 S cm−1 at 25 °C and lower activation energy (0.26 eV) than PVDF based SPEs (1.77 × 10−5 S cm−1 and 0.49 eV). The PVDF blended with the P(VDF-TrFE-CTFE) or dielectric fillers such as BaTiO3 further confirm that the hybrid electrolytes with a larger er show a higher ionic conductivity. In addition, very tight interfaces of P(VDF-TrFE-CTFE) based SPEs with both the cathode and Li metal anode are constructed to ensure a stable interfacial resistance during cycling. The LiFePO4/Li and LiNi0.8Co0.1Mo0.1O2/Li batteries using P(VDF-TrFE-CTFE) based SPEs present a stable cycling performance at 25 °C. This work proposes a new strategy and opens a new research area to construct SPEs with high ionic conductivity by greatly increasing the er of polymers.
TL;DR: In this article, the interfacial issues between sulfide electrolytes and electrodes have been the main challenges for their applications in all-solid-state batteries (ASSBs), and strategies for solving these issues and stabilizing the electrode-electrolyte interfaces have been discussed.
TL;DR: In this paper, the sandwiched hybrid solid electrolytes were precisely tailored and successfully fabricated to assemble into all-solid-state lithium-ion batteries, which were systematically evaluated on microstructure, morphology, thermal stability and electrochemical performance.
TL;DR: In this paper, a flexible polymer/garnet solid electrolyte is prepared with poly(ethylene oxide), poly(vinylidene fluoride), Li6.75La3Zr1.75Ta0.25O12, lithium bis(trifluoromethanesulfonyl)imide and oxalate, which exhibits an ionic conductivity of 2.0 × 10−4 S cm−1 at 55 °C, improved mechanical property, wide electrochemical window (4.8 V vs. Li/Li+), enhanced thermal st
TL;DR: Electrochemical analysis and theoretical modeling demonstrate that the interface layer provides fast ion transport path and plays a key role in achieving high and stable ionic conductivity for PEOm -Li21 Si5 composite solid electrolyte.
Abstract: To achieve high ionic conductivity for solid electrolyte, an artificial Li-rich interface layer of about 60 nm thick has been constructed in polymer-based poly(ethylene oxide)-lithium bis(trifluoromethanesulfonyl)imide composite solid electrolyte (briefly noted as PEOm ) by adding Li-based alloys. As revealed by high-resolution transmission electron microscopy and electron energy loss spectroscopy, an artificial interface layer of amorphous feature is created around the Li-based alloy particles with the gradient distribution of Li across it. Electrochemical analysis and theoretical modeling demonstrate that the interface layer provides fast ion transport path and plays a key role in achieving high and stable ionic conductivity for PEOm -Li21 Si5 composite solid electrolyte. The PEOm -5%Li21 Si5 composite electrolyte exhibits an ionic conductivity of 3.9 × 10-5 S cm-1 at 30 °C and 5.6 × 10-4 S cm-1 at 45 °C. The LiFePO4 | PEOm -5%Li21 Si5 | Li all-solid-state batteries could maintain a stable capacity of 129.2 mA h g-1 at 0.2 C and 30 °C after 100 cycles, and 111.3 mA h g-1 after 200 cycles at 0.5 C and 45 °C, demonstrating excellent cycling stability and high-rate capability.
TL;DR: In this paper, a cross-linked poly(biphenyl piperidine)s (PAP-OH-8%) membrane is proposed to solve the trade-off problem between ionic conductivity and stability of AEMs.
TL;DR: Li et al. as discussed by the authors synthesized a PEO-LLTO framework solid electrolyte (PLLF electrolyte) with vertically bicontinuous phase, which exhibited a remarkable ionic conductivity of 2.04 × 10−4 S cm−1.
TL;DR: In this article, a polyethylene oxide (PEO) based polymer-ceramic hybrid solid electrolyte was introduced to improve the performance of solid polymer electrolytes (SPEs).
Abstract: Compared with traditional lead-acid batteries, nickel–cadmium batteries and nickel-hydrogen batteries, lithium-ion batteries (LIBs) are much more environmentally friendly and much higher energy density. Besides, LIBs own the characteristics of no memory effect, high charging and discharging rate, long cycle life and high energy conversion rate. Therefore, LIBs have been widely considered as the most promising power source for mobile devices. Commonly used LIBs contain carbonate based liquid electrolytes. Such electrolytes own high ionic conductivity and excellent wetting ability. However, the use of highly flammable and volatile organic solvents in them may lead to problems like leakage, thermo runaway and parasitic interface reactions, which limit their application. Solid polymer electrolytes (SPEs) can solve these problems, while they also bring new challenges such as poor interfacial contact with electrodes and low ionic conductivity at room temperature. Many approaches have been tried to solve these problems. This article is divided into three parts to introduce polyethylene oxide (PEO) based polymer-ceramic hybrid solid electrolyte, which is one of the most efficient way to improve the performance of SPEs. The first part focuses on polymer-lithium salt (LiX) matrices, including their ionic conduction mechanism and impact factors for their ionic conductivity. In the second part, the influence of both active and passive ceramic fillers on SPEs are reviewed. In the third part, composite SPEs’ preparation methods, including solvent casting and thermocompression, are introduced and compared. Finally, we propose five key points on how to make composite SPEs with high ionic conductivity for reference.
TL;DR: In this paper, a free-standing covalent organic framework membrane (TpPa-SO 3 H) with excellent stability and mechanical properties was designed for high salinity gradient energy conversion.
Abstract: Both high ionic conductivity and selectivity of a membrane are required for efficient salinity gradient energy conversion. An efficient method to improve energy conversion is to align ionic transport along the membrane thickness to address low ionic conductivity in traditional membranes used for energy harvesting. Here, we fabricate a free-standing covalent organic frameworks membrane (TpPa-SO 3 H) with excellent stability and mechanical properties. This membrane with one-dimensional nanochannels and high charge density demonstrates high ionic conductivity and selectivity. Its power density can reach up to 5.9 W/m 2 by mixing artificial seawater and river water. Based on our results, we propose that the high energy conversion is attributed to the high ion conductivity through aligned one-dimensional nanochannels and high ion selectivity via the size of the nanochannel at ~1 nm in the membrane. This study paves the way for designing covalent organic framework membranes for high salinity gradient energy conversion.
TL;DR: Li et al. as discussed by the authors proposed a glass-ceramic Li3.2 P0.8 Sn 0.2 S4 superionic conductor to achieve high ionic conductivity, excellent air-stability and good Li metal compatibility.
Abstract: The development of all-solid-state Li metal batteries (ASSLMBs) has attracted significant attention due to their potential to maximize energy density and improved safety compared to the conventional liquid-electrolyte-based Li-ion batteries. However, it is very challenging to fabricate an ideal solid-state electrolyte (SSE) that simultaneously possesses high ionic conductivity, excellent air-stability, and good Li metal compatibility. Herein, a new glass-ceramic Li3.2 P0.8 Sn0.2 S4 (gc-Li3.2 P0.8 Sn0.2 S4 ) SSE is synthesized to satisfy the aforementioned requirements, enabling high-performance ASSLMBs at room temperature (RT). Compared with the conventional Li3 PS4 glass-ceramics, the present gc-Li3.2 P0.8 Sn0.2 S4 SSE with 12% amorphous content has an enlarged unit cell and a high Li+ ion concentration, which leads to 6.2-times higher ionic conductivity (1.21 × 10-3 S cm-1 at RT) after a simple cold sintering process. The (P/Sn)S4 tetrahedron inside the gc-Li3.2 P0.8 Sn0.2 S4 SSE is verified to show a strong resistance toward reaction with H2 O in 5%-humidity air, demonstrating excellent air-stability. Moreover, the gc-Li3.2 P0.8 Sn0.2 S4 SSE triggers the formation of Li-Sn alloys at the Li/SSE interface, serving as an essential component to stabilize the interface and deliver good electrochemical performance in both symmetric and full cells. The discovery of this gc-Li3.2 P0.8 Sn0.2 S4 superionic conductor enriches the choice of advanced SSEs and accelerates the commercialization of ASSLMBs.
TL;DR: In this article, a rational designed intermolecular interaction in composite electrolytes that utilizing contaminants as reaction initiator to generate Li + conducting ether oligomers, which further emerge as molecular crosslinkers between inorganic fillers and polymer matrix, creating dense and homogeneous interfacial Li + immigration channels in the composite electrolyte.
Abstract: Solid-state lithium metal batteries built with composite polymer electrolytes using cubic garnets as active fillers are particularly attractive owing to their high energy density, easy manufacturing and inherent safety. However, the uncontrollable formation of intractable contaminant on garnet surface usually aggravates poor interfacial contact with polymer matrix and deteriorates Li + pathways. Here we report a rational designed intermolecular interaction in composite electrolytes that utilizing contaminants as reaction initiator to generate Li + conducting ether oligomers, which further emerge as molecular cross-linkers between inorganic fillers and polymer matrix, creating dense and homogeneous interfacial Li + immigration channels in the composite electrolytes. The delicate design results in a remarkable ionic conductivity of 1.43×10 -3 S cm -1 and an unprecedented 1000 cycles with 90% capacity retention at room temperature is achieved for the assembled solid-state batteries.
TL;DR: In this paper, a one-step gas-phase synthesis method for sulfide solid electrolytes (SEs) with oxide raw materials in ambient air, completely getting rid of the glovebox and thus making large-scale production possible, is reported.
Abstract: Sulfide solid electrolytes (SEs) are recognized as one of the most promising candidates for all-solid-state batteries (ASSBs), due to their superior ionic conductivity and remarkable ductility. However, poor air stability, complex synthesis process, low yield, and high production cost obstruct the large-scale application of sulfide SEs. Herein, a one-step gas-phase synthesis method for sulfide SEs with oxide raw materials in ambient air, completely getting rid of the glovebox and thus making large-scale production possible, is reported. By adjusting substituted elements and concentrations, the ionic conductivity of Li4- x Sn1- x Mx S4 can reach 2.45 mS cm-1 , which represents the highest value among all reported moist-air-stable and recoverable lithium-ion sulfide SEs reported. Furthermore, ASSBs with air/water-exposed and moderate-temperature-treated Li3.875 Sn0.875 As0.125 S4 even maintains superior performances with the highest reversible capacity (188.4 mAh g-1 ) and the longest cycle life (210 cycles), which also breaks the record. Therefore, it may become one of the most critical breakthroughs during the development of sulfide ASSBs toward its practical application and commercialization.