Salt-in-Salt Reinforced Carbonate Electrolyte for Li Metal Batteries.

The instability of carbonate electrolyte with metallic Li greatly limits its application in high-voltage Li metal batteries. Here, a "salt-in-salt" strategy is applied to boost the LiNO3 solubility in the carbonate electrolyte with Mg(TFSI)2 carrier, which enables the inorganic-rich solid electrolyte interphase (SEI) for excellent Li metal anode performance and also maintains the cathode stability. In the designed electrolyte, both NO3 - and PF6 - anions participate in the Li+ -solvent complexes, thus promoting the formation of inorganic-rich SEI. Our designed electrolyte has achieved a superior Li CE of 99.7 %, enabling the high-loading NCM811||Li (4.5 mAh cm-2 ) full cell with N/P ratio of 1.92 to achieve 84.6 % capacity retention after 200 cycles. The enhancement of LiNO3 solubility by divalent salts is universal, which will also inspire the electrolyte design for other metal batteries.

Enhancing Li+ Transport in NMC811||Graphite Lithium-Ion Batteries at Low Temperatures by Using Low-Polarity-Solvent Electrolytes.

LiNix Coy Mnz O2 (x+y+z=1)||graphite lithium-ion battery (LIB) chemistry promises practical applications. However, its low-temperature (≤ -20 °C) performance is poor because the increased resistance encountered by Li+ transport in and across the bulk electrolytes and the electrolyte/electrode interphases induces capacity loss and battery failures. Though tremendous efforts have been made, there is still no effective way to reduce the charge transfer resistance (Rct ) which dominates low-temperature LIBs performance. Herein, we propose a strategy of using low-polarity-solvent electrolytes which have weak interactions between the solvents and the Li+ to reduce Rct , achieving facile Li+ transport at sub-zero temperatures. The exemplary electrolyte enables LiNi0.8 Mn0.1 Co0.1 O2 ||graphite cells to deliver a capacity of ≈113 mAh g-1 (98 % full-cell capacity) at 25 °C and to remain 82 % of their room-temperature capacity at -20 °C without lithium plating at 1/3C. They also retain 84 % of their capacity at -30 °C and 78 % of their capacity at -40 °C and show stable cycling at 50 °C.

Formation of LiF-rich Cathode-Electrolyte Interphase by Electrolyte Reduction.

The capacity of transition metal oxide cathode for Li-ion batteries can be further enhanced by increasing the charging potential. However, these high voltage cathodes suffer from fast capacity decay because the large volume change of cathode breaks the active materials and cathode-electrolyte interphase (CEI), resulting in electrolyte penetration into broken active materials and continuous side reactions between cathode and electrolytes. Herein, a robust LiF-rich CEI was formed by potentiostatic reduction of fluorinated electrolyte at a low potential of 1.7 V. By taking LiCoO2 as a model cathode, we demonstrate that the LiF-rich CEI maintains the structural integrity and suppresses electrolyte penetration at a high cut-off potential of 4.6 V. The LiCoO2 with LiF-rich CEI exhibited a capacity of 198 mAh g-1 at 0.5C and an enhanced capacity retention of 63.5 % over 400 cycles as compared to the LiF-free LiCoO2 with only 17.4 % of capacity retention.

Interfacial Design for a 4.6 V High-Voltage Single-Crystalline LiCoO2 Cathode.

Single-crystalline cathode materials have attracted intensive interest in offering greater capacity retention than their polycrystalline counterparts by reducing material surfaces and phase boundaries. However, the single-crystalline LiCoO2 suffers severe structural instability and capacity fading when charged to high voltages (4.6 V) due to Co element dissolution and O loss, crack formation, and subsequent electrolyte penetration. Herein, by forming a robust cathode electrolyte interphase (CEI) in an all-fluorinated electrolyte, reversible planar gliding along the (003) plane in a single-crystalline LiCoO2 cathode is protected due to the prevention of element dissolution and electrolyte penetration. The robust CEI effectively controls the performance fading issue of the single-crystalline cathode at a high operating voltage of 4.6 V, providing new insights for improved electrolyte design of high-energy-density battery cathode materials.

Understanding LiI-LiBr Catalyst Activity for Solid State Li2S/S Reactions in an All-Solid-State Lithium Battery.

Li||MoS2 solid-state batteries have higher volumetric energy density and power density than Li||Li2S batteries. However, they suffer from energy and power decay due to the formation of lithium sulfide that has low ionic/electronic conductivity and a strong Li-S bond. Herein, we overcome these challenges by incorporating the catalytic LiI-LiBr compound and carbon black into MoS2. The comprehensive simulations, characterizations, and electrochemical evaluations demonstrated that LiI-LiBr significantly reduces Li+/S2- interaction and increases the ionic conductivity of Li2S, thus enhancing the reaction kinetics and Li2S/S redox reversibility. MoS2@LiI-LiBr@C||Li cells with an areal capacity of 0.87 mAh cm-2 provide a reversible capacity of 816.2 mAh g-1 at 200 mA g-1 and maintain 604.8 mAh g-1 (based on the mass of MoS2) for 100 cycles. At a high areal capacity of 2 mAh cm-2, the battery still delivers reversible capacity of 498 mAh g-1. LiI-LiBr-carbon additive can be broadly applied for all transition-metal sulfide cathodes to enhance the cyclic and rate performance.

Fluorinated Interface Layer with Embedded Zinc Nanoparticles for Stable Lithium-Metal Anodes.

Lithium-metal batteries are promising candidates for the next-generation energy storage devices. However, notorious dendrite growth and an unstable interface between Li and electrolytes severely hamper the practical implantation of Li-metal anodes. Here, a robust solid electrolyte interphase (SEI) layer with flexible organic components on the top and plentiful LiF together with lithiophilic Zn nanoparticles on the bottom is constructed on Li metal based on the spray quenching method. The fluorinated interface layer exhibits remarkable stability to shield Li from the aggressive electrolyte and restrain dendrite growth. Accordingly, the modified Li electrode delivers a stable cycling for over 400 cycles at 3 mA cm-2 in symmetric cells. An improved capacity retention is also achieved in a full cell with a LiFePO4 cathode. This novel design of the artificial SEI layer offers rational guidance for the further development of high-energy-density lithium-metal batteries.

Design of a Solid Electrolyte Interphase for Aqueous Zn Batteries.

Aqueous Zn batteries are challenged by water decomposition and dendrite growth due to the absence of a dense Zn-ion conductive solid electrolyte interphase (SEI) to inhibit the hydrogen evolution reaction (HER). Here, we design a low-concentration aqueous Zn(OTF)2 -Zn(NO3 )2 electrolyte to in situ form a robust inorganic ZnF2 -Zn5 (CO3 )2 (OH)6 -organic bilayer SEI, where the inorganic inner layer promotes Zn-ion diffusion while the organic outer layer suppresses water penetration. We found that the insulating Zn5 (OH)8 (NO3 )2 ⋅2 H2 O layer is first formed on the Zn anode surface by the self-terminated chemical reaction of NO3 - with Zn2+ and OH- generated via HER, and then it transforms into Zn-ion conducting Zn5 (CO3 )2 (OH)6 , which in turn promotes the formation of ZnF2 as the inner layer. The organic-dominated outer layer is formed by the reduction of OTF- . The in situ formed SEI enables a high Coulombic efficiency (CE) of 99.8 % for 200 h in Ti∥Zn cells, and a high energy density (168 Wh kg-1 ) with 96.5 % retention for 700 cycles in Zn∥MnO2 cells with a low Zn/MnO2 capacity ratio of 2:1.

High-Energy Aqueous Sodium-Ion Batteries.

Water-in-salt electrolytes (WISE) have largely widened the electrochemical stability window (ESW) of aqueous electrolytes by formation of passivating solid electrolyte interphase (SEI) on anode and also absorption of the hydrophobic anion-rich double layer on cathode. However, the cathodic limiting potential of WISE is still too high for most high-capacity anodes in aqueous sodium-ion batteries (ASIBs), and the cost of WISE is also too high for practical application. Herein, a low-cost 19 m (m: mol kg-1 ) bi-salts WISE with a wide ESW of 2.8 V was designed, where the low-cost 17 m NaClO4 extends the anodic limiting potential to 4.4 V, while the fluorine-containing salt (2 m NaOTF) extends the cathodic limiting potential to 1.6 V by forming the NaF-Na2 O-NaOH SEI on anode. The 19 m NaClO4 -NaOTF-H2 O electrolyte enables a 1.75 V Na3 V2 (PO4 )3 ∥Na3 V2 (PO4 )3 full cell to deliver an appreciable energy density of 70 Wh kg-1 at 1 C with a capacity retention of 87.5 % after 100 cycles.

An Inorganic-Rich Solid Electrolyte Interphase for Advanced Lithium-Metal Batteries in Carbonate Electrolytes.

In carbonate electrolytes, the organic-inorganic solid electrolyte interphase (SEI) formed on the Li-metal anode surface is strongly bonded to Li and experiences the same volume change as Li, thus it undergoes continuous cracking/reformation during plating/stripping cycles. Here, an inorganic-rich SEI is designed on a Li-metal surface to reduce its bonding energy with Li metal by dissolving 4m concentrated LiNO3 in dimethyl sulfoxide (DMSO) as an additive for a fluoroethylene-carbonate (FEC)-based electrolyte. Due to the aggregate structure of NO3 - ions and their participation in the primary Li+ solvation sheath, abundant Li2 O, Li3 N, and LiNx Oy grains are formed in the resulting SEI, in addition to the uniform LiF distribution from the reduction of PF6 - ions. The weak bonding of the SEI (high interface energy) to Li can effectively promote Li diffusion along the SEI/Li interface and prevent Li dendrite penetration into the SEI. As a result, our designed carbonate electrolyte enables a Li anode to achieve a high Li plating/stripping Coulombic efficiency of 99.55 % (1 mA cm-2 , 1.0 mAh cm-2 ) and the electrolyte also enables a Li||LiNi0.8 Co0.1 Mn0.1 O2 (NMC811) full cell (2.5 mAh cm-2 ) to retain 75 % of its initial capacity after 200 cycles with an outstanding CE of 99.83 %.

Lithium/Sulfide All-Solid-State Batteries using Sulfide Electrolytes.

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.

Potassium Hexafluorophosphate Additive Enables Stable Lithium-Sulfur Batteries.

Uncontrollable dendrite growth and low Coulombic efficiency are the two main obstacles that hinder the application of rechargeable Li metal batteries. Here, an optimized amount of potassium hexafluorophosphate (KPF6, 0.01 M) has been added into the 2 M LiTFSI/ether-based electrolyte to improve the cycling stability of lithium-sulfur (Li-S) batteries. Due to the synergistic effect of self-healing electrostatic shield effect from K+ cations and the LiF-rich solid electrolyte interphases derived from PF6- anions, the KPF6 additive enables a high Li Coulombic efficiency of 98.8% (1 mA cm-2 of 1 mAh cm-2). The symmetrical Li cell can achieve a stable cycling performance for over 200 cycles under a high Li utilization up to 33.3%. Meanwhile, the polysulfide shuttle has been restrained due to the higher concentration of the LiTFSI in the electrolyte. As a result, the assembled Li-S full cell displays excellent capacity retention with only 0.25% decay per cycle in the final electrolyte. Our work offers a smart approach to improve both the anode and cathode performance by the electrolyte modification of rechargeable Li-S batteries.

Coupling a Sponge Metal Fibers Skeleton with In Situ Surface Engineering to Achieve Advanced Electrodes for Flexible Lithium-Sulfur Batteries.

Lithium-sulfur batteries (LSBs) are regarded as promising next-generation energy storage systems, however, the uncontrollable dendrite formation and serious polysulfide shuttling severely hinder their commercial success. Herein, a powerful 3D sponge nickel (SN) skeleton plus in situ surface engineering strategy, to address these issues synergistically, is reported, and a high-performance flexible LSB device is constructed. Specifically, the rationally designed spray-quenched lithium metal on the SN matrix (solid electrolyte interface (SEI)@Li/SN), as dendrite inhibitor, combines the merits of the 3D lithiophilic SN skeleton and the in situ formed SEI layer derived from the spray-quenching process, and thereby exhibits a steady overpotential within 75 mV for 1500 h at 5 mA cm-2 /10 mA h cm-2 . Meanwhile, in situ surface sulfurization of the SN skeleton hybridizing with the carbon/sulfur composite (SC@Ni3 S2 /SN) serves as efficient lithium polysulfide adsorbent to catalyze the overall reaction kinetics. COMSOL Multiphysics simulations and density functional theory calculations are further conducted to explore the underlying mechanisms. As a proof of concept, the well-designed SEI@Li/SN||SC@Ni3 S2 /SN full cell shows excellent electrochemical performance with a negative/positive ratio in capacity of ≈2 and capacity retention of 99.82% at 1 C under mechanical deformation. The novel design principles of these materials and electrodes successfully shed new light on the development of flexible LSBs.

Rational Designed Mixed-Conductive Sulfur Cathodes for All-Solid-State Lithium Batteries.

All-solid-state lithium-sulfur batteries (ASSLSBs) hold great promise for safe and high-energy-density energy storage. However, developing high-performance sulfur cathodes has been proven difficult due to low electronic and ionic conductivities and large volume change of sulfur during charge and discharge. Here, we reported an approach to synthesize sulfur cathodes with a mixed electronic and ionic conductivity by infiltrating a solution consisting of Li3PS4 (LPS) solid electrolyte and S active material into a mesoporous carbon (CMK-3). This approach leads to a uniform dispersion of amorphous Li3PS7 (L3PS) catholyte in an electronically conductive carbon matrix, enabling high and balanced electronic/ionic conductivities in the cathode composite. The inherent porous structure of CMK-3 also helps to accommodate the strain/stress generated during the expansion and shrinkage of the active material. In sulfide-based all-solid-state batteries with Li metal as the anode, this cathode composite delivered a high capacity of 1025 mAh g-1 after 50 cycles at 60 °C at 1/8C. This work highlights the important role of high and balanced electronic and ionic conductivities in developing high-performance sulfur cathodes for ASSLSBs.

High Interfacial-Energy Interphase Promoting Safe Lithium Metal Batteries.

Engineering a stable solid electrolyte interphase (SEI) is critical for suppression of lithium dendrites. However, the formation of a desired SEI by formulating electrolyte composition is very difficult due to complex electrochemical reduction reactions. Here, instead of trial-and-error of electrolyte composition, we design a Li-11 wt % Sr alloy anode to form a SrF2-rich SEI in fluorinated electrolytes. Density functional theory (DFT) calculation and experimental characterization demonstrate that a SrF2-rich SEI has a large interfacial energy with Li metal and a high mechanical strength, which can effectively suppress the Li dendrite growth by simultaneously promoting the lateral growth of deposited Li metal and the SEI stability. The Li-Sr/Cu cells in 2 M LiFSI-DME show an outstanding Li plating/stripping Coulombic efficiency of 99.42% at 1 mA cm-2 with a capacity of 1 mAh cm-2 and 98.95% at 3 mA cm-2 with a capacity of 2 mAh cm-2, respectively. The symmetric Li-Sr/Li-Sr cells also achieve a stable electrochemical performance of 180 cycles at an extremely high current density of 30 mA cm-2 with a capacity of 1 mAh cm-2. When paired with LiFePO4 (LFP) and LiNi0.8Co0.1Mn0.1O2 (NCM811) cathodes, Li-Sr/LFP cells in 2 M LiFSI-DME electrolytes and Li-Sr/NMC811 cells in 1 M LiPF6 in FEC:FEMC:HFE electrolytes also maintain excellent capacity retention. Designing SEIs by regulating Li-metal anode composition opens up a new and rational avenue to suppress Li dendrites.

Bi-containing Electrolyte Enables Robust and Li Ion Conductive Solid Electrolyte Interphase for Advanced Lithium Metal Anodes.

The notorious lithium dendrite growth, causing the safety concern, hinders the practical application of high-capacity Li metal anodes for rechargeable batteries. Here, a robust and highly ionic conductive solid electrolyte interphase (SEI) layer to protect Li metal anode is in-situ constructed by introducing trace additive of tetrapotassium heptaiodobismuthate (K4BiI7) into electrolyte. The K4BiI7-added electrolyte enables Li metal anode to display a stable cycling for over 600 cycles at 1.0 mA cm-2/1.0 mAh cm-2 and over 400 cycles at 5.0 mA cm-2/5.0 mAh cm-2. In situ optical microscopy observations also conform the suppression of Li dendrites at high current density. Moreover, the in-situ SEI layer modified Li anode exhibits an average Coulombic efficiency of 99.57% and less Li dendrite growth. The Li-S full sells with the modified electrolyte also show improved electrochemical performance. This research provides a cost-efficient method to achieve a highly ionic conductive and stable SEI layer toward advanced Li metal anodes.

In Situ Solid Electrolyte Interphase from Spray Quenching on Molten Li: A New Way to Construct High-Performance Lithium-Metal Anodes.

Uncontrollable growth of Li dendrites and low utilization of active Li severely hinder its practical application. Construction of an artificial solid electrolyte interphase (SEI) on Li is demonstrated as one of the most effective ways to circumvent the above problems. Herein, a novel spray quenching method is developed in situ to fabricate an organic-inorganic composite SEI on Li metal. By spray quenching molten Li in a modified ether-based solution, a homogeneous and dense SEI consisting of organic matrix embedded with inorganic LiF and Li3 N nanocrystallines (denoted as OIFN) is constructed on Li metal. Arising from high ionic conductivity and strong mechanical stability, the OIFN can not only effectively minimize the corrosion reaction of Li, but also greatly suppresses the dendrite growth. Accordingly, the OIFN-Li anode presents prominent electrochemical performance with an enhanced Coulombic efficiency of 98.15% for 200 cycles and a small hysteresis of <450 mV even at ultrahigh current density up to 10 mA cm-2 . More importantly, during the full cell test with limited Li source, a high utilization of Li up to 40.5% is achieved for the OIFN-Li anode. The work provides a brand-new route to fabricate advanced SEI on alkali metal for high-performance alkali-metal batteries.

Exploring Self-Healing Liquid Na-K Alloy for Dendrite-Free Electrochemical Energy Storage.

The development of high-performance dendrite-free liquid-metal anodes at room temperature is of great importance for the advancement of alkali metal batteries. Herein an intriguing self-healing liquid dendrite-free Na-K alloy, fabricated by a facile room-temperature alloying process, aiming for application in potassium-ion batteries is reported. Through extensive investigation, its self-healing characteristics are rooted upon a thin solid K2 O layer (KOL) coated on the liquid Na-K alloy. The KOL not only acts as a protective layer to prevent the Na-K alloy from making contact with the electrolyte, but also greatly improves the wetting capability and adhesion between the liquid alloy and the carbon matrix (e.g., carbon fiber cloth (CFC)) to form a stable interface. Consequently, the as-prepared CFC/KOL@Na-K alloy anode exhibits prominent electrochemical performance with smaller hysteresis (less than 0.3 V beyond 140 cycles at 0.4 mA cm-2 ), better capacity retention, and higher Coulombic efficiency than the CFC/bare Na-K alloy counterpart. When coupled with a potassium Prussian blue (PPB) cathode, the full cell manifests higher capability retention and improved cycling stability. This research deepens the understanding of self-healing Na-K alloys and opens a new way to achieve high-performance dendrite-free alkali metal anodes for application in rechargeable batteries.

[Study on relationship between operation timing and clinical prognosis of cases with Bell palsy].

OBJECTIVE: To study on relationship between diverse handling time following onset and clinical prognosis of cases with Bell palsy. METHOD: Two hundred and sixteen cases with Bell palsy, who were admitted in our department between Jun. 2006 and Dec. 2009, were collected and divided into 6 groups according to disease time: 1-2 months, > 2 - 3 months, > 3 - 4 months, > 4 - 5 months, > 5 - 6 months, and > 6 months. Cases in all groups received subtotal course decompression of facial nerve and other compound treatment, and the relationship between handling timing and clinical prognosis were compared. RESULT: It was found that the difference of prognosis and handling timing was statistically significant, after comparison between all groups with Facial Grading Standards (H-B) as the standard to assess prognosis. CONCLUSION: Clinical prognosis of cases with Bell palsy was related to alternative handling time, and subtotal course decompression of facial nerve was recommended to be performed as early as possible for those cases who were irresponsive after conservative treatment for one month.

Correlation analysis of prognostic and pathological features of patients with chronic sinusitis and nasal polyps following endoscopic surgery.

The aim of this study was to evaluate the therapeutic value of pathological indicators to predict the efficacy of endoscopic sinus surgery (ESS) in patients with chronic rhinosinusitis (CRS) with nasal polyps. A total of 53 patients with CRS with nasal polyps, who had undergone endoscopic surgery at least one year before, were surveyed for their clinical symptoms. Surgical specimen biopsies were consulted and related pathological indicators were measured. The association between the main symptoms of CRS with nasal polyps following ESS and pathological indicators were statistically analyzed. The main symptoms of patients with CRS with nasal polyps following ESS were nasal congestion, thick nasal discharge, rhinorrhea or sneezing. Goblet cells are associated with the symptoms of sneezing and thick nasal discharge, pathological gland formation is associated with dizziness, and the degree of tissue edema is associated with post-nasal discharge (P<0.05). Pathological indicators aid the prediction of the efficacy of nasal ESS in patients with CRS with nasal polyps.