Interphase Engineering Enhanced Electro-chemical Stability of Prelithiated Anode.

Prelithiation is an essential technology to compensate for the initial lithium loss of lithium-ion batteries due to the formation of solid electrolyte interphase (SEI) and irreversible structure change. However, the prelithiated materials/electrodes become more reactive with air and electrolyte resulting in unwanted side reactions and contaminations, which makes it difficult for the practical application of prelithiation technology. To address this problem, herein, interphase engineering through a simple solution treatment after chemical prelithiation is proposed to protect the prelithiated electrode. The used solutions are carefully selected, and the composition and nanostructure of the as-formed artificial SEIs are revealed by cryogenic electron microscopy and X-ray photoelectron spectroscopy. The electrochemical evaluation demonstrates the unique merits of this artificial SEI, especially for the fluorinated interphase, which not only enhances the interfacial ion transport but also increases the tolerance of the prelithiated electrode to the air. The treated graphite electrode shows an initial Coulombic efficiency of 129.4%, a high capacity of 170 mAh g-1 at 3 C, and negligible capacity decay after 200 cycles at 1 C. These findings not only provide a facile, universal, and controllable method to construct an artificial SEI but also enlighten the upgrade of battery fabrication and the alternative use of advanced electrolytes.

Air-Stable Na3.5C6O6 as a Sodium Compensation Additive in Cathode of Na-Ion Batteries.

Sodium-ion battery (SIB) is a candidate for the stationary energy storage systems because of the low cost and high abundance of sodium. However, the energy density and lifespan of SIBs suffer severely from the irreversible consumption of the Na-ions for the formation of the solid electrolyte interphase (SEI) layer and other side reactions on the electrodes. Here, Na3.5C6O6 is proposed as an air-stable high-efficiency sacrificial additive in the cathode to compensate for the lost sodium. It is characteristic of low desodiation (oxidation) potential (3.4-3.6 V vs. Na+/Na) and high irreversible desodiation capacity (theoretically 378 mAh g-1). The feasibility of using Na3.5C6O6 as a sodium compensation additive is verified with the improved electrochemical performances of a Na2/3Ni1/3Mn1/3Ti1/3O2ǀǀhard carbon cells and cells using other cathode materials. In addition, the structure of Na3.5C6O6 and its desodiation path are also clarified on the basis of comprehensive physical characterizations and the density functional theory (DFT) calculations. This additive decomposes completely to supply abundant Na ions during the initial charge without leaving any electrochemically inert species in the cathode. Its decomposition product C6O6 enters the carbonate electrolyte without bringing any detectable negative effects. These findings open a new avenue for elevating the energy density and/or prolonging the lifetime of the high-energy-density secondary batteries.

Polymer Competitive Solvation Reduced Propylene Carbonate Cointercalation in a Graphitic Anode.

Polymer electrolytes have been studied as an alternative to organic liquid electrolytes but suffer from low ionic conductivity. Propylene carbonate (PC) proves to be an interesting solvent but is incompatible with graphitic anodes due to its cointercalation effect. In this work, adding poly(ethylene oxide) (PEO) into a PC-based electrolyte can alter the solvation structure as well as transform the solution into a polymer electrolyte with high ionic conductivity. By spectroscopic techniques and calculations, we demonstrate that PEO can compete with PC in solvating the Li+ ions, reducing the Li+-PC bond strength, and making it easier for PC to be desolvated. Due to the unique solvation structure, PC-cointercalation-induced graphite exfoliation is inhibited, and the reduction stability of the electrolyte is improved. This work will extend the applications of the PC-based electrolytes, deepen the understandings of the solvation structure, and spur designs of advanced electrolytes.

Experimental Corroboration of Lithium Orthothioborate Superionic Conductor by Systematic Elemental Manipulation.

The Li superionic conductor Li3BS3 has been theoretically predicted as an ideal solid electrolyte (SE) due to its low Li+ migration energy barrier and high ionic conductivity. However, the experimentally synthesized Li3BS3 has a 104 times lower ionic conductivity. Herein, we investigate the effect of a series of cation and anion substitutions in Li3BS3 SE on its ionic conductivity, including Li3-xM0.05BS3 (M = Cu, Zn, Sn, P, W, x = 0.05, 0.1, 0.2, 0.25), Li3-yBS2.95X0.05 (X = O, Cl, Br, I, y = 0.05, 0.1) and Li2.75-xP0.05BS3-xClx (x = 0.05, 0.1, 0.15, 0.2, 0.4, 0.6). Amorphous ionic conductor Li2.55P0.05BS2.8Cl0.2 has a high ion conductivity of 0.52 mS cm-1 at room temperature with an activation energy of 0.41 eV. The electrochemical performance of all-solid-state batteries with Li2.55P0.05BS2.8Cl0.2 SEs show stable cycling with a discharge capacity retention of >97% after 200 cycles at 1C under 55 °C.

Highly Efficient Spatially-Temporally Synchronized Construction of Robust Li3 PO4 -rich Solid-Electrolyte Interphases in Aqueous Li-ion Batteries.

Solid electrolyte interphase (SEI) makes the electrochemical window of aqueous electrolytes beyond the thermodynamics limitation of water. However, achieving the energetic and robust SEI is more challenging in aqueous electrolytes because the low SEI formation efficiency (SFE) only contributed from anion-reduced products, and the low SEI formation quality (SFQ) negatively impacted by the hydrogen evolution, resulting in a high Li loss to compensate for SEI formation. Herein, we propose a highly efficient strategy to construct Spatially-Temporally Synchronized (STS) robust SEI by the involvement of synergistic chemical precipitation-electrochemical reduction. In this case, a robust Li3 PO4 -rich SEI enables intelligent inherent growth at the active site of the hydrogen by the chemical capture of the OH- stemmed from the HER to trigger the ionization balance of dihydrogen phosphate (H2 PO4 - ) shift to insoluble solid Li3 PO4 . It is worth highlighting that the Li3 PO4 formation does not extra-consume lithium derived from the cathode but makes good use of the product of HER (OH- ), prompting the SEI to achieve 100 % SFE and pushing the HER potential into -1.8 V vs. Ag/AgCl. This energetic and robust SEI offers a new way to achieve anion/concentration-independent interfacial chemistry for the aqueous batteries.

Transforming a Primary Li-SOCl2 Battery into a High-Power Rechargeable System via Molecular Catalysis.

Li-SOCl2 batteries possess ultrahigh energy densities and superior safety features at a wide range of operating temperatures. However, the Li-SOCl2 battery system suffers from poor reversibility due to the sluggish kinetics of SOCl2 reduction during discharging and the oxidation of the insulating discharge products during charging. To achieve a high-power rechargeable Li-SOCl2 battery, herein we introduce the molecular catalyst I2 into the electrolyte to tailor the charging and discharging reaction pathways. The as-assembled rechargeable cell exhibits superior power density, sustaining an ultrahigh current density of 100 mA cm-2 during discharging and delivering a reversible capacity of 1 mAh cm-2 for 200 cycles at a current density of 2 mA cm-2 and 6 mAh cm-2 for 50 cycles at a current density of 5 mA cm-2. Our results reveal the molecular catalyst-mediated reaction mechanisms that fundamentally alter the rate-determining steps of discharging and charging in Li-SOCl2 batteries and highlight the viability of transforming a primary high-energy battery into a high-power rechargeable system, which has great potential to meet the ever-increasing demand of energy-storage systems.

Expandable Li Percolation Network: The Effects of Site Distortion in Cation-Disordered Rock-Salt Cathode Material.

Cation-disordered rock-salt (DRX) materials receive intensive attention as a new class of cathode candidates for high-capacity lithium-ion batteries (LIBs). Unlike traditional layered cathode materials, DRX materials have a three-dimensional (3D) percolation network for Li+ transportation. The disordered structure poses a grand challenge to a thorough understanding of the percolation network due to its multiscale complexity. In this work, we introduce the large supercell modeling for DRX material Li1.16Ti0.37Ni0.37Nb0.10O2 (LTNNO) via the reverse Monte Carlo (RMC) method combined with neutron total scattering. Through a quantitative statistical analysis of the material's local atomic environment, we experimentally verified the existence of short-range ordering (SRO) and uncovered an element-dependent behavior of transition metal (TM) site distortion. A displacement from the original octahedral site for Ti4+ cations is pervasive throughout the DRX lattice. Density functional theory (DFT) calculations revealed that site distortions quantified by the centroid offsets could alter the migration barrier for Li+ diffusion through the tetrahedral channels, which can expand the previously proposed theoretical percolating network of Li. The estimated accessible Li content is highly consistent with the observed charging capacity. The newly developed characterization method here uncovers the expandable nature of the Li percolation network in DRX materials, which may provide valuable guidelines for the design of superior DRX materials.

Tailoring Electronic Structure to Achieve Maximum Utilization of Transition Metal Redox for High-Entropy Na Layered Oxide Cathodes.

Charge compensation from cationic and anionic redox couples accompanying Na+ (de)intercalation in layered oxide cathodes contributes to high specific capacity. However, the engagement level of different redox couples remains unclear and their relationship with Na+ content is less studied. Here we discover that it is possible to take full advantage of the high-voltage transition metal (TM) redox reaction through low-valence cation substitution to tailor the electronic structure, which involves an increased ratio of Na+ content to available charge transfer number of TMs. Taking NaxCu0.11Ni0.11Fe0.3Mn0.48O2 as the example, the Li+ substitution increases the ratio to facilitate the high-voltage TM redox activity, and further F-ion substitution decreases the covalency of the TM-O bond to relieve structural changes. As a consequence, the final high-entropy Na0.95Li0.07Cu0.11Ni0.11Fe0.3Mn0.41O1.97F0.03 cathode demonstrates ∼29% capacity increase contributed by the high-voltage TMs and exhibits excellent long-term cycling stability due to the improved structural reversibility. This work provides a paradigm for the design of high-energy-density electrodes by simultaneous electronic and crystal structure modulation.

Unraveling the Reaction Mystery of Li and Na with Dry Air.

Li and Na metals with high energy density are promising in application in rechargeable batteries but suffer from degradation in the ambient atmosphere. The phenomenon that in terms of kinetics, Li is stable but Na is unstable in dry air has not been fully understood. Here, we use in situ environmental transmission electron microscopy combined with theoretical simulations and reveal that the different stabilities in dry air for Li and Na are reflected by the formation of compact Li2O layers on Li metal, while porous and rough Na2O/Na2O2 layers on Na metal are a consequence of the different thermodynamic and kinetics in O2. It is shown that a preformed carbonate layer can change the kinetics of Na toward an anticorrosive behavior. Our study provides a deeper understanding of the often-overlooked chemical reactions with environmental gases and enhances the electrochemical performance of Li and Na by controlling interfacial stability.

In Situ Detecting Thermal Stability of Solid Electrolyte Interphase (SEI).

Solid electrolyte interphase (SEI) plays an important role in regulating the interfacial ion transfer and safety of Lithium-ion batteries (LIBs). It is unstable and readily decomposed releasing much heat and gases and thus triggering thermal runaway. Herein, in situ heating X-ray photoelectron spectroscopy is applied to uncover the inherent thermal decomposition process of the SEI. The evolution of the composition, nanostructure, and the released gases are further probed by cryogenic transmission electron microscopy, and gas chromatography. The results show that the organic components of SEI are readily decomposed even at room temperature, releasing some flammable gases (e.g., H2 , CO, C2 H4 , etc.). The residual SEI after heat treatment is rich in inorganic components (e.g., Li2 O, LiF, and Li2 CO3 ), provides a nanostructure model for a beneficial SEI with enhanced stability. This work deepens the understanding of SEI intrinsic thermal stability, reveals its underlying relationship with the thermal runaway of LIBs, and enlightens to enhance the safety of LIBs by achieving inorganics-rich SEI.

Short- and long-term outcomes of Roux-en-Y and Billroth II with Braun reconstruction in total laparoscopic distal gastrectomy: a retrospective analysis.

BACKGROUND: The controversy surrounding Roux-en-Y (R-Y) and Billroth II with Braun (BII + B) reconstruction as an anti-bile reflux procedure after distal gastrectomy has persisted. Recent studies have demonstrated their efficacy, but the long-term outcomes and postoperative quality of life (QoL) among patients have yet to be evaluated. Therefore, we compared the short-term and long-term outcomes of the two procedures as well as QoL. METHODS: The clinical data of 151 patients who underwent total laparoscopic distal gastrectomy (TLDG) at the Gastrointestinal Surgery Department of the Second Hospital of Fujian Medical University from January 2016 to December 2019 were retrospectively analyzed. Of these, 57 cases with Roux-en-Y procedure (R-Y group) and 94 cases with Billroth II with Braun procedure were included (BII + B group). Operative and postoperative conditions, early and late complications, endoscopic outcomes at year 1 and year 3 after surgery, nutritional indicators, and quality of life scores at year 3 postoperatively were compared between the two groups. RESULTS: The R-Y group recorded a significantly longer operative time (194.65 ± 21.52 vs. 183.88 ± 18.02 min) and anastomotic time (36.96 ± 2.43 vs. 27.97 ± 3.74 min) compared to the BII + B group (p < 0.05). However, no other significant differences were observed in terms of perioperative variables, including blood loss (p > 0.05). Both groups showed comparable rates of early and late complications. Endoscopic findings indicated similar food residuals at years 1 and 3 post-surgery for both groups. The R-Y group had a lower occurrence of residual gastritis and bile reflux at year 1 and year 3 after surgery, with a statistically significant difference (p < 0.001). Reflux esophagitis was not significantly different between the R-Y and BII + B groups in year 1 after surgery (p = 0.820), but the R-Y group had a lower incidence than the BII + B group in year 3 after surgery (p = 0.023). Nutritional outcomes at 3 years after surgery did not differ significantly between the two groups (p > 0.05). Quality of life scores measured by the QLQ-C30 scale were not significantly different between the two groups. However, on the QLQ-STO22 scale, the reflux score was significantly lower in the R-Y group than in the BII + B group (0 [0, 0] vs. 5.56 [0, 11.11]) (p = 0.003). The rest of the scores were not significantly different (p > 0.05). CONCLUSION: Both R-Y and B II + B reconstructions are equally safe and efficient for TLDG. Nevertheless, the R-Y reconstruction reduces the incidence of residual gastritis, bile reflux, and reflux esophagitis, as well as postoperative reflux symptoms, and provides a better quality of life for patients. R-Y reconstruction is superior to BII + B reconstruction for TLDG.

Approaching Practically Accessible Solid-State Batteries: Stability Issues Related to Solid Electrolytes and Interfaces.

Solid-state batteries have been attracting wide attention for next generation energy storage devices due to the probability to realize higher energy density and superior safety performance compared with the state-of-the-art lithium ion batteries. However, there are still intimidating challenges for developing low cost and industrially scalable solid-state batteries with high energy density and stable cycling life for large-scale energy storage and electric vehicle applications. This review presents an overview on the scientific challenges, fundamental mechanisms, and design strategies for solid-state batteries, specifically focusing on the stability issues of solid-state electrolytes and the associated interfaces with both cathode and anode electrodes. First, we give a brief overview on the history of solid-state battery technologies, followed by introduction and discussion on different types of solid-state electrolytes. Then, the associated stability issues, from phenomena to fundamental understandings, are intensively discussed, including chemical, electrochemical, mechanical, and thermal stability issues; effective optimization strategies are also summarized. State-of-the-art characterization techniques and in situ and operando measurement methods deployed and developed to study the aforementioned issues are summarized as well. Following the obtained insights, perspectives are given in the end on how to design practically accessible solid-state batteries in the future.

Mobile Ions in Composite Solids.

Fast ion conduction in solid-state matrices constitutes the foundation for a wide spectrum of electrochemical systems that use solid electrolytes (SEs), examples of which include solid-state batteries (SSBs), solid oxide fuel cells (SOFCs), and diversified gas sensors. Mixing different solid conductors to form composite solid electrolytes (CSEs) introduces unique opportunities for SEs to possess exceptional overall performance far superior to their individual parental solids, thanks to the abundant chemistry and physics at the new interfaces thus created. In this review, we provide a comprehensive and in-depth examination of the development and understanding of CSEs for SSBs, with special focus on their physiochemical properties and mechanisms of ion transport therein. The origin of the enhanced ionic conductivity in CSEs relative to their single-phase parents is discussed in the context of defect chemistry and interfacial reactions. The models/theories for ion movement in diversified composites are critically reviewed to interrogate a general strategy to the design of novel CSEs, while properties such as mechanical strength and electrochemical stability are discussed in view of their perspective applications in lithium metal batteries and beyond. As an integral component of understanding how ions interact with their composite environments, characterization techniques to probe the ion transport kinetics across different temporal and spatial time scales are also summarized.

Medium- to long-term outcomes of vaginally assisted laparoscopic sacrocolpopexy in the treatment of stage III-IV pelvic organ prolapse.

BACKGROUND: Vaginally assisted laparoscopic sacrocolpopexy (VALS) refers to the placement of synthetic meshes through the vagina in addition to traditional laparoscopic sacrocolpopexy. In this study, we aimed to investigate the medium- to long-term efficacy and safety of VALS for treating stage III-IV pelvic organ prolapse (POP). METHODS: The study was designed as a case series at a single center. Patients with stage III-IV POP in our hospital from January 2010 to December 2018 were included. Perioperative parameters, objective and subjective outcomes, and complications were assessed. RESULTS: A total of 106 patients completed the follow-up and were included in our study. Within a median follow-up duration of 35.4 months, the objective cure ratio of VALS reached 92.45% (98/106), and the subjective success rate was 99.06% (105/106). Patients reported significant improvements in subjective symptoms. In eight patients suffering anatomic prolapse recurrence, two posterior POP cases were treated by posterior pelvic reconstruction surgery, while six anterior POP cases did not need surgical therapies. The reoperation rate was 1.89% (2/106). No intraoperative complications occurred. Three patients (2.83%) had postoperative fever, and one (0.94%) had wound infection during hospitalization. Six patients (5.66%) had mesh exposure on the vaginal wall, and de novo urinary incontinence occurred in two patients (1.89%) during the follow-up period. CONCLUSION: VALS is an effective and safe surgical method for treating severe POP. Therefore, VALS should be considered in the treatment of severe POP due to its favorable subjective and objective outcomes, relatively low rate of infection and acceptable rate of mesh exposure.

Anionic Effect on Enhancing the Stability of a Solid Electrolyte Interphase Film for Lithium Deposition on Graphite.

Graphitic carbons and their lithium composites have been utilized as lithium deposition substrates to address issues such as the huge volume variation and dendritic growth of lithium. However, new problems have appeared, including the severe exfoliation of the graphite particles and the instability of the solid electrolyte interphase (SEI) film when metallic lithium is plated on the graphite. Herein, we enhance the stability of the SEI film on the graphite substrate for lithium deposition in an electrolyte of lithium bis(fluorosulfonyl)imide (LiFSI) dissolved in the carbonate solvent, thereby improving the lithium plating/stripping cycle on it. The FSI- anion was found to be responsible for the formation of a compact SEI film under the lithium plating potential and could protect the graphite substrate. These findings refresh the understanding of the SEI stability and provide a suggestion on the design and development of electrolytes for the lithium batteries.

Competitive Solvation Enhanced Stability of Lithium Metal Anode in Dual-Salt Electrolyte.

The development of lithium metal batteries is hindered by the low Coulombic efficiency and poor cycling stability of the metallic lithium. The introduction of consumptive LiNO3 as an additive can improve the cycling stability, but its low solubility in the carbonate electrolytes makes this strategy impractical for long-term cycling. Herein we propose LiNO3 as a cosalt in the LiPF6-LiNO3 dual-salt electrolyte to enhance the cycling stability of lithium plating/stripping. Competitions among the components and the resultant substitution of NO3- for PF6- in the solvation shell facilitate the formation of a Li3N-rich solid electrolyte interphase (SEI) film and suppress the LiPF6 decomposition. The highly Li+ conductive and stable SEI film effectively tailors the lithium nucleation, suppresses the formation of lithium dendrites, and improves the cycling performance. The competitive solvation has profound importance for the design of a complex electrolyte to meet the multiple requirements of secondary lithium batteries.

DDKA-QKDN: Dynamic On-Demand Key Allocation Scheme for Quantum Internet of Things Secured by QKD Network.

In the era of the interconnection of all things, the security of the Internet of Things (IoT) has become a new challenge. The theoretical basis of unconditional security can be guaranteed by using quantum keys, which can form a QKD network-based security protection system of quantum Internet of Things (Q-IoT). However, due to the low generation rate of the quantum keys, the lack of a reasonable key allocation scheme can reduce the overall service quality. Therefore, this paper proposes a dynamic on-demand key allocation scheme, named DDKA-QKDN, to better meet the requirements of lightweight in the application scenario of Q-IoT and make efficient use of quantum key resources. Taking the two processes of the quantum key pool (QKP) key allocation and the QKP key supplement into account, the scheme dynamically allocates quantum keys and supplements the QKP on demand, which quantitatively weighs the quantum key quantity and security requirements of key requests in proportion. The simulation results show that the system efficiency and the ability of QKP to provide key request services are significantly improved by this scheme.

An Image Encryption Scheme Based on Logistic Quantum Chaos.

This paper proposes an image encryption scheme based on logistic quantum chaos. Firstly, we use compressive sensing algorithms to compress plaintext images and quantum logistic and Hadamard matrix to generate the measurement matrix. Secondly, the improved flexible representation of the quantum images (FRQI) encoding method is utilized for encoding the compressed image. The pixel value scrambling operation of the encoded image is realized by rotating the qubit around the axis. Finally, the quantum pixel is encoded into the pixel value in the classical computer, and the bit-level diffusion and scrambling are performed on it. Numerical analysis and simulation results show that our proposed scheme has the large keyspace and strong key sensitivity. The proposed scheme can also resist standard attack methods such as differential attacks and statistical analysis.

APR-QKDN: A Quantum Key Distribution Network Routing Scheme Based on Application Priority Ranking.

As the foundation of quantum secure communication, the quantum key distribution (QKD) network is impossible to construct by using the operation mechanism of traditional networks. In the meantime, most of the existing QKD network routing schemes do not fit some specific quantum key practicality scenarios. Aiming at the special scenario of high concurrency and large differences in application requirements, we propose a new quantum key distribution network routing scheme based on application priority ranking (APR-QKDN). Firstly, the proposed APR-QKDN scheme comprehensively uses the application's priority, the total amount of key requirements, and the key update rate for prioritizing a large number of concurrent requests. The resource utilization and service efficiency of the network are improved by adjusting the processing order of requests. Secondly, the queuing strategy of the request comprehensively considers the current network resource situation. This means the same key request may adopt different evaluation strategies based on different network resource environments. Finally, the performance of the APR-QKDN routing scheme is compared with the existing schemes through simulation experiments. The results show that the success rate of application key requests of the APR-QKDN routing scheme is improved by at least 5% in the scenario of high concurrency.

Insights into Lithium and Sodium Storage in Porous Carbon.

The lithium and sodium storage behavior of porous carbon remains controversial, though it shows excellent cycling stability and rate performances. This Letter discloses the insertion, adsorption, and filling properties of porous carbon. 7Li nuclear magnetic resonance (NMR) spectroscopy recognized inserted and adsorbed lithium in this porous carbon but did not observe any other forms of lithium above 0.0 V vs. Li+/Li. In addition, although lithium insertion mainly takes place at low potentials, adsorption was found to be the main form of lithium storage throughout the investigated potential range. Such a storage feature is responsible for the excellent rate performance and high specific capacity of porous carbon. Raman spectroscopy further demonstrated the structural reversibility of the carbon in different potential ranges, verifying the necessity to optimize the potential range for a better cycling performance. These findings provide insights for the design and application of porous carbon.