Electrochemical coupling in subnanometer pores/channels for rechargeable batteries.

Subnanometer pores/channels (SNPCs) play crucial roles in regulating electrochemical redox reactions for rechargeable batteries. The delicately designed and tailored porous structure of SNPCs not only provides ample space for ion storage but also facilitates efficient ion diffusion within the electrodes in batteries, which can greatly improve the electrochemical performance. However, due to current technological limitations, it is challenging to synthesize and control the quality, storage, and transport of nanopores at the subnanometer scale, as well as to understand the relationship between SNPCs and performances. In this review, we systematically classify and summarize materials with SNPCs from a structural perspective, dividing them into one-dimensional (1D) SNPCs, two-dimensional (2D) SNPCs, and three-dimensional (3D) SNPCs. We also unveil the unique physicochemical properties of SNPCs and analyse electrochemical couplings in SNPCs for rechargeable batteries, including cathodes, anodes, electrolytes, and functional materials. Finally, we discuss the challenges that SNPCs may face in electrochemical reactions in batteries and propose future research directions.

A LiF-Rich Solid Electrolyte Interphase in a Routine Carbonate Electrolyte by Tuning the Interfacial Chemistry Behavior of LiPF6 for Stable Li Metal Anodes.

Lithium (Li) dendrite growth in a routine carbonate electrolyte (RCE) is the main culprit hindering the practical application of Li metal anodes. Herein, we realize the regulation of the LiPF6 decomposition pathway in RCE containing 1.0 M LiPF6 by introducing a "self-polymerizing" additive, ethyl isothiocyanate (EITC), resulting in a robust LiF-rich solid electrolyte interphase (SEI). The effect of 1 vol % EITC on the electrode/electrolyte interfacial chemistry slows the formation of the byproduct LixPOFy. Such a LiF-rich SEI with EITC polymer winding exhibits a high Young's modulus and a uniform Li-ion flux, which suppresses dendrite growth and interface fluctuation. The EITC-based Li metal cell using a Li4Ti5O12 cathode delivers a capacity retention of 81.4% over 1000 cycles at 10 C, outperforming its counterpart. The cycling stability of 1 Ah pouch cells was further evaluated under EITC. We believe that this work provides a new method for tuning the interfacial chemistry of Li metal through electrolyte additives.

Engineering Triple-Phase Interfaces Enabled by Layered Double Perovskite Oxide for Boosting Polysulfide Redox Conversion.

The electrocatalytic conversion of polysulfides is crucial to lithium-sulfur batteries and mainly occurs at triple-phase interfaces (TPIs). However, the poor electrical conductivity of conventional transition metal oxides results in limited TPIs and inferior electrocatalytic performance. Herein, a TPI engineering approach comprising superior electrically conductive layered double perovskite PrBaCo2O5+δ (PBCO) is proposed as an electrocatalyst to boost the conversion of polysulfides. PBCO has superior electrical conductivity and enriched oxygen vacancies, effectively expanding the TPI to its entire surface. DFT calculation and in situ Raman spectroscopy manifest the electrocatalytic effect of PBCO, proving the critical role of enhanced electrical conductivity of this electrocatalyst. PBCO-based Li-S batteries exhibit an impressive reversible capacity of 612 mAh g-1 after 500 cycles at 1.0 C with a capacity fading rate of 0.067% per cycle. This work reveals the mechanism of the enriched TPI approach and provides novel insight into designing new catalysts for high-performance Li-S batteries.

Regulating Electrochemical Kinetics of CoP by Incorporating Oxygen on Surface for High-Performance Li-S Batteries.

Lithium-sulfur (Li-S) batteries are widely studied because of their high theoretical specific capacity and environmental friendliness. However, the further development of Li-S batteries is hindered by the shuttle effect of lithium polysulfides (LiPSs) and the sluggish redox kinetics. Since the adsorption and catalytic conversion of LiPSs mainly occur on the surface of the electrocatalyst, regulating the surface structure of electrocatalysts is an advisable strategy to solve the obstacles in Li-S batteries. Herein, CoP nanoparticles with high oxygen content on surface embedded in hollow carbon nanocages (C/O-CoP) is employed to functionalize the separators and the effect of the surface oxygen content of CoP on the electrochemical performance is systematically explored. Increasing the oxygen content on CoP surface can enhance the chemical adsorption to lithium polysulfides and accelerate the redox conversions kinetics of polysulfides. The cell with C/O-CoP modified separator can achieve the capacity of 1033 mAh g-1 and maintain 749 mAh g-1 after 200 cycles at 2 C. Moreover, DFT calculations are used to reveal the enhancement mechanism of oxygen content on surface of CoP in Li-S chemistry. This work offers a new insight into developing high-performance Li-S batteries from the perspective of surface engineering.

Risk model based on MRI fusion biopsy characteristics predicts biochemical recurrence after radical prostatectomy.

BACKGROUND: To determine the prostate cancer biochemical recurrence-related fusion biopsy characteristics before radical surgery and to establish the risk prediction model of biochemical recurrence of prostate cancer. METHODS: Three hundred and four patients undergoing radical surgery for prostate cancer at Huadong Hospital affiliated to Fudan University between 2009 and 2020 for preoperative magnetic resonance imaging (MRI) before biopsy with suspicious prostate cancer lesions. Each case was followed by a 10 + x needle combination of targeted biopsy (intentional or robotic fusion) with systematic biopsy. Prostate-specific antigen levels were measured at 1, 3, and 6 months postoperatively, followed by reexamination every 6 months. Survival analysis was performed by the Kaplan-Meier method, univariate and multivariate analysis by Cox, and Logistic risk regression models. RESULTS: Higher Prostate Imaging Reporting And Data System (PI-RADS) scores (p < 0.001), suspicious extracapsular invasion (p < 0.001), and seminal vesicle invasion (p < 0.001) on MRI, the largest lesion diameter on MRI (p = 0.006), higher biopsy International Society of Urological Pathology (ISUP) grade group (p < 0.001) related to higher biochemical recurrence rates, higher pathological staging (p < 0.001), and a greater probability of local lymph node metastasis (p < 0.001). We accurately predicted the biochemical recurrence of prostate cancer after radical surgery based on preoperative features including the long diameter of the largest MRI lesion more than 23 mm, seminal vesicle invasion on MRI, and targeted fusion biopsy ISUP grade >3 Risk stratified classification (AUC = 0.729, p < 0.001). In our cohort, this risk stratification had a larger area under the curve than predictive models based only on magnetic resonance parameters and traditional risk scores. CONCLUSIONS: In this cohort, seminal vesicle invasion on MRI, the long diameter of the largest MRI lesion, and targeted fusion biopsy ISUP grade grope are significantly predictive of pathologic features and biochemical recurrence after prostate surgery. The risk stratification integrating the three parameters could better predict the biochemical recurrence than the traditional model.

Extensive cytokine analysis in synovial fluid of osteoarthritis patients.

OBJECTIVE: Osteoarthritis (OA) is a joint disease characterized by articular cartilage loss and afflicts many people worldwide. However, diagnostic methods and treatment options remain limited and are often characterized by low sensitivity and low efficacy. The focus of the present study was to identify proteomic biomarkers in synovial fluid to improve diagnosis and therapy of OA patients. METHODS: Antibody array technology was utilized for protein expression profiling of synovial fluid from 24 OA patients and 24 healthy persons. RESULTS: Compared with healthy persons, twenty proteins showed lower expression levels in OA patients, while thirty proteins had higher levels. Among these differential proteins, GITRL, CEACAM-1, FSH, EG-VEGF, FGF-4, PIGF, Cystatin EM and NT-4 were found for the first time to be differentially expressed in OA. Bioinformatics analysis showed that most of these differential proteins were involved leukocytes events, and some differentially expressed proteins including IL-18, CXCL1, CTLA4, MIP-3b, CD40, MMP-1, THBS1, CCL11, PAI-1, BAFF, aggrecan, angiogenin and follistatin were located in central positions of the protein-protein interaction (PPI) network. CONCLUSION: We speculate that leukocyte proliferation and migration to the joint may be an important pathogenesis of OA, which needs a further validation. The central proteins of the PPI network may play a more pivotal role in OA. The newly identified differentially expressed proteins may be novel biomarkers for OA diagnosis and targets for OA therapy.

Irisin promotes osteogenic differentiation of bone marrow mesenchymal stem cells by activating autophagy via the Wnt//ß-catenin signal pathway.

Osteogenic differentiation of bone marrow mesenchymal stem cells (BMSCs) plays a crucial role in osteoporosis. Irisin, an exercise-induced muscle-dependent myokine, has been reported to stimulate the development of brown adipose tissue and regulate energy expenditure. The present study aimed to investigate the effects of irisin on autophagy in BMSCs. Furthermore, the osteogenic differentiation ability was evaluated, as well as the activation of autophagy. It was found that 40 µM irisin for 48 h was an appropriate concentration and time period, with regards to cell viability, which was measured with a Cell Counting Kit-8. Moreover, the increasing expression levels of microtubule-associated protein light chain 3 (Lc3)-I/II and autophagy related 5 (Atg5) by irisin demonstrated the upregulation of autophagy. Mechanistically, bafilomycin A1 and Atg5 small interfering RNA were used to evaluate the possible mechanism of autophagy activated by irisin, and it was identified that irisin may upregulate autophagy by increasing the Atg12-Atg5-Atg16L complex. In addition, with the increasing level of autophagy, osteogenesis and the Wnt/ß-catenin signal pathway were also enhanced. However, inhibition of autophagy by bafilomycin A1 negatively regulated osteogenic differentiation. Collectively, the present results suggested that irisin may stimulate autophagy in BMSCs and that osteogenic differentiation may be enhanced by stimulating autophagy.

Hierarchical Mn3 O4 Anchored on 3D Graphene Aerogels via C-O-Mn Linkage with Superior Electrochemical Performance for Flexible Asymmetric Supercapacitor.

Flexible asymmetric supercapacitors are more appealing in flexible electronics because of high power density, wide cell voltage, and higher energy density than symmetric supercapacitors in aqueous electrolyte. In virtues of excellent conductivity, rich porous structure and interconnected honeycomb structure, three dimensional graphene aerogels show great potential as electrode in asymmetric supercapacitors. However, graphene aerogels are rarely used in flexible asymmetric supercapacitors because of easily re-stacking of graphene sheets, resulting in low electrochemical activity. Herein, flower-like hierarchical Mn3 O4 and carbon nanohorns are incorporated into three dimensional graphene aerogels to restrain the stack of graphene sheets, and are applied as the positive and negative electrode for asymmetric supercapacitors devices, respectively. Besides, a strong chemical coupling between Mn3 O4 and graphene via the C-O-Mn linkage is constructed and can provide a good electron-transport pathway during cycles. Consequently, the asymmetric supercapacitor device shows high rate cycle stability (87.8 % after 5000 cycles) and achieves a high energy density of 17.4 µWh cm-2 with power density of 14.1 mW cm-2 (156.7 mW cm-3 ) at 1.4 V.

3D Starfish-Like FeOF on Graphene Sheets: Engineered Synthesis and Lithium Storage Performance.

To address the problems associated with poor conductivity and large volume variation in practical applications as a conversion cathode, engineering of hierarchical nanostructured FeOF coupled with conductive decoration is highly desired, yet rarely reported. Herein, 3D starfish-like FeOF on reduced graphene oxide sheets (FeOF/rGO) is successfully prepared, for the first time, through a combination of solvothermal reaction, self-assembly, and thermal reduction. Integrating the structural features of the 3D hierarchical nanostructure, which favorably shorten the path for electron/ion transport and alleviate volumetric changes, with those of graphene wrapping, which can further enhance the electrical conductivity and maintain the structural stability of the electrode, the as-prepared FeOF/rGO composite exhibits a superior lithium-storage performance, including a high reversible capacity (424.5 mA h-1 g-1 at 50 mA g-1 ), excellent stability (0.016 % capacity decay per cycle during 180 cycles), and remarkable rate capability (275.8 mA h-1 g-1 at 2000 mA g-1 ).

SnS2 /SnO2 Heterostructures towards Enhanced Electrochemical Performance of Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries have been recognized as outstanding candidates for energy storage systems due to their superiority in terms of energy density. To meet the requirements for practical use, it is necessary to develop an effective method to realize Li-S batteries with high sulfur utilization and cycle stability. Here, a strategy to construct heterostructure composites as cathodes for high performance Li-S batteries is presented. Taking the SnS2 /SnO2 couple as an example, SnS2 /SnO2 nanosheet heterostructures on carbon nanofibers (CNFs), named C@SnS2 /SnO2 , were designed and synthesized. Considering the electrochemical performance of SnS2 /SnO2 heterostructures, it is interesting to note that the existence of heterointerfaces could efficiently improve lithium ion diffusion rate so as to accelerate the redox reaction significantly, thus leading to the enhanced sulfur utilization and more excellent rate performance. Benefiting from the unique structure and heterointerfaces of C@SnS2 /SnO2 materials, the battery exhibited excellent cyclic stability and high sulfur utilization. This work may provide a powerful strategy for guiding the design of sulfur hosts from selecting the material composition to constructing of microstructure.

Regulating the Interlayer Spacing of Graphene Oxide Membranes and Enhancing their Stability by Use of PACl.

Graphene oxide (GO) is an ideal membrane material for water treatment due to its outstanding physicochemical properties and unique lamellar structure. However, the separation performance and practical application of GO membranes are mainly affected by the interlayer spacing and stability in aqueous solutions. Here, we report a novel and facile approach to fabricating GO membranes with adjustable interlayer spacing and high stability in aqueous solutions through cross-linking with polyaluminum chloride (PACl). With this approach, the lamellar spacing can be adjusted by changing the OH/Al ratios (B values) of the PACl, and the GO nanosheets can be tightly bonded by the strong electrostatic effect that PACl provides between them. The average interlayer spacing of the GO layer could be varied approximately in the range of 0.80-1.09 nm. The PACl-GO membranes demonstrated excellent stability in water and inorganic/organic solutions when the concentration of PACl was 0.1, 1, and 10 mM, remaining unchanged for at least 2 weeks. Moreover, the PACl-GO membranes featured exceptional sieving capabilities for model and natural organic substrates, while it was also observed that increasing the interlayer spacing of the PACl-GO membranes increased both the membrane flux and the separation performance of organic matter.

A Pseudolayered MoS2 as Li-Ion Intercalation Host with Enhanced Rate Capability and Durability.

As a popular strategy, interlayer expansion significantly improves the Li-ion diffusion kinetics in the MoS2 host, while the large interlayer spacing weakens the van der Waals force between MoS2 monolayers, thus harming its structural stability. Here, an oxygen-incorporated MoS2 (O-MoS2 )/graphene composite as a self-supported intercalation host of Li-ion is prepared. The composite delivers a specific capacity of 80 mAh g-1 in only 36 s at a mass loading of 1 mg cm-2 , and it can be cycled 3000 times (over 91% capacity retention) with a 5 mg cm-2 loading at 2 A g-1 . The O-MoS2 exhibits a dominant 1T phase with an expanded layer spacing of 10.15 Å, leading to better Li-ion intercalation kinetics compared with pristine MoS2 . Furthermore, ex situ X-ray diffraction tests indicate that O-MoS2 sustains a stable structure in cycling compared with the gradual collapse of pristine MoS2 , which suffers from excessive lattice breathing. Density functional theory calculations suggest that the MoOx (OH)y pillars in O-MoS2 interlayers not only expand the layer spacing, but also tense the MoS2 layers to avoid exfoliation in cycling. Therefore, the O-MoS2 shows a pseudolayered structure, leading to remarkable durability besides the outstanding rate capability as a Li-ion intercalation host.

Ultrathin MXene Nanosheets Decorated with TiO2 Quantum Dots as an Efficient Sulfur Host toward Fast and Stable Li-S Batteries.

Being conductive and flexible, 2D transition metal nitrides and carbides (MXenes) can serve in Li-S batteries as sulfur hosts to increase the conductivity and alleviate the volume expansion. However, the surface functional groups, such as OH and F, weaken the ability of bare MXenes in the chemisorption of polysulfides. Besides, they create numerous hydrogen bonds which make MXenes liable to restack, resulting in substantial loss of active area and, thus, inaccessibility of ions and electrolyte. Herein, a facile, one-step strategy is developed for the growth of TiO2 quantum dots (QDs) on ultrathin MXene (Ti3 C2 Tx ) nanosheets by cetyltrimethylammonium bromide-assisted solvothermal synthesis. These QDs act as spacers to isolate the MXene nanosheets from restacking, and preserve their 2D geometry which guarantees larger electrode-electrolyte contact area and higher sulfur loading. The stronger adsorption energy of polysulfides with TiO2 (than with Ti3 C2 Tx ), as proven by density functional theory calculations, is essential for better on-site polysulfide retention. The ultrathin nature and protected conductivity ensure rapid ion and electron diffusion, and the excellent flexibility maintains high mechanical integrity. In result, the TiO2 QDs@MXene/S cathode exhibits significantly improved long-term cyclability and rate capability, disclosing a new opportunity toward fast and stable Li-S batteries.

A Conductive Ni2 P Nanoporous Composite with a 3D Structure Derived from a Metal-Organic Framework for Lithium-Sulfur Batteries.

Sulfur cathodes have attracted significant attention as next-generation electrode material candidates due to their considerable theoretical energy density. The main challenge in developing long-life Li-S batteries is to simultaneously suppress the shuttle effect and high areal mass loading of sulfur required for practical applications. To solve this problem, we have designed a novel nickel phosphide nanoporous composite derived from metal-organic frameworks (MOFs) as sulfur host materials. Homogeneous distribution of Ni2 P nanoparticles significantly avoids soluble polysulfides migrating out of the framework through strong chemical interactions, and the conductive 3D skeleton offers an accelerating electron transport. As a result, S@Ni2 P/NC has exhibited an enhanced performance of 1357 mAh g-1 initially at 0.2 C (1 C=1675 mA g-1 ) and remaining at 946 mAh g-1 after 300 cycles. Even at an areal mass loading of sulfur as high as 4.6 mg cm-2 , the electrode still showed an excellent specific capacity of 918 mAh g-1 .

Electrocatalysis in Lithium Sulfur Batteries under Lean Electrolyte Conditions.

The presence of electrocatalysis in lithium-sulfur batteries has been proposed but not yet sufficiently verified. In this study, molybdenum phosphide (MoP) nanoparticles are shown to play a definitive electrocatalytic role for the sulfur cathode working under lean electrolyte conditions featuring a low electrolyte/active material ratio: the overpotentials for the charging and discharging reactions are greatly decreased. As a result, sulfur electrodes containing MoP nanoparticles show faster kinetics and more reversible conversion of sulfur species, leading to improvements in charging/discharging voltage profiles, capacity, rate performance, and cycling stability. Taking advantage of the electrocatalytic properties of MoP, high-performance sulfur electrodes were successfully realized that are steadily cyclable at a high areal capacity of 5.0 mAh cm-2 with a challenging electrolyte/sulfur (E/S) ratio of 4 µLE mg-1 S .

T-Nb2O5 quantum dots prepared by electrodeposition for fast Li ion intercalation/deintercalation.

T-Nb2O5 quantum dots were electrodeposited on Ti nanorod arrays to prepare Ti@T-Nb2O5 core-shell array electrodes. The particle size of T-Nb2O5 could be manipulated by adjusting the depositing current density, and quantum dots several nanometers in size could be obtained at a deposition current of 6 mA cm-2. Benefiting from the ultra-small particle size of T-Nb2O5 and the array structure, Ti@T-Nb2O5 nanorod arrays exhibited good rate capability and durability when used as self-supported Li ion battery anodes. The arrays possessed capacities of 350 and 70 mAh g-1 at rate currents of 0.06 and 30 A g-1, respectively. Furthermore, the electrodes maintained 500 cycles without obvious decay at a high rate current of 30 A g-1.

Ultrastrong Polyoxyzole Nanofiber Membranes for Dendrite-Proof and Heat-Resistant Battery Separators.

Polymeric nanomaterials emerge as key building blocks for engineering materials in a variety of applications. In particular, the high modulus polymeric nanofibers are suitable to prepare flexible yet strong membrane separators to prevent the growth and penetration of lithium dendrites for safe and reliable high energy lithium metal-based batteries. High ionic conductance, scalability, and low cost are other required attributes of the separator important for practical implementations. Available materials so far are difficult to comply with such stringent criteria. Here, we demonstrate a high-yield exfoliation of ultrastrong poly(p-phenylene benzobisoxazole) nanofibers from the Zylon microfibers. A highly scalable blade casting process is used to assemble these nanofibers into nanoporous membranes. These membranes possess ultimate strengths of 525 MPa, Young's moduli of 20 GPa, thermal stability up to 600 °C, and impressively low ionic resistance, enabling their use as dendrite-suppressing membrane separators in electrochemical cells. With such high-performance separators, reliable lithium-metal based batteries operated at 150 °C are also demonstrated. Those polyoxyzole nanofibers would enrich the existing library of strong nanomaterials and serve as a promising material for large-scale and cost-effective safe energy storage.

Graphene Aerogels with Anchored Sub-Micrometer Mulberry-Like ZnO Particles for High-Rate and Long-Cycle Anode Materials in Lithium Ion Batteries.

Graphene aerogels (GAs) anchoring hierarchical, mulberry-like ZnO particles are fabricated in situ using a one-step solvothermal reaction. The resulting composites can function as anodes in lithium ion batteries, where they exhibit a high capacity and cyclic stability. The reversible capacities obtained are 365, 320, and 230 mA h g-1 at current densities of 1, 2, and 10 A g-1 . Their high reversible capacity is 445 mA h g-1 at a current density of 1.6 A g-1 ; this value is maintained even after the 500th cycle, The excellent electrochemical performance is attributed to strong oxygen bridges between ZnO and graphene, where C-O-Zn linkages provide a good pathway for electron transport during charge/discharge cycles. Additionally, the hierarchical structure of the ZnO microballs suppresses stacking among the graphene layers, allowing the GAs to accelerate the transport of lithium ions. Furthermore, the GA framework enhances the electrical conductivity and buffer any volume expansion.

MoS2 Nanosheets Supported on 3D Graphene Aerogel as a Highly Efficient Catalyst for Hydrogen Evolution.

The development of efficient catalysts for electrochemical hydrogen evolution is essential for energy conversion technologies. Molybdenum disulfide (MoS2 ) has emerged as a promising electrocatalyst for hydrogen evolution reaction, and its performance greatly depends on its exposed edge sites and conductivity. Layered MoS2 nanosheets supported on a 3D graphene aerogel network (GA-MoS2 ) exhibit significant catalytic activity in hydrogen evolution. The GA-MoS2 composite displays a unique 3D architecture with large active surface areas, leading to high catalytic performance with low overpotential, high current density, and good stability.

pH-controllable on-demand oil/water separation on the switchable superhydrophobic/superhydrophilic and underwater low-adhesive superoleophobic copper mesh film.

Recently, materials with controlled oil/water separation ability became a new research focus. Herein, we report a novel copper mesh film, which is superhydrophobic and superhydrophilic for nonalkaline water and alkaline water, respectively. Meanwhile, the film shows superoleophobicity in alkaline water. Using the film as a separating membrane, the oil/water separating process can be triggered on-demand by changing the water pH, which shows a good controllability. Moreover, it is found that the nanostructure and the appropriate pore size of the substrate are important for realization of a good separation effect. This paper offers a new insight into the application of surfaces with switchable wettability, and the film reported here has such a special ability that allows it to be used in other applications, such as sewage purification, filtration, and microfluidic device.