Hybrid Binder Chemistry with Hydrogen-Bond Helix for High-Voltage Cathode of Sodium-Ion Batteries.

Since sodium-ion batteries (SIBs) have become increasingly commercialized in recent years, Na3V2(PO4)2O2F (NVPOF) offers promising economic potential as a cathode for SIBs because of its high operating voltage and energy density. According to reports, NVPOF performs poorly in normal commercial poly(vinylidene fluoride) (PVDF) binder systems and performs best in combination with aqueous binder. Although in line with the concept of green and sustainable development for future electrode preparation, aqueous binders are challenging to achieve high active material loadings at the electrode level, and their relatively high surface tension tends to cause the active material on the electrode sheet to crack or even peel off from the collector. Herein, a cross-linkable and easily commercial hybrid binder constructed by intermolecular hydrogen bonding (named HPP) has been developed and utilized in an NVPOF system, which enables the generation of a stable cathode electrolyte interphase on the surface of active materials. According to theoretical simulations, the HPP binder enhances electronic/ionic conductivity, which greatly lowers the energy barrier for Na+ migration. Additionally, the strong hydrogen-bond interactions between the HPP binder and NVPOF effectively prevent electrolyte corrosion and transition-metal dissolution, lessen the lattice volume effect, and ensure structural stability during cycling. The HPP-based NVPOF offers considerably improved rate capability and cycling performance, benefiting from these benefits. This comprehensive binder can be extended to the development of next-generation energy storage technologies with superior performance.

Janus Binder Chemistry for Synchronous Enhancement of Iodine Species Adsorption and Redox Kinetics toward Sustainable Aqueous Zn-I2 Batteries.

Currently, the desired research focus in energy storage technique innovation has been gradually shifted to next-generation aqueous batteries holding both high performance and sustainability. However, aqueous Zn-I2 batteries have been deemed to have great sustainable potential, owing to the merits of cost-effective and eco-friendly nature. However, their commercial application is hindered by the serious shuttle effect of polyiodides during reversible operations. In this work, a Janus functional binder based on chitosan (CTS) molecules was designed and prepared; the polar terminational groups impart excellent mechanical robustness to hybrid binders; meanwhile, it can also deliver isochronous enhancement on physical adsorption and redox kinetics toward I2 species. By feat of highly effective remission to shuttle effect, the CTS cell exhibits superb electrochemical storage capacities with long-term robustness, specifically, 144.1 mAh g-1, at a current density of 0.2 mA g-1 after 1500 cycles. Simultaneously, the undesired self-discharging issue could be also well-addressed; the Coulombic efficiency could remain at 98.8 % after resting for 24 h. More importantly, CTS molecules endow good biodegradability and reusable properties; after iodine species were reloaded, the recycled devices could also deliver specific capacities of 73.3 mAh g-1, over 1000 cycles. This Janus binder provides a potential synchronous solution to realize high comprehensive performance with high iodine utilization and further make it possible for sustainable Zn-I2 batteries.

Interfacial-Confined Isochronous Conversion to Biphasic Selenide Heterostructure with Enhanced Adsorption Behaviors for Robust High-Rate Na-Ion Storage.

Sodium-ion batteries (SIBs) have gradually become one of the most promising energy storage techniques in the current era of post-lithium-ion batteries. For anodes, transitional metal selenides (TMSe) based materials are welcomed choices , owing to relatively higher specific capacities and enriched redox active sites. Nevertheless, current bottlenecks are blamed for their poor intrinsic electronic conductivities, and uncontrollable volume expansion during redox reactions. Given that, an interfacial-confined isochronous conversion strategy is proposed, to prepare orthorhombic/cubic biphasic TMSe heterostructure, namely CuSe/Cu3 VSe4 , through using MXene as the precursor, followed by Cu/Se dual anchorage. As-designed biphasic TMSe heterostructure endows unique hierarchical structure, which contains adequate insertion sites and diffusion spacing for Na ions, besides, the surficial pseudocapacitive storage behaviors can be also proceeded like 2D MXene. By further investigation on electronic structure, the theoretical calculations indicate that biphasic CuSe/Cu3 VSe4 anode exhibits well-enhanced properties, with smaller bandgap and thus greatly improves intrinsic poor conductivities. In addition, the dual redox centers can enhance the electrochemical Na ions storage abilities. As a result, the as-designed biphasic TMSe anode can deliver a reversible specific capacity of 576.8 mAh g-1 at 0.1 A g-1 , favorable Na affinity, and reduced diffusion barriers. This work discloses a synchronous solution toward demerits in conductivities and lifespan, which is inspiring for TMSe-based anode development in SIBs systems.

2D Exfoliation Chemistry Towards Covalent Pseudo-Layered Phosphate Framework Derived by Radical/Strain-Synergistical Process.

2D compounds exfoliated from weakly bonded bulk materials with van der Waals (vdW) interaction are easily accessible. However, the strong internal ionic/covalent bonding of most inorganic crystal frameworks greatly hinders 2D material exfoliation. Herein, we first proposed a radical/strain-synergistic strategy to exfoliate non-vdW interacting pseudo-layered phosphate framework. Specifically, hydroxyl radicals (⋅OH) distort the covalent bond irreversibly, meanwhile, H2O molecules as solvents, further accelerating interlayered ionic bond breakage but mechanical expansion. The innovative 2D laminar NASICON-type Na3V2(PO4)2O2F crystal, exfoliated by ⋅OH/H2O synergistic strategy, exhibits enhanced sodium-ion storage capacity, high-rate performance (85.7 mAh g-1 at 20 C), cyclic life (2300 cycles), and ion migration rates, compared with the bulk framework. Importantly, this chemical/physical dual driving technique realized the effective exfoliation for strongly coupled pseudo-layered frameworks, which accelerates 2D functional material development.

Entropy-Regulated Cathode with Low Strain and Constraint Phase-Change Toward Ultralong-Life Aqueous Al-Ion Batteries.

During multivalent ions insertion processes, intense electrostatic interaction between charge carriers and host makes the high-performance reversible Al3+ storage remains an elusive target. On account of the strong electrostatic repulsion and poor robustness, Prussian Blue analogues (PBAs) suffer severely from the inevitable and large strain and phase change during reversible Al3+ insertion. Herein, we demonstrate an entropy-driven strategy to realize ultralong life aqueous Al-ion batteries (AIBs) based on medium entropy PBAs (ME-PBAs) host. By multiple redox active centers introduction, the intrinsic poor conductivity can be enhanced simultaneously, resulting in outstanding capabilities of electrochemical Al3+ storage. Meanwhile, the co-occupation at metal sites in PBA frameworks can also increase the M-N bond intensity, which is beneficial for constraining the phase change during consecutive Al3+ reversible insertion, to realize an extended lifespan over 10,000 cycles. Based on the calculation at different operation states, the fluctuation of ME-PBA lattice parameters is only 1.2 %. Assembled with MoO3 anodes, the full cells can also deliver outstanding electrochemical properties. The findings highlight that, the entropy regulation strategy could uncover the isochronous constraint on both strain and phase transition for long-term reversible Al3+ storage, providing a promising design for advanced electrode materials for aqueous multivalent ions batteries.

"Pore-Hopping" Ion Transport in Cellulose-Based Separator Towards High-Performance Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) have great potential for large-scale energy storage. Cellulose is an attractive material for sustainable separators, but some key issues still exist affecting its application. Herein, a cellulose-based composite separator (CP@PPC) was prepared by immersion curing of cellulose-based separators (CP) with poly(propylene carbonate) (PPC). With the assistance of PPC, the CP@PPC separator is able to operate the cell stably at high voltages (up to 4.95 V). The "pore-hopping" ion transport mechanism in CP@PPC opens up extra Na+ migration paths, resulting in a high Na+ transference number (0.613). The separator can also tolerate folding, bending and extreme temperature under certain circumstances. Full cells with CP@PPC reveal one-up capacity retention (96.97 %) at 2C after 500 cycles compared to cells with CP. The mechanism highlights the merits of electrolyte analogs in separator modification, making a rational design for durable devices in advanced energy storage systems.

TiVCTx MXene/Chalcogenide Heterostructure-Based High-Performance Magnesium-Ion Battery as Flexible Integrated Units.

Magnesium-ion batteries (MIB) have gradually attracted attention owing to their high theoretical capacity, high safety, and low cost. A bimetallic metal-organic framework self-sacrificing template and a co-assembly strategy are used to prepare a high-performance, stable cycling NiSe2 -CoSe2 @TiVCTx (NCSe@TiVC) heterostructure MIB cathode that can be used as a flexible integrated unit to power future self-powered systems. Benefiting from the synergistic effect of TiVCTx MXene and NCSe, the NCSe@TiVC heterostructure electrode has a discharge-specific capacity of 136 mAh g-1 at 0.05 A g-1 and high cycling stability of over 500 cycles; the assembled pouch-cell device as flexible integrated unit exhibits good practicability. The magnesium ion storage mechanism is also validated using quantitative kinetic analysis, ex situ XRD, and XPS techniques. Density functional theory analysis indicates the most stable Mg-atom adsorption sites in the heterostructure. This study broadens the possibilities for applying the TiVCTx MXene heterostructure to energy storage materials and future self-powered flexible systems.

Natural ore molybdenite as a high-capacity and cheap anode material for advanced lithium-ion capacitors.

Hybrid lithium-ion capacitors (LICs) receive special interests because they work by combining the merits of high-capacity lithium-ion batteries and high-rate capacitors in a Li salt containing electrolyte, so as to bridge the gap between the two devices. One of main challenges for LICs is to develop inexpensive and superior anode materials at high rates. In this work, natural molybdenite was utilized as precursor to achieve the scalable production of cheap MoS2/carbon composites. This molybdenite-derived MoS2/carbon electrode can not only exhibit excellent Li+-storage performances including ultrahigh specific capacity (1427 mAh g-1after 1000 cycles at 1 A g-1) and rate capability (554 mAh g-1at 10 A g-1), but also possess four-times higher tap density than that of commercial graphite. By employing MoS2/carbon as the anode and activated carbon as the cathode, the as-assembled LIC device delivers both high energy//high power density and long cycle lifespan. Furthermore, the price is nearly 200 orders of magnitude lower than the traditional high-purity chemicals, which can be easily scaled up to achieve high-throughput production.

Benefits and Risks of Subsection Laminectomy with Pedicle Screw Fixation for Ossification of the Ligamentum Flavum of the Thoracic Spine: A Retrospective Study of 30 Patients.

BACKGROUND This study aimed to evaluate the effectiveness of subsection laminectomy with pedicle screw fixation (SLPF) for the treatment of ossification of the ligamentum flavum of the thoracic spine. MATERIAL AND METHODS Thirty patients (age, 40-71 years) with ossification of the ligamentum flavum of the thoracic spine underwent SLPF (13 men, 17 women). Operative time, intraoperative blood loss, preoperative and postoperative change in thoracic kyphosis, and perioperative complications were recorded. The Japanese Orthopedic Association (JOA) score for severity of myelopathy and the American Spinal Injury Association (ASIA) motor and sensory impairment scale were used before and after surgery. RESULTS Mean operative time for SLPF was 208.4±38.3 min and mean intraoperative blood loss was 689.3±171.7 ml. The mean JOA score significantly increased from 5.7±1.9 before surgery to 8.8±2.2 at one month after surgery and 9.3±2.7 at the last follow-up (P<0.01). Postoperative improvement in neurological function increased by 68.3±14.4%. The postoperative ASIA grades significantly improved compared with the preoperative grades (P<0.01). The mean local Cobb angle significantly decreased from 17.8±4.3° before surgery to 15.4±3.6° at one month after surgery and 15.8±3.8° at the last follow-up (P<0.01). Three patients (10%) had operative cerebrospinal fluid (CSF) leak. Postoperatively, one patient had neurological deterioration, two patients had deep venous thrombosis (DVT), and one patient developed a wound infection. CONCLUSIONS SLPF was an effective procedure for the treatment of ossification of the ligamentum flavum of the thoracic spine.

Imaging Factors that Distinguish Between Patients with Asymptomatic and Symptomatic Cervical Spondylotic Myelopathy with Mild to Moderate Cervical Spinal Cord Compression.

BACKGROUND Not all patients with spinal cord compression due to cervical spondylotic myelopathy (CSM) have clinical symptoms and signs. The aim of this study was to investigate and compare the imaging findings in asymptomatic and symptomatic patients with CSM with mild to moderate cervical spinal cord compression. MATERIAL AND METHODS A retrospective clinical study included 68 patients. Group A (n=30) had no symptoms and signs; group B (n=38) had symptoms and signs of cervical myelopathy. The age, sex, body mass index (BMI), history of steroid treatment, duration of symptoms, number of spondylotic cervical segments, Torg ratio, range of motion (ROM), incidence of cervical segmental instability, overall curvature of the cervical spine, direction of spinal cord compression, and spinal cord magnetic resonance imaging (MRI) signal intensity were compared. RESULTS For groups A and B, the Torg ratio was 90.3% and 83.6% (P<0.05), the incidence of cervical segmental instability was 23.3% and 65.8% (P<0.05), and the incidence of a spinal cord high intensity signal was 13.3% and 86.9% (P<0.05). Logistic regression analysis showed myelopathy as a dependent variable, independently associated with cervical segmental instability (OR=5.898, P=0.037), an MRI T2-weighted intramedullary high signal (OR=9.718, P=0.002), and Torg ratio (OR=0.155, P=0.006). CONCLUSIONS Cervical segmental instability, a high intramedullary signal on T2-weighted MRI, and the Torg ratio had the greatest capacity to distinguish between asymptomatic and symptomatic patients with CSM with mild to moderate cervical spinal cord compression.