Quantifying Degradation Parameters of Single-Crystalline Ni-Rich Cathodes in Lithium-Ion Batteries.

Single-crystal LiNix Coy Mnz O2 (SC-NCM, x+y+z=1) cathodes are renowned for their high structural stability and reduced accumulation of adverse side products during long-term cycling. While advances have been made using SC-NCM cathode materials, careful studies of cathode degradation mechanisms are scarce. Herein, we employed quasi single-crystalline LiNi0.65 Co0.15 Mn0.20 O2 (SC-NCM65) to test the relationship between cycling performance and material degradation for different charge cutoff potentials. The Li/SC-NCM65 cells showed >77 % capacity retention below 4.6 V vs. Li+ /Li after 400 cycles and revealed a significant decay to 56 % for 4.7 V cutoff. We demonstrate that the SC-NCM65 degradation is due to accumulation of rock-salt (NiO) species at the particle surface rather than intragranular cracking or side reactions with the electrolyte. The NiO-type layer formation is also responsible for the strongly increased impedance and transition-metal dissolution. Notably, the capacity loss is found to have a linear relationship with the thickness of the rock-salt surface layer. Density functional theory and COMSOL Multiphysics modeling analysis further indicate that the charge-transfer kinetics is decisive, as the lower lithium diffusivity of the NiO phase hinders charge transport from the surface to the bulk.

Assessing Long-Term Cycling Stability of Single-Crystal Versus Polycrystalline Nickel-Rich NCM in Pouch Cells with 6 mAh cm-2 Electrodes.

Lithium-ion batteries based on single-crystal LiNi1- x - y Cox Mny O2 (NCM, 1-x-y ≥ 0.6) cathode materials are gaining increasing attention due to their improved structural stability resulting in superior cycle life compared to batteries based on polycrystalline NCM. However, an in-depth understanding of the less pronounced degradation mechanism of single-crystal NCM is still lacking. Here, a detailed postmortem study is presented, comparing pouch cells with single-crystal versus polycrystalline LiNi0.60 Co0.20 Mn0.20 O2 (NCM622) cathodes after 1375 dis-/charge cycles against graphite anodes. The thickness of the cation-disordered layer forming in the near-surface region of the cathode particles does not differ significantly between single-crystal and polycrystalline particles, while cracking is pronounced for polycrystalline particles, but practically absent for single-crystal particles. Transition metal dissolution as quantified by time-of-flight mass spectrometry on the surface of the cycled graphite anode is much reduced for single-crystal NCM622. Similarly, CO2 gas evolution during the first two cycles as quantified by electrochemical mass spectrometry is much reduced for single-crystal NCM622. Benefitting from these advantages, graphite/single-crystal NMC622 pouch cells are demonstrated with a cathode areal capacity of 6 mAh cm-2 with an excellent capacity retention of 83% after 3000 cycles to 4.2 V, emphasizing the potential of single-crystalline NCM622 as cathode material for next-generation lithium-ion batteries.

Composition and Architecture Design of Double-Shelled Co0.85 Se1- x Sx @Carbon/Graphene Hollow Polyhedron with Superior Alkali (Li, Na, K)-Ion Storage.

The exploration of materials with reversible and stable electrochemical performance is crucial in energy storage, which can (de) intercalate all the alkali-metal ions (Li+ , Na+ , and K+ ). Although transition-metal chalcogenides are investigated continually, the design and controllable preparation of hierarchical nanostructure and subtle composite withstable properties are still great challenges. Herein, component-optimal Co0.85 Se1- x Sx nanoparticles are fabricated by in situ sulfidization of metal organic framework, which are wrapped by the S-doped graphene, constructing a hollow polyhedron framework with double carbon shells (CoSSe@C/G). Benefiting from the synergistic effect of composition regulation and architecture design by S-substitution, the electrochemical kinetic is enhanced by the boosted electrochemistry-active sites, and the volume variation is mitigated by the designed structure, resulting in the advanced alkali-ion storage performance. Thus, it delivers an outstanding reversible capacity of 636.2 mAh g-1 at 2 A g-1 after 1400 cycles for Li-ion batteries. Remarkably, satisfactory initial charge capacities of 548.1 and 532.9 mAh g-1 at 0.1 A g-1 can be obtained for Na-ion and K-ion batteries, respectively. The prominent performance combined with the theory calculation confirms that the synergistic strategy can improve the alkali-ion transportation and structure stability, providing an instructive guide for designing high-performance anode materials for universal alkali-ion storage.

Garcinol prevents oxidative stress-induced bone loss and dysfunction of BMSCs through NRF2-antioxidant signaling.

There are multiple published data showing that excessive oxidative stress contributes to bone loss and even bone tissue damage, and it is also correlated with the pathophysiology of bone degenerative diseases, including osteoporosis (OP). Garcinol, a polyisoprenylated benzophenone derivative, has been recently established as an anti-oxidant agent. However, it remains elusive whether Garcinol protects bone marrow mesenchymal stem cells (BMSCs) and bone tissue from oxidative stress-induced damage. Here, we explored the potential effects of Garcinol supplementation in ameliorating oxidative stimulation-induced dysfunction of BMSCs and bone loss in osteoporotic mice. In this study, we verified that Garcinol exerted potent protective functions in the hydrogen peroxide (H2O2)-induced excessive oxidative stress and dysfunction of BMSCs. Besides, Garcinol was also identified to improve the reduced bone mass and abnormal lineage commitment of BMSCs in the condition of OP by suppressing the oxidative stimulation. Subsequent analysis revealed that nuclear factor erythroid 2-related factor 2 (NRF2) might be a key regulator in the sheltering effects of Garcinol on the H2O2-regulated oxidative stress, and the protective functions of Garcinol was mediated by NRF2-antioxidant signaling. Collectively, Garcinol prevented oxidative stress-related BMSC damage and bone loss through the NRF2-antioxidant signaling, which suggested the promising therapeutic values of Garcinol in the treatment of oxidative stress-related bone loss. Therefore, Garcinol might contribute to treating OP.

A study of the capacity fade of a LiCoO2/graphite battery during the temperature storage process at 45 °C under different SOCs.

Lithium-ion batteries with lithium cobalt oxide (LiCoO2) as a cathode and graphite as an anode are promising energy storage systems. However, the high-temperature storage mechanism under different states of charge (SOCs) conditions in batteries remains inadequately elucidated, and a clear storage policy has yet to be established. This study investigates and compares the capacity decay mechanism of a 63 mA h LiCoO2/graphite battery at 45 °C under various SOCs (100%, 75%, 50%, 30%, 0%), while also analysing the underlying reasons for this decay. The exhibited capacity recovery rates under 30% SOC and 100% SOC were significantly higher compared with those of the 50% and 75% SOC levels. Additionally, an analysis was conducted on battery storage under 0% SOC conditions, revealing its unsuitability for storage. By disassembling and analysing the batteries after storage, it was found that the dead lithium (Li) and cobalt (Co) in the anode gradually increased with the extension of storage time when stored under the same SOC. Finally, storage schemes under different SOCs are proposed, providing valuable suggestions for battery storage.

Strengthening the interfacial stability of single-crystal LiNi0.88Co0.09Mn0.03O2 cathode with multiple-function surface modification.

The instability in the structural integrity caused by interfacial issues is commonly regarded as the primary drawback of Ni-rich layered cathode materials (LiNixCoyMn1-x-yO2, where x  ≥ 0.8), which must be addressed before their commercial application. Herein, a novel multiple-function surface modification strategy is proposed based on the single crystal structure to in-situ achieve the construction of a coating layer and surface doping with Ce element to enhance the structural stability of the LiNi0.88Co0.09Mn0.03O2 (NCM). Notably, the introduction of Ce-O bonding adjusts the local oxygen coordination to achieve a more stabilized structure of the oxygen framework, which inhibits the evolution of lattice oxygen and enhances conductivity. Additionally, by benefiting from the in-situ synthesized coating layer of LixCeO2, the occurrence of side reactions on the surface is effectively alleviated, resulting in a reduction in electrode polarization. Combined with comprehensive electrochemical tests, it is confirmed that the improved electrochemical performance originates from the reduction of the detrimental H2-H3 phase transition and enhanced conductivity. As expected, the modified material with 1 wt% content of Ce (NCM@Ce) exhibits a high initial discharge capacity of 196.3 mAh g-1 with a capacity retention of 79.7 % after 200 cycles, and its energy density reaches 574.3 Wh kg-1 after 200 cycles.

Generation of a competing endogenous RNA network and validation of BNIP1 expression in the lung of irradiated mice.

BACKGROUND: Radiation-induced lung injury (RILI) is a serious complication of radiation therapy, and it is mediated by long non-coding RNAs (lncRNAs). STUDY DESIGN AND METHODS: Mouse lung tissues were examined using RNA-Seq and RNA-Seq libraries 72 h after the administration of 6 Gy of X-ray irradiation. The target mRNAs were functionally annotated and the target lncRNA-based miRNAs and target miRNA-based mRNAs were predicted after irradiation to establish the lncRNA-miRNA-mRNA ceRNA axis. RESULTS: The analyses showed that relative to unirradiated controls, 323 mRNAs, 114 miRNAs, and 472 lncRNAs were significantly up-regulated following irradiation, whereas 1907 mRNAs, 77 miRNAs, and 1572 lncRNAs were significantly down-regulated following irradiation. Voltage-gated ion channels, trans-membrane receptor protein tyrosine kinases, and vascular endothelial growth factor have all been associated with dysregulated miRNA-mRNA relationships. KEGG pathway analysis of the dysregulated miRNA-mRNA targets revealed involvement in pathways associated with the hedgehog signaling pathway-fly, ErbB signaling, VEGF signaling, axon guidance, and focal adhesion. KEGG analysis of differentially expressed showed enrichment of mRNAs in primary immunodeficiency, the intestinal immune axis for IgA production, hematopoietic cell lineages, systemic lupus erythematosus, and Th1 and Th2 cell differentiation. Finally, the ceRNA network revealed that BNIP1 was a critical mRNA modulated by the most significant upregulation of lncRNA E230013L22Rik. CONCLUSION: In summary, the lncRNA-miRNA-mRNA ceRNA axis of RILI was constructed following irradiation in a mouse model. RNA dysregulation in the early stage of RILI may lead to severe complications at a later stage, with BNIP1 contributing to radiation-induced cellular apoptosis in RILI.

Evaluation of the lncRNA-miRNA-mRNA ceRNA network in lungs of miR-147 -/- mice.

Background: Previous studies have documented important roles for microRNA-147 (miR-147) in inflammation, radiation-induced injury, cancer, and a range of other diseases. Murine lungs exhibit high levels of miRNA, mRNA, and lncRNA expression. However, very little research to date has focused on the lncRNA-miRNA-mRNA competing endogenous RNA (ceRNA) networks associated with miR-147, and the regulation of lncRNAs and miRNAs in this setting remains poorly understood. Methods: After establishing a miR-147-/- model mouse, samples of lung tissue were harvested for RNA-sequencing, and differentially expressed lncRNAs, miRNAs, and mRNAs were identified. The miRNA targets of these lncRNAs and the identified miRNAs were first overlapped to facilitate the prediction of target mRNAs, with analyses then examining the overlap between these targets and mRNAs that were differentially expressed. Then, these target mRNAs were subjected to pathway enrichment analyses. These results were ultimately used to establish a miR-147-related ceRNA network. Results: Relative to wild-type mice, the lungs of miR-147-/- mice exhibited 91, 43, and 71 significantly upregulated lncRNAs, miRNAs, and mRNAs, respectively, together with 114, 31, and 156 that were significantly downregulated. The lncRNA-miRNA-mRNA network established based on these results led to the identification of Kcnh6 as a differentially expressed hub gene candidate and enabled the identification of a range of regulatory relationships. KEGG pathway enrichment showed that the mRNA targets of differentially expressed lncRNAs and miRNAs in the mice were associated with tumor-related signaling, endometrial cancer, bladder cancer, and ErbB signaling. Conclusion: These results suggest that the identified ceRNA network in miR-147-/- mice shapes tumor-associated signaling activity, with miR-147 potentially regulating various lncRNAs and miRNAs through Kcnh6, ultimately influencing tumorigenesis. Future studies of the lncRNA, miRNA, and mRNA regulatory targets shown to be associated with miR-147 in the present study may ultimately lead to the identification of novel clinically relevant targets through which miR-147 shapes the pathogenesis of cancer and other diseases.

Revealing Lithium Configuration in Aged Layered Oxides for Effective Regeneration.

Layered oxides LiNixCoyMnzO2 are widely used as the main cathode material for high-energy lithium-ion batteries. Over long-term cycling, irreversible phase transformations in layered oxides usually occur along with the loss of active lithium, which directly reflects in the sharp decrease of capacity. However, it is difficult to accurately and rapidly determine lithium content in aged materials, raising extreme impediments in the direct recycling of layered oxides. Herein, we propose a facile method for quick and accurate calculation of the residual lithium content through the developed relationship of shear strain and the states of charge. Based on this recognization, a discharge capacity close to the original capacity of the pristine material is achieved in the regenerated material by combining a hydrothermal method with annealing treatment. The recycled material demonstrates a dramatic improvement in electrochemical properties, especially the high rate performance. This method not only effectively realizes the quantitative regeneration of cathode materials but also provides a possible strategy for the future development of direct regeneration.

The regulatory roles of miR-26a in the development of fracture and osteoblasts.

Background: MicroRNAs (miRNAs) play a vital role in the bone development and bone regeneration. In this study, we investigated the effects of miR-26a in osteoblasts and fractures. Methods: Human osteoblasts were cultured and used for analysis. To identify differential miRNAs in blood samples from patients with fractures and healthy controls, quantitative real-time polymerase chain reaction (qRT-PCR) analysis was performed. Human osteoblasts were transfected with miR-26a mimics, miR-26a inhibitor, or their corresponding negative controls (NCs), respectively. MTT assay was performed to identify the effects of miR-26a on the cell viability of osteoblasts. EdU staining was applied to detect the proliferation of osteoblasts. Trypan blue staining was utilized to analyze the effects of miR-26a on the cell death of osteoblasts. Terminal deoxynucleotidyl transferase mediated dUTP nick-end labeling (TUNEL) staining was used to detect apoptotic osteoblasts. Alizarin red S (ARS) staining and qRT-PCR analysis were utilized to measure the mineralized nodule formation to evaluate the bone formation of osteoblasts. Dual luciferase reporter assay and western blot analysis were performed to detect the relationship between miR-26a and its target gene. Results: The results of qRT-PCR analysis identified miR-26a as our miRNA of interest and indicated that miR-26a was significantly decreased in patients with fractures. Overexpression of miR-26a significantly increased the cell viability and proliferation of osteoblasts. An increase in miR-26a reduced the cell death and apoptosis of osteoblasts, and promoted the osteoblastic activity and mineralized nodule formation. Dual luciferase reporter assay, qRT-PCR and western blot analysis showed that miR-26a could negatively regulate the expression of phosphatase and tensin homolog (PTEN). Conclusions: MiR-26a promoted new bone regeneration via regulating the functions of osteoblasts by targeting its target gene PTEN. Therefore, we propose that targeting miR-26a may be a novel therapeutic method for bone regeneration and treating fractures.

Improving interfacial stability of ultrahigh-voltage lithium metal batteries with single-crystal Ni-rich cathode via a multifunctional additive strategy.

Electrode (including cathode and anode) /electrolyte interfaces play a vital role in determining battery performance. Especially, high-voltage lithium metal batteries (HVLMBs) with the Ni-rich layered oxide ternary cathode (NCM) can be considered a promising energy storage technology due to their outstanding energy density. However, it is still extremely challenging to address the unstable electrode/electrolyte interface and structural collapse of polycrystalline NCM at high voltage, greatly restraining its practical applications. In this work, a novel electrolyte additive, tris(2-cyanoethyl) borate (TCEB), has been used to construct the robust nitrogen (N) and boron (B)-rich protective films on single-crystal LiNi0.6Co0.1Mn0.3O2 (SNCM) cathode and lithium metal anode surfaces, which could effectively mitigate parasitic reactions against electrolyte corrosion and retain the structural integrity of electrode. Remarkably, the SNCM||Li metal cell using TCEB-containing electrolyte maintains unprecedentedly superb capacity retention of 80% after 100 cycles at an ultrahigh charging voltage of 4.7 V (versus Li/Li+). This finding provides a valuable reference to construct a stable electrode/electrolyte interface for the HVLMBs with achieving high-energy density.

The influence of water in electrodes on the solid electrolyte interphase film of micro lithium-ion batteries for the wireless headphone.

During the production of micro lithium-ion batteries (LIBs), which are widely used in wireless headphones and other small portable devices, numerous factors can affect their quality, among which the content of water plays a crucial role. In this work, the influence of water in electrodes on the performances of micro LIBs is studied deeply. When the content of water increases, both the rate performance and the cycling performance of the batteries fade. The discharge capacity retention of the battery from high water content sample group H (group H) is 81.81% after 350 cycles at 2C, while that of the battery from low water content sample group L (group L) is 89.89% under the same condition. As for the rate performance, the discharge capacity of group H is only 58.66% of group L at 5C. To take a step further, it is mainly because an overgrowth of the solid electrolyte interphase film happen with the growth of water content. Accordingly, excess lithium ions are consumed and the porous structure of the anode is destroyed. Considering the results above, we believe that this work can offer a theory foundation to carry out the failure analysis of micro batteries.

Enabling high energy lithium metal batteries via single-crystal Ni-rich cathode material co-doping strategy.

High-capacity Ni-rich layered oxides are promising cathode materials for secondary lithium-based battery systems. However, their structural instability detrimentally affects the battery performance during cell cycling. Here, we report an Al/Zr co-doped single-crystalline LiNi0.88Co0.09Mn0.03O2 (SNCM) cathode material to circumvent the instability issue. We found that soluble Al ions are adequately incorporated in the SNCM lattice while the less soluble Zr ions are prone to aggregate in the outer SNCM surface layer. The synergistic effect of Al/Zr co-doping in SNCM lattice improve the Li-ion mobility, relief the internal strain, and suppress the Li/Ni cation mixing upon cycling at high cut-off voltage. These features improve the cathode rate capability and structural stabilization during prolonged cell cycling. In particular, the Zr-rich surface enables the formation of stable cathode-electrolyte interphase, which prevent SNCM from unwanted reactions with the non-aqueous fluorinated liquid electrolyte solution and avoid Ni dissolution. To prove the practical application of the Al/Zr co-doped SNCM, we assembled a 10.8 Ah pouch cell (using a 100 µm thick Li metal anode) capable of delivering initial specific energy of 504.5 Wh kg-1 at 0.1 C and 25 °C.

Fabrication of CoSe@NC nanocubes for high performance potassium ion batteries.

Potassium-ion batteries (PIBs) are considered as a promising candidate for large-scale energy storage. While exploring suitable anode materials are of vital need for the practical applications of PIBs. Herein, a well-designed heterostructured anode material CoSe nanocubes wrapped by N-doped carbon (CoSe@NC), has been successfully fabricated by simple annealing ZIF-67 nanocubes followed by in-situ selenization process. It is noted that ZIF-67 nanocubes are used as an effective template for the formation of porous structure, which can facilitate the construction of heterogeneous interface between CoSe and N-doped carbon (NC), effectively stabilizing CoSe with conversion reaction product Co0, increasing the diffusion mobility of electrons and K+-ions, and alleviating huge volume change. As expected, the heterostructured CoSe@NC nanocubes exhibit excellent K+-storage performance, which can display a rather high initial charge capacity (388.7 mAh g-1 at 0.1 A g-1 with the columbic efficiency of 70%), superior cyclic stability (309.6 mA h g-1 after 500 cycles at 2 A g-1), and exceptional rate capability (365.9 mAh g-1 at 2 A g-1). In terms of the low-cost and facile production approach for CoSe@NC, which makes the CoSe@NC a promising anode material for PIBs.

Understanding the enhancement effect of boron doping on the electrochemical performance of single-crystalline Ni-rich cathode materials.

Ni-rich layered oxides are considered as promising cathode materials for Li-ion batteries (LIBs) due to their satisfying theoretical specific capacity and reasonable cost. However, poor cycling stability caused by structural collapse and interfacial instability of the Ni-rich cathode material limits the further applications of commercialization. Herein, a series of B-doped single-crystal LiNi0.83Co0.05Mn0.12O2 (NCM) are designed and fabricated, aiming to improve the structural stability and enlarge the Li+-ions diffusion paths simultaneously. It reveals that B-doping at TM layers will facilitate the formation of stronger B-O covalent bonds and expand the layered distance, significantly enhancing the thermodynamics and kinetic of NCM electrode. With the synergistic effect of single-crystalline architecture and appropriate B-doping, it can effectively alleviate the occurrence of internal strain with structural degradation and boost the intrinsic rate capability synchronously. As anticipated, the 0.6 mol % B-doped NCM electrode exhibits enhanced rate property and superior cycle stability, even at the harsh condition of high-temperature and elevated cut-off voltage. Remarkably, when tested in pouch-type full-cell, it maintains high reversible capacity with superior capacity retention of 91.35% over 500 cycles with only 0.0173% decay per cycle. This research illustrates the feasibility of B-doping and single-crystalline architecture to improve the electrochemical performance, which is beneficial to understand the enhancement effect and provides the design strategy for the commercialization progress of Ni-rich cathode materials.

In situ inorganic conductive network formation in high-voltage single-crystal Ni-rich cathodes.

High nickel content in LiNixCoyMnzO2 (NCM, x ≥ 0.8, x + y + z = 1) layered cathode material allows high specific energy density in lithium-ion batteries (LIBs). However, Ni-rich NCM cathodes suffer from performance degradation, mechanical and structural instability upon prolonged cell cycling. Although the use of single-crystal Ni-rich NCM can mitigate these drawbacks, the ion-diffusion in large single-crystal particles hamper its rate capability. Herein, we report a strategy to construct an in situ Li1.4Y0.4Ti1.6(PO4)3 (LYTP) ion/electron conductive network which interconnects single-crystal LiNi0.88Co0.09Mn0.03O2 (SC-NCM88) particles. The LYTP network facilitates the lithium-ion transport between SC-NCM88 particles, mitigates mechanical instability and prevents detrimental crystalline phase transformation. When used in combination with a Li metal anode, the LYTP-containing SC-NCM88-based cathode enables a coin cell capacity of 130 mAh g-1 after 500 cycles at 5 C rate in the 2.75-4.4 V range at 25 °C. Tests in Li-ion pouch cell configuration (i.e., graphite used as negative electrode active material) demonstrate capacity retention of 85% after 1000 cycles at 0.5 C in the 2.75-4.4 V range at 25 °C for the LYTP-containing SC-NCM88-based positive electrode.

[Value of magnesium sulfate and/or valium in preventing local anesthetic toxicity of sacral block].

OBJECTIVE: To study the effects of magnesium sulfate and/or valium in preventing local anesthetic toxicity induced by sacral block. METHODS: A total of 240 adult patients scheduled for sacral block were randomized equally into four groups matched for sex, age and body weight. Ten minutes before sacral block, the patients in group B received valium (0.1 mg/kg), group C received magnesium sulfate (50 mg/kg), group D received both valium (0.1 mg/kg) and magnesium sulfate (50 mg/kg). The control (group A) received neither valium nor magnesium sulfate. Local anesthetic toxicity was observed and recorded in all the groups. RESULTS: Local anesthetic toxicity was significantly decreased in group B and group C compared with group A (P<0.05), and the toxicity was even more significantly decreased in group D(P<0.01 vs group A). CONCLUSION: Local anesthetic toxicity of sacral block can be significantly decreased by intravenous injection of valium or magnesium sulfate, and their combination produces stronger effects.