Amorphous Chloride Solid Electrolytes with High Li-Ion Conductivity for Stable Cycling of All-Solid-State High-Nickel Cathodes.

Solid electrolytes (SEs) are central components that enable high-performance, all-solid-state lithium batteries (ASSLBs). Amorphous SEs hold great potential for ASSLBs because their grain-boundary-free characteristics facilitate intact solid-solid contact and uniform Li-ion conduction for high-performance cathodes. However, amorphous oxide SEs with limited ionic conductivities and glassy sulfide SEs with narrow electrochemical windows cannot sustain high-nickel cathodes. Herein, we report a class of amorphous Li-Ta-Cl-based chloride SEs possessing high Li-ion conductivity (up to 7.16 mS cm-1) and low Young's modulus (approximately 3 GPa) to enable excellent Li-ion conduction and intact physical contact among rigid components in ASSLBs. We reveal that the amorphous Li-Ta-Cl matrix is composed of LiCl43-, LiCl54-, LiCl65- polyhedra, and TaCl6- octahedra via machine-learning simulation, solid-state 7Li nuclear magnetic resonance, and X-ray absorption analysis. Attractively, our amorphous chloride SEs exhibit excellent compatibility with high-nickel cathodes. We demonstrate that ASSLBs comprising amorphous chloride SEs and high-nickel single-crystal cathodes (LiNi0.88Co0.07Mn0.05O2) exhibit ∼99% capacity retention after 800 cycles at ∼3 C under 1 mA h cm-2 and ∼80% capacity retention after 75 cycles at 0.2 C under a high areal capacity of 5 mA h cm-2. Most importantly, a stable operation of up to 9800 cycles with a capacity retention of ∼77% at a high rate of 3.4 C can be achieved in a freezing environment of -10 °C. Our amorphous chloride SEs will pave the way to realize high-performance high-nickel cathodes for high-energy-density ASSLBs.

Stable All-Solid-State Lithium Metal Batteries Enabled by Machine Learning Simulation Designed Halide Electrolytes.

Solid electrolytes (SEs) with superionic conductivity and interfacial stability are highly desirable for stable all-solid-state Li-metal batteries (ASSLMBs). Here, we employ neural network potential to simulate materials composed of Li, Zr/Hf, and Cl using stochastic surface walking method and identify two potential unique layered halide SEs, named Li2ZrCl6 and Li2HfCl6, for stable ASSLMBs. The predicted halide SEs possess high Li+ conductivity and outstanding compatibility with Li metal anodes. We synthesize these SEs and demonstrate their superior stability against Li metal anodes with a record performance of 4000 h of steady lithium plating/stripping. We further fabricate the prototype stable ASSLMBs using these halide SEs without any interfacial modifications, showing small internal cathode/SE resistance (19.48 Ω cm2), high average Coulombic efficiency (∼99.48%), good rate capability (63 mAh g-1 at 1.5 C), and unprecedented cycling stability (87% capacity retention for 70 cycles at 0.5 C).

Trace Doping of Multiple Elements Enables Stable Cycling of High Areal Capacity LiNi0.5 Mn1.5 O4 Cathode.

High-voltage spinel cobalt-free LiNi0.5 Mn1.5 O4 (LNMO) is one of the most promising cathode candidates for next-generation lithium-ion batteries (LIBs) due to its high specific capacity, high operating voltage, and low cost. However, inferior electronic conductivity, transition metal dissolution, and fast capacity degradation of LNMO, especially in high mass loading for high areal capacity, are the critical material challenges for its practical application. Herein, trace multiple Cr-Fe-Cu elements doping of LiNi0.45 Cr0.0167 Fe0.0167 Cu0.0167 Mn1.5 O4 (CFC0.5-LNMO) cathode is achieved by a blow-spinning strategy to exhibit very stable cycling at a practical level of areal capacity up to 3 mAh cm-2 . It is demonstrated that the Cu, Fe, and Cr doping into the LNMO lattice can suspend the Mn dissolution and improve the Li ion diffusivity and electronic conductivity of the LNMO host. As a result, the obtained CFC0.5-LNMO cathode exhibits an excellent rate performance (1.75 mAh cm-2 at 1C) and long cycling stability under an areal capacity of 3 mAh cm-2 (78% capacity retention over 300 cycles at 0.5C).

Scallion-Inspired Graphene Scaffold Enabled High Rate Lithium Metal Battery.

Graphene-based one-dimensional macroscopic assemblies (GBOMAs) have attracted great attention and extensive efforts have been devoted to enabling great progress. However, their applications are still restricted to less functionalized electronics, and the superior potentials remain scarce. Herein, inspired by natural scallion structure, a novel strategy was introduced to effectively improve battery performances through the mesoscale scallion-like wrapping of graphene. The obtained RGO/Ag-Li anodes demonstrated an ultralow overpotential of ∼11.3 mV for 1800 h at 1 mA cm-2 in carbonate electrolytes, which is superior to those of the most previous reports. Besides, this strategy can also be further expanded to the high mass loading of various cathode nanomaterials, and the resulting RGO/LiFePO4 cathodes exhibited remarkable rate performance and cycle stability. This work opens a new avenue to explore and broaden the applications of GBOMAs as scaffolds in fabricating full lithium batteries via maximizing their advantages derived from the unique structure and properties.

Blow-Spinning Enabled Precise Doping and Coating for Improving High-Voltage Lithium Cobalt Oxide Cathode Performance.

Lithium cobalt oxide (LiCoO2) possesses an attractive theoretical specific capacity (274 mAh g-1) and high discharge voltage (∼4.2 V vs Li+/Li). However, only a half of the theoretical capacity of LiCoO2 is available in commercialized lithium ion batteries because of the intrinsic structural instability and detrimental interface of LiCoO2 at the charging voltage over 4.2 V. Here, a facile blow-spinning synthetic method is developed to realize precise doping and simultaneous self-assembly coating of LiCoO2 particles, achieving a record performance among present LiCoO2 cathodes. Owing to the spatial confinement effect of microfibers fabricated by blow-spinning, homogeneously Mn and La doped in the LiCoO2 host and uniformly Li-Ti-O segregated at the LiCoO2 surface can be realized in every batch of samples. It is demonstrated that the Mn and La codoping can suspend the intrinsic instability and increase the Li+ diffusivity of the LiCoO2 host, and the Ti-based coating can stabilize the interface of LiCoO2 particles at the charging voltage up to 4.5 V. As a result, the obtained comodified LiCoO2 cathode shows the best rate performance (1.85 mAh cm-2 at 2C) and longest cycling stability under an areal capacity of 2.04 mAh cm-2 (83% capacity retention over 300 cycles at 0.3C), in comparison to previously reported LiCoO2 cathodes.

Low Cost Metal Carbide Nanocrystals as Binding and Electrocatalytic Sites for High Performance Li-S Batteries.

Lithium sulfur (Li-S) batteries are considered as promising energy storage systems for the next generation of batteries due to their high theoretical energy densities and low cost. Much effort has been made to improve the practical energy densities and cycling stability of Li-S batteries via diverse designs of materials nanostructure. However, achieving simultaneously good rate capabilities and stable cycling of Li-S batteries is still challenging. Herein, we propose a strategy to utilize a dual effect of metal carbide nanoparticles decorated on carbon nanofibers (MC NPs-CNFs) to realize high rate performance, low hysteresis, and long cycling stability of Li-S batteries in one system. The adsorption experiments of lithium polysulfides (LiPS) to MC NPs and corresponding theoretical calculations demonstrate that LiPS are likely to be adsorbed and diffused on the surface of MC NPs because of their moderate chemical bonding. MC NPs turn out to have also an electrocatalytic role and accelerate electrochemical redox reactions of LiPS, as proven by cyclic voltammetry analysis. The fabricated Li-S batteries based on the W2C NPs-CNFs hybrid electrodes display not only high specific capacity of 1200 mAh/g at 0.2C but also excellent rate performance and cycling stability, for example, a model setup can be operated at 1C for 500 cycles maintaining a final specific capacity of 605 mAh/g with a degradation rate as low as 0.06%/cycle.

Prawn Shell Derived Chitin Nanofiber Membranes as Advanced Sustainable Separators for Li/Na-Ion Batteries.

Separators, necessary components to isolate cathodes and anodes in Li/Na-ion batteries, are consumed in large amounts per year; thus, their sustainability is a concerning issue for renewable energy storage systems. However, the eco-efficient and environmentally friendly fabrication of separators with a high mechanical strength, excellent thermal stability, and good electrolyte wettability is still challenging. Herein, we reported the fabrication of a new type of separators for Li/Na-ion batteries through the self-assembly of eco-friendly chitin nanofibers derived from prawn shells. We demonstrated that the pore size in the chitin nanofiber membrane (CNM) separator can be tuned by adjusting the amount of pore generation agent (sodium dihydrogen citrate) in the self-assembly process of chitin nanofibers. By optimizing the pore size in CNM separators, the electrochemical performance of the LiFePO4/Li half-cell with a CNM separator is comparable to that with a commercialized polypropylene (PP) separator. More attractively, the CNM separator showed a much better performance in the LiFePO4/Li cell at 120 °C and Na3V2(PO4)3/Na cell than the PP separator. The proposed fabrication of separators by using natural raw materials will play a significant contribution to the sustainable development of renewable energy storage systems.

Free-Standing Copper Nanowire Network Current Collector for Improving Lithium Anode Performance.

Lithium metal is one of the most attractive anode materials for next-generation lithium batteries due to its high specific capacity and low electrochemical potential. However, the poor cycling performance and serious safety hazards, caused by the growth of dendritic and mossy lithium, has long hindered the application of lithium metal based batteries. Herein, we reported a rational design of free-standing Cu nanowire (CuNW) network to suppress the growth of dendritic lithium via accommodating the lithium metal in three-dimensional (3D) nanostructures. We demonstrated that as high as 7.5 mA h cm(-2) of lithium can be plated into the free-standing copper nanowire (CuNW) current collector without the growth of dendritic lithium. The lithium metal anode based on the CuNW exhibited high Coulombic efficiency (average 98.6% during 200 cycles) and outstanding rate performance owing to the suppression of lithium dendrite growth and high conductivity of CuNW network. Our results demonstrate that the rational nanostructural design of current collector could be a promising strategy to improve the performance of lithium metal anode enabling its application in next-generation lithium-metal based batteries.

Large-Scale Syntheses of Zinc Sulfide⋠(Diethylenetriamine)0.5 Hybrids as Precursors for Sulfur Nanocomposite Cathodes.

Nanostructured metal sulfide-amine hybrid materials have attracted attention because of their unique properties and versatility as precursors for functional inorganic nanomaterials. However, large-scale synthesis of metal sulfide-amine hybrid nanomaterials is limited by hydrothermal and solvothermal preparative reaction conditions; consequently, incorporation of such materials into functional nanomaterials is hindered. An amine molecule-assisted refluxing method was used to synthesize highly uniform zinc sulfide⋅(diethylenetriamine)0.5 (ZnS⋅(DETA)0.5 ) hybrid nanosheets and nanobelts in a large scale. The obtained ZnS⋅(DETA)0.5 hybrid nanomaterials can be used as efficient precursors to fabricate functional ZnS nanomaterials and carbon encapsulated sulfur (S@C) nanocomposite cathodes for Li-S batteries.

Scalable template synthesis of resorcinol-formaldehyde/graphene oxide composite aerogels with tunable densities and mechanical properties.

Resorcinol-formaldehyde (RF) and graphene oxide (GO) aerogels have found a variety of applications owing to their excellent properties and remarkable flexibility. However, the macroscopic and controllable synthesis of their composite gels is still a great challenge. By using GO sheets as template skeletons and metal ions (Co(2+), Ni(2+), or Ca(2+)) as catalysts and linkers, the first low-temperature scalable strategy for the synthesis of a new kind of RF-GO composite gel with tunable densities and mechanical properties was developed. The aerogels can tolerate a strain as high as 80% and quickly recover their original morphology after the compression has been released. Owing to their high compressibility, the gels might find applications in various areas, for example, as adsorbents for the removal of dye pollutants and in oil-spill cleanup.

Identification and Validation of a Novel Anoikis-Related Gene Signature for Predicting Survival in Patients With Serous Ovarian Cancer.

Background: Ovarian cancer is an extremely deadly gynecological malignancy, with a 5-year survival rate below 30%. Among the different histological subtypes, serous ovarian cancer (SOC) is the most common. Anoikis significantly contributes to the progression of ovarian cancer. Therefore, identifying an anoikis-related signature that can serve as potential prognostic predictors for SOC is of great significance. Methods: We intersected 308 anoikis-related genes (ARGs) and identified those significantly associated with SOC prognosis using univariate Cox regression. A LASSO Cox regression model was constructed and evaluated using Kaplan-Meier and receiver operating characteristic (ROC) analyses in TCGA (The Cancer Genome Atlas) and GSE26193 cohorts. We conducted quantitative real-time polymerase chain reaction (qPCR) to assess mRNA levels and applied bioinformatics to investigate the correlation between risk groups and gene expression, mutations, pathways, tumor immune microenvironment (TIME), and drug sensitivity in SOC. Results: Among 308 ARGs, 28 were significantly associated with SOC prognosis. A 13-gene prognostic model was established through LASSO Cox regression in TCGA cohort. High-risk group had poorer prognosis than low-risk group (median overall survival (mOS): 34.2 vs. 57.1 months, hazard ratio (HR): 2.590, 95% confidence interval (CI): 0.159 - 6.00, P < 0.001). The area under the curve (AUC) values of 0.63, 0.65, and 0.74 reflected the predictive performance for 3-, 5-, and 8-year overall survival (OS) in GSE26193 validation cohort. Functional enrichment, pathway analysis, and TIME analysis identified distinct characteristics between risk groups. Drug sensitivity analysis revealed potential drug advantages for each group. Furthermore, qPCR validation once again confirmed the effectiveness of the risk model in SOC patients. Conclusions: We developed and validated a robust ARG model, which could be used to predict OS in SOC patients. By systematically analyzing the correlation between the risk score of the ARGs signature model and various patterns, including the TIME and drug sensitivity, our findings suggest that this prognostic model contributes to the advancement of personalized and precise therapeutic strategies. Nevertheless, further validation studies and investigations into the underlying mechanisms are warranted.

The LINC00261/MiR105-5p/SELL axis is involved in dysfunction of B cell and is associated with overall survival in hepatocellular carcinoma.

Background: Previous studies have been reported the immune dysfunction of various live tissues. However, the potential molecular mechanism of post-transcriptional regulation of immune related genes in hepatocellular carcinoma (HCC) is still not clear. We tried to identify crucial immune related biomarkers associated with HCC patients' outcomes and to reveal the transcriptional regulation. Method: The fractions of 22 immune cells in tumor and adjacent tissues were estimated by CIBERSORT. Kruskal-Wallis test and differentially expressed analyzes were used for comparative studies. Cox proportional hazard regression model, Kaplan-Meier estimates and Log-rank test were used for survival analyses. Results: From The Cancer Genome Atlas (TCGA), the gene, lncRNA and miRNA expression profiles of 379 HCC samples with clinical information were used for comparative studies. Eleven adaptive and innate immune cell types were significantly altered in HCC samples, including B cell memory, regulatory T cells and follicular helper T cells. Differentially expressed competing endogenous RNA (ceRNA) network associated with patients' overall survival was identified. Then, the novel pathway, including LINC00261, MiR105-5p and selectin L(SELL) was found and may be potential novel biomarkers for patients' outcomes and immunotherapy. Furthermore, SELL was significantly positively correlated (correlation coefficients: 0.47-0.69) with 12 known gene signatures of immunotherapy except for programmed cell death 1 (PDCD1). Conclusions: Our findings could provide insights into the selection of novel LINC00261/MiR105-5p/SELL pathway which is associated with overall survival and may impact on efficacy of immunotherapy in HCC.

Superior Fast-Charging Lithium-Ion Batteries Enabled by the High-Speed Solid-State Lithium Transport of an Intermetallic Cu6 Sn5 Network.

Superior fast charging is a desirable capability of lithium-ion batteries, which can make electric vehicles a strong competition to traditional fuel vehicles. However, the slow transport of solvated lithium ions in liquid electrolytes is a limiting factor. Here, a Lix Cu6 Sn5 intermetallic network is reported to address this issue. Based on electrochemical analysis and X-ray photoelectron spectroscopy mapping, it is demonstrated that the reported intermetallic network can form a high-speed solid-state lithium transport matrix throughout the electrode, which largely reduces the lithium-ion-concentration polarization effect in the graphite anode. Employing this design, superior fast-charging graphite/lithium cobalt oxide full cells are fabricated and tested under strict electrode conditions. At the charging rate of 6 C, the fabricated full cells show a capacity of 145 mAh g-1 with an extraordinary capacity retention of 96.6%. In addition, the full cell also exhibits good electrochemical stability at a high charging rate of 2 C over 100 cycles (96.0% of capacity retention) in comparison to traditional graphite-anode-based cells (86.1% of capacity retention). This work presents a new strategy for fast-charging lithium-ion batteries on the basis of high-speed solid-state lithium transport in intermetallic alloy hosts.

Extremely fast-charging lithium ion battery enabled by dual-gradient structure design.

Extremely fast-charging lithium-ion batteries are highly desirable to shorten the recharging time for electric vehicles, but it is hampered by the poor rate capability of graphite anodes. Here, we present a previously unreported particle size and electrode porosity dual-gradient structure design in the graphite anode for achieving extremely fast-charging lithium ion battery under strict electrode conditions. We develop a polymer binder-free slurry route to construct this previously unreported type particle size-porosity dual-gradient structure in the practical graphite anode showing the extremely fast-charging capability with 60% of recharge in 10 min. On the basis of dual-gradient graphite anode, we demonstrate extremely fast-charging lithium ion battery realizing 60% recharge in 6 min and high volumetric energy density of 701 Wh liter-1 at the high charging rate of 6 C.

Lithium Fluoride in Electrolyte for Stable and Safe Lithium-Metal Batteries.

Electrolyte engineering via fluorinated additives is promising to improve cycling stability and safety of high-energy Li-metal batteries. Here, an electrolyte is reported in a porous lithium fluoride (LiF) strategy to enable efficient carbonate electrolyte engineering for stable and safe Li-metal batteries. Unlike traditionally engineered electrolytes, the prepared electrolyte in the porous LiF nanobox exhibits nonflammability and high electrochemical performance owing to strong interactions between the electrolyte solvent molecules and numerous exposed active LiF (111) crystal planes. Via cryogenic transmission electron microscopy and X-ray photoelectron spectroscopy depth analysis, it is revealed that the electrolyte in active porous LiF nanobox involves the formation of a high-fluorine-content (>30%) solid electrolyte interphase layer, which enables very stable Li-metal anode cycling over one thousand cycles under high current density (4 mA cm-2 ). More importantly, employing the porous LiF nanobox engineered electrolyte, a Li || LiNi0.8 Co0.1 Mn0.1 O2 pouch cell is achieved with a specific energy of 380 Wh kg-1 for stable cycling over 80 cycles, representing the excellent performance of the Li-metal pouch cell using practical carbonate electrolyte. This study provides a new electrolyte engineering strategy for stable and safe Li-metal batteries.

A Special Cranial Nucleus (CSF-Contacting Nucleus) in Primates.

BACKGROUND: There is a unique nucleus (CSF-contacting nucleus) in the brain of rat. It has been demonstrated in our previous research. The extraordinary feature of this nucleus is that it is not connected to any parenchymal organ but to the CSF. In primates, however, the presence or absence of this nucleus has not been proven. Confirmation of the presence of this nucleus in primates will provide the structural basis for brain-CSF communication and help to understand the neurohumoral regulatory mechanisms in humans. METHODS: The tracer cholera toxin B subunit conjugated to horseradish peroxidase (CB-HRP) was injected into the CSF in the lateral ventricle (LV) of primate rhesus monkeys. After 48 h, the monkeys were perfused and the brain was dissected out, and sectioned for CB-HRP staining. The CB-HRP positive structures were observed under confocal and electron microscopy. The three-dimensional (3D) structure of the CB-HRP positive neurons cluster was reconstructed by computer software. RESULTS: (1) CB-HRP labeling is confined within the ventricle, but not leakage into the brain parenchyma. (2) From the midbrain inferior colliculus superior border plane ventral to the aqueduct to the upper part of the fourth ventricle (4V) floor, a large number of CB-HRP positive neurons are consistently located, form a cluster, and are symmetrically located on both sides of the midline. (3) 3D reconstruction shows that the CB-HRP positive neurons cluster in the monkey brain occupies certain space. The rostral part is large and caudal part is thin appearing a "rivet"-like shape. (4) Under electron microscopy, the CB-HRP positive neurons show different types of synaptic connections with the non-CSF-contacting structures in the brain. Some of the processes stretch directly into the ventricle cavity. CONCLUSION: Same as we did in rats, the CSF-contacting nucleus is also existed in the primate brain parenchyma. We also recommend listing it as the XIII pair of cranial nucleus, which is specialized in the communications between the brain and the CSF. It is significant to the completing of innervation in the organism.

The CSF-Contacting Nucleus Receives Anatomical Inputs From the Cerebral Cortex: A Combination of Retrograde Tracing and 3D Reconstruction Study in Rat.

OBJECTIVE: This study aimed to investigate the direct monosynaptic projections from cortical functional regions to the cerebrospinal fluid (CSF)-contacting nucleus for understanding the functions of the CSF-contacting nucleus. METHODS: The Sprague-Dawley rats received cholera toxin B subunit (CB) injections into the CSF-contacting nucleus. After 7-10 days of survival time, the rats were perfused, and the whole brain and spinal cord were sliced under a freezing microtome at 40 µm. All sections were treated with the CB immunofluorescence reaction. The retrogradely labeled neurons in different cortical areas were revealed under a confocal microscope. The distribution features were further illustrated under 3D reconstruction. RESULTS: The retrogradely labeled neurons were identified in the olfactory, orbital, cingulate, insula, retrosplenial, somatosensory, motor, visual, auditory, association, rhinal, and parietal cortical areas. A total of 12 functional areas and 34 functional subregions showed projections to the CSF-contacting nucleus in different cell intensities. CONCLUSION: According to the connectivity patterns, we conclude that the CSF-contacting nucleus participates in cognition, emotion, pain, visceral activity, etc. The present study firstly reveals the cerebral cortex→CSF-contacting nucleus connections, which implies the multiple functions of this special nucleus in neural and body fluid regulations.

Novel Projections to the Cerebrospinal Fluid-Contacting Nucleus From the Subcortex and Limbic System in Rat.

Objective: To identify the novel projections received by the cerebrospinal fluid (CSF)-contacting nucleus from the subcortex and limbic system to understand the biological functions of the nucleus. Methods: The cholera toxin subunit B (CB), a retrograde tracer, was injected into the CSF-contacting nucleus in Sprague-Dawley rats. After 7-10 days, the surviving rats were perfused, and the whole brain and spinal cord were sliced for CB immunofluorescence detection. The CB-positive neurons in the subcortex and limbic system were observed under a fluorescence microscope, followed by 3D reconstructed with the imaris software. Results: CB-positive neurons were found in the basal forebrain, septum, periventricular organs, preoptic area, and amygdaloid structures. Five functional areas including 46 sub-regions sent projections to the CSF-contacting nucleus. However, the projections had different densities, ranging from sparse to moderate, to dense. Conclusions: According to the projections from the subcortex and limbic system, we hypothesize that the CSF-contacting nucleus participates in emotion, cognition, homeostasis regulation, visceral activity, pain, and addiction. In this study, we illustrate the novel projections from the subcortex and limbic system to the CSF-contacting nucleus, which underlies the diverse and complicated circuits of the nucleus in body regulations.

Characterizing topological charge of optical vortices by using an annular aperture.

We explore the spatial frequency property of the far-field diffraction intensity pattern of an optical vortex after passing through an annular aperture in detail. The result reveals that the spatial spectrum consists of alternate bright and dark rings and, in particular, the number of the bright rings is nicely identical to the absolute value of the topological charge. Based on this property, we present and demonstrate a simple technique to characterize the topological charge of an optical vortex through its diffraction intensity pattern after an annular aperture.

Tri-arm multipinhole interferometer for wavefront measurement and diffractive imaging.

We propose a tri-arm (or Y-shaped) multipinhole (MP) interferometer for wavefront measurement based on a specially designed tri-arm MP plate. We demonstrate that the complex amplitude of a wavefront sampled by the tri-arm MP plate inserted between the object and the detector plane can be extracted directly from the Fourier transform of a far-field diffraction intensity pattern without the need for any iterative algorithm. A form of coherent diffractive imaging based on a rotatable tri-arm MP plate is also demonstrated, which provides a feasible approach for lensless diffractive imaging in real time.