Enhancing Electrode Performance through Triple Distribution Modulation of Active Material, Conductive Agent, and Porosity.

The increasing demand for large-scale energy storage propels the development of lithium-ion batteries with high energy and high power density. Low tortuosity electrodes with aligned straight channels have proved to be effective in building such batteries. However, manufacturing such low tortuosity electrodes in large scale remains extremely challenging. In contrast, high-performance electrodes with customized gradients of materials and porosity are possible to be made by industrial roll-to-roll coating process. Yet, the desired design of gradients combining materials and porosity is unclear for high-performance gradient electrodes. Here, triple gradient LiFePO4 electrodes (TGE) are fabricated featuring distribution modulation of active material, conductive agent, and porosity by combining suction filtration with the phase inversion method. The effects and mechanism of active material, conductive agent, and porosity distribution on electrode performance are analyzed by experiments. It is found that the electrode with a gradual increase of active material content from current collector to separator coupled with the distribution of conductive agent and porosity in the opposite direction, demonstrates the best rate capability, the fastest electrochemical reaction kinetics, and the highest utilization of active material. This work provides valuable insights into the design of gradient electrodes with high performance and high potential in application.

Space-Confined Guest Synthesis to Fabricate Sn-Monodispersed N-Doped Mesoporous Host toward Anode-Free Na Batteries.

Severe issues including volume change and dendrite growth on sodium metal anodes hinder the pursuit of applicable high-energy-density sodium metal batteries. Herein, an in situ reaction approach is developed that takes metal-organic frameworks as nano-reactor and pore-former to produce a mesoporous host comprised of nitrogen-doped carbon fibers embedded with monodispersed Sn clusters (SnNCNFs). The hybrid host shows outstanding sodiophilicity that enables rapid Na infusion and ultralow Na nucleation overpotential of 2 mV. Its porous structure holds a high Na content and guides uniform Na deposition. Such host provides favorable Na plating/stripping with an average Coulombic efficiency of 99.96% over 2000 cycles (at 3 mA cm-2 and 3 mA h cm-2 ). The Na-infused SnNCNF anode delivers extreme Na utilization of 86% in symmetric cells (at 10 mA cm-2 and 10 mA h cm-2 ), outstanding rate capability and cycle life in Na-SnNCNF||Na3 V2 (PO4 )3 full cells (at 1 A g-1 for over 1000 cycles with capacity retention of 92.1%). Furthermore, high-energy/power-density anode-less and anode-free Na cells are achieved. This work presents an effective heteroatom-doping approach for fabricating multifunctional porous carbon materials and developing high-performance metal batteries.

Codoped porous carbon nanofibres as a potassium metal host for nonaqueous K-ion batteries.

Potassium metal is an appealing alternative to lithium as an alkali metal anode for future electrochemical energy storage systems. However, the use of potassium metal is hindered by the growth of unfavourable deposition (e.g., dendrites) and volume changes upon cycling. To circumvent these issues, we propose the synthesis and application of nitrogen and zinc codoped porous carbon nanofibres that act as potassium metal hosts. This carbonaceous porous material enables rapid potassium infusion (e.g., < 1 s cm-2) with a high potassium content (e.g., 97 wt. %) and low potassium nucleation overpotential (e.g., 15 mV at 0.5 mA cm-2). Experimental and theoretical measurements and analyses demonstrate that the carbon nanofibres induce uniform potassium deposition within its porous network and facilitate a dendrite-free morphology during asymmetric and symmetric cell cycling. Interestingly, when the potassium-infused carbon material is tested as an active negative electrode material in combination with a sulfur-based positive electrode and a nonaqueous electrolyte solution in the coin cell configuration, an average discharge voltage of approximately 1.6 V and a discharge capacity of approximately 470 mA h g-1 after 600 cycles at 500 mA g-1 and 25 °C are achieved.

Exchange of Li and AgNO3 Enabling Stable 3D Lithium Metal Anodes with Embedded Lithophilic Nanoparticles and a Solid Electrolyte Interphase Inducer.

Three-dimensional (3D) current collectors can effectively mitigate the volumetric expansion of working lithium metal anodes (LMAs). However, the practical utilization of 3D current collectors for lithium metal batteries remains unsatisfactory because of inhomogeneous deposition of lithium ions and an unstable solid electrolyte interphase (SEI). Herein, a facile method based on the exchange reaction between Li and AgNO3 is exploited to embed Ag nanoparticles (NPs) and LiNO3 in a carbon paper (ALCP@Li). The Ag NPs act as a seed for even lithium deposition inside the carbon matrix by virtue of their excellent lithiophilicity. Simultaneously, LiNO3 plays an effective role in stabilizing LMAs by evolving a robust N-rich SEI. As a result, such 3D LMAs show a high Coulombic efficiency in half-cells (200 cycles, 99% at 1 mA cm-2, 1 mAh cm-2) and a low overpotential (60 mV). When paired with commercial thick NCM622 and LiFePO4 cathodes, the 3D LMA-based full cells exhibit stable cycling in carbonate electrolytes.

Decarboxylation-Induced Defects in MOF-Derived Single Cobalt Atom@Carbon Electrocatalysts for Efficient Oxygen Reduction.

Developing transition metal single-atom catalysts (SACs) for oxygen reduction reaction (ORR) is of great importance. Zeolitic imidazolate frameworks (ZIFs) as a subgroup of metal-organic frameworks (MOFs) are distinguished as SAC precursors, due to their large porosity and N content. However, the activity of the formed metal sites is limited. Herein, we report a decarboxylation-induced defects strategy to improve their intrinsic activity via increasing the defect density. Carboxylate/amide mixed-linker MOF (DMOF) was chosen to produce defective Co SACs (Co@DMOF) by gas-transport of Co species to DMOF upon heating. Comparing with ZIF-8 derived SAC (Co@ZIF-8-900), Co@DMOF-900 with more defects yet one fifth Co content and similar specific double-layer capacitance show better ORR activity and eight times higher turnover frequency (2.015 e s-1 site-1 ). Quantum calculation confirms the defects can weaken the adsorption free energy of OOH on Co sites and further boost the ORR process.

Metal-organic framework membranes with single-atomic centers for photocatalytic CO2 and O2 reduction.

The demand for sustainable energy has motivated the development of artificial photosynthesis. Yet the catalyst and reaction interface designs for directly fixing permanent gases (e.g. CO2, O2, N2) into liquid fuels are still challenged by slow mass transfer and sluggish catalytic kinetics at the gas-liquid-solid boundary. Here, we report that gas-permeable metal-organic framework (MOF) membranes can modify the electronic structures and catalytic properties of metal single-atoms (SAs) to promote the diffusion, activation, and reduction of gas molecules (e.g. CO2, O2) and produce liquid fuels under visible light and mild conditions. With Ir SAs as active centers, the defect-engineered MOF (e.g. activated NH2-UiO-66) particles can reduce CO2 to HCOOH with an apparent quantum efficiency (AQE) of 2.51% at 420 nm on the gas-liquid-solid reaction interface. With promoted gas diffusion at the porous gas-solid interfaces, the gas-permeable SA/MOF membranes can directly convert humid CO2 gas into HCOOH with a near-unity selectivity and a significantly increased AQE of 15.76% at 420 nm. A similar strategy can be applied to the photocatalytic O2-to-H2O2 conversions, suggesting the wide applicability of our catalyst and reaction interface designs.

Metal-Organic Framework Membranes Encapsulating Gold Nanoparticles for Direct Plasmonic Photocatalytic Nitrogen Fixation.

Photocatalytic nitrogen fixation reaction can harvest the solar energy to convert the abundant but inert N2 into NH3. Here, utilizing metal-organic framework (MOF) membranes as the ideal assembly of nanoreactors to disperse and confine gold nanoparticles (AuNPs), we realize the direct plasmonic photocatalytic nitrogen fixation under ambient conditions. Upon visible irradiation, the hot electrons generated on the AuNPs can be directly injected into the N2 molecules adsorbed on Au surfaces. Such N2 molecules can be additionally activated by the strong but evanescently localized surface plasmon resonance field, resulting in a supralinear intensity dependence of the ammonia evolution rate with much higher apparent quantum efficiency and lower apparent activation energy under stronger irradiation. Moreover, the gas-permeable Au@MOF membranes, consisting of numerous interconnected nanoreactors, can ensure the dispersity and stability of AuNPs, further facilitate the mass transfer of N2 molecules and (hydrated) protons, and boost the plasmonic photocatalytic reactions at the designed gas-membrane-solution interface. As a result, an ammonia evolution rate of 18.9 mmol gAu-1 h-1 was achieved under visible light (>400 nm, 100 mW cm-2) with an apparent quantum efficiency of 1.54% at 520 nm.

Bulk COFs and COF nanosheets for electrochemical energy storage and conversion.

Covalent organic frameworks (COFs) as an emerging class of crystalline porous materials have received much attention due to their tunable porosity, modifiable skeletons, and atomically precise structures. Besides, COFs can provide multiple high-rate charge carrier transport (electron, hole, and ion) pathways, including conjugated skeletons, overlapped π electron clouds among the stacked layers, and open channels with a variable chemical environment. Therefore, they have shown great potential in electrochemical energy storage (EES) and conversion (EEC). However, in bulk COFs, the defects always impede charge carrier conduction, and the difficulties in reaching deep-buried active sites by either electrons or ions lead to limited performance. To overcome these obstacles, numerous research studies have been carried out to obtain COF nanosheets (NSs). This review first describes the preparation strategies of COF NSs via bottom-up and top-down approaches. Then, the applications of bulk COFs and COF NSs in EES and EEC are summarized, such as in batteries, supercapacitors, and fuel cells. Finally, key challenges and future directions in these areas are discussed.

Peripheral Blood Leukocyte RNA-Seq Identifies a Set of Genes Related to Abnormal Psychomotor Behavior Characteristics in Patients with Schizophrenia.

BACKGROUND Schizophrenia is a multigene disease with a complex etiology and different clinical manifestations. It is of great significance to understand the etiology and pathogenesis of schizophrenia patients from different clinical dimensions and to interpret the potential molecular changes of schizophrenia patients from different clinical dimensions. MATERIAL AND METHODS RNA-Seq was performed on peripheral blood leukocytes of 50 patients with schizophrenia and 50 healthy controls. Phenotypic information of patients with schizophrenia was collected during blood sampling. Differentially expressed genes (DEGs) were screened by the edgeR package of R software. To better analyze the correlation between DEG expression values, explore the potential association between differential genes and clinical dimensions of schizophrenia, and identify hub genes, we constructed a DEG co-expression network using weighted gene co-expression network analysis (WGCNA). RESULTS We provide the transcription profiles of peripheral blood leukocytes in patients with schizophrenia and found a gene module (including 89 genes) closely related to the clinical dimension of abnormal psychomotor behavior in schizophrenia. CONCLUSIONS The findings enhance our understanding of the biological processes of schizophrenia, enabling us to identify specific clinical dimensions of genes for diagnosis and prognostic markers and possibly for targeted therapy.

Synergistic Effects of Inorganic-Organic Protective Layer for Robust Cycling Dendrite-Free Lithium Metal Batteries.

The advantages in high theoretical capacity and low electrochemical potential have made Li metal one of the most promising anode materials satisfying the surging requirement of high energy density for the next-generation batteries. However, safety issues caused by the Li dendrite growth during cycling have greatly thwarted its application. Herein, a hybrid artificial protective layer, constructed by the one-step method through chemical reactions between Li metal and 1H,1H,1H,2H-perfluorodecyltrimethoxysilane, is demonstrated to guide Li deposition and protect lithium batteries from the destruction of Li dendrites. A synergistic effect of the inorganic and organic components in the protective layer significantly enhances the electrochemical performance of symmetric Li|Li and Li|LiFePO4 cells. This work provides a facile, simple, and scalable method to design a hybrid artificial protective layer for long-lifespan Li metal batteries.

Fast Ion Transport Pathway Provided by Polyethylene Glycol Confined in Covalent Organic Frameworks.

Covalent organic frameworks (COFs) with well-tailored channels are able to accommodate ions and offer their conduction pathway. However, due to strong Coulombic interaction and the lack of transport medium, directly including lithium salts into the channels of COFs results in limited ion transport capability. Herein, we propose a strategy of incorporating low-molecular-weight polyethylene glycol (PEG) into COFs with anionic, neutral, or cationic skeletons to accelerate Li+ conduction. The PEG confined in the well-aligned channels retains high flexibility and Li+ solvating ability. The ion conductivity of PEG included in a cationic COF can reach 1.78 × 10-3 S cm-1 at 120 °C. The simplicity of this strategy as well as the diversity of crystalline porous materials holds great promise to design high-performance all-solid-state ion conductors.

Zinc/Nickel-Doped Hollow Core-Shell Co3 O4 Derived from a Metal-Organic Framework with High Capacity, Stability, and Rate Performance in Lithium/Sodium-Ion Batteries.

Transition-metal oxides are one of the most promising anode materials for energy storage in lithium- and sodium-ion batteries (LIBs and NIBs, respectively). To improve the electrochemical performance of metal oxides (e.g., Co3 O4 ), such as capacity and cyclability, a convenient strategy (with a metal-organic framework as a template) is introduced to generate Zn- or Ni-doped Co3 O4 . The obtained hollow core-shell nanosized Co3 O4 (denoted as Zn/Ni-Co-Oxide) derived from pyrolyzing zinc or nickel co-doped ZIF-67 (Co(mIm)2 ; mIm=methylimidazole) shows a drastically enhanced capacity of 1300 mAh g-1 at a high current density of 5000 mA g-1 , compared with that of pristine cobalt oxide (800 mAh g-1 ) in LIBs. A zinc-doped Zn-Co-Oxide demonstrates a stable capacity of 1600 mAh g-1 at 1000 mA g-1 for 700 cycles and an excellent performance in full coin cells (cycled with LiNi0.5 Co0.3 Mn0.2 O2 ). Moreover, NIB tests show a stable capacity of 300 mAh g-1 for more than 250 cycles.

Three-Dimensional Anionic Cyclodextrin-Based Covalent Organic Frameworks.

Three-dimensional covalent organic frameworks (3D COFs) are promising crystalline materials with well-defined structures, high porosity, and low density; however, the limited choice of building blocks and synthetic difficulties have hampered their development. Herein, we used a flexible and aliphatic macrocycle, namely γ-cyclodextrin (γ-CD), as the soft struts for the construction of a polymeric and periodic 3D extended network, with the units joined via tetrakis(spiroborate) tetrahedra with various counterions. The inclusion of pliable moieties in the robust open framework endows these CD-COFs with dynamic features, leading to a prominent Li ion conductivity of up to 2.7 mS cm-1 at 30 °C and excellent long-term Li ion stripping/plating stability. Exchanging the counterions within the pores can effectively modulate the interactions between the CD-COF and CO2 molecules.

A Lithium Ion Highway by Surface Coordination Polymerization: In Situ Growth of Metal-Organic Framework Thin Layers on Metal Oxides for Exceptional Rate and Cycling Performance.

A thin layer of a highly porous metal-organic framework material, ZIF-8, is fabricated uniformly on the surface of nanostructured transition metal oxides (ZnO nanoflakes and MnO2 nanorods) to boost the transfer of lithium ions. The novel design and uniform microstructure of the MOF-coated TMOs (ZIF-8@TMOs) exhibit dramatically enhanced rate and cycling performance comparing to their pristine counterparts. The capacities of ZIF-8@ZnO (nanoflakes) and ZIF-8@MnO2 (nanorods) are 28 % and 31 % higher that of the pristine ones at the same current density. The nanorods of ZIF-8@MnO2 show a capacity of 1067 mAh g-1 after 500 cycles at 1 Ag-1 and without any fading. To further improve the conductivity and capacity, the ZIF-8-coated materials are pyrolyzed at 700 °C in an N2 atmosphere (ZIF-8@TMO-700 N). After pyrolysis, a much higher capacity improvement is achieved: ZIF-8@ZnO-700 N and ZIF-8@MnO2 -700 N have 54 % and 69 % capacity increases compared with the pristine TMOs, and at 1 Ag-1 , the capacity of ZIF-8@MnO2 -700 N is 1060 mAh g-1 after cycling for 300 cycles.

Metal-Organic Frameworks (MOFs) as Sandwich Coating Cushion for Silicon Anode in Lithium Ion Batteries.

A novel metal-organic framework (MOF) sandwich coating method (denoted as MOF-SC) is developed for hybrid Li ion battery electrode preparation, in which the MOF films are casted on the surface of a silicon layer and sandwiched between the active silicon and the separator. The obtained electrodes show improved cycling performance. The areal capacity of the cheap and readily available microsized Si treated with MOF-SC can reach 1700 µAh cm(-2) at 265 µA cm(-2) and maintain at 850 µAh cm(-2) after 50 cycles. Beyond the above, the commercial nanosized Si treated by MOF-SC also shows greatly enhanced areal capacity and outstanding cycle stability, 600 µAh cm(-2) for 100 cycles without any apparent fading. By virtue of the novel structure prepared by the MOFs, this new MOF-SC structure serves as an efficient protection cushion for the drastic volume change of silicon during charge/discharge cycles. Furthermore, this MOF layer, with large pore volume and high surface area, can adsorb electrolyte and allow faster diffusion of Li(+) as evidenced by decreased impedance and improved rate performance.

MOF derived composites for cathode protection: coatings of LiCoO2 from UiO-66 and MIL-53 as ultra-stable cathodes.

A mechanochemical synthetic method of preparing LiCoO2 coated by MOF-derived metal oxide composites is introduced. Mono-dispersed ZrO2 and Al2O3 are applied as protection layers. These composites show 148 mA h g(-1) at a current density of 2325 mA g(-1) and excellent thermal stability (55 °C).

In situ growth of MOFs on the surface of si nanoparticles for highly efficient lithium storage: Si@MOF nanocomposites as anode materials for lithium-ion batteries.

A simple yet powerful one-pot strategy is developed to prepare metal-organic framework-coated silicon nanoparticles via in situ mechanochemical synthesis. After simple pyrolysis, the thus-obtained composite shows exceptional electrochemical properties with a lithium storage capacity up to 1050 mA h g(-1), excellent cycle stability (>99% capacity retention after 500 cycles) and outstanding rate performance. These characteristics, combined with their high stability and ease of fabrication, make such Si@MOF nanocomposites ideal alternative candidates as high-energy anode materials in lithium-ion batteries.

A novel anode material derived from organic-coated ZIF-8 nanocomposites with high performance in lithium ion batteries.

A general method of preparing nanocomposites from a metal-organic framework coated with hydroxyl, pyrrolyl and/or carboxyl functionalized organics is introduced. Pyrolysis of these nanocomposites gives anode materials with improved discharge capacity (750 mA h g(-1)) and cyclability. They also show enhanced Coulombic efficiency over the initial 5-10 cycles and decreased internal impedance.