Progress on Transition Metal Ions Dissolution Suppression Strategies in Prussian Blue Analogs for Aqueous Sodium-/Potassium-Ion Batteries

Aqueous sodium-ion batteries(ASIBs)and aqueous potassium-ion batteries(APIBs)present significant potential for large-scale energy storage due to their cost-effectiveness,safety,and environmental compatibility.Nonetheless,the intricate energy storage mechanisms in aqueous electrolytes place stringent require-ments on the host materials.Prussian blue analogs(PBAs),with their open three-dimensional framework and facile synthesis,stand out as leading candidates for aqueous energy storage.However,PBAs possess a swift capacity fade and limited cycle longevity,for their structural integrity is compromised by the pronounced dis-solution of transition metal(TM)ions in the aqueous milieu.This manuscript provides an exhaustive review of the recent advancements concerning PBAs in ASIBs and APIBs.The dissolution mechanisms of TM ions in PBAs,informed by their structural attributes and redox processes,are thoroughly examined.Moreover,this study delves into innovative design tactics to alleviate the dissolution issue of TM ions.In conclusion,the paper consolidates various strategies for suppressing the dissolution of TM ions in PBAs and posits avenues for prospective exploration of high-safety aqueous sodium-/potassium-ion batteries.

Novel MOF shell-derived surface modification of Li-rich layered oxide cathode for enhanced lithium storage

Li-rich layered oxide materials have attracted increasing attention because of their high specific capacity(>250 mAh g^(-1)). However, these materials typically suffer from poor cycling stability and low rate performance. Herein, we propose a facile and novel metal-organic-framework(MOF) shell-derived surface modification strategy to construct NiCo nanodots decorated(~5 nm in diameter) carbon-confined Li_(1.2)Mn_(0.54) Ni_(0.13)Co_(0.13)O_2 nanoparticles(LLO@C&NiCo). The MOF shell is firstly formed on the surface of as-prepared Li_(1.2)Mn_(0.54)Ni_(0.13)Co_(0.13)O_2 nanoparticles via low-pressure vapor superassembly and then is in situ converted to the NiCo nanodots decorated carbon shell after subsequent controlled pyrolysis.The obtained LLO@C&NiCo cathode exhibits enhanced cycling and rate capability with a capacity retention of 95% after 100 cycles at 0.4 C and a high capacity of 159 mAh g^(-1) at 5 C, respectively, compared with those of LLO(75% and 105 mAh g^(-1)). The electrochemical impedance spectroscopy and selected area electron diffraction analyses after cycling demonstrate that the thin C&NiCo shell can endow LLO with high electronic conductivity and structural stability, indicating the undesired formation of the spinel phase initiated from the particle surface is efficiently suppressed. Therefore, this presented strategy may open a new avenue on the design of high-performance electrode materials for energy storage.

Interface-modulated fabrication of hierarchical yolk-shell Co3O4/C dodecahedrons as stable anodes for lithium and sodium storage

Transition-metal oxides （TMOs） have gradually attracted attention from resear- chers as anode materials for lithium-ion batteries （LIBs） and sodium-ion batteries （SIBs） because of their high theoretical capacity. However, their poor cycling stability and inferior rate capability resulting from the large volume variation during the lithiation/sodiation process and their low intrinsic electronic con- ductivity limit their applications. To solve the problems of TMOs, carbon-based metal-oxide composites with complex structures derived from metal-organic frameworks （MOFs） have emerged as promising electrode materials for LIBs and SIBs. In this study, we adopted a facile interface-modulated method to synthesize yolk-shell carbon-based Co3O4 dodecahedrons derived from ZIF-67 zeolitic imida- zolate frameworks. This strategy is based on the interface separation between the ZIF-67 core and the carbon-based shell during the pyrolysis process. The unique yolk-shell structure effectively accommodates the volume expansion during lithiation or sodiation, and the carbon matrix improves the electrical conductivity of the electrode. As an anode for LIBs, the yolk-shell Co3O4/C dodecahedrons exhibit a high specific capacity and excellent cycling stability （1,100 mAh.g-1 after 120 cycles at 200 mA-g-1）. As an anode for S1Bs, the composites exhibit an outstand- ing rate capability （307 mAh-g-1 at 1,000 mA-g-1 and 269 mAh.g-1 at 2,000 mA-g-1）. Detailed electrochemical kinetic analysis indicates that the energy storage for Li＋ and Na＋ in yolk-sheU Co3O4/C dodecahedrons shows a dominant capacitive behavior. This work introduces an effective approach for fabricating carbon- based metal-oxide composites by using MOFs as ideal precursors and as electrode materials to enhance the electrochemical performance of LIBs and SIBs.

Carbon-supported and nanosheet-assembled vanadium oxide microspheres for stable lithium-ion battery anodes

Naturally abundant transition metal oxides with high theoretical capacity have attracted more attention than commercial graphite for use as anodes in lithium-ion batteries. Lithium-ion battery electrodes that exhibit excellent electrochemical performance can be efficiently achieved via three-dimensional （3D） architectures decorated with conductive polymers and carbon. As such, we developed 3D carbon-supported amorphous vanadium oxide microspheres and crystalline V203 microspheres via a facile solvothermal method. Both samples were assembled with ultrathin nanosheets, which consisted of uniformly distributed vanadium oxides and carbon. The formation processes were clearly revealed through a series of time-dependent experiments. These microspheres have numerous active reaction sites, high electronic conductivity, and excellent structural stability, which are all far superior to those of other lithium-ion battery anodes. More importantly, 95% of the second-cycle discharge capacity was retained after the amorphous microspheres were subjected to 7,000 cycles at a high rate of 2,000 mA/g. The crystalline microspheres also exhibited a high-rate and long-life performance, as evidenced by a 98% retention of the second-cycle discharge capacity after 9,000 cycles at a rate of 2,000 mA/g. Therefore, this facile solvothermal method as well as unique carbon-supported and nanosheet-assembled microspheres have significant potential for the synthesis of and use in, respectively, lithium-ion batteries.

Ammonium Ion and Structural Water Co-Assisted Zn^(2+) Intercalation/De-Intercalation in NH_(4)V_(4)O_(10)∙0.28H_(2)O

Main observation and conclusion The cathode material plays a crucial role in the performances of aqueous zinc-ion batteries(ZIBs).Herein,we report an ammonium vanadate(NH_(4)V_(4)O_(10)∙0.28H_(2)O,NHVO)aqueous ZIB cathode material.The obtained NHVO microflowers manifest high discharge capacity(410 mA·h∙g^(-1) at 0.2 A∙g^(-1)).

Interface-modulated approach toward multilevel metal oxide nanotubes for lithium-ion batteries and oxygen reduction reaction

Metal oxide hollow structures with multilevel interiors are of great interest for potential applications such as catalysis, chemical sensing, drug delivery, and energy storage. However, the controlled synthesis of multilevel nanotubes remains a great challenge. Here we develop a facile interface-modulated approach toward the synthesis of complex metal oxide multilevel nanotubes with tunable interior structures through electrospinning followed by controlled heat treatment. This versatile strategy can be effectively applied to fabricate wire-in-tube and tube- in-tube nanotubes of various metal oxides. These multilevel nanotubes possess a large specific surface area, fast mass transport, good strain accommodation, and high packing density, which are advantageous for lithium-ion batteries （LIBs） and the oxygen reduction reaction （ORR）. Specifically, shrinkable CoMn204 tube-in-tube nanotubes as a lithium-ion battery anode deliver a high discharge capacity of -565 mAh-g-1 at a high rate of 2 A.g-~, maintaining 89% of the latter after 500 cycles. Further, as an oxygen reduction reaction catalyst, these nanotubes also exhibit excellent stability with about 92% current retention after 30,000 s, which is higher than that of commercial Pt/C （81%）. Therefore, this feasible method may push the rapid development of one-dimensional （1D） nanomaterials. These multifunctional nanotubes have great potential in many frontier fields.

Two imprinted genes primed by DEMETER in the central cell and activated by WRKY10 in the endosperm

The early development of the endosperm is crucial for balancing the allocation of maternal nutrients to offspring.This process is believed to be evolutionarily associated with genomic imprinting,resulting in parentally biased allelic gene expression.Beyond Fertilization Independent Seed(FIS)genes,the number of imprinted genes involved in early endosperm development and seed size determination remains limited.This study introduces early endosperm-expressed HAIKU(IKU)downstream Candidate F-box 1(ICF1)and ICF2 as maternally expressed imprinted genes(MEGs)in Arabidopsis thaliana.Although these genes are also demethylated by DEMETER(DME)in the central cell,their activation differs from the direct DME-mediated activation seen in classical MEGs such as the FIS genes.Instead,ICF maternal alleles carry pre-established hypomethylation in their promoters,priming them for activation by the WRKY10 transcription factor in the endosperm.On the contrary,paternal alleles are predominantly suppressed by CG methylation.Furthermore,we find that ICF genes partially contribute to the small seed size observed in iku mutants.Our discovery reveals a two-step regulatory mechanism that highlights the important role of conventional transcription factors in the activation of imprinted genes,which was previously not fully recognized.Therefore,the mechanism provides a new dimension to understand the transcriptional regulation of imprinting in plant reproduction and development.