Anion storing,oxygen vacancy incorporated perovskite oxide composites for high-performance aqueous dual ion hybrid supercapacitors

Dual ion storage hybrid supercapacitors(HsCs)are considered as a promising device to overcome the limited energy density of existing supercapacitors while preserving high power and long cyclability.However,the development of high-capacity anion-storing materials,which can be paired with fast charg-ing capacitive electrodes,lags behind cation-storing counterparts.Herein,we demonstrate the surface faradaic OH-storage mechanism of anion storing perovskite oxide composites and their application in high-performance dual ion HsCs.The oxygen vacancy and nanoparticle size of the reduced LaMnO_(3)(r-LaMnO_(3))were controlled,while r-LaMnO_(3) was chemically coupled with ozonated carbon nanotubes(oCNTs)for the improved anion storing capacity and cycle performance.As taken by in-situ and ex-situ spectroscopic and computational analyses,OH-ions are inserted into the oxygen vacancies coordi-nating with octahedral Mn with the increase in the oxidation state of Mn during the charging process or vice versa.Configuring OH-storing r-LaMnO_(3)/oCNT composite with Na*storing MXene,the as-fabricated aqueous dual ion HSCs achieved the cycle performance of 73.3%over 10,000 cycles,delivering the max-imum energy and power densities of 47.5 w h kg^(-1) and 8 kw kg^(-1),respectively,far exceeding those of previously reported aqueous anion and dual ion storage cells.This research establishes a foundation for the unique anion storage mechanism of the defect engineered perovskite oxides and the advancement of dual ion hybrid energy storage devices with high energy and power densities.

Boosted Storage Kinetics in Thick Hierarchical Micro-Nano Carbon Architectures for High Areal Capacity Li-Ion Batteries

A practical and effective approach to increase the energy storage capacity of lithium ion batteries(LIBs)is to boost their areal capacity.Developing thick electrodes is one of the most crucial ways to achieve high areal capacity but limited by sluggish ion/electron transport,poor mechanical stability,and high-cost manufacturing strategies.Here we address these constraints by engineering a unique hierarchical-networked 10 mm thick all-carbon electrode,providing a scalable strategy to produce high areal capacity LIB electrodes.The hierarchical-networked structure utilizes micrometer-sized carbon fibers(MCFs)as building blocks,nano-sized carbon nanotubes(CNTs)as good continuous network with excellent electrical conductivity,and pyrolytic carbon as the binder and active material with excellent storage capacity.The combination of the above features endows our HNT-MCF/CNT/PC electrode with excellent performance including high reversible capacity of 15.44 mAh cm^(-2) at 2.0 mA cm^(-2) and exhibits excellent rate capability of 2.50 mAh cm^(-2) under 10.0 mA cm^(-2) current density.The Li-ion storage mechanism in HNT-MCF/CNT/PC involves dual-storage mechanism including intercalation and surface adsorption(pseudocapacitance)confirmed by the cyclic voltammetry and symmetric cell analysis.This work provides insights into the construction of high mechanical stability thick electrode for the next generation high areal capacity LIBs and beyond.

Realizing the highly reversible Zn^(2+)and Na^(+) dual ions storage in high-crystallinity nickel hexacyanoferrate microcubes for aqueous zinc-ion batteries

Prussian blue analogues(PBAs)with the 3D open framework are regarded as promising cathode candidates for aqueous Zinc ion batteries(ZIBs).Among various PBAs,nickel hexacyanoferrate(NiHCF)has attracted considerable attention because of its high operating voltage and economic merit.However,the cyclability of NiHCF is unsatisfactory due to poor structural stability during Zn^(2+) ions insertion/deinsertion.Moreover,the ion storage mechanism of NiHCF in aqueous electrolytes has not been fully revealed yet.Herein,high-crystallinity NiHCF(HC-NiHCF)microcubes with improved structural stability and larger crystal plane spacing are synthesized.For the first time,highly reversible Zn2+ions and Na+ions co-insertion/extraction are achieved for the HC-NiHCF microcubes in mixed aqueous electrolyte,as evidenced by various observations including two separated discharge plateaus and sequential changes of Na 1s and Zn 2p signals in ex-situ X-ray photoelectron spectroscopy(XPS).As a result,a high specific capacity of 73.9 mAh g^(−1) is obtained for the HC-NiHCF microcubes at 0.1 A g−1,combined with enhanced cycle stability(75%vs.16.4%)over 1000 cycles at 2 A g^(−1).The reversible Zn^(2+) ions and Na+ions co-insertion in HC-NiHCF microcubes reveals a new ion storage mechanism of Ni-based PBAs in aqueous electrolytes.