Ultracentrifugation: An effective novel route to ultrafast nanomaterials for hybrid supercapacitors

Energy storage devices are some of the most important environmental technologies that are highly influential in advancing our life in the future society. Specifically, electrochemical capacitor is an energy facilitator that exhibits an efficient/economical charging and discharging characteristics with long lifespan. Thus, the capacitor technology is regarded as promising due to an increasing effectiveness when combined with renewable (solar/wind/micro hydraulic) energy sources. In this connection, Li–ion-based hybrid supercapacitors and their functional materials are being vigorously researched in hopes to improve their capacity/voltage and therefore their energy density. Transition metal oxides are among the most popular materials utilized in this purpose. Thanks to high voltage and associated high energy density, they are tuned as both high energy and high power materials. In recent years, the structural/textural properties of oxides, including particle size, crystallinity, defects, and porosity, were successfully fine-tuned to achieve high rate performance over 300 C . The present review will describe pseudo-capacitive nanosized oxides prepared with in situ synthesis technique called “ultracentrifugation”, showing ultrafast electrochemical response even more than EDLC

Steric effects in adsorption of ions from mixed electrolytes into microporous carbon

With the goal to improve the capacitance in electrochemical double-layer capacitors (EDLCs) many studies on pore size/ion size relationship have been undertaken to achieve a better understanding of the charge storage mechanism in the electrochemical double-layer in confinement. A significant capacitance increase was achieved by using carbon electrodes with micropores (b1 nm), when the carbon pore size was close to the ion size. In this paper, the accessibility of narrow pores is investigated by selecting a carbon with a small pore size (b0.7 nm) and electrolyte mixtures with different ion sizes. It has been shown that the adsorption capacitance limitation observed for large cations and anions could be overcome by adding ions with a smaller effective size. This result demonstrates that the pores are accessible when their size matches the effective ion size and contradicts the surface saturation assumption; effective ion size which exceeds the pore size leads to current limitation. This work confirms that the steric effect is involved when ions are adsorbed into pores and highlights the importance of controlling ion size/pore size relationship for optimisation of the capacitive performance of EDLC devices

Enhanced Electrochemical Performance of Ultracentrifugation-Derived nc-Li3VO4/MWCNT Composites for Hybrid Supercapacitors

Nanocrystalline Li3VO4 dispersed within multiwalled carbon nanotubes (MWCNTs) was prepared using an ultracentrifugation (uc) process and electrochemically characterized in Li-containing electrolyte. When charged and discharged down to 0.1 V vs Li, the material reached 330 mAh g–1 (per composite) at an average voltage of about 1.0 V vs Li, with more than 50% capacity retention at a high current density of 20 A g–1. This current corresponds to a nearly 500C rate (7.2 s) for a porous carbon electrode normally used in electric double-layer capacitor devices (1C = 40 mA g–1 per activated carbon). The irreversible structure transformation during the first lithiation, assimilated as an activation process, was elucidated by careful investigation of in operando X-ray diffraction and X-ray absorption fine structure measurements. The activation process switches the reaction mechanism from a slow “two-phase” to a fast “solid-solution” in a limited voltage range (2.5–0.76 V vs Li), still keeping the capacity as high as 115 mAh g–1 (per composite). The uc-Li3VO4 composite operated in this potential range after the activation process allows fast Li+ intercalation/deintercalation with a small voltage hysteresis, leading to higher energy efficiency. It offers a promising alternative to replace high-rate Li4Ti5O12 electrodes in hybrid supercapacitor applications

Cation-Disordered Li3VO4: Reversible Li Insertion/Deinsertion Mechanism for Quasi Li-Rich Layered Li1+x[V1/2Li1/2]O2 (x = 0–1)

The reversible lithiation/delithiation mechanism of the cation-disordered Li3VO4 material was elucidated, including the understanding of structural and electrochemical signature changes during cycling. The initial exchange of two Li induces a progressive and irreversible migration of Li and V ions from tetrahedral to octahedral sites, confirmed by the combination of in situ/operando X-ray diffraction and X-ray absorption fine structure analyses. The resulting cation-disordered Li3VO4 can smoothly and reversibly accommodate two Li and shows a Li+ diffusion coefficient larger by 2 orders of magnitude than the one of pristine Li3VO4, leading to improved electrochemical performance. This cation-disordered Li3VO4 negative electrode offers new opportunities for designing high-energy and high-power supercapacitors. Furthermore, it opens new paths for preparing disordered compounds with the general hexagonal close-packing structure, including most polyanionic compounds, whose electrochemical performance can be easily improved by simple cation mixing

Dual-Cation Electrolytes for High-Power and High-Energy LTO//AC Hybrid Capacitors

Dual-cation electrolyte systems, which contain two cations [Li+ and spiro-1,1′-bipyrrolidinium (SBP+), are proposed to enhance the power capability of hybrid capacitors composed of thick Li4Ti5O12 (LTO) negative (200 μm) and activated carbon (AC) positive electrodes (400 μm), which thus reduces the resistive overvoltage in the system. Detailed studies of the mass transport properties based on the combination of spectroscopy and electrochemical analysis have shown that the presence of SBP+, despite slower Li+ transport in the electrolyte bulk, further reduces overvoltage associated with migration limitation in the thick LTO electrode macropores. This study on the dual-cation electrolyte quantifies the influence of the addition of a supporting electrolyte and shows interest in SBPBF4 addition for increasing the output power density of hybrid capacitors with a thick electrode configuration

Ultrafast charge–discharge characteristics of a nanosized core–shell structured LiFePO4 material for hybrid supercapacitor applications

Highly dispersed crystalline/amorphous LiFePO4 (LFP) nanoparticles encapsulated within hollow-structured graphitic carbon were synthesized using an in situ ultracentrifugation process. Ultracentrifugation triggered an in situ sol–gel reaction that led to the formation of core–shell LFP simultaneously hybridized with fractured graphitic carbon. The structure has double cores that contain a crystalline LFP (core 1) covered by an amorphous LFP containing Fe3+ defects (core 2), which are encapsulated by graphitic carbon (shell). These core–shell LFP nanocomposites show improved Li+ diffusivity thanks to the presence of an amorphous LFP phase. This material enables ultrafast discharge rates (60 mA h g-1 at 100C and 36 mA h g-1 at 300C) as well as ultrafast charge rates (60 mA h g-1 at 100C and 36 mA h g-1 at 300C). The synthesized core–shell nanocomposites overcome the inherent one-dimensional diffusion limitation in LFP and yet deliver/store high electrochemical capacity in both ways symmetrically up to 480C. Such a high rate symmetric capacity for both charge and discharge has never been reported so far for LFP cathode materials. This offers new opportunities for designing high-energy and high-power hybrid supercapacitors

Stabilizing the Structure of LiCoPO4 Nanocrystals via Addition of Fe3+: Formation of Fe3+ Surface Layer, Creation of Diffusion-Enhancing Vacancies, and Enabling High-Voltage Battery Operation

Factors affecting the cyclability of the Fe-substituted LiCoPO4 (LiCo0.8Fe0.2PO4, LCFP) material were elucidated, including both the structural and electrode/electrolyte stability. Electrochemical characterization of the synthesized LCFP nanoparticles lends clear evidence for improved electrochemical stability of LCP, as well as enhanced rate capability, with Fe3+ substitution. Surface analysis using X-ray photoelectron spectroscopy (XPS) and electron energy loss spectroscopy (EELS) suggest that Fe enrichment on the surface of LCFP occurs through the oxidation of Fe2+ into Fe3+ in the synthesis process. The Fe3+-rich phase on the LCP surface enhances the stability of the delithiated phase, preventing oxidative reactions with electrolytes during high-voltage operation. This surface protection persists as long as the electrochemical reduction of Fe3+ is avoided by ensuring that the full range of operating voltages lie above the Fe3+/Fe2+ redox potential. Our findings may offer new approaches to stabilize the structure of LCP and other high-voltage positive electrodes for use in 5 V-class Li-ion batteries

Noncrystalline Nanocomposites as a Remedy for the Low Diffusivity of Multivalent Ions in Battery Cathodes

Rechargeable batteries using multivalent metals are among the most promising next-generation battery systems due to their high capacity, high safety, and low cost compared with lithium-ion batteries. However, strong cation−anion interaction degrades diffusion in solid cathodes, an effect that must be mitigated to yield practical multivalent metal batteries. We show that a highly defective iron phosphate−carbon composite prepared by ultracentrifugation serves as a reversible insertion/deinsertion for magnesium ions with, and operates beyond, a 2-V cell voltage at room temperature. A composite of noncrystalline particles that embeds the surrounding carbon structure enhances the magnesium-ion diffusion in the solid phase with stability for cycle life. X-ray absorption spectroscopy, transmission electron microscopy with energy-dispersive X-ray spectroscopy, and high-energy X-ray scattering measurements demonstrate magnesium-ion insertion and extraction in the defective iron phosphate without conversion reactions. This work suggests promising applications for highly defective structures as intercalation hosts for multivalent ions

Recent Advances in Supercapacitors: Ultrafast Materials Make Innovations

Electrical energy storage (EES) devices are at the core of the environmental technologies that are highly influential in advancing our life in a future society. Among different EES technologies, electric double layer capacitors (EDLCs) are considered as promising devices due to their high-power, safe and long-lived characteristics. One of the approaches to further enhance the cell voltage and energy density of EDLCs while maintaining their high power is to replace the activated carbon with ultrafast lithium ion battery materials. Increasing their cell voltage and energy density contribute to decrease a number of serial cell connection and a volumetric package, respectively. In this article, we introduce examples of the synthesis of several nanomaterials using our original ultracentrifugation process, allowing the in-situ growth of active materials onto carbon surface enables ultrafast electrochemical response for 2nd and 3rd generation supercapacitors

Prolonged Electrochemical Cycling Characteristics of ZnSiP2 Prepared with Mixed Crystalline-Amorphous Domains

This paper presents an innovative approach wherein mechanical alloying and mechanical cation-disordering techniques are combined to synthesize peculiar zinc silicide phosphide (ZnSiP2) anode materials under controlled atmosphere. In this method, Zn atoms and P atoms are simultaneously incorporated into the parent Si crystal structure, resulting in A(II)xB(IV)yPx+y solid solutions with precise control over nanodomain structures of mixed crystalline-amorphous phases. This distinctive nanoarchitecture of the ZnSiP2 anode, featuring an amorphous ionic-conduction phase network, facilitates the smooth transport of Li+ ions, thereby enabling an exceptionally prolonged electrochemical cycling performance, surpassing 200 cycles. In this study, we attempted to unravel the microstructure of ZnSiP2 using transmission electron microscopy (TEM). It was observed that when synthesized under an inert Argon atmosphere, the material formed a polycrystalline structure consisting of numerous nanocrystals (5–10 nm) assembled. Additionally, when attempts were made to reduce synthesis costs by conducting the synthesis under ambient atmospheric (Air) conditions, amorphous regions were generated. This amorphous region within the polycrystalline ZnSiP2 microstructure represents a novel finding. The electrochemical impedance measurements and galvanostatic intermittent titration technique (GITT) analysis conducted in this study not only revealed but also characterized the enhanced cycling performance of this unique ZnSiP2 anode structure