Capacitive tendency concept alongside supervised machine-learning toward classifying electrochemical behavior of battery and pseudocapacitor materials.

In recent decades, more than 100,000 scientific articles have been devoted to the development of electrode materials for supercapacitors and batteries. However, there is still intense debate surrounding the criteria for determining the electrochemical behavior involved in Faradaic reactions, as the issue is often complicated by the electrochemical signals produced by various electrode materials and their different physicochemical properties. The difficulty lies in the inability to determine which electrode type (battery vs. pseudocapacitor) these materials belong to via simple binary classification. To overcome this difficulty, we apply supervised machine learning for image classification to electrochemical shape analysis (over 5500 Cyclic Voltammetry curves and 2900 Galvanostatic Charge-Discharge curves), with the predicted confidence percentage reflecting the shape trend of the curve and thus defined as a manufacturer. It's called "capacitive tendency". This predictor not only transcends the limitations of human-based classification but also provides statistical trends regarding electrochemical behavior. Of note, and of particular importance to the electrochemical energy storage community, which publishes over a hundred articles per week, we have created an online tool to easily categorize their data.

Investigating the Perovskite Ag1-3xLaxNbO3 as a High-Rate Negative Electrode for Li-Ion Batteries.

The broader development of the electric car for tomorrow's mobility requires the emergence of new fast-charging negative electrode materials to replace graphite in Li-ion batteries. In this area, the design of new compounds using innovative approaches could be the key to discovering new negative electrode materials that allow for faster charging and discharging processes. Here, we present a partially substituted AgNbO3 perovskite material by introducing lanthanum in the A-site. By creating two vacancies for every lanthanum introduced in the structure, the resulting general formula becomes Ag1-3xLax□2xNbO3 (with x ≤ 0.20 and where □ is a A-site vacancy), allowing the insertion of lithium ions. The highly substituted Ag0.40La0.20□0.40NbO3 oxide shows a specific capacity of 40 mAh.g-1 at a low sweep rate (0.1 mV s-1). Interestingly, Ag0.70La0.10□0.20NbO3 retains 64% of its capacity at a very high sweep rate (50 mV s-1) and about 95% after 800 cycles. Ex situ 7Li MAS NMR experiments confirmed the insertion of lithium ions in these materials. A kinetic analysis of Ag1-3xLax□2xNbO3 underlines the ability to store charge without solid-state ion-diffusion limitations. Furthermore, in situ XRD indicates no structural modification of the compound when accommodating lithium ions, which can be considered as zero-strain material. This finding explains the interesting capacity retention observed after 800 cycles. This paper thus demonstrates an alternative approach to traditional insertion materials and identifies a different way to explore not-so common electrode materials for fast energy storage application.

Electrode Design for MnO2-Based Aqueous Electrochemical Capacitors: Influence of Porosity and Mass Loading.

The purpose of this study is to highlight the influence of some fabrication parameters, such as mass loading and porosity, which are not really elucidated and standardized during the realization of electrodes for supercapacitors, especially when using metal oxides as electrode materials. Electrode calendering, as one stage during the fabrication of electrodes, was carried out step-by-step on manganese dioxide electrodes to study the decreasing porosity effect on the electrochemical performance of a MnO2 symmetric device. One other crucial parameter, the mass loading, which has to be understood and well used for realistic supercapacitors, was investigated concurrently. Gravimetric, areal and volumetric capacitances are highlighted, varying the porosity for low-, medium- and large-mass loading. Low-loading leads to the best specific capacitances but is not credible for realistic supercapacitors, except for microdevices. Down 50% porosities after calendering, capacitances are increased and become stable faster, suggesting a faster wettability of the dense electrodes by the electrolyte, especially for high-mass loading. EIS experiments performed on electrodes without and with calendering lead to a significant decrease of the device's time response, especially at high loading. A high-mass loading device seems to work as a power battery, whereas electrode calendaring, which allows decreasing the time response, leads to an electrical behavior closer to that expected for a supercapacitor.

Investigating the Cycling Stability of Fe2WO6 Pseudocapacitive Electrode Materials.

The stability upon cycling of Fe2WO6 used as a negative electrode material for electrochemical capacitors was investigated. The material was synthesized using low temperature conditions for the first time (220 °C). The electrochemical study of Fe2WO6 in a 5 M LiNO3 aqueous electrolyte led to a specific and volumetric capacitance of 38 F g-1 and 240 F cm-3 when cycled at 2 mV·s-1, respectively, associated with a minor capacitance loss after 10,000 cycles. In order to investigate this very good cycling stability, both surface and bulk characterization techniques (such as Transmission Electron Microscopy, Mössbauer spectroscopy, and magnetization measurements) were used. Only a slight disordering of the Fe3+ cations was observed in the structure, explaining the good stability of the Fe2WO6 upon cycling. This study adds another pseudocapacitive material to the short list of compounds that exhibit such a behavior up to now.

Unveiling Pseudocapacitive Charge Storage Behavior in FeWO4 Electrode Material by Operando X-Ray Absorption Spectroscopy.

In nanosized FeWO4 electrode material, both Fe and W metal cations are suspected to be involved in the fast and reversible Faradaic surface reactions giving rise to its pseudocapacitive signature. In order to fully understand the charge storage mechanism, a deeper insight into the involvement of the electroactive cations still has to be provided. The present paper illustrates how operando X-ray absorption spectroscopy is successfully used to collect data of unprecedented quality allowing to elucidate the complex electrochemical behavior of this multicationic pseudocapacitive material. Moreover, these in-depth experiments are obtained in real time upon cycling the electrode, which allows investigating the reactions occurring in the material within a realistic timescale, which is compatible with electrochemical capacitors practical operation. Both Fe K-edge and W L3 -edge measurements point out the involvement of the Fe3+ /Fe2+ redox couple in the charge storage while W6+ acts as a spectator cation. The result of this study enables to unambiguously discriminate between the Faradaic and capacitive behavior of FeWO4 . Beside these valuable insights toward the full description of the charge storage mechanism in FeWO4 , this paper demonstrates the potential of operando X-ray absorption spectroscopy to enable a better material engineering for new high capacitance pseudocapacitive materials.

Sparsely Pillared Graphene Materials for High-Performance Supercapacitors: Improving Ion Transport and Storage Capacity.

Graphene-based materials are extensively studied as promising candidates for supercapacitors (SCs) owing to the high surface area, electrical conductivity, and mechanical flexibility of graphene. Reduced graphene oxide (RGO), a close graphene-like material studied for SCs, offers limited specific capacitances (100 F·g-1) as the reduced graphene sheets partially restack through π-π interactions. This paper presents pillared graphene materials designed to minimize such graphitic restacking by cross-linking the graphene sheets with a bifunctional pillar molecule. Solid-state NMR, X-ray diffraction, and electrochemical analyses reveal that the synthesized materials possess covalently cross-linked graphene galleries that offer additional sites for ion sorption in SCs. Indeed, high specific capacitances in SCs are observed for the graphene materials synthesized with an optimized number of pillars. Specifically, the straightforward synthesis of a graphene hydrogel containing pillared structures and an interconnected porous network delivered a material with gravimetric capacitances two times greater than that of RGO (200 F·g-1 vs 107 F·g-1) and volumetric capacitances that are nearly four times larger (210 F·cm-3 vs 54 F·cm-3). Additionally, despite the presence of pillars inside the graphene galleries, the optimized materials show efficient ion transport characteristics. This work therefore brings perspectives for the next generation of high-performance SCs.

Ni(OH)2 and NiO Based Composites: Battery Type Electrode Materials for Hybrid Supercapacitor Devices.

Nanocomposites of Ni(OH)2 or NiO have successfully been used in electrodes in the last five years, but they have been falsely presented as pseudocapacitive electrodes for electrochemical capacitors and hybrid devices. Indeed, these nickel oxide or hydroxide electrodes are pure battery-type electrodes which store charges through faradaic processes as can be shown by cyclic voltammograms or constant current galvanostatic charge/discharge plots. Despite this misunderstanding, such electrodes can be of interest as positive electrodes in hybrid supercapacitors operating under KOH electrolyte, together with an activated carbon-negative electrode. This study indicates the requirements for the implementation of Ni(OH)2-based electrodes in hybrid designs and the improvements that are necessary in order to increase the energy and power densities of such devices. Mass loading is the key parameter which must be above 10 mg·cm−2 to correctly evaluate the performance of Ni(OH)2 or NiO-based nanocomposite electrodes and provide gravimetric capacity values. With such loadings, rate capability, capacity, cycling ability, energy and power densities can be accurately evaluated. Among the 80 papers analyzed in this study, there are indications that such nanocomposite electrode can successfully improve the performance of standard Ni(OH)2 (+)//6 M KOH//activated carbon (−) hybrid supercapacitor.

TiO2(B) nanoribbons as negative electrode material for lithium ion batteries with high rate performance.

Nanosized TiO(2)(B) has been investigated as a possible candidate to replace Li(4)Ti(5)O(12) or graphite as the negative electrode for a Li-ion battery. Nanoribbon precursors, classically synthesized in autogenous conditions at temperatures higher than 170 °C in alkaline medium, have been obtained, under reflux (T ∼ 120 °C, P = 1 bar). After ionic exchange, these nanoribbons exhibit a surface area of 140 m(2) g(-1), larger than those obtained under autogenous conditions or by solid state chemistry. These nanoparticles transform after annealing to isomorphic titanium dioxide. They mainly crystallize as the TiO(2)(B) variety with only 5% of anatase. This quantification of the anatase/TiO(2)(B) ratio was deduced from Raman spectroscopy measurement. TEM analysis highlights the excellent crystallinity of the nanosized TiO(2)(B), crystallizing as 6 nm thin nanoribbons. These characteristics are essential in lithium batteries for a fast lithium ion solid state diffusion into the active material. In lithium batteries, the TiO(2)(B) nanoribbons exhibit a good capacity and an excellent rate capability (reversible capacity of 200 mA h g(-1) at C/3 rate (111 mA g(-1)), 100 mA h g(-1) at 15C rate (5030 mA g(-1)) for a 50% carbon black loaded electrode). The electrode formulation study highlights the importance of the electronic and ionic connection around the active particles. The cycleability of the nano-TiO(2)(B) is another interesting point with a capacity loss of 5% only, over 500 cycles at 3C.