Understanding the electrochemical performance and diffusion kinetics of HC$||$Na$_3$V$_2$(PO$_4$)$_3$/C full cell battery for energy storage applications
Madhav Sharma, Rajendra S. Dhaka
备注：
to be published in Indian Journal of Physics and Applied Physics
The efficient energy storage devices are crucial to meet the soaring global energy demand for sustainable future. Recently, the sodium-ion batteries (SIBs) have emerged as one of the excellent cost effective solution due to the uniform geographical distribution and abundance of sodium. Here, we use hard carbon (HC) as an anode and Na$_3$V$_2$(PO$_4$)$_3$/C (NVP/C) as a cathode to fabricate a HC$||$NVP/C full cell battery and understand its electrochemical performance and diffusion kinetics. These materials are characterized through the analysis of x-ray diffraction and Raman spectroscopy to confirm their single phase and structure. The full cell demonstrates a high operating voltage of $\sim$3.3 V, with minimal polarization of 0.05 V, attributed to the lower working voltage of the HC. Interestingly, for the full cell battery we find the specific capacity of around 70 mAh/g at 0.1 C and even around 35 mAh/g at high current rate of 5 C along with high rate capability up to 55 cycles. The diffusion kinetics of the full cell battery is investigated through detailed analysis of CV curves at various scan rates, and the diffusion coefficient is found to be 5--8$\times$10$^{-11}$ cm$^2$/s for the anodic as well as cathodic peaks.
Here, we correlate the nanoscale morphology and chemical composition of solid electrolyte interphases (SEI) with the electrochemical property of graphite-based composite electrodes. Using electrochemical strain microscopy (ESM) and X-ray photoelectron spectroscopy (XPS), changes of chemical composition and morphology (Li and F distribution) in SEI layers on the electrodes as a function of solid electrolyte contents are analyzed. As a result, we find a strong correlation between morphological variations on the electrode, Li and F distribution in SEI layer, and Coulomb efficiency. This correlati…
Smoothed Boundary Method Framework for Electrochemical Simulation of Li-ion Battery Cathode with Complex Microstructure: Model, Formulation and Parameterization
Comprehensive parameter and electrochemical dataset for a 1 Ah graphite/LNMO battery cell for physical modelling as a blueprint for data reporting in battery research
Deutsches Zentrum für Luft- und Raumfahrt (DLR)（德国航空航天中心）；University of Stuttgart（斯图加特大学）；SINTEF Industry（辛特夫工业研究所）；Univ. Grenoble Alpes, CEA, Liten（格勒诺布尔阿尔卑斯大学，法国原子能和替代能源委员会，LITEN）；SINTEF Digital（辛特夫数字研究所）
We present a refined Mn-Zn-H$_2$O Pourbaix diagram with the emphasis on parameters relevant for the Zn/MnO$_2$ rechargeable cells. It maps out boundaries of electrochemical stability for MnO$_2$, ZnMn$_2$O$_4$, ZnMn$_3$O$_7$, and MnOOH. The diagram helps to rationalize experimental observation on processes and phases occurring during charge/discharge, including the position of charge/discharge redox peaks and capacity fade observed in rechargeable aqueous Zn-ion batteries for stationary storage. The proposed Pourbaix diagram is validated by observing the pH-dependent transformation of electrol…
The morphologies of crystalline lithium peroxide (Li2O2) discharge products in Li-O2 batteries have been shown to exhibit a dependency on subtle variations within the battery cell-operating environment including exposure to ambient air, moisture, or additives. As a result, imaging battery discharge products in real time under carefully controlled environmental conditions is a challenging obstacle for complete mechanistic understanding of Li2O2 growth and deposition during discharge in metal-air batteries. Here, we report the design of a completely enclosed cell for high-resolution in situ AFM …
Additive manufacturing and 3D printing in particular have the potential to revolutionize existing fabrication processes where objects with complex structures and shapes can be built with multifunctional material systems. For electrochemical energy storage devices such as batteries and supercapacitors, 3D printing methods allows alternative form factors to be conceived based on the end use application need in mind at the design stage. Additively manufactured energy storage devices require active materials and composites that are printable and this is influenced by performance requirements and t…
This report presents some of the key laboratory electrochemical battery testing methods that are used in fuel cell research. Methods such as voltammetry, chronoamperometry, chronopotentiometry, and electrochemical impedance spectroscopy are of major importance. All the electrochemical corrosion tests are performed through a tri-electrode polarization cell setup containing a reference electrode, a counter electrode, and the working electrode (metal sample of interest) in an electrolyte solution. All three electrodes are connected to a potentiostat. Corrosion of metal occurs through an oxidation…
Aqueous asymmetric electrochemical capacitor, with their high power density and superior cycle stability in comparison to conventional batteries, are presently considered as the most promising contender for energy storage. However, fabricating an electrode material and choosing a suitable aqueous electrolyte are vital in developing an electrochemical capacitor device with high charge storage capacity. Herein, we report a feasible method to synthesize MnO2/Vertical graphene nanosheets (VGN) and Fe2O3/VGN as positive and negative electrodes, respectively. The surface of VGN skeleton is independe…
This is the first quantitative analysis of mechanical reliability of all-solid state batteries. Mechanical degradation of the solid electrolyte (SE) is caused by intercalation-induced expansion of the electrode particles, within the constrain of a dense microstructure. A coupled electro-chemo-mechanical model was implemented to quantify the material properties that cause a SE to fracture. The treatment of microstructural details is essential to the understanding of stress-localization phenomena and fracture. A cohesive zone model is employed to simulate the evolution of damage. In the numerica…
Battery function is determined by the efficiency and reversibility of the electrochemical phase transformations at solid electrodes. The microscopic tools available to study the chemical states of matter with the required spatial resolution and chemical specificity are intrinsically limited when studying complex architectures by their reliance on two dimensional projections of thick material. Here, we report the development of soft X-ray ptychographic tomography, which resolves chemical states in three dimensions at 11-nm spatial resolution. We study an ensemble of nano-plates of lithium iron …
Two-dimensional carbides and nitrides of transition metals, known as MXenes, are a fast-growing family of 2D materials that draw attention as energy storage materials. So far, MXenes are mainly prepared from Al-containing MAX phases (where A = Al) by Al dissolution in F-containing solution, but most other MAX phases have not been explored. Here, a redox-controlled A-site-etching of MAX phases in Lewis acidic melts is proposed and validated by the synthesis of various MXenes from unconventional MAX phase precursors with A elements Si, Zn, and Ga. A negative electrode of Ti3C2 MXene material obt…
Energy demands of modern society require efficient means of energy conversion and storage. Nanocarbons have been identified as versatile materials which combine many desirable properties, allowing them to be used in electrochemical power sources, from electrochemical capacitors to fuel cells. Efficient production of nanocarbons requires innovative and scalable approaches which allow for tuning of their physical and chemical properties. Carbonization of polymeric nanostructures has been demonstrated as a promising approach for production of high-performance nanocarbons with desired morphology a…
With the rapid development of economy, the consumption of fossil fuels, and the increasing environment pollution, there is in urgent need of seeking clean and renewable energy sources, as well as highly efficient and low-cost energy storage technologies. Concerning electrochemically active materials, transition metal oxides (TMOs) are regarded as the most promising candidates for the next generation SCs and have been widely reported. Therefore, in this review, we mainly pay attention to TMOs with excellent electrochemical performance. This review is divided into four parts: (a) the background …
In Li-ion batteries the electrochemical potential drives the redox reactions occurring at the interface between electrolyte and storage material, typically active particles for porous electrodes, allowing Li ions intercalation/extraction from electrodes. The limiting factor of the process is not solely related to the electrochemical affinity, but also to structural features as the morphology of the electrodes. In this note, the relevance of the electrodes architecture is investigated numerically, in terms of the electro-chemo-mechanical response of a battery cell with homogeneous electrodes an…
Herein, in-situ reduction of bismuth and graphene oxide was performed by a solvothermal method under a nitrogen atmosphere, and the resulting Bi on RGO nanocomposites were used as an anode material for Mg-ion batteries. The nanocomposite of 60% Bi:40% RGO is a beneficial anode material, delivering a discharge capacity as high as 413 and 372 mAh per g at the specific current of 39 mA per g in the 1st and 50th cycles, respectively. In addition, it shows high-rate capability with the discharge capacities of 381, 372, 354, 295, and 238 mAh per g at the specific currents of 53, 100, 200, 500, and 7…
Additive manufacturing has revolutionized the building of materials direct from design, allowing high resolution rapid prototyping in complex 3D designs with many materials. 3D printing hasenabled high strength damage-tolerant structures, bioprinted artificial organs and tissues, ultralight metals, medicine, education, prosthetics, architecture, consumer electronics,and as a prototyping tool for engineers and hobbyists alike. 3D printing has emerged as a useful tool for complex electrode and material assembly method for batteries and supercapacitors in recent years. The field initially grew fr…
Identifying overpotential components of electrochemical systems enables quantitative analysis of polarization contributions of kinetic processes under practical operating conditions. However, the inherently coupled kinetic processes lead to an enormous challenge in measuring individual overpotentials, particularly in composite electrodes of lithium-ion batteries. Herein, the full decomposition of electrode overpotential is realized by the collaboration of single-layer structured particle electrode (SLPE) constructions and time-resolved potential measurements, explicitly revealing the evolution…
Performance Classification and Remaining Useful Life Prediction of Lithium Batteries Using Machine Learning and Early Cycle Electrochemical Impedance Spectroscopy Measurements
We report a comprehensive study on the electrochemical performance of four different Transition Metal Oxides encapsulated inside carbon nanotubes (CNT). Irrespective of the type of oxide-encapsulate, all these samples exhibit superior cyclic stability as compared to the bare-oxide. Innovative use of camphor during sample synthesis enables precise control over the morphology of these self-organized carbon nanotube structures, which in turn appears to play a crucial role in the magnitude of the specific capacity. A comparative evaluation of the electrochemical data on different samples bring for…
In order to develop a better understanding of electrochemical $\mathrm{O_2}$ reduction in non-aqueous solvents, we apply two-photon photoelectron spectroscopy to probe the dynamics of $\mathrm{O_2}$ reduction at a DMSO/Cu(111) model battery interface. By analyzing the temporal evolution of the photoemission signal, we observe the formation of $\mathrm{O_2^-}$ from a trapped electron state at the DMSO/vacuum interface. We find the vertical binding energy of $\mathrm{O_2^-}$ to be 3.80 $\pm$ 0.05 eV, in good agreement with previous results from electrochemical measurements, but with improved acc…
Lithium (Li) metal anodes are essential for developing next-generation high-energy-density batteries. However, Li dendrite/whisker formation caused short-circuiting issue and short cycle life have prevented lithium metal from being viably used in rechargeable batteries. Numerous works have been done to study how to regulate the Li growth in electrochemical cycling by using external stacking forces. While it is widely agreed that stack pressure positively affects the lithium plating/stripping process, the optimized pressure range provided by different works varies greatly because of the differe…
Chemical transformation of MgH2/V2O5 composite to Mg-V-O rock salt and its influence on the electrochemical Li conversion and hydrogen storage characteristics of MgH2
University of Aveiro（阿威罗大学）；LASI - Intelligent Systems Associate Laboratory（智能系统联合实验室）；International Iberian Nanotechnology Laboratory (INL)（伊比利亚纳米技术国际实验室）
Batteries are the most abundant form of electrochemical energy storage. Lithium and sodium ion batteries account for a significant portion of the battery market, but high-performance electrochemically active materials still need to be discovered and optimized for these technologies. Recently, tin(II) oxide (SnO) has emerged as a highly-promising battery electrode. In this work, we present a facile synthesis method to produce SnO nanoparticles whose size and shape can be tailored by changing the solvent nature. We study the complex relationship between wet chemistry synthesis conditions and res…
We report the electrochemical performance of nanostructures of Na$_{0.66}$V$_4$O$_{10}$ as cathode material for rechargeable batteries. The Rietveld refinement of room temperature x-ray diffraction pattern shows the monoclinic phase with C2/m space group. The cyclic voltammetry curves of prepared half-cells exhibit redox peaks at ~3.1 and 2.6~V, which are due to two-phase transition reaction between V$^{5+/4+}$ and can be assigned to the single step deintercalation/intercalation of Na-ion. We observe a good cycling stability with specific discharge capacity (measured vs. Na$^+$/Na) between 80 …
How surface chemistry influences reactions occurring thereupon has been a long-standing question of broad scientific and technological interest for centuries. Recently, it has re-emerged as a critical question in a subdiscipline of chemistry - electrochemistry at heterointerphases, where the answers have implications for both how, and in what forms, humanity stores the rising quantities of renewable electric power generated from solar and wind installations world-wide. Here we consider the relation between the surface chemistry at such interphases and the reversibility of electrochemical trans…
