Performance Classification and Remaining Useful Life Prediction of Lithium Batteries Using Machine Learning and Early Cycle Electrochemical Impedance Spectroscopy Measurements
Christian Parsons, Adil Amin, Prasenjit Guptasarma
We presents an approach for early cycle classification of lithium-ion batteries into high and low-performing categories, coupled with the prediction of their remaining useful life (RUL) using a linear lasso technique. Traditional methods often rely on extensive cycling and the measurement of a large number of electrochemical impedance spectroscopy (EIS) frequencies to assess battery performance, which can be time and resource consuming. In this study, we propose a methodology that leverages specific EIS frequencies to achieve accurate classification and RUL prediction within the first few cycles of battery operation. Notably, given only the 20 kHz impedance response, our support vector machine (SVM) model classifies batteries with 100\% accuracy. Additionally, our findings reveal that battery performance classification is frequency agnostic within the high frequency ($<20$ kHz) to low-frequency (32 mHz) range. Our model also demonstrates accurate RUL predictions with $R^2>0.96$ based on the out of phase impedance response at a single high (20 kHz) and a single mid-frequency (8.8 Hz), in conjunction with temperature data. This research underscores the significance of the mid-frequency impedance response as merely one among several crucial features in determining battery performance, thereby broadening the understanding of factors influencing battery behavior.
We demonstrate that failure of time-invariance assumption in the modeling of electrochemical systems by equivalent circuits can lead to the formation of low frequency "inductive loops" that manifest themselves as positive imaginary parts of the impedance function. Assuming that the properties of the equivalent circuits change slowly in time we perform an asymptotic analysis and obtain a new integral representation of the impedance function that reduces to the standard one at high frequencies, while exhibiting inductive loops at low frequencies.
Herein we report on a detailed investigation of the irreversible capacity in the first cycle of pyrolytic graphite electrodes in aluminum batteries employing 1-ethyl-3-methylimidazolium chloride:aluminum trichloride (EMIMCl:AlCl3) as electrolyte. The reaction mechanism, involving the intercalation of AlCl4 in graphite, has been fully characterized by correlating the micro/nanostructural modification to the electrochemical performance. To achieve this aim a combination of X-ray diffraction (XRD), small angle X-ray scattering (SAXS) and computed tomography (CT) has been used. The reported result…
Embedding silicon nanoparticles in an intermetallic matrix is a promising strategy to produce remarkable bulk anode materials for lithium-ion (Li-ion) batteries with low potential, high electrochemical capacity and good cycling stability. These composite materials can be synthetized at a large scale using mechanical milling. However, for Si-Ni3Sn4 composites, milling also induces a chemical reaction between the two components leading to the formation of free Sn and NiSi2, which is detrimental to the performance of the electrode. To prevent this reaction, a modification of the surface chemistry…
The class of two-dimensional metal carbides and nitrides known as MXenes offer a distinct manner of property tailoring for a wide range of applications. The ability to tune the surface chemistry for expanding the property space of MXenes is thus an important topic, although experimental exploration of new surface terminals remains a challenge. Here, we synthesized Ti3C2 MXene with unitary, binary and ternary halogen terminals, e.g. -Cl, -Br, -I, -BrI and -ClBrI, to investigate the effect of surface chemistry on the properties of MXenes. The electrochemical activity of Br and I element result i…
Solid state batteries have emerged as a potential next-generation energy storage device due to safety and energy density advantages. Development of electrolyte is one of the most important topics in solid state batteries. Electrochemical Impedance Spectroscopy (EIS) is a popular measurement technique to obtain the conductivity and diagnose the electrolyte. Current interpretation mainly uses the semicircle part of the curves and discards other information revealed by EIS such as the slope of the curve at low frequency. What is worse, some features on the curve are not fully interpreted. To bett…
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 …
MoO2/C-composites have been fabricated for the first time by a tartaric acid/glucose-assisted sol-gel method with post-annealing at 500 °C for 1 h in N2 flow. The synthesized materials were fully characterized with respect to structure, morphology, and electrochemical properties. Compared with tartaric acid-assisted products, the adoption of glucose as carbon source effectively increases the carbon content in the composites. Irrespective of the organic component, the composites exhibit low crystallinity and small grain size. This results in good electrochemical performance of the anode materia…
We establish, in general terms, the conditions to be satisfied by a time-fractional approach formulation of the Poisson-Nernst-Planck model in order to guarantee that the total current across the sample be solenoidal, as required by the Maxwell equation. Only in this case the electric impedance of a cell can be determined as the ratio between the applied difference of potential and the current across the cell. We show that in the case of anomalous diffusion, the model predicts for the electric impedance of the cell a constant phase element behaviour in the low frequency region. In the parametr…
Sodium ion batteries (SIBs) are considered as an efficient alternative for lithium-ion batteries (LIBs) owing to the natural abundance and low cost of sodium than lithium. In this context, the anode materials play a vital role in rechargeable batteries to acquire high energy and power density. In order to demonstrate transition metal dichalcogenide (TMD) as potential anode materials, we have synthesized MoSeTe sample by conventional flux method, and the structure and morphology are characterized using x-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), transmission el…
We synthesized the pure and co-doped titanium dioxide (TiO$_2$) electrodes via spin coating. We examined the optical and electronic properties of as-prepared thin film electrodes with co-doping of transition metals and non-metals. The co-doping of Cu, Zn, and N increase the absorption of the radiation in the visible region. The doping leads to the formation of defect states in the electrodes. In this article, we have studied the carrier kinetics in pristine and co-doped TiO2 electrodes. To study the role of dopants in carrier transport of the synthesized TiO2 based electrodes, the electrochemi…
We report the electrochemical investigation of 5% Al doped MoS$_2$@rGO composite as a high-performance anode for sodium (Na)-ion batteries. The x-ray diffraction (XRD), Raman spectroscopy and high-resolution transmission electron microscopy characterizations reveal that the Al doping increase the interlayer spacing of (002) plane of MoS$_2$ nanosheets and form a stable 1T phase. The galvanostatic charge-discharge measurements show the specific capacity stable around 450, 400, 350, 300 and 200 mAhg$^{-1}$ at current densities of 0.05, 0.1, 0.3, 0.5 and 1~Ag$^{-1}$, respectively. Also, we observ…
Li3VO4/C composites have been synthesized by a sol-gel method and post-annealing at 650 °C for 1 h in N2 flow using either tartaric acid, malic acid, or glucose as both chelating agents and carbon source. The presence of these organic additives crucially affects morphology and crystallite size of the final product. It is found that the electrochemical properties of Li3VO4/C as anode material for Li-ion batteries (LIBs) are influenced by the morphology, texture and carbon content of the material. When using carboxylic acids as carbon source composites with mesoporous structure and a high surfac…
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…
The polyanionic compound Na2MnSiO4 is regarded as one of the promising cathode materials for Na-ion batteries due to good specific capacity with its attractive prospect of utilization of two electrons in the redox processes. So, in this study, we have performed the thermodynamic and electronic structure analysis of Na2MnSiO4 using first principles density functional theory calculations. The intermediate ground state configurations for Na2MnSiO4of Na de-intercalation were found using the cluster expansion method and are used to obtain the 0 K voltage profile as a function of Na concentration. T…
It is well known that the spatial distribution of the carbon-binder domain (CBD) offers a large potential to further optimize lithium-ion batteries. However, it is challenging to reconstruct the CBD from tomographic image data obtained by synchrotron tomography. In the present paper, we consider several approaches to segment 3D image data of two different cathodes into three phases, namely active material, CBD and pores. More precisely, we focus on global thresholding, a local closing approach based on EDX data, a k-means clustering method, and a procedure based on a neural network that has be…
Electrochemical Impedance Spectroscopy and Raman studies are performed on fast ion conducting, AgI-Ag2O-MoO3 glasses, over a wide range of composition to understand the features of structure, ion migration and their correlation. These features essentially involve diffusion and relaxation. The coefficients associated with diffusion process, especially, the diffusion coefficient, diffusion length and relaxation time has been determined by applying Nguyen-Breitkopf method. Besides, by tuning the concentration of the constituents, it is possible to obtain samples those exhibit two important struct…
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…
Varying the amounts of silicon and carbon, different composites have been prepared by ball milling of Si, Ni$_{3.4}$Sn$_4$, Al and C. Silicon and carbon contents are varied from 10 to 30 wt.% Si, and 0 to 20 wt.% C. The microstructural and electrochemical properties of the composites have been investigated by X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and electrochemical galvanostatic cycling up to 1000 cycles. Impact of silicon and carbon contents on the phase occurrence, electrochemical capacity and cycle-life are compared and discussed. For C-content comprised between 9 and…
In search of the potential cathode materials for sodium-ion batteries and to understand the diffusion kinetics, we report the detailed analysis of electrochemical investigation of honeycomb structured Na$_{2}$Ni$_{2}$TeO$_{6}$ material using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), galvanostatic charge-discharge (GCD) and galvanostatic intermittent titration technique (GITT). We found the discharge capacities of 82 and 77 mAhg$^{-1}$ at 0.05~C and 0.1~C current rates, respectively, and the mid-working potential of $\approx$3.9~V at 1~C and high capacity retention …
We present a refined Mn-Zn-H$_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 coloration mechanisms in electrochromic (EC) systems can be probed by comparing the dynamics of the electrical and optical responses. In this paper, the linear frequency-dependent electrical and optical responses of an amorphous tungsten oxide thin film were measured simultaneously by a combination of two techniques$\text{---}$that is, electrochemical impedance spectroscopy (EIS) and the so-called color impedance spectroscopy (CIS). This was done at different bias potentials, which can be associated with different intercalation levels. Equivalent circuit fitting to the EIS spectra was used…
Electrochemical performance and diffusion kinetics of a NASICON type Na$_{3.3}$Mn$_{1.2}$Ti$_{0.75}$Mo$_{0.05}$(PO$_4$)$_3$/C cathode for low-cost sodium-ion batteries
Improved Electrochemical Performance and Diffusion kinetics by Boron-doping in Na$_{0.66}$Mn$_{0.8}$Fe$_{0.2}$O$_{2}$ Layered Cathodes for Sodium-Ion Batteries
Indian Institute of Technology Delhi（印度德里理工学院）；Hindu College, University of Delhi（德里大学印度教学院）；Indian Institute of Technology Delhi-Abu Dhabi（印度德里理工学院阿布扎比分校）
The practical applications of lithium selenium (Li-Se) batteries are impeded primarily due to the dissolution and migration of higher order polyselenides (Li2Sen) into the electrolyte (known as shuttle effect) and inactive deposition of lower order polyselenides. The high electrical conductivity and mechanical strengths of MXenes make them a suitable candidate to provide adequate anchoring to prevent polyselenides dissolution and improved electrochemical performance. Herein, we used density functional theory (DFT) calculations to understand the binding mechanism of Li2Sen on graphene and surfa…
Downsizing well-established materials to the nanoscale is a key route to novel functionalities, in particular if different functionalities are merged in hybrid nanomaterials. Hybrid carbon-based hierarchical nanostructures are particularly promising for electrochemical energy storage since they combine benefits of nanosize effects, enhanced electrical conductivity and integrity of bulk materials. We show that endohedral multiwalled carbon nanotubes (CNT) encapsulating high-capacity (here: conversion and alloying) electrode materials have a high potential for use in anode materials for lithium-…
Combined frequency-resolved techniques are suitable to study electrochromic (EC) materials. We present an experimental setup for simultaneous electrochemical and color impedance studies of EC systems in transmission mode and estimate its frequency-dependent uncertainty by measuring the background noise. We define the frequency-dependent variables that are relevant to the combined measurement scheme, and a special emphasis is given to the complex optical capacitance and the complex differential coloration efficiency, which provide the relation between the electrical and optical responses. Resul…
Molecular interpretability of the bulk electrochemical impedance of concentrated electrolytes
Yusuf Hamied Department of Chemistry, University of Cambridge（剑桥大学尤素夫·哈米德化学系）；Department of Chemistry, Durham University（杜伦大学化学系）；Sorbonne Université, CNRS, Physical Chemistry of Electrolytes and Interfacial Nanosystems (PHENIX)（索邦大学，法国国家科学研究中心，电解质和界面纳米系统物理化学（PHENIX））；Réseau sur le Stockage Electrochimique de l’Energie (RS2E), FR CNRS 3459（电化学储能网络（RS2E），FR CNRS 3459）
