Search Results (33)

High lithium and manganese oxides (HLMs), also known as lithium- and manganese-rich oxides (LMR), are an alternative to the state-of-the-art (SoA) cathode materials for Li-ion battery cells due to their high specific capacity, working potential, and potential elimination of cobalt from their composition. Nevertheless, they are claimed to undergo accelerated capacity and potential fade. In this work, an extensive electrochemical characterization is conducted while revisiting the most relevant literature on HLM. The classical galvanostatic cycling is used to conduct differential voltage and incremental capacity analyses, while impedance spectroscopy and galvanostatic intermittent titration techniques are applied to complement this test. The results are complemented with online electrochemical mass spectrometry and postmortem characterization. Loss of anode active material is identified as the main degradation mechanism, aggravated by potential slippage. Moreover, the hypotheses on degradation mechanisms are further confirmed by changing the voltage cutoffs of the cells, limiting the Li₂MnO₃ activation. The results are benchmarked with SoA LiNi_0.8Mn_0.1Co_0.1O₂-based cells with a promising balance for HLM in some cases. This work serves as a guide to assist in the interpretation (and avoid misinterpretation) of the results with Li-ion batteries consisting of HLM electrodes. Full article

Prussian blue (PB) and its analogs (PBAs) are considered ideal cathode materials for sodium-ion batteries (SIBs) due to the following merits, including high redox potential, simple synthesis methods, and excellent structural stability. Herein, we synthesized a high-entropy PB cathode material, Na_1.20Mn_0.38Fe_0.15Ni_0.14Co_0.15Cu_0.16[Fe(CN)₆]_0.82□_0.18·0.38H₂O (HE-HCF), through a facile co-precipitation method. The five transition metals in HE-HCF have similar atomic sizes and electronegativity, collectively occupying the high-spin Fe-HS sites. The manganese-based system design reduces the preparation cost, and the high-entropy doping approach further decreases the content of crystalline water in the structure. Benefiting from the synergistic effects of the multiple component elements, HE-HCF demonstrates a capacity retention rate of 72.7% at 0.1 A g⁻¹. Moreover, it even maintains 85.3% of its initial capacity after 1000 cycles at 1 A g⁻¹. Electrochemical impedance spectroscopy (EIS) and galvanostatic intermittent titration technique (GITT) analyses further confirm that HE-HCF exhibits low charge transfer resistance and a small reaction activation energy. Full article

Conventional applications of the Galvanostatic Intermittent Titration Technique (GITT) and EIS for estimating chemical diffusivity in battery electrodes face issues such as insufficient relaxation time to reach equilibrium, excessively long pulse durations that violate the short-time diffusion assumption, and the assumption of sequential electrode reaction and diffusion processes. In this work, a quasi-equilibrium criterion of 0.1 mV h⁻¹ was applied to NMC622 electrodes, yielding 8–9 h relaxations below 3.8 V, but above 3.8 V, voltage decayed linearly and indefinitely, even upon discharging titration, showing unusual nonmonotonic relaxation behavior. The initial 36-s transients of a 10-min galvanostatic pulse and diffusion impedance in series with the electrode reaction yielded consistent diffusivity values. However, solid-state diffusion in spherical active particles within porous electrodes, where ambipolar diffusion occurs in the pore electrolyte with $t_{+}=0.3$, requires a physics-based three-rail transmission line model (TLM). The corrected diffusivity may be three to four times higher. An analytic two-rail TLM approximating the three-rail numerical model was applied to temperature- and frequency-dependent EIS data. This approach mitigates parameter ambiguity and unphysical correlations in EIS. Physics-based EIS enables the identification of multistep energetics and the diagnosis of performance and degradation mechanisms. Full article

Natrium superionic conductor (NASICON) compounds have emerged as a rising star in the field of sodium-ion batteries (SIBs) owing to their stable framework structure and high Na⁺ ionic conductivity. The NASICON-structured Na₂VTi(PO₄)₃ manifests significant potential as Na⁺ storage material, characterized by decent rate capability and cyclability. However, the low redox potential of Ti³⁺/Ti⁴⁺ and undesirable energy density limit its practical applications. We developed a NASICON-structured Na₃Co_2/3V_2/3Ti_2/3(PO₄)₃ (NCTVP) cathode material by doping an appropriate amount of cobalt into Na₂VTi(PO₄)₃. Cobalt doping introduces a Co³⁺/Co²⁺ redox couple at ~4.1 V and activates the V⁵⁺/V⁴⁺ redox at ~3.9 V, resulting in significantly increased medium discharge voltage and capacity. NCTVP demonstrates a high capacity of over 160 mAh g⁻¹ at 20 mA g⁻¹. With a medium discharge voltage of ~2.7 V, the energy density of NCTVP reaches 432.0 Wh kg⁻¹. NCTVP also demonstrates desirable cycling stability (87.4% retention for 100 cycles at 50 mA g⁻¹). In situ X-ray diffraction discloses a solid solution reaction mechanism for NCTVP, while the galvanostatic intermittent titration technique demonstrates fast Na⁺ diffusion kinetics. NCTVP also demonstrates high capacity and good cyclability in full cells. This contribution demonstrates an effective approach for the construction of NASICON materials for SIBs. Full article

The development of high energy and power density sodium-ion batteries (SIBs) has attracted increasing interest in the last two decades due to the abundance and cost-effectiveness of sodium resources. Herein, this study developed a self-templating synthetic method to construct MoSe₂ nanosheets which were intercalated by ZnSe nanoparticles and were anchored on the in situ reduced graphene oxide layers. The thus-fabricated composites exhibited excellent Coulombic efficiency, a remarkable rate capability and an exceptionally long cycle life when being utilized as the anode in SIBs. Specifically, a reversible capacity of 265 mAh g⁻¹ was achieved at 20 A g⁻¹, which could be maintained for 6400 cycles. At an ultra-high rate of 30.0 A g⁻¹, the anode retained a capacity of 235 mAh g⁻¹ after 9500 cycles. Such a strong performance was attributed to its unique porous structure and synergistic interactions of multi-components. The underlying sodium storage mechanism was further investigated through various techniques such as in situ X-ray diffraction spectroscopy, the galvanostatic intermittent titration method, etc. Overall, this study illustrates the great potential of clad-structured multicomponent hybrids in developing high-performance SIBs. Full article

To develop an advanced anode for lithium-ion batteries, the electrochemical performance of a novel material comprising a porous artificial carbon (PAC)–Si composite was investigated. To increase the pore size and surface area of the composite, ammonium bicarbonate (ABC) was introduced during high-energy ball-milling, ensuring a uniform distribution of silicon within the PAC matrix. The physical and structural properties of the developed material were evaluated using several advanced techniques, including X-ray diffraction (XRD), transmission electron microscopy (TEM), and galvanostatic intermittent titration (GITT). Artificial graphite contains several macropores that can accommodate volume hysteresis and provide effective sites for anchoring Si nanoparticles, enabling efficient electrochemical reactions. GITT analysis revealed that the PAC-Si-CB-ABC composite exhibited superior lithium-ion diffusion compared to conventional graphite. The developed PAC(55%)-Si(45%)-CB-ABC electrode with PAA as the binder demonstrated a reversible capacity of 850 mAh g⁻¹ at 100 mA g⁻¹ and a high-rate capability of 600 mAh g⁻¹ at 2000 mA g⁻¹. A full cell employing the NCM622 cathode exhibited reversible cyclability of 128.9 mAh g⁻¹ with a reasonable energy density of 323.3 Wh kg⁻¹. These findings suggest that the developed composite is a useful anode system for advanced lithium-ion batteries. Full article

Fluorinated carbon cathode materials have extremely high theoretical specific energy among known cathode materials of lithium primary batteries. Nevertheless, current fluorinated carbon cannot meet the performance demands of future applications due to the rate performance. This work innovatively applies hollow carbon spheres with a porous structure as carbon sources to prepare fluorinated hollow porous carbon spheres (FHPCS) with high energy density and power density. The porous structure provides more reaction sites for the fluorination process and also shortens the diffusion path of lithium ions during the discharge. Additionally, the hollow porous structure offers more interfacial contact areas and reduces volumetric expansion during discharge reactions. The Li/CF_x primary battery has a maximum specific energy of 2007 Wh kg⁻¹ and a maximum power density of 30,400 W kg⁻¹ and can have a capacity retention rate of 80.8% at a current density of 16 A g⁻¹. In addition, FHPCS also has the highest specific energy of 1999 Wh kg⁻¹ and 1711 Wh kg⁻¹ in Na/CF_x and K/CF_x primary batteries, respectively. The diffusion efficiency of an alkali metal ion is analyzed by the different discharge depths with electrochemical impedance spectroscopy and galvanostatic intermittent titration technique. This effort introduces a new high-performance fluorinated carbon featuring a hollow porous structure and puts forward an innovative approach to designing fluorinated carbon materials. Full article

Reduced-order electrothermal models play a key role in the design and control of lithium-ion cell stacks, calling for accurate model parameter calibration. This paper presents a complete electrical and thermal experimental characterization procedure for the coupled modeling of cylindrical lithium-ion cells in order to implement them in a prototype Formula SAE hybrid racing car. The main goal of the tests is to determine how the cell capacity varies with the temperature and the discharge current to predict the open-circuit voltage of the cell and its entropic component. A simple approach for the characterization of the battery equivalent electrical circuit and a two-step thermal characterization method are also shown. The investigations are carried out on four commercial 18650 NMC lithium cells. The model was shown to predict the battery voltage with an RMS error lower than 20 mV and the temperature with an RMS error equal to 0.5 °C. The authors hope that this manuscript can contribute to the development of standardized characterization techniques for such cells while offering experimental data and validated models that can be used by researchers and BMS designers in different applications. Full article

The electroanalytical behavior of SnS_x (x = 1, 2) encapsulated into a carbon phase was studied using the galvanostatic intermittent titration technique (GITT) and electrochemical impedance spectroscopy (EIS). These techniques are widely utilized in battery systems to investigate the diffusion of alkali metal cations in anode and cathode materials depending on the concentration of ions in the host material. Here, we report different calculation methods showing how the applied model affects the derived diffusion coefficient. The calculated value of the apparent chemical diffusion coefficient of sodium ions ($D_{{\mathrm{N}\mathrm{a}}^{+}}$) is in the range of 1 × 10⁻¹⁰ to 1 × 10⁻¹⁵ cm²/s depending on the technique, mathematical protocol, geometry of the electrode material, and applied potential. Full article

Given the relevance of lithium and post-lithium batteries as electrochemical energy storage systems, the peculiar crystalline structure of V₂O₅ and its doping capacity play key roles in lithium-ion battery technology. To integrate them in high-efficiency modules, systematic methodologies are required to estimate the state of charge in a reliable way and predict the Li-V₂O₅ battery’s performance according to their electrochemical phenomena, including two plateaus in the galvanostatic cycling curves and the dynamic behavior governed by the energy demand. Most state of charge estimation and battery modeling procedures are focused on conventional Li-batteries that show a unique plateau. In this work, we propose a systematic methodology based on the galvanostatic intermittent titration technique and electrochemical impedance spectroscopy to study battery performance in the time and frequency domains, respectively. The proposed methodology, with a time–frequency correlation, promotes a deeper understanding of the electrochemical phenomena and general behavior of Li-V₂O₅ batteries, allowing for its subsequent extrapolation to more complex and higher-capacity lithium and post-lithium batteries used in high-power applications with a minimum error. Full article

Cation-disordered rock salt (DRX) cathodes exhibit high specific capacity due to the simultaneous use of anionic and cationic redox reactions. However, DRX systems face severe challenges that limit their practical applications; a most important challenge is their poor rate performance. In this work, the structure and morphology of Li_1.17Ti_0.58Ni_0.25O₂ (LTNO) were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), etc. In combination with various electrochemical characterizations, we found that the sluggish kinetics of anionic redox within LTNO can be the key reason for the inferior rate performance. By sample relaxation at moderate temperature and X-ray absorption near edge structure (XANES), the ligand-to-metal charge transfer process is verified to occur between O and Ni and exhibits a prolonged characteristic time of 113.8 min. This time-consuming charge transfer process is verified to be the very fundamental origin of the slow kinetics of oxygen oxidation and reduction. This claim is further supported by the galvanostatic intermittent titration technique (GITT) at different temperatures. These findings provide essential guidance for understanding and further optimizing cathodes with anion redox reactions not only in the context of DRX cathodes but also conventional Li-rich cathodes. Full article

This paper presents an innovative and efficient methodology for the determination of the solid-state diffusion coefficient in electrode materials with phase transitions for which the assumption of applying the well-known formula from the work of Weppner et al. is not satisfied. This methodology includes a k-means machine learning screening of Galvanostatic Intermittent Titration Technique (GITT) steps, whose outcomes feed a physics-informed algorithm, the latter involving a pseudo-two-dimensional (P2D) electrochemical model for carrying out the numerical simulations. This methodology enables determining, for all of the 47 steps of the GITT characterization, the dependency of the Na⁺ diffusion coefficient as well as the reaction rate constant during the sodiation of an NVPF electrode to vary between $9$ × ${10}^{-18}$ and $6.8$ × ${10}^{-16}$ m²·s⁻¹ and between $2.7$ × ${10}^{-14}$ and $1.5$ × ${10}^{-12}$ m^2.5·mol^−0.5·s⁻¹, respectively. This methodology, also validated in this paper, is (a) innovative since it presents for the first time the successful application of unsupervised machine learning via k-means clustering for the categorization of GITT steps according to their characteristics in terms of voltage; (b) efficient given the considerable reduction in the number of iterations required with an average number of iterations equal to 8, and given the fact the entire experimental duration of each step should not be simulated anymore and hence can be simply restricted to the part with current and a small part of the rest period; (c) generically applicable since the methodology and its physics-informed algorithm only rely on “if” and “else” statements, i.e., no particular module/toolbox is required, which enables its replication and implementation for electrochemical models written in any programming language. Full article

The operating temperature of a battery energy storage system (BESS) has a significant impact on battery performance, such as safety, state of charge (SOC), and cycle life. For weather-resistant aluminum batteries (AlBs), the precision of the SOC is sensitive to temperature variation, and errors in the SOC of AlBs may occur. In this study, a combination of the experimental charge/discharge data and a 3D anisotropic homogeneous (Ani-hom) transient heat transfer simulation is performed to understand the thermal effect of a novel battery system, say an aluminum-ion battery. The study conducts a turbulence fluid dynamics method to solve the temperature distribution of the battery rack, and the entropy generation method analyzes the heat generation of AlB during the charging/discharging process. The AlB is modeled by a second-order Thevenin equivalent circuit to estimate the status of the battery. An extended Kalman filter is applied to obtain the accurate SOC for monitoring the battery cell. The current study conducts the Galvanostatic Intermittent Titration Technique (GITT) on aluminum-ion batteries under different operation temperatures: 25 °C, 40 °C, 60 °C, and 80 °C. According to the sensitivity analysis of the SOC, the temperature sensitivity tends to or greater than one, $S_T\ge 1$, while the operation temperature is above 40 °C, and the SOC modification of EKF_tmep estimator improves the battery state of charge in the error range below 1%. Full article

Niobates are very promising anode materials for Li⁺-storage rooted in their good safety and high capacities. However, the exploration of niobate anode materials is still insufficient. In this work, we explore ~1 wt% carbon-coated CuNb₁₃O₃₃ microparticles (C-CuNb₁₃O₃₃) with a stable shear ReO₃ structure as a new anode material to store Li⁺. C-CuNb₁₃O₃₃ delivers a safe operation potential (~1.54 V), high reversible capacity of 244 mAh g⁻¹, and high initial-cycle Coulombic efficiency of 90.4% at 0.1C. Its fast Li⁺ transport is systematically confirmed through galvanostatic intermittent titration technique and cyclic voltammetry, which reveal an ultra-high average Li⁺ diffusion coefficient (~5 × 10^–11 cm² s⁻¹), significantly contributing to its excellent rate capability with capacity retention of 69.4%/59.9% at 10C/20C relative to 0.5C. An in-situ XRD test is performed to analyze crystal-structural evolutions of C-CuNb₁₃O₃₃ during lithiation/delithiation, demonstrating its intercalation-type Li⁺-storage mechanism with small unit-cell-volume variations, which results in its capacity retention of 86.2%/92.3% at 10C/20C after 3000 cycles. These comprehensively good electrochemical properties indicate that C-CuNb₁₃O₃₃ is a practical anode material for high-performance energy-storage applications. Full article

The slow diffusion dynamics hinder aqueous MnO₂/Zn batteries’ further development. Here, a Ni/Fe bimetallic co-doped MnO₂ (NFMO) cathode material was studied by density functional theory (DFT) calculation and experimental characterization techniques, such as cyclic voltammetry (CV), galvanostatic intermittent titration technique (GITT) and electrochemical impedance spectra (EIS). The results indicated that the energy band structure and electronic state of MnO₂ were effectively optimized due to the simultaneous incorporation of strongly electronegative Ni and Fe ions. Consequently, the NFMO cathode material exhibited a faster charge transfer and ion diffusion dynamics than MnO₂ (MO), thus, the assembled NFMO/Zn batteries delivered excellent rate performance (181 mA h g⁻¹ at 3 A g⁻¹). The bimetallic ions co-doping strategy provides new directions for the development of oxide cathode materials towards high-performance aqueous zinc-ion batteries. Full article