Lithium-ion batteries (LIBs) dominate the electrochemical energy storage field currently, yet undergraduate materials science and engineering students often encounter LIB technology primarily via classroom studies. Despite having a fundamental knowledge of electrochemistry, still hands-on experience with cell construction, testing, and performance analysis is missing. This article describes a structured, short-term laboratory module, allowing students to apply fundamental electrochemical principles by assembling and evaluating lithium-ion coin cells. Students construct CR2032 coin cells with graphite anodes and lithium oxide-based cathodes (particularly lithium cobalt oxide or lithium manganese oxide) and test their electrochemical performance under controlled cycling settings. This report shows the analysis of six basic charts, assisting the discussion of important performance metrics such as capacity retention and coulombic efficiency. The subject is purposely comprehensive and analytical, pushing students to use theoretical knowledge, while gaining also practical understanding of experimental constraints and design choices. In addition, general battery-related difficulties and future prospects are raised to encourage additional theoretical and experimental research. This hands-on teaching approach is straightforward, versatile, and easily adaptable to various battery chemistries or extended testing of performance deterioration during cycling.

Herein, a novel open-source software for predicting the performance of single particles of electrode materials under galvanostatic charging conditions is presented. The model improves previous work by incorporating different thermodynamic approaches to describe the interaction between intercalated ions, and the software provides tools for fitting different kinetic parameters and generating potential/capacity profiles or concentration/distance profiles to be analyzed. These features allow for detailed studies of the factors limiting the charging rate of active materials in which ions are intercalated. The diagnostic diagram is constructed through simulations of the capacity reached for a given potential cut-off, represented in the domain of two dimensionless parameters. These parameters represent kinetic and particle-size limitations for Li-ion storage. The present tool aims to facilitate the analysis of single-particle experiments, taking advantage of two different computational languages, popular in scientific computing: Python and C++. The software integrates a Python interface, for user-friendly interaction, with a C++ computational core allowing parallelization via OpenMP, for high computational performance. The software supports different thermodynamic approaches: Langmuir-Frumkin intercalation model and equilibrium potentials derived from experimental data. The inclusion of experimental insertion isotherms allows for the construction of realistic capacity diagrams. The open-source software is available at https://github.com/fernandezfran/galpynostatic/.

As20Se80 glass (g-As20Se80) was studied under static high pressure using in situ Raman spectroscopy, x-ray diffraction, and electrical measurements. With increasing pressure, g-As20Se80 shows a breakdown of intermediate-range ordering around 6 GPa and then becomes metallic above 9 GPa. It subsequently undergoes a pressure-induced crystallization, towards the beta-Po-type crystal structure (c-AsSe4 phase), above 20 GPa. Crystalline c-AsSe4 remains in this structure up to at least 35 GPa. This structure is identical with the one observed for pure c-Se, albeit at much higher pressures. The pressure-induced metallization and crystallization are fully reversible upon pressure release, with considerable hysteresis. The results are discussed in comparison with the general structural phase diagram of c-Se under pressure and the implication of pressure-induced crystallization towards understanding the nature of the glass transition.

Ionogels composed of solid matrices and ionic liquids are promising candidates as solid-state electrolytes for sodium (Na) metal batteries due to their nonflammability, high thermal stability, and desirable electrochemical and interfacial properties. Among various solid matrices, nanoscale materials are particularly attractive for increasing the mechanical modulus of ionogel electrolytes, contributing to the suppression of Na dendrite growth on metal anodes. However, the mechanistic understanding of this suppression remains limited. Here, size-controlled talc nanosheets are introduced as solid matrices to investigate their influence on the ionogel modulus and the corresponding Na dendrite growth behavior, facilitating the rational design of ionogel electrolytes for dendrite suppression. Talc nanosheets with reduced lateral dimensions and thicknesses provide larger surface areas, enhancing the ionogel modulus through stronger immobilization of ionic liquids. High-modulus ionogels with smaller nanosheets promote uniform Na deposition and reinforce the resistance of the electrolytes to vertical Na dendrite growth. Moreover, smaller talc nanosheets improve the Na-ion transference number of ionogel electrolytes. The resulting talc nanosheet ionogel electrolytes enable Na3V2(PO4)3|Na cells to exhibit favorable rate capability at room temperature with capacity retention over 99% after 500 cycles at a rate of 0.5 C.

Various carbonaceous anode materials have been developed to improve both the rate and capacity characteristics of Li-ion batteries (LIBs), and yet the performances of the anodes depend on the quality of the inevitable and uncontrollable growth of the solid-electrolyte interphase (SEI), resulting from the electrolyte reduction and decomposition during the initial cycles. Here, we propose the fabrication of an artificial SEI (Art-SEI), enabling tuning of specific properties, such as the chemical composition, electrochemical impedance, and thickness of the interfacial film. In this work, a genuine Art-SEI was conformally fabricated via molecular layer deposition (MLD), utilizing as one of the precursors a commercial battery electrolyte itself, with a cross-linker-functionalized film grown on the surface of the carbonaceous anode materials, along with a Li-ion source. This type of air- and moisture-stable Art-SEI possesses enhanced protective characteristics, and it mitigates the irreversible capacity loss associated with the SEI buildup during the formation cycles while substantially improving Li-ion battery cycling performances.

The community is exploring sustainable alternatives for grid-scale energy storage. Besides lithium-ion batteries (LIBs), such technologies with a focus on sustainability aspects offer only a limited solution for grid-scale energy storage. Rechargeable metal-air batteries (MABs) based on affordable abundant multivalent metal anodes in aqueous medium provide promising theoretical metrics, such as volumetric capacity, but do not completely fulfill their potential when scaled from lab to commercial products. Both the metal anode and the air cathode need to be addressed: corrosion, hydrogen evolution reaction (HER) during charging, and passivation all diminish the anode's effective volumetric energy density and shelf life, while the air cathode's challenges include sluggish kinetics, low efficiency, and poor stability. Nevertheless, this Perspective highlights iron-air MABs as an appealing sustainable alternative for grid-scale energy storage, since iron is abundant and affordable, recyclable, has multielectron reversible redox activity, historically rich experience in production and processing, and is safe to handle. Given that further research will be directed to exploring the composition and design of electrolytes and electrodes, it may lead to advances in scaling and commercialization, as well as reducing the environmental impact of secondary batteries utilized for grid-scale energy storage in the next decades.

Energy-efficient, safe, and reliable Li-ion batteries (LIBs) are required for a wide range of applications. The introduction of ultra-thick graphite anodes, desired for high energy densities, meets limitations in internal electrode transport properties, leading to detrimental consequences. Yet, there is a lack of experimental tools capable of providing a complete view of local processes. Here, a multi-modal operando measurement approach is introduced, enabling quantitative spatio-temporal observations of Li concentrations and intercalation phases in ultra-thick graphite electrodes. Neutron imaging and diffraction concurrently provide correlated multiscale information from the scale of the cell down to the crystallographic scale. In particular, the evolving formation of the solid electrolyte interphase (SEI), observation of gradients in total lithium content, as well as in the formation of ordered LixC6 phases and trapped lithium are mapped throughout the first charge-discharge cycle of the cell. Different lithiation stages co-exist during charging and discharging; delayed lithiation and delithiation processes are observed in central regions of the electrode, while the SEI formation, potential plating, and dead lithium are predominantly found closer to the interface with the separator. The study emphasizes the potential to investigate Li-ion diffusion and the kinetics of lithiation phase formation in thick electrodes.

Replacing common polymeric binder materials in lithium-ion batteries (LIBs) with more sustainable and environmentally friendly options is one of the challenges in designing new generations of LIBs. Here, we explain how incorporating protein-based polymers into the binder formulation can enhance binder performance in the graphite anode of LIBs. The electrode preparation with these binders involves an atypical thermal treatment (“baking”) that causes structural transformation. The effect of baking temperature on battery performance is examined using various methods covering morphological, structural, and electrochemical aspects. We find that baking the binders at temperatures above 120 °C removes tightly bound water molecules, which impair LIB performance. Water removal promotes intra- and inter-molecular bond formation among the binder components, while the primary covalent structure of these binders remains unchanged. Ultimately, using thermally treated binders enhances the electrochemical performance of graphite anodes and provides strong adhesion. The ideas presented here could significantly influence the design of new binders for LIBs.

Ionogels are attractive solid-state electrolytes for lithium (Li) metal batteries due to their nonflammability, favorable electrochemical properties, and broad processing compatibility. However, they typically present limited Li-ion conductivity resulting from low Li-ion transference numbers, constraining their battery performance. Here, ionogel electrolytes with high Li-ion conductivity are introduced based on liquid-phase-exfoliated talc nanosheets and an imidazolium ionic liquid. While serving as a solid matrix to confine the ionic liquid and solidify the ionogel electrolytes, the talc nanosheets reduce the formation of Li-ion complexes with the ionic liquid anions, thus improving Li-ion mobility. These effects are promoted by the large surface area of the talc nanosheets, significantly enhancing the Li-ion transference number of the ionogel electrolytes. The resulting talc nanosheet ionogel electrolytes show high Li-ion conductivity up to 0.9 mS cm-1 at room temperature, enabling the fabrication of solid-state LiFePO4|Li batteries with superlative rate performance and excellent cycling stability.

We provide a comprehensive approach to a methodology to evaluate the performance of lithium-ion batteries and related intercalation systems at the single-particle level, by constructing diagrammatic representations. The idea that underlies these methodologies is using two dimensionless/scaling parameters, which allow the evaluation of a series of experimental parameters and making predictions in a simple, fast and visual way. In both cases, the model considers the finite diffusion of ions in materials and the charge transfer at the electrode/ electrolyte interface. The present work also aims to bring experimental single-particle measurements and single- particle models closer, providing the theoretical background necessary to deduce these scalable parameters, and may inspire more sophisticated theoretical developments in the future, considering other aspects of the nature of the composites. While revisiting relevant work in the area, the present work presents the following novel features: 1- It introduces new scaling kinetic parameter, which makes the diagrams independent of particle geometry. 2- It defines a new metric to evaluate the performance of electrode materials comparatively in terms of their diffusional and charge transfer properties. 3-It derives analytic limits to the behaviour of the model that are universal, in the sense that they do not depend on the intercalation isotherm of the material. 4-It applies artificial intelligence using a deep neural network trained to approximate the results of physics-based simulations, replicating the theoretical state of charge maps with excellent accuracy.

Lithium-ion batteries (LIBs) are the most advanced energy storage systems, meeting the current business, industrial and social demands. Two factors are currently driving the research in the batteries field: first is the constant demand for better performance, and the second is the urgent call to minimize the ecological impacts related to battery manufacturing, employment, and decommission. Biomaterials demonstrate complex and diverse structures and unique physicochemical properties that can be easily modified. These features are very advantageous for the preparation of lithium and Li-ion cell components. The adoption of biomaterials substantially benefits the development of a clean and sustainable battery industry. The main areas of implementing biomaterials in electrodes, separators, and binders for high-energy lithium and LIBs are identified, and the latest achievements in the fields are outlined in this work. While advanced development in the field of LIBs provides solid grounds to consider that the application of biomaterials has great potential, future implementation of such materials in commercial LIBs production is yet to be fully realized, and there is still a need for a large volume of research work. The main points of future work and perspective in this research area are outlined in this review. The present review describes recent efforts and achievements in the field of bio-derived materials and biomimetic-related designs and preparation techniques and methods, overcoming the challenges associated with future Li-ion batteries and Li metal-based batteries development and production.

Lithium metal batteries paired with high-voltage LiNi0.5Mn1.5O4 (LNMO) cathodes are a promising energy storage source for achieving enhanced high energy density. Forming durable and robust solid-electrolyte interphase (SEI) and cathode-electrolyte interface (CEI) and the ability to withstand oxidation at high potentials are essential for long-lasting performance. Herein, advanced electrolytes are designed via trio-functional additives to carbonate-based electrolytes for 5 V Li||LNMO and graphite||LNMO cells achieving 88.3% capacity retention after 500 charge-discharge cycles. Theoretical calculations reveal that adding adiponitrile facilitates the presence of more hierarchical DFOB- and PF6 - dual anion structure in the solvation sheath, leading to a faster de-solvation of the Li cation. By combining both fluorine and nitrile additives, an efficient synergistic effect is obtained, generating robust thin inorganic SEI and CEI films, respectively. These films enhance microstructural stability; Li dendrite growth on the Li electrode is being suppressed at the anode side and transition-metals dissolution from the cathode is being mitigated, as evidenced by cryo-transmission electron microscopy and synchrotron studies.

In this work, we evaluate the reliability of a recently developed model for estimating kinetic parameters for different materials used in lithium-ion batteries. This model considers non-interacting Li-ions being inserted under constant current conditions, assuming finite diffusion inside the particles and charge transfer limitations at the electrode/electrolyte interface. Here, we are interested in evaluating the effect of neglecting the particular insertion isotherms of the materials on the fittings made for diffusion coefficients and electrochemical rate constants. With this purpose, equilibrium isotherms of different materials are extracted from an open-access Li-ion battery parameter database. This thermodynamic information is introduced into the model to perform simulations and obtain the maximum state of charge reached as a function of C-rate. This data is then fitted to the model without interactions using our open-source Python package. The fitted values obtained for the diffusion coefficients are finally compared with the reference values from the database to estimate the accuracy of the model for different real-world systems.

The growing demand for clean and efficient energy sources has been a direct result of the serious effect on the climate and the environment associated with high emissions of pollutants that are mainly produced by fossil fuel-based energy generators. Currently, green technology like proton exchange membrane fuel cells (PEMFC) can produce zero-emissions energy power by primarily using the electrochemical reactions of hydrogen and oxygen to generate electrical energy. Additionally, due to their high activity, Platinum (Pt) nanoparticles (NPs) distributed on a carbon catalyst support are considered the most efficient catalyst materials used in this technology. However, the main drawbacks of this technology are (i) the scarcity of Pt, making it very expensive for widespread fuel cell application and commercialization, and (ii) the susceptibility of the carbon support to corrosion and degradation when operating even at the most typical PEMFC conditions. Carbon corrosion can induce the loss of Pt NPs' active surface area when Pt detaches from the carbon support or agglomerates into larger Pt NPs, leading to premature performance losses in a PEMFC. In this work, we propose a novel approach to prevent carbon corrosion by selectively depositing a corrosion-resistant thin layer (~2 nm) of titanium nitride (TiN) only on the surface of the carbon support while the catalyst centers are left uncoated and accessible for reagent reactions (oxygen O and H + protons). TiN was used as the coating material because of its attractive properties, such as electronic conductivity, enough to enable the free movement of electrons from the current collector toward the catalytic centers. The TiN layer would also act as an anchoring mechanism of Pt NPs, preventing their mobility on the carbon support and subsequent agglomeration. The deposition of TiN layers was carried out at 150°C with a hollow-cathode plasma-assisted atomic layer deposition (HCPA-ALD) reactor and using tetrakis(dimethylamino)titanium (IV) as the metal precursor in Ar/N 2 plasma, from which nitrogen was used as the co-reactant. Before HCPA-ALD, to prevent TiN from depositing on top of the Pt NPs, the surface of Pt NPs was selectively coated with a thin film of oleylamine (OAm), a polymer that would only absorb onto Pt NPs, which is later removed from the catalyst system (after the HCPA-ALD process is finished) by heat treatment at 185°C. Here we will mainly focus on the TiN deposition process and the subsequent transmission electron microscopy (TEM) characterization performed on these nanoparticles, which allows us to prove the successful formation of homogenous coatings and architecture characteristics of these nanoparticles after oleylamine application and TiN deposition. Electrochemical characterization, including cyclic voltammetry (CV) and oxygen reduction reaction (ORR), was performed in a rotating disc electrode (RDE) to further confirm the activity and effectiveness of our designed catalyst. Our preliminary results have shown that highly conformal TiN can be successfully grown onto Pt/C nanoparticles (as powders) by using HCPA-ALD with a custom-made agitator mechanism. The second phase of this research will be focused on inspecting the degradation mechanisms this novel catalyst system experiences after potential cycling in a Membrane Electrode Assembly (MEA).

The increasing demand for energy storage technologies has prompted the exploration of side-by-side technologies, that can complement the current Lithium-ion battery industry with cheaper and more abundant materials that can be incorporated in a myriad of new electrochemical cell designs. To meet these goals, a novel approach for electrolyte design using quantum-mechanical density function theory (DFT) modeling was implemented in concert with experimental electrochemical characterization to culminate in a predictive model that can be tailored to a specific cell chemistry. Physical characteristics as dielectric constant, solvent acidity, basicity etc. influence fluoride speciation, solvation and electrolyte performance, in an iterative fashion to enable characterization prediction of 19F NMR shifts, ionic conductivity mechanisms and fluoride reactivity in a myriad of liquid phase organic solvent. Herein, Silicon (Si) anode batteries were constructed with fluoride-based electrolytes to yield optimal ionic conductivity, adequate anode surface activation, current density and electrochemical stability with corresponding cell characterization and operation mechanism. Our novel and functional tools enable optimal utilization of active Si anode-based batteries with complementary advanced cathode materials, bringing forth the next generation of electrochemical energy storage systems based on an active Si anode. With increasing demand for novel cell chemistries, silicon provides a unique and exciting opportunity for high energy density batteries. Here, we provide synergistic computational density function theory modeling and experimental methods for optimal electrolyte parameters culminating in a functional silicon RedOx battery with prolonged battery life and optimized performance.image

With growing demand for energy storage alternatives, silicon-air batteries have gained attention due to their impressive theoretical specific energy (8470 Wh kgSi-1) and theoretical specific capacity (3820 mAh gSi-1). Although current challenges, such as corrosion, low anode mass conversion efficiency, and limited power output, restrict their practical use and commercialization potential, the ongoing advancement of materials and efficient electronic components open up a range of potential applications for Silicon-air (Si-air) batteries. This study investigates the feasibility of employing a single alkaline or non-aqueous silicon-air battery to power low-power transient electronic device. Initially, their electrochemical behavior, corrosion parameters, and performance were assessed, yielding crucial parameters for the circuit design. Short-term galvanostatic discharge experiments demonstrated the effective operation of Si-air battery under varying current densities in both electrolytes without passivation issues. Subsequently, a proof-of-concept for self-consumed and self-destructive transient electronic device is presented, wherein a full-cell Si-air battery with non-aqueous and aqueous electrolytes was operated while powering a light-emitting diode (LED) as a practical illustrative application. Silica Thou Art and Unto Silica Shalt Thou Return: The silicon life cycle begins with quartz sand (silica) processed into wafers, serving as a semiconductor source and energetic fuel, potentially ending up as silica. This study introduces how Si-air batteries, powered by silicon, could energize transient electronics, enabling partial self-destruction for enhanced data security and limited device lifespan - an innovative application merging energy storage and electronics. image

Electrode stability critically impacts energy storage device performance, and despite theoretical recognition, directly observing the evolving electrode-electrolyte interface during the charge-discharge cycle of a supercapacitor remains challenging. This work directly addresses the technical gap by employing liquid-cell-assisted in situ transmission electron microscopy. This innovative approach realizes real-time observation of the dynamic response of the activated carbon electrode during an electrical cycling of the supercapacitor cells. Driving the cell potential above a certain threshold potential during cycling leads to gas evolution that initiates a cascade of events, causing the active carbon to disintegrate. This is being manifested in the electrode's mass loss and rapid capacity decline upon further cycling. A nanolayer oxide coating of the activated carbon electrode using atomic layer deposition effectively suppresses electrode-electrolyte reactions, stabilizing the electrode and improving the electrochemical properties. The first in situ transmission electron microscopy liquid cell design using an activated carbon substrate represents a breakthrough in understanding supercapacitor degradation, offering a working strategy for electrode dynamics investigation of various energy storage devices.