Lithium Ion Secondary Batteries Research Articles

Characteristics and properties of anode materials for lithium-ion batteries

Lithium-ion secondary batteries (LIBs) are battery systems with high energy densities. They are essential components of todays information-rich, mobile societys portable, entertainment, computing, and telecommunications technology. After 1981, most of the research on anode materials mainly focused on the anode containing Li, such as LiAl alloy, LiC alloy, etc. These materials have high prices, unstable cycling performance, and are difficult to be commercialized. The successful commercialization of LIBs began in 1991 with SONYs manufacturing of petroleum coke-based anode materials. Among them, anode plays a crucial role in LIBs. Anode materials that have been commercialized include carbon, alloys, and lithium titanate. Lithium-ion batteries using carbon anode materials and lithium titanate anode materials can meet the needs of electric vehicles (EVs) and large-scale energy storage applications to a certain extent, and alloy anode materials can promote the energy density of LIBs. The properties of the commercialized anode materials are covered in this paper. Next generation anode materials such as silicon anode materials are also introduced.

World experience of legislative regulation for Lithium-ion electric vehicle batteries considering their second-life application in power sector

Understanding and incorporating global regulatory experiences and standards related to battery management is of greatest importance, particularly when considering the rapid evolution of the electric vehicle (EV) market and its implications for energy storage and sustainability. This is especially relevant for Ukraine, where the burgeoning secondary market for EVs and a keen interest in renewable energy sources underscore the need for proactive policy-making and standardization to address the challenges of battery second life and recycling. This article delves into the role of Electric Vehicle Lithium-Ion batteries within the ambit of the circular economy, underscoring the significance of legislative frameworks across the globe with a particular focus on European initiatives in light of Ukraine's EU integration ambitions. This encompasses extending battery life through recycling and repurposing, thereby ensuring both economic viability and minimal environmental footprint. The narrative outlines the varied legislative landscapes internationally, noting the differences in strategies from Asia's technological and safety emphasis to Europe's robust regulatory directives aimed at battery lifecycle management. In Europe, the drive towards sustainable battery utilization is marked by comprehensive policies like the EU Battery Directive and the emerging Regulation on Batteries and Waste Batteries, which set forth ambitious recycling targets and introduce innovative concepts like the battery passport. Drawing from this global overview, the article posits a set of recommendations for Ukraine, suggesting the development of extensive battery management legislation, adoption of European standards to smooth the path towards EU membership, investment in recycling infrastructures, fostering of public-private partnerships, and public awareness initiatives. These recommendations are designed to elevate Ukraine's position in the sustainability, promoting environmental stewardship and economic competitiveness. The growing importance of secondary lithium-ion batteries for electric vehicles in supporting and harmonizing renewable energy sources is emphasized, and accordingly, the need for adequate legislation and standardization to support a closed-loop economy. Keywords: Lithium-Ion Batteries, Second-Life Application, EV Battery Life Cycle, Circular Economy, Repurpose, Reuse, Recycling, Standards, Regulation, Legislation.

Flexible High Lithium-Ion Conducting PEO-Based Solid Polymer Electrolyte with Liquid Plasticizers for High Performance Solid-State Lithium Batteries.

Lithium-ion secondary batteries (LIB) with high energy density have attracted much attention for electric vehicle (EV) applications. However, LIBs have a safety problem because these batteries contain a flammable organic electrolyte. As such, all-solid secondary batteries that are not flammable have been extensively reported recently. In this study, we have focused on polymer electrolytes, which is flexible and is expected to address the safety problem. However, the conventional polymer electrolytes have low electrial conductivity at room temperature. Various attempts have been made to solve this problem, such as the addition of inorganic fillers and ionic liquids; however, these composite polymer electrolytes have not yet reached a practical level of lithium-ion conductivity. In this study, high electrical conductivity and lithium dendrite formation-free PEO based composite electrolytes are developed with both a filler of Li6,4La3Zr1.4Ta0.6O12 and liquid plasticizers of tetraethylene glycol dimethyl ether and 1,2 dimethoxyethane. The proposed flexible polymer electrolyte shows a high electrical conduciviy of 6.01×10-4 S cm-1 at 25 °C.

Thermodynamic stability and ionic conductivity in lithium–germanium binary system

Lithium–germanium binary compounds are promising anode materials for secondary lithium-ion batteries due to their high capacity, low operating voltage, and high electronic conductivity of lithiated Ge. For their successful application in batteries, it is essential to know the temperature stability of different Li–Ge phases and the variation of their ionic conductivity depending on the operating temperatures of the batteries. This work aims to comprehensively study the thermodynamic stability and ionic conductivity in Li–Ge binary compounds using a combination of first-principle computations and machine-learning interatomic potentials. We calculated convex hulls of the Li–Ge system at various temperatures and a temperature–composition phase diagram was obtained, delineating stability fields of each phase. Our calculations show that at temperatures higher than 590 K, LiGe undergoes a I41/a–P4/mmm transition, which leads to a change in the ionic conductivity. We show that all stable and metastable Li–Ge compounds have high ionic conductivity, but LiGe and Li7Ge12 have the lowest lithium diffusion. Trajectories of diffusion and Ge arrangements depend on lithium concentration. Based on advanced theoretical approaches, this study provides insights for the development of Li–Ge materials in lithium-ion and lithium-metal battery applications.

Structures, electronic properties, and delithiation thermodynamics of the heteroepitaxial α-Al2O3//LiMn2O4 (001) and (111) interfaces

Surface coatings play a pivotal role in enhancing the performance of secondary lithium-ion batteries by mitigating undesirable electrolyte activity towards the cathode materials. Metal oxide candidates have been investigated extensively, with α-Al2O3 emerging as a particularly promising coating material owing to its exceptional mechanical and thermal stability alongside low electrical conductivity. Despite the extensive exploration of this application of α-Al2O3, insight into the interplay between the coating layer and the cathode substrate remains incomplete. To address this lack of knowledge, this study employs density functional theory calculations with a Hubbard Hamiltonian and long-range dispersion corrections (DFT+U-D3) to comprehensively investigate the interfacial geometries, stabilities, and electronic properties of α-Al2O3-coated LiMn2O4 (001) and (111) interfaces of varying thicknesses. The individual surfaces were modelled first before constructing the interfaces. We found that the α-Al2O3 (112¯0) and (0001) surfaces match the LiMn2O4 (001) and (111) facets well, exhibiting {1132} and {3121} configurations, respectively, with corresponding misfits of 2.40 and 2.75 %. We calculated the largest adhesion energies of 0.16 and 0.10 eV/Å2 for monolayers with the {1132} and {3121} configurations, respectively, with the stability decreasing as the thickness of the α-Al2O3 layer increases. Further analysis reveals a minor charge accumulation on the substrate, attributed to charge accumulation on the oxygen atoms that participate in the Al-O bond. In contrast, we observed a depletion of charge on the manganese atoms that form the MnO6 units. The vacancy formation energies increase following partial delithiation, prompting minor charge depletion on neighbouring Mn atoms in the form of charge redistribution. The calculated work function increases with respect to the pristine surfaces, indicating that the coated interfaces are less reactive.

Charge/discharge performance of flame-synthesized TiO2/C composite nanoparticles as anode materials

A flame-synthesized TiO2-based anode material was developed by conducting in-situ composition of TiO2 particles and amorphous carbon particles in a flame. The particle characteristics of the collected composite particles were subsequently examined, and the performances of lithium-ion secondary batteries that used these composite particles as anode materials were measured and evaluated. The aggregates of synthesized and collected particles were confirmed through SEM, EDS, and XRD analysis, revealing a mixture of amorphous carbon particles and TiO2 particles with ranging in size from about 40 to 80 nm. Analysis of the charge/discharge test results on these coin cells indicates that TiO2 and amorphous carbon determine capacity retention and discharge capacity, respectively. Considering both capacity and retention of the cells, optimal flame synthesis conditions were found.

Relating Chemo-Mechanical Hysteresis and Formation Protocols for Anode-Free Lithium Metal Batteries

Cell formation is an energy and time-intensive empirically-guided process crucial to manufacturing secondary lithium-ion batteries. As the rechargeable battery industry moves towards manufacturing lithium metal batteries—where a metallic lithium negative electrode is used instead of a porous graphite composite—the cell formation process may need reconsidering. The effects of formation rate and cycling protocol on lithium metal battery performance are poorly understood. In this work, we used operando acoustic transmission to measure physical changes during the formation cycles and the effect of formation cycling protocols on the long-term cycling of anode-free lithium metal pouch cells—where all the lithium inventory comes from the positive electrode and is deposited as metallic lithium on copper foil during initial charge. We show that a faster C/3 formation protocol results in comparable cycling performance and cell stiffness change to a slower C/10 formation step. Variations in acoustic metrics across different electrolytes tested are attributed to differences in gas formation, cell swelling, and lithium deposition morphology. NMC811 cathodes paired with a high-concentration ether electrolyte are shown to be particularly prone to gas formation, which is mitigated by using a localized high-concentration ether electrolyte and single-crystal NMC532. The results highlight differences in formation behavior between anode-free lithium metal cells and lithium-ion cells. These are important to consider when bringing new manufacturing plants online for lithium metal batteries.

개선된 고상 합성법을 통한 LiNi 0.5 Mn 1.5 O 4 양극재 연구

In this study, LiNi 0.5 Mn 1.5 O 4 was synthesized from various raw materials, including NiO, Ni 2 O 3 , MnO 2 , and Mn 3 O 4 . An improved solid-phase synthesis method was then used to reduce impurities through uniform mixing via bead milling and to achieve a consistent secondary particle shape and distribution through spray drying. The LiNi 0.5 Mn 1.5 O 4 was obtained by selecting materials optimized for rate capability and by applying an improved synthesis process. X-ray diffraction and scanning electron microscopy analyses confirmed that LiNi 0.5 Mn 1.5 O 4 successfully synthesized primary and secondary particles. This result showed that LiNi 0.5 Mn 1.5 O 4 , when subjected to an improved solid-phase synthesis, reduces production costs ,enhances its commercial value, and can be applied to lithium-ion secondary batteries to achieve high energy density and high voltage. In short, LiNi 0.5 Mn 1.5 O 4 can be used as an efficient energy storage material.

Synthesis and anode properties of co-oligomers containing 3,4-diphenyl-1,1-disubstituted-2,5-silolene and ethynylene for lithium-ion secondary batteries

Synthesis and anode properties of co-oligomers containing 3,4-diphenyl-1,1-disubstituted-2,5-silolene and ethynylene for lithium-ion secondary batteries

Development of Novel High Capacity Fluoride Ion Battery Cathode Utilizing Anion Redox of Sulfur

All-solid-state fluoride-ion batteries (FIBs), which are based on the shuttling of fluoride ions, have been considered as one of the promising alternates for next-generation energy storage devices because of high theoretical energy density and safety. Benefiting from the multi-covalent fluorination process, metal/metal fluorides (M/MFx) have been firstly utilized as electrode materials for FIBs with high theoretical energy densities.[1] However, M/MFx systems suffer from exceptionable volume expansion upon fluorination process due to the close-packed metal atoms, which would cause blockage of the F- diffusion pathway, resulting in devastating damage to the electrode-electrolyte interfaces. To solve these problems, cathode materials that utilize topotactic fluoride ion intercalation reactions, similar to the electrode materials applied in lithium-ion secondary batteries, are being developed.[2] Cathode materials that utilize topotactic intercalation of fluoride ions are often composed of heavier elements than the cathodes of lithium-ion batteries that use the same type of reaction mechanism, and effective anion redox is required if capacity is to be increased beyond that of lithium-ion secondary batteries.In this research, we investigated Sr2F2Fe2OS2 (SFFOS) compound with a layered structure as a novel cathode material for all-solid-state FIBs, and evaluated its electrochemical properties and elucidated the charge compensation mechanism using anion redox of sulfur.SFFOS was synthesized by a solid-state reaction under vacuum environment using SrF2, SrO, Fe, and S.[3] SFFOS/La0.9Ba0.1F2.9/vapor grown carbon fiber (VGCF) was used as the composite cathode, La0.9Ba0.1F2.9 as the electrolyte and Pb/PbF2/ La0.9Ba0.1F2.9/VGCF as the composite anode to construct the electrochemical cell. Charge-discharge measurements were carried out in the cut-off voltage range of -1.5 to 1.5 V at 140°C. Ex-situ X-ray Diffraction (XRD), X-ray absorption spectroscopy (XAS) measurements of Fe K-edge, S K-edge, O K-edge and F K-edge were carried out under different state of charge during the 1st and the 2nd cycle.SFFOS showed reversible intercalation/de-intercalation of fluoride ions and a capacity of ~6.1 fluoride ions per unit cell (403 mAh g-1). The charge compensation mechanism was revealed for SFFOS by XAS measurements, where S redox contributed to the whole voltage range from -1.5 V to 1.5 V vs. Pb/PbF2, and Fe+2/+3 redox contributed from the middle SOC. The S-S dimers were formed upon charging, which was similar to the trapped O2 molecules observed in lithium-excess metal oxide during charge process[4]. Not only can the F- anions insert around Fe to form Fe-F bonds, but the excess F- anions can also occupy the Sr-S interstitial layers in the original lattice. Compared to the Fe-based layered oxide Sr3Fe2O5, the Fe-based oxysulfide SFFOS showed a lower average voltage but a higher specific capacity. We believe that this study could provide a new understanding of sulfur-based charge compensation and electrochemical fluorination reactions. Reference s : [1] D. Zhang, K. Yamamoto, Y. Uchimoto et al., J. Mater. Chem. A, 2021, 9, 406–412.[2] Y. Wang, K. Yamamoto, Y. Uchimoto, et al., Chem. Mater., 2022, 34, 609–616.[3] Kabbour H, Janod E, Corraze B, et al ., J. Am. Chem. Soc., 2008, 130(26): 8261-8270.[4] R. A. House, P. G. Bruce, et al., Nat. Energy 2020, 5, 777–785. Figure 1

Intercalation Reaction Mechanism of Fluoride-Ions in (Ca, Sr)FeO2 Cathodes with Infinite Layer Structure for All-Solid-State Fluoride-Ion Batteries

Fluoride ion batteries, which use fluoride ions as carriers, are attracting attention as the next generation of storage batteries because of their theoretical high energy density. Conventional research has focused on metal/metal fluorides such as Cu/CuF2 as cathode materials.[1] However, these cathodes have disadvantages of the power density and cyclability due to the rapid decrease in electronic conductivity and large volume change during fluorination and defluorination. To solve these problems, cathode materials that utilize topotactic fluoride ion intercalation reactions, similar to electrode materials applied in lithium-ion secondary batteries, are being developed[2]. However, these materials have the disadvantage of relatively small capacity, compared to metal/metal fluorides.In this study, we focused on SrFeO2and Ca-doped SrFeO2 cathodes with infinite layer structure as new high-capacity intercalation cathodes, and evaluated its electrochemical properties and clarified the charge compensation mechanism.Ca1-xSrxFeO2 (x = 0, 0.2, 0.4, 0.6, 0.8, 1.0) was synthesized by a low-temperature reduction method using CaH2. Ca1-xSrxFeO2/La0.9Ba0.1F2.9/vapor grown carbon fiber (VGCF) was used as the composite cathode, La0.9Ba0.1F2.9 as the electrolyte and Pb/PbF2/ La0.9Ba0.1F2.9/VGCF as the composite anode to construct the electrochemical cell of the piezoelectric material. Charge-discharge measurements were carried out in the cut-off voltage range of -1.5 to 3.0 V at 140°C. X-ray absorption spectroscopy (XAS) measurements of Fe K-edge, O K-edge, and F K-edge and resonant inelastic X-ray scattering (RIXS) measurements of O K-edge were performed on the samples after charging and discharging.All the Ca1-xSrxFeO2 (x = 0, 0.2, 0.4, 0.6, 0.8, 1.0) cathode showed voltage plateaus around -0.5 V and 1.5 V during charging, and the maximum discharge capacity (580 mAh g-1) was obtained when x = 0.8, and the cathodes could be repeatedly charged and discharged. XAS of the Fe K-edge revealed that Fe compensated for the charge in the flat potential region around -0.5 V. XAS and RIXS measurements of the O K-edge revealed that the charge compensation was carried out by the formation of O2 molecules (oxidation of oxide ions), as which is observed in lithium-excess metal oxide on charge process[4], in the voltage plateau around 1.5 V. Using inexpensive Ca and Fe, we succeeded in developing an intercalation cathode material that significantly exceeds the capacity of conventional lithium-ion battery cathodes.

(Invited) Electrochemical and Postmortem Analyses of 18650-Type Li-Ion Secondary Battery Degraded at High and Low Temperature Environments

Lithium-ion secondary batteries have been widely used as small-size and lightweight energy sources for applications of laptops, robots and electric vehicles. For realizing a high performance, the energy sources are required to have high energy density with high reliability. The batteries are charged and discharged repeatedly based on anode and cathode reactions, which both accompany side reactions to a greater or less extent. The battery degradation phenomena are well explained by kinetics of chemical reactions evaluated by non-destructive examination.1 To understand the battery degradation mechanism for developing a durable one, it is indispensable to clarify the side reactions occurred to cause the degradation. For that purpose, differential capacity curves (dQ/dV vs. V) and electrochemical impedance spectroscopy (EIS) were employed as electrochemical measurements.2 To support the mechanism estimated by the measurements, postmortem analyses were conducted using SEM, XPS and XRD. These investigations were performed to the commercially available 18650 cell consisting of Li(Ni, M)O2 (M: metal elements to partially replace Ni) as the cathode material and graphite as the anode material. The employed loads were calendar deterioration and charge/discharge cycle deterioration.3,4 Firstly, the calendar deterioration behavior of the 18650-type battery was evaluated by storing them at 80 °C for different durations. The results indicate that the battery capacity decreased with the increasing number of storage days in a high-temperature environment. From the differential capacity curves, we found that the change in the overvoltage, which was caused by the electrode reaction, that appeared at approximately 4.2 V was most significant. To analyze this phenomenon, EIS of the deteriorated battery was measured at 4.2 V, and it was confirmed that the cathode-based resistance of the battery increased significantly at this potential. Furthermore, postmortem analysis revealed that the cathode active material of the tested batteries clearly deteriorated; however, no significant change in the active material in the anode was observed. Therefore, it is considered that the cathode materials of nickel-based lithium-ion secondary batteries deteriorate by storing at 80 °C, thereby resulting in reduced battery capacity and increased cathode component resistance after storing at high temperatures.Secondly, cycle deterioration behaviors of the lithium-ion batteries in different operating temperature were studied. Compared with the deterioration in the high-temperature range, the degree of decrease in battery capacity at the low temperature was greater, and the more severe the deterioration was shown at temperatures far from the safe temperature range. From the differential capacity analysis, the peaks corresponding to the anode was significantly reduced at the voltage of the initial charging stage after cycle deterioration at low temperature. This means that the lithium ions intercalated into/deintercalated from the graphite layer decreased. In addition, EIS of the batteries before and after cycle deterioration was measured at each deteriorated temperature. Based on these, postmortem analysis was conducted with a major focus on the anode after 20-cycle deterioration at low temperature. From the SEM observation, the anode can be known to grow thicker with generating cracks and gas pockets. According to the XPS measurements, it is found that Li2CO3 and LiF are generated by decomposition of electrolytic solution at the anode surface.Overall, it was clarified that the deterioration at high temperature affected the cathode and that at low temperature affected the anode.

Niobium Oxide Anode with Lattice Structure Self-Optimization for High-Power and Nearly Zero-Degeneration Battery Operation.

Li+ insertion-induced structure transformation in crystalline electrodes vitally influence the energy density and cycle life of secondary lithium-ion battery. However, the influence mechanism of structure transformation-induced Li+ migration on the electrochemical performance of micro-crystal materials is still unclear and the strategy to profit from such structure transformation remains exploited. Here, an interesting self-optimization of structure evolution during electrochemical cycling in Nb2 O5 micro-crystal with rich domain boundaries is demonstrated, which greatly improves the charge transfer property and mechanical strength. The lattice rearrangement activates the Li+ diffusion kinetics and hinders the particle crack, thus enabling a nearly zero-degeneration operation after 8000 cycles. Full cell paired with lithium cobalt oxides displays an exceptionally high capacity of 176mAhg-1 at 8000mAg-1 and excellent long-term durability at 6000mAg-1 with 63% capacity retention over 2000 cycles. Interestingly, a unique fingerprint based on the intensity ratio of two X-ray diffraction peaks is successfully extracted as a measure of Nb2 O5 electrochemical performance. The structure self-optimization for fast charge transfer and high mechanical strength exemplifies a new battery electrode design concept and opens up a vast space of strategy to develop high-performance lithium-ion batteries with high energy density and ultra-long cycle life.

Recovery of Lithium from Waste Lithium-ion Batteries-A Review

The use of lithium-ion batteries (LIBs) is on stimulating expansion and is expected to increase remarkably. The primary and secondary LIBs have been extensively used in electronic industries and are surging high in hybrid electric vehicles. The considerable use of LIBs could lead to the high accumulation of lithium and lead to the dissipation of the natural lithium reserves. The waste LIBs contain toxic chemicals and heavy metals that are hazardous to the environment. Thus, tremendous research work is being carried out for recycling spent LIBs. This will minimise the pollution from inappropriate disposal of Li in e-waste and would aim towards sustainable development. This review introduces the structure of LIBs and different composition of cathode material used in LIBs. It further discusses the various technologies including pre-treatment processes, pyrometallurgy and hydrometallurgy involved in recovering Li from waste LIBs. Additionally, challenges and suggestions for improving current recycling process have been presented.

A Study on dFMEA-based Fire Risk Assessment of Lithium-ion Secondary Battery Testing Cells

In this study, Design Failure Mode and Effects Analysis (dFMEA) was performed to evaluate the fire risk of lithium-ion secondary battery testing cells used during the research and development stage. dFMEA was used for the failure risk analysis, risk assessment, and risk priority analysis of the anode, cathode, separator, electrolyte, and cell design of the testing cell. In addition, the evaluation criteria, including severity, occurrence, and detection, was reorganized into three categories and optimized for the testing cell application. Based on the failure risk analysis, a total of 11 causes of failure were identified. In particular, explosion and thermal runaway were predicted when a nickel-cobalt-manganese (NCM)-based anode material with a high nickel content was used, the separator had a high thermal contraction rate and low tensile strength characteristics, and there were errors in the electrolyte composition optimization. This cause of failure was classified as a moderate risk with a high fire risk by the risk priority analysis. Therefore, at the research and development stage, it is critical to evaluate the mutual reactivity and preliminary physical properties of battery materials and to construct safety equipment to reduce fire damage.

Ultrasonic Battery Management System for Lamb wave mode tracking on Lithium-ion pouch cells

During charging and discharging, lithium-ion secondary batteries (LIBs) change their mechanical properties due to intercalation and deintercalation of lithium-ions in the electrodes. In this work, a novel ultrasonic battery management system (UBMS) with dedicated FPGA hard- and software has been developed that can track these mechanical changes by using ultrasonic sensors. In particular, the group velocity of the fundamental Lamb mode A0 is tracked and compared with the proposed simulation model. Previous studies have shown that the Young’s modulus of the anode coating changes significantly during cycling. By incorporating this information into the simulation, a change in this value will drastically affect the group velocity of the propagating wave mode A0, which can also be seen in the measurements carried out. To represent a realistic use case, the behaviour of the Lamb mode A0 is measured at different temperatures, which have a big influence on the group velocity of the propagating wave mode. The collected ultrasonic BMS data was further used to develop a state-of-charge (SOC) and temperature estimator. The accuracy of this novel method is discussed. With the addition of the ultrasonic sensors, the BMS can have a larger and better database that can be used to provide a more accurate estimate of the mechanical properties of LIBs and their SOC and temperature.

Electrochemical Performance According to High-Capacity Silicon Active Materials in Lithium Ion Batteries

Carbon has been used as stable anode material for lithium-ion secondary batteries. However, instead of graphite with a low capacity, a new material with a high capacity that can increase the energy density per volume or mass of a lithium ion secondary battery is required. Among the various candidates, silicon has a high capacity of about 4000 mAh/g, making it a major research subject. Graphite is a combination of 6 carbon atoms and 1 lithium ion, but silicon accepts 4.4 lithium ions per atom, resulting in high volume expansion. In this way, excessive volume expansion causes cracks in the electrode and electrochemical disconnection, which eventually leads to a decrease in battery capacity. The large volume change and low electrical conductivity of silicon limits its application to anodes. Potential silicon-based materials include silicon oxide-based (SiOx), carbon-silicon composite (SiC), and pure silicon (pure Si). Silicon-based oxides have the advantages of high capacity and stable battery life, but have the limitations of low initial efficiency and low electrical conductivity. Carbon-composite silicon has high initial efficiency, high ionic conductivity, high capacity, and can be applied in the same slurry system as existing graphite electrodes. Selection of a stable binder and conductive material is important for active use of silicon-based materials. Promising binders include polyvinyl alcohol (PVA), polyacrylic acid (PAA), and polyacrylamide (PAM), and conductive materials include single-walled carbon nano tube (SWCNT), multi-walled carbon nano tube (MWCNT), and carbon-based conductive materials. In this study, we applied poly(vinyl alcohol-co-acrylic acid) random copolymer polymer as a binder and analyzed the characteristics of silicon-based batteries with various conductive materials. Slurry analyzes such as slurry dispersibility, phase stability, and rheology were performed. The initial efficiencies and cycle performances of different types of silicon-based materials were compared. It was confirmed that the type of silicon-based negative electrode material and the type of conductive material affect battery performance.

Concentrated Electrolyte for Stable Lithium Metal Anode

Secondary lithium-ion batteries have been widely used as energy storage systems for portable electronics and electric vehicles. Instead of applying graphite as the anode, lithium (Li) metal has an ultrahigh theoretical capacity (3860 mAh/g) that could significantly increase battery’s energy density. Li dendrite formation is considered the main issue when using Li-metal anodes. Therefore, anode-free batteries are suggested as a solution to this obstacle. However, the major problem with anode-free batteries is their inferior cycling performance than reported lithium metal batteries, resulting from the formation of a fragile and fractured Solid-Electrolyte Interphase (SEI).To establish a robust SEI, novel lithium bis(trifluoromethylsulphonyl)imide (LiTFSI) and LiNO3-based electrolytes with four different ratios were prepared in the co-solvent system (1,3-dioxolane and 1,2-dimethoxyethane). Compared to the other three electrolytes, concentrated electrolyte (4M LiTFSI + 2 wt.% LiNO3 or 4+2) in Li||LiFePO4 cells indicated the highest initial discharge capacity of 154 mAh/g with a capacity retention of 78% after 50 cycles. Scanning electron microscopy was conducted to investigate the SEI morphology after the initial charge/discharge process. The deposited Li on the Li metal was highly dense, and no spiky or needle-like Li clusters were detected. Additionally, electrochemical impedance spectroscopy of the cells was measured after 1, 3, 5, and 10 cycles, respectively. The cells with 4+2 showed the smallest SEI resistance after different cycles, corresponding to a stable and less-resistive SEI formation.

Tape Casting for Development of Thermal Batteries

Thermal (thermally activated) batteries are primary batteries which operate at temperatures ranging from 350°C to 650°C. Due to its long shelf life and high power density (up to 8kW kg-1)1, thermal batteries have been used reliably for military applications such as providing back up power for aircraft hydraulics, missiles and even the Galileo probe.2 Currently, thermal batteries are manufactured by a labour intensive pellet pressing method which limits the design and thickness of the batteries. To improve the power density of thermal batteries, tape casting has been examined. Tape casting is a common method of manufacturing commercial secondary lithium-ion batteries. Tape casting enables relatively thin films of battery components to be utilized which minimises the thickness of the battery components and gives the option to alter the design of the battery itself.Despite its many years in operation for important military applications, processing of thermal batteries into functional cast films has not been achieved so far due to the high operational temperatures of thermal batteries which negate the use of standard polymers. To counter this issue, high temperature polymers, inorganic binders and carbon nanotubes have been examined for their use as binders for thermal battery component inks. Their thermal stability was examined using STA and the oxidation of pyrite was analysed through EDS and PXRD. Successful processing of the constituent battery components is hoped to drastically improve the electrochemical performance of the cell and decrease the manufacturing cost of the batteries. R. A. Guidotti, G. L. Scharrer, E. Binasiewicz and F. W. Reinhardt, 1998.R. A. Guidotti and P. Masset, J. Power Sources, 2006, 161, 1443-1449.

Polysulfide Rejection Strategy in Lithium-Sulfur Batteries Using an Ion-Conducting Gel-Polymer Interlayer Membrane.

Lithium-sulfur batteries (LiSBs) are emerging as promising alternative to conventional secondary lithium-ion batteries (LiBs) due to their high energy density, low cost, and environmental friendliness. However, preventing polysulfide dissolution is a great challenge for their commercial viability. The present work is focused on preparing a lithium salt and ionic liquid (IL) solution (SIL) impregnated ion (lithium ion)-conducting gel-polymer membrane (IC-GPM) interlayer to prevent polysulfide migration toward the anode by using an electrostatic rejection and trapping strategy. Herein, we introduce an SIL-based freestanding optimized IC-GPM70 (70 wt % SIL) interlayer membrane with high lithium-ion conductivity (2.58 × 10-3 S cm-1) along with excellent thermal stability to suppress the migration of polysulfide toward the anode and prevent polysulfide dissolution in the electrolyte. Because of the coulombic interaction, the anionic groups, -CF2 of the β-phase polymer host PVdF-HFP, TFSI- anion of IL EMIMTFSI, and anion BOB- of LIBOB salt, allow hopping of positively charged lithium ions (Li+) but reject negatively charged and relatively large-sized polysulfide anions (Sx-2, 4 <x <8). The cationic group EMIM+ of the IL is electrostatically able to attract and trap the polysulfides in the interlayer membrane. Since the shuttle effect of lithium polysulfides in LiSBs has been suppressed by the prepared IC-GPM70 interlayer, the resulting lithium-sulfur cell exhibits significantly higher cycling stability (1200 cycles), rate performance (1343, 1208, 1043, 875, and 662 mAh g-1 at 0.1C, 0.2C, 0.5C, 1C, and 2C, respectively), and structural integrity during cycling than its counterpart without the IC-GPM70 interlayer. The interlayer membrane has been found to improve the performance and durability of LiSBs, thus making them a viable alternative to conventional LiBs.