ABSTRACT
A Mn2+-Li-Nb disordered rock-salt oxide cathode is prepared by a solid-state reaction under 5% H2/N2, and its electrochemical property shows a high voltage plateau at 4.8 V, with irreversible structural changes in the 1st cycle due to O redox processes; this is supported by powder X-ray diffraction and ex situ laboratory Mn K-edge XANES data.
ABSTRACT
The phase separation dynamics in graphitic anodes significantly affects lithium plating propensity, which is the major degradation mechanism that impairs the safety and fast charge capabilities of automotive lithium-ion batteries. In this study, we present comprehensive investigation employing operando high-resolution optical microscopy combined with non-equilibrium thermodynamics implemented in a multi-dimensional (1D+1D to 3D) phase-field modeling framework to reveal the rate-dependent spatial dynamics of phase separation and plating in graphite electrodes. Here we visualize and provide mechanistic understanding of the multistage phase separation, plating, inter/intra-particle lithium exchange and plated lithium back-intercalation phenomena. A strong dependence of intra-particle lithiation heterogeneity on the particle size, shape, orientation, surface condition and C-rate at the particle level is observed, which leads to early onset of plating spatially resolved by a 3D image-based phase-field model. Moreover, we highlight the distinct relaxation processes at different state-of-charges (SOCs), wherein thermodynamically unstable graphite particles undergo a drastic intra-particle lithium redistribution and inter-particle lithium exchange at intermediate SOCs, whereas the electrode equilibrates much slower at low and high SOCs. These physics-based insights into the distinct SOC-dependent relaxation efficiency provide new perspective towards developing advanced fast charge protocols to suppress plating and shorten the constant voltage regime.
ABSTRACT
As electric vehicles become more widely used, there is a higher demand for lithium-ion batteries (LIBs) and hence a greater incentive to find better ways to recycle these at their end-of-life (EOL). This work focuses on the process of reclamation and re-use of cathode material from LIBs. Black mass containing mixed LiMn2O4 and Ni0.8Co0.15Al0.05O2 from a Nissan Leaf pouch cell are recovered via two different recycling routes, shredding or disassembly. The waste material stream purity is compared for both processes, less aluminium and copper impurities are present in the disassembled waste stream. The reclaimed black mass is further treated to reclaim the transition metals in a salt solution, Ni, Mn, Co ratios are adjusted in order to synthesize an upcycled cathode, LiNi0.6Mn0.2Co0.2O2 via a co-precipitation method. The two reclamation processes (disassembly and shredding) are evaluated based on the purity of the reclaimed material, the performance of the remanufactured cell, and the energy required for the complete process. The electrochemical performance of recycled material is comparable to that of as-manufactured cathode material, indicating no detrimental effect of purified recycled transition metal content. This research represents an important step toward scalable approaches to the recycling of EOL cathode material in LIBs.
ABSTRACT
A major transition to electric vehicles (EVs) is underway globally, as countries target reductions in greenhouse gas emissions from the transport sector. As this rapid growth continues, significant challenges remain around how to sustainably manage the accompanying large volumes of waste from end-of-life lithium-ion batteries that contain valuable rare earth and critical materials. Here, we show that high-shear exfoliation in aqueous surfactants can upcycle spent graphite anodes recovered from an EV into few-layer graphene dispersions. For the same hydrodynamic conditions, we report a process yield that is 37.5% higher when using spent graphite anodes as the precursor material over high-purity graphite flakes. When the surfactant concentration is increased, the average atomic layer number reduces in a similar way to that of high-purity precursors. We find that the electrical conductance of few-layer graphene produced using the graphite flake precursor is superior and identify the limitations when using aqueous surfactant solutions as the exfoliation medium for spent graphite anode material. Using these nontoxic solution-processable nanomaterial dispersions, functional paper-based electronic circuit boards were fabricated, illustrating the potential for end-to-end, environmentally sustainable upcycling of spent EV anodes into new technologies.
ABSTRACT
Niobium oxides are an emerging class of anode materials for use in high-power lithium-ion batteries. Galvanostatic cycling and electrochemical impedance spectroscopy (EIS) were used in this study to investigate the influence of electrode porosity, electrode mass ratio, and cycling rate on the capacity, cycle life, and ionic conductivity of Li-ion battery cells based on a modified micron-sized MoNb12O33 (MNO) anode powder. Both electrode and cell designs were found to have a significant impact on the rate performance and cycle life of Li-ion half- and full cells. A higher specific capacity, improved rate performance, and a longer cycle life were obtained in both anode and cathode half-cells by lowering the electrode porosity through calendaring. MNO/Li half-coin cells displayed excellent cyclability, reaching 80% state of health (SOH) after 600 cycles at C/2 charge and 1C discharge. MNO/NMC622 full-coin cells displayed a high capacity of 179 mAh g-1 at 100 mA g-1 (0.5 mA cm-2) and excellent cyclability at 25 °C, reaching 70% SOH after over 1000 cycles at 1 mA cm-2 after optimizing their N/P ratio. Excellent cyclability was obtained at both 1C/1C and fast 2C/2C cycling, reaching 80% SOH after 700 and 470 cycles, respectively. Full-coin and small pouch cells had outstanding rate performance as they could be charged from 0 to 84% capacity in less than 5 min at 10 mA cm-2 and to 70% SOC in 120 s at 20 mA cm-2.
ABSTRACT
Sodium-ion batteries are a prospective sustainable alternative to the ubiquitous lithium-ion batteries due to the abundancy of sodium, and their cobalt free cathodes. The high nickel O3-type oxides show promising energy densities, however, a time dependency in the rheological properties of the composite electrode slurries is observed, which leads to inhomogeneous coatings being produced. A combination of electron microscopy and infra-red spectroscopy were used to monitor the O3-oxide surface changes upon exposure to air, and the effect upon the rheology and stability of the inks was investigated. Upon exposure to air, NaOH rather than Na2CO3 was observed on the surfaces of the powder through FTIR and EDS. The subsequent gelation of the slurry was initiated by the NaOH and dehydrofluorination with crosslinking of PVDF was observed through the reaction product, NaF. Approximately 15% of the CF bonds in PVDF undergo this dehydrofluorination to form NaF. As observed in the relaxation time of fitted rheological data, the gelation undergoes a three-stage process: a dehydrofluorination stage, creating saturated structures, a crosslinking stage, resulting in the highest rate of gelation, and a final crosslinking stage. This work shows the mechanism for instability of high nickel containing powders and electrode slurries, and presents a new time dependent oscillatory rheology test that can be used to determine the process window for these unstable slurry systems.
ABSTRACT
O3-type layered oxide materials are considered to be a highly suitable cathode for sodium-ion batteries (NIBs) due to their appreciable specific capacity and energy density. However, rapid capacity fading caused by serious structural changes and interfacial degradation hampers their use. A novel Sn-modified O3-type layered NaNi1/3Fe1/3Mn1/3O2 cathode is presented, with improved high-voltage stability through simultaneous bulk Sn doping and surface coating in a scalable one-step process. The bulk substitution of Sn4+ stabilizes the crystal structure by alleviating the irreversible phase transition and lattice structure degradation and increases the observed average voltage. In the meantime, the nanolayer Sn/Na/O composite on the surface effectively inhibits surface parasitic reactions and improves the interfacial stability during cycling. A series of Sn-modified materials are reported. An 8%-Sn-modified NaNi1/3Fe1/3Mn1/3O2 cathode exhibits a doubling in capacity retention increase after 150 cycles in the wide voltage range of 2.0-4.1 V vs Na/Na+ compared to none, and 81% capacity retention is observed after 200 cycles in a full cell vs hard carbon. This work offers a facile process to simultaneously stabilize the bulk structure and interface for the O3-type layered cathodes for sodium-ion batteries and raises the possibility of similar effective strategies to be employed for other energy storage materials.
ABSTRACT
The electrode drying process (DP) is a crucial step in the lithium-ion battery manufacturing chain and plays a fundamental role in governing the performance of the cells. The DP is extremely complex, with the dynamics and their implication in the production of electrodes generally being poorly understood. To date, there is limited discussion of these processes in the literature due to the limitation of the existing in situ metrology. Here, ultrasound acoustic measurements are demonstrated as a promising tool to monitor the physical evolution of the electrode coating in situ. These observations are validated by gravimetric analysis to show the feasibility of the technique to monitor the DP and identify the three different drying stages. A possible application of this technique is to adjust the drying rates based upon the ultrasound readings at different drying stages and to speed up the drying time. These findings prove that this measurement can be used as a cost-effective and simple tool to provide characteristic diagnostics of the electrode, which can be applied in large-scale coating manufacturing.
ABSTRACT
Batteries are crucial for building a clean and sustainable society, and their performance is highly affected by aging status. Reliable battery health assessment, however, is currently restrained by limited access to sufficient aging data, resulting from not only complicated battery operations but also long aging experimental time (several months or even years). Refining industrial datasets (e.g., the field data from electric vehicle batteries) unlocks opportunities to acquire large-volume aging data with low experimental efforts. We introduce the potential of combining industrial data with accelerated aging tests to recover high-quality battery aging datasets, through a migration-based machine learning. A comprehensive dataset containing 8,947 aging cycles with 15 operational modes is collected for evaluation. While saving up to 90% experimental time, aging data can be recovered with ultra-low error within 1%. It provides an alternative solution to significantly improve data shortage issues for assessment of battery and energy storage aging.
ABSTRACT
The electrode drying process is a crucial step in the manufacturing of lithium-ion batteries and can significantly affect the performance of an electrode once stacked in a cell. High drying rates may induce binder migration, which is largely governed by the temperature. Additionally, elevated drying rates will result in a heterogeneous distribution of the soluble and dispersed binder throughout the electrode, potentially accumulating at the surface. The optimized drying rate during the electrode manufacturing process will promote balanced homogeneous binder distribution throughout the electrode film; however, there is a need to develop more informative in situ metrologies to better understand the dynamics of the drying process. Here, ultrasound acoustic-based techniques were developed as an in situ tool to study the electrode drying process using NMC622-based cathodes and graphite-based anodes. The drying dynamic evolution for cathodes dried at 40 and 60 °C and anodes dried at 60 °C were investigated, with the attenuation of the reflective acoustic signals used to indicate the evolution of the physical properties of the electrode-coating film. The drying-induced acoustic signal shifts were discussed critically and correlated to the reported three-stage drying mechanism, offering a new mode for investigating the dynamic drying process. Ultrasound acoustic-based measurements have been successfully shown to be a novel in situ metrology to acquire dynamic drying profiles of lithium-ion battery electrodes. The findings would potentially fulfil the research gaps between acquiring dynamic data continuously for a drying mechanism study and the existing research metrology, as most of the published drying mechanism research studies are based on simulated drying processes. It shows great potential for further development and understanding of the drying process to achieve a more controllable electrode manufacturing process.
ABSTRACT
Economically viable electric vehicle lithium-ion battery recycling is increasingly needed; however routes to profitability are still unclear. We present a comprehensive, holistic techno-economic model as a framework to directly compare recycling locations and processes, providing a key tool for recycling cost optimization in an international battery recycling economy. We show that recycling can be economically viable, with cost/profit ranging from (-21.43 - +21.91) $·kWh-1 but strongly depends on transport distances, wages, pack design and recycling method. Comparing commercial battery packs, the Tesla Model S emerges as the most profitable, having low disassembly costs and high revenues for its cobalt. In-country recycling is suggested, to lower emissions and transportation costs and secure the materials supply chain. Our model thus enables identification of strategies for recycling profitability.
ABSTRACT
This literature review covers the solubility and processability of fluoropolymer polyvinylidine fluoride (PVDF). Fluoropolymers consist of a carbon backbone chain with multiple connected C-F bonds; they are typically nonreactive and nontoxic and have good thermal stability. Their processing, recycling and reuse are rapidly becoming more important to the circular economy as fluoropolymers find widespread application in diverse sectors including construction, automotive engineering and electronics. The partially fluorinated polymer PVDF is in strong demand in all of these areas; in addition to its desirable inertness, which is typical of most fluoropolymers, it also has a high dielectric constant and can be ferroelectric in some of its crystal phases. However, processing and reusing PVDF is a challenging task, and this is partly due to its limited solubility. This review begins with a discussion on the useful properties and applications of PVDF, followed by a discussion on the known solvents and diluents of PVDF and how it can be formed into membranes. Finally, we explore the limitations of PVDF's chemical and thermal stability, with a discussion on conditions under which it can degrade. Our aim is to provide a condensed overview that will be of use to both chemists and engineers who need to work with PVDF.
ABSTRACT
A novel low cost sodium-ion battery electrolyte additive ZSM-5 nanozeolite, which improves cycle life, is demonstrated in a Na-ion cell. The addition of this zeolitic small molecule scavenger removes electrolyte decomposition products, and has beneficial properties compared to traditional organic additives such as fluoroethylene carbonate (FEC). Capacity retention after 480 cycles improves from 40% (none) compared to 62% (ZSM-5). This is due to the enhanced interface stability over the cell life-time, as shown by XPS.
ABSTRACT
Electrochemical protocols for reducing formation time and maximising cycle life in a sodium ion battery are proposed. The formation protocols comprise low current cycles within a targeted voltage window. After accelerated cell aging tests, the impedance and cycle life are evaluated. Maximum life time is obtained for formation within the 3.6-3.8 V window. 250 cycles are observed to 80% of initial capacity with accelerated ageing, compared to 90 cycles with no formation.
ABSTRACT
Driving range and fast charge capability of electric vehicles are heavily dependent on the 3D microstructure of lithium-ion batteries (LiBs) and substantial fundamental research is required to optimise electrode design for specific operating conditions. Here we have developed a full microstructure-resolved 3D model using a novel X-ray nano-computed tomography (CT) dual-scan superimposition technique that captures features of the carbon-binder domain. This elucidates how LiB performance is markedly affected by microstructural heterogeneities, particularly under high rate conditions. The elongated shape and wide size distribution of the active particles not only affect the lithium-ion transport but also lead to a heterogeneous current distribution and non-uniform lithiation between particles and along the through-thickness direction. Building on these insights, we propose and compare potential graded-microstructure designs for next-generation battery electrodes. To guide manufacturing of electrode architectures, in-situ X-ray CT is shown to reliably reveal the porosity and tortuosity changes with incremental calendering steps.
ABSTRACT
Sodium-ion batteries are a promising battery technology for their cost and sustainability. This has led to increasing interest in the development of new sodium-ion batteries and new analytical methods to non-invasively, directly visualise battery chemistry. Here we report operando 1H and 23Na nuclear magnetic resonance spectroscopy and imaging experiments to observe the speciation and distribution of sodium in the electrode and electrolyte during sodiation and desodiation of hard carbon in a sodium metal cell and a sodium-ion full-cell configuration. The evolution of the hard carbon sodiation and subsequent formation and evolution of sodium dendrites, upon over-sodiation of the hard carbon, are observed and mapped by 23Na nuclear magnetic resonance spectroscopy and imaging, and their three-dimensional microstructure visualised by 1H magnetic resonance imaging. We also observe, for the first time, the formation of metallic sodium species on hard carbon upon first charge (formation) in a full-cell configuration.
ABSTRACT
An amendment to this paper has been published and can be accessed via a link at the top of the paper.
ABSTRACT
Rapid growth in the market for electric vehicles is imperative, to meet global targets for reducing greenhouse gas emissions, to improve air quality in urban centres and to meet the needs of consumers, with whom electric vehicles are increasingly popular. However, growing numbers of electric vehicles present a serious waste-management challenge for recyclers at end-of-life. Nevertheless, spent batteries may also present an opportunity as manufacturers require access to strategic elements and critical materials for key components in electric-vehicle manufacture: recycled lithium-ion batteries from electric vehicles could provide a valuable secondary source of materials. Here we outline and evaluate the current range of approaches to electric-vehicle lithium-ion battery recycling and re-use, and highlight areas for future progress.
ABSTRACT
Lithium-ion battery (LIB) manufacturing is based around the slurry tape casting of electrodes followed by the assembly of the dried electrodes into cells with a separator and electrolyte. Many aspects of the manufacturing process can affect the performance of a lithium-ion cell. One of the least understood aspects in academia is the effect of degradation of the materials during the manufacturing processes or the 'shelf-life' of the materials and components. Here, we discuss some of the time limitations and degradation issues observed during the manufacturing and testing of the components from an industrially sourced LiNi0.6Mn0.2Co0.2O2 (NMC-622)//graphite cell, and the affect that the component storage has, upon both the performance and the properties of the materials and cells. The materials are stored either in a dry room, vacuum oven or in a laboratory environment and the effect of the atmosphere upon the degradation components of the electrodes and electrolyte is characterized by analytical surface techniques and electrochemical analysis. We note that all storage affects the electrochemical performance, even storage in a vacuum oven or dry room. We propose that the electrodes and electrolytes should be used immediately after manufacture; however, we propose alternative methods for storage in case this is not possible. This article is part of a discussion meeting issue 'Energy materials for a low carbon future'.
ABSTRACT
In this paper we report the synthesis of the new layered perovskite oxide carbonate, Ba3Yb2O5CO3. This phase is formed when 3BaCO3 : 1Yb2O3 mixtures are heated in air at temperatures ≤1000 °C, while above this temperature the carbonate is lost and the simple oxide phase Ba3Yb4O9 is observed. The structure of Ba3Yb2O5CO3 was determined from neutron diffraction studies and consists of a tripled perovskite with double Yb-O layers separated by carbonate layers, the first example of a material with such a structure. Further studies showed that analogous Ba3Ln2O5CO3 phases could be formed for other rare earths (Ln = Y, Dy, Ho, Er, Tm and Lu). The results highlight the ability of the perovskite structure to accommodate carbonate groups, and emphasise the need to consider their potential presence particularly for perovskite systems prepared in lower temperature synthesis routes.
