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At least 199 records · Page 11

Effects of Salt Aggregation in Perfluoroether Electrolytes

Electrolytes comprised of polymers mixed with salts have great potential for enabling the use of Li metal anodes in batteries for increased safety. Ionic conductivity is one of the key performance metrics of these polymer electrolytes and achieving high room-temperature conductivity remains a challenge to date. For a bottom-up design of the polymer electrolytes, we must first understand how the structure of polyelectrolytes on a molecular level determines their properties. Here, we use classical molecular dynamics to study the solvation structure and ion diffusion in electrolytes composed of a short-chain perfluoroether with LiFSI or LiTFSI salts. Density functional theory is also used to provide some insights into the structures and energies of the salt interactions with the perfluoroether. We observe the formation of aggregates of salts in the fluorinated systems even at low salt concentrations. The fluorine-fluorine attraction in the solvent is the governing factor for creating the salt aggregates. The aggregates’ size and lifetime change with concentration and anion. These simulations provide an insight into the structure and dynamics of perfluoroether based electrolytes that can be used to improve Li-ion batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of thermal environments on fast charging Li-ion batteries

Battery thermal management systems (BTMSs) are expected to keep the battery temperature at a moderate level (~30 °C) to minimize the thermally exacerbated degradation. However, during fast charging, a strong cooling system is required to restrict the temperature rise of Li-ion batteries (LiBs), which significantly increases the cost and weight of battery packs, and induces a large temperature variation inside the battery. Here, in this work, we find that all these drawbacks could be relieved by allowing LiBs to charge at higher temperatures. Since the fast charging of a LiB only takes a tiny fraction of its lifetime, the aging rate is limited even at a charging temperature of 60 °C. Three types of thermal environments are proposed: kept constant at 30 °C, preheated to 60 °C, and adiabatic fast charging. With an experimentally validated electrochemical-thermal (ECT) coupled model, we explore the interplay between thermal management and the fast-charging performance. It is found that a gradually increasing temperature profile is the best option to balance the lithium plating and thermal management of the battery. Combining adiabatic fast charging with a preheating step, we can achieve minimal cooling need, perfect temperature uniformity within a battery, and fast-charging capability simultaneously.

25 ENERGY STORAGE↗

The Key Role of Grain Boundary Dynamics in Revolutionizing the Potential of Solid Electrolytes

Solid electrolytes (SEs) have the potential to enhance the safety and performance of Li-metal batteries. However, the existence of grain boundaries in polycrystalline SEs presents a significant challenge for both ionic and electronic migration, promoting the propagation of detrimental lithium dendrites. This study compares the roles of grain boundaries in electrical properties of three distinct SEs including garnet-type Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 (LLZO), argyrodite-type Li 6 PS 5 Cl (LPSC), and NASICON-type Li 1+x+y Al x (Ti,Ge) 2-x Si y P 3-y O 12 (LATP). Results demonstrate that the electronic and ionic conductivities of solid-state electrolytes are affected differently by grain boundaries, depending on the specific type of electrolyte. For instance, LLZO and LATP experience dielectric breakdown at 3.7 and 5.3 V, respectively, while LPSC does not exhibit such behavior. Here, a new chemical modification is proposed that simultaneously alters the composition of both the surface and grain boundaries of SEs, ultimately reducing electronic conductivity for the LLZO SEs. Consequently, the proposed LLZO exhibits unprecedented dendrite-free cycling stability, achieving a remarkable 12 000-h lifetime at room temperature, surpassing conventional strategies such as surface coatings in dendrite mitigation. This study highlights the significance of modifying grain boundaries to design safe and durable Li-metal batteries. It provides new insights for developing SEs that are highly resistant to dendrite formation.

36 MATERIALS SCIENCE↗

Topology-enhanced mechanical stability of swelling nanoporous electrodes

Abstract Materials like silicon and germanium offer a 10-fold improvement in charge capacity over conventional graphite anodes in lithium-ion batteries but experience a roughly threefold volume increase during lithiation, which challenges ensuring battery integrity. Nanoporous silicon, created by liquid-metal-dealloying, is a potentially attractive anode design to mitigate this challenge, exhibiting both higher capacity and extended cycle lifetimes. However, how nanoporous structures accommodate the large volume change is unknown. Here, we address this question by using phase-field modeling to produce nanoporous particles and to investigate their elastoplastic swelling behavior and fracture. Our simulations show that enhanced mechanical stability results from the network topology consisting of ligaments connected by bulbous, sphere-like nodes. The ligaments forcefully resist elongation while the nodes, behaving like isolated spherical particles, experience large stresses driving fracture. However, being smaller compared to a sphere of the same volume as the entire nanoporous particle, the nodes are more protected against fracture.

36 MATERIALS SCIENCE↗

Jumpstart Opportunities to Unleash Leadership in Energy Storage (JOULES)

Current-generation Li-ion batteries with cobalt- and nickel-containing cathodes and graphite anodes are approaching performance and cost limits. In this program, 24M Technologies, Inc. (24M) is teaming with the Massachusetts Institute of Technology (MIT) and University of Michigan (UM) to develop low cost and fast charging sodium metal batteries with good low-temperature performance and high energy density, building upon previous work performed under ARPA-E programs. Key achievements include optimization of solid electrolyte and anode current collector, optimized cathode active materials, development of high-performance electrolyte formulations, and integration of these components into full cells. The cell design incorporates (1) an ultra-thick cathode (>9 mAh/cm 2 ) comprising advanced cobalt-free, sodium cathode active material, (2) advanced fast-charging electrolyte (up to 12 mS/cm) developed using machine learning and automated high-throughput screening technology by UM, and (3) ceramic modified separator that enable smooth Na transport and deposition, developed at MIT, enabling a high-energy density anode-free configuration and maximizing the energy density of sodium batteries. The team has successfully combined these approaches to sodium chemistry and paved the way to meeting the fast-charging, high-energy density, and low-cost requirements of next-generation drone, electric vertical take-off and -landing, and electric vehicle batteries. Performance for anode-free sodium cells developed under this program is more powerful than the commercial Li-ion batteries. The final deliverable cell design has achieved over 300 Wh/kg and volumetric energy density above 800 Wh/L (Table 1). Additionally, the team has achieved over (1) a lifetime of 340 cycles, (2) 80% capacity retention at -20 °C (compared 25 °C), and (3) the ability to fast charge to 80% SOC in 20 minutes.

25 ENERGY STORAGE↗

Combining Spatial and Temporal Resolution in Cryo-TEM of Device Materials: Preprint

Cryogenic transmission electron microscopy (cryo-TEM) has been instrumental to reducing the effects of electron-beam sample interactions and enabling higher spatial resolution studies of beam sensitive materials. However, the process of thinning and freezing samples for cryo-TEM characterization is often complex and frequently involves removing materials from their environment or stimuli of interest for extended times. This can allow for structural relaxation, diffusion, and other dynamic processes to occur prior to characterization; for energy materials like battery electrodes, this makes it difficult to precisely correlate the imaged structure with native structures that evolve in-situ during device processing, operation, or aging. Here, we present methods to prepare cryo-TEM samples from energy materials during these critical processes in the relevant device lifetimes. This offers insights into improving the temporal resolution of cryo-TEM, while still exploiting its ability to achieve high spatial resolutions in characterizing beam sensitive materials.

BASIC BIOLOGICAL SCIENCES,MATERIALS SCIENCE↗

Anode Upcycling via Tailored Solvent Treatment

To achieve a truly closed-loop direct recycling process for lithium-ion batteries, all component materials must be recovered. To date, direct recycling method development has primarily focused on the high-value transition-metal cathode materials, while the inherently lower-value graphite has been challenging to recover in a cost-effective manner. However, end-of-life graphite contains a unique engineered value due to the presence of the solid electrolyte interphase (SEI). Growth of the SEI during the cell's active lifetime stabilizes the electronically reactive graphite surface through an irreversible consumption of Li, and thus necessitates both excess lithiation of the cathode and a costly and time-intensive formation procedure during manufacturing. An optimized pre-formed SEI that capitalizes on existing SEI components from end-of-life batteries has the potential to significantly reduce cathode lithiation requirements and eliminate the critical bottleneck of formation cycling during cell remanufacturing. Further, retaining Li at the anode obviates the need for a separate Li leaching and recovery step, improving the overall efficiency of the direct recycling line. In this work, we present a novel approach to "upcycling" spent graphite through use of tailored chemical treatment to remove adverse (i.e., highly resistive and/or poorly passivating) SEI species while retaining beneficially passivating components. We have explored a rational set of solvents spanning a range of polarity, proticity, and molecular size to evaluate structure-property-performance relationships between applied solvent(s), removed and remaining SEI species, and electrochemical response of the resulting graphite product. Further, we have developed and optimized a robust and holistic analysis procedure that couples symmetric-cell electrochemical testing, multi-modal materials characterization, and advanced electrochemical modeling. These analysis results inform a set of correlative metrics for graphite performance relative to both solvent properties and upcycled SEI composition. We demonstrate effective tunability in the residual SEI composition by varying solvent identity and concentration, and report on several promising solvent systems that achieve comparable or performance to pristine graphite.

anode recycling↗

Solvent-Mediated, Reversible Ternary Graphite Intercalation Compounds for Extreme-Condition Li-Ion Batteries

Traditional Li-ion intercalation chemistry into graphite anode exclusively utilizes the co-intercalation-free or co-intercalation mechanism. The latter mechanism is based on ternary graphite intercalation compounds (t-GICs), where glyme solvents were explored and proved to deliver unsatisfied cyclability in LIBs. Herein, we report a novel intercalation mechanism, that is, in-situ synthesis of t-THF-GICs in the tetrahydrofuran (THF) electrolyte via a spontaneous, controllable reaction between binary-GICs and free THF molecules during initial graphite lithiation. The spontaneous transformation from b-GIC to t-GIC, which is different from conventional co-intercalation chemistry, is characterized and quantified via operando synchrotron X-ray and electrochemical analyses. The resulting t-GIC chemistry obviates the necessity for complete Li-ion desolvation, facilitating rapid kinetics and synchronous charge/discharge of graphite particles even under high current densities. Consequently, the graphite anode demonstrates unprecedented fast charging (1 min), dendrite-free low-temperature performance, and ultralong lifetimes exceeding 10,000 cycles. Full cells coupled with layered cathode, display remarkable cycling stability upon a 15-min charging and excellent rate capability even at -40 °C. Furthermore, our chemical strategies are shown to extend beyond Li-ion batteries to encompass Na-ion and K-ion batteries, underscoring their broad applicability. Our work contributes to the advancement of graphite intercalation chemistry and presents a low-cost, adaptable approach to achieving fast-charging and low-temperature batteries.

25 ENERGY STORAGE↗

Levelized Cost of Charging Electric Vehicles

This data set includes the levelized cost of charging (LCOC) and lifetime fuel cost savings (LFCS) values as reported in "Levelized Cost of Charging of Electric Vehicles in the United States." Values are reported at the state and national levels for battery electric vehicles (BEVs) and plug-in hybrid electric vehicles (PHEVs). The data set also includes the four annual direct current fast charging (DCFC) station load profiles used to approximate the levelized cost of DCFC charging. Each profile provides 15-min resolved power requirements for one full year. Borlaug, B., Salisbury, S., Gerdes, M., and Muratori, M., Levelized Cost of Charging Electric Vehicles in the United States, Joule (2020), https://doi.org/10.1016/j.joule.2020.05.013.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Levelized Cost of Charging Electric Vehicles

This data set includes the levelized cost of charging (LCOC) and lifetime fuel cost savings (LFCS) values as reported in "Levelized Cost of Charging of Electric Vehicles in the United States." Values are reported at the state and national levels for battery electric vehicles (BEVs) and plug-in hybrid electric vehicles (PHEVs). The data set also includes the four annual direct current fast charging (DCFC) station load profiles used to approximate the levelized cost of DCFC charging. Each profile provides 15-min resolved power requirements for one full year. Borlaug, B., Salisbury, S., Gerdes, M., and Muratori, M., Levelized Cost of Charging Electric Vehicles in the United States, Joule (2020), https://doi.org/10.1016/j.joule.2020.05.013.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Recent Advances in Rechargeable Aluminum-Ion Batteries and Considerations for Their Future Progress

Owing to their high theoretical capacity and reliable operational safety, nonaqueous rechargeable aluminum batteries (RABs) have emerged as a promising class of battery materials and been intensively studied in recent years; however, a lack of suitable, high-performing positive electrode materials, along with the need for air-sensitive and expensive ionic liquid electrolytes, has significantly hindered the practical use of RABs in large-scale applications. Therefore, we sought to carefully analyze positive electrode materials and the associated electrolytes that have been reported in these battery systems in order to stimulate the design of the next generation of high-performance and low-cost RABs. In this review, we have summarized the electrode materials that have been used in both nonaqueous and aqueous RAB systems and provided a rational classification based on the types of materials used and their respective structures. Additionally, we have reviewed electrolytes employed in RABs and have categorized them according to two main types of applications, either for fixed battery systems or for use in portable devices. Here, a systematic account of recent developments on RABs, with a focus on electrode materials, innovative perspectives, and impending research efforts on future RABs, has been included. Finally, a proposed liquid RAB system is discussed with the aim of solving issues regarding fast-charging and long operational lifetimes, followed by insights into solid RABs for use in both portable and multistructural RAB systems.

25 ENERGY STORAGE↗

Multifunctional Coatings on Sulfide‐Based Solid Electrolyte Powders with Enhanced Processability, Stability, and Performance for Solid‐State Batteries

Abstract Sulfide‐based solid‐state electrolytes (SSEs) exhibit many tantalizing properties including high ionic conductivity and favorable mechanical properties for next‐generation solid‐state batteries. Widespread adoption of these materials is hindered by their intrinsic instability under ambient conditions, which makes them difficult to process at scale, and instability at the Li||SSE and cathode||SSE interfaces, which limits cell performance and lifetime. Atomic layer deposition is leveraged to grow thin Al 2 O 3 coatings on Li 6 PS 5 Cl powders to address both issues simultaneously. These coatings can be directly grown onto Li 6 PS 5 Cl particles with negligible chemical modification of the underlying material and enable exposure of powders to pure and H 2 O‐saturated oxygen environments for ≥4 h with minimal reactivity, compared with significant degradation of the uncoated powder. Pellets fabricated from coated powders exhibit ionic conductivities up to 2× higher than those made from uncoated material, with a simultaneous decrease in electronic conductivity and significant suppression of chemical reactivity at the Li‐SSE interface. These benefits result in significantly improved room temperature cycle life at high capacity and current density. It is hypothesized that this enhanced performance derives from improved intergranular properties and improved Li metal adhesion. This work points to a completely new framework for designing active, stable, and scalable materials for next‐generation solid‐state batteries.

36 MATERIALS SCIENCE↗

High‐Nickel Heterostructured Cathodes with Local Stoichiometry Control for High‐Voltage Operation

The growing demand for lithium‐ion batteries to power electric vehicles and other energy‐dense devices continues to fuel the need for cathodes of increasingly higher nickel in cathodes. The relentless pursuit of high Ni content, however, raises concerns on compromising cell lifetime and safety, especially under high‐voltage operation. Alternative to the traditional design of uniform or core–shell composition, we report a rational control of local stoichiometry in high‐Ni cathodes, enabling their high thermal and cycling stabilities—up to 258 °C at the fully charged state and 91.4% capacity retention for 100 cycles between 2.7 and 4.4 V. Multimodal synchrotron X‐ray characterization unveils the heterostructure of secondary particles, featuring a high‐Ni core (LiNi 0.90 Mn 0.05 Co 0.05 O 2 ) covered by a thin Ni‐gradient layer that remains stable over prolonged cycling due to suppressed oxygen release and structural deterioration. This work underlines, the intricate interplay between local stoichiometry and redox reactions in stabilizing high‐Ni cathodes for high‐voltage operation while ensuring safety.

36 MATERIALS SCIENCE↗

Enhancing nanostructured nickel-rich lithium-ion battery cathodes via surface stabilization

Layered, nickel-rich lithium transition metal oxides have emerged as leading candidates for lithium-ion battery (LIB) cathode materials. High-performance applications for nickel-rich cathodes, such as electric vehicles and grid-level energy storage, demand electrodes that deliver high power without compromising cell lifetimes or impedance. Nanoparticle-based nickel-rich cathodes seemingly present a solution to this challenge due to shorter lithium-ion diffusion lengths compared to incumbent micrometer-scale active material particles. However, since smaller particle sizes imply that surface effects become increasingly important, particle surface chemistry must be well characterized and controlled to achieve robust electrochemical properties. Moreover, residual surface impurities can disrupt commonly used carbon coating schemes, which result in compromised cell performance. Using x-ray photoelectron spectroscopy, here we present a detailed characterization of the surface chemistry of LiNi0.8Al0.15Co0.05O2 (NCA) nanoparticles, ultimately identifying surface impurities that limit LIB performance. With this chemical insight, annealing procedures are developed that minimize these surface impurities, thus improving electrochemical properties and enabling conformal graphene coatings that reduce cell impedance, maximize electrode packing density, and enhance cell lifetime fourfold. Overall, this work demonstrates that controlling and stabilizing surface chemistry enables the full potential of nanostructured nickel-rich cathodes to be realized in high-performance LIB technology.

Lim, Jin-Myoung↗

In situ electrochemical recomposition of decomposed redox-active species in aqueous organic flow batteries

Aqueous organic redox flow batteries (AORFBs) offer a safe and potentially inexpensive solution to the problem of storing massive amounts of electricity produced from intermittent renewables. However, molecular decomposition is the major barrier preventing AORFBs from being commercialized. Structural modifications can improve molecular stability at the expense of increased synthetic cost and molecular weight. Utilizing 2,6-dihydroxy-anthraquinone (DHAQ), without further structural modification, we demonstrate that electrochemical regeneration could be a viable route to achieve low-cost, long-lifetime AORFBs. In situ (online) NMR and EPR and complementary electrochemical analyses reveal that decomposition compounds i.e., 2,6-dihydroxy-anthrone (DHA) and its tautomer, 2,6-dihydroxy-anthranol (DHAL), can be converted back to DHAQ in two steps: first DHA(L) 2- are oxidized to the dimer (DHA) 2 4- at - 0.32 V vs. SHE by one-electron transfer; subsequently, the (DHA) 2 4- is oxidized to DHAQ 2- at +0.57 V vs. SHE by three-electron transfer. Electrochemical regeneration rejuvenates not only DHAQ 2- , but also the positive electrolyte – rebalancing the states of charge of both electrolytes without introducing extra ions. We demonstrate the repeated capacity recovery with DHAQ | potassium ferro-/ferricyanide flow battery in basic conditions, and show the approach is also effective for anthraquinone-2,7-disulfonate in acid. Electrochemical regeneration strategies may extend the useful lifetime of many water-soluble organic molecules with anthraquinone core structures in electrochemical cells.

25 ENERGY STORAGE↗

1 kV 150 A Bidirectional Isolated DC/DC Converter With Full Range ZVS For Charger Application

This paper focusses on the development of a bidirectional DC/DC converter based on dual active bridge (DAB) converter for 1 kV class fast charger applications. A novel modulation technique is proposed to achieve zero voltage switching across the entire operating range of a vehicle battery system. The topology includes a tap changer to support multiple class of vehicles. The full range ZVS operation will allow high efficiency operation even at light load, reduced dv/dt to improve transformer insulation lifetime and mitigate EMI impact. A 1 kV class, 150 A prototype was developed to validate the proposed concepts.

Kandula, Prasad↗

Molecular Design Considerations for Azobenzene Anolytes

Realization of high-density batteries requires the development of anolytes that display highly negative reduction potentials, solubility, and persistence in the charged state. Azobenzenes have garnered interest as potential anolytes for redox flow batteries. Here, we report the synthesis of a family of substituted azobenzene derivatives and evaluation of their solution-phase electrochemical properties. Systematic synthetic derivatization of this scaffold allows (1) access to anolytes of varying solubility, including intrinsically liquid derivatives that represent potential high-density charge carriers; (2) systematic variation of the reduction potential, and in some cases redox inventory, that provides azobenzenes with highly negative reduction potentials; and (3) control of the lifetime of the azobenzene radical anions that result from one-electron reduction. Electrokinetic experiments demonstrated that fast electron transfer occurs for all derivatives examined. Spectroscopic characterization of monoreduced azobenzene derivatives establishes that decomposition of the azobenzene radical anion proceeds via bimolecular disproportionation. Together, these results provide an experimental basis for the optimization of azobenzene anolytes for electrochemical storage applications, including redox flow batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Comprehensive Total Cost of Ownership Quantification for Vehicles with Different Size Classes and Powertrains

In order to accurately compare the costs of two vehicles, the total cost of ownership (TCO) should consist of all costs related to both purchasing and operating the vehicle. This TCO analysis builds on previous work to provide a comprehensive perspective of all relevant vehicle costs of ownership. In this report, we present what we believe to be the most comprehensive explicit financial analysis of the costs that will be incurred by a vehicle owner. This study considers vehicle cost and depreciation, financing, fuel costs, insurance costs, maintenance and repair costs, taxes and fees, and other operational costs to formulate a holistic total cost of ownership and operation of multiple different vehicles. For each of these cost parameters that together constitute a comprehensive TCO, extensive literature review and data analysis were performed to find representative values in order to build a holistic TCO for vehicles of all size classes. The light- and heavy-duty vehicles selected for analysis in this report are representative of those that are on the road today and expected to be available in the future. Important additive analyses in this study include systematic analysis of vehicle depreciation, in-depth examination of insurance premium costs, comprehensive maintenance and repair estimates, analysis of all relevant taxes and fees, and considerations of specific costs applicable to commercial vehicles. We find that cars depreciate faster than light trucks and that older plug-in electric vehicles have a greater depreciation rate than newer electric vehicles. Light-duty vehicle (LDV) insurance costs show comparable costs for different powertrains, and lower costs for larger size classes. Medium- and heavy-duty vehicle (MHDV) insurance costs vary significantly by vocation. Electric and electrified powertrains have lower maintenance and repair costs than internal combustion engine (ICE) powertrains for all vehicle sizes, relative to vehicle price. MHDV maintenance and repair costs depend heavily on vocation and duty cycle. LDV taxes and fees are comparable across powertrain types and size classes, though marginally higher registration fees exist for alternative fuel vehicles. MHDV fees depend on the vocation, weight rating, and state. Many electric tractor trailers would be affected by additional battery weight, reducing the available payload capacity, and this cost can be substantial. Electric vehicle charging for commercial vehicles can be time-consuming; labor rates can cause this cost to dominate TCO. With improved knowledge of each of the cost components, we calculate a lifetime TCO for comparison across vehicles of different types and attributes. For a simulated small sport utility vehicle in 2025, modeled using Autonomie, the hybrid electric vehicle (HEV) has the lowest cost, followed by the conventional ICE vehicle. For MHDV, TCO can be drastically different depending on the vocation. Long-haul vehicles typically have the lowest per-mile costs. Excluding labor costs, the class 4 delivery has a comparable TCO to the day cab. Vocational trucks, refuse trucks, and transit buses have a high per-mile cost of ownership due to maintenance and insurance. For all of these vehicles, the cost of operating the vehicle is heavily weighted by the labor of the driver, followed by the fuel costs. While the HEV begins as the lowest cost powertrain for passenger vehicles, fuel cells are forecast to reach cost parity by 2030 when hydrogen prices reach $\$ 5$/kg while battery electric vehicles (BEV) reach cost parity by 2035 at a battery cost of $\$ 98$ per usable kWh of capacity, with these two technologies being the lowest cost in 2050. For the class 8 day cab tractor, the HEV and ICE vehicle begin as the lowest cost powertrains, and the 250-mile BEV reduces in cost from the most expensive to the least expensive by 2030.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗