Entropic stabilization in lithium-rich transition metal layered oxides – A perspective
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Engineering topics
Publications and source records attributed to Meng, Ying Shirley.
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LiNi x Co y Mn 1-x-y O 2 (0 < x, y < 1, NCM) is the dominant positive material for the state-of-the-art lithium-ion batteries. However, the sensitivity of NCM materials to moisture makes their manufacturing, storage, transportation, electrode processing and recycling complicated. Although it is recognized that protons play a critical role in their structure stability and performance, proton exchange with Li + in NCM materials has not been well understood. Here, we employ advanced characterizations and computational studies to elucidate how protons intercalate into the layered structure of NCM, leading to the leaching of Li + and the formation of protonated NCM. It is found that protonation facilitates cation rearrangement and formation of impurity phases in NCM, significantly deteriorating structural stability. The adverse effects induced by protons become increasingly pronounced with a higher Ni content in NCM. Through a comprehensive investigation into the thermodynamics and kinetics of protonation, we discover that Li deficiencies in NCM materials can be resolved via solution process in the presence of Li + ions and controlled proton concentration. The underlying mechanism of relithiation is further explored through materials characterizations and kinetics modeling. This work provides crucial insights into controlling structural and compositional defects of Li-ion battery positive material in complicated processing environment.
The cathode-electrolyte interphase plays a pivotal role in determining the usable capacity and cycling stability of electrochemical cells, yet it is overshadowed by its counterpart, the solid-electrolyte interphase. This is primarily due to the prevalence of side reactions, particularly at low potentials on the negative electrode, especially in state-of-the-art Li-ion batteries where the charge cutoff voltage is limited. However, as the quest for high-energy battery technologies intensifies, there is a pressing need to advance the study of cathode-electrolyte interphase properties. Here, we present a comprehensive approach to analyse the cathode-electrolyte interphase in battery systems. We underscore the importance of employing model cathode materials and coin cell protocols to establish baseline performance. Additionally, we delve into the factors behind the inconsistent and occasionally controversial findings related to the cathode-electrolyte interphase. In conclusion, we also address the challenges and opportunities in characterizing and simulating the cathode-electrolyte interphase, offering potential solutions to enhance its relevance to real-world applications.
A systematic methodology for the quantification of lithium inventory is developed and the degradation mechanisms of high-voltage lithium batteries are revealed.
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Successful integration of metallic lithium anodes into secondary batteries could enhance energy density and enable new forms of electrified transportation. However, the outlook for widespread lithium metal adoption in energy storage devices remains mixed. This comes in part from existing gaps in our understanding of the relationships connecting the initial state of lithium, its evolution with cycling, and end-of-life state. It remains important to develop standardized protocols for material and cell characterization, cycling performance, safety, and recycling procedures for lithium metal-based batteries. In February 2023 a cohort of scientists and engineers from academia, national laboratories, and industry gathered to converge on a list of critical challenges and action items to provide better understanding of lithium metal evolution and to enhance academic, governmental, and industrial partnerships to address these challenges. Here, we highlight the major discussion topics revolving around the manufacturing of lithium metal, its related metrology and integration into battery form factors, and best practices testing its electrochemical performance relevant to automotive applications. We introduce a power-controlled discharge testing protocol for research and development cells, in alignment between major automotive stakeholders, that may reveal lithium metal battery dynamics closer to practical driving behavior.
Hybrid organic-inorganic perovskite solar cells (PSCs) have shown promise for next-generation photovoltaics. Here, this study presents a simple approach for enhancing the performance and stability of PSCs by substituting the center carbon atom of the common hole transport material (HTM) Spiro-MeOTAD with a silicon atom. This modification, termed Si-Spiro, results in an increased hole mobility. A density functional theory simulation indicates that the enhanced hole mobility is due to the structural change of Si-Spiro. Electron beam-induced current microscopy measurements indicate improved charged extraction at the Si-Spiro/perovskite interface. A power conversion efficiency of 22.5% is achieved in Si-Spiro-based PSCs, outperforming standard Spiro-MeOTAD. Additionally, Si-Spiro-based PSCs demonstrate enhanced stability, maintaining over 90% of performance over 120 h of one-sun operation. Depth-profiling X-ray photoelectron spectroscopy revealed that Si-Spiro effectively blocks metal ion migration, which contributes to its enhanced stability. The findings suggest that Si-Spiro could be promising a HTM for high-performing, stable PSCs.
Presented are new, earth-abundant lithium superionic conductors, Li 3 Y(PS 4 ) 2 and Li 5 PS 4 Cl 2 , that emerged from a comprehensive screening of the Li—P—S and Li-M-P—S chemical spaces. Both candidates are derived from the relatively unexplored quaternary silver thiophosphates. One key enabler of this discovery is the development of a first-of-its-kind high-throughput first principles screening approach that can exclude candidates unlikely to satisfy the stringent Li+ conductivity requirements using a minimum of computational resources. Both candidates are predicted to be synthesizable, and are electronically insulating. Systems and methods according to present principles enable new, all-solid-state rechargeable lithium-ion batteries.
Lithium phosphorus oxynitride (LiPON) is an amorphous solid electrolyte that has been extensively studied over the last three decades. Despite the promise of pairing it with various electrode materials, LiPON’s rigidity and air sensitivity set limitations to understanding its intrinsic properties. We report a methodology to synthesize LiPON in a free-standing form that manifests remarkable flexibility and a Young’s modulus of ∼33 GPa. We use solid-state nuclear magnetic resonance and differential scanning calorimetry to quantitatively reveal the chemistry of the Li/LiPON interface and the presence of a well-defined LiPON glass-transition temperature of 207 °C. Combining interfacial stress and a gold seeding layer, our free-standing LiPON shows a uniformly dense deposition of lithium metal without the aid of external pressure. This free-standing LiPON film offers opportunities to study fundamental properties of LiPON for interface engineering for solid-state batteries.
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Disclosed are compositions, devices, systems and fabrication methods for stretchable composite materials and stretchable electronics devices. In some aspects, an elastic composite material for a stretchable electronics device includes a first material having a particular electrical, mechanical or optical property; and a multi-block copolymer configured to form a hyperelastic binder that creates contact between the first material and the multi-block copolymer, in which the elastic composite material is structured to stretch at least 500% in at least one direction of the material and to exhibit the particular electrical, mechanical or optical property imparted from the first material. In some aspects, the stretchable electronics device includes a stretchable battery, biofuel cell, sensor, supercapacitor or other device able to be mounted to skin, clothing or other surface of a user or object.
Aqueous acidic batteries as a good choice to respond battery diversity, delivering safety, cost, environmental friendliness and high-power necessary for renewable energy storage. However, the practical adoption is greatly challenged by low-voltage and energy density due to the inadequate metal anode materials. Here we report an interfacial regulated Sn metal anode as the solution of the last piece of the puzzle. In this study, the ease of recycling, low potential, fast redox kinetics, and high capacity of Sn perfectly fit the battery system, and the Sn metal shedding critical issue is successfully suppressed by promoting uniform deposition for added interaction from alloying. Consequently, this reversible Sn anode with 442 mAh g -1 matches well to different types of cathodes. The as-assembled acidic batteries also demonstrate sufficient output voltage (up to 1.7 V), energy density (up to 312 Wh kg -1 based on both electrodes), kinetics (up to 24 C) and stability (up to 2400 cycles).
Non-equilibrium defects often dictate the macroscopic properties of materials. They largely define the reversibility and kinetics of processes in intercalation hosts in rechargeable batteries. Recently, imaging methods have demonstrated that transient dislocations briefly appear in intercalation hosts during ion diffusion. Despite new discoveries, the understanding of impact, formation and self-healing mechanisms of transient defects, including and beyond dislocations, is lacking. Here, operando X-ray Bragg Coherent Diffractive Imaging (BCDI) and diffraction peak analysis capture the stages of formation of a unique metastable domain boundary, defect self-healing, and resolve the local impact of defects on ionic diffusion in Na x Ni 1-y MnyO 2 intercalation hosts in a charging sodium-ion battery. Results, applicable to a wide range of layered intercalation materials due to the shared nature of framework layers, elucidate new dynamics of transient defects and their connection to macroscopic properties, and suggest how to control the nanostructure dynamics.
“Thick electrode using high voltage cathode” can be considered, since this research focuses on high voltage cathode materials.
To enable cobalt-free LiNi 0.5 Mn 1.5 O 4 (LNMO) electrode and novel electrolyte formulation for use in next-generation Li-ion batteries (LIB) capable of high energy density, long cycle life and low cost, several methods were developed throughout this project. To enhance the performance of LNMO, Fe-doping on LNMO, laser treatment and atomic layer deposition (ALD) were adopted. Moreover, dry electrode method has successfully helped to fabricate ultra-high loading LNMO with stable performance. The improvement at anode side includes ALD-coating as well as pre-lithiation of graphite anode. In the novel electrolyte development, it was found that all-fluorinated electrolyte with appropriate additives can effectively extend both cycle and calendar life of LNMO full cells at practical loadings. Additional diagnosis of LNMO full cells showed that different types of carbon and porosity of separator play a critical role in the success of LNMO’s high voltage operation. The combined effort throughout the project pushed forward the understanding and commercialization of LNMO at practical level.