Division Of Medical Sciences Research Articles

(Invited) Novel Q Carbon Anodes for Sodium-Ion Batteries

The main goal of this research is to develop low-cost anodes for sodium-ion batteries. Lack of standard carbon intercalation/insertion anode for sodium-ion batteries has greatly hindered its application. Two types of Q carbons have been studied as a potential anode material for sodium-ion batteries. Q1 carbon exhibits a high initial columbic efficiency of 81% but has a low-capacity retention of less than 60%. Whereas Q2 carbon has a low initial columbic efficiency of 58% but has a high-capacity retention of 81%. Q2 exhibited a stable capacity of 168 mAh/g at a cycling rate of C/3 which is comparable to other high performing hard carbon anodes. This work will discuss in detail about the synthesis procedure, microstructural and electrochemical performance of the Q carbons. This study reports the successful pathway of using Q carbon as a promising anode for sodium ion batteries.ACKNOWLEDGEMENTSThis research was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division.

(Invited) Slug-Flow Manufacturing of Uniform and Tunable Battery Cathode Materials

The main goal of this research is to develop a low-cost scalable continuous manufacturing platform for Ni-rich cathodes. In this work, we demonstrate the synthesis and electrochemical performance of Ni-rich layered oxide [Li[Ni0.8Mn0.1Co0.1]O2 (NMC811)], an efficient low-cobalt cathode for the next generation lithium-ion batteries using a three-phase slug-flow reactor.1-5 The slug flow reactor is used to continuously produce uniform, high purity NMC811 with spherical morphology using oxalate precursor chemistry. The precursor material is then reacted with Li salts to prepare high purity cathode materials. The as-prepared NCM811 possess a high tap density of 2.4 g mL-1 and a high specific capacity of 202 mAh g-1 at 0.1C.5 A novel coating method has been developed to produce a stable LiF layer on the cathode surface to improve the cycling stability of the material.6 This work will discuss in detail about the synthesis procedure, microstructural and electrochemical performance of the cathode material produced by the slug flow manufacturing process. This demonstration provides a pathway towards scaling up the cathode synthesis process for large-scale energy storage applications.3 AcknowledgementsThis research was supported by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Advanced Materials and Manufacturing Technologies Office, the National Science Foundation (Grant No. CMMI-1940948). Battery testing research was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division. References Mou, A. Patel, S. Mallick, B. P. Thapaliya, M. P. Paranthaman, J. Mugumya, M. L. Rasche, R. B. Gupta, S. Saleh, S. Kothe, E. Baral, G. P. Pandey, H. Lopez, M. Jiang, “Scalable advanced Li(Ni0.8Co0.1Mn0.1)O2 cathode materials from a slug-flow continuous process,” ACS Omega 7 (46) 42408-42417 (2022)Jiang, Z. Zhu, E. Jimenez, C. D. Papageorgiou, J. Waetzig, A. Hardy, M. Langston and R. D. Braatz. “Continuous-flow tubular crystallization in slugs spontaneously induced by hydrodynamics”. Cryst. Growth Des. 14, 851–860 (2014).Mou, and M. Jiang. “Fast continuous non-seeded cooling crystallization of glycine in slug flow: Pure α-form crystals with narrow size distribution”. J. Pharm. Innov. 15, 281–294 (2020). Mallick, A. Patel, X-G. Sun,M. P. Paranthaman, M. Mou, J. Mugumya, M. Jiang, M. L. Rasche, H. Lopez, and R. B. Gupta, "Low-cobalt active cathode materials for high-performance lithium-ion batteries: synthesis and performance enhancement methods," J. Mater. Chem. A 11, 3789-3821 (2023).Mou, A. Patel, S. Mallick, K. Jayanthi, X. -G. Sun, M. P. Paranthaman, S. Kothe, E. Baral, S. Saleh, J. H. Mugumya, M. L. Rasche, R. B. Gupta, H. Lopez, M. Jiang, Slug-flow co-precipitation synthesis of uniformly-sized oxalate precursor microparticles for good reproducibility, tap density, and electrochemical performance of Li(Ni0.8Co0.1Mn0.1)O2 cathode materials, ACS. Appl. Energy Mater., 2023, 6, 3213−3224.Xiao-Guang Sun, Charl J Jafta, Susheng Tan, Albina Borisevich, Ram B Gupta, Mariappan Parans Paranthaman, "Facile surface coatings for performance improvement of NMC811 battery cathode materials, "J. Electrochem. Soc. 169 (2) 020565 (2022).

The First 5-year Integrated Doctoral Program Exploring the Frontiers of Pharmaceutical Sciences

To empower the next generation of students to become leaders that play active roles in various fields in society, research universities must offer attractive and meaningful doctor of philosophy (PhD) programs in their graduate schools. The Graduate School of Pharmaceutical Sciences, at Kyoto University has trained a large number of researchers who are leading drug discovery science and clinical pharmacy in academia as well as in the pharmaceutical industry, in medical organization and in government. However, due to changes in the trends of students and the evolving skill requirements of future PhD holders to handle the challenges of a changing society, it is necessary to revise the curriculum of our graduate school. Thus, we will reform the graduate and undergraduate school programs by implementing a so-called late specialization program and a double mentoring system and aim to nurture emergent researchers who will explore uncharted areas in pharmaceutical sciences. Toward this goal, we established the Division of Medical Frontier Sciences in April 2022 to replace the former Division of Bioinformatics and Chemical Genomics. This program is Japan's first five-year integrated doctoral course in the field of pharmaceutical sciences. In this review, I will introduce the background leading to its development construction and provide an overview of the characteristics of this five-year integrated doctoral program.

A Japan-Poland Collaboration for Coupling Molecular Nanomagnetism and Luminescent Thermometry.

This invited Team Profile was created by the Laboratory of Advanced Functional Materials (Tokoro Lab), Division of Materials Science, Faculty of Pure and Applied Sciences, University of Tsukuba (Japan); the Multifunctional Luminescent Materials Group (Szymon Group, MLMG), Faculty of Chemistry, Jagiellonian University, Kraków (Poland); and the Solid State Physical Chemistry Group (Ohkoshi Lab), Department of Chemistry, School of Science, The University of Tokyo (Japan). They recently published an article on a bimetallic cyanido-bridged TbIII -CoIII framework exhibiting a desolvation-induced structural transformation providing high-symmetry trigonal-prismatic [TbIII (NC)6 ]3- complexes. This induces a strong magnetic anisotropy leading to single-molecule magnet behavior with an energy barrier of 854(26) K, which appears in the cryogenic temperatures range, together with the concomitant luminescent thermometry effect. "Desolvation-Induced Highly Symmetrical Terbium(III) Single-Molecule Magnet Exhibiting Luminescent Self-Monitoring of Temperature", J. Wang, J. J. Zakrzewski, M. Zychowicz, Y. Xin, H. Tokoro, S. Chorazy, S. Ohkoshi, Angew. Chem. Int. Ed. 2023, 62, e202306372.

A Japan–Poland Collaboration for Coupling Molecular Nanomagnetism and Luminescent Thermometry

AbstractThis invited Team Profile was created by the Laboratory of Advanced Functional Materials (Tokoro Lab), Division of Materials Science, Faculty of Pure and Applied Sciences, University of Tsukuba (Japan); the Multifunctional Luminescent Materials Group (Szymon Group, MLMG), Faculty of Chemistry, Jagiellonian University, Kraków (Poland); and the Solid State Physical Chemistry Group (Ohkoshi Lab), Department of Chemistry, School of Science, The University of Tokyo (Japan). They recently published an article on a bimetallic cyanido‐bridged TbIII−CoIII framework exhibiting a desolvation‐induced structural transformation providing high‐symmetry trigonal‐prismatic [TbIII(NC)6]3− complexes. This induces a strong magnetic anisotropy leading to single‐molecule magnet behavior with an energy barrier of 854(26) K, which appears in the cryogenic temperatures range, together with the concomitant luminescent thermometry effect. “Desolvation‐Induced Highly Symmetrical Terbium(III) Single‐Molecule Magnet Exhibiting Luminescent Self‐Monitoring of Temperature”, J. Wang, J. J. Zakrzewski, M. Zychowicz, Y. Xin, H. Tokoro, S. Chorazy, S. Ohkoshi, Angew. Chem. Int. Ed. 2023, 62, e202306372.

Quantum Healthy Longevity for healthy people, planet, and growth

Quantum Healthy Longevity for healthy people, planet, and growth

How Halide Sub-Lattice Affects Li Ion Transport in Antiperovskites

Li-based antiperovskites (LiAP, Li3-x OH x X, X = Cl, Br) are an emergent class of Li-ion conductors that are potential candidates for electrolytes in all-solid-state batteries. As a material class, pLiAP shows vast compositional design freedom; however, the resulting properties are susceptible to synthesis and processing methodologies. For example, proton incorporation and halide mixing stabilize the perovskite cubic phase near room temperature, and halides mixtures near the eutectic points drive the solid-state reaction temperature down, allowing for faster synthesis and processing conditions (< 1 h). The mixed halogen compositions, such as Li2OHCl0.37Br0.63, also show a 30-fold improvement in room temperature ionic conductivity of a single halide structure, 1.5 x 10-6 vs. 4.9 x 10-8 S cm-1 (Li2OHCl). Despite the growing interest in these materials, important questions remain about LiAPs on the structure-property correlation upon halide substitution and the correlations between the OH/halide dynamics and the Li-ion transport. We thus attempted to deconvolute how proton dynamics and halide substitution enhance or impede ionic conduction in pLiAP at compositions near the halide salts' eutectic points.We combined infrared spectroscopy and nuclear magnetic resonance (NMR) with first-principles density functional theory (DFT) calculations to deconvolute halide mixing effects from local proton dynamics on Li-ion transport. The NMR results and ab initio molecular dynamics suggest that Li+ transport is more strongly correlated with halide dynamics. While the hydroxide does stabilize the highly conductive cubic structure, it limits correlative ionic transport and thus lowers Li+ conductivity.Experiment design, data analysis, and manuscript preparation (RLS) were supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Science and Engineering. Synthesis (THB and JN) were supported by Asst. Secretary, Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (VTO) through the Advanced Battery Materials Research (BMR) Program. P. J. acknowledges partial support by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under Award DE-FG02-96ER45579. H. F. was supported from U.S. Department of Energy (Award No. DE-EE0008865). This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. The NMR characterization part of the work is supported by the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, and Basic Energy Sciences. The NMR work was performed at the W. R. Wiley Environmental Molecular Sciences Laboratory, a DOE User Facility sponsored by the Office of Biological and Environmental Research, located at Pacific Northwest National Laboratory. Figure 1

General Meeting of the Division of Chemistry and Materials Sciences of the Russian Academy of Sciences

General Meeting of the Division of Chemistry and Materials Sciences of the Russian Academy of Sciences

General Meeting of the Division of Chemistry and Materials Science of the Russian Academy of Sciences

General Meeting of the Division of Chemistry and Materials Science of the Russian Academy of Sciences

In Situ Neutron and Impedance Analysis of the Phase Evolution during Lithium-Indium Chloride Dehydration

Rare-earth alkali halides (REAHs) have been shown to have superionic conductivity and are promising candidates for solid lithium electrolytes. The library of superionic materials of the form Li3MX6 (along with various substitutions) where M = Sc, Y, La, Er, and X = Cl, Br, I is ever increasing.[1] The most notable examples have room temperature lithium ionic conductivity surpassing 1 mS cm-1. Lithium Indium Chloride has been shown to adopt a similar structure to the Li3MX6 REAHs and has high conductivity, 1.5 mS cm-1.[2] A significant advantage that Li3MX6-based materials have over other solid electrolytes, such as garnets, is their low synthesis and processing cost.[3] As an example, we will describe how Li3InCl6 can be synthesized from concentrated aqueous solution through controlled dehydration.[3-4] Here, we probe this dehydration/reaction using a multimodal approach that combines in situ neutron diffraction, thermogravimetry, differential scanning calorimetry, and in situ impedance spectroscopy. Figure 1 shows the phase transitions as determined by in situ neutron scattering. Clearly, we observe three phase transitions, with the high conductivity phase forming at ~120 oC. We show that hydrate is readily cold-pressed into dense pellets that offer remarkable adhesion to a roughened blocking electrode surface. Controlled dehydration further maintains the pellet's density; however, removing trace H2O leads to mechanical strain and fracturing. This report provides a pathway for the direct synthesis and processing of REAHs from concentrated aqueous solutions.[4] This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Division of Materials Science and Engineering. This research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory.[1] Park, K.-H.; Kaup, K.; Assoud, A.; Zhang, Q.; Wu, X.; Nazar, L. F. High-Voltage Superionic Halide Solid Electrolytes for All-Solid-State Li-Ion Batteries. ACS Energy Lett. 2020, 5, 2, 533–539.[2] Li, X.; Liang, J.; Luo, J.; Norouzi Banis, M.; Wang, C.; Li, W.; Deng, S.; Yu, C.; Zhao, F.; Hu, Y.; Sham, T.-K.; Zhang, L.; Zhao, S.; Lu, S.; Huang, H.; Li, R.; Adair, K. R.; Sun, X. Air-Stable Li3InCl6 Electrolyte with High Voltage Compatibility for All-Solid-State Batteries. Energy Environ. Sci. 2019, 12, 2665-2671.[3] Li, W.; Liang, J.; Li, M.; Adair, K. R.; Li, X.; Hu, Y.; Xiao, Q.; Feng, R.; Li, R.; Zhang, L.; Lu, S.; Huang, H.; Zhao, S.; Sham, T.-K.; Sun, X. Unraveling the Origin of Moisture Stability of Halide Solid- State Electrolytes by In Situ and Operando Synchrotron X-Ray Analytical Techniques. Chem. Mater. 2020,32, 16, 7019–7027.[4] Sacci, R.L.; Bennett, T.H.; Drews, A.R.; Anandan, V.; Kirkham, M.J.; Daemen, L.L.; Nanda, K. Phase evolution during lithium indium halide superionic conductor dehydration. J. Mater. Chem. A, 2021,9, 990-996. Figure 1

(Invited) Novel Approaches for the Study of Disordered Rocksalt Oxyfluoride Intercalation Cathodes

Novel approaches for the study of disordered rocksalt oxyfluoride intercalation cathodes Raynald Giovine,a Yuefan Ji,a Ashlea Patterson,a Emily Foley,a Zhengyan Lun,c Daniil Kitchaev,a,b Bin Ouyang,d Jinhyuk Lee,c,e Yuan Yue,f Yang Ha,g Wanli Yang,g Wei Tong,f Gerbrand Ceder,c,d Raphaële Clémenta a. Materials Department, University of California, Santa Barbara, CA 93106.b. Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139.c. Department of Materials Science and Engineering, University of California, Berkeley, CA 94720.d. Materials Science Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720.e. Department of Mining and Materials Engineering, McGill University, Montreal, QC, H3A 0C5, Canada.f. Energy Storage and Distributed Resources Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720.g. Advanced Light Source Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720.Disordered rocksalt oxides and oxyfluorides (DRX) have recently emerged as a promising class of lithium-ion cathodes, with initial capacities up to 300 mAh/g and initial energy densities up to 1000 Wh/kg.[1] The presence of extensive disorder and the ability to partially replace O by F result in unique Li+ diffusion and redox properties. Yet, the structure of such compounds is particularly difficult to characterize, as a result of the intrinsic disorder on the cation lattice, the small particle size required for reasonable rate performance, and the inability of x-ray and neutron diffraction to distinguish between O and F.In this presentation, I will show that high resolution ex situ solid-state NMR is uniquely suited for the study of cation short-range order[2] and structural degradation mechanisms resulting in rapid capacity fade upon cycling, and to assess the solubility limit of F into the rocksalt structure. Our findings indicate that the limited F solubility in disordered rocksalts depends on cathode composition and does not impede their performance, that one major source of impedance build up during cycling is degradation of common Li-ion electrolyte salts at high voltage,[3] as well as metal dissolution, and that cation short-range order can be eliminated through the formation of ‘high entropy’ compounds.[4] These insights allow us to establish links between composition and electrochemical properties and establish design rules for next-generation intercalation-type Li-ion cathodes.

The 4f-Hybridization Strength in Ce m Mn In3m+2n Heavy-Fermion Compounds Studied by Angle-Resolved Photoemission SpectroscopySupported by the National Natural Science Foundation of China (Grant Nos. 12074436 and 11574402), and the Innovation-Driven Plan in Central South University (Grant No. 2016CXS032). J.R. and P.M.O. acknowledge support through the Swedish Research Council (VR) and the Swedish National Infrastructure for Computing (SNIC), for computing

We systemically investigate the nature of Ce 4f electrons in structurally layered heavy-fermion compounds Ce m M n In3m + 2n (with M = Co, Rh, Ir, and Pt, m = 1, 2, n = 0–2), at low temperature using on-resonance angle-resolved photoemission spectroscopy. Three heavy quasiparticle bands f 0, and , are observed in all compounds, whereas their intensities and energy locations vary greatly with materials. The strong f 0 states imply that the localized electron behavior dominates the Ce 4f states. The Ce 4f electrons are partially hybridized with the conduction electrons, making them have the dual nature of localization and itinerancy. Our quantitative comparison reveals that the –f 0 intensity ratio is more suitable to reflect the 4f-state hybridization strength.

Polypeptide-based batteries toward sustainable and cyclic manufacturing

Polypeptide-based batteries toward sustainable and cyclic manufacturing

Mortality and critical care unit admission associated with the SARS-CoV-2 lineage B.1.1.7 in England: an observational cohort study

SummaryBackgroundA more transmissible variant of SARS-CoV-2, the variant of concern 202012/01 or lineage B.1.1.7, has emerged in the UK. We aimed to estimate the risk of critical care admission, mortality in patients who are critically ill, and overall mortality associated with lineage B.1.1.7 compared with non-B.1.1.7. We also compared clinical outcomes between these two groups.MethodsFor this observational cohort study, we linked large primary care (QResearch), national critical care (Intensive Care National Audit & Research Centre Case Mix Programme), and national COVID-19 testing (Public Health England) databases. We used SARS-CoV-2 positive samples with S-gene molecular diagnostic assay failure (SGTF) as a proxy for the presence of lineage B.1.1.7. We extracted two cohorts from the data: the primary care cohort, comprising patients in primary care with a positive community COVID-19 test reported between Nov 1, 2020, and Jan 26, 2021, and known SGTF status; and the critical care cohort, comprising patients admitted for critical care with a positive community COVID-19 test reported between Nov 1, 2020, and Jan 27, 2021, and known SGTF status. We explored the associations between SARS-CoV-2 infection with and without lineage B.1.1.7 and admission to a critical care unit (CCU), 28-day mortality, and 28-day mortality following CCU admission. We used Royston-Parmar models adjusted for age, sex, geographical region, other sociodemographic factors (deprivation index, ethnicity, household housing category, and smoking status for the primary care cohort; and ethnicity, body-mass index, deprivation index, and dependency before admission to acute hospital for the CCU cohort), and comorbidities (asthma, chronic obstructive pulmonary disease, type 1 and 2 diabetes, and hypertension for the primary care cohort; and cardiovascular disease, respiratory disease, metastatic disease, and immunocompromised conditions for the CCU cohort). We reported information on types and duration of organ support for the B.1.1.7 and non-B.1.1.7 groups.FindingsThe primary care cohort included 198 420 patients with SARS-CoV-2 infection. Of these, 117 926 (59·4%) had lineage B.1.1.7, 836 (0·4%) were admitted to CCU, and 899 (0·4%) died within 28 days. The critical care cohort included 4272 patients admitted to CCU. Of these, 2685 (62·8%) had lineage B.1.1.7 and 662 (15·5%) died at the end of critical care. In the primary care cohort, we estimated adjusted hazard ratios (HRs) of 2·15 (95% CI 1·75–2·65) for CCU admission and 1·65 (1·36–2·01) for 28-day mortality for patients with lineage B.1.1.7 compared with the non-B.1.1.7 group. The adjusted HR for mortality in critical care, estimated with the critical care cohort, was 0·91 (0·76–1·09) for patients with lineage B.1.1.7 compared with those with non-B.1.1.7 infection.InterpretationPatients with lineage B.1.1.7 were at increased risk of CCU admission and 28-day mortality compared with patients with non-B.1.1.7 SARS-CoV-2. For patients receiving critical care, mortality appeared to be independent of virus strain. Our findings emphasise the importance of measures to control exposure to and infection with COVID-19.FundingWellcome Trust, National Institute for Health Research Oxford Biomedical Research Centre, and the Medical Sciences Division of the University of Oxford.

(Invited) Carbon Nanostructures for Energy Storage Applications

The main goal of this research is to develop carbon nanostructures for next generation energy storage applications. The tailored morphology of the end-of-life tire rubber with a sulfonation process followed by pyrolysis yielded a high-quality nanostructured carbon and the applicability of these hard carbons was demonstrated in energy storage applications. We will report on our recent neutron studies on the surface chemistry of the carbon material, vibrational spectroscopy of the molecular structure, chemical bonding such as C-H bonding, and intermolecular interactions of the carbon materials. In addition, we will also report our recent success with tire-derived carbon with either tin oxide or antimony/antimony oxide based composites as a low-cost, environmentally benign, and high capacity anode material for energy storage applications.ACKNOWLEDGEMENTSMThe research was sponsored by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division.

Projective representation of D 6 group in twisted bilayer graphene* *Project supported by DOE Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under Award DE-SC0010526.

Within the framework of continuum model, we study the projective representation of emergent D 6 point group in twisted bilayer graphene. We then construct tight-binding models of the lowest bands without and with external electromagnetic fields, based on the projective representation.

NexusLIMS: A Laboratory Information Management System for Shared-Use Electron Microscopy Facilities.

This work introduces NexusLIMS, an electron microscopy laboratory information management system designed and implemented by the Office of Data and Informatics and the Materials Science and Engineering Division at NIST for a multi-user electron microscopy co-op facility. NexusLIMS comprises network infrastructure, shared information technology resources, a custom software package to harvest and extract experimental information and construct experimental metadata records, and an intuitive web-based user-facing interface for searching, browsing, and examining research data. These metadata records conform to the Nexus Experiment schema, which is introduced in this work. The NexusLIMS suite of tools requires minimal input and adjustments to user behavior, instead relying on existing organizational procedures and the collection of information from a multitude of sources to construct a complete picture and record of a research experiment. The underlying infrastructure and design considerations for a multi-user data management system are discussed. The core codebase for NexusLIMS is made publicly available alongside this work, and its modular design encourages the adaptation of the presented methods at other research organizations.

Light Propagation and Radiative Exciton Transport in Two-Dimensional Layered Perovskite Microwires

The work at UT Dallas was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under Award No. DESC0010697.

In Situ Neutron Scattering to Elucidate the Mechanism of Rapid Lithium Ion-Conducting Garnet Synthesis Using Nanoparticles

Consumer safety is a market force that is impeding high energy-dense lithium metal batteries from entering the marketplace. As such, research and development into solid electrolytes (SE) have yielded several promising candidates for solid-state batteries. However, each class of SEs comes with particular problems that either increase processing cost, or decrease performance relative to current liquid electrolytes, or both. For example, Lipon and other similar lithium silicates and phosphates are stable against high voltage cathodes (>4.5 V) and lithium metal; however, their conductivity is poor, leading to low power density. Lithium phosphorus sulfides (LPS) have the opposite problem, high conductivity, and instability. Ceramic phases such as Li7La3Zr2O12 (LLZO) have attractive advantages to both classes of materials, inherently high Li conductivity and chemical robustness. However, these advantages come with a cost: complicated processing in terms of high-temperature synthesis and interface control. Concerning the first perceived processing problem, temperatures used for the solid-state synthesis of LLZO are 1000 °C or greater. These temperatures not only adds to the manufacturing costs, but it also promotes lithium evaporation, which then requires the addition of 5-20% excess lithium precursor; costs increase further. Because Li loss leads to a Li concentration gradient resulting in a mixed-phase product, single-phase cubic LLZO synthesis requires manual separation or multiple grinds and calcines. Therefore, we need a new method for LLZO synthesis, and to do that, we need to understand the reaction pathway.This work demonstrates a method to improve the reaction kinetics and purity of LLZO through the use of nanoparticles of a known intermediate to improve the reaction kinetics and purity of LLZO. We will show in situ neutron scattering results that suggest the formation of La2Zr2O7 during typical LLZO occurs right before LLZO. This fact led to a strategy for reducing both synthesis time and temperature. We describe an efficient synthesis pathway for Al-doped LLZO using La3Zr2O x nanoparticles with nitrate precursors. The reaction is completed within one hour and produces a porous network of LLZO.This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Division of Materials Science and Engineering. This research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory.

Ionic Liquids at the Electrode Interface: Insights into Surface Passivation and Framework Expansion of Hard Carbon Anodes

Ionic liquids are being extensively explored as an alternative to carbonate-based electrolytes in reversible batteries, as they can exhibit lower flammability and volatility, and better overall safety. The polarity and acidity/basicity of ionic liquids can be tuned to control solubility, and can influence the electrochemical window and interfacial properties when used in batteries. In this study, 1-ethyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl) imide (EMIM.TFSI) and 1-methyl-1-propypyrrolidinium bis(trifluoromethanesulfonyl)imide (MPPY.TFSI) were selected because they are well-known, relatively stable ionic liquids with large electrochemical windows which show strikingly different behavior with carbonaceous anodes due to differences in interface passivation. High surface area mesoporous hard carbon anodes were employed to provide a large signal from the interfacial chemistry of these electrolytes during reversible cycling. A combination of operando small-angle neutron scattering (SANS) and ex-situ electrochemical studies were used to understand the differences in solid electrolyte interphase (SEI) for these ionic liquids, and the relationship of SEI formation to hard carbon microstructural changes. Reversible hard carbon expansion is observed in the first cycle for the electrolyte lithium bis(trifluoro-methanesulfonyl)imide (LiTFSI)/EMIM.TFSI related to EMIM+ intercalation and deintercalation before a stable SEI is formed, while a largely irreversible framework expansion of 15% is observed for the LiTFSI/MPPY.TFSI electrolyte. There is only relatively minor expansion and contraction in subsequent cycles after a suitable solid electrolyte interphase (SEI) has formed. Irreversible framework expansion in conjunction with SEI formation is found to be essential for the stable cycling of hard carbon electrodes.[1]Acknowledgement: Research was sponsored by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division. Research at Spallation Neutron Source user facility was sponsored by the Division of Scientific User Facilities, Office of Basic Energy Sciences, US Department of Energy, under contract DE-AC05-00OR22725 with UT-Battelle, LLC.[1] Bridges, C.A.; Sun, X.G.; Guo, B.K.; Heller, W.T.; He, L.L.; Paranthaman, M.P.; Dai, S. “Observing Framework Expansion of Ordered Mesoporous Hard Carbon Anodes with Ionic Liquid Electrolytes via in Situ Small-Angle Neutron Scattering.” ACS Energy Lett. 2017, 2, (7), 1698-1704.