bluuebunny/crossref_metadata_2025_split huggingface dataset:
Quantifying the Thermochemistry of Solid-State Lithium Metal Battery Reactions Using Differential Scanning Calorimetry
Authors: Bhargava Bhuvsmita , Johnson Nathan B , Chang Jonathan , Albertus Paul 
Published: November 2022

It is commonly assumed that the introduction of solid-state electrolytes implies the improved safety of high-energy batteries due to the removal of the combustible organic solvents in present Li-ion cells. However, safety is a multifaceted issue that involves thermal runaway onset temperature, self-heating rates, total generated energy, maximum temperature, gas or other material releases from a cell, thermal runaway prevention mechanisms, etc.1 In addition, the use of lithium metal anodes (which melt at 180°C) for high energy density cells may introduce previously unconsidered safety issues not faced by Li-ion cells, in which no molten and reactive lithium metal is present during a thermal runaway. Quantitative heat flow data on reaction thermochemistry among solid-state battery cell components can be gathered using differential scanning calorimetry on milligram-scale samples that include the key components of a full cell stack. While a principal exothermic reaction observed in previous DSC work2 is the formation of Li2O from molten Li and O2 released upon metal oxide cathode decomposition, this work did not include current collectors or carbon and binder, which add further competing reactions such as the oxidation of binder, and lithium/current collector alloying. In addition, the measured heat flows in a DSC test that includes several cell components are critically dependent on the mass ratio of materials present in the cell, for example the electrode capacity ratio. In this talk we present our own DSC measurements on the onset temperatures, total heat release, and rate of heat release for numerous combinations of cell components (e.g., Li metal, solid electrolyte separators, cathode active materials, cathode inactive components) for prospective solid-state batteries.
References:
(1) Bates, A. M.; Preger, Y.; Torres-Castro, L.; Harrison, K. L.; Harris, S. J.; Hewson, J. Are Solid-State Batteries Safer than Lithium-Ion Batteries? Joule
2022, 6 (4), 742–755.
(2) Inoue, T.; Mukai, K. Are All-Solid-State Lithium-Ion Batteries Really Safe?−verification by Differential Scanning Calorimetry with an All-Inclusive Microcell. ACS Appl. Mater. Interfaces
2017, 9 (2), 1507–1515.
Surface-Substituted Prussian Blue Analog Cathode for Sustainable Potassium-Ion Batteries
Authors: Ge Junmin , Fan Ling , Rao Apparao M. , Zhou Jiang , Lu Bingan 
Published: November 2022

While lithium-ion batteries still dominate energy storage applications, aqueous potassium-ion batteries have emerged as
a complementary technology due to their combined advantages in cost and safety. Realizing their full potential, however, is
not without challenges. One is that among the limited choices of cathode materials, the more sustainable Prussian blue analogs
suffer from fast capacity fading when manganese is present. Here we report a potassium manganese hexacyanoferrate
K1.82Mn[Fe(CN)6]0.96·0.47H2O cathode featuring an in situ cation engineered surface where iron is substituted for manganese.
With this engineered surface, the cathode design exhibits a discharge capacity of 160 mAh g−1 and 120 mAh g−1 at 300 mA g−1

and 2,500 mA g−1, respectively, and sustains 130,000 cycles (more than 500 days) with negligible capacity loss. Pairing the
current cathode with a 3,4,9,10-perylenetetracarboxylic diimide anode yields a full potassium-ion cell that delivers an energy
density as high as 92 Wh kg−1 and retains 82.5% of the initial capacity after 6,500 cycles at 1,500 mA g−1. The unprecedented
electrochemical performance is attributed to the suppressed manganese dissolution as a result of the shielding surface
layer. This work is expected to open an avenue for the rational design of high-performance cathode materials with redox-active manganese for rechargeable batteries.
High-Performance All-Solid-State Li-S Batteries Enabled by Reaction Kinetics Enhancement and Interface Stabilization
Authors: Zhu Hongli , Sun Xiao 
Published: November 2022

Compared to the conventional lithium-sulfur (Li-S) batteries using liquid electrolytes, all-solid-state lithium-sulfur batteries (ASSLSBs) own the merits of eliminating polysulfide shuttle effects, potentially higher energy density, and superior safety. However, there are challenges of low utilization of sulfur caused by poor ion and electron conductions in the cathode, huge interfacial resistance due to the contact loss caused by huge volume change of sulfur during cycling, and sluggish reaction kinetics and higher thermodynamic barriers because of the one-step reaction from S8 to Li2S reactions. Also, the carbon additive could accelerate the decomposition of sulfide solid-state electrolyte (SSE) resulting newborn impedance. Therefore, it is significant to interface engineering the carbon additive through surface modification and functionalization to improve the electrochemical stability, charge transfer, and reaction kinetics in ASSLSBs.
Herein, for the first time, we designed a highly conductive carbon fiber decorated with vertically grown MoS2 nanosheets and applied it in ASSLSBs. The chemical and electrochemical compatibility among MoS2, sulfur, and sulfide SSE can greatly improve the stability of the cathode and therefore maintain pristine interfaces between the different compositions for stable ion and electron transport. The presence of electrical-conductive metallic 1T MoS2 and its uniform distribution on carbon fiber without aggregation benefit the electron transfer between carbon and sulfur. Meanwhile, the unique layered structure of MoS2 can be intercalated by a large amount of Li atoms and therefore facilitate both ionic and electronic conductivity. In consequence, the charge transfer and reaction kinetics were greatly enhanced, and the decomposition of SSEs was successfully relieved. As a result, our ASSLSB delivered an ultrahigh initial discharge capacity of 1456 mAh g-1 with ultrahigh initial coulombic efficiency and maintained high-capacity retention of 78 % at 0.1 C after 220 cycles. The batteries also obtained remarkable rate performance of 1069 mAh g-1 at 1 C. This study pioneered new idea that fabricating the high performance ASSLSBs through developing surface functionalized and stabilized conductive carbon additives with metal sulfides.
Chemo-Mechanics in All Solid State Composite Cathodes
Authors: Hatzell Kelsey 
Published: November 2022

Decarbonization of transportation systems will require a suite of battery technologies depending on the mode and scale. Solid state batteries are an energy dense and non-flammable alternative to conventional batteries and is currently being explored for passenger vehicles and portable electronics1,2. While there is considerable interest in understanding lithium metal anodes for solid state batteries, many significant challenges still exist in solid state cathodes. Solid state cathodes are composites and usually include a combination of active material, solid electrolyte and binder3. The composition, microstructure, and properties of the cathode has significant implications for rate performance, energy density, and lifetime of these systems. Here we examine composite solid state cathodes comprised of argyrodite Li6PS5Cl and LiNi0.8Co0.1Mn0.1O2. We examine how composition and structure influences performance with a specific lens on understanding how chemo-mechanical transformations and buried solid-solid interfaces evolved during cycle operation. In addition we show how external operating conditions (temperature/pressure) influence stress generation in these systems. In this talk we will discuss how we combine novel bench-top experiments with advanced operando x-ray characterization tools to quantify stress and correlate it to structure.
[1]Shen, F., Dixit, M. B., Zaman, W., Hortance, N., Rogers, B., & Hatzell, K. B. (2019). Composite electrode ink formulation for all solid-state batteries. Journal of The Electrochemical Society, 166(14), A3182.
[2]Hatzell, K. B., & Zheng, Y. (2021). Prospects on large-scale manufacturing of solid state batteries. MRS Energy & Sustainability, 8(1), 33-39.
[3]Ren, Y., Hortance, N., & Hatzell, K. (2022). Mitigating Chemo-Mechanical Failure in Li-S Solid State Batteries with Compliant Cathodes. Journal of The Electrochemical Society.
Preparation of Li-Si-P-S-O-N Glasses: The Impact of Lipon Incorporation on Ionic Conductivity
Authors: Torres III Victor Manuel , Martin Steve , Philipp Presley 
Published: November 2022

Lithium glassy solid electrolytes (GSEs) are an alternative to liquid electrolytes in the development of solid-state batteries. Mixed oxy-sulfide nitride GSEs incorporate the useful properties of sulfide glasses, which show high ionic conductivity, of oxide glasses which display excellent chemical stability, and of nitride glasses which exhibit good electrochemical stability. In our investigation of these new GSEs, the following compositional series was explored Li2S + SiS2 + [(1-x)Li0.67PO2.83 + xLiPON]. Differential scanning calorimetry (DSC) was employed to determine the crystallization and glass temperatures of these GSEs. In addition, electrochemical impedance spectroscopy (EIS) was used to determine the temperature-dependent ionic conductivity of theses GSEs. X-ray Photoelectron Spectroscopy (XPS) was conducted on the glasses to further understand the chemical bonding environment of nitrogen. It was found that x = 0.2 displayed the highest ionic conductivity suggesting that nitrogen incorporation can be used to optimize mixed oxy-sulfide glasses.
Support of this research by NSF Grant NSF-DMR-1936913 is acknowledged.
Ab Initio Insights into the Solid Electrolyte Interphase Formation in Lithium Metal Batteries with Carbonate Electrolytes
Authors: Kuai Dacheng , Balbuena Perla B. 
Published: November 2022

As the research endeavors push the performance of widely used Li-ion battery to its theoretical limit, there are strong urges to develop next-generation energy storage devices. Li metal is a promising candidate battery anode material which can bring the energy density to a higher level. There are safety and cycling efficiency issues associated with the Li-metal battery (LMB), and the metal dendrite nucleation and lithium whisker formation are largely responsible for them. The solid electrolyte interphase (SEI) generated from the reactions between lithium metal and battery electrolyte components can regulate the lithium-ion diffusion and deposition which protects anode materials from undesired consumptions. According to the experimental evidence, the SEI from carbonate electrolytes may contain inorganic components including Li2O, Li2CO3, LiF, as well as organic structures such as polymers and oligomers with carbonate and carbonyl structures. However, the exact composition and ionic diffusion properties of SEI are challenging to be directly characterized via experimental techniques.
In this work, we initiated the elucidation of the SEI composition by investigating plausible reaction pathways. The inorganic structures are mainly resulted from the degradation of electrolyte solvent and salt species upon contact with the anode material. Ab initio molecular dynamics (AIMD) simulation was implemented to track the interfacial reduction of ethylene carbonate (EC), vinylene carbonate (VC) and lithium hexafluorophosphate (LiPF6). Bader charge analysis demonstrated that the LiPF6 reduction requires consecutive uptake of outside electrons, no matter such reaction happens right on the metallic surface or in electrolyte phase. The final product of the LiPF6 degradation was determined to be Li3P, and the reaction thermochemistry was computed based on density functional theory (DFT). The experimentally measured battery electrochemical performance enhancement of the VC additive has been reported while the chemical mechanism behind such phenomenon was less discussed. We modeled the degradation and polymerization reactions of EC and VC molecules in the LMB environment. VC has significantly smaller energy barrier than EC to generate the lithium-carbonyl complexes and the oligomer/polymer species which takes longer time scale to form. In addition, the solvated lithium cation was found to have significant contribution to the polymerization reaction thermodynamics. The most kinetically favored pathways and products for EC and VC polymerization were identified via DFT calculations. Multiscale simulation based on the computed thermodynamic information was able to provide a glimpse of the microscopic morphology inside the SEI.
Multiscale Modeling of Solid Electrolyte Interphase Growth in Lithium-Ion Batteries
Authors: Verma Ankit , Weddle Peter J , Schulze Maxwell , Abraham Daniel P. , DeCaluwe Steven C. , Colclasure Andrew M. 
Published: November 2022

Calendar and cycle life of lithium-ion batteries (LIBs) are predominantly dictated by the passivating nature of the solid electrolyte interphase (SEI) film growth on battery anodes. Graphitic anodes exhibit stable SEI growth which enables ubiquitous commercialization of LIBs. In contrast, silicon anodes exhibit poorly passivating SEI characteristics including rapid thickness and composition changes during cycling (“breathing”) and sensitivity to electrolyte composition and surface functionalization. In this work, we develop a chemically complex continuum-level multicomponent, multiphase coupled thermodynamics-reaction-transport SEI model to unravel the mechanisms of SEI growth in LIB anodes. Atomistic calculations in conjunction with experimental datasets are utilized to ascertain the dominant decomposition pathways towards predominant SEI components like Li2EDC, Li2O, Li2CO3, LiMC, LiF etc. and inform the continuum model predictions. Furthermore, experimental voltage-hold measurements are utilized to validate the SEI model parasitic currents/composition evolution profiles enabling prediction of voltage regimes for stable SEI growth with favorable SEI composition. The development of such chemically complex SEI models will aid predictive electrolyte screening for the growth of stable and passivating SEI layers on next generation anodes like silicon.
Figure 1(a) shows a schematic of the detailed SEI model incorporating species and charge transport through the pore and solid phases of the SEI for LEDC formation. Figure (b) showcases experimental leakage currents during V-hold at 100 mV and 250 mV for Li-Si half cells and the detailed SEI model fits. Figure (c) shows the SEI composition profiles predicted by the model and the formation of inner inorganic (Li2CO3, Li2O) - outer organic (LEDC) bilayer SEI. Interestingly, inorganic LiF from FEC decomposition is predicted to form throughout the SEI.

Figure 1
Understanding the Parameters Influencing the Impedance Response of Sulfur-Carbon Composite Cathode in Lithium-Sulfur Batteries
Authors: Nojabaee Maryam , Gerle Martina , Häcker Joachim , Wagner Norbert , Friedrich K. Andreas 
Published: November 2022

Lithium-sulfur (Li-S) batteries, which in recent years have been aimed at a high gravimetric energy density of 500-600 Wh kg-1, indicate particular potential in aerospace applications such as aircraft, satellites and drones.1,2 In light of this, the German Aerospace Center (DLR) has been pursuing a strategy of developing and researching metal-sulfur batteries for a decade. Herewith, we present the results of a fundamental study on the investigation of structural and compositional parameters affecting the electrochemical performance of sulfur-carbon composite cathode.
Highly porous carbon materials are widely employed in composite cathodes in Li-S batteries to compensate for the non-conductive property of the sulfur element. Indeed, this would have significant effects not only on the conductivity of the cathode, but also on the diffusion and charge transfer parameters. Herewith, we have systematically studied porous carbon-based electrodes employing electrochemical impedance spectroscopy. Using a suitable transmission-line model peculiar to the porous electrodes, the resistance of bulk and pore electrolyte, inter-particles, and charge transfer is defined and quantified. The dependence of the identified processes at the open circuit voltage on the fraction of the active material, the porosity of utilized carbon and thickness of the electrode is investigated elaborately. It is indicated that the electrolyte resistance in the pore increases on increasing the content of active material, electrode thickness and on reducing the pore size distribution of the C component.
Additionally, an innovative symmetrical three-electrode cell configuration with an integrated Li-ring serving as counter electrode is implemented, enabling the investigation of the cathode impedance at different depths of discharge to shed light on the kinetics of the charge transfer depending on the infiltration method. To this end, various porous carbon materials such as Ketjenblack® (mesoporous) and carbon aerogel (microporous) in combination with different sulfur infiltration techniques including gas, melt and mechanical mixing have been employed as model systems3. The thermodynamic and kinetics of charge transfer mechanisms as a function of infiltration method as well as the variation of the charge transfer resistances upon discharge/charge are discussed in details4.

A. Fotouhi, D. J. Auger, L. O’Neill, T. Cleaver and S. Walus, Energies, 2017, 10, 1937.

Sripad S., Viswanathan V. (2017), ACS. Energy. Lett.2, 1669-1673

M. Nojabaee, B. Sievert, M. Schwan, J. Schettler, F. Warth, N. Wagner, B. Milow, K. Andreas Friedrich, J. Mater. Chem. A, 2021,9, 6508-6519.

Martina Gerle, Norbert Wagner, Joachim Häcker, Maryam Nojabaee, Andreas Friedrich J. Electrochem. Soc., 2022, 169, 030505.
Development of Argyrodite-Based Sulfide Electrolytes for Next-Generation Solid-State Li Batteries
Authors: Yang Guang , Self Ethan , Brahmbhatt Teerth , Mills Anna , Tsai Wan-Yu , Hallinan Daniel , Chen Xi , Delnick Frank , Nanda Jagjit 
Published: November 2022

Advances in solid electrolytes (SEs) with superionic conductivity and stabilized electrode-electrolyte interfaces are key enablers for all-solid-state batteries (SSBs) to meet the energy density and cost targets for next-generation batteries for electric vehicles. Argyrodite sulfide-based electrolytes with the nominal composition Li6PS5X; where X= Cl and/or Br, I provide several key advantages over other types of SE counterparts, including (i) exceptionally high ionic conductivities up to 10-2 S/cm at room temperature (comparable to nonaqueous liquid electrolytes), (ii) availability of low temperature and inexpensive synthesis routes to produce glass, glass-ceramic, and crystalline structures, and (iii) soft mechanical properties facilitating material processing and solid-state battery (SSB) fabrication.
Several key challenges exist for the practical use of the argyrodite sulfide-based electrolyte in an SSB: (i) scale-up synthesis to produce phase-pure materials, (ii) rationale processing method development to produce free-standing thin film SSEs, and (iii) identifying buried interfacial side-reaction products at the electrode/electrolyte interfaces using advanced characterization tools.
In this talk, we will present our recent achievements focusing on tackling each of these challenges, including (i) solution-based synthesis of Li6PS5X; (ii) optimizing binder, slurry composition, and processing method to make Li6PS5X thin film (<50 µm) SSEs, and (iii) combining in-situ Raman spectroscopy and microscopy with complementary electrochemical impedance spectroscopy (EIS) to explore electrode/ Li6PS5X interfacial stability.

Acknowledgment

This research conducted at Oak Ridge National Laboratory, managed by UT Battelle, LLC, for the U.S. Department of Energy (DOE) is sponsored by the Office of Energy Efficiency and Renewable Energy (EERE) in the Vehicle Technologies Office (VTO) through the Advanced Battery Materials Research (BMR) Program.
3D Asymmetric Bilayer Garnet Hybridized High-Energy-Density Lithium-Sulfur Batteries
Authors: Shi Changmin , Nolan Adelaide , Takeuchi Saya , Fu Zhezhen , Dura Joseph , Wachsman Eric 
Published: November 2022

Li7La3Zr2O12 (LLZO) has high ionic conductivity and stability against a Li metal anode making it a promising solid electrolyte for Lithium-Sulfur batteries. However, typically reported discharge capacity does not achieve theoretical. Therefore, we addressed this by forming a stable sulfur cathode/LLZO interface through a poly(ethylene oxide) (PEO)-based interlayer, with a small amount of catholyte used to maintain physical contact and ionic conduction between sulfur cathode and the PEO-based interlayer. With a thin bilayer LLZO and the stabilized sulfur cathode/LLZO interface, the hybridized Li-S batteries achieved an initial discharge capacity of 1307 mAh/g at a current density of 0.2 mA/cm2 (0.03C) at room temperature (22°C) without any indication of a polysulfide shuttle. With specific optimization, an energy density of 1308 Wh/L and 485 Wh/kg is achievable.
The mechanisms regarding the cell stabilization are presented: 1). X-ray Diffraction and X-ray Photoelectron Spectroscopy indicate that the PEO-based interlayer which physically separates the sulfur cathode and LLZO, is both chemically and electrochemically stable with LLZO. 2). Due the physical separation between liquid electrolyte and LLZO through the PEO-based film, the proton/Li+ exchange with the moisture in liquid electrolytes was avoided. 3). PEO-based interlayer can adapt to the stress/strain associated with sulfur volume expansion during lithiation to protect LLZO from failure.
Assessing Mediated Redox Flow Battery Reaction Progression
Authors: Koenig Gary , Gupta Devanshi , Wang Jing , Zhang Yuxuan 
Published: November 2022

One potential next generation battery system is mediated redox flow batteries (RFBs). With mediated RFBs, soluble electroactive species (redox shuttles) deliver power via electrochemical reactions in a flow-through stack reactor much like a conventional RFB. However, the redox shuttles then undergo chemical redox in a coupled chemical reactor system with solid electroactive materials. The use of solid electroactive material for chemical energy storage results in substantial increases in volumetric energy density for the system.
Mediated RFBs with different configurations for the chemical redox reactor have previously been reported. In this work, a packed bed reactor system will be described, where the impact of varying different experimental parameters on the chemical redox progression will be highlighted. Generally, the progression of the chemical redox can be tracked in the lab by taking advantage of electrochemical analytical techniques. However, additional assessment of the reaction progression using neutron imaging will also be discussed. Neutron imaging offered a unique opportunity to access the spatial progression of the chemical redox in the packed bed reactor. The combination of techniques for assessing the chemical redox progression provides insights into the limiting processes in the reactor systems.
(Invited) Accelerating Material Design for Aqueous Organic Redox Flow Batteries
Authors: Wang Wei 
Published: November 2022

Aqueous soluble organic (ASO) redox-active materials have recently shown great promise as alternatives to transition metal ions to be employed as energy-bearing active materials in redox flow batteries for large-scale energy storage because of their structural tunability, cost-effectiveness, availability, and safety features. Development so far however has been limited to a small palette of organics that are aqueous soluble. How to quickly identify and design organic molecules for the targeted properties became a critical challenge in accelerating the aqueous organic flow battery development.
In this presentation, a data-driven material design process is discussed. This process incorporates database building, machine learning modeling for properties prediction, and the subsequent material synthesis and testing. Examples including Fluorenone and Phenizane derivative development for the flow battery application will be discussed.