bluuebunny/crossref_metadata_2025_split huggingface dataset:
Operando Characterization of Plating and Stripping Dynamics of Li-Mg Alloy Anode and Sulfide Solid Electrolyte Interface
Authors: Zhao Lihong , Wu Chaoshan , Ai Qing , Guo Liqun , Chen Zhaoyang , Liang Yanliang , Lou Jun , Fan Zheng , Yao Yan 
Published: September 2023

All-solid-state lithium metal batteries are projected to offer one of the highest specific energy among rechargeable batteries, positioning them as a front-runner for electric vehicle applications. Lithium metal anodes outperform conventional graphite anodes in terms of cell-level energy density. However, maintaining a conformal metal–electrolyte contact is a great challenge. The volumetric change of the lithium metal anode during stripping produces voids, which deteriorates the Li–electrolyte contact. To address this challenge, β-phase Li solid solution (i.e., Li-Mg alloy) has been shown to exhibit improved contact with the solid electrolyte during stripping. Moreover, Li solid solution has a similar electrochemical potential as Li, making it a potential replacement for Li metal anodes without sacrificing cell-level energy density. In this study, we show that the chemical properties of the alloy play an essential role in the morphological stability of metal–solid electrolyte interface. We compare the stripping behavior of pure Li and Li-Mg alloy anodes in argyrodite electrolyte and characterize the morphological evolution of the interface using operando scanning electron microscopy (SEM). We also analyze the electro-chemo-mechanical properties of Li and Li alloy anodes during stripping with galvanostatic electrochemical impedance spectroscopy (GEIS) to compare the influence of composition change and interfacial void on the electrode overpotential and interface resistance. Our research visualizes the morphological and compositional evolution of alloy metal anode during stripping and rationalizes their improved interfacial stability against solid electrolytes.
Acknowledgment: This work was supported by the U.S. Department of Energy's Office of Energy Efficiency and Renewable Energy (EERE) under the Vehicle Technologies Program under Contract DE-EE0008864.

Figure 1
Hybrid Material Concepts for Thiophosphate-Based Solid-State Batteries
Authors: Vargas-Barbosa Nella Marie , Puls Sebastian , Woolley Henry Michael 
Published: September 2023

Solid-state batteries (SSBs) could replace conventional lithium-ion batteries due to the possibility of increasing the energy density of the cells by using lithium metal as the anode material.[1] Among the many electrolyte candidates for lithium SSBs, the lithium thiophosphates are particularly interesting due to their high ionic conductivities at room temperature (>1 mS/cm). However, the (electro)chemical stability of these solid electrolytes is limited and not fully compatible with state-of-the-art high-potential cathode active materials[2] or the lithium metal anode.[3] At the cell level, the formation of interparticle voids between the various battery components (solid electrolyte, cathode active material, anode material, additives, decomposition interphases) hinder the net transport during cycling. To address the latter electro-chemo-mechanical challenges, we are exploring hybrid material approaches, in which we combine established materials (solid electrolytes, liquid electrolytes and/or polymer additives) with state-of-the-art cathode active materials and test their electrochemical performance in solid-state battery (half-)cells. Such cycling results are complimented by detailed electrochemical transport studies in symmetrical cells using DC polarization and electrochemical impedance spectroscopy, including transmission-line modeling. ex.situ chemically-specific spectroscopic methods are used to support our hypotheses and interpretation of the electrochemical results. Taken together, we attain a better picture on the positive (or negative) role hybrid materials play in SSBs. In this talk, we will showcase two hybrid systems, namely ionic liquid/thiophosphate lithium hybrid electrolytes and conductive polymers additives in NMC-based catholyte composites for Li6PS5Cl cells. The first part of the talk we will discuss the results in which we evaluate the performance of liquid electrolyte-solid electrolyte materials against lithium metal using galvanostatic electrochemical impedance spectroscopy. In the second part, we elucidate the partial ionic and electronic transport in polymer electrolyte-Li6PS5Cl-NMC catholytes as a function of polymer content using impedance spectroscopy and its effect in the cycling performance, both the stability as well as the magnitude of the discharge capacities. These systems serve as a good starting point for the further development and incorporation of hybrid materials in SSBs.
Literature: [1] W. G. Zeier and J. Janek Nature Energy, 2016, 1, 16141. [2] G.F. Dewald, S. Ohno, M.A. Kraft, R. Kroever, P. Till, N.M. Vargas-Barbosa, J. Janek, W.G. Zeier Chem. Mater. 2019, 31, 8328. [3] L. M. Riegger, R. Schlem, J. Sann, W. G. Zeier, J. Janek, Angew. Chem. Int Ed 2021, 60, 6718.

Figure 1
Effect of Nanostructured Inorganic Ceramic Filler on Poly(ethylene oxide)-Based Solid Polymer Electrolytes
Authors: Kirchberger Anna Maria , Walke Patrick , Nilges Tom 
Published: September 2023

In view of the ongoing changes in energy science and technology, the possibilities of energy storage are getting increasingly important. In particular, storing electrical energy is more complex than with fossil fuels.
Lithium-Ion batteries are the most commonly used media for energy storage, but they also have some safety-related problems: toxic decomposition products can leak out and the devices can catch fire. Research is underway to find alternatives to minimize this potential hazards. Great improvements in safety matters can be achieved by replacing liquid electrolytes with ceramic/polymer hybrid electrolytes. These hybrid electrolytes combine the advantages of polymer electrolytes with the benefits of inorganic ceramic fillers.1 Flexibility, good contact ability and in addition the good processability is provided through the polymer. The inorganic ceramic filler in contrast adds mechanical stability, opens new pathways for the Lithium-Ions and can enhance the stability of the electrolyte.
Figure 1: different Lithium-ion pathways in ceramic/polymer hybrid electrolytes dependent on different filler amounts. 2

In this work the impact of the manufacturing method on the conductivity of a series of electrolytes was examined. Therefore, hot pressing, solution casting and electrospinning were tested. Also, different distribution methods for the particles in the material were tested to monitor the influence of agglomeration on the conductivity. The materials were characterized regarding the crystallinity using X-Ray diffraction, the surface and particle distribution was monitored with SEM/EDX, the thermal character was investigated using DSC, the conductivity was determined using impedance spectroscopy and the electrochemical behavior was tested using cyclic voltammetry. Furthermore, the Arrhenius equation was used to interpret the results of impedance spectroscopy regarding their activation energy. The addition of inorganic ceramic fillers leads to an enhancement of the ionic conductivity in PEO based electrolytes and increases processability and stability of the electrolyte. In this work conductivities of 10-5 S/cm were reached at room temperature. The performance of the electrolyte was increased above three orders of magnitude compared to a PEO electrolyte without inorganic ceramic fillers.

Walke, P.; Kirchberger, A.; Reiter, F.; Esken, D.; Nilges, T., Effect of nanostructured Al2O3 on poly(ethylene oxide)-based solid polymer electrolytes. Zeitschrift für Naturforschung B
2021,
76 (10-12), 615-624.

Chen, L.; Li, Y.; Li, S.-P.; Fan, L.-Z.; Nan, C.-W.; Goodenough, J. B., PEO/garnet composite electrolytes for solid-state lithium batteries: From “ceramic-in-polymer” to “polymer-in-ceramic”. Nano Energy
2018,
46, 176-184.

Figure 1
Thermodynamic Modelling and Experimental Study of Nasicon Sub-Systems for Application as Solid State Electrolyte
Authors: Gonde Shivani , Sergeev Dmitry , Yazhenskikh Elena , Müller Michael 
Published: September 2023

Solid state electrolytes are crucial for enhancement of the safety and practicability of batteries. NASICON (
Na Super Ionic Conductor) is proposed as replacement for β″-Al2O3 [1], because of its excellent structural strength and conductivity which is attributed to its structure wherein Na migrates in 3D voids providing ionic conductivity of 0.2 S·cm-1 (300 °C). Furthermore, the processing temperature is relatively low (~700 °C), and high Na abundance makes it cheaper than Li-ion batteries.
The NASICON phase with formula Na1+xZr2SixP3-xO12 [0≤x≤3] is found to be conductive and is a part of the complex Na2O-SiO2-P2O5-ZrO2 system. For a successful material design, thermodynamic properties (phase equilibria, heat capacity, stability, etc.) for all subsystems must be known, and for prediction of the properties, a reliable and consistent database is imperative. To accomplish these milestones, a thermodynamic database of the quaternary oxide system including the NASICON phase is being developed using Calculation of Phase Diagrams (CALPHAD) method.
As part of this development, underlying binary systems such as Na2O-ZrO2 and ternary systems such as ZrO2-SiO2-P2O5 are studied. After preliminary results, the phase diagram construction is in progress with DTA/TG, XRD, and the experimental data along with literature values after critical analysis will be utilized for generation of Gibbs energies for all phases in the system. Using the thermodynamic dataset obtained, phase equilibria are predicted in agreement with the experimental data. The current state of work will be presented.

References:

B. Goodenough: “Fast Na+-ion transport in skeleton structures”, Mater. Res. Bull. 11(2) (1976) 203-220.

Warhus: “Thermodynamics of NASICON (Na1+xZr2SixP3-xO12)”, J. Solid State Chem. 72(1) (1988) 113-125.

Figure 1
Investigation of Ultra-Low Temperature Li/CF
x
Batteries in the Liquefied Gas Electrolyte
Authors: Liu Alex Ruili , Yin Yijie , Holoubek John , Li Weikang , Meng Shirley 
Published: September 2023

Lithium-fluorinated carbon (Li/CFx) is one of the most promising chemistries to serve as a reliable high-energy density primary energy storage system in applications where rechargeability is not required. Though Li/CFx demonstrates high energy density (>2100 Wh kg–1) under ambient conditions, achieving such a high energy density when exposed to subzero temperatures remains challenging, particularly under high current density.
Liquefied gas electrolytes (LGE) are regarded as one of the most promising electrolyte systems, offering excellent ionic conductivities at wide temperature ranges from -80 to + 60 oC due to low viscosity and low freezing point of gas molecules. Moreover, the LGE can significantly improve the capacity retention of Li-metal batteries operated at reduced temperatures.
Here, we report a liquefied gas electrolyte with an anion-pair solvation structure based on dimethyl ether with a low melting point (−141 oC) and low viscosity (0.12 mPa×S, 20 oC), leading to high ionic conductivity (> 3.5 mS cm–1) between −70 and 60 oC. Besides that, through systematic X-ray photoelectron spectroscopy (XPS) integrated with transmission electron microscopy (TEM) characterizations, we evaluate the CFx interphase from the low-temperature discharge process. We conclude that the fast transport and anion-pairing solvation structure of the electrolyte bring about reduced charge transfer resistance at low temperatures, which resulted in significantly enhanced performance of Li/CFx cells (1690 Wh kg–1, −60 oC;1172 Wh kg–1, −70 oC based on active materials). Utilizing 50 mg cm-2 loading CFx electrodes, the Li/CFx displayed 1530 Wh kg–1 at −60 oC. This work provides insights into the electrolyte design that may overcome the operational limits of batteries in extreme environments.
Fallen Leaves-Based Femtosecond-Laser-Induced-Graphene for High-Performance Flexible Micro-Supercapacitors
Authors: Lee Yeong A , Jang Kyuyeon , Dinh Le Truong-Son , Nam Han Ku , Yang Dongwook , Kim Byunggi , Yim Kanghoon , Kim Seung-Woo , Kim Young-Jin , Yoon Hana 
Published: September 2023

The rapid growth of wearable and portable electronics has led to the development of microscale energy storage devices. Among these devices, microsupercapacitors (MSCs) have emerged as promising flexible energy storage devices owing to their high power density, fast charge/discharge rate, and long-term cycling stability [1-4]. Flexible MSCs were mainly made from non-biodegradable synthetic polymers, resulting a massive electronic waste. Moreover, complex manufacturing processes increase production costs.
To address these challenges, we present a novel approach to fabricate green and flexible MSCs using naturally fallen leaves as a carbon precursor [5]. Our method utilize ultrashort laser pulses to create highly conductive and intrinsically flexible microelectrodes without any additional materials. The laser-induced-graphene is formed on leaves in ambient air, resulting in hierarchically porous graphene with 3D mesoporous few-layer structures.
Our green flexible MSCs demonstrated excellent electrochemical performance and were confirmed to work as a power sources for various applications such as LEDs and thermometers. Furthermore, our approach offers a low-cost, renewable, and environmentally friendly alternative to traditional manufacturing processes. Overall, our green and flexible MSCs have significant potential for use in energy-storage devices for flexible/wearable electronics.
References
[1] M. F. El-Kady, R. B. Kaner, Nat. Commun. 4, 1475 (2013).
[2] S.-K. Hyeong, M. Park, S.-I. Kim, S. Park, K.-H. Choi, M. Im, N. Kim, T.-W. Kim, S. Lee, J.-W. Park, S. Bae, J.-H. Lee, S.-K. Lee, Adv. Mater. Technol. 7, 2101105 (2022)

[3] D. Pech, M. Brunet, H. Durou, P. Huang, V. Mochalin, Y. Gogotsi, P. -L. Taberna, P. Simon, at. Nanotech. 5, 651 (2010).
[4] Y. Lee, J. Lim, Y. Cho, H. Lee, S. Park, G.-W. Lee, C.-Y. Yoo, S. Park, V. Murukeshan, S. Kim, Y.-J. Kim, H. Yoon, Chem. Eng. J. 386, 123972 (2020)

[5] T. –S. Le, Y. Lee, H. Nam, K. Jang, D. Yang, B. Kim, K. Yim, S.-W. Kim, H. Yoon, Y.-J. Kim, Adv. Funct. Mater. 32, 2107768 (2022)
Lithium Morphology Evolution through Crosslinked Poly(ethylene oxide) Solid Polymer Electrolyte
Authors: Owensby Kyra , Tsai Wan-Yu , Sahore Ritu , Chen Xi 
Published: September 2023

Solid-state, lithium metal batteries are promising candidates for developing the safe, energy-dense devices needed to transition to an electrified economy. However, lithium is highly reactive, making it thermodynamically unstable when in contact with many electrolyte materials. Achieving uniform Li plating and stripping during cycling is the key for enabling high energy Li metal batteries. The lithium stripping and plating mechanism is complicated as it can be affected by the cathode, electrolyte and lithium anode, and the resulting solid electrolyte interphase (SEI). In particular, the mechanism is not well understood in solid polymer electrolytes.
In this work, we investigate lithium morphology evolution through a solid polymer electrolyte at different stages of battery cycling. Crosslinked poly(ethylene oxide) (xPEO) solid polymer electrolyte is used as a model electrolyte and full cells using single crystal LiNi0.6Mn0.2Co0.2O2 (NMC622) cathode, dry xPEO electrolyte and lithium from two commercial sources are assembled. Our results show that different lithium sources lead to different Coulombic efficiencies and capacity fade rate of the full cells assembled. The lithium morphology evolution at different stages of cycling is examined using scanning electron microscopy and the lithium plating/stripping mechanism are compared between these two commercial lithium anodes. Furthermore, the lithium morphology is compared to a gel polymer composite electrolyte with the same host polymer (xPEO). The dry solid polymer produces a smoother morphology than the gel polymer composite electrolyte without pit formation. A better understanding of the roles of each of these components (pristine Li surface chemistry, microstructure, dry vs gel polymer electrolyte) is essential to control for uniform lithium stripping and plating.
Fabrication of Internal Electric Field Sns/Sb2S3 with Engineered Porous Structure for Fast Kinetics Sodium Ion Storage
Authors: Mu Yuhe , He Wei , Sagar Lamsal Buddhi , Pokharel Jyotshna , Zhou Yue 
Published: September 2023

Benefiting from the abundance and low cost of sodium, sodium-ion batteries show great potential as lithium-ion batteries in application of large-scale energy storage. However, anode material graphite with high theoretical capacity 372 mAh g-1, low charge-discharge plateau potential and good cyclability, widely applied in lithium-ion batteries, exhibited poor electrochemical performance. The larger radius of Na-ion compared to Li-ion hinders the mass and ion transfer during charge-discharge cycling. Thus, anode material with large abundance, stability and high conductivity is crucial for the development and further application of sodium-ion batteries.
Sodium-ion batteries have the potential to benefit greatly from metallic sulfide anodes, which offer high theoretical capacities. Unfortunately, the practical use of these anodes is limited by poor electrochemical performance, as sulfides tend to expand significantly in volume and Na+ ions exhibit sluggish kinetics during cycling. We have developed a facile and scalable approach to synthesizing a SnS/Sb2S3 heterostructure that is porous and bimetallic, with an additional sulfur and nitrogen co-doped carbon matrix encapsulation (SnS/Sb2S3@SNC). The PAN precursor is mixed homogeneously with SnSbx and S with a ball milling process. The sulfur evaporates from the mixture and reacts with the SnSbx alloy, leading to the formation of bimetallic sulfides SnS/Sb2S3. As a result, voids are generated, which in turn contributes to the development of a porous structure. At the same time, the PAN is carbonized, generating a S, N co-doped carbon matrix. SnS and Sb2S3 are two highly promising anode materials for sodium-ion batteries, with high theoretical specific capacity of 1022 mAh g-1 and 947 mAh g-1, respectively. Moreover, bimetallic sulfides possess different bandgap make them ideal components for generating a strong internal electric field on the hetero-interface, which allows to improve the charge carrier transport and interface reaction kinetics. The porous nature of the structure can contain the volume expansion of sulfides during cycling, thereby ensuring superior structural stability. The distinctive heterostructure, in combination with the S, N co-doped carbon matrix, enables fast-charge transport and accelerate Na-ion storage kinetics.
The SnS/Sb2S3@SNC anode demonstrates impressive electrochemical performance, with high capacities of 425 mAh g-1 at 200 mA g-1 after 100 cycles, and 302 mAh g-1 at 500 mA g-1 after 400 cycles. Additionally, the SnS/Sb2S3 @SNC anode exhibits remarkable rate capability, with a capacity of over 200 mAh g-1 at a high current density of 5000 mA g-1.

Figure 1
In-Operando Isothermal Microcalorimetry to Accelerate Screening of New Battery Chemistries
Authors: May Jeremy , Lau Hang Kuen 
Published: September 2023

Screening new cell chemistries using traditional electrochemical methods is a time prohibitive process that significantly slows the pace of research. These methods involve cycling the cell until signs of degradation or sufficient capacity fade are evident, and typically take months to complete. In-operando isothermal microcalorimetry is an established but underutilized technique for measuring the activity of parasitic, or non-reversible reactions during charge cycling [1,2,3,4]. A parasitic reaction is a blanket term for any side reactions that occur within a battery, including solvent breakdown, lithium plating, self-discharge reactions, and growth or decomposition of the solid electrolyte interphase. Battery formulations with high parasitic heat are strongly correlated with early cell failure. Compared to electrochemical cycling, the average parasitic heat over the full voltage range can be determined in a time frame as low as 2 weeks, allowing researchers to realize a time savings up to 75%. Additional time savings are also possible if only a narrow voltage range is of interest.
In this study, we present results that demonstrate the measurement of the parasitic heat of a commercial 18650 lithium-ion battery using the TA Instruments Battery Cycler Microcalorimeter Solution. This method involves slow galvanostatic cycling at isothermal conditions with a simultaneous measurement of heat flow, voltage, and applied current. The parasitic heat is isolated from the total heat flow using the Integration-Subtraction method, with calculations performed automatically by the software [1]. The coulombic efficiency is also measured per cycle, showing an inverse relationship to the parasitic power. As a screening tool, this data could be used to select battery formulations most likely to meet performance goals in long-term cycling experiments, rather than wasting valuable time and lab space on a trial-and-error approach. The results highlight how in-operando isothermal microcalorimetry is a powerful screening tool for investigating the efficiency of new cell chemistries and electrolyte formulations in a fraction of the time compared to traditional methods.
[1] L.J. Krause, L.D. Jensen, V.L. Chevrier. Measurement of Li-Ion Battery Electrolyte Stability by Electrochemical Calorimetry. J. Electrochem. Soc. 2017, 164 (4), A889-A896.
[2] L.J. Krause, L.D. Jensen, J.R. Dahn. Measurement of Parasitic Reactions in Li Ion Cells by Electrochemical Calorimetry. J. Electrochem. Soc. 2012, 159 (7), A937-A943.
[3] J.C. Burns, Adil Kassam, N.N. Sinha, L.E. Downie, Lucie Solnickova, B.M. Way, J.R. Dahn. Predicting and Extending the Lifetime of Li-Ion Batteries. J. Electrochem. Soc.
2013, 160, A1451.
[4] E. R. Logan, A. J. Louli, Matthew Genovese, Simon Trussler,and J. R. Dahn. Investigating Parasitic Reactions in Anode-Free Li Metal Cells with Isothermal Microcalorimetry. J. Electrochem. Soc.
2021, 168, 060527.