bluuebunny/crossref_metadata_2025_split huggingface dataset:
An Unwanted Guest in the Electrochemical Oxidation of High-Voltage Li-Ion Battery Electrolytes: The Life of a Superacidic Proton
Authors: Ilic Stefan , Zorko Milena , Farinazzo Bergamo Dias Martins Pedro , Liu Haoyu , Yang Jingtian , Zhang Zhengcheng , Connell Justin G. , Key Baris , Cabana Jordi , Strmcnik Dusan 
Published: December 2024

Lithium-ion batteries (LIBs) are central to the urgent societal need to decarbonize both transportation and energy storage on the grid. Unfortunately, despite their attractive energy/power density and high coulombic efficiency, further improvement of this technology – especially their durability – is desperately needed. To support these efforts, our study focuses on fundamental understanding of the decomposition pathways for LIB electrolytes at the cathode-electrolyte interface (CEI), as the nature of these reactions directly controls the extent to which cell capacity and voltage decays in these systems. In this study, we employ electrochemical methods, coupled with product analysis using NMR spectroscopy and mass spectrometry, to determine the decomposition mechanisms for a model electrolyte (1.3 M LiClO4 in EC) and demonstrate the impact of these mechanisms on technologically relevant systems (1.0 M LiPF6 in EC/EMC). Remarkably, we discover the electrochemical formation of superacidic protons, which provides a unified origin for a myriad of side reactions in every individual component of the CEI. In particular, electrochemically generated protons chemically catalyze EC decomposition into CO2 and other short and long chain ethers. They also react with LiPF6 to form the weaker acid HF and are involved in a direct acid-base reaction with the cathode active material, causing the leaching of transition metals into the electrolyte. Collectively, the results of this study all point to the urgent need to either mitigate this proton formation or introduce benign harvesting additives via new electrolyte design strategies.
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The submitted manuscript has been created by UChicago Argonne, LLC, Operator of Argonne National Laboratory (“Argonne”). Argonne, a U.S. Department of Energy Office of Science laboratory, is operated under Contract No. DE-AC02-06CH11357. The U.S. Government retains for itself, and others acting on its behalf, a paid-up nonexclusive, irrevocable worldwide license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, by or on behalf of the Government. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan. http://energy.gov/downloads/doe-public-access-plan
Development of Eco-Friendly Binders for Silicon Anodes in All-Solid-State Batteries Under Low Operating Pressure
Authors: Jun Seunggoo , Lim Haechannara , Song Yongbae , Jung Yoon Seok 
Published: December 2024

The growing demand for vehicle electrification and sophisticated energy storage systems is driving research into lithium-ion batteries (LIBs) with high energy density. Employing inorganic materials as solid electrolytes (SEs) presents a compelling strategy to enhance the energy density and safety profile of these batteries. Nonetheless, the integration of Li metal anodes (LMAs) in all-solid-state batteries (ASSBs) still presents dendrite issues, and without specific protective layers like C-Ag, cycle stability remains a challenge. In contrast, Si anodes, which are not subject to these limitations, may offer a viable alternative. However, Si anodes in LIBs are prone to extreme volume expansion (> 300%) during charge-discharge cycles, causing fractures and loss of electrical contact. Si ASSBs can have electrodes in the form of pure Si and a composite with the SEs. Recent studies suggest that each exhibits different failure mechanisms. Specifically, in the case of pure Si, numerous vertical cracks in the electrode and delamination with SE layer have been reported. In low-operating pressure, the resistance to electronic conduction in Si anode is further exacerbated. ASSBs present significant environmental concerns related to their manufacturing and recycling processes, which frequently incorporate hazardous substances such as NMP solvent and fluorinated polymers, including PVDF and PTFE. To commercialize ASSBs, two issues must be resolved.
In our study, we designed an aqueous-process-based binder for eco-friendly strategies and utilized it for low pressure operating Si ASSBs. Additionally, the binder significantly contributes improving electrical conductivity during the delithiation process with adhesion properties, as observed by an electrical conductivity measurement cell. The NCM/Si full cell exhibited high discharge capacity at 30°C and 5 MPa with high rates. Our design demonstrates enhanced performance of ASSBs under reduced pressure conditions, addressing a critical aspect of practical applicability.
[1] H. S. Tan Darren et al., Science 2021, 373, 1494.
[2] H. Huo et al., Nat. Mater. 2024, 23, 543.
Surface Reaction of Argyrodite-Type Sulfide Solid Electrolyte in Air with a Dew Point of −20°C
Authors: Sano Hikaru , Otoyama Misae , Morino Yusuke , Ito Daisuke 
Published: December 2024

Sulfide solid electrolytes are expected to be used for practical all solid-state batteries because they combine high formability with high ionic conductivity. However, unlike oxide and organic solid electrolytes, sulfide solid electrolytes have problems such as toxic hydrogen sulfide generation and conductivity degradation due to even slight moisture. In this study, we investigated the details of the denaturation of argyrodite-type sulfide solid electrolyte (ASSE) by a small amount of water, with the aim of further increasing the water resistance of ASSE. The denaturation of ASSE in air with moisture at the dew point −20 °C, which is comparable to a typical dry room environment, was already reported; EIS and XRD revealed only the surface of ASSE degraded by moisture in the air. Surface analysis was also conducted and revealed that surface degraded components such as Li2CO3, Li2SO4 are formed on the surface.
In this study, the effects of oxygen and carbon dioxide were also examined in addition to water. Details of the denaturation was investigated using XRD, XPS, IR and Raman. This investigation revealed that the denaturant is formed only on the surface by moisture, that the denaturant is oxidized by oxygen, and that Li2CO3 is formed by carbon dioxide. More details will be discussed at the meeting site.
Synthesis Mechanisms of over-Stoichiometric Rocksalt-Type Li Superionic Conductors
Authors: Zhao Xinye , Chen Yu , Ceder Gerbrand 
Published: December 2024

Oxides materials with a face-centered cubic (fcc) anion sublattice are generally unsuitable for use as solid-state electrolytes as such structural framework typically exhibits high migration energy barrier, preventing a facile Li transport [1,2]. A recent discovery involving a class of over-stoichiometric rocksalt (ORX) compounds has shown promise for achieving fast Li conduction in oxide materials by introducing Li-Li face-sharing configurations in a spinel-like arrangement (s-phase) [3]. In general, it is challenging to create rocksalts in which the cation to anion ratio is larger than 1. As a result, the fast-conducting s-phase has been observed to be formed only in nano-sized domains that originate through a specific cooling process from a high-temperature disordered rocksalt. To further optimize the ORX-based Li superionic conductors, we conducted a systematic study combining first-principles calculations and experiments to understand the formation mechanism of the s-phase. Taking the reported ORX-Li17In9SnO24 material as a prototype compound, we explored the detailed thermodynamic landscape in the Li-In-Sn-O (LISO) space, comparing the stability of several competing phases at different synthesis temperatures. Our insights into the synthesizability of s-phase have led to large improvements in Li conductivity in ORX-LISO compounds compared to the previous report [3]. In this presentation, we will present the key thermodynamic and kinetic mechanisms governing the formation of the unusual s-phase and discuss how a combination of equilibrium and non-equilibrium routes can be applied to synthesize a general ORX compound for solid-state electrolyte application.
[1] Z. Zhang et al., Energy
Environ. Sci. 11, 1945–1976 (2018).
[2] K. J. Kim, M. Balaish, M. Wadaguchi, L. Kong and J. L. M. Rupp, Adv. Energy
Mater. 11, 2002689 (2020).
[3] Y. Chen, Z. Lun, X. Zhao et al., Nat. Mater. 23, 535–542 (2024).
Electrodeposited High-Voltage Cathodes for Next-Generation Solid-State Batteries
Authors: Shyam Badri , Joshi Prerna , Anderson Tanner , Zahiri Beniamin , Yang Heng , Cook John B. , Braun Paul V. , Busbee John 
Published: December 2024

Dense, monolithic high-voltage cathodes have direct implications for a step-change advance in the specific energy and energy density of next-generation solid-state batteries (SSBs) which offer several advantages over traditional Li-ion batteries (LIBs). Solid electrolytes possess improved chemical stability with Li metal, dimensional stability (enabling separate electrolyte optimization for low and high voltages along with the possibility of bipolar stacking), and wider thermal stability than liquid electrolytes. Consequently, SSBs can offer higher specific energy, wider operating voltage and temperature windows, and potentially improved safety at the cell level.
Xerion’s dense LiCoO2 (DirectPlateTM LCO) cathodes are fabricated via a novel, high-temperature molten salt electrodeposition process and are distinctly different from conventional slurry-cast electrodes. They combine several advantages for next-generation SSBs. They are strongly bonded to the current collector foil, highly dense (typically < 10% porosity) with no catholyte requirement, can be tailored with a dominant crystal orientation based on electrodeposition conditions, and do not contain any carbon or polymer additives known to lead to parasitic side-reactions in SSBs. Taken together, at the cell-level, the effect is a direct increase in both the specific energy (Wh/kg) due to increase in cathode active material, as well as energy density (Wh/l) due to lower porosity. The electrode architecture and cell configuration for Xerion-based SSBs closely resembles the classic layer-by-layer fabrication approach used for thin film batteries (TFBs) but possesses much larger cell capacities, enabling the use of this cathode architecture for the consumer electronics market (100 mAh to 5 Ah).
In this talk, I will showcase Xerion’s molten salt electrodeposition platform as well as the electrochemical properties of Xerion’s DirectPlateTM LiCoO2 cathodes with an emphasis on their performance in SSBs. I will discuss a) the effects of cathode crystal orientation and the electrode-electrolyte interface on cell performance, and b) the merits of using Xerion’s dense cathode architecture compared to composite cathodes containing solid electrolyte (as catholyte). I will conclude with the performance and safety implications of cathode porosity and surface roughness of Xerion’s DirectPlateTM LCO cathodes.
Low-Temperature Sintering of NASICON-Type LAGP Its Application to All-Solid-State Batteries
Authors: Yamada Hirotoshi , Yamasaki Ryoya , Onoue Yusuke , Matsumoto Kazuki 
Published: December 2024

All-solid-state batteries (ASSBs) are one of the next-generation batteries towards carbon neutral societies. While sulfide-based ASSBs are on the stage for their practical application, oxide-based ones are still under the feasibility studies, mainly because of their interfacial issues: interphases and/or contact areas that would limit the energy and the power of the ASSBs. These issues are more severe for the full-inorganic ASSBs without any organic electrolytes, although they would extend the application fields of the next-generation batteries: high voltage batteries and batteries for severer environment (vacuum, high temperature, etc.). In this study, materials and processes of NASICON-type solid electrolytes are developed to prepare the electrochemically active interfaces between the solid electrolytes and the active materials.
For the NASICON ASSBs, Li1.5Al0.5Ge1.5(PO4)3 (LAGP) was prepared by a solution method using oxalic acid as a chelate. LAGP obtained by sintering the precursor at 600°C exhibited rather high total conductivity of 2 × 10−5 S/cm, which was further increased to 1.6 × 10−4 S/cm by mild-hot-pressing at 10 MPa. The NASICON ASSBs fabricated with TiO2 anode (2.5 mg/cm2) and LiCoPO4 cathode exhibited an initial discharge capacity of 66 mAh/g (0.17 mAh/cm2).
The study demonstrated that 3V-class ASSBs worked at room temperature, although the ASSB has not been optimized yet. The performance of the NASICON-based ASSBs would be further improved by optimizing materials/processes/architecture towards novel batteries.

Figure 1
Orientation Control of Perovskite Electrolyte Using Phase Transformation from Ruddlesden-Popper Type Nanoplate Synthesized By Hydrothermal Reaction
Authors: Mimura Kenichi , Itasaka Hiroki , Hamao Naoki , Liu Zheng , Hamamoto Koichi 
Published: December 2024

Oxide type all-solid-state battery has attracted a great deal of attention its high energy density and safety. Perovskite-type (Li3x,La2/3-x)TiO3 (LLTO) has high ionic conductivity and it is one of the candidate electrolyte for an all-solid-state battery. Various efforts are underway to improve the properties. Facet-controlled nanocrystals can assemble into highly ordered nanostructures, and their orientation control and epitaxial grain growth during sintering are expected to improve their electrical properties. In this study, we focused on the orientation of LLTO ceramics. To control the orientation of electrolyte, we tried to fabricate perovskite LLTO platelet nanocrystals (nanoplates). LLTO nanoplates were synthesized by hydrothermal reaction using aqueous Ti complex as a starting material and NaOH as a mineralizer [1]. The pellet made from LLTO nanoplates is sintered at 1000 ºC which is lower sintering temperature than LLTO microparticles. However, the ionic conductivity is as low as 10-6 S/cm. STEM-EDX analysis revealed that this is due to the Na ions remaining at the Li site of the perovskite structure. We found that Ruddlesden-Popper (R-P) type layered perovskite Li2La2Ti3O10 nanoplates can be synthesized by selecting LiOH instead of NaOH as the mineralizer to prevent substitution of Li to Na ion. The R-P nanoplate is a single crystal having c-plane of R-P phase. The pellet made from R-P nanoplate has highly orientation of c-axis along to the press direction. This pellet is also able to sinter relatively low temperature at 1200 ºC with keeping orientation, but R-P phase shows extremely low ionic conductivity of 3.2x10-8 S/cm. As Li site of R-P phase is fully occupied by Li ion, Li ions are difficult to move. However, ionic conductivity of the direction of c-plane is higher than that of the c-axis direction. This result suggests that Li ion is located interlayer and Li ion is easy to move in c-plane of R-P structure. When this pellet is sintered at 1400 ºC, R-P phase has transformed to perovskite LLTO with keeping orientation. Transformation to perovskite phase is caused by vaporization of Li ion from R-P structure and it shows good conductivity of 1.1x10-4 S/cm.
Reference
[1] K. Mimura, N. Hamao, H. Itasaka, Z. Liu, K. Hamamoto, J. Sol-Gel Sci. Tech. 104, 599 (2022).
Acknowledgement: This study is based on results obtained from a project, JPNP20005, subsidized by the New Energy and Industrial Technology Development Organization (NEDO).
From Useless to Useful - Particle Engineered Li6PS5Cl for Solid-State Pouch Cells
Authors: Malmer Mika Serna , Tran Quoc-Anh , Agrawal Meenal , Ellingsen Ingeborg Sellæg , Häusler Michael , Brunner Roland , Zettl Roman , Hennige Volker , Mehraj Ud Din Mir , Rettenwander Daniel , Fadillah Laras 
Published: December 2024

Solid-state batteries have been pointed out as a promising battery technology for the future, as it offers solutions to common issues with Li-ion batteries, especially regarding safety concerns due to the flammable nature of the liquid electrolyte. Additionally, the potential volumetric and gravimetric energy densities of solid-state batteries are expected to surpass the ones of Li-ion batteries.1 Despite significant progress in developing solid-state batteries, the pathway from successful lab-scale cells to more commercially viable pouch cells remains a major bottleneck towards their commercialisation. This is especially true with the use of inorganic solid electrolytes.2,3

Recent studies have shown that the particle size ratio between the cathode material and the solid electrolyte plays a key role to achieve low tortuosity, hence, increasing power density. However, commercially available products suffer from wide particle size distributions with chunks of particles even larger than the composite cathode thickness, which introduces challenges in respect of the densification, leading to poor kinetics.
This study focuses on the optimisation of LPSCl particles and the subsequent densification of slurry-based casted LPSCl tapes and monolayer pouch cells (composed by Si anodes and NMC811 cathodes) as a function of the LPSCl particle size distribution and the pre-pressing conditions. A wide variety of characterization tools are applied, such as FIB-SEM, X-ray computed tomography, and temperature and pressure dependent impedance spectroscopy to correlate microstructure with Li-ion transport, as well as galvanostatic cycling to link them to cell performance.

References

Janek, J. & Zeier, W. G. A solid future for battery development. Nat Energy
1, (2016).

Wang, C., Kim, J. T., Wang, C. & Sun, X. Progress and Prospects of Inorganic Solid‐State Electrolyte‐Based All‐Solid‐State Pouch Cells. Advanced Materials
35, (2023).

Wang, C. et al. All-solid-state lithium batteries enabled by sulfide electrolytes: From fundamental research to practical engineering design. Energy and Environmental Science
14, (2021).
Tuning the Properties of PEO/PAN-Based Electrospun Membranes for Solid-State Li- and Na-Ion Batteries
Authors: Springl Elisabeth , Nilges Tom 
Published: December 2024

Long-term independence from fossil and nuclear energy sources is essential to achieve the 1.5-degree target of the Paris Agreement and reduce dependence on energy imports [1]. Expanding electromobility is crucial in the transport sector to reduce CO2 emissions. Lithium-ion batteries (LIBs) are the key technology for the mobility transition and storage of renewable energy from wind, water, and sun. Thermal, electrical, or mechanical mishandling of lithium-ion batteries can cause thermal runaways and battery failure. Replacing the liquid electrolyte with a solid one in a so-called all-solid-state battery system can minimize the risk of these LIBs malfunctions [2]. Solid polymer electrolytes, standing out for their mechanical flexibility and electrochemical stability, are among the most promising candidates for replacing liquid-based electrolytes in LIBs [3]. Here, we present a solid polymer electrolyte based on a polyacrylonitrile (PAN) and polyethylene oxide (PEO) blend, whose mechanical flexibility and suppressed crystallinity are ensured by the production technique electrospinning.
Adding the structure-giving polymer PAN to the ion-conducting polymer PEO leads to a free-standing membrane with enhanced thermal stability up to 100 °C, above the melting point of PEO, which is checked using scanning electron microscopy. The arising beneficial phase-separated fiber structure and its resulting properties, such as morphology and conductivity, can be tuned and optimized by the production parameters of electrospinning. If the composition of polymer to plasticizer and conducting salt is kept constant, low humidity during the electrospinning process and a short period between the production of the polymer electrolyte and its drying in vacuo, as well as an enhanced drying procedure, lower the porosity and increase the ionic conductivity by up to two orders of magnitude to 0.4 mScm-1 at 328 K. We ensured the capability of reversible lithium transport through the membrane in a symmetric Li-metal|polymer-electrolye|Li-metal cell. Furthermore, we compared our lithium-based system with a sodium system, following a beyond-lithium approach, both with the bis(trifluoromethanesulfonyl)imide-anion. All polymer membranes’ crystallinity was analyzed by X-ray diffraction, and their conductivity and activation energy were determined by impedance spectroscopy and using the Arrhenius equation. Swapping lithium with more abundant sodium leads to a decrease in conductivity of one order of magnitude. The elastic, free-standing membranes with a dense fiber structure show the great potential of electrospun solid polymer electrolytes in all-solid-state batteries.
References
[1] Paris Agreement to the United Nations Framework Convention on Climate Change, T.I.A.S. 16, 1104 (2015).
[2] Q. Wang, B. Mao, S. I. Stoliarov and J. Sun, Prog. Energy Combust. Sci.,
73, 95–131 (2019).
[3] Y. Zhao, L. Wang, Y. Zhou, Z. Liang, N. Tavajohi, B. Li and T. Li, Adv. Sci.,
8(7), 2003675 (2021).
Improvement of Grain-Boundary Resistance of Li7La3Zr2O12 By Coating with Li2CO3: A Study on Improving Electrochemical Performance of All-Solid-State Batteries
Authors: Park Jae-Wan , Shim Jae-Hyun 
Published: December 2024

In recent years, the primary concern in the electric vehicle (EV) market has been the short driving range and long charging times associated with single charges. However, the market is now facing another bottleneck due to safety issues. Lithium-ion batteries (LIBs) utilizing organic liquid electrolytes pose significant safety risks due to their low thermal stability and high fire hazard. To address this fundamental issue, there is a push to replace liquid electrolytes in current LIBs with solid-state electrolytes (SSEs). Among the materials used as electrolytes in solid-state batteries, oxide-based SSEs offer a wider potential window of 5 V or more compared to organic liquid electrolytes (<4.5 V). Their high elastic modulus and ion conductivity enable them to suppress the growth of lithium dendrites, allowing for the use of high-capacity lithium metal as the anode material. Additionally, oxide-based SSEs possess advantages such as high stability in air, high mechanical strength, and high oxidation voltage. However, they also exhibit higher interfacial resistance and lower lithium ion conductivity than sulfide-based SSEs, typically reported in the range of 10⁻³ ~ 10⁻⁴ S/cm.
This study focused on enhancing the grain-boundary resistance of Li7La3Zr2O12 (LLZO) by coating its surface with Li2CO3. LLZO pellets were coated with Li2CO3 through a solution process and then sintered to form a solid-state electrolyte. X-ray diffraction (XRD) was utilized to analyze the crystal structure of the sintered LLZO pellets, while scanning electron microscopy (SEM) was used to evaluate the density of constituent elements and the surface structure. Electrochemical impedance spectroscopy (EIS) was employed to observe changes in lithium ion conductivity due to grain-boundary properties. The results demonstrated that Li2CO3-coated LLZO pellets exhibited lower grain-boundary resistance and higher lithium ion conductivity compared to uncoated LLZO pellets. Finally, all-solid-state batteries (ASSBs) were fabricated using the sintered Li2CO3-coated LLZO pellets, and their electrochemical properties were evaluated to predict improvements in battery performance due to grain-boundary properties. The findings of this study suggest that coating LLZO with Li2CO3 can significantly enhance the grain-boundary resistance and performance of all-solid-state batteries.