bluuebunny/crossref_metadata_2025_split huggingface dataset:
Evaluating Kinetics of Composite Cathodes of All-Solid-State Batteries
Authors: Minnmann Philip , Bielefeld Anja , Ruess Raffael , Burkhardt Simon , Dreyer Sören L. , Trevisanello Enrico , Adelhelm Philipp , Richter Felix H. , Strauss Florian , Brezesinski Torsten , Ehrenberg Helmut , Janek Jürgen 
Published: November 2022

ASSBs (all-solid-state batteries) are promoted as an energy dense and safe alternative to current Li-ion batteries (LIBs) and attract great interest from academia and industry. In contrast to LIBs, which employ a liquid organic electrolyte, they utilize a solid electrolyte. This substitution promises to eliminate the flammability of the battery and to simplify the cell design.
While recent research efforts have concentrated on miniaturizing and eventually even removing the anode host material in batteries, the relative portion of the cathode needs to be maximized, as cathodes are the only component that can increase energy density by increasing its fraction. In a simplified view, the cathode kinetics are determined by the cathode microstructure, the volume fractions of the constituents and the properties of electrolyte and cathode active material (CAM).
Liquid electrolytes can easily penetrate porous composite cathodes, but rigid SEs can not do the same, resulting in residual porosity in the cathode. This porosity can lower active interface area between CAM and SE, and increase tortuosity of ionic and electronic charge transport pathways. Sufficient ionic and electronic transport pathways in composite cathode structures are, however, essential because cathode active material particles that are either electronically or ionically isolated cannot contribute to the charging or discharging process.
We analyse the requirements for SSB cathodes and determine charge transport bottlenecks by impedance spectroscopy of a reference system consisting of a thiophosphate based solid electrolyte and a nickel rich layered CAM. Different cathode microstructures are analysed and their charge transport properties are quantified as partial conductivities. From the obtained partial conductivities, we calculated tortuosity factors and correlated them to cell performance with complementary cycling data of all-solid-state batteries in order to determine charge transport bottlenecks. We find, that ionic charge transport and consequently cathode kinetics are highly dependent on the SE particle size distribution
In addition, we analyse the requirements for CAMs for SSBs and develop design principles for different CAM types that aim to further increase cathode performance.
Enabling Si-Dominant Anodes with Focus on Binder
Authors: Kloker Gabriele , Vrankovic Dragoljub , Frey Martin , Anjass Montaha 
Published: November 2022

Since current chemistries in lithium ion batteries (LIBs) including graphite anode reached their energy density limits, a promising candidate on anode side is the abundantly available silicon with its enormous capacity, but showing several failure mechanisms based on its extensive swelling (>300%). This leads to excessive solid electrolyte interphase (SEI) formation and electrode delamination during cycling, which can be reduced by the modification of the active material itself, e.g. carbon-embedded silicon (Si/C), but still these materials show the same failure mechanisms in a less pronounced manner. Regarding the costs and availability, the next generation anode is desired to be based on metallurgical silicon, where one promising path to enable Si-dominant anodes is the design of advanced binder systems to maintain a stable network around the active material during cycling. However, in most studies new binders are mainly tested in electrodes with low active material content and low loadings while lacking of full cell data, which makes it impossible to estimate the capability and influence of the binder to mitigate the failure mechanisms in full cell operation.
In this work, several modifications of the binder are combined with commercial Si/C material and bare micro-sized silicon with 100% silicon as active material. The electrodes are tested in half coin cells and small full pouch cells with ~60 mAh capacity. To examine the performance in detail and understand the underlying failure mechanisms, post-mortem analysis was conducted.
The already commonly used polyacrylic acid (PAA) can be further adapted to the respective anode active material (AAM) via partial neutralization with e.g. LiOH to tune the interaction with the AAM and reduce the first cycle losses due to the reaction of the carboxylic groups with lithium. Nevertheless, the influence of PAA/LiPAA on the failure mechanisms and maintenance of the electrode, especially on full cell basis, are not yet fully understood. In this work, the effect of the partial neutralization on the full cell performance of a NMC811-Si/C cell is shown with the anode consisting of 91.5% Si/C material, 8% binder and 0.5% conductive additive (single-wall carbon nanotubes SWCNTs). The full cells show 3.5% higher FCE with 70% neutralized LiPAA in comparison to acidic PAA in the anode, while maintaining the same cycle life.
Understanding the Role of Al(TFSI)3 Additive at the Solid Electrolyte Interphase (SEI) for Improved Lithium-Ion Batteries with Silicon Anodes Via Solid-State NMR
Authors: Liu Haoyu , Park Sohyun , Dogan Fulya , Vaughey John T. , Key Baris 
Published: November 2022

Introducing multivalent cation salts (e.g., Ca2+, Mg2+, and Al3+) has been proven to improve electrochemical performance such as capacity, cyclability, Coulombic efficiency, and calendar life of Si anode by the in situ formation of inert Li-Metal-Si ternary phases.1–3 Among these ions Al3+ is of great interest with large positive charge and small radius, providing potential new chemistry.
In this work, Al(TFSI)3 was synthesized and purified and 0.1 M was added as a second salt into the Gen2 (1.2 M LiPF6 in 30 wt % EC + 70 wt % EMC) electrolyte with 3 wt % FEC. Then NMC532/commercially relevant Si anode full-cells were assembled, stabilized with three formation cycles at a C/10 rate and divided into two groups, one with extended cycling and the other held at 4.1 V for one month to investigate calendar life. Meanwhile, non-Al(TFSI)3 cells were also prepared and tested from the same batch as baselines for the study. Multi-nuclei solid-state MAS-NMR including 1H, 7Li, 13C, 19F, 27Al, and 29Si of the Si powder collected from those samples after electrochemical testing at both 300 MHz and 500 MHz showed detailed information of different species formed. It was confirmed that Al additive stabilized Si species at the SEI and suppressed side reactions with the electrolyte by forming Li-Al-Si Zintl phase. Specifically, cross-polarization (CP) experiments such as 13C{1H} and 29Si{1H} allowed the selective investigation and detection of the species in close proximity to protons at the SEI. This additive strategy can be combined with the novel electrolyte, binder, and Si anode material to pave new avenues towards the commercialization of Si-based lithium-ion batteries.
Acknowledgement
This work was part of the Silicon Consortium Program (SCP) and was done at Argonne supported by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy under grant DE-AC02-06CH11357.
References

B. Han et al., ACS Appl. Mater. Interfaces, 11, 29780–29790 (2019).

X. Li et al., Chem. Mater., 33, 4960–4970 (2021).

Y. Zhang et al., Advanced Energy Materials, 11, 2101820 (2021).
Investigation of High-Performance All-Solid-State Lithium-Ion Batteries Based on High Ionic Conductivity Li7La3Zr2O12 Solid Electrolyte.
Authors: Hong Da-Been , Shim Jae-Hyun , Kim Yoo-Shin 
Published: November 2022

As interest in battery safety is increasing in the battery industry, interest in all-solid-state lithium-ion batteries and their most important material, solid electrolytes, is increasing. Among all solid electrolytes, garnet-type Li7La3Zr2O12 (LLZO) has proven to be one of the most promising electrolytes due to its high Li ion conductivity, wide potential window and electrochemical stability to metallic lithium anodes. In particular, cubic garnet-type LLZO solid electrolytes are attracting a lot of attention in the development of all-solid-state batteries with high safety, high energy density and long cycles.
In this study, the optimal composition and sintering temperature were derived by adding Al, W, and Nb to synthesize a garnet-structured LLZO-based solid electrolyte powder and to form a stable cubic phase. In particular, Al, W, and Nb were doped to improve the ionic conductivity of the prepared LLZO-based solid electrolyte, and the ionic conductivity of the LLZO sintered body according to the doping composition and sintering process conditions was evaluated.
Comparative Evaluation of Polycrystalline and Monocrystalline LiNi0.96Mn0.02Co0.02O2 Cathodes
Authors: Kim Seokhun , Nagaraj Aditya , Min Sangkee , Shin Youngho 
Published: November 2022

Lithium-ion batteries (LIBs) require Ni-rich cathode material with a high capacity to meet the growing demand for powering electric vehicles and other energy-dense devices. However, significant challenges remain to improve capacity retention during cycling and thermal-abuse tolerance of this material.
Alternative to the traditional polycrystalline Ni-rich cathode material, we report here a monocrystalline Ni-rich cathode material prepared via a hydrothermal process. Ni-rich composition (LiNi0.96Mn0.02Co0.02O2) was selected for comparative evaluation of polycrystalline cathode material via a co-precipitation process and monocrystalline cathode material via a hydrothermal process. A detailed description of the advanced CSTR co-precipitation process and the developed hydrothermal process applied to this material synthesis is presented.
The excellent physical and electrochemical properties of the monocrystalline cathode material prepared by the developed hydrothermal process will be reported through analysis of coin half-cell, SEM, EDS, ICP-MS, nanoindentation, and other advanced characterization techniques. This work underlines the developed hydrothermal process in producing monocrystalline cathode material which is a rapid, robust, and scalable process with economic feasibility.
Cell-to-Cell Variation in Thermal Runaway Behavior
Authors: Zhang Liwen , Liu Lu , Zhao Peng 
Published: November 2022

As one of the most promising energy storage mediums, Lithium-ion batteries (LIBs) have attracted extensive research interest. A major challenge associated with LIB application is thermal runaway, which can be triggered during overheating, overcharging, collision, and other abused conditions, leading to a direct threat to lives and properties. Here, we select Li-ion batteries with lithium cobalt oxide cathode and graphite anode (18650, Samsung), which are relatively simple and extensively investigated, to revisit thermal runaway. The experiment is conducted using an accelerating rate calorimeter (EV+ ARC, Thermal Hazard Technology) following the standard heat-wait-seek strategy, and is repeated for 9 similar new cells with 100% state of charge (SOC). Key features such as onset temperature of self-heating, the onset temperature of thermal runaway, maximum heat release rate, thermal runaway
delay time, and maximum temperature are measured experimentally. Although the cells are all brand new and have been initiated similarly, obvious cell-to-cell variability has been observed during thermal runaway. Major differences exhibit in the measured exothermic onset temperature, delay time, and mass losses; however, each cell nevertheless shows highly consistent activation energy processed from the heat release rate. Additionally, thermal runaway models are established in COMSOL to simulate the experimental conditions, with and without the effect of reactant consumption during the heating stage. It is shown that the widely used four-step thermal runway model cannot quantitatively capture the activation energy from the heat release rate. To improve the kinetic modeling and accommodate the cell-to-cell variability, statistical analysis is conducted to process the experimental results. Mean
and standard deviation of the frequency factor and activation energy has been acquired to determine the lower and upper bound of the kinetic modeling using a one-step global chemistry. The measured and simulated thermal runaway delay time has reached a reasonable agreement, with the uncertainty of the kinetic model considered. The identified cell-to-cell variability is most likely due to manufacturing inconsistencies, which should not only be considered for cell-level safety evaluation but also the design and evaluation of battery modules and packs.
(Digital Presentation) Particle Size and Transition-Metal Chemistry Determine the Impact of Li-Excess on Disordered Rock-Salt Li-Ion Cathode Materials
Authors: Lee Jinhyuk 
Published: November 2022

The development of Co-free Li-excess disordered rock-salt (DRX) cathodes (e.g., Li1.2Mn0.4Ti0.4O2) for Li-ion batteries and interpretation through the percolation theory of Li diffusion have directed researchers to consider “Li-excess” (x > 1.1 in Li
x
TM
2-x
O
2
; TM = transition metal) as being essential to achieving high performance [1]. While the percolation theory provided an important insight into Li-transport in DRX materials, it leaves a critical impression that those DRXs without Li-excess will not deliver high capacity and thus are unsuitable as Li-ion cathode materials. However, the majority of DRX materials are made into pulverized nanoparticles whose small particle sizes (diameter < 150 nm) should render Li transport easy to achieve even with slow intrinsic Li diffusivity, making us question if Li-excess is necessary for designing DRX cathodes [2]. Moreover, the introduction of Li-excess requires a high degree of oxygen redox (along with TM-redox) in the materials to store electrons during cycling, leading to various O-redox-related side reactions (e.g., O-loss) that trigger fast capacity/voltage loss.
In this presentation, we show that Li-excess is not necessary for some DRX-cathodes demonstrated by Li1.05Mn0.90Nb0.05O2 (M90) and Li1.20Mn0.60Nb0.20O2 (M60), which both deliver high capacity (>250 mAh/g) regardless of their Li-excess level [3]. By contextualizing this finding within the broader space of DRX materials and confirming with DFT calculations, we reveal that the percolation effect is not crucial at the nanoparticle scale, which most DRX materials developed so far have assumed by having the pulverized nanoparticle morphology [2]. Instead, Li-excess is required to decrease the charging voltage of certain DRX cathodes, which otherwise would experience difficulties in charging due to their very high TM-redox potential. Our findings show the double roles of Li-excess – modifying the cathode voltage and improving Li diffusion – that must be simultaneously considered to understand the necessity of Li-excess for high-capacity DRX cathodes.
[1] J. Lee & G. Ceder et al., Science
343, 519-522 (2014)
[2] H. Li & J. Lee et al., Joule
6, 53-91 (2022)
[3] J. Lee & J. Li et al., Adv. Energy Mater., 2100204 (2021)
Preparation and Physicochemical Properties of Nanomaterial/Fullerene Composites
Authors: Imahori Hiroshi 
Published: November 2022

Bismuthene, an exfoliated two-dimensional material obtained from bulk bismuth, has drawn significant attention because of its unique electronic properties. Few-layered bismuthene (FLBi) with an average thickness of 1.0 nm was synthesized by the ball mill and sonication method. The FLBi ﬁlm was fabricated onto a semiconducting SnO2 electrode by electrophoretic deposition (SnO2/FLBi). In the ﬂash-photolysis time-resolved microwave conductivity measurement, the SnO2/FLBi ﬁlm showed a rise of conductivity upon photoexcitation, supporting the occurrence of the electron injection from the photoexcited FLBi to the conduction band of SnO2. The SnO2/FLBi on a transparent ﬂuorine-doped tin oxide (FTO) electrode was used for photoelectrochemical devices. Photocurrents produced by the FTO/SnO2/FLBi electrode were larger than those produced by the FTO/SnO2 and FTO/FLBi electrodes because of the eﬃcient electron injection. Moreover, FLBi was noncovalently functionalized with fullerene C60 in a mixed solvent of toluene and acetonitrile. Upon photoexcitation, the composite of FLBi and C60 exclusively led to the occurrence of photoinduced energy transfer from C60 to FLBi without generating the charge-separated state. These results give fundamental insights into the feasibility toward the construction of FLBi-based optoelectronic devices.
Supramolecular composites consisting of fullerene C60 and carbon nanodiamond (ND) were prepared through spontaneous complexation of C60 aggregates onto the surface of ND aggregates in N-methylpyrrolidone. The resultant C60-ND composite was fabricated onto a nanostructured SnO2 electrode by an electrophoretic deposition method. Formation of the C60-ND composite was supported by dynamic light scattering and field-emission scanning electron microscopy. The C60-ND composite on the SnO2 electrode revealed high incident photon-to-current efficiencies in the visible region in comparison with the single component system of C60 or ND. The enhanced photocurrent generation of the C60-ND composite may originate from the photoinduced charge separation at the interface between C60 and ND. These results will give important insight into the design of all-nanocarbon optoelectronic devices.
[1] T. Umeyama, Y. Okawada, T. Ohara, and H. Imahori, Chem. Asian J., 14, 4042-4047 (2019).
[2] T. Umeyama, H. Xu, T. Ohara, Y. Tsutsui, S. Seki, H. Imahori, J. Phys. Chem. C, 125, 13954-13962 (2021).
Coal-Based Nanoporous Carbon Electrode for High-Performance Supercapacitor: Surface and Diffusion Charge Kinetics in Aqueous and Non-Aqueous Electrolytes
Authors: Abdulsalam Jibril , Bada Samson 
Published: November 2022

South Africa generates around 60 million tonnes of coal discards each year, with over 1.2 billion tonnes landfilled in discard dumps and slurry ponds. The huge quantity of coal discards generated within the past decades, which is a significant liability to the mining industry and the environment, presents an opportunity to reuse this resource. This study investigated the potential of nanoporous carbon material from coal discard via KOH activation for use as electrode material in supercapacitors. Hierarchical morphology is seen via scanning electron microscopy (SEM). Raman spectroscopy reveals structural defects, X-ray Diffraction spectroscopy (XRD) confirms the material's amorphous nature, and N2 at 77k adsorption reveals a carbon material with high porosity and a surface area of 1424 m2/g.
Electrochemical analysis reveals that the charge storage mechanism of the material is surface-controlled (non-faradaic) in the non-aqueous (TEABF4/ACN) electrolyte and diffusion-controlled (faradaic) mechanism in the aqueous (Na2SO4) electrolyte. The material has a higher specific capacitance (162 F/g) and cycling stability of 87.1% capacitance retention after 5000 cycles in Na2SO4. The material exhibits a better rate capability in TEABF4/ACN with 92.3% capacitance retention. A symmetrical two-electrode device using Swagelok T-cell assembly achieves energy densities of 15.5 and 10.4 Wh/kg in Na2SO4 and TEABF4/ACN, respectively, and a power density of 100 W/kg in both electrolytes. The variation in the capacitive performance of the material in both electrolytes is due to differences in electrolyte ion size, ionic conductivity, and pore structure. This study not only establishes a link between the structure of coal-based nanoporous carbon and its electrochemical performance in both electrolytes but also demonstrates the potential of coal-based functional materials for sustainable energy storage.
Competition and Productivity: Evidence from Peruvian Municipalities
Authors: Schiffbauer Marc , Sampi James , Coronado Javier 
Published: November 2022

Abstract
This paper uses new data on the removal of local, sector-specific barriers to firm entry across 1,800 municipalities in Peru to estimate the impact on firm productivity and markups. New legislation in 2013 strengthened the national competition authority's mandate to enforce the elimination of local entry barriers, providing a quasi-experimental setting to identify the impact of competition on productivity within the controlled institutional environment of a single country. We find that the elimination of local entry barriers boosted productivity, pointing to the critical role of subnational market entry barriers in explaining countries’ laggard productivity performances despite liberalized national regulatory environments.
Communicating through Defaults
Authors: Altmann Steffen , Falk Armin , Grunewald Andreas 
Published: November 2022

Abstract
We report the results of two laboratory experiments and a representative survey that investigate how default effects are shaped by information asymmetries and strategic incentives. We document that defaults are more informative when the interests of default setters and decision makers are more closely aligned. Decision makers’ propensity to accept defaults depends, both, on the alignment of interests and the quality of their information. In a second experiment, we demonstrate that decision makers are more likely to follow defaults than to accept (equally informative) advice. Complementary evidence from a representative survey underlines that consumers commonly perceive defaults as being set strategically.
Who Opts In? Composition Effects and Disappointment from Participation Payments
Authors: Ambuehl Sandro , Ockenfels Axel , Stewart Colin 
Published: November 2022

Abstract
Participation payments are used in many transactions about which people know little but can learn more: incentives for medical trial participation, signing bonuses for job applicants, or price rebates on consumer durables. Who opts into the transaction when given such incentives? We theoretically and experimentally identify a composition effect whereby incentives disproportionately increase participation among those for whom learning is harder. Moreover, these individuals use less information to decide whether to participate, which makes disappointment more likely. The learning-based composition effect is stronger in settings in which information acquisition is more difficult.
Community Norms and Lexical Frequency Shape U.S. Bilingual Children’s Subject Pronoun Expression
Authors: Lease Sarah , Shin Naomi L. , Bird-Brown Emily 
Published: November 2022

Abstract
This study explores variable Spanish subject pronoun expression (e.g., yo veo ~ veo) in Spanish-English speaking children in different regions of the United States (U.S.): Los Angeles (LA), California, and the Tri-Cities area of the state of Washington. We also compare the U.S. children to monolingual Spanish-speaking children in Mexico. Binary logistic regression analyses of 2,064 verb tokens produced by nine U.S. children and nine children in Mexico, ages 5;11 to 7 years old, show that the children are sensitive to linguistic factors that typically influence children’s Spanish subject pronoun expression in their respective communities. In addition, we find that the LA children’s subject pronoun expression is predicted by lexical frequency. A subsequent analysis of the LA children’s frequent verbs uncovers two phrases with high degrees of prefabrication, yo creo and yo no sé, which, we argue, obscure the LA children’s sensitivity to Reference, all while acting as central exemplars of a [1sg+cognitive verb] construction.