bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Material, Fabrication and Cell Design for High Loading Li-S Batteries Towards Commercialization
Authors: Dai Fang , Xiao Qiangfeng , Yang Li , Cai Mei 
Published: February 2020

Development of novel energy storage systems with improved efficiency and reduced cost is highly desired due to the emerging storage applications, such as grid storage system. Lithium-sulfur battery (Li-S) has been recognized as one promising system beyond conventional Li-ion system due to its high gravimetric energy density and low material cost, which is superior to most of current Li-ion batteries.
Unfortunately, the further commercialization was prohibited by some major issues of Li-S system, such as shuttling effect, which are still not fully surpassed after years’ development. In addition, conflict also exists between the overall electrochemical performance and active material loading. Other issues such as electrolyte amount are also critical. Both chemistry and engineering research and development are necessary to address all those issues that delay the large-scale industrial manufacturing and commercialization of the Li-S batteries.
In order to eventually push for further industrial manufacturing and commercialization, we have spent years working on the Li-S chemistry for balanced solution. Here we’d like to share some results from our works on the Li-S system. A well-engineered carbon framework will be introduced and discussed for high sulfur loading electrodes fabrication. Corresponding critical parameters, as well as the performance evaluation of the obtained high loading electrode will be also discussed. The high loading of S on both material (> 75 wt%) and electrode level (> 70 wt %, > 3 mAh/cm2) enables a much improved electrochemical performance of the large size pouch format Li-S cell. A protected Li anode also helps improving Coulombic Efficiency and preventing shuttling effect. In addition, influence of polymer binder and electrolyte on the optimized electrodes will be discussed. Besides the cell performance, we’ll also share the principle on material screening, cell fabrication and cell design.
(Invited) Sulfide-Based Solid Electrolytes for Solid State Batteries
Authors: Liang Chengdu 
Published: February 2020

Sulfide
-Based Solid Electrolytes for Solid
State Batteries

Chengdu Liang , Yongsheng Guo, Chengyong Liu
Research Institute,
Ningde Contemporary Amperex Technology Limited，
Fujian Province 352100, China
The energy density of lithium ion batteries is now approaching the theoretical limit. Therefore, the development of next-generation batteries is of great technical interest nowadays. Solid state lithium batteries have attracted considerable attention because the replacement of an organic liquid electrolyte with a safer and more reliable inorganic solid electrolyte simplifies the battery design and improves safety and durability of the battery [1].
A crucial material to develop solid state batteries is a solid electrolyte with high Li+ ion conductivity at room temperature. Among different kinds of solid electrolytes, inorganic sulfide-based solid electrolytes are one of the most promising candidates for solid state lithium batteries due to the high ionic conductivity, wide electrochemical window and ease of forming framework structures [2-3]. However, there are still many challenges for the commercialization of solid state lithium batteries with sulfide-based electrolyte [4-5], for instance, the electrolyte/electrodes interface and air stability of sulfide-based electrolytes need to be further improved, and advanced manufacturing technologies are required as well.
In this presentation, several strategies to enhance ionic conductivity of sulfide-based solid electrolytes are deliberated; an ionic conductivity as high as 3.0 mS/cm has been achieved. We will then summarize the research progresses of solid state lithium batteries with sulfide-based electrolytes based on our work. Future research trends and perspectives for facilitating further improvement on the performance of sulfide-based solid state batteries will also be discussed.

Reference

[1] CW Sun, Nano Energy 33 (2017) 363.
[2] ZC Liu, CD Liang, J. Am. Chem. Soc., 135(3) (2013) 975.
[3] D. Liu, Materials Science and Engineering B 213(2016)169.
[4] A. Sakuda, Solid State Ionics 285 (2016) 112.
[5] J. C. Bachman, Chem. Rev. 2016, 116, 140.

*Corresponding author.

Email: LiangCD@Catlbattery.com.
Formate Fuel Production From the Electroreduction of CO2 on Nanostructured SnOx Coated on Gas Diffusion Electrode
Authors: Zhang Qi , Li Yanan , Hou Xiao fan , Jung Joey , Qiao Jinli 
Published: February 2020

Due to the extensive use of non-renewable fossil fuels, the crisis in energy is growing, and the gas CO2, which is a product of the burning of hydrocarbons, is contributing to global warming and to acidification of the oceans. Therefore, the issue about carbon dioxide (CO2) capure, sorage and utilization has inspired intensive interests. [2,3] In the various methods of CO2 utilization and recycling, electrochemical reduction of CO2 to transform to useful chemicals or fuels is a potentially efficient way. However, in the procesure of CO2 electroreduction, there is a challenge of the slow kinetic of CO2 electroreduction. [4,5] Overcoming the problems of CO2 reduction under mild conditions would enable solve the energy crisis and the global warming.
In the past few decades, researchers found that many metal oxide nanopowders could be the perfect catalysts in the CO2 electroreduction for their controllable various morphologies.[1] In this work, we report the synthesis of SnOx nanocatalysts loaded on the multi-walled carbon nanotubes (MWCNTs), which electrochemical catalyzed CO2 to formate, HCOOH, on the room-temperature with an electrochemical cell having a catalytic SnOx cathode. We controlled different special morphologies by one-step hydrothermal method from SnCl2 precursors. The highest faradaic and energy efficiencies of 65% and 28% were obtained at −1.40 V vs. SCE with particles that were obtained by KOH reduction from a SnCl2 precursor and showed excellent stability in prolonged electrolysis.
References
[1]C. Zhao, J.L. Wang, J.B. Goodenough Chemical Communication, 52,12175(2016).
[2] R. Williams, R.S. Crandall, A. Bloom, Applied Physics Letters, 33,381 (1978).
[3] A.S. Agarwal, Y. Zhai, D. Hill, N. Sridhar, ChemSusChem, 4,1301 (2011).
[4] M. Gattrell, N. Gupta, A. Co, Energy Conversion and Management, 48,1255 (2007).
[5] N. S. Spinner, J. A. Vega and W. E. Mustain, Catalysis Science & Technology, 2,19(2012).
(Invited) Metal-Supported Solid Oxide Fuel Cells with High Power Density
Authors: Tucker Michael C 
Published: February 2020

Metal-supported solid oxide fuel cells (MS-SOFC) display a number of advantages over conventional all-ceramic SOFCs, including low-cost structural materials (e.g. stainless steel), mechanical ruggedness, excellent tolerance to redox cycling, and extremely fast start-up capability. Challenges for MS-SOFCs include: oxidation of the metal support, especially at 800°C and above; the possibility of the stainless steel exacerbating Cr poisoning of the cathode catalyst; fabrication and materials set restrictions arising from the requirement that stainless steel be sintered in reducing atmosphere; and, only moderate performance and lifetime have been demonstrated to date.
These advantages and challenges suggest that MS-SOFCs may be well-suited for portable, ruggedized, fast-start, intermittent-fuel, or other unique and innovative applications. Nissan has developed the world’s first light-duty vehicle with a conventional SOFC stack for traction power, fueled by bio-ethanol reformate. Because of the desire for rapid-start capability, developing MS-SOFC cell and stack technology for this vehicular application is a priority. The small volume allowance for the SOFC stack on-board a small vehicle furthermore demands high power density from the MS-SOFC. In this work, we seek to maximize MS-SOFC power density.
This work is an extension of our previous efforts focusing on co-sintered, YSZ-based MS-SOFCs with porous metal supports on both anode and cathode sides, with catalysts deposited into both electrodes via infiltration. These features provide for a mechanically rugged cell that can be processed with low-cost scalable techniques, and high surface-area catalysts that provide excellent performance by avoiding interdiffusion or coarsening during cell sintering. To support the vehicular traction application, in this work we further develop catalyst infiltration processing for MS-SOFCs to dramatically increase power density. The goal is to increase cell performance by improving infiltration of conventional catalyst compositions (lanthanum strontium manganite (LSM), Ni, doped ceria) into electrode backbones of conventional yttria-stabilized zirconia (YSZ). Various aspects of the infiltration procedure were optimized, including: precursor composition and dilution with water; catalyst loading; and, crystallization temperature. Figure 1 shows the resulting high performance. Peak power of 1.1 and 1.9 W/cm2 is achieved at 700°C and 800°C, respectively, and the 800°C performance is the highest reported for stainless steel-supported MS-SOFCs to date. Figure 2 shows initial stability of the MS-SOFC. Testing is ongoing, and operation for >1000 h and post-mortem analysis will also be presented. Demonstration of redox cycling and rapid-start tolerance will be discussed.
Acknowledgements
Funding for this work was provided by Nissan Motor Co., Ltd. through Strategic Partnership Projects Agreement FP00004436. This work was funded in part by the U.S. Department of Energy under contract no. DE-AC02-05CH11231.

Figure 1
(High Temperature Materials Division J. Bruce Wagner, Jr. Award Address) Disorder and Transport in Pyrochlore Oxides
Authors: Kreller Cortney R. , Valdez James Anthony , Holesinger Terry , Wang Yongqiang , Uberuaga Blas , Tang Ming 
Published: February 2020

Numerous avenues are currently being explored to enhance ionic conductivity in solid oxide materials, including dopants, nano-structuring, and strain engineering. Their effect on material properties, specifically mobile carrier concentration and mobility, needs to be understood and ultimately exploited to develop advanced functional materials. Crystalline disorder in complex oxides can have a pronounced effect on mass transport, but the role of disorder within the complex landscape of material and microstructural defects is not uniquely understood.
In this work, we seek to explore the relationship between intrinsic disorder and oxygen ion conduction. We are using radiation damage, not to study the fundamental damage response, but rather as a tool to induce and control the extent of disorder in oxide materials. The pyrochlore compounds, A2B2O7, consist of both ordered cation and anion sublattices. The introduction of anti-site disorder, where the A and B cations switch positions, is accompanied by increasing disorder on the anion sublattice, and complete randomization of the A- and B-site cations results in the defect fluorite phase. Several workers have previously studied the influence of structural disorder on ionic conductivity by introducing disorder through dopants, temperature, or pressure. It has previously been suggested that disorder increases carrier concentration by freeing the fixed vacancy from the ordered anion sublattice of the pyrochlore structure, while order, on the other hand, may serve to increase mobility by providing a preferential ion transport pathway. This is in contrast to recent modeling results that indicate that both carrier concentration and mobility increase with disorder. In the present work we have chosen to investigate the end members of the Gd2(ZrxTi1-x)2O7 system in order to gain a better understanding of the interplay between disorder and ionic transport. Gd2Zr2O7 is an intrinsic fast-ion conductor that is also very radiation tolerant, whereas Gd2Ti2O7 is a poor ionic conductor that is much more susceptible to amorphization under irradiation than the zirconates. Electrochemical Impedance Spectroscopy is used to measure the conductivity of materials with varying degrees of irradiation-induced structural disorder in order to better understand how the underlying transport mechanisms depend on crystalline disorder.

Acknowledgements

This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division.
Electric Field-Assisted Pressureless Sintering of Ceramic Protonic Conductors
Authors: Muccillo R. , Esposito Vincenzo , de Florio Daniel Zanetti , Muccillo E. N.S. 
Published: February 2020

Gadolinium, yttrium and samarium-doped barium cerate (BCGd, BCY and BCSm, respectively) polycrystalline green pellets were submitted to electric field-assisted pressureless sintering experiments isothermally in the temperature range 800-1200oC under 100-200 V cm-1 electric fields, limiting to 1-5 A the electric current pulse amplitude. The sintering experiments were carried out in ambient atmosphere with the pellets positioned inside a vertical dilatometer furnace with Pt-Ir electrodes connected either to a power supply for applying the electric field or to an impedance analyzer for collecting [-Z''(ω) x Z'(ω)] data to evaluate the bulk and the grain boundary contributions to the electrical resistivity. Near full density was achieved in the sintered samples. The combined results of dilatometry and impedance spectroscopy measurements before and after flash sintering show substantial improvement of the electrical conductivity of flash sintered specimens. Joule heating is assumed to be the primary effect of the electric current pulse through the specimens. Improved grain-to-grain contact and the removal of depleted chemical species due to Joule heating at the space charge region are proposed, respectively, as the reasons for the almost total disappearance of the grain boundary component in the impedance diagrams and the improvement of the bulk electrical conductivity.
Intermediate Temperature Synthesis and SOFC Anode Application of Cerium Silicate-Based Oxy-Apatites
Authors: Lee Sunghwan , Ramanathan Shriram 
Published: February 2020

Oxy-apatites based on rare earth silicates (A10x(SiO4)6O2±x, A=rare earth cation) are of increasing interest for solid oxide fuel cell (SOFC) application due to the high conductivity at moderate temperatures (<1000 K). Here, we report on the intermediate-temperature synthesis (973 K) of thin film oxy-apatites and high total conductivity of the cerium silicate-based apatites at temperatures <750 K: the Ce4.67(SiO4)3O-based apatites (~80 nm-thick) were synthesized at 973 K at very low oxygen partial pressure (p(O2)<10-17atm) and the incorporation of ZnO into the cerium silicate system leads to the high total conductivity of ~0.05-0.2 S/cm. The formation of oxy-apatites was identified by in-situ conductivity measurements as a function of p(O2), x-ray diffraction analysis and x-ray photoelectron spectroscopy. In particular, the in-situ conductivity measurements confirm that the dominant conduction mechanisms of this class of materials are mainly dependent on oxygen interstitials.
Since these materials are prepared at low p(O2) and are stable in reducing atmospheres, Ce4.67(SiO4)3O-based thin film apatites exhibiting high conductivity are of relevance as anodes for intermediate temperature thin film SOFC application. In order to evaluate the performance of the apatite anode in SOFC devices, thin film apatites were grown on Sc-stabilized ZrO2/LSCF electrolyte/cathode substrates. Bilayer anode of apatite/Pt and Ni-apatite composite anode were also utilized in the identical electrolyte/cathode system and the performance were compared. The noteworthy SOFC performance (e.g., peak power density of ~100 mW/cm2 at 748 K) and superior stability were observed in Ni-apatite SOFCs due to higher catalytic activity and low contact resistance at the electrolyte/anode interface compared to those with a single layer apatite anode and bilayers of apatite/Pt anode. The present study demonstrating intermediate temperature synthesis of Ce4.67(SiO4)3O-based oxy-apatites and their high conductivity may significantly contribute to the field of intermediate temperature thin film SOFC application.

Figure 1
Concentrated Gradient Cathode Materials with LiNi0.9Mn0.05Co0.05O2 Core and LiNi0.33Mn0.33Co0.33O2 Surface Composition
Authors: Shin Youngho , Kahvecioglu Feridun Ozgenur , Krumdick Gregory 
Published: February 2020

Layered nickel-rich cathode material, LiNi0.9Co0.05Mn0.05O2, exhibits high specific capacity of approximately 220 mAh/g-oxide and shows attracted significant interest for use in plug-in hybrid electric vehicles owing to its high capacity and low cost. However, significant challenges remain to improve capacity retention during cycling and thermal-abuse tolerance of this material.
To improve the electrochemical performance and stability of this kind nickel-rich LiNixMnyCozO2 (NMC, x ≥ 0.6, x+y+z=1) cathode material for the usage in practical batteries, concentrated gradient cathode materials have been investigated. This family of materials shows the gradual decrease of nickel concentration and increase of manganese concentration from the center towards the outer layer of the particle [1-2].
Even though concentrated gradient cathode material is one of promising approaches to mitigate the capacity fade during cycling and thermal runaway of layered nickel-rich cathode materials, its working mechanism has not been fully understood yet. In this study, we explore two types of concentrated gradient cathode materials, core-shell and core-gradient, with nickel-rich LiNi0.9Mn0.05Co0.05O2 core and LiNi0.33Mn0.33Co0.33O2 surface composition which have LiNi0.8Mn0.1Co0.1O2 as overall composition. The precursors were synthesized using hydroxide co-precipitation method using a 20L batch reactor and then dried, mixed with lithium source and calcined. We report the characterized physical properties of the prepared core-shell and core-gradient materials. The detailed electrochemical performance comparison of the prepared materials with commercial NMC811 and NMC333 will be discussed.
Acknowledgement
Funding for this work from the Office of Vehicle Technologies of the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, is gratefully acknowledged. The submitted abstract 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.
References

Y.-K. Sun, S.-T. Myung, M.H. Kim, J. Prakash and K. Amine, J. Am. Chem. Soc. 127(38), 13411 (2005).

U.-H. Kim, E.-J. Lee, C. S. Yoon, S.-T. Myung and Y.-K. Sun, Adv. Energy Mater. 6, 1601417 (2016)
Evolution of the Cathode-Electrolyte Interface of Li1
-
xNi0.8Co0.15Al0.05O2 Electrodes Due to Electrochemical and Thermal Stress
Authors: Lebens-Higgins Zachary , Faenza Nicholas , Sallis Shawn , Pereira Nathalie , Amatucci Glenn , Piper Louis F.J. 
Published: February 2020

The electrode-electrolyte interfaces (EEIs) play important roles in lithium ion batteries, often determining the capacity retention, safety, and lifetime. The EEI of the positive electrode is far less understood than its negative counterpart. In addition to possible electrolyte oxidation products, layered cathodes often exhibit pronounced surface phase transformations that can also limit the performance of the battery. For example, recent experiments have correlated charge-transfer impedance growth with surface phase transformations at Li1-xNi0.80Co0.15Al0.05O2(NCA) surfaces, which result from surface oxygen loss. [1] Electrolyte reactions with the active material play a role in surface oxygen loss as coating layers [2] and electrolyte additives [3] can mitigate impedance growth and capacity fade. Determining reaction pathways that promote surface oxygen loss is essential to optimizing the selection of coating layers or additives that further improve capacity retention.
Here we report on our surface studies of NCA, to examine the evolution of the cathode-electrolyte interface (CEI) for stressed NCA electrodes held at high voltages (≥4.5V). Using a combination of surface sensitive x-ray absorption spectroscopy and x-ray photoelectron spectroscopy, we correlate transition metal reduction with electrolyte decomposition species at the cathode surface. From comparison of NCA electrodes held under various constant voltage conditions, we examine the influence of voltage and temperature on the formation of electrolyte decomposition species. Our work provides insight into possible reaction mechanisms that influence changes of the CEI layer for electrodes under thermal and electrochemical stress.
This work was supported as part of NECCES, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0012583
[1] S. Sallis et al., App. Phys. Lett. 108 (2016) 263902
[2] I. D. Scott et al., Nano Letts. 11 (2011) 414
[3] R. Wagner et al., Appl. Mater. Interfaces. (2016) 30871

Figure 1
Structural Properties and Functional Electrochemistry of Spinel Type Iron Oxide Structures
Authors: Takeuchi Esther S , Marschilok Amy C , Takeuchi Kenneth J 
Published: February 2020

In recent years, binary transition metal oxides such as magnetite, Fe3O4, zinc ferrite, ZnFe2O4, magnesium ferrite, MgFe2O4 and copper ferrite, CuFe­2O4, have gained significant attention as prospective electrodes for lithium based batteries. These materials hold interest due to the low cost iron center, their low environmental impact, and in particular for their high theoretical capacities. Through a combined insertion and conversion mechanism theoretical capacities of up to 1000 mAh/g would be possible, thus, storing more energy than typical insertion materials. Interestingly, along with the commonality of the iron metal center, the materials often have spinel or inverse spinel structures. The densely packed structure of these spinel materials has led to the demonstration that smaller crystallite size samples can provide higher practical energy density than larger size samples. This presentation will provide insight into the role of crystallite size as well as the lithiation/delithiation mechanisms of this class of bimetallic iron oxide structures.