bluuebunny/crossref_metadata_2025 huggingface dataset:
Nitrous Oxide As an Oxidizer for Dual Use Fuel Cell / Thrust Systems in Space Applications
Authors: Tsui Lok-kun , Plumley John Bryan , Peng Thomas , Garzon Fernando H
Published: February 2020

Nitrous oxide (N2O), a non-toxic chemical which can be stored in a liquefied state under moderate pressures

(52 bar) without cryogenic storage, is a reactant which can be used to generate electricity or propel a

spacecraft. It has been investigated as a cold gas propellant, monopropellant, and bipropellant; particularly

in the field of small satellites.[1,2] Nitrous oxide can also be used to generate electricity by acting as the

oxidizer in a fuel cell where N2O reduction occurs at the cathode and a fuel such as H2 is oxidized at the

anode.[3] Although the equilibrium potential in standard state aqueous electrolytes is 1.76 V vs SHE,

[3] large overpotentials in aqueous electrolytes make it difficult to efficiently extract power from this reaction. The

electrochemical reduction can be more readily achieved in a solid-oxide fuel cell (SOFC) with an oxygen

ion conductor for an electrolyte following the reactions in equations 1 and 2.[4] SOFCs also enable the use

of alternative fuels such as hydrocarbons, CO, and NH3. Additionally, the reaction product N2 is expected

to be usable as a cold gas propellant.

Cathode: 𝑁2𝑂 + 2𝑒− → 𝑁2 + 𝑂2− (1)

Anode: 𝐻2 + 𝑂2− → 𝐻2𝑂 + 2𝑒− (2)

We report on a SOFC device consisting of a Ni anode, a LaSrMnO3 cathode, and a Sc-doped ZrO2

electrolyte substrate. The maximum operating power which can be extracted from this system using N2O

as an oxidizer and H2 as a fuel, the conversion efficiency of N2O to N2, and a comparison of the performance

of N2O with air and O2 are all evaluated under a range of operating temperatures and flow rates.

References

1. V. Zakirov, M. Sweeting, T. Lawrence, and J. Sellers, Acta Astronautica., 48, 353–362 (2001).

2. V. Tarantini, B. Risi, R. Spina, N. G. Orr, and R. E. Zee, in Small Satellites Systems and Services

Symposium, p. 1–12 (2016).

3. A. Aziznia, A. Bonakdarpour, E. L. Gyenge, and C. W. Oloman, Electrochim. Acta, 56, 5238–5244

(2011).

4. T. Li, M. F. Rabuni, L. Kleiminger, G. H. Kelsall, U. W. Hartley, K. Lim, Energy Environ. Sci., 9, 3682–3686 (2016).
(Invited) Electrochemistry’s Role in Current and Future Environmental Control and Life Support Systems
Authors: Brown Brittany R
Published: February 2020

The current Environmental Control and Life Support System (ECLSS) Oxygen Generation System (OGS) onboard the International Space Station (ISS) utilizes electrochemistry in order to generate oxygen consumed by the crew. The OGS consists of two major components, the Oxygen Generation Assembly (OGA) and the Carbon Dioxide Reduction System (CDRS). The OGA electrolyzes water to produce oxygen (O2) and hydrogen (H2). Oxygen is released into the cabin for crew consumption, and the hydrogen byproduct is recycled back to the CDRS, which utilizes the H2 to generate the water for OGA from metabolic carbon dioxide (CO2). As exploration of our solar system progresses, development of technologies to limit earth reliance is vital. The current state of the art (SOA) O2 recovery system is capable of recovering approximately 50% of O2 from metabolic CO2. For future long duration missions, the target recovery goal is 90% with a minimum of 75% recovery is required. To help reach this goal, several investigations are underway that involve electrochemical processes. These processes are utilized for several different applications, such as electrodeposition of O2 recovery fouled catalyst, the development of an advanced microfluidic electrochemical reactor, and a hydrogen separator that utilizes electrochemical techniques to recover H2 from a methane post processor. These electrochemical approaches address different issues that future ECLSS OGSs face but share one common end goal, maximizing O2 recovery for long duration missions. Here, we will discuss the electrochemical aspects of both current and future ECLS Systems and how the development of these technologies may aide in future long duration life support systems.
Electrochemistry and the Origin of Life
Authors: Jones John-Paul , Barge Laura M , Krause Frederick C. , Hermis Ninos Y , Billings Keith J. , Perl Scott M
Published: February 2020

There is considerable international interest in the origin of life, both on Earth and icy worlds such as Europa, Enceladus, Ceres, and Titan. These ocean worlds may contain hydrothermal vents at the interfaces between their salty oceans and rocky cores and have been prioritized by NASA in the search for evidence of life in our solar system.1 Hydrothermal vents on Earth have been shown to produce voltage and current in the field2,3 and may be related to the origin of life.4 Electrochemistry certainly plays a role here, with hot reductants flowing from the crust and interacting with oceans through porous, partially conductive minerals. Understanding the natural systems that exist on Earth and may have contributed to the emergence of life, and determining similarities to hydrothermal vents on ocean worlds, is a critical step in exploring these unknown environments.

We have attempted to model these systems using both cyclic voltammetry and fuel cell experiments,5 with results presented here. While there is a plethora of potential redox couples which could be exploited in nature at hydrothermal vents, one of the most active reductants is H2S, which is produced at many black smoker chimneys and reacts with various metals to generate compounds such as FeS and FeS2, both of which are known electroactive materials. Studies on these materials indicate that they may produce energy which could be directly used by simple organisms on the outside of the chimneys and in turn feed larger organisms. This chain of energy utilization exists without solar irradiation, thus giving credence to the hypothesis that life may exist at the bottom of the ocean on the icy moons around Jupiter and Saturn.6

ACKNOWLEDGEMENT

The work described here was carried out at the Jet Propulsion Laboratory, California Institute of Technology, under contract with the National Aeronautics and Space Administration (NASA) supported by JPL’s Research and Technology Development program.

References:

A. R. Hendrix et al., Astrobiology, 19 (2019).

R. Nakamura et al., Angew. Chemie Int. Ed., 49, 7692–7694 (2010).

M. Yamamoto et al., Angew. Chemie Int. Ed., 56, 5944 (2017).

G. Macleod, C. McKeown, A. J. Hall, and M. J. Russell, Orig. life Evol. Biosph., 24, 19–41 (1994).

L. M. Barge, F. C. Krause, J.-P. Jones, K. Billings, and P. Sobron, Astrobiology, 18, 1147–1158 (2018).

K. P. Hand, R. W. Carlson, and C. F. Chyba, Astrobiology, 7, 1006–1022 (2007).

Figure 1
Measuring Soluble Properties of Planetary Science Samples: Sensor and System Development Since the Wet Chemistry Laboratory
Authors: Noell Aaron C , Jaramillo Elizabeth A , Quinn Richard C. , Ricco Antonio , Kounaves Samuel P , Hecht Michael H
Published: February 2020

The measurement of the soluble properties (pH, eH, conductivity, specific ion concentrations, etc.) of planetary science samples provides important information on the habitability of a location, the bulk components of a sample, the potential for undesired effects on analysis protocols, and the history/preservation of the sample (e.g., geologic weathering, radiation processing, etc.). Electrochemical sensors are an ideal means to measure soluble properties because they excel at detecting ionic species in solution. The Wet Chemistry Lab (WCL) on the 2007 Mars Phoenix Lander was the first planetary science instrument to focus on soluble inorganic ion measurements and used an array of electrochemical sensors. WCL’s discovery of significant quantities of perchlorate salts in the Martian regolith helped reshape our understanding of Martian chemistry and the search for past or present life there.

As NASA starts on a new chapter of exploration with potential missions to further out locations like the Ocean Worlds of Europa and Enceladus, it is a natural fit to adapt the successful WCL instrument for operation on bodies where the samples could be ice or liquid. Since the successful operation of WCL on Mars there have been a number of projects to improve sensor capabilities, develop microfluidic implementations, and prepare for Ocean World mission scenarios. This work has led to a number of developments, including: 1. Production of Ag/AgCl reference electrodes that are stable for use during flight missions. 2. Cyclic voltammetry methods for the specific detection of SO4
2- and NO3
-. 3. Adaptation of hydrogel-based ion-sensitive electrodes (ISEs) for use in microfluidic arrays. 4. The development of solid-contact ISEs for use during flight missions. 5. Radiation testing of ISE ionophores. 6. The development of microfluidic infrastructure based on successful small satellite payloads.

The combination of all this work has led to a significant increase in sensor/system performance and robustness in preparation for potential missions to Ocean Worlds.
Electrochemistry for Life Detection on Ocean Worlds
Authors: Thomson Seamus D. , Quinn Richard C. , Ricco Antonio , Koehne Jessica E.
Published: February 2020

Biological redox is a promising indicator of life for NASA’s future exploration missions of Ocean Worlds. Electrochemical sensors are valuable tools for detecting these biological redox signatures on Earth; however their application to planetary exploration has been limited. All forms of life on Earth contain cellular machinery that can transform and regulate chemical energy through electron transfer pathways performed by key classes of naturally-occurring biological redox molecules including flavins, nicotinamides, porphyrins, and quinones. In this study, we use electrochemical techniques to measure these redox molecules in a synthetic seawater solution. This study also appropriates an electrochemical immunoassay technique for alkaline phosphatase detection, where comparison of the unique redox signatures of enzyme substrates and products reflect enzymatic activity. Naturally-occurring redox molecules exhibit unique redox signatures with anodic peak locations indicative of their respective molecular class. In this work, we report measured limits of detection as low as 10 nM and 3.13 aM for naturally-occurring redox molecules and alkaline phosphatase respectively. Overall, the findings of this study demonstrate that electrochemical sensors are effective tools for life detection applications for future Ocean Worlds missions.
Reversible Electrochemical Mirrors for Thermal Control in Space Vehicles
Authors: Plumley John Bryan , Ganley Emily Nicole , Tsui Lok-kun , Garzon Fernando H , Han Sang , Peng Thomas
Published: February 2020

Transparent, conductive substrates are investigated for surface emissivity control for thermal space applications by means of reversible Ag electroplating. Transmittance and reflectance measurements are used to demonstrate change in mirror formation and de-formation during Ag deposition cycling in electrochemical cells. Ag was cycled consecutively over 1000 times on Pt-doped indium tin oxide (ITO) in gamma-butyrolactone (GBL) electrolyte, and it was determined that the ITO electrode was not stable for long term cycling, with electrode degradation and irreversible deposit buildup being observed on the working electrode. Other alternative IR transparent conductive electrodes were investigated for long term stability, in particular conductive diamond coated silicon cathodes and Ag mesh anodes. In addition, air free preparation of reversible electrochemical devices was shown to improve cycling behavior.
Pulsed Electrodeposition of Carbon Dioxide Reduction Electrocatalysts for Space Applications
Authors: Skinn Brian , Sen Sujat , Leonard McLain Evan , Wang Dan , Brushett Fikile R. , Taylor E. J.
Published: February 2020

Space programs around the globe have begun to consider the logistical demands of missions beyond the orbital neighborhood of Earth. Unlike local installations such as the International Space Station, long-range missions will not have the option to resupply critical materials from Earth. Thus, the development of capabilities for what is often termed "In-Situ Resource Utilization" (ISRU) have been a continuing focus of research through NASA and other agencies. One particular long-range mission of interest is to place human astronauts on Mars; the major component of the thin Martian atmosphere is carbon dioxide, making CO2 a natural input to ISRU technologies for production of carbon-containing materials. Production of mission consumables from in-situ Mars resources will be critical to enabling human exploration of Mars, in part by minimizing the number and size of descent/ascent vehicles. Potential ISRU products from CO2 include that seem likely to provide significant mission benefits with minimal infrastructure required are propellants (e.g., hydrocarbons), fuel cell reactants (e.g., formic acid, methanol, carbon monoxide), and life support consumables (e.g., oxygen).

The first portion of this talk will comprise a high-level overview of the chemical transformations that can be imparted to CO2 via electrocatalysis on gas-diffusion electrodes (GDEs), in the form of a summary of literature reports on the catalytic performance of various single-metal and metal-alloy systems. The remainder will encompass an exposition of the electrocatalytic performance of tin and copper single-metal GDE electrocatalysts prepared by pulsed electrodeposition. These metals are well known for their ability to reduce carbon dioxide to formic acid and hydrocarbons/carbon monoxide, respectively, and are under active development to this end in numerous academic research groups and industrial entities. These experimental results clearly demonstrate the power and flexibility of the pulse/pulse-reverse electrodeposition approach to catalyst fabrication, as evidenced by the appreciable effects of the pulsed-waveform electrodeposition parameters on CO2 electroreduction product distribution and total current density.
(Invited) Electrolyte Design and Solution Mediation Processes in Metal-Oxygen and Metal-Sulfur Batteries
Authors: Lu Yi-Chun
Published: February 2020

Energy storage system is a critical enabling factor for deploying unstable and intermittent renewable power sources such as solar and wind power sources. Energy storage devices including metal-oxygen and metal-sulfur batteries have received extraordinary attentions owing to their high energy density. In this presentation, we will discuss fundamental redox processes and design strategies in these battery systems. We exploit various spectroscopic techniques coupled with single-cell electrochemical characterizations to probe the sulfur and oxygen reactions. In addition, we will discuss new redox chemistries as alternative anode materials to metals and synergistic interplay between solvent and redox-active materials at solid and liquid interfaces that commonly exist in these high-energy-density energy storage systems.

Acknowledgement:

This work was supported by a grant from the Research Grants Council (RGC) of the Hong Kong Special Administrative Region (HK SAR), China, T23-601/17-R and a grant from the Innovation and Technology Commission of the Hong Kong Special Administrative Region, China (Project No. ITS/063/18).
Solving Barriers to Commercialization of Cells with Lithium Metal Anodes
Authors: Crowther Owen
Published: February 2020

Commercially available Li-ion batteries using graphite or graphite-silicon blended anodes are currently approaching a cell level specific energy of 300 Wh kg−1. The use of lithium metal instead as an anode an intriguing possibility to further increase cell level specific energies to 400 Wh kg−1 and beyond. Lithium is an ideal anode because it is the lightest metal and highly electronegative. However, attempts to commercialize cells using lithium metal anodes have been slowed by poor cycle life and safety issues. This is because nonuniform lithium plating leads to the growth of dendrites that cause loss of active lithium and can eventually lead to internal cell shorts.

Safe cell cycle life must be improved to 50-100 cycles for special purpose applications like unmanned aerial vehicles, >300 cycles for portable power applications and >1000 cycles for electric vehicle applications. This performance must be maintained during the challenge of scaling cell size from <5 mAh coin cells with relative low areal capacities less than 2 mAh cm−2 used in most literature research to larger cell sizes such as (>2000 mAh) pouch cells and 18650/21700 cylindrical cells with practical areal capacities >4.5 mAh cm−2.

The advantages and disadvantages of several potential cell designs will be discussed including using lithium metal with conventional Li-ion cathodes, nonlithithated metal oxides and fluorides, sulfur and air cathodes, as well as other advanced concepts. Several types of electrolytes including liquid, polymer and ceramic will be evaluated based on ability to limit dendrites and manufacturability. Other methods to limit dendrite propagation such as surface pretreatments and pulse plating will also be covered.

Finally, the performance of prototype cells developed at EaglePicher using lithium metal anode will be highlighted. Figure 1 shows a 2 Ah prototype pouch cell using a lithium anode, high nickel cathode and nonaqueous electrolyte. The cell demonstrates an extremely high specific energy of >375 Wh kg−1 but a poor cycle life of ~25 cycles to 80% retention. This presentation will focus on design considerations for cells with lithium anodes, as well as improving the cycle life and safety characteristics of these cells. Several methods for improving both of these areas will discussed. Incorporation of these methods and the performance improvement of 2 and 10 Ah pouch cells using the lithium anode will presented.

Figure 1
(Invited) Considerations of Ionic Charge Carriers for Aqueous Rechargeable Batteries
Authors: Ji Xiulei
Published: February 2020

There is a pressing need for new battery technologies in two key areas: high-energy power batteries for electric vehicles, and large-scale storage batteries to buffer the output from the renewable-but-intermittent solar and wind power generation. For storage batteries, the goal is to minimize the levelized energy cost over the devices’ lifetime. This means that electrode materials containing rare and expensive elements should be avoided. Secondly, the cycle life of storage batteries must be excellent — ideally over 10,000 cycles. Thirdly, these batteries should be quickly rechargeable to store, for example, energy from wind farms. Most importantly, storage batteries should be intrinsically safe, i.e., nonflammable. To meet this list of requirements, batteries with aqueous electrolytes relish several distinct advantages. Aqueous electrolytes are cheaper and safer. The simplicity of an aqueous chemistry environment may facilitate long battery longevity, and its high conductivity brings an innate power advantage. In battery chemistry design, one of the most important considerations is the choice of working charge carriers. To date, a majority of battery technologies rely on metal-ion charge carriers. Surprisingly, non-metal cations, particularly proton-containing cations, i.e., H+, H3O+,1 and NH4
+,1,2, have received exceedingly little attention. The simplest form of hydrogen cation, a single proton, is nearly “invisible” with a measured radius of ~0.89 fm or ~2.1 fm, using muon or e- spectroscopy, respectively. Due to the negligible strain of hosting protons, the rate capability and cycle life of proton batteries have the potential to be far superior to those of existing batteries. In this talk, I will introduce some of our new results, experimental and computational, on the storage of new charge carriers in battery chemistry for grid-storage purposes, particularly related to the Grotthuss mechanism3 and the ion/electrode interactions. I will compare different charge carriers in terms of their correlations to electrochemical properties, such as capacity fading, polarization, and operation potentials.

References:

Wang, X., Bommier, C., Jian, Z., Li, Z., Chandrabose, R. S., Rodríguez Pérez, I., Ji*, X.“Hydronium-Ion Batteries with Perylenetetracarboxylic Dianhydride Crystals as an Electrode” Chem. Int. Ed. 56, (2017): 2909-2913 doi:10.1002/ange.201700148

Wu, X., Qi, Y., Hong, J. J., Hernandez, A. S., Ji*, X. “Rocking-Chair NH4-Ion Battery: A Highly Reversible Aqueous Energy Storage System” Angewandte Chemie International Edition
56, (2017) 13026-13030 doi: 10.1002/anie.201707473

Wu, X., Hong, J. J., Shin, W., Ma, L., Liu, T., Bi, X., Yuan, Y., Qi, Y. (undergraduate), Surta, T., Huang, W., Neuefeind, J., Wu, T., Greaney*, P. A., Lu*, J., and Ji* X., “Diffusion-Free Grotthuss Topochemistry for High-rate and Long-Life Proton Batteries" Nature Energy, (2019) DOI: 10.1038/s41560-018-0309-7
Electrolyte Chemistries of Mg Batteries
Authors: Liu T. Leo
Published: February 2020

Mg is earth abundant and low-cost (ca. 24 times cheaper than Li), and as an anode material, Mg is safe to use (vs. Li, Li-ion, or Na-ion batteries). Its high gravimetric capacity (2,333 Ah/kg) and high reduction potential (-2.37 V vsSHE) allow the assembly of high-energy density batteries. However, despite rapid research progress, the lack of high performance Mg2+conductive electrolytes still presents a primary technical hurdle for developing practical Mg batteries. The presentation will cover our research efforts in developing high performance Mg electrolytes for Mg rechargeable batteries. Specifically, we will present the synthesis and electrochemical performance of ternary Mg/MgCl2/AlCl3(MMAC) electrolytes and a novel Cl free perfluorinated pinacolatoborate Mg electrolyte (Mg-FPB). These MMAC and Mg-FPB electrolytes exhibited up to 100% Coulumbic efficiency, and 164 mV overpotenail for Mg deposition, and up to 4.5 V vs Mg anodic stability. Solution and interfacial chemistry of the presented Mg electrolytes will be discussed in detail. In addition, we will share our results on applying these advanced electrolytes in developing high energy density Mg/S and Mg/MnO2 rechargeable batteries.

References:

(1) Luo, J.; Bi, Y.; Zhang, L.; Zhang, X. Liu, T. L.*, Angew. Chem. Int. Ed. 2019, DOI: anie.201902009. (2) Luo, J; .He, S.; Liu, T. L.* ACS Energy Letters 2017, 2, 1197-1202. (3) He, S.; Luo, J. Liu, T. L.*,J. Mater. Chem. A 2017, 12718-12722. (4) He, S.; Neilson, K. V.; Luo, J..; Liu, T. L.*, Energy Storage Mater 2017, 8, 184-188.(5) Liu, T.;* Shao, Y.; Li, G.; Gu, M.; Hu, J.; Xu, S.; Nie, Z.; Chen, X.; Wang, C.; Liu, J. J. Mater. Chem. A.
2014,2, 3430. (6) Liu, T.;* Cox, J. T.; Hu, D.; Deng, X.; Hu, J.; Hu, M. Y.; Xiao, J.; Shao, Y.; Tang, K.; Liu, J. Chem. Commun.
2015, 51, 2312. (7) Filed US patent applications on Mg electrolytes (8) Group website: www.tianbiaoliu.org.
Low Concentration Electrolytes for Lithium-Sulfur Batteries
Authors: Glaser Rebecca , Johnson Billy , Wu Feixiang , Ready Jud , Sanghadasa Mohan , Yushin Gleb
Published: February 2020

As a promising cathode material due to its high theoretical capacity (1166 mAh/g) lithium sulfide (Li2S) has been the focus of research worldwide. In addition to being based on inexpensive, widely-available, and non-toxic sulfur, Li-Li2S or Li-S batteries offer remarkably high specific energy, which is critically important for weight-sensitive applications. Previous research demonstrated that highly concentrated electrolytes (e.g., 2.5-5M) may reduce polysulfide dissolution and improve performance of cells with Li2S cathodes.1
,
2 However, salts in the organic electrolyte are fairly expensive and relatively heavy. In addition, high salt concentrations reduce Li+ mobility and may severely limit the rate performance of high loading cathodes. In contrast, low concentration electrolytes have not been explored for Li-S batteries, despite being significantly lighter, cheaper and less viscous than their high concentration counterparts. Furthermore, salts and additives that are not soluble in some solvents used in Li-S batteries at high concentrations can offer sufficient solubility at low concentrations, thus offering more options for the design of high-loading and high performance Li-Li2S or Li-S cells. In our study, we examine a broad range of low concentration electrolytes with various salt and solvent combinations and ratios. In contrast to our initial expectations, some low-concentration electrolytes demonstrated strong rate performance. We also examine lifetime performance and performance with high loading cathodes. In this talk, we will discuss the impact of electrolyte salt chemistries, their mixtures, relative concentrations and solvent compositions on electrolyte conductivity, the anode and cathode solid electrolyte interphase layers (CEI and SEI) as well as cell rate performance and stability.

(1) Lee, J. T.; Zhao, Y.; Thieme, S.; Kim, H.; Oschatz, M.; Borchardt, L.; Magasinski, A.; Cho, W. Il; Kaskel, S.; Yushin, G. Adv. Mater.
2013, 25 (33), 4573–4579.

(2) Suo, L.; Hu, Y. S.; Li, H.; Armand, M.; Chen, L. Nat. Commun.
2013, 4, 1–9.
Promises and Challenges Facing Lithium Metal Batteries
Authors: Wu Sheng-Hui , Wu Wei-Hsin , Chao Chung-Hsiang , Chang Chih-Ching , Fang Jason
Published: February 2020

Nowadays, due to rapid development in technology, regardless of automobile industry, portable devices and energy storage system, the requirement of energy density, capacity and operating voltage becomes higher and higher. Traditionally, graphite anode with low capacity is limited to develop advanced lithium ion battery(LIB) and is hard to achieve the high-tech product specification; therefore, battery industries have started to focus on silicon-carbon composite materials in substitution. However, it also faces its limitation to achieve energy density of 700 Wh L-1. Using lithium metal as the anode material seems to be the only route to achieve 1000 Wh L-1 due to its extremely high capacity (3860 mAh g-1), lightness (0.59 g cm-3), and low reduction potential (-3.04 V). Consequently, more and more battery experts and researchers have devoted themselves to lithium metal battery (LMB) research.

Nevertheless, lithium as active metal easily reacts with electrolyte producing poor solid electrolyte interphase (SEI) with high internal resistance leading to low coulombic efficiency and short cycle life. During charge and discharge process, lithium plating and stripping leads to non-even deposition. As a further matter, under extreme environment, such as high current density and charge density, dendritic dendrite easily forms resulting in safety issue including failure of separator and short circuit. Based on the above issues, lithium metal battery could be hardly commercialized. Therefore, battery design should be aimed at lithium metal anode instead of traditional LIB anode. First of all, innovative electrolyte system which benefits the formation of highly-stable SEI should be established. Secondly, the artificial SEI on lithium anode is served as the first line of defense against dendrite due to excellent mechanical strength and elasticity. Finally, it is important to develop a structured anode for improving lithiophilic property, uniform electric field and solving volume expansion issue.
On Improving the Cycling Stability of P2-Type Na0.67Ni0.33Mn0.67O2 Cathode Material By Ti-Substitution for Na-Ion Batteries
Authors: Pahari Debanjana , Puravankara Sreeraj
Published: February 2020

The extensive studies over the last decade have established Na-ion batteries (NIBs) as one of the cheaper alternatives to Li-ion batteries (LIBs) [1-2]. P2-type Na0.67Ni0.33Mn0.67O2 has stood out among layered oxide based electrode materials providing the best over-all electrochemical performance. The electrodes can exert up to 92.5% of its theoretical capacity (160 mAhg-1) at a voltage higher than 3 V accounted for the Ni2+/Ni4+ redox. However, at higher voltages, electrodes suffer irreversibility due to P2-O2 structural transition [3]. Recent studies in suppressing this transition by partial substitution with various metals on either Ni or Mn lattice site have suggested enhancing cycling stability [4-7]. In this study, a novel cathode material with Ti-substitution on Ni site, P2-type Na0.67Ni0.25Ti0.08Mn0.67O2 has been synthesized via solid-state synthesis method and characterized electrochemically. Na0.67Ni0.25Ti0.08Mn0.67O2 electrodes have been observed to be highly reversible at higher voltage ranges. The electrodes have an initial discharge capacity of 125 mAhg-1 and can retain around 84% of this capacity (105 mAhg-1) even after 50 cycles at 0.1C when cycled at an upper cut-off voltage of 4.3 V (Figure 1). Na0.67Ni0.25Ti0.08Mn0.67O2 electrodes are believed to suppress the irreversible P2-O2 transformation by diverting the charging reaction through a more reversible P2-OP4 transition.

References

[1] A. Eftekhari, D. W. Kim, J. Power Sources 2018, 395, 336-348.

[2] J. Y. Hwang, S. T. Myung, Y. K. Sun, Chem. Soc. Rev. 2017. 46, 3529-3614.

[3] G. Singh, N. Tapia-Ruiz, J.M. Lopez del Amo, U. Maitra, J.W. Somerville, A.R. Armstrong, J. Martinez de Ilarduya, T. Rojo, P.G. Bruce, Chem. Mater. 2016, 28, 5087-5094.

[4] T. Y. Yu, J. Y. Hwang, D. Aurbach, Y. K. Sun, ACS Appl. Mater. Interfaces 2017, 9, 44534-44541.

[5] K. Kubota, Y. Yoda, S. Komaba, J. Electrochem. Soc. 2017, 164, A2368-A2373.

[6] J. Xu, D. H. Lee, R. J. Clément, X. Yu, M. Leskes, A. J. Pell, G. Pintacuda, X. Q. Yang, C. P. Grey, Y. S. Meng, Chem. Mater. 2014, 26, 1260-1269.

[7] W. Zhao, A. Tanaka, K. Momosaki, S. Yamamoto, F. Zhang, Q. Guo, H. Noguchi, Electrochim. Acta 2015, 170, 171-181.

Figure 1
A High Voltage Sodium Ion Battery Based on Low-Cost Sodium Iron Sulfate Cathode Material
Authors: Li Shiyu , Zhao Jianqing , Gao Lijun
Published: February 2020

It is desirable to develop alternative electrochemical devices with comparable performance but lower cost to substitute for lithium-ion batteries. Sodium-ion batteries show very similar electrochemical mechanism to lithium-ion batteries. The abundant sodium resource can considerably reduce the cost of energy storage devices as compared with lithium-ion batteries. In this work, a new derivative of sodium iron sulfates, Na6Fe5(SO4)8 (NFS), is developed as cathode material for sodium-ion batteries. The NFS is synthesized from sodium carbonate, sodium sulfate and iron sulfate raw materials, and it shows a high working voltage of 3.7 V vs. Na+/Na. When combined with carbon nanotube (CNT), the NSF@CNT composite demonstrates increased electronic conductivity and superior electrochemical performance. A 3.6 V sodium-ion full battery is constructed based on NFS@CNT cathode and hard carbon (HC) anode materials. Such a full NFS@CNT//HC cell can deliver an energy density towards 350 Wh kg-1 and cycling stability over prolonged 1000 cycles at 2 C. This work offers a low-cost sodium-ion full battery with an impressive high working voltage and energy/power densities for possible stationary energy storage applications.
Pb-Based Nanocomposite Anodes for Li- and Na-Ion Batteries
Authors: Han Jinhyup , Park Jehee , Kim Youngsik , Ahmed Shabbir , Lee Eungje , Johnson Christopher S.
Published: February 2020

Anode materials that undergo alloying and conversion type electrochemical reactions are studied as alternative electrodes to graphite and hard carbon with the promise of higher capacities, and potentially higher energy densities. Little studied however are lead (Pb) and lead oxides (PbO, Pb3O4) that have advantages of low cost and high volumetric energy density [1]. In fact when the Argonne BatPaC model is used with Pb as anode, and layered sodium transition metal oxide cathode are coupled together the energy density for a sodium-ion pouch cell design is 549 Wh/L, and the cost is projected quite low at 63.5 USD/kWh [2]. These metrics are certainly competitive with many grid storage battery systems. However, lead toxicity is a concern. But Pb has always been one of the most recycled materials in the world, with a high recycling rate close to 99 % in the United States [3]. Certainly, with the rapid in-line progress of lithium- and sodium-ion battery recycling technologies, lead-based materials could become a viable contender for high-energy, low-cost anodes in the future if the performance can be improved and validated.

In this presentation, we report novel Pb-O-C nanocomposite anodes synthesized by simple high energy ball milling process. The electrochemical test data from lithium and sodium cells show higher reversible capacity and improved cycle stability when compared to previously reported data of lead and lead oxides materials.[4-5] The reaction mechanism and effect of nanocomposite structure with improved performance will be discussed.

[1] M.N. Obrovac and V.L. Chevrier, Chem. Rev., 2014, 114, 11444-11502.

[2] P. Nelson, K. Gallagher, I. Bloom, Dennis Dees, and Shabbir Ahmed, BatPaC, Argonne National Laboratory. (n.d.). http://www.cse.anl.gov/batpac.

[3] L. Gaines, Sustainable Materials and Technologies, 2014, 1-2, 2-7.

[4] M. Martos, J. Morales and L. J. E. A. Sanchez, Electrochimica Acta, 2003, 48, 615-621.

[5] L. D. Ellis, B. N. Wilkes, T. D. Hatchard and M. N. Obrovac, Journal of The Electrochemical Society, 2014, 161, A416-A421.
NaM2(PO4)(SO4)2 (M= Fe, V, Cr) As Electroactive Materials for Na-Ion Batteries
Authors: Ben Yahia Hamdi , Alkhateeb Alaa , Essehli Rachid
Published: February 2020

To date, research on sodium-ion batteries started to gain more interest. It is mainly motivated by the large abundance of sodium and the hope to produce batteries that are cheaper compared to LIBs and less prone to resource issues and safety concerns [1-3].

NASICON compounds have been well investigated as possible electroactive materials for sodium-, lithium-, and magnesium-ion batteries. In this paper, we report on the structural and electrochemical properties of the NASICON phases NaFe2-xMx(PO4)(SO4)2 (M=V, Cr and 0 < x < 1) [4] . The crystal structures were solved by the Rietveld method using powder X-ray diffraction (PXRD) data. The electrochemical performances were examined by galvanometric cycling and cyclic voltammetry. The stability of the NASICON structure during cycling was also followed by ex-situ PXRD experiments.

The NaFe2-xMx(PO4)(SO4)2 powders (0 < x < 1) were synthesized via a solid state synthesis route from stoichiometric mixtures of NaNO3 (Aldrich, ≥99 %), Fe(NO₃)₃·9H₂O (Aldrich, ≥98%), Cr(NO₃)₃·9H₂O (Aldrich, ≥98%), NH4VO₃ (Aldrich, ≥99%), (NH4)2SO4 (Aldrich, ≥99 %), NH4H2PO4 (Merk, ≥99%) and citric acid C6H8O7 (Riedel-deHaën) (CA). The starting raw materials, dissolved in an aqueous medium, were stirred at 80oC until evaporation of water. The resulting powders were calcined at 500oC for several hours under argon to obtain pure NaFe2-xVx(PO4)(SO4)2 powders. TGA experiments performed on all the samples resulted in a 30% weight loss which corresponds to the departure of two SO2 molecules, and hence confirm the chemical compositions of NaFe2-xVx(PO4)(SO4)2. This was also confirmed by EDS analyses. The crystal structure of the NaFe2-xVx(PO4)(SO4)2 were solved using X-ray powder diffraction data. A phase transition from R-3c (x = 0) to R-3 (x > 0) was observed during the replacement of iron by vanadium. The structure can be described as a covalent skeleton [(Fe/V)2P3O12]- built of Fe/VO6 octahedra and XO4 tetrahedra (X= S, P), which forms 3D interconnected channels with several types of interstitial positions where sodium and vacancies are distributed. The cycling performances of NaFe2-xVx(PO4)(SO4)2 were studied in cells embedding (NaPF6:EC:PC) electrolyte and Na-metal (Figure 1). Additional details will be provided during the conference.

Figure 1. Charge/discharge curves of NaFe2-xVx(PO4)(SO4)2 at the rate of C/10 vs. Na+/Na (a) and capacity retention for x = 0.4 (b) and rate capability for x = 0.4 (c).

Reference:

[1] Makino, K.; Katayama, Y.; Miura, T.; Kishi, T., J. Power Sources 2002, 112, 85−89.

[2] Gaubicher, J.; Wurm, C.; Goward, G.; Masquelier, C., Nazar, L., Chem. Mater. 2000, 12, 3240−3242.

[3] Jian, Z.; Zhao, L.; Pan, H.; Hu, Y.-S.; Li, H.; Chen, W., Chen, L., Electrochem. Commun. 2012, 14, 86−89.

[4] H. Ben Yahia, R. Essehli, R. Amin, K. Boulahya, T. Okumura, I. Belharouak, Journal of Power Sources 382 (2018) 144-151.

Figure 1
A Polymer Scaffold Binder Structure for Improving Long-Term Cycle Performance of Lithium Metal Powder Electrode
Authors: Jin Dahee , Roh Youngjoon , Byun Seoungwoo , Kim Dohwan , Ryou Myung-Hyun , Lee YongMin
Published: February 2020

Lithium metal anode is being revalued as a candidate for large-scale battery systems, such as electric vehicles (EVs) and energy storage systems (ESSs), owing to its high theoretical density and lowest negative potential. However, to commercialize lithium metal in large-scale battery systems, the formation of dendrite and continuous side reactions during repeated cycling must be suppressed.

In our previous contribution, we improved this problem by using Li metal powder (LiMP), which was compressed on a Cu foil with a small amount of binder instead of bare lithium metal foil. Due to higher surface area of LiMP, the actual current density felt by LiMP is much lower than that of general lithium foil. Nevertheless, during repeated cycling, the high-surface-area structure of LiMP became flatter and is finally covered with numerous dendrites.

Herein, we report a LiMP electrode with a scaffold barrier using polyimide (PI) binder. As PI binder forms its own barrier structure at the interstitial region between LiMP particles, the energy density of the cell can be enhanced without additional hosting materials or processes. Especially, the scaffold structure of PI binder can confine the Li stripping/plating reactions within the matrix. Furthermore, we investigated their electrochemical properties, such as DC-IR based on hybrid pulse power characterization (HPPC), cycle performance, and Li plating/stripping mechanism.
A Novel Ternary Ordered Intermetallics Cu3znsb As Anode for Sodium-Ion Storage
Authors: Pahari Debanjana , Misra Samiran , Jana Partha P , Puravankara Sreeraj
Published: February 2020

Among the high capacity anodes, antimony (Sb) shows a high theoretical capacity of 660 mAh/g by forming Na3Sb, safer working potential and less volume expansion compared to graphite anodes for Na-ion batteries(NIBs) [1]. Sb-based intermetallic systems can actively take part in sodiation /de-sodiation reaction. The relatively small volume change during charge-discharge reactions makes them promising anodes for Na-ion batteries. Cu2Sb has extensively been studied as intermetallic Sb-based anode for Na-ion storage. The anodes are capable of transferring three electrons in the redox reaction giving rise to a capacity of 250 mAh/g which is closely 77% of its theoretical capacity [2]. In this study, a ternary intermetallic Sb-based alloy Cu3ZnSb has been investigated to attain better electrochemical performance.

Ternary Cu3ZnSb crystallises in tetragonal space group P4/nmm (129) with lattice parameters a = 4.2171 (3) Å and c = 8.6925 (11) Å [3]. The structure is built up with [Cu3Sb] slabs that correspond to the unit cells of Cu2Sb and planer 44 nets of Zn atoms. The planar nets of Zn atoms are interspersed between two adjacent [Cu3Sb] slabs. The structure of Cu3ZnSb can be viewed as stacking of Cu2Sb-unit cells interleaved with CsCl type b’-brass (CuZn) layers along c-direction (Figure 1a).

Ternary Cu3ZnSb anodes exhibit an initial discharge capacity of 323 mAh/g when cycled at a rate of 0.05C in the voltage range of 0.005 – 2 V (Figure 1b). The average voltage can be calculated as 0.4 V with respect to Na/Na+. Although, the discharge capacity fades in the initial cycles, from the 6th cycle onwards a reversible capacity of 56 mAh/g has been observed for the pristine material.

References

Darwiche , C. Marino , M. T. Sougrati , B. Fraisse , L. Stievano and L. Monconduit, J. Am. Chem. Soc.
,
2012,134, 20805 – 20811.

Baggetto , E. Allcorn , R. R. Unocic , A. Manthiram and G. M. Veith, J. Mater. Chem. A
,
2013, 1, 11163 - 11169.

Misra, B. Koley, S. Chatterjee, S. Mallick, and P. P. Jana Inorg. Chemi. 2018
,
57 (19), 11970-11977.

Figure 1
(Invited) Advanced Na-Metal Halide Batteries: Challenges and Opportunities
Authors: Li Guosheng
Published: February 2020

Sodium (Na)-based battery technologies with low cost (from using earth-abundant Na) and prolonged cycle life are gaining much attention for large-scale energy storage applications. Among the widely studied Na-based systems, intermediate-temperature Na-metal halide (IT Na-MH) batteries have demonstrated several advantages over conventional Na-S batteries, including superior battery safety, higher open-circuit voltage, lower operating temperature, and ease of assembly. In here, we will present and summarize technical challenges and opportunities associated with IT Na-MH battery technologies for large-scale energy storage applications.
(Invited) Sulfur-Equivalent Cathode Material for Room-Temperature Li-S and Na-S Batteries
Authors: Li Yanguang
Published: February 2020

Many problems of Li-S batteries essentially root in their polysulfide intermediates. While conventional wisdom mainly focuses on trapping polysulfides at the cathode using various functional materials, few strategies are available at present to fully resolve or circumvent this long-standing issue. In this study, we propose the concept of sulfur-equivalent cathode materials, and demonstrate the great potential of amorphous MoS3 as such a material for room-temperature Li-S and Na-S batteries. When evaluated in Li-S batteries, MoS3 exhibits sulfur-like behavior with large reversible specific capacity when normalized to the sulfur weight (~1400 mAh/gS at 50 mA/gS), excellent cycle life (~850 mAh/gS after 1000 cycles at 1 A/gS), exceptional high rate capability (420 mAh/gS at 20 A/gS) and possibility to achieve high areal capacity (~2.8 mAh/cm2). Most remarkably, it is also fully cycleable in the carbonate electrolyte under a relatively high temperature of 55oC. MoS3 can also be used as the cathode material of even more challenging Na-S batteries to enable an unprecedented performance. In-situ XAS experiments evidence that MoS3 preserves its chain-like structure free of polysulfide intermediates during repetitive battery cycling.
Precision Electroanalytical Measurements of Li/Solid-State Electrolyte Interfaces
Authors: Westover Andrew S. , Dudney Nancy J.
Published: February 2020

Synthesizing ideal interfaces between Li metal and electrolytes is one of the keys to high energy batteries. Thermodynamic calculations suggest that virtually all solid-state electrolytes are not stable with Li metal. However, practical experience with LLZO, Lipon, and other solid-state electrolytes have demonstrated extraordinary apparent stability. This discrepancy is likely due to the kinetics of the reaction with Li metal but makes it difficult to accurately predict practical stability of Li metal with solid-state electrolytes. Here we present a simple electroanalytical technique that enables us to precisely measure the maximum amount of Li that reacts with a solid-state electrolyte and the maximum possible thickness of an interfacial layer. Using this technique, we demonstrate that a maximum of 10 nm of Li reacts with 5 nm of Lipon to form an interfacial layer that is less than 10 nm thick and does not propagate. Finally, we demonstrate that this technique is broadly applicable to a wide variety of Li/solid-state electrolyte systems. This method demonstrates a clean and simple path to evaluate the practical stability of solid-state electrolytes with Li metal that can increase understanding and accelerate their development.

Acknowledgements: This work was supported by the ARPA-E IONICS program, U.S. Department of Energy, award DE-AR0000775.
Impact of Salt Concentration on Lithium Dendritic Growth in a Rigid SEO Polymer Electrolyte
Authors: Frenck Louise , Maslyn Jacqueline A. , Balsara Nitash P.
Published: February 2020

In a society increasingly concerned by its impact on the environment and the urgent issue of climate change, there is great demand for an energy storage device with higher energy density and power capability (especially for electric vehicles and power grid). The use of the high energy density lithium metal anode jointly with a solid polymer electrolyte could enable the development of large-scale battery applications. Yet, dendritic lithium formation leading to short circuit currently limits its practical applications. Therefore, understanding the fundamentals of dendrite nucleation and growth is necessary to design robust battery systems.

In this work, the nucleation and growth of lithium dendrite is studied in function of salt concentration in lithium-lithium symmetric cells in a rigorous manner. Complete electrochemical characterization of a solid block copolymer polystyrene-polyethylene oxide mixed with lithium salt (LiTFSI) will be presented, as well as the cell lifetime under galvanostatic cycling. We have discovered an unexpected relationship between cell lifetime and salt concentration. X-ray micro-tomography was used to underpin the relationship between salt concentration and dendrite nucleation and morphology.
The Impact of Selectively Plasticized Poly (ethylene oxide) (PEO) Block in Nanostructured Polystyrene−PEO−Polystyrene Triblock Copolymer Electrolytes
Authors: Yang Guang , Cao Pengfei , Chen Xi Chelsea , Self Ethan Craig , Zhao Sheng , Ge Sirui , Zhu Chenhui , Lehmann Michelle , Saito Tomonori , Delnick Frank M. , Nanda Jagjit
Published: February 2020

All polymer electrolytes, including block polymer (BP) electrolytes exhibit low ionic conductivity compared to liquid electrolytes. For homopolymer electrolytes, the ionic conductivity can be increased by incorporating plasticizer into the polymer network. However, the subsequent weakened mechanical structure of the network precludes its use in many practical applications. In this work, we selectively plasticize the PEO block in a polystyrene PS-PEO-PS triblock copolymer electrolyte using a PEO-like plasticizer: tetraethylene glycol dimethyl ether (TEGDME). Unlike its homopolymer (PEO) electrolyte counterpart, the mechanical properties of the PS-PEO-PS triblock copolymer electrolyte are not drastically degraded by this plasticizer because it is immiscible in the nonpolar PS block domains.

Polymer electrolyte membranes were cast from lithium trifluoromethanesulfonate (LiTFS) solutions with the corresponding polymers. The molar ratio of ethylene oxide to Li+ is 16 for all electrolytes (nEO:nLi = 16:1). The ionic conductivity of the PS-PEO-PS electrolyte at 80 °C is about one order of magnitude lower than that of the homopolymer (PEO) counterpart at the same temperature. However, the shear modulus (G’) of the PS-PEO-PS electrolyte is about three orders of magnitude higher than the homopolymer, indicating the mechanical properties of the copolymer electrolyte is primarily dominated by the PS phase. The addition of TEGDME plasticizer to the PEO homopolymer electrolyte resulted in a ~10% increase in conductivity. The addition of same amount of TEGDME to the PS-PEO-PS electrolyte resulted in ~100% increase in conductivity. Compared to the dry electrolyte counterpart, the low isothermal frequency (ω = 0.1 rad/s) elastic modulus, G’ of the TEGDME plastized PS-PEO-PS was reduced to half at 80 °C (on the order of 106 Pa). Surprisingly, G’ of the plastized membrane surpassed its dry PS-PEO-PS counterpart at higher frequency values (17 < ω < 100 rad/s).

This counter intuitive result is further explored using: 1) Fourier-transform infrared spectroscopy (FTIR) to elucidate the salt solvation and coordination to ether oxygens, and 2) small angle X-ray scattering (SAXS) to decipher the domain spacing of the adjacent copolymer blocks.

Acknowledgment

This work is supported by Dr. Imre Gyuk, Manager, Energy Storage Program, Office of Electricity Delivery and Reliability, Department of Energy. CC acknowldge partial financial support by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division.