bluuebunny/crossref_metadata_2025_split huggingface dataset:
On the Viability of Carbon Dioxide in-Situ Resource Utilization (ISRU) to Produce Chemical Feedstocks on Mars
Authors: Usen Nazreen Mohamed Shahid , Sankarasubramanian Shrihari , Chambers Bradley 
Published: September 2023

The vision of a sustained human presence in space and extraterrestrial bodies necessitates an ever-larger share of life sustaining materials to be produced by in-situ resource utilization (ISRU). In this context, on Mars, NASA envisions the transformation of Martian atmospheric carbon dioxide into potential feed stocks through a process of climate enhancing resource utilization (with the technology being applicable for CO2 utilization on Earth as well) [1]. Amongst the potential raw materials present on Mars, the presence of stable brines in the liquid phase [2] (due to dissolved perchlorate salts suppressing the freezing point of water to < 213K) along with the availability [3] of 95 vol.% atmospheric CO2, can enable the development of a CO2-H2O electrolyzer to produce CO2 reduction products and O2. In this work, we examine the viability of such an electrolyzer system operating at or near Martian ambient conditions by developing thermodynamic and electrochemical polarization models of this system for various CO2 reduction products. Given the extreme operating conditions, the models were first applied to existing experimental data from an operational water electrolyzer under simulated Martian conditions to evaluate fit [2]. For the proposed CO2-H2O electrolyzer, the Nernst potential for various reactions, the anode/cathode catalysts, their corresponding overpotentials and separator conductivity were calculated or parameterized from experiments in the literature. This was integrated into the polarization model to predict the performance of these electrolyzers under Martian conditions and for various desired products. The polarization curves were calculated for the following possible reaction products; CO (# of e- = 2), HCHO (# of e- = 4), CH3OH (# of e- = 6), CH4 (# of e- = 8), C2H4 and C2H5OH (# of e- = 12) under both Earth and Mars conditions. CH4 and C2H5OH were found to be thermodynamically favored products as compared to other(s) across the range of operational temperatures from 230 K to 298 K. CO, HCHO and C2H4 can serve as potential feed stocks for downstream processing into other useful chemicals on Mars and strategies are discussed for their selective production.
REFERENCES
[1]. NASA, small business innovation research (SBIR) & small business technology transfer (STTR) program, 2022 phase I solicitation
[2].Gayen, P., Sankarasubramanian, S., & Ramani, V. K., Fuel and oxygen harvesting from Martian regolithic brine. Proceedings of the National Academy of Sciences, 117(50), 31685, (2020).
[3].Meyen, Forrest E., et al. "Thermodynamic model of Mars oxygen ISRU experiment (MOXIE)." Acta Astronautica 129, 82 (2016).

Figure 1. Calculated electromotive force of the production of various CO2 reduction products.

Figure 1
Zinc/ Manganese Oxide Aqueous Electrolyte Batteries: Electrochemical Reaction Mechanisms Beyond Ion Insertion
Authors: Takeuchi Kenneth J. , Takeuchi Esther S. , Marschilok Amy C. 
Published: September 2023

The consistent delivery of clean electrical energy is a global challenge where the current electric grid infrastructure distributes electrical energy from the generation source to the end user.
Widespread integration of inherently intermittent renewable energy sources such as wind and solar into the electric grid electrical energy storage into the electric grid demands incorporation of energy storage. Further, energy storage would enable control over when the electrical energy is used improving grid reliability and resiliency. Thus, stationary energy storage for the electric grid is a critical and timely application for batteries.
Rechargeable aqueous zinc/ manganese oxide (Zn/MnO2) batteries are an appealing target for scalable stationary energy storage applications due to their low cost, safety, and environmentally benign components. Notably, manganese oxide is a versatile material where several polymorphs are viable cathode materials in aqueous zinc ion batteries. However, there is need for more complete understanding of the electrochemical reaction mechanisms, to continue to advance the system. This presentation will feature investigations of the reaction mechanisms with a focus on operando methods. X-ray diffraction, Mn K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) measurements supported by ex situ transmission electron microscopy (TEM) will be presented. The findings provide a foundation for advancing the battery systems based on aqueous electrolyte zinc anode chemistries suitable for scalable stationary energy storage.
(Invited) Commercialisation of Sustainable Sodium Ion Batteries
Authors: Brant William Robert , Younesi Reza 
Published: September 2023

As the world continues to face one crisis after another, the demand for renewable energy and a reliable supply of abundant raw materials is stronger than ever. This is becoming abundantly clear for Li-ion batteries whose adoption in electric vehicles and stationary energy storage is rapidly expanding. In line with this growth, the limited supply of critical raw materials such as Li, Co and Ni is driving up prices. Thus, batteries based on alternate, abundant raw materials are critical. Consequently, in November 2022 IUPAC announced sodium-ion batteries amongst the top ten emerging technologies in Chemistry 2022 [1].
Since 2015 we have been developing a sodium-ion battery prototype with low-cost materials and a keen focus on maintaining safety and sustainability. The battery cell consists of Prussian white (Na2Fe[Fe(CN)6]) as the positive electrode, hard carbon as the negative and sodium bis(oxalate)borate (NaBOB) as fluorine-free salt dissolved in non-flammable alkyl phosphate-based solvents such as triethyl phosphate (TEP) and trimethyl phosphate (TMP) as the electrolyte solution. Our early successes in the low cost synthesis of Prussian white led to the spin-off company ALTRIS which is now focused on the commercialization of sodium-ion batteries. The company has successfully raised funding in seed and Series A funding rounds. With the funding ALTRIS has started construction of an industrial scale manufacturing unit with the annual capacity of 2,000 tonnes of Prussian white to enable 1 GWh of sodium-ion batteries.
Part of the on-going success of Altris is the close collaboration to the research teams within the Ångström Advanced Battery Center and the concurrent developments of material understanding and pilot industrial scale implementation. In this contribution an update of the company progress will be presented including a brief history as well as future plans for cell production. A focus will be placed on how fundamental investigations at Uppsala University are accelerating material development for solving problems such as moisture sensitivity and structural degradation.
[1] Gomollón-Bel, F., Chem. Int.
2022, 44(4), 4
Fulfilling the High Capacity of Zn Anodes in Rechargeable Alkaline Zn Batteries
Authors: Chen Qing , Li Liangyu , Ma Yilin 
Published: September 2023

A Zn anode in an alkaline electrolyte is often discharged to a shallow depth for an adequate cycle life. It limits the overall cell energy density and undermines its competitiveness against ever-improving lithium-ion cells. Our lab has been pushing the capacity limit of the alkaline Zn anode by understanding its failure mechanism and designing electrode microstructures and electrolyte alkalinity. I will discuss how we can revamp the paths of phase transition between Zn and ZnO by building a bi-continuous porous Zn anode and how a super-alkaline electrolyte can stabilize the anode at 60% depth of discharge. The mechanisms underlying the designs, including the interface-controlled structural evolution and the structural diffusion of alkaline electrolytes, will be explained to shed light on the future development of rechargeable Zn batteries.
References:
1. Li, L.; Tsang, Y. C. A.; Xiao, D.; Zhu, G.; Zhi, C.; Chen, Q. Phase-Transition Tailored Nanoporous Zinc Metal Electrodes for Rechargeable Alkaline Zinc-Nickel Oxide Hydroxide and Zinc-Air Batteries. Nat Commun
2022, 13, 2870.
2. Zhu, G.; Xiao, D.; Chen, Q. Spontaneous Formation of Porous Zinc in Rechargeable Zinc Batteries. J.
Electrochem. Soc.
2021, 168, 110524.
Molten Sodium Batteries – Lewis Acidity of AlCl3/NaI Catholyte Impedes NaSICON Interface
Authors: Maraschky Adam M. , Meyerson Melissa L , Percival Stephen J. , Peretti Amanda S. , Spoerke Erik D. , Small Leo J. 
Published: September 2023

Low temperature molten sodium batteries with sodium metal anodes, NaSICON solid-state separators, and sodium halide salt catholytes are low cost, earth-abundant technologies for grid-scale energy storage.1-3 We compared batteries with NaI/AlCl3-based molten salt catholytes of differing Lewis acidities at 110 °C. Batteries with >50 mol% AlCl3 (acidic catholytes) experienced a linear decline in energy efficiency during cycling, whereas batteries with >50 mol% NaI (basic catholytes) maintained 95% energy efficiency for 100 cycles (5 months) at 2.5 mA cm-2. A 3-electrode cell was developed, enabling electrochemical identification of the NaSICON-catholyte interface as the source of increased impedance. Complementary physical and chemical characterization of the NaSICON exposed to acidic and basic catholytes showed no changes in crystallinity, bulk morphology, or bulk chemical composition, but surface sensitive X-ray photoelectron spectroscopy (XPS) revealed subtle changes in the local NaSICON surface chemistry. In addition, Raman spectroscopy indicated that basic catholytes lack the dimer species Al2Cl6I- present in acidic catholytes. These results suggest that one means to enable efficient and stable battery cycling is maintaining Lewis-basic NaI/AlCl3, which avoids deleterious interactions at the NaSICON-catholyte interface. Recent progress towards achieving high cycling rates in these molten salt systems will also be shared.
References

L. J. Small, A. Eccleston, J. Lamb, A. C. Read, M. Robins, T. Meaders, D. Ingersoll, P. G. Clem, S. Bhavaraju and E. D. Spoerke, J. Power Sources, 360, 569 (2017).

S. J. Percival, L. J. Small and E. D. Spoerke, J. Electrochem. Soc., 165, A3531 (2018).

M. M. Gross, S. J. Percival, L. J. Small, J. Lamb, A. S. Peretti and E. D. Spoerke, ACS Appl. Energy Mater., 3, 11456 (2020).

Sandia National Laboratories is a multi-mission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC., a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525.
Synthesis and Thermal Evaporation Deposition of Sodium Oxychloride Solid-State Electrolyte for Sodium-Ion Batteries
Authors: Ly Karen , Zheng Fan , Smirnova Alevtina 
Published: September 2023

Sodium-ion batteries have attracted significant attention by offering an alternative option to lithium-ion batteries. Solid-state sodium oxyhalides (Na3OX, X = Cl, Br, I) have the advantage of cost-effective synthesis from raw materials in a time-effective manner. In this study, sodium oxychloride (Na3OCl) antiperovskite was synthesized using a novel approach that allowed for facile synthesis outside of an argon glovebox. The ionic conductivity of Na3OCl pellets compressed between graphite-coated copper foil was tested in the temperature range of 160˚C and 200˚C using electrochemical impedance spectroscopy (EIS). Arrhenius plots demonstrated linear behavior in the whole temperature range with a calculated activation energy of 0.98 eV. At lower temperatures, EIS data was not available likely due to high impedance from the thickness of the electrolyte pellet, high activation energy, or slow migration of sodium ions through the Na3OCl structure. To decrease electrolyte thickness, we implement physical vapor deposition (PVD) thermal evaporation to coat thin films (<100 µm) of the electrolyte onto graphite-coated copper foil and sodium-based cathodes for use in symmetric cell and half-cell configurations. The melting and crystallization temperatures were determined using differential scanning calorimetry (DSC). The purity of as-synthesized sodium oxychloride and PVD-deposited layer was evaluated using X-ray diffraction (XRD). The results on chemical composition and crystal-to-glass phase transformations are produced from in-situ X-ray diffraction (XRD) spectroscopy in the temperature range from 25˚C up to the melting point of Na3OCl. Cross-sectional SEM images of PVD-deposited sodium oxychloride showed an even distribution of sodium, oxygen, and chlorine. However, XRD analysis of deposited layers showed that sodium oxychloride had a tendency to decompose into the precursors during deposition. This work is focused on maintaining the sodium oxychloride composition and structure during PVD thermal evaporation by optimizing the PVD deposition parameters.
The authors acknowledge financial support from the NSF IUCRC program for the “Center for solid-state electric power storage” (#2052631) and support from the South Dakota Board of Regents for the “Governor’s Research Center (GRC) for electrochemical energy storage”.
Li-S Solid State Pouch Cell with Flexible SSE
Authors: Zhang Xiaoxiao , Qu Huainan , Qiu Dantong , Ding Tianyao , Liu Miao , Zheng Dong , Qu Deyang 
Published: September 2023

An all-solid-state Li battery (ASSLB) is believed to be one of the most promising candidates to achieve high energy density of 500 Wh kg–1.After extensive exploration, several sulfide solid electrolytes have been synthesized with ionic conductivities in the order of 10–3 S cm–1 or even higher[1, 2]. With the successful development of various SSE materials, the major obstacle remaining is to demonstrate high energy density at a cell or battery level. Pelleting, dry processing, slurry coating, extrusion, and embedding into template have been explored for the manufacture of an SSE[3]. Despite the high energy density at the material-level and the electrode-level, the cell-level energy density of pellet format was still rather unsatisfactory (<50 Wh kg-1), which was mainly due to the thick SSE pellet (0.5–1 mm). Besides, the pelletizing process itself can only be limited to lab-scale research due to its high cost and poor practicability.
To boost cell-level energy density and render the mass production feasible, sheet-type cells with a thin SSE and a thick cathode have been recognized as a “must-develop” technology within the battery community. Dry processing of SSE and electrode was developed using sulfur carbon as the cathode and sulfide Li6PS5Cl as the electrolyte. A small amount of PTFE (0.75% in SSE and 1% in cathode) was applied as the binder. After grinding and rolling at 80 oC, the sheet-type cathode (2*3.5 cm2) and SSE (2.4*3.9 cm2) with respective thickness of 90 and 200 um were obtained. With LiIn alloy as the anode, the pouch cell delivered a discharge capacity of 1200 mAh g–1 at 0.05C after the first cycle activation at 60 oC. The results indicated the feasibility of dry processing technology to fabricate sheet-type SSE and electrode.
Figure 1. Voltage curves of the pouch cell during the first three cycles tested at 0.05C at 60 oC.
(1) Kato, Y.; Hori, S.; Saito, T.; Suzuki, K.; Hirayama, M.; Mitsui, A.; Yonemura, M.; Iba, H.; Kanno, R. High-Power All-Solid-State Batteries Using Sulfide Superionic Conductors. Nat. Energy
2016, 1, 1–7.
(2) Kamaya, N.; Homma, K.; Yamakawa, Y.; Hirayama, M.; Kanno, R.; Yonemura, M.; Kamiyama, T.; Kato, Y.; Hama, S.; Kawamoto, K.; Mitsui, A. A Lithium Superionic Conductor. Nat. Mater.
2011, 10, 682–686.
(3) Emley, B.; Liang, Y.; Chen, R.; Wu, C.; Pan, M.; Fan, Z.; Yao, Y. On the Quality of Tape-Cast Thin Films of Sulfide Electrolytes for Solid-State Batteries. Mater. Today Phys.
2021, 18. 100397.

Figure 1
Effect of Surface Nature on Stripping of in Situ li Anodes and Enhancement of Its Stripping Capacity
Authors: Lee Kiwoong , Sakamoto Jeff 
Published: September 2023

Li-metal solid-state batteries (LMSSBs) have been considered disruptive technologies for the widespread adoption of EVs due to their improved safety and higher energy density. Recently, in situ Li anode formation on solid-electrolytes (SEs) has garnered interest owing to its low manufacturing cost, high purity, and enhanced energy density. Thus, there have been intense efforts to understand the mechano-electrochemical properties of in situ Li anodes. Our previous work has demonstrated that the accessible capacity of in situ thin Li decreases as current density increases. This result indicates that more Li will remain inaccessible as the stripping rate increases, leading to the reduced energy density of LMSSB cells. To minimize the amount of inaccessible Li at high stripping rates, it is essential to investigate the factors affecting the stripping capacities of in situ Li and devise a new way to achieve enhanced stripping capacities at high stripping rates.
First, this study focuses to understand the correlation between the stripping capacity of in situ thin Li and the nature of the surface. This study demonstrates that the nature of the surface can dramatically affect the stripping capacity. When discharging at room temperature and 3 mA/cm2, approximately 50% of the accessible capacity of in situ plated Li was achieved.
Furthermore, this study demonstrates that stripping Li under conditions that more closely resemble an EV duty cycle improves the accessible capacities at high stripping rates. By introducing short intermittent rest periods during stripping, the Li/LLZO interface can be relaxed as Li vacancies at the interface can be moved away, preventing voids to forms. Also, even if voids form at the interface, the growth of voids can be delayed because of rewetting mechanisms during the rest periods.
This study is expected to not only provide insight into the stripping properties of in situ Li, but also suggest future guidelines for the practical discharge protocols of anode-free LMSSBs with commercially-relevant discharge rates.
(Invited) Ion Transport and Interface Resistance in Polymer-Based Composite Electrolytes and Composite Cathode
Authors: Chen Xi 
Published: September 2023

Solid-state electrolytes are promising to enable the next generation batteries with higher energy density and improved safety. However, each major class of solid electrolytes has intrinsic weaknesses. By combining different classes of solid electrolytes, such as a polymer electrolyte and an oxide ceramic electrolyte, one can potentially overcome the intrinsic weaknesses of each component and develop a composite electrolyte to achieve high ionic conductivity, good mechanical properties, good chemical stability, and adhesion with the electrodes.
In this presentation, we show that the interfacial resistance strongly affects the ionic conductivity of polymer/oxide ceramic composite electrolytes, in both the ceramic-in-polymer design where ceramic particles are dispersed within the polymer electrolyte matrix as well as the polymer-in-ceramic design where a three dimensionally interconnected ceramic scaffold is developed. The quantification of the interfacial resistance, the origin of this resistance, as well as the strategies to minimize it are discussed.
In a second case, we examine the effect of interfaces on ion transport in a polymer based composite cathode consisting of LiFePO4 (LFP), carbon and poly(ethylene oxide) (PEO) with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The structure and dynamics of PEO and lithium ion mobility are studied by small angle neutron scattering and quasi-elastic neutron scattering. The results show that Li ion mobility in PEO/LiTFSI in the composite cathode is only 30% of the bulk electrolyte. This suggests a key bottleneck that limits the rate performance of polymer-based solid-state batteries originates from the sluggish ion transport in the polymer electrolyte confined in the cathode.
Succinonitrile-Lithium Salt Composite As a Solid Catholyte for Llzo-Based All-Solid-State Batteries
Authors: Go Wooseok , Tucker Mike C , Doeff Marca M. 
Published: September 2023

All-solid-state batteries (ASSB) have come into the spotlight as next-generation batteries because of their potential high energy density and low flammability. LLZO (Li7La3Zr2O12) is a prominent solid electrolyte material for ASSBs due to its high ionic conductivity (>1 x 10-4 S/cm at room temperature) and compatibility with Li metal. However, for its use in ASSBs, there are challenges including forming intimate contact with the active electrode material. Because both LLZO and the cathode active material are rigid, employing a soft solid catholyte between them can be a solution to ensure intimate contact. The solid catholyte must be ionically conductive, and stable against oxidation (> 4.5 V vs. Li/Li+).
Organic Ionic Plastic Crystals (OIPC) are a class of materials that is soft and waxy at room temperature. When the OIPC is mixed with Li salts, the mixture has high ionic conductivity and a wide electrochemical window. Succinonitrile (SN) is an OIPC material, and SN with Li salts are reported to have high ionic conductivities (> 1x10-4 S/cm), good oxidation stability (>5 V vs. Li/Li+), and low flammability as well [1][2]. Despite the favorable properties of the SN-Li salt composite, poor chemical stability with Li metal makes it difficult to use it alone as a solid electrolyte [1]. For its use as a solid catholyte, chemical stability with Li metal is not an issue, making it a prominent candidate material. However, studies for its use as a solid catholyte with LLZO are limited.
In this talk, we describe the properties of Succinonitrile-Lithium salt composites focusing on their suitability as solid catholytes in LLZO-based ASSBs. SN is mixed with different kinds of Li salts including LiTFSI and LiBOB to form composites. Their electrochemical properties are compared and the contact between the composite and LLZO is observed. The performance of all-solid-state cells with the mixtures will also be evaluated at room temperature. It is hoped that this work can motivate efforts toward developing LLZO cells using OIPC materials.
[1] Alarco P.J, et al Nat. Mater., 3, 476 (2004)
[2] Effat M.B, et al J. Power Sources, 226802, 436 (2019)