bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) A Brief History of Sodium-Ion Battery Research
Authors: Doeff Marca M. 
Published: September 2023

Interest in sodium-ion batteries (NIBs) has never been greater than it is now. This is in great part due to concerns about the sustainability and cost of energy storage devices based on lithium. Another advantage to sodium-ion systems is their similarity to lithium-ion batteries (LIBs); knowledge gained over the past few decades on the latter has been leveraged to rapidly develop the former. For this reason, sodium-ion batteries are the closest to commercialization of all the “Beyond Lithium-Ion Battery” chemistries. NIBs are particularly attractive for large-scale energy storage, but may also have a place in vehicular applications, particularly if vehicle-to-grid systems are considered.
Intercalation of sodium into host structures such as TiS2 was described as early as 1978.[1] A few attempts at making “rocking chair” batteries based on sodium followed a few years later, including one using Na0.7CoO2 as the positive electrode and a sodium-lead alloy as the negative.[2] In 1993, the first NIB using a disordered carbon anode was described.[3] Although performance was poor by today’s standards, it set the stage for further work in the area. However, research on NIBs languished for several decades after this while the battery community largely turned its attention to the newly commercialized Li-ion systems. It was not until the early 2010s that interest picked up again, as LIBs matured and concerns about lithium supply security heightened.
This talk will cover the history of sodium-ion battery research, including the speaker’s early contributions to the field, as well as her more recent work on titanate anodes. An overview of the advantages and possible applications of NIBs will be included.

[1] M. S. Whittingham, Prog. Solid State Chem. 12 , 41 (1978).

[2] L. W. Shacklette, T.R. Jow, and L. Townsend, J. Electrochem. Soc. 135, 2669 (1988).

[3] M. M. Doeff, Y. Ma, S.J. Visco and L.C. De Jonghe, J. Electrochem. Soc. 140, L169 (1993).
(Invited) Architected Zinc Anodes Enable Next-Generation Aqueous Rechargeable Batteries
Authors: Long Jeffrey W. , DeBlock Ryan H. , Chervin Christopher N. , Parker Joseph F. , Rolison Debra R. 
Published: September 2023

Zinc-based batteries offer the compelling benefits of a high-capacity, abundant anode material and the use of aqueous electrolytes for ease of assembly and safe operation. To solve the standing roadblock to rechargeable zinc-based batteries—shape change and dendrite formation under demanding cycling conditions—we adapt lessons of 3D electrode design from our prior breakthroughs with energy-storing nanoarchitectures. Zinc “sponge” form factors are fabricated by fusing 50–100 mm zinc particles into a porous, monolithic structure. Electrochemical reaction fronts are distributed throughout these 3D-wired zinc architectures, effectively thwarting dendrite formation and homogeneously distributing reaction products, even at high current density [1,2]. Over the development course of the NRL Zn sponge anode, each successive generation has been further optimized with manufacturability as a foremost consideration, such that the current sponge formulation is readily and simply processed at increasing scale to sizes necessary for relevant energy-storage applications. Zinc sponges are evaluated in multiple battery configurations including zinc–air, nickel–zinc, and silver–zinc to validate such performance characteristics as cycle life and specific power. We are also expanding 3D architecture concepts to other metals of relevance for battery applications.
[1] J.F. Parker, C.N. Chervin, E.S. Nelson, D.R. Rolison, J.W. Long, “Wiring zinc in three dimensions re-writes battery performance―Dendrite-free cycling.” Energy Environ. Sci., 7, 1117–1124 (2014).
[2] J.F. Parker, C.N. Chervin, I.R. Pala, M. Machler, M.F. Burz, J.W. Long, and D.R. Rolison, “Rechargeable nickel–3D zinc batteries: An energy-dense, safer alternative to lithium-ion.” Science, 356, 415–418 (2017).
An Ion Exchange Membrane-Free, Ultrastable Zinc-Iodine Battery Enabled by Functionalized Graphene Electrodes
Authors: Dang Hoang , Sellathurai Andrew J , Barz Dominik PJ 
Published: September 2023

Global warming requires a shift in the energy economy towards renewable energy sources, such as solar and wind energy, to meet the ever-increasing worldwide energy demand while having lesser negative impact on the environment. The integration of such sustainable energy resources into the existing infrastructure, however, is challenging due to their fluctuations and intermittences requiring the development of efficient (intermediate) energy storage systems. The ultimate goal for these systems pertains to high performance, durability, safety, facile scalability, cost, and environmental-friendliness. The aqueous rechargeable zinc-iodine (Zn-I2) battery is promising due to the high theoretical capacities of Zn (820 mAh gZn
-1) and I2 (211 mA h gI2
-1) along with the very high solubilities in aqueous media. Other advantages include the abundance of the electrode materials and the safety of the aqueous electrolyte. The high energy density of aqueous zinc-based batteries is a result of the multi-electron redox reactions and the low electrochemical potential of Zn (-0.763 V vs. RHE) in mildly acidic electrolytes such as in a Zn-I2 battery. In addition, compared to other alkali metals such as lithium, sodium, and potassium, metallic Zn is relatively stable in an aqueous environment over a wide temperature range.
Several challenges need to be addressed for Zn-I2 batteries to be competitive; namely, self-discharge, sluggish kinetics, low practical energy density, as well as the dendrite formation on the Zn anode. In this work, we design a high-performance Zn-I2 battery with an unusual long-term stability which is based on a novel design of electrodes and electrolyte. In detail, a three-dimensional functionalized graphene cathode facilitates the iodide redox reactions and also immobilizes dissolved polyiodides; thus, suppressing the detrimental shuttling effect. Furthermore, we design a composite anode made of Zn coated with a film of reduced graphene oxide. This modification significantly enhances the performance and stabilizes the anode during repeated Zn stripping/plating preventing dendrite formation. The electrolyte is formulated in a way that, along with the graphene-based cathode, allows for the utilization of an economical glass fiber separator instead of the commonly employed ion-exchange membranes, which are expensive and have relatively high ohmic resistances. Our novel Zn-I2 battery design exhibit high current efficiencies of nearly 100%, along with stable specific capacities of 257, 186, 150, 84 mAh g-1 at corresponding current densities of 1, 2, 5, 10 A g-1. Furthermore, a long-term capacity retention of 96.7% at 5 A g-1 over 2000 cycles is achieved, outperforming most comparable aqueous batteries.
(Invited) Development of Layered NaMeO2 Materials for Na-Ion Batteries
Authors: Komaba Shinichi , Hosaka Tomooki , Tatara Ryoichi , Kubota Kei 
Published: September 2023

We first reported hard carbon//O3-NaNi1/2Mn1/2O2 full cell in 2011 [1] and have studied various layered oxides for Na-ion batteries for over a decade. [2, 3] Table 1 shows the variety of directly crystallizable oxides of A
x
MeO2 (A = Li, Na, and K) on 3d transition metal species. [3] Clearly, Na
x
MeO2 crystalizes with a wider variety of 3d transition metals without Na/Me cation-mixing unlike Li/Me due to the proper difference in ionic radii between Na+ and Me3+ ions. [3] The wide variety of 3d metals and crystal structures such as O3, P3, and P2 types including the distorted ones are found only in the Na system, unlike Li and K cases. Such structural variety gives us so wide selection of Na
x
MeO2 materials, which is highly attractive to develop high-performance positive electrodes. This talk will provide our strategies and insights into materials development based on our recent work on designing polymorphs and metal substitutions for Na
x
MeO2.
The correlation between crystal polymorphism and electrochemical properties was investigated in detail by studying a series of Na-Mn-O layered oxides, including distorted and undistorted P2-type Na2/3MnO2, [4, 5] α-NaMnO2, [6] and β-NaMnO2. [7] These results show strong correlations between the electrochemical performance and crystal structure and provide new insight into utilizing the MnIII/IV redox couple.
To maximize the energy density and cycle performance of the layered oxide materials, we studied O3-type Na2/3+x
[Ni1/3Mn2/3
−

x

−

y
Fe
x
Ti
y
]O2 (x = 1/6–1/3, y = 0–1/2), which can be regarded as solid solutions of Na2/3[Ni1/3Mn2/3]O2, Na2/3[Ni1/3Ti2/3]O2, and Na[Ni1/3Mn1/3Fe1/3]O2, as shown in the phase diagram of Figure 1. We synthesized 27 samples, which have O3-type structures in different compositions. Importantly, their electrode performance is significantly affected by the ratio of Na, Ni, Mn, Fe, and Ti in the materials, and we finally found the optimal material in the series of solid solutions is O3-type Na5/6[Ni1/3Mn1/6Fe1/6Ti1/3]O2. [2]
Based on the experimental data of more than 100 samples synthesized over the past decade, we developed machine-learning models to predict reversible capacity, operating potential, and cyclability using composition descriptors. Moreover, we experimentally validated the optimal compositions predicted by machine learning and demonstrated new promising O3-type materials.
[1] S. Komaba, W. Murata et al., Adv. Funct. Mater., 21, 3859 (2011).
[2] S. Komaba, Chem. Lett., 49, 1507–1516 (2020).
[3] K. Kubota, S. Komaba et al., Adv. Energy Mater., 8, 1703415 (2018).
[4] S. Kumakura, S. Komaba, Angew. Chem. Int. Ed., 128, 12952–12955 (2016).
[5] E. J. Kim, S. Komaba et al., ACS Appl. Energy Mater., 5, 12999–13010 (2022).
[6] K. Kubota, S. Komaba et al., J. Mater. Chem. A, 9, 26810–26819 (2021).
[7] M. Shishkin, S. Komaba, H. Sato et al., Chem. Mater., 30, 1257 (2018).

Figure 1
A Drive Towards Elemental Simplicity in Cathode Design by Controlling Grain Growth Behavior
Authors: Promi Anika Tabassum , Lin Feng 
Published: September 2023

Sodium-ion battery technologies are emerging as an alternative to lithium-ion batteries by utilizing the earth abundant, widely distributed, and low-cost sodium resources. Among different types of sodium ion cathodes, transition metal based layered oxide cathodes have a superior edge due to their comparatively higher energy density, lower cost, environment friendly raw materials, and similar synthesis chemistry as the already commercialized lithium-ion battery cathode materials. They also enable the incorporation of iron, an abundant, low-cost, and environmentally benign element, replacing the toxic and expensive cobalt.
In such layered oxide-based cathodes, transition metals exhibit heterogenous elemental and oxidation state distribution at different depths of the particles (e.g., from the surface to bulk) which can influence the stability, mechanical integrity, and electrochemical performance of these particles to a significant extent. The inherent local structural and electronic state heterogeneity developed in these materials during synthesis can modulate the charge distribution heterogeneity and consequent phase transitions during cycling, ultimately controlling the battery performance.
In this work, a sodium transition metal layered oxide cathode is synthesized using a co-precipitation method followed by high temperature calcination under different calcination durations. Calcining the material at different conditions lead to the formation of particles with different morphologies and grain growth behavior. Using electron microscopy and Xray diffraction techniques, the grain growth behavior at different stages of calcination is studied. This will guide the design of particles with better morphologies and grain orientation which demonstrate improved electrochemical performance. Transition metal distribution and oxidation state change at different depths of the particles are probed using synchrotron based Xray absorption spectroscopy and three-dimensional Transmission Xray microscopy. The particles are probed at the surface, subsurface and deep into the bulk, which show heterogeneity in the distribution of transition metal oxidation state and provide insight into the phase transitions during calcination. This study can pave the way for better understanding of phase evolution during synthesis and improved design of cathode particle morphology and composition by identifying and eliminating the detrimental phases occurring during different stages of calcination.
(Invited) Insights into the Effects of Doping on Structural Phase Evolution of Sodium Nickel Manganese Oxide Cathodes for High-Energy Sodium Ion Batteries
Authors: Omenya Fredrick , Li Xiaolin , Reed David 
Published: September 2023

High-performance and low-cost transition metal (TM) layered oxides using earth abundant elements are promising cathodes for Na-ion batteries. However, it is challenging to obtain desired materials because the large Na size, different Na occupations and various layer stacking sequences multiply the complication in determining the structure of a given composition and exacerbate uncertainty to the structure-property correlation. In this work, we use the attainment of desired NaxMnyNizTM1−y-zO2-based cathode materials as model compound to demonstrate a general roadmap for batch development of sodium layered cathodes towards practical applications. Several cost-effective O3 and P2/O3 hybrid cathode materials have been obtained, all of which demonstrate excellent performance.
Acknowledgement: This work is supported by the U.S. Department of Energy (DOE) Office of Electricity under contract No. 57558. PNNL is operated by Battelle Memorial Institute for the DOE under contract DE-AC05-76RL01830
Sustainable and Cost-Effective Bio-Waste-Derived Hard Carbon Synthesis for Sodium-Ion Batteries
Authors: Moon Hyein , Innocenti Alessandro , Zarrabeitia Maider , Passerini Stefano , Liu Huiting , Zhang Huang , Weil Marcel 
Published: September 2023

The commercialization of sodium-ion batteries (SIBs) is around the corner to support on electrification of various applications, especially focused on light electromobility and stationary applications. The anode of choice in SIBs is hard carbon (HC) following the success story of graphite anode in lithium-ion batteries. [1-4] One of the greatest advantages of HC is that the bio-waste precursor can be used, enhancing sustainability and provides cheap material price from its abundance. However, bio-waste HC often undergoes a strong acidic/basic pre-/post-treatment for removing impurities and increasing carbon yield but decreases initial Coulombic efficiency (ICE) and total sodium uptake in turn. [5,6]

We attempted to find a more sustainable solvent to replace the traditional method for such HCs. In this work, the morphology, microstructure, and electrochemical performance characteristics of hazelnut shells-derived HCs were investigated when processed in different pre-treatment agents (i.e., no pre-treatment, acid treatment, and water washing). [7] The results reveal that hazelnut shell derived-HCs produced via facile and sustainable water washing outperform those obtained via other processing methods in terms of ICE, capacity uptake and retention. Moreover, the applicability of the hazelnut shell-derived HC is demonstrated in a sodium-ion full-cell. Finally, the cost-ecological effectiveness of sustainably processed HC compared to acid processed one was investigated and confirmed by life cycle assessment (LCA) and cost analysis.
[1] CATL, “CATL Unveils Its Latest Breakthrough Technology by Releasing Its First Generation of Sodium-ion Batteries,” 2021.
[2] L. Cailloce, https://newscnrsfr/articles/a-battery-revolution-in-motion
2015.
[3] S. Kuze, J. Kageura, S. Matsimoto, T. Nakayama, M. Makidera, M. Saka, T. Yamaguchi, T. Yamamoto, K. Nakane, R&D Report
2013, 1–13.
[4] A. Rudola, A. J. R. Rennie, R. Heap, S. S. Meysami, A. Lowbridge, F. Mazzali, R. Sayers, C. J. Wright, J. Barker, Journal of Materials Chemistry A
2021, 9, 8279–8302.
[5] S. Ghosh, R. Santhosh, S. Jeniffer, V. Raghavan, G. Jacob, K. Nanaji, P. Kollu, S. K. Jeong, A. N. Grace, Sci. Rep.
2019, 9, 16315.
[6] K. L. Hong, L. Qie, R. Zeng, Z. Q. Yi, W. Zhang, D. Wang, W. Yin, C. Wu, Q. J. Fan, W. X. Zhang, Y. H. Huang, Journal of Materials Chemistry A
2014, 2, 12733–12738.
[7] H. Moon, A. Innocenti, H. Liu, H. Zhang, M. Weil, M. Zarrabeitia, S. Passerini, ChemSusChem
2022 DOI: 10.1002/cssc.202201713
Single-Ion Conducting Polymer Electrolytes for Sodium Batteries
Authors: Dong Xu , Steinle Dominik , Bresser Dominic 
Published: September 2023

Sodium-ion batteries have attracted extensive attention recently owing to the announcements of several companies to commercialize this technology in the (very) near future. Just like commercial lithium-ion batteries, though, these batteries are comprising and/or will comprise a liquid electrolyte – with all its advantages and challenges. Thinking one step ahead (as also done by a few companies already), the next step might be the transition to (“zero-excess”) sodium-metal batteries, which will require fundamentally new electrolyte solutions, and just like for lithium-metal batteries, these might be based, e.g., on polymers.
Herein, we present our latest results on single-ion conducting polymer electrolytes for sodium-metal batteries. These polymer electrolytes do not only show higher ionic conductivity than its lithium analogues (>2.5 mS cm-1 at 40 °C), but moreover the same beneficial properties in terms of high electrochemical stability towards oxidation, highly reversible sodium plating and stripping, and excellent cycling stability of Na‖Na3V2(PO4)3 cells for more than 500 cycles. The results thus show that single-ion conducting polymer electrolytes are very promising candidates for high-performance sodium batteries.
Screen Printed All-Solid-State Sodium-Ion Batteries Based on Hydroborates
Authors: Schwenzel Julian , Bardenhagen Ingo , Thomas Jan 
Published: September 2023

Sodium Ion batteries have high potential to create high performance batteries without scarce elements. However, the theoretical energy density of the liquid electrolyte system is only around half of that of a lithium-ion battery. This could be improved by application of a sodium metal anodes which seems to be possible only with solid electrolytes. An attractive solid electrolyte system are Hydroborates which shows excellent ionic conductivities over 1 mS/cm at room temperature with a electrochemical stability window of 0 – 3 V vs Na/Na+ thus, making them perfect for the usage of metallic sodium [1]. Moreover, they can easily be processed by dissolution and precipitation, which allows for advanced processing techniques. In this contribution, we are going to present the processing of all-solid-state SIBs based on hydrobrates via screen-printing. This technique is especially suited for producing customized cell sizes, while manufacturing the cells layer-by-layer. We will show the printing process of electrodes as well as separators and first morphological and electrochemical results for these components.
[1] L. Duchêne, A. Remhof, H. Hagemann, C. Battaglia, Energy Storage Materials, 25, 2020, 782-794,
Fabrication of Solid-State Li-S Battery Components for Electric Aviation
Authors: Dornbusch Donald , Viggiano Rocco P. , Lin Yi , Wu James , Connell John , Lvovich Vadim 
Published: September 2023

The development of high-energy, high-safety, and high-power batteries beyond electric automobile requirements is vital for future electric aviation applications. The transition to non-volatile solid-state electrolytes (SSE) promises many advantages over traditional flammable liquid electrolytes, and may also be an enabling technology for next generation chemistries. However, significant manufacturing challenges must be overcome before the adoption of such technology. Electrolytes developed in this study were produced as sulfide-polymer composites with densified thicknesses between 20-30 microns using several processing techniques [1]. Ionic conductivity and lithium metal compatibility for the composites were compared and shown to retain reasonable ionic conductivity with improved flexibility and scalability which identifies a critical path for the production of practical solid-state batteries. Films were produced 10-15 times thinner than comparable bulk cold pressed powder electrolytes and achieved thicknesses comparable to commercial polyolefin separators (25 micron) used in commercial liquid containing lithium-ion cells. Composite conductivities were maintained above 0.2mS/cm, which holds promise for future electric aviation applications. Processing techniques are investigated to further improve electrochemical performance.
[1] Donald A. Dornbusch, Rocco P. Viggiano, John W. Connell, Yi Lin, Vadim F. Lvovich. Practical considerations in designing solid state Li-S cells for electric aviation, Electrochimica Acta, 2021, 139406, ISSN 0013-4686, https://doi.org/10.1016/j.electacta.2021.139406.
Li3InCl6 Electrolyte with High Voltage Compatibility for All-Solid-State Batteries
Authors: Bahmani Farzaneh , Rodmyre Collin , Smirnova Alevtina 
Published: September 2023

Identifying a highly Li+ -conductive solid-state electrolyte (SSE) with good chemical and electrochemical stability is crucial for enabling safe, energy-dense all-solid-state lithium metal batteries. Lithium halide SSEs have come into the spotlight owing to high ionic conductivities (>10−3 S cm−1 at room temperature), excellent electrode interface stability, low-cost mass production, good compatibility with high-voltage electrodes, and wide electrochemical window. The study is focused on indium halides due to the high stability of InX6
3− (X = Cl or Br) octahedrons, flexibility with electrodes as well as electrochemical stability at high voltages.
Regarding LiNi0.8Co0.15Al0.05O2 (NCA) cathode, double doping with manganese and titanium provides improved electrochemical performance and decreased degradation during charge-discharge cycles. Furthermore, small amounts of dopants at the cationic sites increase the voltage range. We will study the role of metal (Mn, Ti) doping on NCA cathode and its electrochemical behavior in solid-state batteries.
The results regarding the assembled Mn- Ti doped NCA/ Li3InCl6/Li electrochemical cells will be presented in terms of their capacity, rate capability, and stability. This study opens new possibilities for using Li3InCl6 as a promising electrolyte with a high-voltage cathode for application in all-solid-state lithium-metal batteries.