bluuebunny/crossref_metadata_2025 huggingface dataset:
(Invited) Achieving Stable Interfacial Reactions in Sodium Batteries through Electrolyte Engineering
Authors: LE Phung M-L , Jin Yan , Vo Thanh D , Tran Nhan , Xu Yaobin , Xiao Biwei , Engelhard Mark H. , Wang Chongmin , Zhang Ji-Guang
Published: September 2023

Cost and lithium supply issues supply are compelling reasons to consider sodium batteries as potential alternatives to the better-known lithium-ion analogs for large-scale applications, including vehicles. Sodium-ion batteries have been the most highly developed system, with some commercialized systems demonstrate practical energy levels exceeding those of Li-ion batteries with LiFePO4. Further improvement in energy densities requires the development of new high-performance electrode materials (cathode/anode) and compatible electrolytes to achieve milestones in cycle life. In this work, we report the electrolyte engineering basically focusing on the electrolyte formulation (salt/additive selection), solvation structure of the electrolyte, and tuning on SEI/CEI composition. Our strategies thus enable high energy density of Na-metal and Na-ion batteries with remarkable cycle life. The presented insights differ from a prevailing stabilizing interfacial reaction that can be achieved by tuning SEI/CEI composition and providing a guiding principle in electrolyte design for sodium batteries.
Role of Conducting Polymer in Aqueous Zinc Ion Batteries
Authors: Lee Sseunggyeong , Hyeonseo Lee , Hwang Jang-Yeon , Kim Jaekook
Published: September 2023

Owing to high safety and low cost, aqueous rechargeable zinc-ion batteries (ZIBs) is currently a major research topic. In this study, we propose the microwave-assisted hydrothermal synthesis of polypyrrole (PPy)-coated Na1.1V3O7.9 (P-NVO) nanorods for the first time as a highenergy and high-power cathode material for ZIBs. The highly conductive PPy surface-coating layer is significant to enhance the electronic conductivity and Zn2+ diffusion kinetics, leading to utilize the V3+/V4+/V5+ multiple redox reactions of the NVO cathode in ZIBs. Compared to the NVO cathode, therefore, the P-NVO cathode offers higher discharge capacity, power capability and cycling stability; in particular, PPy coating triggers the full theoretical capacity of the NVO cathode (527 mAh g-
1 with ~ 3 mol Zn insertion per formula unit) and directly reflects a superior energy density of 408 Wh kg-1. Even at a high current density of 6000 mA g-
1, the P-NVO cathode sustains 1000 cycles with almost 100% capacity retention. Galvanostatic intermittent titration technique, cyclic voltammetry, in situ X-ray diffraction, and ex situ X-ray absorption near edge structure analyses are combined to verify the superior Zn2+ storage mechanism of the P-NVO cathode.
(Invited) Interaction and Transformation of Defects during Sodium-Ion Intercalation
Authors: Singer Andrej
Published: September 2023

Non-equilibrium defects often dictate macroscopic functional properties of materials. In energy materials, dislocations and planar defects significantly modify reversibility and kinetics. Nevertheless, transient imperfections briefly appearing during ionic transport have been challenging to capture, limiting understanding of their life cycle and impact. I will present our recent operando x-ray diffraction, x-ray nanoimaging, and resonant x-ray scattering results in sodium-ion intercalation compounds. Three-dimensional coherent x-ray imaging reveals the transformation and self-healing of a metastable domain boundary, glissile dislocation loop, and stacking faults. I will also discuss structure-selective x-ray spectroscopy, which allows us to link the long-range order with redox reactions in layered oxides during intercalation. The presence of high dimensional defects in energy materials observed with operando nanoimaging suggest their abundance and highlights the importance of defect engineering for developing next-generation energy solutions.
(Invited) Investigation of Dynamic Processes within Zinc Aqueous Electrolyte Batteries: In-Situ and Operando Methods
Authors: Takeuchi Esther S. , Marschilok Amy C. , Takeuchi Kenneth J.
Published: September 2023

Emerging new applications such as large-scale storage coupled with intermittent renewable energy generation such as wind and solar demand expanded battery function. However, in beyond lithium batteries full understanding of many processes, including complex phase transitions of electroactive materials, the kinetics of ion transport, and electrode-electrolyte interfacial reactions, remain elusive. Of particular note are systems that contain aqueous electrolytes where multiple charge carriers need to be considered including the possible participation of proton or hydronium ions.

This presentation will explore operando methods and their relevance to zinc anode batteries. Diffraction remains a valuable technique for the characterization of active material evolution as a function of charge and discharge. Further, the use of spectroscopic methods such as x-ray absorption spectroscopy that are not dependent on long range order to obtain useful information are valuable for systems involving poorly crystalline or amorphous materials. Thus, the use of x-ray diffraction, x-ray absorption spectroscopy, and x-ray microfluorescence mapping in relationship to aqueous electrolyte zinc anode systems will be featured.
(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).
"Neutral-Ph" Aqueous Zinc Ion Battery for Utility Energy Storage
Authors: Kong Fantai , Pimentel Nestor , Alvarez Denyce , Chavarria Carissa
Published: September 2023

Solar and wind are the key to meet US National Academies requirement of replacing fossil fuel by renewable energy sources: 30% in 2030 and 50% in 2040. While the intermittent and seasonal nature of solar/wind energy generation will require unusually large-scale energy storage capacity for wide durations of 4-10 hours or longer. As today’s dominant grid energy storage technology, Li ion battery has high energy density and long durability but fire hazards and supply chain concerns. For the utility-scale energy storage applications, fundamentally different electrochemistry with intrinsic safety is required based on earth-abundant elements (e.g., Na, K, Zn, Mg, Ca, Al, Fe, Mn) to avoid the competing demands of LIBs for mobile and EV battery applications. Among emerging beyond LIB chemistries, aqueous zinc ion battery (AZIB) utilizing Zn, Mn, close to neutral-PH aqueous electrolyte is a promising candidate due to raw materials abundance, low cost, nonflammability, low corrosion, high durability, etc. Even though water stability leads to lower operating voltage of AZIB than LIB (1.7 V vs. 4 V), the overall theoretical energy densities are comparable to high ends of LIBs (300 Wh/kg and 500 Wh/L). With further research and development for performance improvements, neutral-PH AZIB could be a very competitive solution for utility energy storage. In this presentation, we show recent efforts from Hunt Energy Enterprises (HEE) to commercialize this class of AZIB system. With the optimized electrolyte control, the system reveals high potential to achieve durability for at least 5,000 cycles under practical current rate. The fundamental and development challenges for this system will be discussed.
(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).
Surface-Engineered Zn-Based Alloys Anodes for Aqueous Zn Batteries
Authors: Yang Yang
Published: September 2023

Safety and durability concerns caused by surface and interface instabilities of high-surface-activity energy materials are challenging modern electrochemical energy conversion and storage systems. In this presentation, I will present our most recent representative works on the surface engineering of functional materials for aqueous batteries. In this work, we designed an in-situ visualized protocol that can exactly mimic the actual electrochemical environments used in aqueous batteries. Using this novel protocol, we observed the dynamic processes of metal plating/stripping on the alloys in aqueous batteries. Comprehensive and systematic studies based on experimental, theoretical, spectroscopic, and microscopic approaches prove that absolute reversibility can be achieved by using the proposed 3D alloys because of the significantly improved Zn diffusion and successfully suppressed dendrite growth. As a proof-of-concept, the novel alloy structures deliver unprecedented stability with nearly 100% Coulombic efficiency over thousands of cycles even under harsh electrochemical conditions, including testing in seawater-based aqueous electrolytes and using a high current density of 80 mA cm-2.
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.
Engineering Routes Towards Practical Sodium-Ion Batteries: Case Studies from Oxides to Polyanion Compounds
Authors: Li Mengya
Published: September 2023

Benefiting from the substantial knowledge accumulated on lithium-ion batteries, tremendous progress rapidly occurred with focus on solving the fundamental issues encountered at the component, system and cost levels in sodium-ion batteries. Of particular interest, P2-type layered oxide, Na2/3Fe1/2Mn1/2O2, has been researched as a potential cathode in SIBs based on its high theoretical capacity of 260 mA h/g and use of noncritical materials. Firstly, we reported a novel synthesis route using low-temperature eutectic reaction to produce highly homogeneous, crystalline, and impurity-free P2-type Na2/3Fe1/2Mn1/2O2 materials. We further synthesized Na
x
NiyMn1-yO2 cathodes with the same eutectic method and investigated the gassing properties of pouch cells when being charged to higher voltages. Even with gained knowledge of how to engineer layered oxide cathodes, the compromised electrochemical performances and associated safety risks at high voltage still hinder their high-energy applications. In contrast, polyanion cathode stands out as a great candidate due to its high nominal voltage and stability in ambient environment. However, pristine Na3V2(PO4)3 often exhibits reversible capacities of around 100 mAh/g for long term cycling, which is still 20% below the theoretical values. To tackle this issue, transition metal (Fe, Mn, Ni) and fluorine ion were introduced as doping elements to improve the specific capacity and cycling stability of polyanion cathodes. Advanced characterization results provided insights in the charge compensation mechanism of these cathodes. Stable electrochemical performances were demonstrated in multiple cell configurations. It is thus believed that these polyanion cathodes are promising for the next generation practical sodium-ion batteries.
High‐Capacity and Stable Sodium‐Sulfur Battery Enabled by Novel Molybdenum Carbide Electrocatalyst and Carbon Nanoporosity
Authors: Hao Hongchang , Mitlin David
Published: September 2023

Room-temperature sodium - sulfur (RT Na-S) batteries are highly promising due to the favorable techno-economics and the greater availability of both sodium and sulfur. RT Na-S cells are held back by several primary challenges including dissolution of polysulfides species in liquid electrolytes, sluggish sulfur redox kinetics, as well as the large cathode volume expansion (170%) on cell discharge. Here, we develop a novel molybdenum carbide (MoC/Mo2C) electrocatalyst to promote Na-S reaction kinetics and extend batteries’ cycling lifetime. MoC/Mo2C nanoparticles is in-situ grown in conjunction with activation of nitrogen-doped hollow porous carbon nanotubes. Sulfur impregnation (50wt.% S) results in unique triphasic architecture termed MoC/Mo2C@PCNT-S. MoC/Mo2C electrocatalyst and carbon nanoporosity synergistically promote the sulfur utilization in carbonate electrolyte. In-situ time-resolved Raman, XPS and optical analysis demonstrate a quasi-solid-state phase transformation within MoC/Mo2C@PCNT-S, where minimal polysulfides are dissolved in electrolyte. As results, MoC/Mo2C@PCNT-S cathodes performed promising rate performance of 987 mAh g-1 at 1 A g-1, 818 mAh g-1 at 3 A g-1, and 621 mAh g-1 at 5 A g-1. The cells delivered a retained capacity of 650 mAh g-1 after 1000 cycles at 1.5 A g-1, which corresponds to only 0.028% capacity decay per cycle. Such promising cycling stability is also obtained for high mass loading cathodes (64wt.% S, 12.7 mg cm-2). Complementary Density Functional Theory (DFT) simulation provide fundamental insight regarding the electrocatalytic role of MoC/Mo2C nanoparticles. Favorable charge transfer between the sulfur and Mo sites on the surface of carbides contributes to a strong binding of Na2Sx (1 ≤ x ≤ 4) on MoC/Mo2C surfaces. Consequently, the formation energy of Na2Sx (1 ≤ x ≤ 4) on MoC/Mo2C is significantly lowered compared to the analogous redox in liquid, as well as the case of baseline ordered carbon.
Performance of Several Excellent Oxide-Based Intercalation Cathodes for Aqueous Zn-Ion Batteries
Authors: Huang Kevin
Published: September 2023

Aqueous Zn-ion batteries (ZIBs) have garnered significant interest in recent years due to their advantages in safety, cost, and energy density, which make them suitable for large-scale stationary energy storage. Cathode materials have been a primary research focus in the early stage of ZIBs development since they are widely deemed a limiting factor to the performance. In general, good ZIB cathode materials are found in oxides with layered and open framework structures, and inorganic/organic hybrids, and follow mechanisms of “intercalation”, “conversion” or a combination of both to store Zn2+ and H+ during discharge. However, dissolution of these cathodes into aqueous electrolytes has been a major cause of the performance degradation of aqueous ZIBs. In this presentation, we first show our fundamental understanding of cathode dissolution mechanisms and development of engineering solutions to address the dissolution and instability issues. We then show through several examples how specially engineered V-oxides based cathodes achieve better dissolution resistance and performance stability using aqueous Zn(OTf)2 and ZnSO4 electrolytes as examples. We expect that the insights in this presentation will advance the understanding of dissolution mechanisms and provide design principles for better cathode materials.
De/Protonation Associated Sustainable Conversion Reaction Applicable to High-Capacity Zinc Storage in Mildly Acidic Aqueous System
Authors: Kim Hee Jae , Jo Jae Hyeon , Kim Ji-Young , Jeong Jiwon , Park Jae-Ho , Jung Hun-Gi , Chung Kyung Yoon , Kim Min Gyu , Lee Naesung , Sohn Kee-Sun , Aniskevich Yauhen , Streltsov Eugene , Myung Seung-Taek
Published: September 2023

We introduce an unexpected finding of the de/protonation associated conversion reaction occurred in K2V3O8 as a promising cathode material for zinc-ion batteries. The structure undergoes a conversion reaction between amorphous V5+
2O5 and V3+OOH upon cycling when a cut-off voltage up to 1.9 V is applied. A combination of operando X-ray diffraction, in situ Raman spectroscopy, X-ray photoelectron spectroscopy, time-of-flight secondary-ion mass spectroscopy, and operando pH measurement analyses reveal that the reaction of the proton (H+) is indispensable for progression of the conversion reaction. The conversion reaction results in a large reversible capacity of 362 mAh g−1 (~97 % of theoretical capacity) at 0.1 C (37 mA g−1) on discharge and an activity even at a rate of 7 C (187 mAh g−1), with the two-electron reaction by the V5+/3+ redox pair evidenced by operando X-ray absorption spectroscopy analysis. These findings underscore the importance of conversion reversibility associated with the proton reaction for a high cut-off voltage, contributing additional capacity to reach the theoretical capacity for cathode materials of zinc-ion batteries in mildly acidic aqueous systems.
Electrodeposited Copper Oxide Cathode for Enhanced Flexible Zn Ion Batteries
Authors: Wang Peng , Andrei Petru
Published: September 2023

Zinc ion batteries (ZIBs) have attracted much interest in large-scale energy storage technologies due to their low cost, intrinsic safety, environment-friendly and high energy density, becoming among the most commercialized secondary batteries after lithium ion batteries. To acquire high energy density, various cathode materials with high specific capacity have been developed, such as Prussian blue analogs, polyanionic compounds, Co, Mn and V-based oxides. Herein, we developed a type of copper oxide on flexible current collectors using an efficient electrodeposition method. The loading of the active materials could be easily controlled by the electrodeposition parameters, such as time, current and voltage. The electrodeposited cathode shows superior specific capacity compared the one synthesized by conventional methods due to the unique morphology, more electrochemical active sites, and better binding with current collector. In addition, the cathode exhibited good flexibility when electrodeposited on a flexible current collector such as graphene, carbon nanotube film, or titanium foam and can be used to build flexible ZIBs. When used in a full cell with Zn metal as anode and a hydrogel electrolyte, the batteries show excellent capacity, rate performance and cycling stability that will be discussed at the conference.
(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
Sodium Intermetallics Enable Stable Sodium Plating and Stripping
Authors: Wang Yixian , Mitlin David
Published: September 2023

Sodium-based secondary batteries are emerging as promising complements and potential alternatives to lithium-ion batteries due to their analogous working mechanism but the greater availability of sodium precursors and the other elements making up the cathodes. Sodium metal batteries (SMBs) hold considerable promise due to the high theoretical capacity (1165 mAh g-1) of the metal anode and the associated low plating/stripping potential. Unfortunately, the metal dendrite growth and an associated unstable solid electrolyte interphase (SEI) prevail with SMBs in a wide range of electrolytes. Creating sodiophilic surfaces to promote metal wetting during deposition and simultaneously reduce the nucleation/growth overpotentials has been proven to be highly effective. In this work, a rapid annealing process is employed to fabricate chalcogen (sulfur, tellurium) intermetallic coated commercial copper foam (CF) as stable hosts for Na metal anodes, termed “S@CF” and “Te@CF”. These sodiophilic substrates demonstrate significantly improved sodium wettability, reduced plating/stripping overpotentials, and Coulombic efficiency (CE) in half-cell configurations. Symmetric cells made of Te@CF with thermally infused Na (Te@CF-TNa) showed stable cycling up to 7000 hours and full cells with Te@CF-TNa anodes and Na3V2(PO4)3 (NVP) cathodes give significantly improved rate capability (up to 30C) and cycling (>10000 cycles at 5C and 10C). Moreover, a prototype of a controllable Na thermal infusion process was proposed for the first time. Post-mortem analysis using cryogenic FIB-SEM (Cryo-EM) indicates that the early-stage electrodeposition behavior plays an important role in dictating the later-state electrochemical stability of the metal anodes. Sodium metal electrodeposits uniformly on the surface of Te@CF, resulting in dense and largely pore-free metal. By contrast, electrodeposition on the baseline uncoated CF collector results in filament-like sodium metal dendrites interspersed with pores and a solid electrolyte interphase (SEI). Density functional theory (DFT) and mesoscale calculations provide combined insights into the relationship between the substrate-metal interaction and the nucleation response, describing the underlying mechanisms that tailor an improved Na deposition morphology on the Te@CF substrate.
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,
Electrolyte Design for Intermediate-Temperature Na-S Batteries with High Energy Density
Authors: Tian Liying , Yang Zhenghao , Yang Yuan
Published: September 2023

The conventional high-temperature sodium sulfur battery is an attractive technology for grid-level energy storage due to its low cost, high energy density and long cycle life. However, this system operates at 300-350 oC, which not only increases cost, but also accelerates degradation and causes potential safety issues. On the other side, Na-S batteries working at intermediate temperatures (e.g., 100-150 oC) have a much worse kinetics due to the formation of solid Na2S2 and Na2S with low ionic diffusivity and electronic conductivity. In this study, we have developed a new electrolyte solvent that can dissolve all sulfides and polysulfides, which avoids the poor kinetics in Na2S2 and Na2S, and allows Na-S batteries to operate at ~75 oC. Based on the 1 molL−1 sulfur catholyte, a high specific capacity of 1640 mAhg−1 is achieved at 0.13 mAcm−2. When increased to the 4 molL−1, the capacity is achieved 830 mAhg−1 and decays only 0.029%/cycle over 250 cycles at 1 mAcm−2. Such a system has potential applications for long-duration energy storage.
Computational Studies of the Effect of Nitrogen Dopants and Oxygen Vacancies on Li+ Conduction in Lithium Lanthanum Titanate Electrolytes
Authors: Wang Jiacheng , Tay Kieran , Wu Nianqiang , Bai Peng
Published: September 2023

Our recent experiments have shown that nitrogen doping can effectively improve the ionic conductivity of lithium lanthanum titanate (LLTO) electrolytes. Herein, computational studies are performed to study the mechanisms of ionic conductivity with density-functional theory and machine learning approaches. To elucidate the relationship between nitrogen concentration and oxygen vacancy, the energy for nitrogen doping into the lattice and the formation energy for oxygen vacancy were computed. Oxygen vacancies were found more likely to be created at higher level of nitrogen dopants. The calculations also discovered the potential formation of nitrogen bonds, generating vacancy-like pathways for Li+ conduction. In addition, the minimum-energy pathways for Li+ migration in pristine and various doped LLTO materials were analyzed using the nudged-elastic band method. To correlate energetics and structural features of the different LLTO materials, several machine learning methods were successfully constructed, where the neighboring sites with oxygen vacancies are identified as the major factor influencing the energies and hopping barriers compared with nitrogen dopants. The new insights can guide the design and synthesis of anion dopped oxide electrolytes in solid-state lithium-ion batteries.
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.
(Invited) Achieving High Areal Capacity and Extreme Critical Current Densities through Tailored Garnet Solid Electrolyte Structures
Authors: Alexander George , Wachsman Eric
Published: September 2023

Garnet structured electrolytes are an exceptional candidate to substitute for organic liquid electrolytes owing to its high ionic conductivity and safety.[1] One of the main issues preventing the commercialization of this electrolyte is limited lithium plating capacity and lithium dendrite shorting.[2] To address this, we invented new single-phase mixed ion electron conducting (MIEC) garnet with comparable lithium-ion and electron conductivity at room temperature. We demonstrate that in a trilayer architecture, with a porous MIEC framework supporting a thin dense garnet solid electrolyte, the critical current density can be as high as 100 mA/cm2, with no dendrite-induced shorting at room temperature and without any stack pressure. The single-phase MIEC conductor spreads the potential uniformly across the material surface preventing dendrite propagation through the dense garnet solid electrolyte layer. Additionally, high lithium stripping capacity and impressive cycling stability were observed at commercial level current densities of well over 10 mA/cm2. The role of the porous MIEC garnet structure is elucidated using various electrochemical and electron microscopy techniques.

Wang, C. et al. Garnet-Type Solid-State Electrolytes: Materials, Interfaces, and Batteries. Chem. Rev.
120, 4257–4300 (2020).

Albertus, P., Babinec, S., Litzelman, S. & Newman, A. Status and challenges in enabling the lithium metal electrode for high-energy and low-cost rechargeable batteries. Nat. Energy 2017 31
3, 16–21 (2017).