bluuebunny/crossref_metadata_2025_split huggingface dataset:
A High-Voltage Potassium-Ion Battery with a Potassium Manganese Hexacyanoferrate Cathode
Authors: Wheeler Samuel , Fiore Michele , Hurlbutt Kevin , Capone Isaac , Fawdon Jack , Pasta Mauro 
Published: July 2021

Potassium-ion batteries (KIBs) are a promising complementary technology to lithium-ion batteries that have the potential to be more sustainable and lower in cost. In KIBs lithium is replaced with potassium, the copper current collector is replaced with aluminium, and cathodes can be cobalt and nickel free. KIBs have the crucial advantage over sodium-ion batteries that potassium can reversibly intercalate into graphite whilst sodium cannot. Graphite offers a low operating voltage, high capacity, and good rate performance as a potassium-ion anode material.
There remain significant scientific challenges in the development of commercial potassium-ion batteries, notably developing high-capacity high-voltage cathode materials and electrolytes that are compatible with high-voltage cathodes and graphite anodes. In a recent perspective we identified potassium manganese hexacyanoferrate (KMF) as the most promising cathode material as it offers high energy density whilst also being low in cost [1]. However, the cyclability and coulombic efficiency of KMF are typically poor owing to parasitic reactions from water remaining in its structure and aluminium current collector corrosion among other mechanisms.
Here we present recent work to improve the performance of the KMF//graphite electrochemical system. Firstly, the citrate-assisted synthesis of KMF is optimised using high throughput synthesis and characterisation techniques to reduce the defect and water content whilst tailoring the particle size [2]. Secondly, an ionic-liquid based electrolyte, 1 M KFSI in Pyr1,3FSI (potassium bis(fluorosulfonyl)imide in N-butyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide)), is employed. This electrolyte successfully forms a passivating layer on the KMF cathode and surpresses aluminium corrosion which enables highly efficient cycling. Additionally, graphite operates exceptionally well with this same ionic-liquid based electrolyte.
We will end by offering our perspective on the current state of this research area and promising research directions.
References:
[1] Dhir, S.; Wheeler, S.; Capone, I.; Pasta, M. Chem
2020, 6 (10), 2442–2460.
[2] Fiore, M.; Wheeler, S.; Hurlbutt, K.; Capone, I.; Fawdon, J.; Ruffo, R.; Pasta, M. Chem. Mater.
2020, 32 (18), 7653–7661.
“Mirror-like” Electrodeposition of Lithium Metal Under a Low-Resistance Artificial Solid Electrolyte Interphase Layer
Authors: Hu Fei , Li Zhuo , Wang Shaofei , Tenhaeff Wyatt 
Published: July 2021

Lithium metal is considered as the “holy grail” for next generation anode materials of energy storages. However, non-uniform electrodeposition of Li metal and dendritic growth result in low Coulombic efficiency and potential short circuits, leading to enormous capacity fading and safety issues. This is one of the key stumbling blocks to further development and commercialization of Li metal batteries. To suppress the dendritic deposition of Li metal, one strategy is to encapsulate the Li metal with an artificial solid electrolyte interface (ASEI) layer. The ideal artificial SEI layer should possess high mechanical strength and stiffness to prevent the intrusion of Li filaments, high Li transference number, low bulk/interfacial resistance, and high ionic yet negligible electronic conductivity. Moreover, recent studies show that the morphology of SEI layer is critical, and it is believed that a homogeneous, isotropic surface is required. The thin film solid electrolyte, lithium phosphorous oxynitride (LiPON), satisfies all of these properties. It has a relatively high shear modulus of 7.7 GPa, unity transference number, electrochemical stability window spanning from 0 up to 5.5 V vs. Li/Li+, ionic conductivity of ~2 × 10-6 S cm-1, electronic conductivity of ~8 × 10-13 S cm-1, and is fabricated as a smooth isotropic, homogenous thin film via physical vapor deposition. However, it remains a challenge to observe uniform, mirror-like electrodeposition of Li metal under the sole protection of LiPON layers.
Herein we propose a multifunctional ASEI that combines the advantages of LiPON coating protection with the enhanced electrolyte/electrode interface wetting conferred by LixAu alloys. “Mirror-like” electrodeposition of Li up to a practical capacity of 3 mAh cm-2 was achieved, guiding a new avenue towards the limited amount of Li electrode enabled by precisely controlled electrodeposition. The lithiation of Au films (as current collectors), significantly reduces nucleation overpotential to zero, promoting uniform electrodeposition of Li metal, thereby a more spatially uniform metal deposit. The low overall resistance ASEI layer (50 Ω cm2), LiPON, separates physically deposited Li and solvents from liquid electrolyte, drastically eliminating the electrolyte reduction and improving Li deposition efficiency. Operando impedance measurements were utilized to in-situ monitor interface differences during Li deposition.

Figure 1
Self-Healing Commodity Polymer Electrolytes for Reliable Li Metal Batteries
Authors: Lorandi Francesca , Liu Tong , Dadashi-Silab Sajjad , Zhao Yuqi , Yin Rongguan , Whitacre Jay , Matyjaszewski Krzysztof 
Published: July 2021

As countries worldwide pledge to decarbonize their economy, the global demand for batteries is rapidly increasing, urging the development of high-specific-energy (> 500 Wh/kg at cell level) and low-cost (< 100$/kWh at pack level) batteries.1 The safety and durability of these devices are of primary importance. Polymer electrolytes are safer than traditional liquid electrolytes, and further benefit from highly tunable structures.2 Thus, polymers can be designed to achieve desired properties, including the ability of self-healing from damages, which can greatly extend battery lifetime. While the synthesis of self-healing polymers often requires specifically designed monomers or other polymerization components, it was recently shown that commodity copolymers, based on methyl methacrylate (MMA) and n-butyl acrylate (nBA) or their derivatives, display self-healing behavior.3 The autonomous self-repair of these copolymers with certain compositions is governed by interchain van der Waals forces.
Herein, this finding was exploited to prepare self-healing polymer electrolytes that ensured long-term performance of high-energy Li metal batteries. The electrolytes were based on polyethylene oxide (PEO), P(MMA-co-nBA) copolymers and Li bis(trifluoromethanesulfonyl)imide (TFSI) salt. Various structures and compositions were explored, including polymer blends and block copolymers made by atom transfer radical polymerization (ATRP) using a functionalized PEO-macroinitiator (Figure 1). The effect of polymer morphology, architecture, weight fraction of PEO and LiTFSI on electrolyte conductivity, thermal and electrochemical stability, Li transference number, mechanical strength and self-healing ability was analyzed.
By recovering ionic conductivity and mechanical strength upon cracks, self-healing electrolytes can suppress the growth of dendrites that hinders the utilization of Li metal anodes.4 Moreover, the viscoelastic nature of these polymers contribute to the creation of conformal interfaces on Li metal.2 Therefore, the optimized commodity self-healing polymer electrolytes were tested in Li metal batteries, demonstrating the ability of the electrolytes to enable long-term stable cycling. In addition, tests were conducted to prove the self-repair of the electrolyte upon damaging the device.

References:

1 J. Liu, Z. Bao, Y. Cui, E. J. Dufek, J. B. Goodenough, P. Khalifah, Q. Li, B. Y. Liaw, P. Liu, A. Manthiram, Y. S. Meng, V. R. Subramanian, M. F. Toney, V. V. Viswanathan, M. S. Whittingham, J. Xiao, W. Xu, J. Yang, X.-Q. Yang, J.-G. Zhang, Nat. Energy 2019, 4, 180-186.

2 J. Lopez, D. G. Mackanik, Y. Cui, Z. Bao, Nat. Rev. Mater. 2019, 4, 312-330.

3 M. W. Urban, D. Davydovich, Y. Yang, T. Demir, Y. Zhang, L. Casabianca, Science 2018, 362, 220-225.

4 L. Zhao, N. R. Sottos, Adv. Energy Mater. 2020, 2003139.

Figure 1: structure of a self-healing copolymer electrolyte and illustration of Li dendrite suppression.

Figure 1
The Mechanical and Electrochemical Behaviour of Red Phosphorus in Lithium, Sodium and Potassium-Ion Batteries
Authors: Capone Isaac , Pasta Mauro 
Published: July 2021

Red phosphorus (RP) is a promising anode material for alkali-ion batteries due to its ability to alloy at low potentials with Li, Na and K to form the phases Li3P, Na3P and KP, delivering a high theoretical capacity of 2596, 2596 and 865 mAh g-1, respectively. However, its main disadvantage is its very large volumetric expansion during the alloying reaction (168% with Li, 331% with Na and 161% with K) that can cause, loss of electrical contact, low Coulombic efficiency, and ultimately poor cycle life. Other alloying materials such as silicon have shown to suffer from the fracturing of the particles during the reaction with lithium. In this work, we discuss if this is the case for phosphorus too [1]. Through comprehensive electrochemo-mechanical characterisation and modelling of the cycling stresses, we show that RP can be cycled at high current densities without fracture. A model that can simulate the volume expansion of RP during the reaction with the alkali metals Li, Na and K, as well as the generation and evolution of stresses on the particles is developed. Its use required the implementation of the elastic, plastic and fracture properties of RP that are measured by novel application of in-situ nanoindentation and powder compression. The validity of the model is also tested through in-situ TEM observation with extreme conditions (anisotropic ion diffusion and high current density) where no catastrophic failure was observed. The mechanical and the electrochemical characterisation, together with the model developed in this work allows for predictions to be made for the application of RP in alkali-ion batteries.
REFERENCE
[1] Capone et al., Matter 2020 3 (6), 2012-2028
Cerium Oxide Nanostructures with Controllable Reactivity for Sensing and Environmental Applications
Authors: Othman Ali , Andreescu Emanuela 
Published: July 2021

Ceria (CeO2) nanostructures are used in a broad range of applications in catalysis, biomedicine, sensing and in the semiconducting industry. Their surface reactivity, catalytic, mechanical and spectral properties provide unique features that have enabled many applications. Examples of emerging applications include their use as therapeutic antioxidants to modulate oxidative stress in biological systems, as redox active probes to design bioanalytical assays. Moreover, ceria nanostructures are widely as a polishing abrasive in the chemical mechanical planarization process (CMP) in the manufacturing of printed circuits by the semiconductor industry. To obtain specific surface properties, as well to improve their redox reactivity, synthesis approaches including surface modification and coating, doping and support functionalization could be used. Studies were designed to investigate the effect of the particle size, dopant and surface coating on the redox reactivity, adsorption/desorption/ligand exchange processes and the optical and catalytic properties of the nanostructures that will be used for the fabrication of CeO2 based sensing platforms and separation devices.
This work provides a critical evaluation of the redox properties of CeO2 nanostructures that can enable rational design and selection of suitable candidates for sensing and environmental applications based on their reactivity and surface properties.
On the Parameters Affecting Calcium Plating and Stripping from Organic Electrolytes – Cases of Electrolyte Optimization
Authors: Forero-Saboya Juan , Ponrouch Alexandre 
Published: July 2021

Among the different next-generation battery technologies, the ones based on divalent cations have recently gained particular attention due to their higher raw material availability and potentially higher energy density when compared with Li-ion. Such is the case of calcium, being the 5th most abundant element in the earth crust and having a standard redox potential only 170 mV above metallic lithium. However, the development of a secondary calcium-metal battery had been hampered by the lack of organic electrolytes allowing for reversible plating and stripping, which was only recently reported by our group and others employing different electrolyte formulations.
The different electrolyte components – salt(s), solvent(s) and additive(s) – are expected to play a significant role in the operation of a calcium-metal battery. Here we will show how the solvation structure of the cation evolves in relation to the solvent employed and the concentration of the salt. Combining conductivity measurements with Raman spectroscopy data, a high tendency to form contact ion pairs is evidenced, which significantly affects the mobility of the ions in the liquid media. The use of different anions and their bonding strength with Ca2+ in solution will be discussed. Combined, the anion and solvent characteristics dictate the solvation of the cation, which in turn can affect the Ca plating and stripping kinetics.
Additionally, the presence of electrolyte contaminants will be explored. The crucial yet very challenging drying of electrolyte containing Ca(BF4)2 in carbonate solvents will be presented. The difficulties to obtain anhydrous and contaminant free solutions from commercially available salts will be discussed and two alternative routes for anhydrous synthesis of the target salt will be presented.
Study of Solid State Lithium Batteries with a Ceramic Electrolyte
Authors: Dussart Thibaut , Stevens Philippe , Toussaint Gwenaelle , Laberty-Robert Christel 
Published: July 2021

Solid state lithium batteries are considered as the next generation of batteries due to its potential higher energy density and better safety compared to Li-ion technology[1]. Oxides, sulfides, polymers and polymer/ceramic hybrid materials can be used as lithium ion conducting solid electrolytes, some of which have very good ionic conductivities (up to 10-3 S.cm-1 at 25°C) and good electrochemical stability[2,3].
Li1,3Al0,3Ti1,7(PO4)3 (LATP) is a potential candidate as a solid electrolyte with an ionic conductivity of 1.10-4 S.cm-1 at 25°C. It is stable up to 5V vs Li/Li+ but it is instable in contact with lithium due to the reduction of Ti4+ in Ti3+ [4]. A thin protective layer of a stable lithium ion conducting material is deposited to avoid contact between LATP and Li metal[5]. The LATP solid electrolyte has been synthesized via solid state synthesis and LATP particles exhibit a cubic morphology.
Aluminum doped Li7La3Z2O12 (LLZO), another good candidate for solid electrolyte, displays a high ionic conductivity >10-4 S.cm-1 [6] and an good stability in contact with lithium metal. LLZO synthesized by the Pechini route exhibit a cubic phase with no impurity phase.
The main challenge is to control this interphase in order to decrease the interfacial resistance. Different strategies are employed to deposit the lithium such as electrochemical deposition and vapor deposition. Full cells are assembled using different positive electrode compositions and characterized in order overcome the technological barriers related to this technology.
[1]T. Placke, R. Kloepsch, S. Dühnen, M. Winter, Lithium ion, lithium metal, and alternative rechargeable battery technologies: the odyssey for high energy density, J. Solid State Electrochem. 21 (2017) 1939–1964. doi:10.1007/s10008-017-3610-7.
[2]J. Janek, W.G. Zeier, A solid future for battery development, Nat. Energy. 1 (2016) 1–4. doi:10.1038/nenergy.2016.141.
[3]Y. Zhu, X. He, Y. Mo, Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations, ACS Appl. Mater. Interfaces. 7 (2015) 23685–23693. doi:10.1021/acsami.5b07517.
[4]P. Hartmann, T. Leichtweiss, M.R. Busche, M. Schneider, M. Reich, J. Sann, P. Adelhelm, J. Janek, Degradation of NASICON-type materials in contact with lithium metal: Formation of mixed conducting interphases (MCI) on solid electrolytes, J. Phys. Chem. C. 117 (2013) 21064–21074. doi:10.1021/jp4051275.
[5]H.S. Kim, Y. Oh, K.H. Kang, J.H. Kim, J. Kim, C.S. Yoon, Characterization of Sputter-Deposited LiCoO2 Thin Film Grown on NASICON-type Electrolyte for Application in All-Solid-State Rechargeable Lithium Battery, ACS Appl. Mater. Interfaces. 9 (2017) 16063–16070. doi:10.1021/acsami.6b15305.
[6]R. Murugan, V. Thangadurai, W. Weppner, Fast lithium ion conduction in garnet-type Li7La3Zr2O12, Angew. Chemie - Int. Ed. 46 (2007) 7778–7781. doi:10.1002/anie.200701144.

Figure 1
(Invited) Molecular Modeling of Lithium and Zinc Electrolytes
Authors: Borodin Oleg , Pollard Travis , Vatamanu Jenel , Schroeder Marshall , Ma Lin , Wang Chunsheng , Xu Kang 
Published: July 2021

In this presentation I will update on the recent progress towards obtaining fundamental understanding and improving three classes of electrolytes: 1) aqueous and hybrid electrolytes for lithium ion batteries including superconcentrated electrolytes; 2) non-aqueous electrolytes and their interaction with the electrodes for high energy density lithium ion batteries; 3) electrolytes for zinc metal batteries.
Accurate molecular dynamics (MD) simulations of these electrolytes using many-body polarizable force field will be used to establish a correlation between the ion transport mechanisms, electrolyte structure and transference number. Reactive modeling will focus on the competitive solvent and salt reduction at the passivated electrochemical interfaces using Born Oppenheimer Molecular Dynamics (BOMD) simulations using DFT functionals. These BOMD simulations included critical factors needed to realistically represent electrolyte reactivity at electrodes such as explicit description of the substrate – electrolyte interactions; accurate representation of electrolyte structure, ion pairing and aggregation near an electrode; and collection of sufficient statistics from multiple unique simulations that were initiated with differing initial configurations. Electrolyte reduction at the passivated interfaces from these simulations will be contrasted with other solvents ranging from ethers with mixed salts or carbonates and results from the representative quantum chemistry (QC) calculations performed on the small model electrolyte clusters to estimate oxidation and reduction.
Anionic Redox Investigation of Na2Mn3O7 Electrode Material for Sodium-Ion Batteries
Authors: Hakim Charifa , Ma Le anh , Younesi Reza , Brandell Daniel , Edstrom Kristina , Saadoune Ismael 
Published: July 2021

NaxMeyOz oxides have attracted wide attention as promising cathode materials for sodium-ion batteries because of their potential high capacity and rate capability (1). The stable cycling performance, usually obtained within a low voltage range, drastically decrease when cycled at high voltage range despite the large initial charge capacity. Thus, it has been suggested that besides storing charge on the transition metal ions, oxygen ions can also participate in the charge compensation mechanisms at high voltage which induces an oxygen loss from the lattice when charging which is the reason behind the poor cycling stability (2).
In this work, the aim is to investigate the anionic redox reactions of Na2Mn3O7 cathode material, within the voltage window of 1.5 – 4.5 V using combined soft X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) which allow us to study the electronic structure of this material.

Keywords: Energy, Storage, Sodium-ion, Cathode, layered oxide, anionic redox, oxygen activity.

References:

Delmas, C., Braconnier, J.-J., Fouassier, C. & Hagenmuller, P. Electrochemical intercalation of sodium in NaxCoO2 bronzes. Solid State Ionics. 3/4, 165–169 (1981)

Assat, G. & Tarascon, J. Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries. Energy
3, 373–386 (2018).

Acknowledgements: The Swedish Research Council (VR) financially supported this work via project 2017-05466
(Invited) Highly Stable Nanocarbon Catalysts for Reversible Energy Storage and Conversion Via Oxygen Electrocatalysis
Authors: Wu Gang 
Published: July 2021

Energy conversion and storage via direct electrochemical oxidation and reduction processes, such as the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), can provide a clean, efficient, and economically viable means of meeting this sustainability challenge, by allowing stored renewable energy to be reliably delivered where and when it is needed. During the development of the highly demanded nonprecious metal catalysts to replace precious metals for these applications, carbon catalysts have many advantages over metal oxides, including excellent electrical conductivity, high surface area, and easy functionalization. However, most carbon-based catalysts suffer from poor activity and stability for the more challenging OER under a highly oxidative conditions. This represents one of grand challenges in energy conversion research societies.
For the first time, this work demonstrated that a new class of large-diameter tubular nanocarbon (>500 nm in diameter) catalyst is capable of catalyzing both the ORR and the OER with activity comparable to Pt and exceeding Ir, respectively, for these two reactions. Most importantly, the tube catalyst exhibited good stability upon cycling across a wide potential window (0 to 1.9 V vs RHE) in 0.1 M NaOH electrolyte. The high OER activity was verified using well-designed electrochemical tests, demonstrating that the current generated during the OER arose solely from oxygen evolution, rather than carbon oxidation. This is the first example of such excellent OER activity and durability of a nanostructured carbon-based electrocatalyst across the complete ORR-OER potential window. The newly developed carbon tubes were synthesized via a one-step template-free graphitization process using inexpensive dicyandiamide (DCDA) precursor as carbon/nitrogen source and a ternary FeCoNi alloy as a catalyst. Generation of a mixed metal catalyst, i.e., FeCoNi during the graphitization process is the key factor to yield the largest tube size for maximum electrochemically accessible surface areas, dominant graphitic nitrogen doping, and thicker tube walls, which are associated with the significantly improved activity and durability. The cost effective, easily scalable, single step and environmentally benign synthesis procedure further favors this nanocarbon’s application as a practical bifunctional electrocatalyst for the ORR and OER, with potential to advance the development and commercialization of regenerative fuel cell systems and rechargeable metal-air batteries. The use of nanostructured carbon as bifunctional ORR/OER catalysts will open up new research direction in this field and further advance the role of carbon nanomaterials in oxygen electrocatalysis for energy conversion and storage.