bluuebunny/crossref_metadata_2025_split huggingface dataset:
New Insights into Parasitic Reactions in Non-Aqueous Alkaline-O2 Batteries
Authors: Mahne Nika , Schafzahl Bettina , Leypold Christian , Kramer Denis , Slugovc Christian , Wilkening Martin , Borisov Sergey M. , Freunberger Stefan A 
Published: February 2020

Non-aqueous lithium-oxygen batteries depend critically on the reversible formation and on the decomposition of lithium oxides on cycling [1-3]. The discharge reaction in the cathode of nonaqueous Li-O2 batteries involves the reduction of O2 and the formation of solid Li2O2. The process is reverse on charge. True reversibility of the cathode reaction in the Li-O2 battery requires a set of qualities to obey the stoichiometry and to match each other during discharge and subsequent charge. These are 1) e-/O2 = 2 both on discharge and charge, 2) to produce/consume exactly one mole of Li2O2 and one mole of O2 per 2e- and on discharge/charge, 3) absence of any other gas evolution, e.g. CO2, or generation of solid products other than Li2O2 during discharge and charge, 4) O2 consumed during discharge matches the amount released on subsequent charge.
Typically these measures deviate more or less significantly from the ideal due to parasitic reactions, whose source has not been entirely identified. Irreversible parasitic reactions have predominantly been ascribed to the reactivity of reduced oxygen species, e.g., superoxide with cell components [4-6]. These species, however, cannot fully explain these observed side reactions. Only better knowledge of parasitic reactions will allow inhibiting them and reaching towards fully reversible cell reactions.
We will discuss recent insights into irreversible parasitic reactions during cycling of a Li-O2 battery, that have so far been overlooked, their detection via newly developed methods and strategies to suppress them effectively [7]. Awareness of these reactions in non-aqueous Li-O2batteries gives a rationale for future research towards achieving highly reversible cell operation.
References

[1] P.G. Bruce; S.A. Freunberger; L.J. Hardwick; J.-M. Tarascon; Nature Mater. 11 (2012) 19.

[2] A.C. Luntz, B.D. McCloskey, Chem. Rev. 114 (2014) 11721.

[3] Y.-C. Lu; B.M. Gallant; D.G. Kwabi et al.; Energy Environ. Sci. 6 (2013) 750.

[4] S.A. Freunberger, Y. Chen, N.E. Drewett, L.J. Hardwick, F. Bardé, P.G. Bruce, Angew. Chem. Int. Ed., 50 (2011) 8609.

[5] M.M. Ottakam Thotiyl, S.A. Freunberger, Z. Peng, Y. Chen, Z. Liu, P.G. Bruce, Nature Mater.12 (2013) 1050.

[6] B.D. McCloskey, A. Valery, A.C. Luntz, et al., J. Phys. Chem. Lett.(2013) 2989.

[7]N. Mahne et al., submitted.
Strategy for Metal Anode Protection in Advanced Energy Storage Systems
Authors: Lin Chuan-Fu , Noked Malachi , Kozen Alex C , Luo Wei , Hu Liangbing , Lee Sang Bok , Rubloff Gary W 
Published: February 2020

To meet the demand for higher capacity longer life batteries in a “next-generation batteries” technology, anodes with substantially higher energy density than current graphite are needed. One class - metal anodes (particularly Li, Na) - offers far higher energy density, but to date their utilization has been impeded by their high surface reactivity (especially to the organic electrolyte) and tendency to form dendrites (a shorting and safety hazard).
We have used atomic layer deposition (ALD) to create highly controlled, thin ceramic type coatings as an artificial solid electrolyte interphases (SEIs) to protect these anode surfaces by preventing dendrite formation and electrolyte decomposition. The ultrathin Al2O3 protective coating on Na stabilizes the Na-electrolyte interface and extends its cycle life under high current density (i.e., high power) cycling conditions. We have also developed a hybrid (elastomer + ceramic-type) protective coating on Li metal by combining ALD ceramic (LiPON) and electrochemical deposition of a polymeric elastomer. The hybrid layer achieves high Li conductivity while suppressing corrosion and due to electrolyte breakdown. The elastomer component provides mechanical flexibility to accommodate volume change both may play roles in the observed mitigation of dendrite growth at high current density.
These results demonstrate promise for achieving high energy density anodes with significantly enhanced chemical stability, electrochemical cyclability, and dendrite protection as needed for a viable beyond Li or Na ion battery technology.
Atomistic Simulation Studies of Lithiated and Sodiated TiO2 nanospheres
Authors: Ngoepe Phuti E , Kgatwane Kenneth M , Matshaba Malili G , Sayle Dean C 
Published: February 2020

Sodium-ion batteries (SIBs) are considered to be a promising low-cost alternative to common lithium-ion batteries. Several electrochemical studies have been carried out on anode nanomaterials of TiO2 and good cyclability and high rate capability has been reported for Li-ion batteries [1]. Recently, its possible application in Na-ion batteries has put it forward as a promising candidate [2,3]. Simulated armorphization and recrystallization technique has been employed to generate nano-architectures of TiO2 [4].
Herein, we present a detailed simulated synthesis for nanospheres of lithiated and sodiated TiO2 where amorphous precursors were crystallised. Mixed polymorphs consisting mainly of brookite, rutile were observed from microstructures and XRDs. Crystallised nanospheres were lithiated and sodiated up to high concentrations to imitate the charging process and related volume expansions were predicted. Structural aspects were deduced from radial distribution functions and differences associated with lithiation and sodiation are quite obvious. Calculated XRDs are generated and compared with experimental results where available. Microstructures of the resulting models are analysed and a wealth of crystallographic defects (i.e. grain boundaries and point defects) were captured and their resulting influence on Li-ion and Na-ion transport are discussed.
References
[1] J. Wei, J.X. Liu, Y.C. Dang, K. Xu, Y.A. Zhou, Adv. Mater. Res. (2013), 750−752, 301.
[2] K.T. Kim, G. Ali, K.Y. Chung, C.S. Yoon, H. Yashiro, Y-K. Sun, J. Lu, K. Amine, and S-T. Myung, Nano Lett. (2014), 14, 416.
[3] L. Wu, D. Bresser, D. Buchholz, G.A. Giffin, C.R. Castro, A. Ochel , and S. Passerini, Adv. Energy. Mater. (2015), 5, 1401142
[4] M.G. Matshaba, D.C. Sayle, T.X.T. Sayle and P.E. Ngoepe, J. Phys. Chem. C, (2016), 120, 14001.
Structural and Chemical Evolution of Li-Excess Li2IrO3 during Electrochemical Cycling
Authors: Li Liang , Lee Eungje , Park Joong Sun , Castro Fernando , Yao Zhenpeng , Fister Timothy T , Freeland John W , Wolverton Christopher , Dravid Vinayak , Thackeray Michael M. , Chan Maria K. Y. 
Published: February 2020

The family of Li-excess layered Li2TMO3 (TM=Mn, Ru, Ir, etc.) compounds has recently drawn considerable attention in the pursuit of improved capacity of Li-ion batteries. Many studies have unambiguously demonstrated the extra capacity of Li2TMO3 associated with oxygen redox behavior.1,2 Unlike Li2MnO3, which suffers from severe structural degradation and capacity fading upon cycling, Li2IrO3 shows negligible structural change and much improved reversibility,3 and thus serves as a model system to understand the structural response of Li-excess cathodes to Li extraction, as well the exact role of oxygen in compensating Li+ loss.
In this study, we employed various experimental techniques as well as first-principles density functional theory (DFT) to investigate the structural and electronic evolution of Li2IrO3 upon electrochemical cycling. It is found that Li2IrO3 undergoes phase transition and slight capacity fading at each cycle. All the thermodynamically stable phases of Li2-xIrO3 (0≤x<2) are identified through a complete structural screening based on electrostatic energy and DFT calculations, and compared with Transmission Electron Microscopy (TEM) and X-ray Diffraction (XRD) experiments. Core Level Spectroscopy is adopted to probe the changes in the oxygen electronic structure at various (de)lithiation stages, and corresponding oxygen K-edge spectra are simulated based on first-principles calculations. The cationic/anionic charge compensation mechanism of Li2IrO3 upon delithiation, as well as its resistance to O2 loss are discussed based on the spectroscopic observations.

Reference:

1. D. Seo, J. Lee, A. Urban, and R. Malik, Nat. Chem., 8, 692–697 (2016)
2. M. Saubanere, E. McCalla, J.M. Tarascon, and M.L. Doublet, Energy Environ. Sci., 984–991 (2016)
3. E. McCalla et al., Science, 350, 1516–1521 (2015)
Supercapacitor Aging and Diagnosis
Authors: El Mejdoubi Asmae , Chaoui Hicham , Gualous Hamid 
Published: February 2020

The lifetime of an energy storage component is the time required to fail. The failure is defined as the lack of ability of a component to fulfill it's specified function. One of its characteristics will be out of the specification. For example the capacitance will be below its specified limit value, or the series resistance will be above its specified value, the component will be leaking, or will be opened.
This paper is about supercapacitor aging and diagnosis. At the first, supercapacitor aging according to the temperature and to the voltage is presented. Experimental tests are realized at constant temperature when the supercapacitors are polarized at the maximum voltage. To quantify the supercapacitor aging, the equivalent series resistance and the equivalent capacitance are measured. To lead to the determination of the supercapacitor lifetime, Arrhenius law, that describes the effect of temperature on the velocity of a chemical reaction, is considered.
The second part of this paper presents an online diagnosis method for supercapacitors’ aging problem. The proposed strategy capitalizes on the capabilities of the sliding mode for the design of a sliding mode observer. Therefore, online parameters’ estimation is achieved, which yields State-of-Health (SoH) prediction. Unlike other methods such as electrochemical impedance spectroscopy, where estimation is performed offline and requires interruption of the system’s operation, this paper presents an online diagnosis method. Moreover, only voltage and current measurements are required. The effectiveness of the proposed online observer is shown through a set of experiments. Results highlight its good performance in parameters estimation with robustness to current’s nonlinearities.
Electrodeposition of MnO2-Based Nanomaterials As Carbon-Free and Binder-Free Cathodes for Li-O2 Battery
Authors: Deng Zhaofeng , Li Chi-Ying Vanessa , Chan Kwong-Yu 
Published: February 2020

Carbon based nanomaterials have been widely used as cathode materials for Li-O2 batteries because of their high conductivity, large surface area, and good ORR catalytic activity. However, instability of carbon under Li-O2 operation poses problems. During recharge, carbon can decompose to form lithium carbonate at high charging potential1, but also react chemically with the discharge product Li2O2
2. Metal oxides, like MnO2 and RuO2, have been investigated as cathode catalysts in Li-O2 batteries3. In this study, MnO2 nanostructure is electrodeposited on stainless steel mesh and applied as a carbon-free and binder-free cathode for non-aqueous Li-O2 battery. To maintain good adhesion and electrical contact between deposited layer and the substrate, the mesh is pre-treated. Benefiting from enhanced electronic contact and large surface area of MnO2, the electrochemical performance is improved. Material characterization and electrochemical impedance spectroscopy (EIS) technique are also utilized to systematically study the electrochemical processes of these carbon-free MnO2-based electrodes.

References

[1] M.M.O.Thotiyl, S. A. Freunberger, Z. Peng, and P. G. Bruce, J. Am. Chem. Soc., 135, 494 (2013)
[2] B. D. McCloskey, A. Speidel, R. Scheffler, D. C. Miller, V. Viswanathan, J. S. Hummelshøj, J. K. Nørskov, and A. C. Luntz, J. Phys. Chem. Lett., 3, 997 (2012)
[3] Z. Ma, X. Yuan, L. Li, Z.F. Ma, D.P. Wilkinson, L. Zhang, and J. Zhang, Energy Environ. Sci., 8, 2144 (2015)

Acknowledgements

This project is financially supported by HKU Seed Fund for Basic Research (Project No.: 201605159011), and University Development Fund for Clean Energy and Environment.
Sub-Micrometer Active Material Particle Synthesis for Solid Dispersion Lithium-Ion Redox Flow Batteries
Authors: Qi Zhaoxiang , Koenig Gary 
Published: February 2020

Solid dispersion lithium-ion redox flow batteries incorporate carbon-free lithium-ion active materials in a flow battery geometry, taking advantage of both the flexibility of a redox flow battery and the high energy density of lithium-ion active materials. This promising technology, however, needs sub-micrometer or nanometer sized active material particles to form well-dispersed fluids. These small particles are also desirable for achieving high rate capability and round trip energy efficiency in conventional battery cells. While many methods have been reported in literature to produce sub-micrometer sized battery particles, often these processes are challenging to scale up for large quantity production. In this poster, we will describe a highly scalable process to produce high performance sub-micrometer battery active materials with an initial demonstration cathode chemistry, LiCoO2. The LiCoO2 produced with this method exhibited excellent electrochemical performance as lithium-ion battery cathode active materials, including high discharge capacity, rate capability, and coulombic efficiency. The LiCoO2 material also performed well as the cathode material dispersed in the electrolyte for solid dispersion lithium-ion redox flow battery applications.
The High Performance Silicon Anodes Including New Water Based Binder in Lithium Ion Batteries
Authors: Kim Soo Jung , Kim Nam Seon , Han Sang Wook , Choi Kwang Sik 
Published: February 2020

Silicon based negative active material has very high charge capacity and is widely applied to a high capacity battery. However, the silicon based negative active material may expand by about 300% to about 400% during charge and discharge.
Recently much attention has been devoted developing functional binders that can improve adhesion on silicon particle and accommodate substantial volume change during the charge/discharge process to maintain the electrode structure.
The binders for silicon electrodes hold stiff polymeric backbones as like carboxymethyl cellulose (CMC), poly(acrylic acid), and alginate show better electrochemical performance than commercial binders. Despite promising progress, the current research on polymer binders for silicon is still far from the practical application where high mass loading is necessary for the high areal capacity.
Here we report high performance silicon anodes using new water based binder including inorganic binder. This polymer matrix is compatible with lithium ion slurry manufacturing process, and can maintain both electric conductivity and mechanical integrity during the battery operation which results in good stability, rate capability, and cycle-life characteristics at high mass loading (>4.5 mg/cm2).
Comparative Studies on Interfacial Kinetics of Ordered and Disordered Spinel LiNi0.5Mn1.5O4
Authors: Amin Md Ruhul 
Published: February 2020

The charge-discharge behavior of LiNi0.5Mn1.5O4, having both the ordered and disordered spinel structures, had been investigated by several research groups [1–5]. However, there are discrepancies with regard to the suitability of the disordered or ordered spinel for better battery performance [3–5]. It is also not clearly understood whether the rate performance of the material is limited by bulk transport properties or interfacial charge transfer reaction kinetics. The purpose of the present work is to elucidate the role of the electrochemical charge transfer kinetics at the electrode/electrolyte interface of Li1-xNi0.5Mn1.5O4 in determining the rate performance of the spinel cathode. The measurements have been carried out on additive free sintered dense plate in order to exclude any extrinsic effect. The exchange current density at the electrode/electrolyte interface is found to be continuously increased with increasing the degree of delithiation for ordered phase (~0.21-6.5mA/cm2) at (x=0.01-0.60), in contrast the disordered phase exhibits gradually decrease of exchange current density in the initial delithiation at the 4V plateau regime (x=0.01-0.04) and again monotonously increases (0.65-6.8mA/cm2) with further delithiation at (x=0.04-0.60). The ionic diffusivity of ordered and disordered phase is found to be ~5x10-10cm2s-1 and ~10-9cm2s-1, respectively, and does not vary much with the degree of delithiation. From the obtained results it appears that the chemical diffusivity during electrochemical use is limited by lithium transport, but is fast enough over the entire state-of-charge range to allow charge/discharge of micron-scale particles at practical C-rates.

References

K. Amine, H. Tukamoto, H. Yasuda and Y. Fujita, J. Electrochem. Soc., 143, 1607 (1996).

Q. M. Zhong, A. Bonakdarpour, M. J. Zhang, Y. Gao and J. R. Dahn, J. Electrochem. Soc., 144, 205 (1997).

H. F. Xiang, X. Zhang, Q. Y.Jin, C. P. Zhang, C. H. Chen and X. W. Ge, J. Power Sources, 183, 355 (2008).

H. M. Wu, I. Belharouak, H. Deng, A. Abouimrane, Y. K. Sun and K. Amine, J. Electrochem. Soc., 156, A1047 (2009).

J. Hassoun, S. Panero, P. Reale and B. Scrosati, Adv. Mater., 21, 4807 (2009).
Investigating the Polysulfides Reactions on the Conducting MagnéLi-Phase Ti4O7 By Means of First Principles Simulations
Authors: Kachmar Ali , Cuisinier Marine , Abouimrane Ali , Belharouak Ilias 
Published: February 2020

There have been new developments of new sulfur cathode materials to enhance the cycling stability of (Li-S) batteries. These new sulfur cathodes are based on metal oxides, which are intrinsically polar materials that can strongly interact with polar polysulfides species because the surface doesn’t need modification for interfacial adsorption [1,2]. I will first present the hybrid functional calculations we performed using the Auxiliary Dynamics Matrix Method (ADMM) [3,4] with varying percentages of exact Hartree−Fock exchange (hfx), ranging from 10 to 50% hfx to compute accurately the band gaps, and to determine the stable surface orientations of the Magnéli-phase of Ti4O7, and Anatase TiO2. Relying on the previous results, I will discuss the first principles molecular dynamics simulations [4] we conducted to investigate the interaction mechanisms, and the dynamics properties of the polysulfides Li2Sx (x=1, 2, 4, 6) on the identified stable surfaces of the Magnéli-phase of Ti4O7, and Anatase TiO2. Finally, I will discuss the role of the explicit solvent molecules in the solubility of the lithium polysulfides at the interfaces of the investigated models.

Reference
s
:

[1] Tao, Xinyong and Wang, Jianguo and Ying, Zhuogao and Cai, Qiuxia and Zheng, Guangyuan and Gan, Yongping and Huang, Hui and Xia, Yang and Liang, Chu and Zhang, Wenkui and Cui, Yi, Nano Letters, 14, 5288-5294, (2014).
[2] Pang, Quan and Kundu, Dipan and Cuisinier, Marine and Nazar, L. F., Nat Commun, 5, 4579, (2015).
[3] Guidon, Manuel and Hutter, Jürg and VandeVondele, Joost, Journal of Chemical Theory and Computation, 6, 2348-2364, (2010).
[4] CP2K, http://www.cp2k.org/
Free-Standing, Binder-Free Titanium Suboxide Nanofiber Based Sulfur Cathodes for Li-S Batteries
Authors: Singh Arvinder , Dillard Caitlin , Kalra Vibha 
Published: February 2020

Lithium sulfur batteries, with a high theoretical specific energy of ~2680 Wh/kg, have attracted great attention in the recent years owing to the direct use of sulfur as a cathode, which is cost-effective, environmentally friendly and naturally abundant. However, shuttling of intermediate polysulfides between cathode and anode is one of the major practical limitations for the realization of Li-S batteries. Others include large volume expansion during lithium insertion, low sulfur utilization, and insulating nature of sulfur and lithium disulfide. Over the years, various carbon and inorganic materials (metal oxides, metal-organic frameworks) have been employed as hosts or polysulfide reservoirs to minimize the shuttling effect and improve the conductivity of cathodes in Li-S batteries. Recently, titanium suboxides (TinO2n-1; n>1), with two Ti3+ and (n-2)Ti4+ (3d0) ions, have been utilized as bifunctional sulphur hosts that not only provide good electrical conductivity, but also chemically bind with the intermediate lithium polysulfide preventing their escape. However, formation of titanium suboxides generally requires high temperature processing, which results in highly dense low surface area material reducing the potential polysulfide-host interaction surface.
Here, we report the use of free-standing, binder-free titanium suboxide nanofibers as host material in sulfur cathodes. Titanium suboxide nanofibers are produced by electrospinning titanium isopropoxide solution in presence of polyvinylpyrrolidone and subsequently, heating at 850˚C to create oxygen vacancies through carbothermal reaction. Sulfur impregnation was carried out by rapid melt-diffusion technique to form final sulfur/titanium suboxide cathodes. Lithium-sulfur coin cell batteries were assembled using as-prepared free-standing cathodes (without any current collector and binder) with ~50 wt% sulfur loading (~1.5 mg cm-2) and cycled at C/5 rate (1C = 1675 mAh g-1) after conditioning at C/10 rate. The initial discharge capacity was ~976 mAh g-1 at C/5 rate, which stabilized to an average capacity of ~738 mAh g-1 after three cycles with coulombic efficiency >97%. The conducting titanium suboxide nanofibers allow the effective utilization of sulfur/Li2S during discharging/charging of cells and help to maintain high discharge capacity (~700 mAh g-1) over 100 cycles. The chemical interaction between these inorganic hosts and lithium polysulfide is under investigation and will be discussed in detail. The electrochemical results presented here show the potential of titanium suboxide family (different n values) as foreseeable solution to the shuttling effect for developing high performance Li-S batteries.

Figure 1
Dual-Functional Polymer Coating on Lithium Anode for Suppressing Dendrite Growth and Polysulfide Shuttling in Li–S Batteries
Authors: Luo Jing , Wu Nae-Lih 
Published: February 2020

Rechargeable Li–S batteries using Li metal as the anode and S as the cathode-active material are attractive energy storage candidates because the couple offers high specific capacities and possesses marketing advantages such as the light weight of Li and low cost of S. However, the commercialization of Li–S batteries remains hindered by several technical hurdles of both the S cathode and Li anode. The multistep electrochemical reactions of the S cathode involve various Li polysulfide intermediates (Li2Sn, 3 ≤ n ≤ 8), some of which are highly soluble in aprotic organic electrolytes. The diffusion of these soluble polysulfides to the Li anode, also known as the polysulfide-shuttling effect, causes a series of problems including self-discharge, loss of active material, and corrosion of the Li anode. Meanwhile, metallic Li anodes are susceptible to the accumulation of dendritic Li deposits on their surfaces because of uneven Li-ion transport on the electrode surface during repeated charge–discharge cycles. This detrimental accumulation can cause low Columbic efficiency and even a short circuit, triggering thermal runaway and even battery explosions.
Although the use of artificial coatings or membranes on Li anode surface has been suggested as a promising approach for suppressing Li dendrite formation, no previous study has simultaneously addressed Li dendrite formation and polysulfide-shuttling. In Li–S batteries, lithium nitrite (LiNO3) has been widely used as an electrolyte additive for maintaining stable anode performance by inhibiting the reactions between polysulfides and the Li surface. However, the long-term feasibility of LiNO3 is limited by its continuous consumption during battery operation. In this presentation, we report the successful development of a cation-selective and dimension-stable coating that can simultaneously suppress Li dendrite and polysulfide shuttling on the Li anode surface