bluuebunny/crossref_metadata_2025_split huggingface dataset:
Hidden Structural Order Controls Li-Ion Transport in Cation-Disordered Oxides
Authors: Ji Huiwen , Urban Alexander , Kitchaev Daniil A , Kwon Deok-Hwang , Artrith Nongnuch , Ophus Colin , Shi Tan , Ceder Gerbrand 
Published: February 2020

The development of cost-effective lithium-ion batteries depends on the discovery of high-energy-density cathode materials composed of nonprecious elements. Traditionally, lithium-ion cathodes are based on two categories, i.e., layered oxides and polyanionic compounds. However, most polyanionic compounds have low specific capacity due to their heavy polyanions. Layered oxides, though more favorable for energy density purposes, often contains the element cobalt, the supply of which is scarce and not sustainable.
The discovery of cation-disordered rocksalts and their percolation rules unlocked an unprecedented chemical space for the exploration of high-capacity lithium-ion cathodes which do not contain Co and have high capacity[1]. The facile Li diffusion in these materials is enabled through a network of Li-rich environments (so-called 0-TM channels) created by excess Li. Following this insight, many new high-energy-density cathode materials that involve mostly earth-abundant elements have been developed, such as Li1.2Mn0.4Ti0.4O2[2], Li1.2Ni1/3Ti1/3Mo2/15O2[3], as well as their fluorinated variants[4, 5].
A prevailing assumption when studying disordered rocksalt cathodes is that all the cation species are randomly distributed. However, we will demonstrate that even minor deviations from randomness, not detectable by typical X-ray diffraction (XRD), can have profound influence on performance. We employ a combination of thorough experimental characterization and multi-scale computer simulations to reveal that cation short-range order is ubiquitous in these long-range disordered materials. More importantly, the short-range order controls Li transport by altering the distribution of local environments and the connectivity between them. By considering a variety of different chemistries, we explain the microscopic origin of short-range order and identify general guidelines for local-structure manipulation for the benefit of Li transport. This breakthrough in the fundamental understanding of structure-property relationship in disordered Li-ion cathodes sets an exciting new direction for future optimization.
[1] J. Lee, et al, Science 343 (2014) 519-522.
[2] N. Yabuuchi, et al, Nature communications 7 (2016) 13814.
[3] J. Lee, et al, Energy & Environmental Science 8 (2015) 3255-3265.
[4] R. Chen, et al, Advanced Energy Materials 5 (2015).
[5] J. Lee, et al, Nature communications 8 (2017) 981.
Advanced Characterization of Solid-Solid Interfaces and Alkali Metal Anodes Via Cryogenic Focused Ion Beam and in Situ methodologies
Authors: Wynn Thomas Andrew , Lee Jungwoo Zema , Cheng Diyi , Meng Ying Shirley 
Published: February 2020

All-solid-state batteries are a potentially safer and more energy dense alternative to the modern lithium ion battery, replacing flammable organic liquid electrolytes and enabling lithium metal anodes. While solid electrolytes have been developed with ionic conductivities far in excess of modern liquid organic electrolytes, electrolyte-electrode interfacial resistance remain an issue. In spite of their fundamental importance, the nature of these interfaces remains obscured, primarily due to the limited methods of characterization of both lithium metal and buried interfaces alike. Recently, cryogenic microscopy techniques—traditionally employed by biological field—have been employed to lithium ion batteries, elucidating the nature of solid-electrolyte interfaces and lithium metal morphologies alike. Of similar difficulty, observation of solid-solid interface dynamics is limited to very few techniques, and has only been demonstrated recently, primarily via in situ transmission electron microscopy (TEM) methodologies.
We present developments in the application of cryogenic focused ion beam (FIB) and in situ TEM to enable fundamental characterization of solid-solid interfaces for lithium ion battery applications. Use of cryogenic temperatures is shown to clearly reduce damage induced in the lithium metal, preserving the morphology and structure, as demonstrated by both three-dimensional FIB slice-and-view and the observation of crystallinity in cryogenic-TEM. This technique is further extended to polymer and sulfide electrolytes, overcoming instability during FIB milling and permitting further characterization via cryo-TEM. Such cryo-prepared samples enable lithium metal for in situ TEM cycling of metal-anode-based solid-state batteries. Further, progress in in situ characterization of solid-state interfaces by TEM will be presented, showing developments in the extraction of electrochemically active nanobatteries for in situ testing applications, providing a platform for dynamic solid-solid interface characterization.
Towards Computational Modeling and Design of Solid-State Lithium-Ion Battery Architectures
Authors: Cobb Corie Lynn , Allu Srikanth 
Published: February 2020

Solid-state Lithium-ion (Li-ion) batteries can revolutionize battery performance due to their inherent safety, high voltage stability, and high conductivity. As the field grows, there is a need for computational tools that can allow engineers to explore the effects of material and geometry and their subsequent impact on battery performance as demonstrated in recent research.1 This will enable optimization of a given battery design without the need for expansive experimental tests. In this poster, we summarize the key components that are needed to enable a multi-physics modeling framework and highlight our initial progress. We use a three-dimensional (3D) computational framework called AMPERES,2 developed at Oak Ridge National Laboratory (ORNL), as a case study to examine the requirements of modeling the electrode-electrolyte interface of solid-state Li-ion batteries. Because AMPERES enables one to model arbitrary battery and electrode configurations, we also illustrate potential 3D architectures that can enhance battery performance. Longer term, our goal is to create a framework that enables rapid design, manufacture, and testing of new electrode architectures for solid-state Li-ion batteries with a focus on both current and emerging chemistries.
References

C. L. Cobb and S. E. Solberg, J. Electrochem. Soc., 164, A1339–A1341 (2017).

S. Allu et al., J. Power Sources, 325, 42–50 (2016).
Enable Model-Based Diagnostics and Prognostics for Lithium-Ion Batteries
Authors: Yang Chuanbo , Smith Kandler , Shi Ying , Santhanagopalan Shriram , Keyser Matthew 
Published: February 2020

Physicochemical processes in lithium ion batteries occur in intricate geometries over a wide range of time and length scales. As the size of the battery increases, macroscopic design factors in combination with highly dynamic environmental conditions significantly influence the electrical, thermal, electrochemical, and mechanical responses of a battery system. Computer-aided engineering tools are helping to accelerate the design and validation of large format cells and battery pack systems, which heavily replies on costly and time-consuming experimental tests previously. Validated physics-based models are effective in predicting electrochemical performance, thermal and mechanical response of cells and packs under normal and abuse scenarios and provide valuable insights not possible through experimental testing alone for diagnostics and prognostic purpose.
NREL pioneered the Multi-Scale Multi-Domain (MSMD) battery model, overcoming challenges in modeling the highly nonlinear multi-scale response of battery systems. The MSMD model provides flexibility and multi-physics expandability through its modularized architecture. The presentation describes present efforts to develop approaches to make the models better suited for engineering diagnostics and prognostic for large lithium-ion battery units by

Enhancing computation speed and stability of the pack-level multi-scale model while still resolving nonlinearities of dynamic battery response across scales from particles to packs

Blending field simulation with system simulation in a selective fashion to balance speed and accuracy. Applicable techniques include domain decomposition, physics segregation and reduced-order models (ROM) that can integrate into the system model

Developing interactive system interface for enhancement of multi-physics integrity

Incorporating spatially distributed model to address 3D non-uniform usage and stress factors.
Novel SEI-Forming Electrolyte Additives for Improved Performance of Silicon-Based Anodes
Authors: Vinograd Andrey , Röser Stephan , Edel Jan , Winter Martin , Placke Tobias 
Published: February 2020

The broad commercial application of high capacity silicon (Si)-based anodes for lithium ion batteries (LIBs) is still hindered by their poor cycling stability caused by large volume changes upon lithiation/delithiation and by the associated continuous electrolyte decomposition and active lithium loss. One suitable strategy to improve the electrochemical performance is to develop improved electrolyte formulations resulting in an efficient solid electrolyte interphase (SEI) formation.
A recent study [1] has shown that the addition of 2 wt-% of 3-methyl-1,4,2-dioxazol-5-one (MDO) to a propylene carbonate (PC)-based electrolyte can significantly improve the cycling stability of lithium nickel manganese cobalt oxide (NMC532)/graphite full cells. Since electrolytes, based only on PC, do not lead to the formation of a stable SEI at the anode, the addition of MDO can be linked to an increased SEI stability, which is necessary for a high cycling stability.
In this study, we develop a systematic approach to investigate the electrochemical performance of MDO and its various side chain modified derivatives as additives for carbonate-based electrolytes in LIB cells with silicon-carbon (Si-C) composite anodes. Our results show that the addition of MDO improves the cycling stability of Si-C/NMC622 cells in comparison to the state-of-the-art additives, such as vinylene carbonate (VC) and fluoroethylene carbonate (FEC). The systematic evaluation of the electrochemical performance of MDO and its analogues, such as 3-phenyl-1,4,2-dioxazol-5-one (PDO), was done using a cycling protocol adapted from Tornheim et al [2]. This method enables the concurrent determination of the electrode capacity retention and area specific impedance (ASI). Post mortem analysis is performed in conjunction with computational studies to understand the decomposition mechanism.
[1] S. Röser, A. Lerchen, L. Ibing, X. Cao, J. Kasnatscheew, F. Glorius, M. Winter, R. Wagner, Chem. Mater. 2017, 29, 7733-7739.
[2] A. Tornheim, C. Peebles, J. A. Gilbert, R. Sahore, J. C. Garcia, J. Bareño, D. P. Abraham, J. Power Sources 2017, 365, 201-209.
Optimization of Electrochemical Performance of Waste LCD Glass-Derived Silicon As Anodes for Lithium Ion Batteries
Authors: Kang Woohyeon , Kim Jae-Chan , Kim Dong-Wan 
Published: February 2020

Silicon has been widely studied as a promising alternative that can replace graphitic anodes owing to its high theoretical specific capacity of 3580 mA h g-1 and appropriate working voltage (~0.1 V vs. Li/Li+) for lithium ion battery (LIB) anodes [1]. Recently, the industrial wastes such as windshields, glass bottles, and rice husks have been utilized as a low cost and eco-friendly Si source [2,3,4]. Waste LCD glass-derived silicon is one of the attractive candidate and this materialization technique also can be a future green technology for resolving an immense LCD waste and insufficient recycling process [5].
In this study, high purity Si were fabricated as LIB anode materials using waste LCD glasses via magnesiothermic reduction. Firstly, we eliminated containing inert impurities (Al2O3, CaO, B2O3, In2O3 etc.) by ball-milling and acid leaching. Then, pre-treated waste LCD glasses were reduced to Si particles at 650 °C for 6 hours in Ar through magnesiothermic reduction and subsequent acid treatment. As the crystallographic analyses, waste LCD glasses were successfully reduced to highly crystalline and pure Si. Waste LCD glass derived Si electrodes exhibited the high initial discharge capacity of 4290 mA h g-1. However, the capacity decreased rapidly, indicating that the electrode underwent rapid pulverization due to drastic volume expansion/fracture upon cycling [6].
To overcome this problem, diverse strategies have been proposed including nanostructuring, incorporating with carbon mediums, and post-processing of the electrode [2,7]. Herein, we elevate the electrochemical performance of waste LCD derived Si through carbon coating and electrode post-processing, that called maturation [7]. Firstly, obtained Si materials were coated by carbon using sucrose at 800 °C in Ar. Then, the electrode was matured by storing it in chamber at ~99% relative humidity for 2 days. The prepared Si electrodes exhibit much better cycling stability than untreated electrodes. This improvement originated from coated carbon and maturation process, which strengthens the cohesion of active materials and the adhesion of active material/current collector, thus less pulverization of the electrode.

References

[1] J. Entwistle, A. Rennie, S. Patwardhan, J. Mater. Chem. A, 6 (2018) 18344-18356.
[2] M. Choi, J.C. Kim, D.W. Kim, Sci. Rep., 8 (2018) 960.
[3] C. Li, C. Liu, W. Wang, Z. Mutlu, J. Bell, K. Ahmed, R. Ye, M. Ozkan, C.S. Ozkan, Sci. Rep., 7 (2017) 917.
[4] Y.-C. Zhang, Y. You, S. Xin, Y.-X. Yin, J. Zhang, P. Wang, X.-s. Zheng, F.-F. Cao, Y.-G. Guo, Nano Energy, 25 (2016) 120-127.
[5] C.-T. Lee, J. of Ind. Eng. Chem., 19 (2013) 1916-1925.
[6] X. Zuo, J. Zhu, P. Müller-Buschbaum, Y.-J. Cheng, Nano Energy, 31 (2017) 113-143.
[7] C.R. Hernandez, A. Etiemble, T. Douillard, D. Mazouzi, Z. Karkar, E. Maire, D. Guyomard, B. Lestriez, L. Roué, Adv. Energy Mater., 8 (2018) 1701787.
Improving Electrochemical Performance of 0.4Li2MnO3-0.6LiNi1/3Co1/3Mn1/3O2 Cathode Materials for Lithium Secondery Batteries with Coating LiNi0.5Mn1.5O4
Authors: Chen Yufang , Zheng Chunman , Xu Jing 
Published: February 2020

Two components of the xLi2MnO3-yLiNi1/3Co1/3Mn1/3O2 have the same framework offer good structure compatibility, but exist large irreversible capacity loss[1] and structure transformation[
2
] when initially charged to 4.5V or higher. Hence there are many researchers focus their interest to investigate the possibility of integrating core-shell structure on reducing the irreversible capacity loss and improving cycle stability[3]. This paper is mainly on the improvement of electrochemical properties of 0.4Li2MnO3-0.6LiNi1/3Co1/3Mn1/3O2. The core cathode material was prepared from co-precipitation process. And the Shell material of LiNi0.5Mn1.5O2 has been integrated onto the surface of the core material using with assistance of PVP, since PVP has an effect of constraining particle size. After absolutely dried, both the coated and pristine samples were post-treated at the same thermal condition (Figure1).
Figure 2(a). presents a compare of first charge-discharge process of the coated and pristine sample, a remarkable change in the activate process, as coating bring up first cycle efficiency from 73.3% to 83.7% operated at a voltage of 2.0~4.8V vs Li0 at an current rate of c/20(1c=250mAh/g).Figure 2(b). shows an enhancement of cycling properties after coated.

Figure 1
Ageing Analysis of Miniature Cylindrical Cell for Fitbit Flex 2 Wristband
Authors: Tan Chaou Choak , Loveridge Melanie J , Remy Guillaume , Walker Marc , Dixon Shaun , Bhagat Rohit , Williams Mark A 
Published: February 2020

Lithium ion battery (LIB) is gaining popularity in energy storage device due to its high energy density per unit mass and has found application in mobile phone, laptops, power tools and electric vehicle. More recently, LIB has also been utilised to power smart wearable devices such as fitness tracker, smart watches and smart glasses. Wearable device is gaining popularity and the market will continue to grow1. With devices shrinking so drastically, the need for smaller but higher energy density battery and good cycle life is more demanding than ever. Understanding battery performance and its degradation process are therefore crucial to give insights on how to extend battery life and reduce capacity-fading.
Here, we performed cell assessment on miniature cylindrical cell extracted from Fitbit Flex 2 fitness tracker and with an attempt to understand capacity-fading process of Fitbit cell utilising electrochemical, teardown and materials analysis. This miniature cylindrical cell is 3.65 x 20 mm in size with energy density of 503Wh/L and nominal capacity of 15mAh.
Teardown analysis on several numbers of non-cycled Fitbit cells have shown severe anode coating delamination from the copper current collector when the jelly roll were unravelled and with anode materials transferred to the separator. Nevertheless, Fitbit cell shows 82 % cell capacity retention after 500 continuous charging and discharging cycles at 3.0-4.35 V, 0.75C rate at 20 °C. Electrochemical Impedance Spectroscopy (EIS) shows increase in internal cell resistance, in which Li+ ion charge-transfer resistance (Rct) is the main contributor. Scanning electron microscope (SEM) with energy dispersive spectroscopy (EDS) shows no visible morphological and compositional changes between fresh and aged cathode, anode and separator. X-ray photoelectron spectroscopy (XPS) reveals surface film contains organic compounds as well as lithium fluoride (LiF) and phosphates other than LiPF6 forming on both cathode and anode surface. XPS also shows increasing LiF and phosphates in cathode and anode surface film. The cause of increasing Rct and the possible source of LiF will be discussed.
1. https://www.statista.com/statistics/610447/wearable-device-revenue-worldwide/ [assessed on 17 January 2019]

Figure 1
Influence of Different Acids on Si/C Anode Pastes pH Values and the Corresponding Electrochemical Performance in Li Ion Cells
Authors: Keßler Elizaveta , Börner Markus , Niehoff Philip , Schappacher Falko , Winter Martin 
Published: February 2020

Silicon particles are applied as anode active material in Li ion batteries to achieve higher energy densities. However, the usage of silicon particles today, comes along with increased aging and safety issues. The lithium uptake by the silicon particles during the charging process is accompanied by huge volume expansion (over 280%).1 Hence, the electrochemical performance suffers from ongoing capacity fading with each cycle due to contact loss between active material particles and the current collector. 2,3

To counter these issues different approaches have been done in literature including the reduction of the silicon particle size, the application of different binders, the use of silicon nanotubes, nanowires or core-shell particles.4,5,6 Acidic pretreatment is also well-known in the framework of surface functionalization of silicon particles. 7,8

In this work phosphoric, sulfuric, salt and oxalic acid were used to achieve better adhesion between active material particles and current collector. It also improves the electrochemical performance by lowering the discharge capacity fading. The pH value of the anode paste was varied to 3.6, 2.8 and 1.4, respectively, to investigate the effect on the adhesion between the silicon particles. To accelerate the reaction between the silicon particles and the appropriate acid the reaction conditions were optimized. The improvement in the electrochemical performance was coherent to the reaction progress, the period individually depended on the used acid.
For all four acid types the application resulted in a decrease of discharge capacity fading. An increase of the anode paste viscosity could be observed during the reaction time. Phosphoric acid turned out to be an appropriate acid for the application in the anode paste as it reached the highest capacity retention after 100 cycles at 1.0C and the best reproducibility. Oxalic acid showed the worst performance as a high ratio of parasitic reactions could be observed in the first charge cycle at 0.1C. With lower pH value bigger agglomerations between silicon particles were shown in SEM images simultaneously deteriorating the performance. The best performance was achieved with a pH value of 3.6 for every acid type.

References

[1] M. N. Obrovac, Chem. Rev. , 114, 23, 11444-11502 (2014).
[2] K. M. Abraham, J. Phys. Chem. Lett., 6, 830 (2015).
[3] W. J. Zhang, J. Power Sources, 196, 13 (2011).
[4] N.-L. Wu, J. Power Sources, 140, 1,139-144 (2005).
[5] R. A. Huggins, Materials for Sustainable Energy, 187-191 (2010)
[6] Y. Cui, Nano Lett., 9, 9, 3370-3374 (2009).
[7] B. L. Lucht, J. Electrochem. Soc., 165 (10), A1991-A1996, 2018.
[8] B. L. Lucht, Langmuir
33 (37), 9254-9261, 2016.

Figure 1
Influence of Conductive Agent in C/Si-Composite Electrodes for High-Energy Lithium Ion Batteries
Authors: Ambrock Karina , Niehoff Philip , Winter Martin , Schappacher Falko 
Published: February 2020

Lithium ion batteries outperform other energy storage technologies in the combination of specific power and specific energy [1]. However, continuous improvement is necessary regarding the ever-increasing demands in terms of high energy densities, long cycle life and improved safety properties. One strategy to increase the specific energy density and decrease the overall cost of lithium ion batteries is the partial substitution of graphite with silicon in the negative electrode. Silicon forms alloys with lithium and offers an extremely high theoretical capacity (3579 mAh g-1) [2, 3]. However, the lithiation and delithiation process of silicon generates mechanical stress due to particle swelling and contraction (∆V ≥ 300%). This stress eventually causes mechanical fracture and pulverization, which in turn leads to active material loss.
Inactive materials and the use of a composite of active materials, silicon and graphite (C/Si), can help to mitigate these degradation effects. The binder ensures adhesion and cohesion of and within the electrode and its different components. Conductive agents improve the electrical conductivity and provide inter-particle as well as particle-current collector contacts. Therefore, the electrode and cell design can largely influence the electrochemical performance and cycle life. Different applications require different ratios of active material, conductive agent and binder.
Especially considering the low electrical conductivity of silicon [4], the use of conductive carbon is inevitable to increase electrical conductivity within the composite electrode. However, with C/Si electrodes, the necessity of conductive agent is questionable, since the graphite present in the composite might be able to provide sufficient electrical conductivity. Furthermore, an excessive amount of inactive material reduces the energy density of the electrode and has to be optimized.
This study focuses on the impact of conductive agent in high energy C/Si composite electrodes. To ensure a high loading and high energy density, the amount of inactive materials were optimized. For that, electrodes were prepared with different amounts of conductive agent and electrochemically tested in coin cells (charge/discharge cycle).

Internationl Energy Agency Technology Roadmap Electric and plug-in hybridelectric devices: Technical report 2011.

Sharma, R. A. and Seefurth R. N. J. Electrochem. Soc. 1976
volume 123
,
1763-1768. 1976,
123 (12), 1763.

Boukamp, B.A., et al.
J Electrochem Soc
1981, 128, 725-729

Pollak, E.,et al.
J. Phys. Chem. C
2007, 111, 30, 11437-11444