bluuebunny/crossref_metadata_2025_split huggingface dataset:
Elucidating Ionic Mobility in Multivalent Spinel Oxides
Authors: Murphy Megan , Alexander Grant C. B , Hirmiz Mark , Bayliss Ryan D , Tucker Matthew G , Cabana Jordi 
Published: July 2021

With lithium-ion batteries seemingly reaching their developmental limits, researchers are exploring new chemistries to obtain the higher energy densities needed for electric vehicles to become more competitive for universal market adoption. Batteries based on Mg chemistries could achieve these goals. Oxides with a spinel structure are predicted to provide a favorable combination of properties to function as attractive magnesium cathodes; however, traditionally, Mg2+ intercalation suffers from sluggish mobility. Theory has predicted the energy barriers for the Mg2+ hops between tetrahedral sites via the vacant octahedral sites are low enough to enable sufficient room temperature transport. Experimental studies have shown potential Mg2+ migration at comparable timescales. While the activation barriers could be extracted, the path followed by the Mg2+ cation during a hop remains to be elucidated.
To better understand the trajectories for multivalent ion mobility in spinel oxides, variable temperature neutron diffraction and pair distribution function (PDF) are used to examine the average and local structure. Reverse Monte Carlo (RMC) profiling is then used to map the ionic pathways via large-box modeling of the crystal structure. Further contrast is provided by studying similarly structured samples where hopping is predicted to face higher activation barriers than Mg and, thus, show slower migration. Insight into how ion mobility is achieved in spinel structured oxides will better inform the design of new battery cathode host structures and electrolytes to help push Mg batteries into commercialization.
Direct Casted LLZO-LITFSI Composite Solid-State Electrolyte for Lithium Ion Batteries
Authors: Zhang Sanpei , Jansen Andrew N. , Lu Wenquan 
Published: July 2021

All-solid-state batteries (ASSBs) based on solid state electrolytes (SSE) has a promising future for safer lithium ion batteries (LIB) with high energy density. However, it has been challenging in large-scale fabricating an SSE separator with transport properties and comparable thickness to a traditional polypropylene separator used in lithium-ion batteries. This problem is especially exaggerated with oxide-based solid electrolytes, such as Li7-3xAlxLa3Zr2O12 (LLZO), where thin films with micrometer scale in thickness using scalable techniques have not been realized.
LLZO SSE separator is commonly made by fabricating pellet and followed by sintering. The resulting film must be thick enough to provide reasonable mechanical strength. However, the thick SSE separator will cause high resistance and low energy density. Here we present a direct casting technique to coat ultrathin LLZO-LITFSI composite electrolyte on the LiFePO4 cathode. Through this technique, the electrolyte layers with different thickness ranging from 50 to 150 µm were prepared and studied electrochemically in ASSB using lithium as the anode. Without any further process and treatment, the ASSBs show a stable cycling performance with a reversible capacity >150 mA h/g (~90% of the theoretical value). This work provides a potential scale-up strategy to manufacture stable and ultrathin garnet-based SSE for all-solid-state batteries.
Acknowledgement
We gratefully acknowledge the support from the U.S. Department of Energy's Vehicle Technologies Office. This work is conducted under the Cell Analysis, Modeling, and Prototyping (CAMP) Facility at Argonne National Laboratory. Argonne National Laboratory is operated for DOE office of Science by UChicago Argonne, LLC, under contract number DE-AC02-06CH11357.
High-Performance Composite Polymer Electrolyte Membranes for Solid-State Lithium-Metal Batteries
Authors: Mehraj Ud Din Mir , Fischer Susanne Maria , Kuhnert Eveline , Häusler Michael , Trimmel Gregor , Slugovc Christian , Rettenwander Daniel 
Published: July 2021

Ceramic-polymer composite electrolytes are among the strong contenders for the development of safe and high-energy density solid-state Li-metal batteries (SSLB). Current composite electrolytes suffer, however, from low conductivity and thermodynamic instability versus cathode materials1-3. In order to overcome the current limitations, we report the preparation of electrolyte membranes based on lithium garnet (LLZO) nanowires synthesized via electrospinning technique, poly (ethylene oxide) (PEO) and a sulfonic-based plasticizer enabled with high Li-ion conductivity of 0.1 mS cm-1 at room temperature. The fabricated flexible membranes show improved electrochemical performances. For example, the cyclic voltammetry results confirm the electrochemical stability of the developed electrolyte membrane in a voltage window of 3 V to 5.5 V that potentially enables utilization of high voltage cathodes such as LiCoPO4. To extend, the electrochemical stability towards low voltage to enable the use of cathode materials operating in a larger or lower voltage range, we engineered the lithium metal surface by a thin layer of Li3N layer that stabilized the developed membranes down to 1.5 V. Integration of the developed electrolyte membranes with high specific capacity cathodes could potentially enable the next generation Li-metal batteries with high energy density.

References:

(1) Croce, F.; Appetecchi, G. B.; Persi, L.; Scrosati, B. Nanocomposite Polymer Electrolytes for Lithium Batteries. Nature
1998, 394(6692), 456-458. https://doi.org/10.1038/28818.
(2) Kuhnert, E.; Ladenstein, L.; Jodlbauer, A.; Slugovc, C.; Trimmel, G.; Wilkening, H.M.R.; Rettenwander, D. Lowering the Interfacial Resistance in Li6.4La3Zr1.4Ta0.6O12|Poly (Ethylene Oxide) Composite Electrolytes. Cell Rep. Phy. Sci.
2020, 1(10), 100214. https://doi.org/10.1016/j.xcrp.2020.100214.
(3) Choudhury, S.; Stalin, S.; Vu, D.; Warren, A.; Deng, Y.; Biswal, P.; Archer, L. A. Solid-State Polymer Electrolytes for High-Performance Lithium Metal Batteries. Nat. Commun.
2019, 10(1), 1-8. https://doi.org/10.1038/s41467-019-12423-y.

Acknowledgement:

The financial support by the Austrian Federal Ministry for Digital and Economic Affairs, the National Foundation for Research, Technology and Development and the Christian Doppler Research Association (Christian Doppler Laboratory for Solid-State Batteries) and the Austrian Science Fund (FWF) (project no. P25702) is gratefully acknowledged.
Improving Cell Resistance and Cycle Life with Solvate/Thiophosphate Hybrid Electrolytes in Lithium Metal and Lithium Sulfur Batteries
Authors: Gewirth Andrew A. , Philip Maria , Shin Minjeong 
Published: July 2021

Solid electrolytes (SEs) have become a practical option for lithium ion and lithium metal batteries due to their improved safety over commercially available ionic liquids. The most promising of the SEs are the thiophosphates whose excellent ionic conductivities at room temperature are comparable to those of the commercially-utilized ionic liquids. Hybrid solid-liquid electrolytes exhibit higher ionic conductivities than their bare solid electrolyte counterparts due to decreased grain boundary resistance, enhanced interfacial contact with electrodes, and decreased degradation at the interface.
In this study, we evaluate a series of hybrid electrolytes made from a ‘solvate’ electrolyte in both Li-Li symmetric cells and in a full cell with a Li2S cathode relative to their bare Li/SE/Li counterparts. Interestingly, hybrid electrolytes made by combining HFE-modified solvates and SE exhibit all the benefits of the interlayer modified SEs, without the necessity of pellet manufacture. The solvate-integrated cathode layer is additionally beneficial for achieving high active material utilization, maintaining intimate interfacial contact, and providing buffer space for volume contraction and expansion. The hybrid Li2S cell exhibited superior cycling performance compared to the solid-state cells in terms of Li2S loading, Li2S utilization, and cycling stability. Finally, we discuss the use of hybrid and high concentration electrolytes to enable other cathode chemistries, particularly those involving conversion.
Nucleation and Growth of Solid Electrolyte Interphase on Lithium Metal Batteries
Authors: Angarita Gomez Maria , Guo Ningxuan , Balbuena Perla B. 
Published: July 2021

Lithium metal anode is considered a great candidate because of its high theoretical capacity and negative electrochemical potential. However, key factors like poor cyclability as well as the safety issues related to the uneven lithium electrodeposition, dendrite growth, and unstable solid electrolyte interphase (SEI) are keeping lithium metal batteries away from commercialization. Different attempts both experimentally and theoretically have been done to decode the exact structure and distribution of SEI, but due to the inherent dynamic behavior as well as the lithium reactivity, the exact structure of the SEI and its growth mechanisms are still unclear. In this study with the use of molecular simulation and computational chemistry tools, we investigate the initial nucleation and growth dynamics of different SEI components that provide us with thermodynamics and structural information about the nucleating SEI.
Different nucleation and growth mechanisms were studied for the SEI components including LiF, Li2O, and LiOH. An initial mechanism of nucleation is based on the assumption that a Li metal cluster represents a portion of the surface where inhomogeneous Li seeds are nucleating, we use ab initio methods to determine the preferential addition sites for OH or O radicals or fluorine anions. This mechanism allows the study of different structures of SEI in lithium-rich environments simulating initial stages of electrolyte decomposition and SEI formation. Multiple models are studied to understand the formation energies and structures for SEI nanocluster formation in which already formed fragments of SEI are joined together to study the formation of larger SEI clusters. Each of the different components of SEI reveals its preferential growth mechanisms showcasing different degrees of crystallinity and electron density distribution leading to a better understanding of the nucleation and growth of SEI.
Exploring the Ion Solvation Environments in Solid-State Polymer Electrolytes through Free-Energy Sampling
Authors: Sundararaman Siddharth , Prendergast David 
Published: July 2021

Lithium-ion batteries are high energy density power sources that find uses in the automobile industry for electric cars and various portable devices like smartphones, laptops etc. There are strong motivations for developing solid-state electrolytes due to safety concerns associated with the combination of flammable liquid electrolytes and cell shorting due to lithium dendrite growth in current technology. A major issue with solid electrolytes is their low conductivity, which limits the power density (rate of charge/discharge), and possible loss of electrical contact due to anode shrinking. Lithium salts dissolved in poly(ether-acetals) are prime candidates for such electrolytes but the major challenge in improving the performance of these batteries is that the exact mechanism of the motion of the Li+ ions in such systems is not yet well understood. Our goal is to understand the underlying structural differences in the lithium coordination environments in these different systems and how this would affect the movement of the lithium ion from one coordination cage to another. This insight will allow us to suggest new compositions for electrolytes with improved performance for battery applications.
Molecular dynamics simulations using newly developed, accurate interaction potentials have helped elucidate possible mechanisms for various transport properties in these systems. The presence of a second coordination shell around the Li ion, observed in some of these systems, seems to distort the first coordination shell, creating a more open cage structure that may help facilitate transport in these polymers. Furthermore, this distorted coordination may also assist in the formation of a lower coordination transition state while the Li ions jump from one cage to another during diffusion. This may be similar to the pathways followed in solid-state transport - either during topotactic intercalation, as ions move from interstitial to interstitial site; or within materials with solid-solid phase transitions related to thermally induced rotations of complex anions. Free energy calculations further elucidate the relative stability of these different Li-ether coordination environments and the possible pathways to move between them (See figure 1 for example). Furthermore, to understand the associated correlations of glass transition temperature in these systems with microscopic chemical details like the polymer backbone chemistry, ion clustering and coordination, we study the trends in these different systems with extensive statistics from long time molecular dynamics simulations at different temperatures and compositions.

Figure 1
(Invited) Revisiting the Structure–Property Relationships in NaSICON Electrode and Electrolytes
Authors: Canepa Pieremanuele , Deng Zeyu , Singh Baltej , Gautam Gopalakrishnan Sai , Cheetham Anthony K. , Masquelier Christian 
Published: July 2021

Sodium (Na) batteries are promising devices for smart grids and electric vehicles due to cost effectiveness arising from the overall abundance of and its even geographical distribution. The energy density of Na-ion batteries is limited by the positive electrode chemistry [1,2]. The Natrium Superionic CONductor (NaSICON) is known for its wide range of electrochemical potentials, its structural and thermal stability and its high conductivity [1-3]. The electrolyte analogue Na1+xZr2SixP3–xO12 (0 ≤ x ≤ 3) is stable toward other NaSiCON electrodes. Despite the share of research on NaSICONs, the structural and thermodynamic properties of these materials require better understanding.
I will analyse the thermodynamic properties of the Na1+xZr2SixP3-xO12 electrolyte by constructing its phase diagram, based on DFT and Monte Carlo simulations. I will discuss the phase diagram as a function of temperature and composition for the rhombohedral phase, which is common in Na3Ti2(PO4)3, Na3V2(PO4)3 and Na3Cr2(PO4)3 [4].
I will chart the chemical space of NaSICON electrodes NaxMM’(PO4)3 (M, M’= Ti, V, Cr, Mn, Fe, etc.), to analyse their thermodynamic stabilities and the intercalation voltages for Na+ ions in 28 distinct NaSICON compositions. I will discuss anomalies in previously reported experimental data in this diverse and important chemical space [5].
[1] Hong, H. Y.-P. Crystal structures and crystal chemistry in the system Na1+xZr2SixP3–xO12. Mater. Res. Bull.1976, 11, 173– 182.
[2] Goodenough, J. B.; Hong, H. Y.-P.; Kafalas, J. A. Fast Na+-ion transport in skeleton structures. Mater. Res. Bull.1976, 11, 203– 220.
[3] Boilot, J. P.; Collin, G.; Colomban, P. Relation structure-fast ion conduction in the NASICON solid solution. J. Solid State Chem. 1988, 73, 160– 171.
[4] Deng, Z.; Gautam, G. S.; Kolli, S. K.; Chotard, J. N., Cheetham, A. K.; Masquelier, C.; Canepa, P. Phase Behavior in Rhombohedral NaSiCON Electrolytes and Electrodes. Chem. Mater. 2020, 32, 18, 7908–7920.
[5] Singh, B.; Wang, Z.; Park, S.; Gautam, G. S.; Chotard, J. N.; Croguennec, L.; Carlier, D.; Cheetham, A. K.; Masquelier, C.; Canepa, P. A Chemical Map of NaSiCON Electrode Materials for Sodium-ion Batteries. J. Mater. Chem. A. 2020, 10.1039/D0TA10688G
Effects of Non-Solvating Fluorinated Solvents in Localized High-Concentration Electrolytes for Lithium Metal Batteries
Authors: Cao Xia , Gao Peiyuan , Ren Xiaodi , Zou Lianfeng , Engelhard Mark H. , Matthews Bethany E. , Hu Jiangtao , Niu Chaojiang , Liu Dianying , Arey Bruce W. , Wang Chongmin , Xiao Jie , Liu Jun , Xu Wu , Zhang Ji-Guang 
Published: July 2021

High-voltage lithium (Li) metal batteries (LMBs) have been revived in recent years due to their high energy density. 1 However, their practical application is still hindered by the poor stability of the Li metal anode (LMA). The electrolyte is critical to the stability of LMA and the performance of LMBs, because the electrolyte formulation and structure determine the properties of the solid electrolyte interphase (SEI) formed on the LMA surface, which acts as a kinetic barrier for the continuous reaction between the LMA and the electrolyte. 2 High-concentration electrolytes (HCEs) and localized high-concentration electrolytes (LHCEs) have been recognized as good alternatives to replace state-of-the-art LiPF6/carbonate electrolytes and overcome the challenges in LMBs. 3 There are three basic components in the LHCEs: conducting salt, solvating solvent and non-solvating solvent (called diluent), forming a unique solvation structure, where highly concentrated salt-solvent clusters are distributed in the diluent. Here we investigated four types of fluorinated solvents in searching for the most suitable diluent for HCEs, including fluorinated ethers, fluorinated carbonate, fluorinated borate or fluorinated orthoformate. Their roles in the electrolyte solvation structures and effects on the electrode/electrolyte interphases will be discussed during the presentation together with battery performance. These systematic investigations and fundamental insights into LHCEs using different fluorinated solvents can guide further design of advanced electrolytes for high-voltage LMBs.
References:

Liu, J.; Bao, Z.; Cui, Y.; Dufek, E. J.; Goodenough, J. B.; Khalifah, P.; Li, Q.; Liaw, B. Y.; Liu, P.; Manthiram, A.; Meng, Y. S.; Subramanian, V. R.; Toney, M. F.; Viswanathan, V. V.; Whittingham, M. S.; Xiao, J.; Xu, W.; Yang, J.; Yang, X.-Q.; Zhang, J.-G., Pathways for practical high-energy long-cycling lithium metal batteries. Nature Energy
2019,
4 (3), 180-186.

Zhang, J.-G.; Xu, W.; Xiao, J.; Cao, X.; Liu, J., Lithium Metal Anodes with Nonaqueous Electrolytes. Chemical Reviews
2020.

Chen, S.; Zheng, J.; Mei, D.; Han, K. S.; Engelhard, M. H.; Zhao, W.; Xu, W.; Liu, J.; Zhang, J.-G., High-Voltage Lithium-Metal Batteries Enabled by Localized High-Concentration Electrolytes. Advanced Materials
2018,
30 (21), 1706102.
Electrophoretic NMR of Concentrated Electrolytes for Li-Ion Batteries: Understanding the Role of Solvent Motion
Authors: Halat David M. , Hickson Darby , Balsara Nitash P. , Reimer Jeffrey A. 
Published: July 2021

In this work cation, anion, and solvent velocities are reported in concentrated Li-ion battery electrolytes using an electrophoretic NMR (eNMR) methodology. Recent computational studies suggest that in concentrated electrolytes, ion aggregation may lead to transport of Li+ in negatively-charged clusters, resulting in negative cationic transference numbers.1,2 Additionally, increasing ion–solvent coordination may lead to a significant non-zero solvent velocity. These unusual transport properties have important implications for fast-charging performance, but as of yet only limited experimental evidence exists for these phenomena.3 Pulsed-field-gradient (PFG) NMR experiments on their own give self-diffusion coefficients but do not report on the drift of charged species, or induced solvent motion; by running PFG under synchronized application of an electric field (i.e., eNMR), the sign and magnitude of electrophoretic mobilities can be determined with spectroscopic specificity. Through 7Li, 19F and 1H eNMR measurements on carbonate- and glyme-based concentrated electrolytes, we show average species velocities in good agreement with conductivity data, and also directly measure transference numbers in the solvent reference frame. eNMR may provide rapid screening of potential electrolytes at various concentrations to discern which systems (both liquid- and polymer-based) possess efficacious transport properties.
(1) France-Lanord, A.; Grossman, J. C. Correlations from Ion Pairing and the Nernst-Einstein Equation. Phys. Rev. Lett.
2019, 122 (13), 136001. https://doi.org/10.1103/PhysRevLett.122.136001.
(2) Molinari, N.; Mailoa, J. P.; Kozinsky, B. General Trend of a Negative Li Effective Charge in Ionic Liquid Electrolytes. The Journal of Physical Chemistry Letters
2019, 10 (10), 2313–2319. https://doi.org/10.1021/acs.jpclett.9b00798.
(3) Gouverneur, M.; Schmidt, F.; Schönhoff, M. Negative Effective Li Transference Numbers in Li Salt/Ionic Liquid Mixtures: Does Li Drift in the “Wrong” Direction? Physical Chemistry Chemical Physics
2018, 20 (11), 7470–7478. https://doi.org/10.1039/C7CP08580J.
Bulk XAS and Xes Spectroscopy Accessing the Origin of Lithium- and Manganese-Rich Cathodes Performances
Authors: Simonelli Laura , Ali Shehab , Sorrentino Andrea , Bresser Dominic , Passerini Stefano , Tonti Dino 
Published: July 2021

Li-rich layered transition metal oxides Li[Li0.2Ni0.16Mn0.56Co0.08]O2 are attractive electrode materials providing high energy densities, relatively good cycling stability with reduced environmental costs [1]. However, their utility in many applications suffers from both voltage and capacity fade, most likely related to structural transformations and not yet fully understood.
The intrinsic complex nature of such materials strictly requires a multi-techniques approach to disentangle the several compositional degrees of freedom involved in their structure. In spite of being rich in Mn, not much attention is generally paid to the role of this component of such cathodes. In effect, it is important to access the Mn oxidation and spin states. Both such parameters are linked to the Mn size and magnetic interactions, and result key in defining the possible phases in which this cation is involved [1, 2-3], fundamental to control the reversibility of the reactions along cycling. Moreover, the Mn redox and spin state resulted correlated with Ni oxidation/reduction, also spatially, suggesting that strains induced on the Mn−O sublattice by the Ni oxidation are not negligible and can be used to control both the structure and the charge compensation mechanisms [2-3].
The results suggest that strategies can be elaborated to control the Li-rich NMC structure, hindering the spinel formation at the benefit of the electrode cycle life, and the charge compensation mechanism, accessing to an optimum O oxidation along the charge.
[1] Rozier, P.; Tarascon, J. M. Li-Rich Layered Oxide Cathodes for
Next-Generation Li-Ion Batteries: Chances and Challenges. J. Electrochem.
Soc. 2015, 162 (14), A2490.
[2] L. Simonelli et al. J. Phys.
Chem.
Lett. 10, (2019), 3359
[3] S. Ali et al. J. Phys.
Chem.
Lett. 12, (2021), 1195