bluuebunny/crossref_metadata_2025_split huggingface dataset:
Designs of Experiments to Optimize Li-Ion Batteries
Authors: Rynne Olivier , Dubarry Matthieu , Lepage David , Molson Corentin , Nicolas Eva , Ayme-Perrot David , Rochefort Dominic , Dollé Mickael 
Published: May 2020

Studies pinpointed the limitation of power-related performance for Li-ion batteries to the microstructure of each electrode.1, 2 This random arrangement of the active material (AM) and carbon filling particles bound by a polymer is typically characterized through physical values such as tortuosity, porosity and Mac Mullin Number.3 There is nonetheless no consensus on what the best formulation is for a given set of electrode components.
The relationship between microstructure and performance is investigated by planning and analyzing a Design of Experiments based on a Complex Mixture Design. Thirty different formulations were characterized where Li4Ti5O12 was the AM, and carbon black and carbon nanofibers were conductive fillers. As for the binder, two were studied: polyvinylidene fluoride and a fluorine-free thermoplastic elastomer.4 All other factors, e.g. rheology or experimenter bias, were closely monitored and finely controlled to remain identical for all samples.
Electrochemical performance were studied at low, medium and high charging speeds to account for different limitations of full capacity retention. Statistical analysis showed clear correlations between the formulation and the electrodes’ capacity with very high descriptive statistics, e.g. R2. Lastly, strong correlations were found between capacity and microstructure, strengthening further the trust in the empirical equations. These robust models helped choosing optimal fluorine-free formulations that surpassed even the highest performing previous electrodes.

1. Vasileiadis, A.; Klerk, N. J. J. d.; Smith, R. B.; Ganapathy, S.; Harks, P. P. R. M. L.; Bazant, M. Z.; Wagemaker, M., Toward Optimal Performance and In‐Depth Understanding of Spinel Li4Ti5O12 Electrodes through Phase Field Modeling. Advanced Functional Materials
2018,
0 (0), 1705992.
2. Ngandjong, A. C.; Rucci, A.; Maiza, M.; Shukla, G.; Vazquez-Arenas, J.; Franco, A. A., Multiscale Simulation Platform Linking Lithium Ion Battery Electrode Fabrication Process with Performance at the Cell Level. The Journal of Physical Chemistry Letters
2017,
8 (23), 5966-5972.
3. Landesfeind, J.; Hattendorff, J.; Ehrl, A.; Wall, W. A.; Gasteiger, H. A., Tortuosity Determination of Battery Electrodes and Separators by Impedance Spectroscopy. Journal of The Electrochemical Society
2016,
163 (7), A1373-A1387.
4. Rynne, O.; Lepage, D.; Aymé-Perrot, D.; Rochefort, D.; Dollé, M., Application of a Commercially-Available Fluorine-Free Thermoplastic Elastomer as a Binder for High-Power Li-Ion Battery Electrodes. Journal of The Electrochemical Society
2019,
166 (6), A1140-A1146.
With this presentation, we want to show the versatility and power of Designs of Experiments to the community, whether for electrode formulation or new material synthesis, as the input parameters can be easily interchangeable.

Figure 1
(Invited) Morphological and Chemical Stability Issues at Interfaces in Solid State Batteries
Authors: Ceder Gerbrand 
Published: May 2020

Interfacial issues are believed to be a key issue challenging the long-time operation of solid-state batteries. In particular on the anode side, where the use of metallic lithium will be a requirement to achieve high energy density, understanding plating morphology and the ability for lithium to penetrate and grow into hard solid electrolytes has been challenging. Using modeling that integrates electrolyte transport with the mechanical behavior of the electrolyte and metallic lithium we show that the ability of lithium to grow through a solid conductor depends on just a few intrinsic materials parameters, which can be used to design more dendrite resistant electrolytes. We also delineate the particular conditions under which electronic conductivity can lead to lithium deposition in the conductor.
On the cathode side the lack of high voltage stability of solid electrolytes and coating materials is the main driver for impedance growth. Using basic chemical principles, similar to those used to make high voltage cathodes, one can design coating materials that remain intact even for high voltage charging. We belief that the development of more quantitative guidelines for interfacial stability is important for advancing the solid-state battery field.
Anion Charge Dependent Lithium Ion Diffusion in Solids
Authors: Xu Zhenming , Zhu Hong 
Published: May 2020

Utilizing solid-state electrolyte materials for lithium-ion batteries not only fundamentally solve the safety problem of the commercial lithium-ion batteries, but also greatly increase the energy density of batteries. Lithium solid-state electrolyte materials should have high conductivities at room temperature comparable to liquid electrolyte, good (electro)chemical stabilities, mechanical properties, and excellent compatibilities with electrodes. The proposed design principles for lithium superionic conductors mainly include the concepts of bcc anion framework, low lithium phonon density center, and high distortion lithium-anion polyhedron. Moreover, the smaller anionic charge is well considered to benefit for the rapid transport of lithium ion, e.g. negative monovalent anions are more favorable for cation diffusion than negative divalent anions.
However, our recent studies of the chalcopyrite-structured sulfides and non-spinel-structured halides show that the lithium-ion migration energy barrier can be effectively reduced by comprehensively regulating the anion charge and lithium-ion coordination environments. For example, for lithium ion diffusion between two adjacent lithium-anion octahedrons through a tetrahedral transition state, the greater the anionic charge is, the lower the lithium ion diffusion energy barrier will be. While for lithium ion diffusion between two adjacent lithium-anion tetrahedrons through an octahedral transition state, the smaller the anion charge is, the lower the lithium ion diffusion barrier will be. According to this design principle and choosing the appropriate cations to isolate the electronic conductive channels, we obtained the quaternary Li2CuPS4 solid electrolyte material with tetrahedral lithium occupations. Li2CuPS4 not only has high thermodynamic stability, but also theoretically possess the high ionic conductivity of 84.9 mS/cm at room temperature. In addition, the non-spinel halide Li3LaI6 with octahedral lithium occupations has relatively high ionic conductivity of 1.23 mS/cm at room temperature, and its thermodynamic stability and electrochemical stability are far superior to sulfides. This new understanding of comprehensively regulating the anion charge and lithium-ion coordination environments to enhance lithium ion transport can be applied for the design and optimization of new superionic conductors.
The Development of High-Throughput Methods in the Study of Solid State Li-Electrolytes
Authors: Jonderian Antranik , McCalla Eric 
Published: May 2020

High-throughput experimentation is a fast and efficient methodology for materials discovery, screening, and optimization. It has, therefore, garnered a lot of attention from battery researchers as a potential way to accelerate the development of next-generation Li-ion batteries and battery systems beyond Li-ion. However, its successful use in battery materials discovery has been extremely limited due to a variety of challenges including: (i) difficulties in synthesizing mg-scale samples that are comparable to bulk samples made by industrial methods, (ii) limited high-throughput characterization acting like a bottleneck even after high throughput synthesis is developed, and (iii) high cost of commercially available high-throughput instrumentation. Here, we develop high throughput techniques for solid-state electrolytes.
First, a novel synthesis approach is used to make 64 mg-scale solid electrolytes simultaneously. The powder samples are prepared by a citrate sol-gel method using an automated dispensing system. These powders were formulated into sixty-four pellets using a home-made high-throughput pellet press die. The samples are then sintered at high temperature to yield the solid electrolytes. The proof of concept here is performed on the Li-La-Ti-O pseudo-ternary system that includes the perovskites Li3xLa2/3-xTiO3, considered candidates for solid-state electrolytes for high energy lithium-ion batteries. Given that vacancies and other defects play an essential role in ionic conductivity, the screening of complete phase diagrams has the potential to reveal phases with optimized defect contents and thus yield improved solid electrolytes.
We have therefore developed a high-throughput characterization suite for solid electrolytes. First, we use a high throughput X-ray diffractometer capable of producing Rietveld quality patterns for mg-scale samples in 10 min such that 64 patterns can be obtained in under 12 h. This system is readily used to produce structural phase diagrams in ternary or even quaternary systems. Next, a high throughput electrochemical impedance spectrometer is used to map the ionic conductivities onto the phase diagrams. Finally, high throughput electrochemistry is used to determine the stability window of the electrolytes. All aspects of this workflow are demonstrated on the Li-La-Ti-O system. This now permits the synthesis and full characterization of approximately 192 compositions per week with one researcher only. This approach is well suited to determine the structure-property relations in complex composition spaces.
The complete ternary Li-La-Ti phase diagram synthesized at 1150 °C with slow cooling was determined and will be presented in detail. The total (ionic + electronic) conductivity of the phase diagram was mapped by the electrochemical impedance spectroscopy. Quenching was performed to verify that transformations during slow cooling are moderate in this system. Consequences for the development of other solid electrolytes will also be discussed.
Improving Ionic Conduction in Solid State Batteries Via Bulk and Interface Structure Design
Authors: Liu Zhantao , Chen Hailong 
Published: May 2020

All-solid-state Li-ion batteries feature higher energy density, wider operation temperature range and better safety properties1 than conventional Li-ion batteries. The search for high performance solid state ionic conductors as the solid electrolyte (SEs) is one of the focuses of the battery field. Design principles for SE have been raised based on computational or experimental explorations. In this work, we will present our material design practices focusing on two factors that we believe to be essential for the performance of SE in solid state batteries: carrier density and interface. Attempts of tuning the carrier and vacancy densities were implemented in selected model systems, including known material systems and new material families, such as Li15P4S16Cl3
2 and other thiophosphates. Drastic improvement on ionic conductivity at room temperature was realized by either increasing the vacancy density or increasing stabilized interstitial sites. Interface design and engineering were also attempted with model systems including oxides, sulfides and halides. The impact of interface on effective conductivity was investigated with electrochemical impedance spectroscopy and complementary crystal structural characterizations including synchrotron X-ray diffraction and pair distribution function analysis. Modeling of interface structure was also employed to further understand the ionic conduction in the solid electrolyte layer and composite electrodes.

1. Auvergniot, J.; Cassel, A.; Ledeuil, J.-B.; Viallet, V.; Seznec, V.; Dedryvère, R., Interface Stability of Argyrodite Li6PS5Cl toward LiCoO2, LiNi1/3Co1/3Mn1/3O2, and LiMn2O4 in Bulk All-Solid-State Batteries. Chemistry of Materials
2017,
29 (9), 3883-3890.
2. Liu, ZT.; Zinkevich, T.; He, XF.; Indris, S.; Xiong, S.; Liu, J.; Xu, W.; Bai, J.; Mo, Yifei; Chen, HL., Li15P4S16Cl3, a new lithium chloro-thiophosphate as a solid state ionic conductor. Inorganic Chemistry, in press.
New Salts for Lithium-Ion Cells - Low Fluorine and Nonfluorine Electrolytes for Higher Safety
Authors: Niedzicki Leszek , Kasprzyk Marta , Trzeciak Tomasz , Wieczorek Wladyslaw 
Published: May 2020

For the last 30 years, Li-ion cells have become the primary choice as power source for all electronic devices, mobile electronics and electric vehicles of all sorts. During this time huge advance took place in electrode active materials, separators and engineering of electrodes. However, lithium salt used in commercially available Li-ion cells (LiPF6) is still the same. It is known for its thermal instability, chemical incompatibility with silicon-based electrodes and reactions with even traces of water resulting in large costs of anhydrous solvents as well as need for desiccation systems of whole factories. Apart from known issues, it is also a reason for enormous fluorine content in Li-ion cells. Salt itself contains as high as 75% of fluorine in its mass. Thus, electrolytes contain ca. 10% of pure fluorine (typical 1 mol/kg concentration). As whole world makes an effort to drop toxic components, prevent formation of toxic wastes, it is also needed to drop use of fluorine in consumer products, including batteries.
Previously, we presented LiTDI salt, which is now on the market, that contains only ca. 30% of fluorine in its mass and can be used at lower concentrations, decreasing fluorine content in the electrolyte to below 1.5-3% (depending on the application and electrolyte composition).
Here we present first non-fluorine salts that successfully work in Li-ion cells environment. This way electrolyte fluorine content can reach 0% for the first time in Li-ion cell technology history. We show that getting rid of fluorine from the electrolyte does not necessarily means that good performance of both electrolyte and a cell is not possible. Ionic conductivity (over 8 mS/cm), and even more important, lithium cation conductivity values (σLi+ over 3 mS/cm) are comparable to those of LiPF6 and LiTDI, while not giving up on stability properties. Both thermal (up to at least 270°C) and electrochemical (at least up to 4.3 V vs Li) stabilities are still at the satisfactory level. It is still possible to use new salts with all active electrode materials available on the market as well as new ones that currently are not possible to use due to their incompatibility with fluorine-containing salts.
In this presentation we will show newest results of development and investigation of novel anions including low-fluorine-content and nonfluorine ones as main electrolytes in Li-ion cells.
A Simple One-Dimensional Transport Model to Explain Inverse Signatures in Lithium-Metal Batteries
Authors: Uppaluri Maitri , Subramaniam Akshay , Subramanian Venkat R. 
Published: May 2020

Lithium metal is being investigated as the negative electrode for lithium batteries due to its high theoretical capacity (3,860 mAh g–1) and negative electrochemical potential (-3.040 V vs standard hydrogen electrode) 1. However, using lithium metal poses several challenges, including dendritic electrodeposition and accumulation of dead lithium. These phenomena can cause the cell to short, and also contribute to poor cyclability 2.
To prevent these issues, it is important to understand the transport of lithium ions and the kinetics that contribute to lithium deposition and stripping on the anode. Lithium deposition and stripping is correlated with unique voltage signatures, based on the morphology 3. Physics-based continuum models can be used to understand lithium ion transport effects on deposition and stripping, and on the emergent voltage signatures.
Our past work studied one-dimensional models for lithium symmetric cells to model charge transport and capture the transitions in voltage observed experimentally 4. In this work, we propose a simple diffusion-based model based on our past work that shows inverse signatures of lithium ion concentration and overpotential for the lithium deposition reaction. We show that using a transport model alone can produce unique inverse voltage signatures. The model used is a one-dimensional moving boundary model, where the deposition and stripping of lithium is modeled as a moving interface.
The cell was simulated at different current densities, and for different variations in diffusivities of the anion and cation in the electrolyte. The current density affects both interface motion and ion transport in the electrolyte. The interplay between these two phenomena then determines characteristic signatures of overpotential and concentration, and ultimately the cell voltage.

References

1. W. Xu, J. Wang, F. Ding, X. Chen, E. Nasybulin, Y. Zhang, and J. G. Zhang, Energy Environ. Sci., 7, 513–537 (2014).
2. D. Lin, Y. Liu, and Y. Cui, Nat. Nanotechnol., 12, 194–206 (2017).
3. K. N. Wood, M. Noked, and N. P. Dasgupta, ACS Energy Lett., 2, 664–672 (2017).
4. A. Subramaniam, J. Chen, T. Jang, R. M. Kasse, M. F. Toney, and N. R. Geise, J. Electrochem. Soc., 166, A3806–A3819 (2019).
Sulfide-Based All-Solid-State Batteries: From Electrolyte Synthesis to Interface Design
Authors: Zhao Feipeng , Liang Jianwen , Sun Xueliang 
Published: May 2020

All-solid-state Li-metal batteries (ASSLMBs) have attracted increasing attentions because of their high specific energy density and advantage of safety compared with conventional liquid electrolyte-based Li-ion batteries (LIBs). Solid-state electrolytes (SSEs) are the key component for ASSLMBs. Sulfide-based SSEs exhibit a very competitive ionic conductivity compared with oxides, polymer-based, and other kinds of SSEs. However, the poor electrode/sulfide SSEs interface and the moisture-sensitivity hinder the development.1

From the point of sulfide SSEs synthesis, we demonstrate that using fluorine (F) incorporation in an Argyrodite Li6PS5Cl sulfide electrolyte (LPSCl) can achieve an ultra-stable Li metal/sulfide SSEs interface. The performance can be comparable to that in the symmetric cells based on liquid electrolytes. The condensed interfacial structure and high fluorinated chemical composition of the in-situ formed interface lead to the high performance.2 In addition, Sn (IV) is employed to partially replace problematic P (V) in Argyrodite sulfide Li6PS5I (LPSI) SSEs to prepare relatively air-stable sulfide SSEs, which is attributed to the strong Sn-S bonding energy in the Sn-substituted LPSI electrolytes (LPSI-Sn). Benefiting from the aliovalent element substitution and I-based chemistry, LPSI-Sn electrolyte can show 125-times increase in the ionic conductivity and significantly improved Li metal compatibility.3

For the interface design, we focus on the improvement of the Li anode/sulfide SSEs interface stability. Inorganic LixSiSy and Li3PS4 protection layer achieved by in-situ growing on the Li metal, which can serve as an effective interlayer to improve chemical/electrochemical stability of Li/sulfide SSEs interface.4-5 The growth of Li dendrites at the interface is suppressed. The side reaction between Li metal anodes and sulfide SSEs is also well controlled.In addition, the Li-ion conductive interlayer has demonstrated favorable ionic conductivity fundamentally. High-rate ASSLMBs can be achieved by using these inorganic Li-ion conductive protection layers.

Re
ferences

1. Q. Zhang, et al. Sulfide-Based Solid-State Electrolytes: Synthesis, Stability, and Potential for All-Solid-State Batteries. Advanced Materials 2019, 31, 1901131.
2. F. Zhao, X. Sun, et al. Ultra-Stable Li Anode Interface Achieved by Incorporating Fluorine in Argyrodite Sulfide Electrolytes. Submitted.
3. F. Zhao, J. Liang, X. Sun, et al. A Versatile Sn-Substituted Argyrodite Sulfide Electrolyte for All-Solid-State Li Metal Batteries. Submitted.
4. J. Liang, X. Li, X. Sun, et al. An Air-Stable and Dendrite-Free Li Anode for Highly Stable All-Solid-State Sulfide-Based Li Batteries. Advanced Energy Materials 2019, 9, 1902125.
5. J. Liang, X. Li, X. Sun, et al. In Situ Li3PS4 Solid-State Electrolyte Protection Layers for Superior Long-Life and High-Rate Lithium-Metal Anodes. Advanced Materials 2018, 30, 1804684.
Assembling an All-Solid-State Ceramic Battery: Assessment of Chemical and Thermal Compatibility of Solid Ceramic Electrolytes and Active Material Using High Temperature X-Ray Diffraction
Authors: Bertrand Marc , Rousselot Steeve , Ayme-Perrot David , Dollé Mickael 
Published: May 2020

Lithium ion batteries (LIBs) are the most known and used batteries for portable energy storage because of their high energy densities, long cycle life and relatively low price. However, they still fall short for the development of long range electric vehicles and stationary applications due to organic liquid electrolytes that are currently electrochemically limited and present safety issues (fire or explosion in case of short-cut or overcharging). Solid oxide electrolytes appear to be one of the solutions because of their non-flammability and wide potential window. Inorganic oxide electrolytes have reasonable ionic conductivities (10-5-10-3 S/cm at ambient temperature), high mechanical strength, and high chemical stability.
Assembling an all ceramic solid-state battery with inorganic oxide electrolyte is challenging as it requires a deep knowledge of the thermal, chemical and electrochemical behavior of each component of the cell. The battery must be a continuous monolithic block with a thin dense electrolyte separator, in order to minimize the polarization. In addition, optimized interfaces between active material and electrolytes must be ensured in the composite electrodes. This is often achieved with oxide-based materials by using high temperature processing.
Thermal expansion occurring during this step can lead to cracks, which will affect the performance and cyclability of the device. The primary driving force of a crack during the fabrication of hybrid ceramic is the stress due to mismatch in the coefficient of thermal expansion (TEC) of the various layers/materials. Moreover, it must be certain that no reaction occurs between active material and electrolytes in the sintering temperature range. These are then two key parameters to address for the development of all ceramic solid-state batteries.
In this work, in situ-XRD has been used to determine the TEC and the thermal stability of various well-known oxide active materials and solid electrolytes. The aim of this presentation is to discuss about the best selection of compatible oxide-based materials to avoid unwanted cracks or reaction during the sintering processing of ceramic solid-state batteries.
(Invited) Point Defects and Doping in Ga2O3 and Related Alloys
Authors: Varley Joel Basile 
Published: May 2020

Ga2O3 and related alloys are a promising platform for realizing wide-band gap semiconductors for use in a number of next-generation electronic devices exploiting their large band gaps and controllable electrical conductivity. Ga2O3 exhibits a band gap (4.8 eV) that can be tuned by In and Al incorporation, with Al-containing alloys increasing the band gap in contrast to In incorporation. While control over defect concentrations and n-type doping of Ga2O3 is rapidly improving, the dopability of alloys has remained largely unexplored. Here we describe the behavior of point defects and n-type dopants in Ga2O3 and consider the prospects of doping in the larger-gap Al-containing alloys using first-principles modelling approaches based on hybrid functional calculations. We consider a number of conventional dopants such as Si, Ge and Sn, as well as newer dopants that have been identified as effective alternatives. These results provide guidance for doping in Ga2O3 and related alloys incorporated into heterostructure devices.
This work was partially performed under the auspices of the U.S. DOE by Lawrence Livermore National Laboratory under contract DE-AC52-07NA27344 and partially supported by the Critical Materials Institute, an Energy Innovation Hub funded by the U.S. DOE, Office of Energy Efficiency and Renewable Energy, Advanced Manufacturing Office.