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How Certain Are the Reported Ionic Conductivities of Thiophosphate-Based Solid Electrolytes? An Interlaboratory StudyClick to copy article linkArticle link copied!
- Saneyuki Ohno*Saneyuki Ohno*Email: [email protected]Institute of Physical Chemistry, Justus-Liebig-University Giessen, Heinrich-Buff-Ring 17, D-35392 Giessen, GermanyCenter for Materials Research (LaMa), Justus-Liebig-University Giessen, Heinrich-Buff-Ring 16, D-35392 Giessen, GermanyMore by Saneyuki Ohno
- Tim BerngesTim BerngesInstitute of Physical Chemistry, Justus-Liebig-University Giessen, Heinrich-Buff-Ring 17, D-35392 Giessen, GermanyCenter for Materials Research (LaMa), Justus-Liebig-University Giessen, Heinrich-Buff-Ring 16, D-35392 Giessen, GermanyMore by Tim Bernges
- Johannes BuchheimJohannes BuchheimInstitute for Technical Chemistry and Environmental Chemistry, Center for Energy and Environmental Chemistry Jena (CEEC Jena), Friedrich-Schiller-University Jena, 07743 Jena, GermanyMore by Johannes Buchheim
- Marc DuchardtMarc DuchardtDepartment of Chemistry, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, D-35032 Marburg, GermanyMore by Marc Duchardt
- Anna-Katharina HatzAnna-Katharina HatzMax Planck Institute for Solid State Research, Heisenbergstrasse 1, 70569 Stuttgart, GermanyDepartment of Chemistry, Ludwig-Maximilians-Universität (LMU), Butenandtstrasse 5-13, 81377 Munich, GermanyCenter for NanoScience, Schellingstrasse 4, 80799 Munich, GermanyMore by Anna-Katharina Hatz
- Marvin A. KraftMarvin A. KraftInstitute of Physical Chemistry, Justus-Liebig-University Giessen, Heinrich-Buff-Ring 17, D-35392 Giessen, GermanyCenter for Materials Research (LaMa), Justus-Liebig-University Giessen, Heinrich-Buff-Ring 16, D-35392 Giessen, GermanyMore by Marvin A. Kraft
- Hiram KwakHiram KwakDepartment of Energy Engineering, Hanyang University, Seoul 04763, South KoreaMore by Hiram Kwak
- Aggunda L. SanthoshaAggunda L. SanthoshaDepartment of Chemistry, Humboldt-University Berlin, Brook-Taylor-Str. 2, 12489 Berlin, GermanyMore by Aggunda L. Santhosha
- Zhantao LiuZhantao LiuThe Woodruff School of Mechanical Engineering, Georgia Institute of Technology, 771 Ferst Drive, Atlanta, Georgia 30332-0245, United StatesMore by Zhantao Liu
- Nicolò MinafraNicolò MinafraInstitute of Physical Chemistry, Justus-Liebig-University Giessen, Heinrich-Buff-Ring 17, D-35392 Giessen, GermanyCenter for Materials Research (LaMa), Justus-Liebig-University Giessen, Heinrich-Buff-Ring 16, D-35392 Giessen, GermanyMore by Nicolò Minafra
- Fumika TsujiFumika TsujiDepartment of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Sakai, Osaka 599-8531, JapanMore by Fumika Tsuji
- Atsushi SakudaAtsushi SakudaDepartment of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Sakai, Osaka 599-8531, JapanMore by Atsushi Sakuda
- Roman SchlemRoman SchlemInstitute of Physical Chemistry, Justus-Liebig-University Giessen, Heinrich-Buff-Ring 17, D-35392 Giessen, GermanyCenter for Materials Research (LaMa), Justus-Liebig-University Giessen, Heinrich-Buff-Ring 16, D-35392 Giessen, GermanyMore by Roman Schlem
- Shan XiongShan XiongThe Woodruff School of Mechanical Engineering, Georgia Institute of Technology, 771 Ferst Drive, Atlanta, Georgia 30332-0245, United StatesMore by Shan Xiong
- Zhenggang ZhangZhenggang ZhangDepartment of Chemistry, Humboldt-University Berlin, Brook-Taylor-Str. 2, 12489 Berlin, GermanyMore by Zhenggang Zhang
- Philipp AdelhelmPhilipp AdelhelmDepartment of Chemistry, Humboldt-University Berlin, Brook-Taylor-Str. 2, 12489 Berlin, GermanyMore by Philipp Adelhelm
- Hailong ChenHailong ChenThe Woodruff School of Mechanical Engineering, Georgia Institute of Technology, 771 Ferst Drive, Atlanta, Georgia 30332-0245, United StatesMore by Hailong Chen
- Akitoshi HayashiAkitoshi HayashiDepartment of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Sakai, Osaka 599-8531, JapanMore by Akitoshi Hayashi
- Yoon Seok JungYoon Seok JungDepartment of Energy Engineering, Hanyang University, Seoul 04763, South KoreaMore by Yoon Seok Jung
- Bettina V. LotschBettina V. LotschMax Planck Institute for Solid State Research, Heisenbergstrasse 1, 70569 Stuttgart, GermanyDepartment of Chemistry, Ludwig-Maximilians-Universität (LMU), Butenandtstrasse 5-13, 81377 Munich, GermanyCenter for NanoScience, Schellingstrasse 4, 80799 Munich, GermanyE-conversion, Lichtenbergstrasse 4a, 85748 Garching, GermanyMore by Bettina V. Lotsch
- Bernhard RolingBernhard RolingDepartment of Chemistry, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, D-35032 Marburg, GermanyMore by Bernhard Roling
- Nella M. Vargas-Barbosa*Nella M. Vargas-Barbosa*Email: [email protected]Max Planck Institute for Solid State Research, Heisenbergstrasse 1, 70569 Stuttgart, GermanyMore by Nella M. Vargas-Barbosa
- Wolfgang G. Zeier*Wolfgang G. Zeier*Email: [email protected]Institute of Physical Chemistry, Justus-Liebig-University Giessen, Heinrich-Buff-Ring 17, D-35392 Giessen, GermanyCenter for Materials Research (LaMa), Justus-Liebig-University Giessen, Heinrich-Buff-Ring 16, D-35392 Giessen, GermanyMore by Wolfgang G. Zeier
This publication is licensed for personal use by The American Chemical Society.
Copyright © 2020 American Chemical Society
Owing to highly conductive solid ionic conductors, all-solid-state batteries attract significant attention as promising next-generation energy storage devices. A lot of research is invested in the search for and optimization of solid electrolytes with higher ionic conductivity. However, a systematic study of interlaboratory reproducibility of measured ionic conductivities and activation energies is missing, making the comparison of absolute values in the literature challenging. In this Viewpoint, we perform an uncertainty evaluation via a round-robin approach using different Li-argyrodites exhibiting orders of magnitude different ionic conductivities as reference materials. Identical samples are distributed to different research laboratories, and the conductivities and activation barriers are measured by impedance spectroscopy. The results show large ranges of up to 4.5 mS cm–1 in the measured total ionic conductivity (1.3–5.8 mS cm–1 for the highest conducting sample, relative standard deviation 35–50% across all samples) and up to 128 meV for the activation barriers (198–326 meV, relative standard deviation 5–15% across all samples), presenting the necessity of a more rigorous methodology including further collaborations within the community and multiplicate measurements.
Fast ionic conductors such as lithium and sodium thiophosphates are currently being investigated for their possible application in all-solid-state batteries. (1,2) Recent research efforts have found a variety of Li+- and Na+-based materials such as the thiophosphates Li10+xM1–xP2+xS12 (M = Si, Ge, Sn), (3−8) Li2S–P2S5 glasses, (9−15) Li6PS5X (X = Cl, Br, I), (16−22) Na3PS4, (23−27) and Na11Sn2PS12. (11,28,29) These materials can exhibit ionic conductivities >1 mS cm–1, making them viable for solid-state battery applications. Throughout the literature, however, we can find a spread in the reported ionic conductivity and activation barrier values, even within the same class of materials. Whereas significant variations in the Li+ ionic transport has been reported as a function of batch variation, particle size, and synthesis procedure, and even due to local sample inhomogeneity, (30,31) to date, no rigorous study on the interlaboratory reproducibility of the ionic conductivity measurement via impedance spectroscopy has been performed. Inspired by the standardization and benchmarking efforts in other communities, e.g., photovoltaics, (32) in this Viewpoint we report a round robin study that considers the reproducibility of ionic conductivity measurements in superionic lithium thiophosphate solid electrolytes.
In this Viewpoint, we chose the lithium argyrodite Li6PS5X as an exemplary class of materials because it provides the possibility to establish statistical trends over several orders of magnitude in the ionic conductivity, ranging from 10–4 mS cm–1 up to a few millisiemens per centimeter. All test samples, namely, Li6.6P0.4Ge0.6PS5I, Li6PS5Cl, Li6PS5Br0.75I0.25, Li6PS5Br0.25I0.75, and Li6PS5I, here identified as samples 1, 2, 3, 4, and 5, respectively, were synthesized by the organizing group according to previous reports. (18,20) To obtain a sufficient amount of homogeneous powder (10 g), each composition was synthesized in multiple batches, followed by X-ray diffraction of each batch to confirm the sample purities (see Figure S1). The resulting sample powders were mixed and homogenized, such that each participating group received 1 g of identical test sample for each composition. Prior to the distribution, the ionic conductivity of all homogenized samples was measured by the organizing group to make sure that the values obtained were similar to previously reported values. All samples were supplied as powders to capture the influence of sample-preparation procedures (i.e., densification procedure, relative density, applied pressure during measurement, and pellet contacting method) on the reported ionic conductivities. Each group was asked to measure temperature-dependent impedance spectra on the supplied samples, including at room temperature (25 °C), using the standard measuring procedure within each lab. All groups were asked to provide the measured impedance spectra and Arrhenius behaviors upon heating (see Figures S2–S10) as well as report the calculated room-temperature conductivities and the activation barriers for all samples, without providing the fitting procedure in order to avoid revealing the identity of the different groups. Further details on the sample preparation and the methodology reported of each group (labeled A–H) are given in the Supporting Information (Tables S2–S10), which include applied pressure upon densification (pelletizing pressure) and during measurement, contacting method, contacting material (Au sputtered and stainless steel pressed), impedance analyzer, excitation voltage, temperature and frequency ranges, the cell constants, and employed powder masses. Hence, the statistical analysis presented here includes the measurement uncertainty of the employed impedance spectroscopy, the uncertainty in the cell constants, as well as the differences in sample preparation for the measurement itself and data analysis procedure.
Under ideal conditions, the impedance spectrum in a Nyquist representation of a polycrystalline solid electrolyte is characterized by two well-resolved semicircles and an electrode polarization. The higher-frequency semicircle would then describe the ionic transport in the grains, whereas the lower-frequency semicircle describes grain boundary contributions to the ionic transport. As is typically observed for Li+ conducting thiophosphates, bulk and grain boundary contributions in Li-argyrodites cannot be deconvoluted at room temperature (see Figures S2 – S10). (18,20) Therefore, in line with the different preparation and measurement procedures, the here-reported ionic conductivity values correspond to the total ionic conductivities of all samples and their corresponding activation barriers. Table S11 summarizes all of the reported values used for this statistical analysis.
The obtained room-temperature conductivities are statistically analyzed using the interquartile range (IQR) method, and the results are shown in Figure 1a as a box plot. Although we observe a large spread in the reported ionic conductivities for all samples (e.g., up to 4.5 mS cm–1 range for sample 1), we were not able to detect any outliers in any of the samples with the IQR method. In the case of samples 1 and 2, the median shows a skewness to lower and higher conductivity values, respectively, whereas for the lower-conducting samples 3, 4, and 5 we observe that the mean and the median are closer to one another. Moreover, the calculated median for the lower-conducting samples is close to the center of the IQR box, which suggests that the spread in the conductivity can be viewed as following a normal distribution. In the particular case of samples 1 and 2, based on this statistical analysis, the samples have very similar median total ionic conductivities, showing the difficulty in comparing different materials across laboratories.
Figure 1
Figure 1. (a) Box plots for the room-temperature total ionic conductivity for all samples in the study. (b) Percentile standard deviations and relative median error percentage for all samples. The relative median error was calculated assuming that the median represents the true total conductivity value, using
Because we do not know what the “true” total ionic conductivity of these samples is, it is challenging to assess the best-practice procedure for the statistical analysis. We can, however, use the different measures of central tendency (median and average) as reasonable estimates for the “true” total ionic conductivity, as well as the standard deviation of the ionic conductivity as the representative expected spread in these samples for the following discussion. It needs to be mentioned that the term “true” total ionic conductivity serves only as a statistical descriptor here; it does not imply that measured values of an individual group represent a “false” ionic conductivity. Note that although the ionic conductivities of all samples range over several orders of magnitude, the calculated average values are close to the median values, and high, but similar, percentages of the standard deviation are found within all samples (see Figure 1b). As the median of any data set is less influenced by extreme values, we take it as the better estimate for the “true” total ionic conductivity and use the calculated average to determine relative median errors for all samples (see Figure 1b). In doing so we observe that for samples with ionic conductivities <1 mS cm–1 this error is less than 10%, whereas in the case of the fastest conductor, the Li6.6P0.4Ge0.6PS5I sample, we obtain a much greater error of 22%.
In the case of the calculated activation barriers, we observe a similar spread in the reported values (see Figure 2). The IQR analysis reveals that in the case of the highest and lowest conducting samples, samples 1 and 5, respectively, one of the values with higher activation barrier is an outlier. Here, the median values for samples 3, 4, and 5 show a skewness to lower activation energies. Only in samples 1 and 2 do we observe that the mean and the median are closer to one another and more centered in the IQR box, again suggesting a normal distribution of the data. In spite of the spread, the percentile standard deviations and relative median errors are much smaller than those for the ionic conductivities, likely because the activation barrier is a parameter that is extracted from the slope of the Arrhenius plot and is therefore less sensitive to extreme values at specific temperatures. Nonetheless, even with the small deviation from the average, the values can correspond to a statistical range of up to 128 meV (198–326 meV). This large range of the activation barriers is significant considering that often values of the activation barriers are reported with a large number of significant figures and changes in series of solid solutions are often within this value of the spread. Moreover, these results suggest that direct comparisons between experimental and theoretically calculated activation barriers are not straightforward and similar values between them do not validate the theory or experimental results.
Figure 2
Figure 2. (a) Box plots for the activation barrier of all samples in the study. (b) Percentile standard deviations and relative median error percentage for all samples. The relative median error was calculated assuming that the median represents the true conductivity value, using .
Because the reported conductivities correspond to total conductivities, one may expect an influence of the densification behavior or resulting relative pellet densities. While nearly 100% relative densities can be achieved in oxide ceramic-based materials via sintering, the mechanical soft nature of the thiophosphate-based electrolytes often leads to densities between 80 and 90% by pressing at ambient temperature. In this study a comparison of the reported ionic conductivities against the densification (pelletizing pressure) pressure, the relative pellet density, the excitation voltage, the cell constant, and pellet thickness show no strong apparent trend in all samples (Figures S11–S20). As an example, Figure 3 shows the absence of clear trends for the ionic conductivity and the activation barrier of sample 2 as a function of pelletizing pressure and cell constant. Although there is no apparent trend as a function of cell constants, a qualitative trend of increasing conductivity with the relative density of the pellet can be observed. However, the trend seen as a function of relative density is not correlated to the pelletizing pressure; that is, a higher relative density is not obtained at higher pelletizing pressures. In addition, whereas no clear influence of the contacting material was identified, an increasing conductivity with increasing applied pressure during measurement was found. This trend does not hold for the Au sputtered samples that were measured without external pressure, indicating the influence of the pressing conditions for pellet preparation on the measured ionic conductivity. These results highlight the effect of sample preparation to the microstructure of the sample and its influence on the measured conductivity. However, it should be noted that the trend with relative densities is not universally observed for all the samples and is less prominent in lower-conducting samples as seen in Figures S11–S20, adding the difficulty of assessing the underlying mechanism of the here-observed variations.
Figure 3
Figure 3. Spread in the total ionic conductivities and activation barriers of sample 2 as a function of various experimental parameters. The dashed line represents the average value and the shaded area the standard deviation from the average.
The absence of universal trends among all the samples on one of the experimental parameters suggests a convolution of influences due to the differences in measurement setups and measurement approaches. One potential reason for the larger discrepancies at high ionic conductivities is the lack of a well-resolved semicircle. In this study, only the samples with a lower ionic conductivity show well-resolved semicircles. An experimental approach for modulating the overall resistance is to change the cell constant (thickness of the pellet divided by the area of the electrode) and with it using enough amount of sample. Note that although changing the cell constant may help to resolve the relevant features in the impedance spectra, the cell constant itself has no influence on the intrinsic conductivity of the material; that is, when normalizing the impedance spectra to the cell constant, the same intercept in the real impedance axis will be obtained. In other words, larger thicknesses will change only the total resistance but not the time constant and frequency range of the occurring transport processes, and a deconvolution of bulk and grain boundaries may be possible only at low temperatures. (33) This may be particularly important in highly conducting samples that lead to low measured resistances in which the influence of the microstructure and resulting grain resistances and microstructure may be more prominent, in comparison to the highly resistive samples. The increasing conductivity with pressure of the stainless-steel contacts, as well as the observed variation as a function of relative densities, in contrast to the values obtained by the Au sputtered samples that do not exhibit any external pressure during measurement, additionally underscores the importance of proper contact between particles, as well as with the electrodes.
To show the influence and beneficial approach of low-temperature measurements, one of the participating groups has the experimental capabilities to perform impedance measurements at temperatures down to −120 °C. At these much lower temperatures it is often possible to separate the grain impedance from the total ionic conductivity. (33)Figure S21 shows the conductivity versus inverse temperature behavior for a representative sample 2 measured to such low temperatures as well as a representative impedance spectrum of sample 2 measured at −100 °C. At temperatures below −75 °C, it is possible to resolve the grain conductivity contributions to the impedance spectrum. Upon fitting and extrapolating the data of grain conductivity versus inverse temperature, the extrapolated line of best fit can estimate the upper-bound values of the reported room-temperature total ionic conductivities in this study. These results underscore, again, the effects of sample microstructure on the ionic conductivity and how under the right measurement conditions it is possible to discriminate between bulk and microstructure effects.
Considering the spread in the obtained conductivities and activation barriers, a few conclusions may be drawn. A larger relative median error can be clearly seen in the samples that exhibit high ionic conductivities >1 mS cm–1 likely due to the convergence of different occurring processes that lead to unresolved processes, which cannot be deconvoluted without a low-temperature measurement.
Additionally, these lithium thiophosphate electrolytes are highly sensitive to atmosphere and, while structurally and chemically comparable, differences in glovebox atmospheres (H2O and O2 content, as well as solvents present) as well as during measurement may interfere with a comparability between groups. Furthermore, pressing in these materials is needed, and a certain degree of microstructural relaxation may occur after pellet consolidation and contacting, making the “sample history” a possible factor in the observed spread. Nevertheless, the large range and uncertainty in the reproducibility of the conductivity and activation barriers suggest the need to adopt a more rigorous approach in the field, as often minor improvements in activation barriers and conductivities are deemed significant.
First, it seems reasonable that for future studies showing changing conductivities and activation barriers, e.g. as a result from isovalent and aliovalent substitutions, measurements in triplicate are necessary, and an accurate description of sample consolidation, contacting, and measurement conditions is needed. Here, three different samples of the same composition should be measured with different cell constants (changing thicknesses as the diameter is often restricted in the cell setup), in order to change the overall cell resistance and report an average value and their respective standard deviations. Measurements at low temperatures to deconvolute processes seems crucial; (33) however, this is often restricted by experimental setups. While the recommendation of triplicate measurements seems trivial, it is not often reported in the literature despite the fact that these triplicates may help to produce more realistic uncertainties in obtained ionic conductivities and activation barriers. While the measurement of triplicates does not fully alleviate the large range that was found throughout the groups, it can provide more meaningful information on qualitative changes in the ionic transport within studies for solid solutions. In the future, measurement standards and standard materials for measurement setup validation may be needed.
Second, especially within this mechanically soft class of materials, there seems to be an influence of the pressure under measurement when measured in press cells (see Figure 3). Therefore, it may be needed to report ionic conductivities as a function of the external pressure applied.
Third, when novel electrolytes with high ionic conductivities >1 mS cm–1 are reported, we suggest sending samples to a collaborative group to corroborate the obtained ionic conductivities.
Fourth, a comparison of experimental conductivity values with diffusion coefficients obtained by nuclear magnetic resonance and with it calculations of Haven ratios may be subject to a large uncertainty based on the experimental range in obtained conductivities. While Haven ratios are often used to explain correlation effects, (34) comparing different measurement techniques may not be very meaningful in extracting information about correlation effects in these systems.
Fifth, often theoretical calculations are internally validated by reproduction of experimental activation barriers. Despite a smaller relative median error, the larger range of up to 128 meV in the experimentally obtained activation barriers suggests that a direct comparison between experiment and theory alone should not be used to validate theoretical nor experimental results.
Overall, within the field of superionic conductors a more rigorous approach for reporting results, including the experimental conditions and triplicate measurements, will be needed to better understand and reliably design solid electrolytes for the use in solid-state batteries.
Supporting Information
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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsenergylett.9b02764.
Synthesis procedure of all samples and X-ray diffraction results; all experimental measurement conditions of the different data sets along with their statistical analysis; measured impedance spectra and Arrhenius plots as well as the comparison of the transport properties against possible sample preparation and measurement influences (PDF)
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Author Information
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- Saneyuki Ohno - Institute of Physical Chemistry, Justus-Liebig-University Giessen, Heinrich-Buff-Ring 17, D-35392 Giessen, Germany; Center for Materials Research (LaMa), Justus-Liebig-University Giessen, Heinrich-Buff-Ring 16, D-35392 Giessen, Germany;
http://orcid.org/0000-0001-8192-996X;
- Nella M. Vargas-Barbosa - Max Planck Institute for Solid State Research, Heisenbergstrasse 1, 70569 Stuttgart, Germany;http://orcid.org/0000-0002-6357-017X;
- Wolfgang G. Zeier - Institute of Physical Chemistry, Justus-Liebig-University Giessen, Heinrich-Buff-Ring 17, D-35392 Giessen, Germany; Center for Materials Research (LaMa), Justus-Liebig-University Giessen, Heinrich-Buff-Ring 16, D-35392 Giessen, Germany;http://orcid.org/0000-0001-7749-5089;
- Aggunda L. Santhosha - Department of Chemistry, Humboldt-University Berlin, Brook-Taylor-Str. 2, 12489 Berlin, Germany;http://orcid.org/0000-0002-2422-2703
- Atsushi Sakuda - Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Sakai, Osaka 599-8531, Japan;http://orcid.org/0000-0002-9214-0347
- Philipp Adelhelm - Department of Chemistry, Humboldt-University Berlin, Brook-Taylor-Str. 2, 12489 Berlin, Germany;http://orcid.org/0000-0003-2439-8802
- Hailong Chen - The Woodruff School of Mechanical Engineering, Georgia Institute of Technology, 771 Ferst Drive, Atlanta, Georgia 30332-0245, United States;http://orcid.org/0000-0001-8283-2860
- Akitoshi Hayashi - Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Sakai, Osaka 599-8531, Japan;http://orcid.org/0000-0001-9503-5561
- Yoon Seok Jung - Department of Energy Engineering, Hanyang University, Seoul 04763, South Korea;http://orcid.org/0000-0003-0357-9508
- Bettina V. Lotsch - Max Planck Institute for Solid State Research, Heisenbergstrasse 1, 70569 Stuttgart, Germany; Department of Chemistry, Ludwig-Maximilians-Universität (LMU), Butenandtstrasse 5-13, 81377 Munich, Germany; Center for NanoScience, Schellingstrasse 4, 80799 Munich, Germany; E-conversion, Lichtenbergstrasse 4a, 85748 Garching, Germany;http://orcid.org/0000-0002-3094-303X
- Bernhard Roling - Department of Chemistry, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, D-35032 Marburg, Germany;http://orcid.org/0000-0001-7383-1495
Acknowledgments
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The research was supported by the Federal Ministry of Education and Research (BMBF) within the project FESTBATT under Grant Numbers 03XP0117A and 03XP0177B. S.O. gratefully acknowledges the Alexander von Humboldt Foundation for financial support through a Postdoctoral Fellowship. P.A. acknowledges support within the research unit Hy-NIB (2017 FGR 0055) funded by the ESF/Thuringia. S.X., Z.L., and H.C. acknowledge the financial support of the U.S. National Science Foundation under Grant Number 1706723.
References
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This article references 34 other publications.
- 1Janek, J.; Zeier, W. G. A solid future for battery development. Nat. Energy 2016, 1, 16141, DOI: 10.1038/nenergy.2016.141Google ScholarThere is no corresponding record for this reference.
- 2Famprikis, T.; Canepa, P.; Dawson, J. A.; Islam, M. S.; Masquelier, C. Fundamentals of inorganic solid-state electrolytes for batteries. Nat. Mater. 2019, 18, 1278– 1291, DOI: 10.1038/s41563-019-0431-3Google Scholar2https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhs1alsL7I&md5=582754f689db47f9562c6f4201f150bfFundamentals of inorganic solid-state electrolytes for batteriesFamprikis, Theodosios; Canepa, Pieremanuele; Dawson, James A.; Islam, M. Saiful; Masquelier, ChristianNature Materials (2019), 18 (12), 1278-1291CODEN: NMAACR; ISSN:1476-1122. (Nature Research)A review. In the crit. area of sustainable energy storage, solid-state batteries have attracted considerable attention due to their potential safety, energy-d. and cycle-life benefits. This Review describes recent progress in the fundamental understanding of inorg. solid electrolytes, which lie at the heart of the solid-state battery concept, by addressing key issues in the areas of multiscale ion transport, electrochem. and mech. properties, and current processing routes. The main electrolyte-related challenges for practical solid-state devices include utilization of metal anodes, stabilization of interfaces and the maintenance of phys. contact, the solns. to which hinge on gaining greater knowledge of the underlying properties of solid electrolyte materials.
- 3Kamaya, N.; Homma, K.; Yamakawa, Y.; Hirayama, M.; Kanno, R.; Yonemura, M.; Kamiyama, T.; Kato, Y.; Hama, S.; Kawamoto, K. A lithium superionic conductor. Nat. Mater. 2011, 10, 682– 686, DOI: 10.1038/nmat3066Google Scholar3https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXpsFaisLc%253D&md5=30637e2968f742a3e1da5f7fa4250644A lithium superionic conductorKamaya, Noriaki; Homma, Kenji; Yamakawa, Yuichiro; Hirayama, Masaaki; Kanno, Ryoji; Yonemura, Masao; Kamiyama, Takashi; Kato, Yuki; Hama, Shigenori; Kawamoto, Koji; Mitsui, AkioNature Materials (2011), 10 (9), 682-686CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)Batteries are a key technol. in modern society. They are used to power elec. and hybrid elec. vehicles and to store wind and solar energy in smart grids. Electrochem. devices with high energy and power densities can currently be powered only by batteries with org. liq. electrolytes. However, such batteries require relatively stringent safety precautions, making large-scale systems complicated and expensive. The application of solid electrolytes is currently limited because they attain practically useful conductivities (10-2 S/cm) only at 50-80°, which is one order of magnitude lower than those of org. liq. electrolytes. Here, the authors report a Li superionic conductor, Li10GeP2S12 that has a new 3-dimensional framework structure. It exhibits an extremely high Li ionic cond. of 12 mS/cm at room temp. This represents the highest cond. achieved in a solid electrolyte, exceeding even those of liq. org. electrolytes. This new solid-state battery electrolyte has many advantages in terms of device fabrication (facile shaping, patterning and integration), stability (non-volatile), safety (non-explosive) and excellent electrochem. properties (high cond. and wide potential window).
- 4Kato, Y.; Hori, S.; Saito, T.; Suzuki, K.; Hirayama, M.; Mitsui, A.; Yonemura, M.; Iba, H.; Kanno, R. High-power all-solid-state batteries using sulfide superionic conductors. Nat. Energy 2016, 1, 16030, DOI: 10.1038/nenergy.2016.30Google Scholar4https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhtVekurs%253D&md5=cc1210221e70bc3e6c06e015effc70deHigh-power all-solid-state batteries using sulfide superionic conductorsKato, Yuki; Hori, Satoshi; Saito, Toshiya; Suzuki, Kota; Hirayama, Masaaki; Mitsui, Akio; Yonemura, Masao; Iba, Hideki; Kanno, RyojiNature Energy (2016), 1 (4), 16030CODEN: NEANFD; ISSN:2058-7546. (Nature Publishing Group)Compared with Li-ion batteries with liq. electrolytes, all-solid-state batteries offer an attractive option owing to their potential in improving the safety and achieving both high power and high energy densities. Despite extensive research efforts, the development of all-solid-state batteries still falls short of expectation largely because of the lack of suitable candidate materials for the electrolyte required for practical applications. Here the authors report Li superionic conductors with an exceptionally high cond. (25 mS cm-1 for Li9.54Si1.74P1.44S11.7Cl0.3), as well as high stability ( ∼0 V vs. Li metal for Li9.6P3S12). A fabricated all-solid-state cell based on this Li conductor has very small internal resistance, esp. at 100 oC. The cell possesses high specific power that is superior to that of conventional cells with liq. electrolytes. Stable cycling with a high c.d. of 18 C (charging/discharging in just 3 min; where C is the C-rate) is also demonstrated.
- 5Harm, S.; Hatz, A.; Moudrakovski, I.; Eger, R.; Kuhn, A.; Hoch, C.; Lotsch, B. V. Lesson Learned from NMR: Characterization and Ionic Conductivity of LGPS-like Li7SiPS8. Chem. Mater. 2019, 31, 1280– 1288, DOI: 10.1021/acs.chemmater.8b04051Google Scholar5https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXitVCntrc%253D&md5=668b8168a1bdb2f69b38868e55113c9aLesson Learned from NMR: Characterization and Ionic Conductivity of LGPS-like Li7SiPS8Harm, Sascha; Hatz, Anna-Katharina; Moudrakovski, Igor; Eger, Roland; Kuhn, Alexander; Hoch, Constantin; Lotsch, Bettina V.Chemistry of Materials (2019), 31 (4), 1280-1288CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)The authors report on the facile solid-state synthesis and characterization of Li7SiPS8, a new member of the tetragonal Li10GeP2S12 (LGPS)-type family of ultrafast Li+ solid electrolytes. The authors analyze the structure, phase stability, and Li+ cond. of tetragonal and orthorhombic LSiPS by pulsed field gradient NMR and impedance spectroscopy, which show conductivities at room temp. of up to 2 mS cm-1. Although ranking tetragonal LiSiPS as an ultrafast solid electrolyte, the obsd. cond. is unexpectedly low compared to other members of this solid-soln. system. Using solid-state NMR, quant. phase anal., and impedance spectroscopy, the authors identify an amorphous thiophosphate side phase with low Si content, which limits the intergrain cond. and, hence, a potentially higher total cond. This case study thus highlights the need for comprehensive structural anal. of LGPS-type materials beyond the cryst. fractions to fully characterize the structure-property relations in these glass-ceramic compds.
- 6Kuhn, A.; Koehler, J.; Lotsch, B. V. Single-crystal X - ray structure analysis of the superionic conductor Li10GeP2S12. Phys. Chem. Chem. Phys. 2013, 15, 11620– 11622, DOI: 10.1039/c3cp51985fGoogle Scholar6https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhtVartLfO&md5=db3f009c9f0afdac6c7b308a7737b132Single-crystal X-ray structure analysis of the superionic conductor Li10GeP2S12Kuhn, Alexander; Koehler, Juergen; Lotsch, Bettina V.Physical Chemistry Chemical Physics (2013), 15 (28), 11620-11622CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)Tetragonal Li10GeP2S12 (LGPS) is the best solid Li ion conductor known to date. So far, the structure of the electrolyte was only detd. from powder diffraction and Rietveld refinement. Here, the authors present the 1st single-crystal structure anal. of the tetragonal LGPS structure. The reported structure is largely verified. However, an addnl. Li position is clearly identified which might have a significant impact on the Li ion dynamics. All Li positions are partially occupied - a prerequisite for Li superionic conductors - and form a network of interconnected Li diffusion pathways. Therefore, probably Li diffusion in this record solid electrolyte is less anisotropic than previously claimed.
- 7Bron, P.; Johansson, S.; Zick, K.; Schmedt auf der Günne, J.; Dehnen, S.; Roling, B. Li10SnP2S12: an affordable lithium superionic conductor. J. Am. Chem. Soc. 2013, 135, 15694– 15697, DOI: 10.1021/ja407393yGoogle Scholar7https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhsFCjt73N&md5=4c73f683533cbd49eb7f05e3499c6bc5Li10SnP2S12: An Affordable Lithium Superionic ConductorBron, Philipp; Johansson, Sebastian; Zick, Klaus; Schmedtauf der Guenne, Joern; Dehnen, Stefanie; Roling, BernhardJournal of the American Chemical Society (2013), 135 (42), 15694-15697CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)The reaction of Li2S and P2S5 with Li4[SnS4], a recently discovered, good Li+ ion conductor, yields Li10SnP2S12, the thiostannate analog of the record holder Li10GeP2S12 and the 2nd compd. of this class of superionic conductors with very high values of 7 mS/cm for the grain cond. and 4 mS/cm for the total cond. at 27°. The replacement of Ge by Sn should reduce the raw material cost by a factor of ∼3.
- 8Krauskopf, T.; Culver, S. P.; Zeier, W. G. The bottleneck of diffusion and inductive effects in Li10Ge1-xSnxP2S12. Chem. Mater. 2018, 30, 1791– 1798, DOI: 10.1021/acs.chemmater.8b00266Google Scholar8https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXjtVWiu7g%253D&md5=63a43a543a5c9994a2e4fa0b19e33605Bottleneck of Diffusion and Inductive Effects in Li10Ge1-xSnxP2S12Krauskopf, Thorben; Culver, Sean P.; Zeier, Wolfgang G.Chemistry of Materials (2018), 30 (5), 1791-1798CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)The lithium-ion conductor Li10GeP2S12 (LGPS) is known to exhibit ionic cond. values ≤12 mS/cm. Unfortunately, counter to chem. intuition, many attempts to enhance the ionic transport in LGPS, e.g., by increasing the Sn fraction in Li10Ge1-xSnxP2S12, have even led to a redn. in the cond. Employing a combination of Rietveld refinements against x-ray diffraction data, speed of sound measurements, and electrochem. impedance spectroscopy, the authors study the structure-property relations governing this behavior. Herein, with increasing Sn4+ fraction in Li10Ge1-xSnxP2S12 a structural bottleneck along the diffusion channels in the z-direction begins to tighten, and with the concomitant increase in the lattice softness, the local ionic bonding interactions between Li+ and S2- become stronger, further increasing the activation barrier. This work provides a likely explanation for the lower cond. exhibited by Li10SnP2S12 and demonstrates that there is more to the underlying lithium diffusion mechanism in the Li10MP2S12 structure.
- 9Hayashi, A.; Hama, S.; Morimoto, H.; Tatsumisago, M.; Minami, T. Preparation of Li2S–P2S5 Amorphous Solid Electrolytes by Mechanical Milling. J. Am. Ceram. Soc. 2001, 84, 477– 479, DOI: 10.1111/j.1151-2916.2001.tb00685.xGoogle Scholar9https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3MXhtlOku7w%253D&md5=634c97a589d9f86aebb56b6a102833b8Preparation of Li2S-P2S5 amorphous solid electrolytes by mechanical millingHayashi, Akitoshi; Hama, Shigenori; Morimoto, Hideyuki; Tatsumisago, Masahiro; Minami, TsutomuJournal of the American Ceramic Society (2001), 84 (2), 477-479CODEN: JACTAW; ISSN:0002-7820. (American Ceramic Society)Amorphous solid electrolytes in the Li2S-P2S5 system were prepd. successfully from a mixt. of cryst. Li2S and P2S5, using a mech. milling technique. The amorphous-forming region was extended to higher Li2S compns. by mech. milling, compared with melt quenching. The pelletized samples of the 75Li2S·25P2S5 (mol%) amorphous powders obtained by mech. milling for 20 h exhibited high cond. (2 × 10-4 S/cm at room temp.) and an activation energy for conduction of 34 kJ/mol. The lithium-ion transport no. of the amorphous powders was almost unity.
- 10Dietrich, C.; Weber, D.; Sedlmaier, S. J.; Indris, S.; Culver, S.; Walter, D.; Janek, J.; Zeier, W. Lithium ion conductivity in Li2S-P2S5 glasses – Building units and local structure evolution during the crystallization of the superionic conductors Li3PS4, Li7P3S11 and Li4P2S7. J. Mater. Chem. A 2017, 5, 18111– 18119, DOI: 10.1039/C7TA06067JGoogle Scholar10https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXht1Olsr3O&md5=cfcd42ed22843da1b70ba04b747fb333Lithium ion conductivity in Li2S-P2S5 glasses - building units and local structure evolution during the crystallization of superionic conductors Li3PS4, Li7P3S11 and Li4P2S7Dietrich, Christian; Weber, Dominik A.; Sedlmaier, Stefan J.; Indris, Sylvio; Culver, Sean P.; Walter, Dirk; Janek, Juergen; Zeier, Wolfgang G.Journal of Materials Chemistry A: Materials for Energy and Sustainability (2017), 5 (34), 18111-18119CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)Motivated by the high lithium ion conductivities of lithium thiophosphate glasses, a detailed study is performed on the local chem. nature of the thiophosphate building units within these materials. Using Raman and 31P MAS NMR (Magic Angle Spinning - NMR) spectroscopy, the continuous change from dominant P2S74- (di-tetrahedral) anions to PS43- (mono-tetrahedral) anions with increasing Li2S fraction in the (Li2S)x(P2S5)(100-x) glasses is obsd. In addn., synchrotron pair distribution function anal. (PDF) of synchrotron X-ray total scattering data is employed to monitor in situ crystn. and phase evolution in this class of materials. Depending on the compn., different cryst. phases evolve, which possess different decompn. temps. into less conducting phases. The results highlight the crit. influence of the local anionic building units on the cation mobility and thermal stability, with PS43- tetrahedra forming the most thermally robust glass ceramics with the highest ionic cond.
- 11Hayashi, A.; Noi, K.; Sakuda, A.; Tatsumisago, M. Superionic glass-ceramic electrolytes for room-temperature rechargeable sodium batteries. Nat. Commun. 2012, 3, 856, DOI: 10.1038/ncomms1843Google Scholar11https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BC38nltleltw%253D%253D&md5=25a3b2cfae7b32f2d61dc2b4e9b53c2eSuperionic glass-ceramic electrolytes for room-temperature rechargeable sodium batteriesHayashi Akitoshi; Noi Kousuke; Sakuda Atsushi; Tatsumisago MasahiroNature communications (2012), 3 (), 856 ISSN:.Innovative rechargeable batteries that can effectively store renewable energy, such as solar and wind power, urgently need to be developed to reduce greenhouse gas emissions. All-solid-state batteries with inorganic solid electrolytes and electrodes are promising power sources for a wide range of applications because of their safety, long-cycle lives and versatile geometries. Rechargeable sodium batteries are more suitable than lithium-ion batteries, because they use abundant and ubiquitous sodium sources. Solid electrolytes are critical for realizing all-solid-state sodium batteries. Here we show that stabilization of a high-temperature phase by crystallization from the glassy state dramatically enhances the Na(+) ion conductivity. An ambient temperature conductivity of over 10(-4) S cm(-1) was obtained in a glass-ceramic electrolyte, in which a cubic Na(3)PS(4) crystal with superionic conductivity was first realized. All-solid-state sodium batteries, with a powder-compressed Na(3)PS(4) electrolyte, functioned as a rechargeable battery at room temperature.
- 12Hayashi, A.; Ohtsubo, R.; Nagao, M.; Tatsumisago, M. Characterization of Li2S–P2S5–Cu composite electrode for all-solid-state lithium secondary batteries. J. Mater. Sci. 2010, 45, 377– 381, DOI: 10.1007/s10853-009-3948-zGoogle Scholar12https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXhsFOlsLzP&md5=46bf6b9d3d69884d24640e94063fb008Characterization of Li2S-P2S5-Cu composite electrode for all-solid-state lithium secondary batteriesHayashi, Akitoshi; Ohtsubo, Ryoji; Nagao, Motohiro; Tatsumisago, MasahiroJournal of Materials Science (2010), 45 (2), 377-381CODEN: JMTSAS; ISSN:0022-2461. (Springer)Electrochem. performance of the Li2S-P2S5-Cu composite materials was examd. in all-solid-state lithium secondary batteries. The 80Li2S·20P2S5 (mol%) solid electrolyte with the addn. of Cu was partially used as an active material with lithium source in all-solid-state cells. The initial discharge capacity of 110 mA-h/g (normalized by the wt. of 80Li2S·20P2S5-Cu), which corresponds to 400 mA-h/g (normalized by the wt. of Li2S), was obtained in the cell using the 80Li2S·20P2S5-Cu composite electrode with the molar ratio of Li2S/Cu = 48/52. Cycling performance and reaction mechanism of the electrode in the solid-state cell were investigated.
- 13Mizuno, F.; Hayashi, A.; Tadanaga, K.; Tatsumisago, M. New, highly ion-conductive crystals precipitated from Li2S-P2S5 glasses. Adv. Mater. 2005, 17, 918– 921, DOI: 10.1002/adma.200401286Google Scholar13https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXjsFWiurg%253D&md5=3359b524cec1b05fdb569fae9160e777New, highly ion-conductive crystals precipitated from Li2S-P2S5 glassesMizuno, Fuminori; Hayashi, Akitoshi; Tadanaga, Kiyoharu; Tatsumisago, MasahiroAdvanced Materials (Weinheim, Germany) (2005), 17 (7), 918-921CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)Novel sulfide Li-ion conducting materials were synthesized by crystn. of mech. milled Li2S-P2S5 glasses. High ambient-temp. conductivities (σ) compared with other electrolytes and a low conduction activation energy are achieved by the formation of a highly conductive new cryst. phase.
- 14Kato, A.; Yamamoto, M.; Sakuda, A.; Hayashi, A.; Tatsumisago, M. Mechanical Properties of Li2S–P2S5 Glasses with Lithium Halides and Application in All-Solid-State Batteries. ACS Appl. Energy Mater. 2018, 1, 1002– 1007, DOI: 10.1021/acsaem.7b00140Google Scholar14https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXjs1WjtrY%253D&md5=2d7e876f7e739b74a36e4059798109acMechanical Properties of Li2S-P2S5 Glasses with Lithium Halides and Application in All-Solid-State BatteriesKato, Atsutaka; Yamamoto, Mirai; Sakuda, Atsushi; Hayashi, Akitoshi; Tatsumisago, MasahiroACS Applied Energy Materials (2018), 1 (3), 1002-1007CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)Mech. properties of solid electrolytes are important as well as ionic cond. to achieve all-solid-state batteries with large capacities and long cycle life. In this study, it is shown that Li2S-P2S5 glasses with lithium halides, esp. LiI, exhibit both high ionic cond. and favorable mech. properties. Mech. properties, such as Young's modulus and formability at powder compaction, are evaluated for the solid electrolytes. The addn. of lithium halides decreases the Young's modulus of the electrolytes. In addn., fewer pores and grain boundaries were obsd. in the powder-pressed pellets of Li2S-P2S5 glasses with lithium halides. All-solid-state batteries using Si electrodes and glass electrolytes with lithium halides exhibited a larger capacity of 20 cycles compared to those without lithium halides. These results provide guidelines for the construction of all-solid-state batteries from the viewpoint of the mech. properties of solid electrolytes.
- 15Oh, D. Y.; Ha, A. R.; Lee, J. E.; Jung, S. H.; Jeong, G.; Cho, W.; Kim, K. S.; Jung, Y. S. Wet-chemical tuning of Li3-xPS4 (0 ≤ x ≤ 0.3) enabled by dual solvents for all-solid-state lithium-ion batteries. ChemSusChem 2020, 13, 146– 151, DOI: 10.1002/cssc.201901850Google Scholar15https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXitVSlsLfP&md5=be8edd60f854f6a8757812ca2a47209eWet-Chemical Tuning of Li3-xPS4 (0≤x≤0.3) Enabled by Dual Solvents for All-Solid-State Lithium-Ion BatteriesOh, Dae Yang; Ha, A. Reum; Lee, Ji Eun; Jung, Sung Hoo; Jeong, Goojin; Cho, Woosuk; Kim, Kyung Su; Jung, Yoon SeokChemSusChem (2020), 13 (1), 146-151CODEN: CHEMIZ; ISSN:1864-5631. (Wiley-VCH Verlag GmbH & Co. KGaA)All-solid-state Li-ion batteries (ASLBs) employing sulfide solid electrolytes are attractive next-generation rechargeable batteries that could offer improved safety and energy d. Recently, wet syntheses or processes for sulfide solid electrolyte materials have opened opportunities to explore new materials and practical fabrication methods for ASLBs. A new wet-chem. route for the synthesis of Li-deficient Li3-xPS4 (0 ≤ x ≤ 0.3) was developed, which is enabled by dual solvents. Owing to its miscibility with THF and ability to dissolve elemental S, o-xylene as a cosolvent facilitates the wet-chem. synthesis of Li3-xPS4. Li3-xPS4 (0 ≤ x ≤ 0.15) derived by using dual solvents shows Li+ cond. of ∼0.2 mS cm-1 at 30°, in contrast to 0.034 mS cm-1 for a sample obtained by using a conventional single solvent (THF, x = 0.15). The evolution of the structure for Li3-xPS4 is also studied by complementary anal. using x-ray diffraction, Raman, and XPS measurements. LiCoO2/Li-In ASLBs employing Li2.85PS4 obtained by using dual solvents exhibit a reversible capacity of 130 mA h g-1 with good cycle retention at 30°, outperforming cells with Li2.85PS4 obtained by using a conventional single solvent.
- 16Deiseroth, H. J.; Kong, S. T.; Eckert, H.; Vannahme, J.; Reiner, C.; Zaiß, T.; Schlosser, M. Li6PS5X: A class of crystalline Li-rich solids with an unusually high Li+ mobility. Angew. Chem., Int. Ed. 2008, 47, 755– 758, DOI: 10.1002/anie.200703900Google Scholar16https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXhslektb8%253D&md5=7d5e85537afd8d458e86abba9f0e1c59Li6PS5X: a class of crystalline Li-rich solids with an unusually high Li+ mobilityDeiseroth, Hans-Joerg; Kong, Shiao-Tong; Eckert, Hellmut; Vannahme, Julia; Reiner, Christof; Zaiss, Torsten; Schlosser, MarcAngewandte Chemie, International Edition (2008), 47 (4), 755-758CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)Halide-substituted lithium argyrodites, Li6PS5X (X = Cl, Br, I), form a new class of Li-rich solids with an unusually high Li mobility. Single-crystal x-ray studies at room temp. and MAS NMR measurements in a wide temp. range provide insights into the Li+ ion dynamics.
- 17Hanghofer, I.; Brinek, M.; Eisbacher, S. L.; Bitschnau, B.; Volck, M.; Hennige, V.; Hanzu, I.; Rettenwander, D.; Wilkening, M. Subsitutional disorder: Structure and ion dynamics of the argyrodites Li6PS5Cl, Li6PS5Br and Li6PS6I. Phys. Chem. Chem. Phys. 2019, 21, 8489– 8507, DOI: 10.1039/C9CP00664HGoogle Scholar17https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXlvFCisb4%253D&md5=2a8ab483deb8f84aa6eb39d3fe013b3fSubstitutional disorder: structure and ion dynamics of the argyrodites Li6PS5Cl, Li6PS5Br and Li6PS5IHanghofer, I.; Brinek, M.; Eisbacher, S. L.; Bitschnau, B.; Volck, M.; Hennige, V.; Hanzu, I.; Rettenwander, D.; Wilkening, H. M. R.Physical Chemistry Chemical Physics (2019), 21 (16), 8489-8507CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)For the development of safe and long-lasting lithium-ion batteries we need electrolytes with excellent ionic transport properties. Argyrodite-type Li6PS5X (X: Cl, Br, I) belongs to a family of such a class of materials offering ionic conductivities, at least if Li6PS5Br and Li6PS5Cl are considered, in the mS cm-1 range at room temp. Although already tested as ceramic electrolytes in battery cells, a comprehensive picture about the ion dynamics is still missing. While Li6PS5Br and Li6PS5Cl show an exceptionally high Li ion cond., that of Li6PS5I with its polarizable I anions is by some orders of magnitude lower. This astonishing effect has not been satisfactorily understood so far. Studying the ion dynamics over a broad time and length scale is expected to help shed light on this aspect. Here, we used broadband impedance spectroscopy and 7Li NMR relaxation measurements and show that very fast local Li ion exchange processes are taking place in all three compds. Most importantly, the diffusion-induced NMR spin-lattice relaxation in Li6PS5I is almost identical to that of its relatives. Considering the substitutional disorder effects in Li6PS5X (X = Br, Cl), we conclude that in structurally ordered Li6PS5I the important inter-cage jump processes are switched off, hindering the ions from taking part in long-range ion transport.
- 18Kraft, M. A.; Culver, S. P.; Calderon, M.; Böcher, F.; Krauskopf, T.; Senyshyn, A.; Dietrich, C.; Zevalkink, A.; Janek, J.; Zeier, W. G. Influence of Lattice Polarizability on the Ionic Conductivity in the Lithium Superionic Argyrodites Li6PS5X (X = Cl, Br, I). J. Am. Chem. Soc. 2017, 139, 10909– 10918, DOI: 10.1021/jacs.7b06327Google Scholar18https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXht1eks7%252FL&md5=aa65995954d3a2803687556f1dc76803Influence of Lattice Polarizability on the Ionic Conductivity in the Lithium Superionic Argyrodites Li6PS5X (X = Cl, Br, I)Kraft, Marvin A.; Culver, Sean P.; Calderon, Mario; Boecher, Felix; Krauskopf, Thorben; Senyshyn, Anatoliy; Dietrich, Christian; Zevalkink, Alexandra; Janek, Juergen; Zeier, Wolfgang G.Journal of the American Chemical Society (2017), 139 (31), 10909-10918CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)In the search for novel solid electrolytes for solid-state batteries, thiophosphate ionic conductors have been in recent focus owing to their high ionic conductivities, which are believed to stem from a softer, more polarizable anion framework. Inspired by the oft-cited connection between a soft anion lattice and ionic transport, this work aims to provide evidence on how changing the polarizability of the anion sublattice in one structure affects ionic transport. Here, we systematically alter the anion framework polarizability of the superionic argyrodites Li6PS5X by controlling the fractional occupancy of the halide anions (X = Cl, Br, I). Ultrasonic speed of sound measurements are used to quantify the variation in the lattice stiffness and Debye frequencies. In combination with electrochem. impedance spectroscopy and neutron diffraction, these results show that the lattice softness has a striking influence on the ionic transport: the softer bonds lower the activation barrier and simultaneously decrease the prefactor of the moving ion. Due to the contradicting influence of these parameters on ionic cond., we find that it is necessary to tailor the lattice stiffness of materials in order to obtain an optimum ionic cond.
- 19Adeli, P.; Bazak, J. D.; Park, K. H.; Kochetkov, I.; Huq, A.; Goward, G. R.; Nazar, L. F. Boosting Solid-State Diffusivity and Conductivity in Lithium Superionic Argyrodites by Halide Substitution. Angew. Chem., Int. Ed. 2019, 58, 8681– 8686, DOI: 10.1002/anie.201814222Google Scholar19https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhtVKqtr7P&md5=23835a7c45329b76c32bd123ed8a1974Boosting Solid-State Diffusivity and Conductivity in Lithium Superionic Argyrodites by Halide SubstitutionAdeli, Parvin; Bazak, J. David; Park, Kern Ho; Kochetkov, Ivan; Huq, Ashfia; Goward, Gillian R.; Nazar, Linda F.Angewandte Chemie, International Edition (2019), 58 (26), 8681-8686CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)Developing high-performance all-solid-state batteries is contingent on finding solid electrolyte materials with high ionic cond. and ductility. Here we report new halide-rich solid soln. phases in the argyrodite Li6PS5Cl family, Li6-xPS5-xCl1+x, and combine electrochem. impedance spectroscopy, neutron diffraction, and 7Li NMR MAS and PFG spectroscopy to show that increasing the Cl-/S2- ratio has a systematic, and remarkable impact on Li-ion diffusivity in the lattice. The phase at the limit of the solid soln. regime, Li5.5PS4.5Cl1.5, exhibits a cold-pressed cond. of 9.4±0.1 mS cm-1 at 298 K (and 12.0±0.2 mS cm-1 on sintering)-almost four-fold greater than Li6PS5Cl under identical processing conditions and comparable to metastable superionic Li7P3S11. Weakened interactions between the mobile Li-ions and surrounding framework anions incurred by substitution of divalent S2- for monovalent Cl- play a major role in enhancing Li+-ion diffusivity, along with increased site disorder and a higher lithium vacancy population.
- 20Kraft, M. A.; Ohno, S.; Zinkevich, T.; Koerver, R.; Culver, S. P.; Senyshyn, A.; Indris, S.; Morgan, B. J.; Zeier, W. G. Inducing high ionic conductivity in the lithium superionic argyrodites Li6+xP1-xGexS5I for all-solid-state batteries. J. Am. Chem. Soc. 2018, 140, 16330– 16339, DOI: 10.1021/jacs.8b10282Google Scholar20https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXitVKltb%252FM&md5=2eb04a02921eedaa529f1899e08f498eInducing High Ionic Conductivity in the Lithium Superionic Argyrodites Li6+xP1-xGexS5I for All-Solid-State BatteriesKraft, Marvin A.; Ohno, Saneyuki; Zinkevich, Tatiana; Koerver, Raimund; Culver, Sean P.; Fuchs, Till; Senyshyn, Anatoliy; Indris, Sylvio; Morgan, Benjamin J.; Zeier, Wolfgang G.Journal of the American Chemical Society (2018), 140 (47), 16330-16339CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Solid-state batteries with inorg. solid electrolytes are currently being discussed as a more reliable and safer future alternative to the current lithium-ion battery technol. To compete with state-of-the-art lithium-ion batteries, solid electrolytes with higher ionic conductivities are needed, esp. if thick electrode configurations are to be used. In the search for optimized ionic conductors, the lithium argyrodites have attracted a lot of interest. Here, the effect is systematically explored of aliovalent substitution in Li6+xP1-xGexS5I using a combination of X-ray and neutron diffraction, as well as impedance spectroscopy and NMR. With increasing Ge content, an anion site disorder is induced and the activation barrier for ionic motion drops significantly, leading to the fastest lithium argyrodite so far with 5.4 ± 0.8 mS cm-1 in a cold-pressed state and 18.4 ± 2.7 mS cm-1 upon sintering. These high ionic conductivities allow for successful implementation within a thick-electrode solid-state battery that shows negligible capacity fade over 150 cycles. The obsd. changes in the activation barrier and changing site disorder provide an addnl. approach toward designing better performing solid electrolytes.
- 21Ohno, S.; Helm, B.; Fuchs, T.; Dewald, G.; Kraft, M. A.; Culver, S. P.; Senyshyn, A.; Zeier, W. G. Further Evidence for Energy Landscape Flattening in the Superionic Argyrodites Li6+xP1-xMxS5I (M = Si, Ge, Sn). Chem. Mater. 2019, 31, 4936– 4944, DOI: 10.1021/acs.chemmater.9b01857Google Scholar21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhtFGqsb7E&md5=009abb1081ef811ec2f01ee88508e1adFurther Evidence for Energy Landscape Flattening in the Superionic Argyrodites Li6+xP1-xMxS5I (M = Si, Ge, Sn)Ohno, Saneyuki; Helm, Bianca; Fuchs, Till; Dewald, Georg; Kraft, Marvin A.; Culver, Sean P.; Senyshyn, Anatoliy; Zeier, Wolfgang G.Chemistry of Materials (2019), 31 (13), 4936-4944CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)All-solid-state batteries are promising candidates for next-generation energy storage devices. Although the list of candidate materials for solid electrolytes has grown in the past decade, there are still many open questions concerning the mechanisms behind ionic migration in materials. In particular, the lithium thiophosphate family of materials has shown very promising properties for solid-state battery applications. Recently, the Ge-substituted Li6PS5I argyrodite was shown to be a very fast Li-ion conductor, despite the poor ionic cond. of the unsubstituted Li6PS5I. Therein, the cond. was enhanced by over three orders of magnitude due to the emergence of I-/S2- exchange, i.e. site-disorder, which led to a sudden decrease of the activation barrier with a concurrent flattening of the energy landscapes. Inspired by this work, two series of elemental substitutions in Li6+xP1-xMxS5I (M = Si and Sn) were investigated in this study and compared to the Ge-analog. A sharp redn. in the activation energy was obsd. at the same M4+/P5+ compn. as previously found in the Ge-analog, suggesting a more general mechanism at play. Furthermore, structural analyses with X-ray and neutron diffraction indicate that similar changes in the Li-sublattice occur despite a significant variation in the size of the substituents, suggesting that in the argyrodites, the lithium substructure is most likely affected by the occurring Li+ - Li+ interactions. This work provides further evidence that the energy landscape of ionic conductors can be tailored by inducing local disorder.
- 22Yubuchi, S.; Uematsu, M.; Hotehama, C.; Sakuda, A.; Hayashi, A.; Tatsumisago, M. An argyrodite sulfide-based superionic conductor synthesized by a liquid-phase technique with tetrahydrofuran and ethanol. J. Mater. Chem. A 2019, 7, 558– 566, DOI: 10.1039/C8TA09477BGoogle Scholar22https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXit1ehsb7K&md5=631057a4de4a3d024b3c6e84d9b383cfAn argyrodite sulfide-based superionic conductor synthesized by a liquid-phase technique with tetrahydrofuran and ethanolYubuchi, So; Uematsu, Miwa; Hotehama, Chie; Sakuda, Atsushi; Hayashi, Akitoshi; Tatsumisago, MasahiroJournal of Materials Chemistry A: Materials for Energy and Sustainability (2019), 7 (2), 558-566CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)Sulfide-based solid electrolytes with halide elements are essential components of advanced all-solid-state batteries. Argyrodite crystals are viable candidates as solid electrolytes for realizing all-solid-state batteries. However, a simple and effective route for the synthesis of these solid electrolytes is required. Herein, argyrodite Li6PS5Br superionic conductors were synthesized from a homogeneous soln. by a liq.-phase technique. The Li6PS5Br solid electrolyte was prepd. in a shorter synthesis time of one day using THF and ethanol as compared with the solid-phase method. More importantly, of all the sulfide-based solid electrolytes prepd. by liq.-phase techniques, Li6PS5Br showed the highest ionic cond. of 3.1 mS cm-1 at 25 °C. The obtained particle size of 1 μm is suitable for application in all-solid-state cells. Moreover, coating electrode active materials with the solid electrolyte using the precursor soln. led to a large contact area between the electrode and electrolyte and improved the cell performance. In addn., infiltrating a porous electrode with the precursor soln. of the solid electrolyte is suitable for forming homogeneous composite electrodes to improve the cell performance. The all-solid-state cell using the Li6PS5Br fine powder with a high cond. of 1 mS cm-1 or more exhibited a reversible capacity of 150 mA h g-1. This technique is effective for the industrial prodn. of solid electrolytes and is applicable to all-solid-state batteries.
- 23Hibi, Y.; Tanibata, N.; Hayashi, A.; Tatsumisago, M. Preparation of sodium ion conducting Na3PS4-NaI glasses by a mechanochemical technique. Solid State Ionics 2015, 270, 6– 9, DOI: 10.1016/j.ssi.2014.11.024Google Scholar23https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhvF2rtbfO&md5=1e10b715694dd842fc06d669e965eca0Preparation of sodium ion conducting Na3PS4-NaI glasses by a mechanochemical techniqueHibi, Yoshiaki; Tanibata, Naoto; Hayashi, Akitoshi; Tatsumisago, MasahiroSolid State Ionics (2015), 270 (), 6-9CODEN: SSIOD3; ISSN:0167-2738. (Elsevier B.V.)Structures and ionic conductivities of the (100 - x)Na3PS4• xNaI (0 ≤ x (mol%) ≤ 33) glasses and glass-ceramics were investigated. In the XRD patterns, halo patterns were obsd. in the compn. range of 0 ≤ x ≤ 29. The glass-ceramics were prepd. by a heat treatment of the glasses. In the glass-ceramics with NaI, an unknown phase which has not been reported was mainly pptd. The Raman spectra of the glasses and glass-ceramics indicated that all samples included the PS43- units. The conductivities of glasses increased with increasing the NaI content, and the 71Na3PS4•29NaI glass showed the highest cond. of 1.4 × 10-5 S cm-1. The conductivities of the glass-ceramics at all compn. were over 10-4 S cm-1.
- 24Tanibata, N.; Deguchi, M.; Hayashi, A.; Tatsumisago, M. All-Solid-State Na/S Batteries with a Na3PS4 Electrolyte Operating at Room Temperature. Chem. Mater. 2017, 29, 5232– 5238, DOI: 10.1021/acs.chemmater.7b01116Google Scholar24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXosVyis70%253D&md5=bb8f474e7c6c127e4c3d8ff5c26f0b97All-Solid-State Na/S Batteries with a Na3PS4 Electrolyte Operating at Room TemperatureTanibata, Naoto; Deguchi, Minako; Hayashi, Akitoshi; Tatsumisago, MasahiroChemistry of Materials (2017), 29 (12), 5232-5238CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)Bulk-type all-solid-state Na/S cells, which are expected to have high capacity, be highly safe, and have low material cost, were fabricated using a Na3PS4 glass-ceramic as a solid electrolyte. The sulfur composite electrodes were prepd. by mech. milling of sulfur active material, a conductive additive (acetylene black), and a Na3PS4 glass-ceramic electrolyte. The all-solid-state Na/S cells used the reaction up to the final discharge product of sulfur active material, Na2S, and achieved a high capacity of ∼1100 mAh (g of S)-1 at room temp. The rate of utilization of sulfur active material was ∼2 times higher than that of high-temp.-operating NAS batteries (com. available NAS batteries, Na/sintered β''-alumina/S), where Na2Sx melts with bridging sulfurs contribute to redox in the sulfur electrodes. The open circuit potential curve of the discharge process of the Na/S batteries operating at room temp. was similar to that of the NAS batteries operating at high temps.; X-ray diffraction and XPS measurement indicated that amorphous Na2Sx with a structure similar to the structure of these melts contributed to sulfur redox reaction in the all-solid-state Na/S cells. A galvanostatic intermittent titrn. technique and impedance measurement suggested that the overpotential during the discharge process in the all-solid-state Na/S cells was mainly derived from the sodium diffusion resistance in the solid sulfur active material. The finding would be an effective guide for achieving higher performance for all-solid-state Na/S cells.
- 25Banerjee, A.; Park, K. H.; Heo, J. W.; Nam, Y. J.; Moon, C. K.; Oh, S. M.; Hong, S. T.; Jung, Y. S. Na3SbS4: A Solution Processable Sodium Superionic Conductor for All-Solid-State Sodium-Ion Batteries. Angew. Chem., Int. Ed. 2016, 55, 9634– 9638, DOI: 10.1002/anie.201604158Google Scholar25https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhtFSqurbO&md5=095d79b76c1ff797b5bc2482d0da6066Na3SbS4: A Solution Processable Sodium Superionic Conductor for All-Solid-State Sodium-Ion BatteriesBanerjee, Abhik; Park, Kern Ho; Heo, Jongwook W.; Nam, Young Jin; Moon, Chang Ki; Oh, Seung M.; Hong, Seung-Tae; Jung, Yoon SeokAngewandte Chemie, International Edition (2016), 55 (33), 9634-9638CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)All-solid-state sodium-ion batteries that operate at room temp. are attractive candidates for use in large-scale energy storage systems. However, materials innovation in solid electrolytes is imperative to fulfill multiple requirements, including high cond., functional synthesis protocols for achieving intimate ionic contact with active materials, and air stability. A new, highly conductive (1.1 mS cm-1 at 25°C, Ea=0.20 eV) and dry air stable sodium superionic conductor, tetragonal Na3SbS4, is described. Importantly, Na3SbS4 can be prepd. by scalable soln. processes using methanol or water, and it exhibits high conductivities of 0.1-0.3 mS cm-1. The soln.-processed, highly conductive solidified Na3SbS4 electrolyte coated on an active material (NaCrO2) demonstrates dramatically improved electrochem. performance in all-solid-state batteries.
- 26Moon, C. K.; Lee, H.-J.; Park, K. H.; Kwak, H.; Heo, J. W.; Choi, K.; Yang, H.; Kim, M.-S.; Hong, S.-T.; Lee, J. H. Vacancy-Driven Na+ Superionic Conduction in New Ca-Doped Na3PS4 for All-Solid-State Na-Ion Batteries. ACS Energy Lett. 2018, 3, 2504– 2512, DOI: 10.1021/acsenergylett.8b01479Google Scholar26https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhslantb%252FN&md5=4ddd8daa12a7448a6278656c2a5313bdVacancy-Driven Na+ Superionic Conduction in New Ca-Doped Na3PS4 for All-Solid-State Na-Ion BatteriesMoon, Chang Ki; Lee, Hyun-Jae; Park, Kern Ho; Kwak, Hiram; Heo, Jongwook W.; Choi, Keunsu; Yang, Hyemi; Kim, Maeng-Suk; Hong, Seung-Tae; Lee, Jun Hee; Jung, Yoon SeokACS Energy Letters (2018), 3 (10), 2504-2512CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)Mech. sinterable sulfide Na+ superionic conductors are key to enabling room-temp.-operable all-solid-state Na-ion batteries (ASNBs) for large-scale energy storage applications. To date, few candidates can fulfill the requirement of a high ionic cond. of ≥1 mS cm-1 using abundant, cost-effective, and nontoxic elements. Herein, the development of a new Na+ superionic conductor, Ca-doped cubic Na3PS4, showing a max. cond. of ∼1 mS cm-1 at 25° is described. Complementary analyses using cond. measurement by the a.c. impedance method, 23Na NMR spectroscopy, and d. functional theory calcns. reveal that the aliovalent substitution of Na+ in Na3PS4 with Ca2+ renders a cubic phase with Na vacancies, which increases the activation barriers but drastically enhances Na-ion diffusion. TiS2/Na-Sn ASNBs employing Ca-doped Na3PS4 exhibit a high charge capacity of 200 mA h g-1 at 0.06 C, good cycling performance, and higher rate capability than those employing undoped cubic Na3PS4.
- 27Fuchs, T.; Culver, S. P.; Till, P.; Zeier, W. G. Defect-Mediated Conductivity Enhancements in Na3–xPn1–xWxS4 (Pn = P, Sb) Using Aliovalent Substitutions. ACS Energy Lett. 2020, 5, 146– 151, DOI: 10.1021/acsenergylett.9b02537Google Scholar27https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXitlOnt7nN&md5=0fdea83a3424dd22edab64becbb8541aDefect-Mediated Conductivity Enhancements in Na3-xPn1-xWxS4 (Pn = P, Sb) Using Aliovalent SubstitutionsFuchs, Till; Culver, Sean P.; Till, Paul; Zeier, Wolfgang G.ACS Energy Letters (2020), 5 (1), 146-151CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)The sodium-ion conducting family of Na3PnS4, with Pn = P, Sb, has gained interest for the use in solid-state batteries due to their high ionic cond. However, significant improvements to the cond. have been hampered by the lack of aliovalent dopants that can introduce vacancies into the structure. Inspired by the need for vacancy introduction into Na3PnS4, the solid solns. with WS42- introduction are explored. The effect of the substitution with WS42- for PS43- and SbS43- is monitored using a combination of X-ray diffraction, Raman, and impedance spectroscopy. With increasing vacancy concn., improvements resulting in a very high ionic cond. of 13 ± 3 mS·cm-1 for Na2.9P0.9W0.1S4 and 41 ± 8 mS·cm-1 for Na2.9Sb0.9W0.1S4 can be obsd. This work acts as a stepping-stone toward further engineering of ionic conductors using vacancy injection via aliovalent substituents.
- 28Zhang, Z.; Ramos, E.; Lalere, F.; Assoud, A.; Kaup, K.; Hartman, P.; Nazar, L. Na11Sn2PS12: A New Solid State Sodium Superionic Conductor. Energy Environ. Sci. 2018, 11, 87– 93, DOI: 10.1039/C7EE03083EGoogle Scholar28https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhvFahtLfP&md5=44d22c10c325f2757a700dadb3e94d04Na11Sn2PS12: a new solid state sodium superionic conductorZhang, Z.; Ramos, E.; Lalere, F.; Assoud, A.; Kaup, K.; Hartman, P.; Nazar, Linda F.Energy & Environmental Science (2018), 11 (1), 87-93CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)We report a new sodium superionic conductor, Na11Sn2PS12, that crystallizes in an unprecedented three-dimensional structure type and exhibits an ionic cond. of 1.4 mS cm-1, with a very low activation energy barrier for Na-ion mobility of 0.25 eV. A combination of structural elucidation via single crystal X-ray diffraction and ab initio mol. dynamics simulations show that Na+-ion conduction pathways flow through equi-energetic sodium-sulfur octahedra interconnected by partial vacancy cross-over sites in all crystallog. dimensions, providing an understanding of the underlying isotropic 3D fast-ion conduction in this material.
- 29Duchardt, M.; Ruschewitz, U.; Adams, S.; Dehnen, S.; Roling, B. Vacancy-Controlled Na+ Superion Conduction in Na11Sn2PS12. Angew. Chem., Int. Ed. 2018, 57, 1351– 1355, DOI: 10.1002/anie.201712769Google Scholar29https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXlt1Oqsw%253D%253D&md5=bbb8f1c8e7a702ca50743a69eba1c793Vacancy-Controlled Na+ Superion Conduction in Na11Sn2PS12Duchardt, Marc; Ruschewitz, Uwe; Adams, Stefan; Dehnen, Stefanie; Roling, BernhardAngewandte Chemie, International Edition (2018), 57 (5), 1351-1355CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)Highly conductive solid electrolytes are crucial to the development of efficient all-solid-state batteries. Meanwhile, the ion conductivities of lithium solid electrolytes match those of liq. electrolytes used in com. Li+ ion batteries. However, concerns about the future availability and the price of lithium made Na+ ion conductors come into the spotlight in recent years. Here we present the superionic conductor Na11Sn2PS12, which possesses a room temp. Na+ cond. close to 4 mS cm-1, thus the highest value known to date for sulfide-based solids. Structure detn. based on synchrotron x-ray powder diffraction data proves the existence of Na+ vacancies. As confirmed by bond valence site energy calcns., the vacancies interconnect ion migration pathways in a 3D manner, hence enabling high Na+ cond. Sodium electrolytes are about to equal the performance of their lithium counterparts.
- 30Smetaczek, S.; Wachter-welzl, A.; Wagner, R.; Rettenwander, D.; Amthauer, G.; Andrejs, L.; Taibl, S. Local Li-ion conductivity changes within Al stabilized Li7La3Zr2O12 and their relationship to three-dimensional variations of the bulk composition. J. Mater. Chem. A 2019, 7, 6818– 6831, DOI: 10.1039/C9TA00356HGoogle Scholar30https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXjsFShu78%253D&md5=116b3fd2a34716807004400cc2e15f6bLocal Li-ion conductivity changes within Al stabilized Li7La3Zr2O12 and their relationship to three-dimensional variations of the bulk compositionSmetaczek, Stefan; Wachter-Welzl, Andreas; Wagner, Reinhard; Rettenwander, Daniel; Amthauer, Georg; Andrejs, Lukas; Taibl, Stefanie; Limbeck, Andreas; Fleig, JuergenJournal of Materials Chemistry A: Materials for Energy and Sustainability (2019), 7 (12), 6818-6831CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)The attractiveness of cubic Li7La3Zr2O12 (LLZO) based garnets lies in their high ionic cond. and the combination of thermal and electrochem. stability. However, relations between the exact chem. compn. and ionic cond. are still not well understood and samples of very similar compn. and processing may show very different properties. In this contribution, the authors studied Al stabilized LLZO by employing a combination of local cond. measurements and 3-dimensional local chem. anal. using laser ablation inductively coupled plasma optical emission spectroscopy (LA-ICP-OES). These measurements revealed significant cond. variations across some samples, with variations up to almost one order of magnitude, as well as an inhomogeneous elemental distribution of Al and Li, largely along the samples. Surprisingly, neither the local Al content nor the local Li content showed a clear correlation with the local Li-ion cond. Accordingly, an in-depth understanding of the conduction properties of Al stabilized LLZO has to conc. on aspects beyond the simple chem. compn. Yet unknown factors (e.g. O vacancies or local cation site occupancies) seem to have a much higher impact on the ionic cond. than the exact stoichiometry.
- 31Wachter-Welzl, A.; Kirowitz, J.; Wagner, R.; Smetaczek, S.; Brunauer, G.C.; Bonta, M.; Rettenwander, D.; Taibl, S.; Limbeck, A.; Amthauer, G.; Fleig, J. The origin of conductivity variations in Al-stabilized Li7La3Zr2O12 ceramics. Solid State Ionics 2018, 319, 203– 208, DOI: 10.1016/j.ssi.2018.01.036Google Scholar31https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXislSrsL0%253D&md5=f0636fbb282602cfda371415d720f611The origin of conductivity variations in Al-stabilized Li7La3Zr2O12 ceramicsWachter-Welzl, A.; Kirowitz, J.; Wagner, R.; Smetaczek, S.; Brunauer, G. C.; Bonta, M.; Rettenwander, D.; Taibl, S.; Limbeck, A.; Amthauer, G.; Fleig, J.Solid State Ionics (2018), 319 (), 203-208CODEN: SSIOD3; ISSN:0167-2738. (Elsevier B.V.)All-solid state batteries have the ability to bring us closer to a zero-emission society. Such battery systems, however, require a powerful solid Li-ion conductor with high stability and exceptionally high Li-ion cond. Cubic Li7La3Zr2O12 (LLZO) garnets are attractive candidates combining high ionic cond. and thermal as well as electrochem. stability. Since the cubic LLZO polymorph is not stable at room temp., supervalent cations, such as Al3+, are needed to stabilize the highly conductive phase. However, strong variations in cond. values were reported even for very similar Al contents, which is crit. for future battery applications. Therefore, the overall performance of 44 samples with nominally identical compn. (Li6.40Al0.20La3Zr2O12), sintered at two different temps. (1150 °C and 1230 °C, resp.) was analyzed by electrochem. impedance spectroscopy. The aim of this work is to elucidate the origin of the strong variations in cond. reported in literature. This study shows that the effective conductivities of the LLZO samples vary between 2 × 10-5 and 8 × 10-4 S cm-1, which cannot be attributed to obvious differences in sample prepn. Furthermore, the stepwise redn. of the sample vol. and repeated measuring of the impedance revealed cond. variations even within a single sample. Finally, preliminary chem. anal. by laser ablation (LA) - inductively coupled plasma (ICP) - mass spectrometry (MS) identified Al inhomogeneities in LLZO, which may be responsible for cond. variations of nominally equal samples.
- 32Gevorgyan, S. A.; Zubillaga, O.; María, J.; De Seoane, V.; Machado, M.; Parlak, E. A.; Tore, N.; Voroshazi, E.; Aernouts, T.; Müllejans, H. Round robin performance testing of organic photovoltaic devices. Renewable Energy 2014, 63, 376– 387, DOI: 10.1016/j.renene.2013.09.034Google Scholar32https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhvFelu7jN&md5=ce56b80244c12615314e8212b27dca18Round robin performance testing of organic photovoltaic devicesGevorgyan, Suren A.; Zubillaga, Oihana; Vega de Seoane, Jose Maria; Machado, Maider; Parlak, Elif Alturk; Tore, Nesrin; Voroshazi, Eszter; Aernouts, Tom; Mullejans, Harald; Bardizza, Giorgio; Taylor, Nigel; Verhees, Wiljan; Kroon, Jan M.; Morvillo, Pasquale; Minarini, Carla; Roca, Francesco; Castro, Fernando A.; Cros, Stephane; Lechene, Balthazar; Trigo, Juan F.; Guillen, Cecilia; Herrero, Jose; Zimmermann, Birger; Sapkota, Subarna Babu; Veit, Clemens; Wurfel, Uli; Tuladhar, Pabitra S.; Durrant, James R.; Winter, Stefan; Rousu, Sanna; Valimaki, Marja; Hinrichs, Volker; Cowan, Sarah R.; Olson, Dana C.; Sommer-Larsen, Peter; Krebs, Frederik C.Renewable Energy (2014), 63 (), 376-387CODEN: RNENE3; ISSN:0960-1481. (Elsevier Ltd.)This study addresses the issue of poor intercomparability of measurements of org. photovoltaic (OPV) devices among different labs. We present a round robin performance testing of novel OPV devices among 16 labs., organized within the framework of European Research Infrastructure Project (SOPHIA) and European Energy Research Alliance (EERA). Three types of OPVs with different structures, dimensions and encapsulations are studied and compared with ref. Si solar cells certified by accredited labs. The agreement of the measurements of these among different labs. is analyzed by focusing on testing procedures, testing equipment and sample designs. A no. of deviations and pitfalls are revealed and based on the analyses, a set of recommendations are suggested for improving the agreement among the measurements of such OPV technologies.
- 33Bron, P.; Dehnen, S.; Roling, B. Li10Si0.3Sn0.7P2S12 - A low-cost and low-grain-buondary resistance lithium superionic conductor. J. Power Sources 2016, 329, 530– 535, DOI: 10.1016/j.jpowsour.2016.08.115Google Scholar33https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhsVGjs7vM&md5=9798002fa1483e9261d730485701177eLi10Si0.3Sn0.7P2S12 - A low-cost and low-grain-boundary-resistance lithium superionic conductorBron, Philipp; Dehnen, Stefanie; Roling, BernhardJournal of Power Sources (2016), 329 (), 530-535CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)Despite remarkable recent advances in the field of solid electrolytes for lithium ion batteries, there is still considerable room for improvements with respect to ionic cond., cost and electrochem. stability. This study tests systematically how much Sn in the superionic conductor Li10SnP2S12 can be replaced by Si or Al, while retaining its tetragonal structure. For comparison, also the known superionic conductors Li10SnP2S12, Li10GeP2S12, and Li10SiP2S12 are synthesized and characterized with respect to their grain and grain boundary resistances. The results show that due to the negligible grain boundary resistance of the new compd. Li10Si0.3Sn0.7P2S12, its total Li+ ion cond. is only 10-20% lower than that of the expensive superionic conductor Li10GeP2S12 and about four times higher than that of Li10SiP2S12.
- 34Vargas-Barbosa, N. M.; Roling, B. Dynamic ion correlations in solid and liquid electrolytes: how do they affect charge and mass transport. ChemElectroChem 2020, 7, 367– 385, DOI: 10.1002/celc.201901627Google Scholar34https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXit12isr%252FM&md5=4a89619ca70b3bcb82f48c3cbb749609Dynamic Ion Correlations in Solid and Liquid Electrolytes: How Do They Affect Charge and Mass Transport?Vargas-Barbosa, N. M.; Roling, B.ChemElectroChem (2020), 7 (2), 367-385CODEN: CHEMRA; ISSN:2196-0216. (Wiley-VCH Verlag GmbH & Co. KGaA)A review. Solid and liq. electrolytes for electrochem. energy storage and conversion cells, such as batteries, supercapacitors and fuel cells, contain often high concns. of mobile ions. Therefore, the ion dynamics in these electrolytes is characterized by pronounced directional correlations between successive ion movements, which exert a strong influence on charge and mass transport. In this manuscript, we review the relevant transport properties of (i) single-ion conducting solid electrolytes and of (ii) liq. electrolytes with a single type of cations and a single type of anions. All transport quantities are based on Onsager's linear irreversible thermodn. and are defined in the lab. frame of ref., so that they can be easily related to correlations functions of the equil. ion dynamics by means of linear response theory. In the case of single-cation conducting solid electrolytes, we discuss how the complex interplay between cation-cation and cation-lattice interactions leads to a competition between cation self-correlations and distinct-cation correlations. In the case of liq. electrolytes, we describe how cation-cation, anion-anion, and cation-anions correlations influence the various transport quantities, such as total ionic cond., Haven ratio, salt diffusion coeff. and cation transference nos. Moreover, we discuss how, in dil. liq. electrolytes, ion correlations can be governed by ion pair formation. Finally, the competition between cation/anion and cation/polymer chain interactions can lead to neg. cation transference nos. in polymer electrolytes, i. e. to cations migrating towards the pos. electrode. Taken together, these case studies showcase how ion correlations in electrolyte systems can strongly influence the overall efficiency of energy storage and conversion devices due to transport limitations.
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Figure 1
Figure 1. (a) Box plots for the room-temperature total ionic conductivity for all samples in the study. (b) Percentile standard deviations and relative median error percentage for all samples. The relative median error was calculated assuming that the median represents the true total conductivity value, using
Figure 2
Figure 2. (a) Box plots for the activation barrier of all samples in the study. (b) Percentile standard deviations and relative median error percentage for all samples. The relative median error was calculated assuming that the median represents the true conductivity value, using .
Figure 3
Figure 3. Spread in the total ionic conductivities and activation barriers of sample 2 as a function of various experimental parameters. The dashed line represents the average value and the shaded area the standard deviation from the average.
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- 2Famprikis, T.; Canepa, P.; Dawson, J. A.; Islam, M. S.; Masquelier, C. Fundamentals of inorganic solid-state electrolytes for batteries. Nat. Mater. 2019, 18, 1278– 1291, DOI: 10.1038/s41563-019-0431-32https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhs1alsL7I&md5=582754f689db47f9562c6f4201f150bfFundamentals of inorganic solid-state electrolytes for batteriesFamprikis, Theodosios; Canepa, Pieremanuele; Dawson, James A.; Islam, M. Saiful; Masquelier, ChristianNature Materials (2019), 18 (12), 1278-1291CODEN: NMAACR; ISSN:1476-1122. (Nature Research)A review. In the crit. area of sustainable energy storage, solid-state batteries have attracted considerable attention due to their potential safety, energy-d. and cycle-life benefits. This Review describes recent progress in the fundamental understanding of inorg. solid electrolytes, which lie at the heart of the solid-state battery concept, by addressing key issues in the areas of multiscale ion transport, electrochem. and mech. properties, and current processing routes. The main electrolyte-related challenges for practical solid-state devices include utilization of metal anodes, stabilization of interfaces and the maintenance of phys. contact, the solns. to which hinge on gaining greater knowledge of the underlying properties of solid electrolyte materials.
- 3Kamaya, N.; Homma, K.; Yamakawa, Y.; Hirayama, M.; Kanno, R.; Yonemura, M.; Kamiyama, T.; Kato, Y.; Hama, S.; Kawamoto, K. A lithium superionic conductor. Nat. Mater. 2011, 10, 682– 686, DOI: 10.1038/nmat30663https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXpsFaisLc%253D&md5=30637e2968f742a3e1da5f7fa4250644A lithium superionic conductorKamaya, Noriaki; Homma, Kenji; Yamakawa, Yuichiro; Hirayama, Masaaki; Kanno, Ryoji; Yonemura, Masao; Kamiyama, Takashi; Kato, Yuki; Hama, Shigenori; Kawamoto, Koji; Mitsui, AkioNature Materials (2011), 10 (9), 682-686CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)Batteries are a key technol. in modern society. They are used to power elec. and hybrid elec. vehicles and to store wind and solar energy in smart grids. Electrochem. devices with high energy and power densities can currently be powered only by batteries with org. liq. electrolytes. However, such batteries require relatively stringent safety precautions, making large-scale systems complicated and expensive. The application of solid electrolytes is currently limited because they attain practically useful conductivities (10-2 S/cm) only at 50-80°, which is one order of magnitude lower than those of org. liq. electrolytes. Here, the authors report a Li superionic conductor, Li10GeP2S12 that has a new 3-dimensional framework structure. It exhibits an extremely high Li ionic cond. of 12 mS/cm at room temp. This represents the highest cond. achieved in a solid electrolyte, exceeding even those of liq. org. electrolytes. This new solid-state battery electrolyte has many advantages in terms of device fabrication (facile shaping, patterning and integration), stability (non-volatile), safety (non-explosive) and excellent electrochem. properties (high cond. and wide potential window).
- 4Kato, Y.; Hori, S.; Saito, T.; Suzuki, K.; Hirayama, M.; Mitsui, A.; Yonemura, M.; Iba, H.; Kanno, R. High-power all-solid-state batteries using sulfide superionic conductors. Nat. Energy 2016, 1, 16030, DOI: 10.1038/nenergy.2016.304https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhtVekurs%253D&md5=cc1210221e70bc3e6c06e015effc70deHigh-power all-solid-state batteries using sulfide superionic conductorsKato, Yuki; Hori, Satoshi; Saito, Toshiya; Suzuki, Kota; Hirayama, Masaaki; Mitsui, Akio; Yonemura, Masao; Iba, Hideki; Kanno, RyojiNature Energy (2016), 1 (4), 16030CODEN: NEANFD; ISSN:2058-7546. (Nature Publishing Group)Compared with Li-ion batteries with liq. electrolytes, all-solid-state batteries offer an attractive option owing to their potential in improving the safety and achieving both high power and high energy densities. Despite extensive research efforts, the development of all-solid-state batteries still falls short of expectation largely because of the lack of suitable candidate materials for the electrolyte required for practical applications. Here the authors report Li superionic conductors with an exceptionally high cond. (25 mS cm-1 for Li9.54Si1.74P1.44S11.7Cl0.3), as well as high stability ( ∼0 V vs. Li metal for Li9.6P3S12). A fabricated all-solid-state cell based on this Li conductor has very small internal resistance, esp. at 100 oC. The cell possesses high specific power that is superior to that of conventional cells with liq. electrolytes. Stable cycling with a high c.d. of 18 C (charging/discharging in just 3 min; where C is the C-rate) is also demonstrated.
- 5Harm, S.; Hatz, A.; Moudrakovski, I.; Eger, R.; Kuhn, A.; Hoch, C.; Lotsch, B. V. Lesson Learned from NMR: Characterization and Ionic Conductivity of LGPS-like Li7SiPS8. Chem. Mater. 2019, 31, 1280– 1288, DOI: 10.1021/acs.chemmater.8b040515https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXitVCntrc%253D&md5=668b8168a1bdb2f69b38868e55113c9aLesson Learned from NMR: Characterization and Ionic Conductivity of LGPS-like Li7SiPS8Harm, Sascha; Hatz, Anna-Katharina; Moudrakovski, Igor; Eger, Roland; Kuhn, Alexander; Hoch, Constantin; Lotsch, Bettina V.Chemistry of Materials (2019), 31 (4), 1280-1288CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)The authors report on the facile solid-state synthesis and characterization of Li7SiPS8, a new member of the tetragonal Li10GeP2S12 (LGPS)-type family of ultrafast Li+ solid electrolytes. The authors analyze the structure, phase stability, and Li+ cond. of tetragonal and orthorhombic LSiPS by pulsed field gradient NMR and impedance spectroscopy, which show conductivities at room temp. of up to 2 mS cm-1. Although ranking tetragonal LiSiPS as an ultrafast solid electrolyte, the obsd. cond. is unexpectedly low compared to other members of this solid-soln. system. Using solid-state NMR, quant. phase anal., and impedance spectroscopy, the authors identify an amorphous thiophosphate side phase with low Si content, which limits the intergrain cond. and, hence, a potentially higher total cond. This case study thus highlights the need for comprehensive structural anal. of LGPS-type materials beyond the cryst. fractions to fully characterize the structure-property relations in these glass-ceramic compds.
- 6Kuhn, A.; Koehler, J.; Lotsch, B. V. Single-crystal X - ray structure analysis of the superionic conductor Li10GeP2S12. Phys. Chem. Chem. Phys. 2013, 15, 11620– 11622, DOI: 10.1039/c3cp51985f6https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhtVartLfO&md5=db3f009c9f0afdac6c7b308a7737b132Single-crystal X-ray structure analysis of the superionic conductor Li10GeP2S12Kuhn, Alexander; Koehler, Juergen; Lotsch, Bettina V.Physical Chemistry Chemical Physics (2013), 15 (28), 11620-11622CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)Tetragonal Li10GeP2S12 (LGPS) is the best solid Li ion conductor known to date. So far, the structure of the electrolyte was only detd. from powder diffraction and Rietveld refinement. Here, the authors present the 1st single-crystal structure anal. of the tetragonal LGPS structure. The reported structure is largely verified. However, an addnl. Li position is clearly identified which might have a significant impact on the Li ion dynamics. All Li positions are partially occupied - a prerequisite for Li superionic conductors - and form a network of interconnected Li diffusion pathways. Therefore, probably Li diffusion in this record solid electrolyte is less anisotropic than previously claimed.
- 7Bron, P.; Johansson, S.; Zick, K.; Schmedt auf der Günne, J.; Dehnen, S.; Roling, B. Li10SnP2S12: an affordable lithium superionic conductor. J. Am. Chem. Soc. 2013, 135, 15694– 15697, DOI: 10.1021/ja407393y7https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhsFCjt73N&md5=4c73f683533cbd49eb7f05e3499c6bc5Li10SnP2S12: An Affordable Lithium Superionic ConductorBron, Philipp; Johansson, Sebastian; Zick, Klaus; Schmedtauf der Guenne, Joern; Dehnen, Stefanie; Roling, BernhardJournal of the American Chemical Society (2013), 135 (42), 15694-15697CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)The reaction of Li2S and P2S5 with Li4[SnS4], a recently discovered, good Li+ ion conductor, yields Li10SnP2S12, the thiostannate analog of the record holder Li10GeP2S12 and the 2nd compd. of this class of superionic conductors with very high values of 7 mS/cm for the grain cond. and 4 mS/cm for the total cond. at 27°. The replacement of Ge by Sn should reduce the raw material cost by a factor of ∼3.
- 8Krauskopf, T.; Culver, S. P.; Zeier, W. G. The bottleneck of diffusion and inductive effects in Li10Ge1-xSnxP2S12. Chem. Mater. 2018, 30, 1791– 1798, DOI: 10.1021/acs.chemmater.8b002668https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXjtVWiu7g%253D&md5=63a43a543a5c9994a2e4fa0b19e33605Bottleneck of Diffusion and Inductive Effects in Li10Ge1-xSnxP2S12Krauskopf, Thorben; Culver, Sean P.; Zeier, Wolfgang G.Chemistry of Materials (2018), 30 (5), 1791-1798CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)The lithium-ion conductor Li10GeP2S12 (LGPS) is known to exhibit ionic cond. values ≤12 mS/cm. Unfortunately, counter to chem. intuition, many attempts to enhance the ionic transport in LGPS, e.g., by increasing the Sn fraction in Li10Ge1-xSnxP2S12, have even led to a redn. in the cond. Employing a combination of Rietveld refinements against x-ray diffraction data, speed of sound measurements, and electrochem. impedance spectroscopy, the authors study the structure-property relations governing this behavior. Herein, with increasing Sn4+ fraction in Li10Ge1-xSnxP2S12 a structural bottleneck along the diffusion channels in the z-direction begins to tighten, and with the concomitant increase in the lattice softness, the local ionic bonding interactions between Li+ and S2- become stronger, further increasing the activation barrier. This work provides a likely explanation for the lower cond. exhibited by Li10SnP2S12 and demonstrates that there is more to the underlying lithium diffusion mechanism in the Li10MP2S12 structure.
- 9Hayashi, A.; Hama, S.; Morimoto, H.; Tatsumisago, M.; Minami, T. Preparation of Li2S–P2S5 Amorphous Solid Electrolytes by Mechanical Milling. J. Am. Ceram. Soc. 2001, 84, 477– 479, DOI: 10.1111/j.1151-2916.2001.tb00685.x9https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3MXhtlOku7w%253D&md5=634c97a589d9f86aebb56b6a102833b8Preparation of Li2S-P2S5 amorphous solid electrolytes by mechanical millingHayashi, Akitoshi; Hama, Shigenori; Morimoto, Hideyuki; Tatsumisago, Masahiro; Minami, TsutomuJournal of the American Ceramic Society (2001), 84 (2), 477-479CODEN: JACTAW; ISSN:0002-7820. (American Ceramic Society)Amorphous solid electrolytes in the Li2S-P2S5 system were prepd. successfully from a mixt. of cryst. Li2S and P2S5, using a mech. milling technique. The amorphous-forming region was extended to higher Li2S compns. by mech. milling, compared with melt quenching. The pelletized samples of the 75Li2S·25P2S5 (mol%) amorphous powders obtained by mech. milling for 20 h exhibited high cond. (2 × 10-4 S/cm at room temp.) and an activation energy for conduction of 34 kJ/mol. The lithium-ion transport no. of the amorphous powders was almost unity.
- 10Dietrich, C.; Weber, D.; Sedlmaier, S. J.; Indris, S.; Culver, S.; Walter, D.; Janek, J.; Zeier, W. Lithium ion conductivity in Li2S-P2S5 glasses – Building units and local structure evolution during the crystallization of the superionic conductors Li3PS4, Li7P3S11 and Li4P2S7. J. Mater. Chem. A 2017, 5, 18111– 18119, DOI: 10.1039/C7TA06067J10https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXht1Olsr3O&md5=cfcd42ed22843da1b70ba04b747fb333Lithium ion conductivity in Li2S-P2S5 glasses - building units and local structure evolution during the crystallization of superionic conductors Li3PS4, Li7P3S11 and Li4P2S7Dietrich, Christian; Weber, Dominik A.; Sedlmaier, Stefan J.; Indris, Sylvio; Culver, Sean P.; Walter, Dirk; Janek, Juergen; Zeier, Wolfgang G.Journal of Materials Chemistry A: Materials for Energy and Sustainability (2017), 5 (34), 18111-18119CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)Motivated by the high lithium ion conductivities of lithium thiophosphate glasses, a detailed study is performed on the local chem. nature of the thiophosphate building units within these materials. Using Raman and 31P MAS NMR (Magic Angle Spinning - NMR) spectroscopy, the continuous change from dominant P2S74- (di-tetrahedral) anions to PS43- (mono-tetrahedral) anions with increasing Li2S fraction in the (Li2S)x(P2S5)(100-x) glasses is obsd. In addn., synchrotron pair distribution function anal. (PDF) of synchrotron X-ray total scattering data is employed to monitor in situ crystn. and phase evolution in this class of materials. Depending on the compn., different cryst. phases evolve, which possess different decompn. temps. into less conducting phases. The results highlight the crit. influence of the local anionic building units on the cation mobility and thermal stability, with PS43- tetrahedra forming the most thermally robust glass ceramics with the highest ionic cond.
- 11Hayashi, A.; Noi, K.; Sakuda, A.; Tatsumisago, M. Superionic glass-ceramic electrolytes for room-temperature rechargeable sodium batteries. Nat. Commun. 2012, 3, 856, DOI: 10.1038/ncomms184311https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BC38nltleltw%253D%253D&md5=25a3b2cfae7b32f2d61dc2b4e9b53c2eSuperionic glass-ceramic electrolytes for room-temperature rechargeable sodium batteriesHayashi Akitoshi; Noi Kousuke; Sakuda Atsushi; Tatsumisago MasahiroNature communications (2012), 3 (), 856 ISSN:.Innovative rechargeable batteries that can effectively store renewable energy, such as solar and wind power, urgently need to be developed to reduce greenhouse gas emissions. All-solid-state batteries with inorganic solid electrolytes and electrodes are promising power sources for a wide range of applications because of their safety, long-cycle lives and versatile geometries. Rechargeable sodium batteries are more suitable than lithium-ion batteries, because they use abundant and ubiquitous sodium sources. Solid electrolytes are critical for realizing all-solid-state sodium batteries. Here we show that stabilization of a high-temperature phase by crystallization from the glassy state dramatically enhances the Na(+) ion conductivity. An ambient temperature conductivity of over 10(-4) S cm(-1) was obtained in a glass-ceramic electrolyte, in which a cubic Na(3)PS(4) crystal with superionic conductivity was first realized. All-solid-state sodium batteries, with a powder-compressed Na(3)PS(4) electrolyte, functioned as a rechargeable battery at room temperature.
- 12Hayashi, A.; Ohtsubo, R.; Nagao, M.; Tatsumisago, M. Characterization of Li2S–P2S5–Cu composite electrode for all-solid-state lithium secondary batteries. J. Mater. Sci. 2010, 45, 377– 381, DOI: 10.1007/s10853-009-3948-z12https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXhsFOlsLzP&md5=46bf6b9d3d69884d24640e94063fb008Characterization of Li2S-P2S5-Cu composite electrode for all-solid-state lithium secondary batteriesHayashi, Akitoshi; Ohtsubo, Ryoji; Nagao, Motohiro; Tatsumisago, MasahiroJournal of Materials Science (2010), 45 (2), 377-381CODEN: JMTSAS; ISSN:0022-2461. (Springer)Electrochem. performance of the Li2S-P2S5-Cu composite materials was examd. in all-solid-state lithium secondary batteries. The 80Li2S·20P2S5 (mol%) solid electrolyte with the addn. of Cu was partially used as an active material with lithium source in all-solid-state cells. The initial discharge capacity of 110 mA-h/g (normalized by the wt. of 80Li2S·20P2S5-Cu), which corresponds to 400 mA-h/g (normalized by the wt. of Li2S), was obtained in the cell using the 80Li2S·20P2S5-Cu composite electrode with the molar ratio of Li2S/Cu = 48/52. Cycling performance and reaction mechanism of the electrode in the solid-state cell were investigated.
- 13Mizuno, F.; Hayashi, A.; Tadanaga, K.; Tatsumisago, M. New, highly ion-conductive crystals precipitated from Li2S-P2S5 glasses. Adv. Mater. 2005, 17, 918– 921, DOI: 10.1002/adma.20040128613https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXjsFWiurg%253D&md5=3359b524cec1b05fdb569fae9160e777New, highly ion-conductive crystals precipitated from Li2S-P2S5 glassesMizuno, Fuminori; Hayashi, Akitoshi; Tadanaga, Kiyoharu; Tatsumisago, MasahiroAdvanced Materials (Weinheim, Germany) (2005), 17 (7), 918-921CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)Novel sulfide Li-ion conducting materials were synthesized by crystn. of mech. milled Li2S-P2S5 glasses. High ambient-temp. conductivities (σ) compared with other electrolytes and a low conduction activation energy are achieved by the formation of a highly conductive new cryst. phase.
- 14Kato, A.; Yamamoto, M.; Sakuda, A.; Hayashi, A.; Tatsumisago, M. Mechanical Properties of Li2S–P2S5 Glasses with Lithium Halides and Application in All-Solid-State Batteries. ACS Appl. Energy Mater. 2018, 1, 1002– 1007, DOI: 10.1021/acsaem.7b0014014https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXjs1WjtrY%253D&md5=2d7e876f7e739b74a36e4059798109acMechanical Properties of Li2S-P2S5 Glasses with Lithium Halides and Application in All-Solid-State BatteriesKato, Atsutaka; Yamamoto, Mirai; Sakuda, Atsushi; Hayashi, Akitoshi; Tatsumisago, MasahiroACS Applied Energy Materials (2018), 1 (3), 1002-1007CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)Mech. properties of solid electrolytes are important as well as ionic cond. to achieve all-solid-state batteries with large capacities and long cycle life. In this study, it is shown that Li2S-P2S5 glasses with lithium halides, esp. LiI, exhibit both high ionic cond. and favorable mech. properties. Mech. properties, such as Young's modulus and formability at powder compaction, are evaluated for the solid electrolytes. The addn. of lithium halides decreases the Young's modulus of the electrolytes. In addn., fewer pores and grain boundaries were obsd. in the powder-pressed pellets of Li2S-P2S5 glasses with lithium halides. All-solid-state batteries using Si electrodes and glass electrolytes with lithium halides exhibited a larger capacity of 20 cycles compared to those without lithium halides. These results provide guidelines for the construction of all-solid-state batteries from the viewpoint of the mech. properties of solid electrolytes.
- 15Oh, D. Y.; Ha, A. R.; Lee, J. E.; Jung, S. H.; Jeong, G.; Cho, W.; Kim, K. S.; Jung, Y. S. Wet-chemical tuning of Li3-xPS4 (0 ≤ x ≤ 0.3) enabled by dual solvents for all-solid-state lithium-ion batteries. ChemSusChem 2020, 13, 146– 151, DOI: 10.1002/cssc.20190185015https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXitVSlsLfP&md5=be8edd60f854f6a8757812ca2a47209eWet-Chemical Tuning of Li3-xPS4 (0≤x≤0.3) Enabled by Dual Solvents for All-Solid-State Lithium-Ion BatteriesOh, Dae Yang; Ha, A. Reum; Lee, Ji Eun; Jung, Sung Hoo; Jeong, Goojin; Cho, Woosuk; Kim, Kyung Su; Jung, Yoon SeokChemSusChem (2020), 13 (1), 146-151CODEN: CHEMIZ; ISSN:1864-5631. (Wiley-VCH Verlag GmbH & Co. KGaA)All-solid-state Li-ion batteries (ASLBs) employing sulfide solid electrolytes are attractive next-generation rechargeable batteries that could offer improved safety and energy d. Recently, wet syntheses or processes for sulfide solid electrolyte materials have opened opportunities to explore new materials and practical fabrication methods for ASLBs. A new wet-chem. route for the synthesis of Li-deficient Li3-xPS4 (0 ≤ x ≤ 0.3) was developed, which is enabled by dual solvents. Owing to its miscibility with THF and ability to dissolve elemental S, o-xylene as a cosolvent facilitates the wet-chem. synthesis of Li3-xPS4. Li3-xPS4 (0 ≤ x ≤ 0.15) derived by using dual solvents shows Li+ cond. of ∼0.2 mS cm-1 at 30°, in contrast to 0.034 mS cm-1 for a sample obtained by using a conventional single solvent (THF, x = 0.15). The evolution of the structure for Li3-xPS4 is also studied by complementary anal. using x-ray diffraction, Raman, and XPS measurements. LiCoO2/Li-In ASLBs employing Li2.85PS4 obtained by using dual solvents exhibit a reversible capacity of 130 mA h g-1 with good cycle retention at 30°, outperforming cells with Li2.85PS4 obtained by using a conventional single solvent.
- 16Deiseroth, H. J.; Kong, S. T.; Eckert, H.; Vannahme, J.; Reiner, C.; Zaiß, T.; Schlosser, M. Li6PS5X: A class of crystalline Li-rich solids with an unusually high Li+ mobility. Angew. Chem., Int. Ed. 2008, 47, 755– 758, DOI: 10.1002/anie.20070390016https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXhslektb8%253D&md5=7d5e85537afd8d458e86abba9f0e1c59Li6PS5X: a class of crystalline Li-rich solids with an unusually high Li+ mobilityDeiseroth, Hans-Joerg; Kong, Shiao-Tong; Eckert, Hellmut; Vannahme, Julia; Reiner, Christof; Zaiss, Torsten; Schlosser, MarcAngewandte Chemie, International Edition (2008), 47 (4), 755-758CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)Halide-substituted lithium argyrodites, Li6PS5X (X = Cl, Br, I), form a new class of Li-rich solids with an unusually high Li mobility. Single-crystal x-ray studies at room temp. and MAS NMR measurements in a wide temp. range provide insights into the Li+ ion dynamics.
- 17Hanghofer, I.; Brinek, M.; Eisbacher, S. L.; Bitschnau, B.; Volck, M.; Hennige, V.; Hanzu, I.; Rettenwander, D.; Wilkening, M. Subsitutional disorder: Structure and ion dynamics of the argyrodites Li6PS5Cl, Li6PS5Br and Li6PS6I. Phys. Chem. Chem. Phys. 2019, 21, 8489– 8507, DOI: 10.1039/C9CP00664H17https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXlvFCisb4%253D&md5=2a8ab483deb8f84aa6eb39d3fe013b3fSubstitutional disorder: structure and ion dynamics of the argyrodites Li6PS5Cl, Li6PS5Br and Li6PS5IHanghofer, I.; Brinek, M.; Eisbacher, S. L.; Bitschnau, B.; Volck, M.; Hennige, V.; Hanzu, I.; Rettenwander, D.; Wilkening, H. M. R.Physical Chemistry Chemical Physics (2019), 21 (16), 8489-8507CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)For the development of safe and long-lasting lithium-ion batteries we need electrolytes with excellent ionic transport properties. Argyrodite-type Li6PS5X (X: Cl, Br, I) belongs to a family of such a class of materials offering ionic conductivities, at least if Li6PS5Br and Li6PS5Cl are considered, in the mS cm-1 range at room temp. Although already tested as ceramic electrolytes in battery cells, a comprehensive picture about the ion dynamics is still missing. While Li6PS5Br and Li6PS5Cl show an exceptionally high Li ion cond., that of Li6PS5I with its polarizable I anions is by some orders of magnitude lower. This astonishing effect has not been satisfactorily understood so far. Studying the ion dynamics over a broad time and length scale is expected to help shed light on this aspect. Here, we used broadband impedance spectroscopy and 7Li NMR relaxation measurements and show that very fast local Li ion exchange processes are taking place in all three compds. Most importantly, the diffusion-induced NMR spin-lattice relaxation in Li6PS5I is almost identical to that of its relatives. Considering the substitutional disorder effects in Li6PS5X (X = Br, Cl), we conclude that in structurally ordered Li6PS5I the important inter-cage jump processes are switched off, hindering the ions from taking part in long-range ion transport.
- 18Kraft, M. A.; Culver, S. P.; Calderon, M.; Böcher, F.; Krauskopf, T.; Senyshyn, A.; Dietrich, C.; Zevalkink, A.; Janek, J.; Zeier, W. G. Influence of Lattice Polarizability on the Ionic Conductivity in the Lithium Superionic Argyrodites Li6PS5X (X = Cl, Br, I). J. Am. Chem. Soc. 2017, 139, 10909– 10918, DOI: 10.1021/jacs.7b0632718https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXht1eks7%252FL&md5=aa65995954d3a2803687556f1dc76803Influence of Lattice Polarizability on the Ionic Conductivity in the Lithium Superionic Argyrodites Li6PS5X (X = Cl, Br, I)Kraft, Marvin A.; Culver, Sean P.; Calderon, Mario; Boecher, Felix; Krauskopf, Thorben; Senyshyn, Anatoliy; Dietrich, Christian; Zevalkink, Alexandra; Janek, Juergen; Zeier, Wolfgang G.Journal of the American Chemical Society (2017), 139 (31), 10909-10918CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)In the search for novel solid electrolytes for solid-state batteries, thiophosphate ionic conductors have been in recent focus owing to their high ionic conductivities, which are believed to stem from a softer, more polarizable anion framework. Inspired by the oft-cited connection between a soft anion lattice and ionic transport, this work aims to provide evidence on how changing the polarizability of the anion sublattice in one structure affects ionic transport. Here, we systematically alter the anion framework polarizability of the superionic argyrodites Li6PS5X by controlling the fractional occupancy of the halide anions (X = Cl, Br, I). Ultrasonic speed of sound measurements are used to quantify the variation in the lattice stiffness and Debye frequencies. In combination with electrochem. impedance spectroscopy and neutron diffraction, these results show that the lattice softness has a striking influence on the ionic transport: the softer bonds lower the activation barrier and simultaneously decrease the prefactor of the moving ion. Due to the contradicting influence of these parameters on ionic cond., we find that it is necessary to tailor the lattice stiffness of materials in order to obtain an optimum ionic cond.
- 19Adeli, P.; Bazak, J. D.; Park, K. H.; Kochetkov, I.; Huq, A.; Goward, G. R.; Nazar, L. F. Boosting Solid-State Diffusivity and Conductivity in Lithium Superionic Argyrodites by Halide Substitution. Angew. Chem., Int. Ed. 2019, 58, 8681– 8686, DOI: 10.1002/anie.20181422219https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhtVKqtr7P&md5=23835a7c45329b76c32bd123ed8a1974Boosting Solid-State Diffusivity and Conductivity in Lithium Superionic Argyrodites by Halide SubstitutionAdeli, Parvin; Bazak, J. David; Park, Kern Ho; Kochetkov, Ivan; Huq, Ashfia; Goward, Gillian R.; Nazar, Linda F.Angewandte Chemie, International Edition (2019), 58 (26), 8681-8686CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)Developing high-performance all-solid-state batteries is contingent on finding solid electrolyte materials with high ionic cond. and ductility. Here we report new halide-rich solid soln. phases in the argyrodite Li6PS5Cl family, Li6-xPS5-xCl1+x, and combine electrochem. impedance spectroscopy, neutron diffraction, and 7Li NMR MAS and PFG spectroscopy to show that increasing the Cl-/S2- ratio has a systematic, and remarkable impact on Li-ion diffusivity in the lattice. The phase at the limit of the solid soln. regime, Li5.5PS4.5Cl1.5, exhibits a cold-pressed cond. of 9.4±0.1 mS cm-1 at 298 K (and 12.0±0.2 mS cm-1 on sintering)-almost four-fold greater than Li6PS5Cl under identical processing conditions and comparable to metastable superionic Li7P3S11. Weakened interactions between the mobile Li-ions and surrounding framework anions incurred by substitution of divalent S2- for monovalent Cl- play a major role in enhancing Li+-ion diffusivity, along with increased site disorder and a higher lithium vacancy population.
- 20Kraft, M. A.; Ohno, S.; Zinkevich, T.; Koerver, R.; Culver, S. P.; Senyshyn, A.; Indris, S.; Morgan, B. J.; Zeier, W. G. Inducing high ionic conductivity in the lithium superionic argyrodites Li6+xP1-xGexS5I for all-solid-state batteries. J. Am. Chem. Soc. 2018, 140, 16330– 16339, DOI: 10.1021/jacs.8b1028220https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXitVKltb%252FM&md5=2eb04a02921eedaa529f1899e08f498eInducing High Ionic Conductivity in the Lithium Superionic Argyrodites Li6+xP1-xGexS5I for All-Solid-State BatteriesKraft, Marvin A.; Ohno, Saneyuki; Zinkevich, Tatiana; Koerver, Raimund; Culver, Sean P.; Fuchs, Till; Senyshyn, Anatoliy; Indris, Sylvio; Morgan, Benjamin J.; Zeier, Wolfgang G.Journal of the American Chemical Society (2018), 140 (47), 16330-16339CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Solid-state batteries with inorg. solid electrolytes are currently being discussed as a more reliable and safer future alternative to the current lithium-ion battery technol. To compete with state-of-the-art lithium-ion batteries, solid electrolytes with higher ionic conductivities are needed, esp. if thick electrode configurations are to be used. In the search for optimized ionic conductors, the lithium argyrodites have attracted a lot of interest. Here, the effect is systematically explored of aliovalent substitution in Li6+xP1-xGexS5I using a combination of X-ray and neutron diffraction, as well as impedance spectroscopy and NMR. With increasing Ge content, an anion site disorder is induced and the activation barrier for ionic motion drops significantly, leading to the fastest lithium argyrodite so far with 5.4 ± 0.8 mS cm-1 in a cold-pressed state and 18.4 ± 2.7 mS cm-1 upon sintering. These high ionic conductivities allow for successful implementation within a thick-electrode solid-state battery that shows negligible capacity fade over 150 cycles. The obsd. changes in the activation barrier and changing site disorder provide an addnl. approach toward designing better performing solid electrolytes.
- 21Ohno, S.; Helm, B.; Fuchs, T.; Dewald, G.; Kraft, M. A.; Culver, S. P.; Senyshyn, A.; Zeier, W. G. Further Evidence for Energy Landscape Flattening in the Superionic Argyrodites Li6+xP1-xMxS5I (M = Si, Ge, Sn). Chem. Mater. 2019, 31, 4936– 4944, DOI: 10.1021/acs.chemmater.9b0185721https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhtFGqsb7E&md5=009abb1081ef811ec2f01ee88508e1adFurther Evidence for Energy Landscape Flattening in the Superionic Argyrodites Li6+xP1-xMxS5I (M = Si, Ge, Sn)Ohno, Saneyuki; Helm, Bianca; Fuchs, Till; Dewald, Georg; Kraft, Marvin A.; Culver, Sean P.; Senyshyn, Anatoliy; Zeier, Wolfgang G.Chemistry of Materials (2019), 31 (13), 4936-4944CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)All-solid-state batteries are promising candidates for next-generation energy storage devices. Although the list of candidate materials for solid electrolytes has grown in the past decade, there are still many open questions concerning the mechanisms behind ionic migration in materials. In particular, the lithium thiophosphate family of materials has shown very promising properties for solid-state battery applications. Recently, the Ge-substituted Li6PS5I argyrodite was shown to be a very fast Li-ion conductor, despite the poor ionic cond. of the unsubstituted Li6PS5I. Therein, the cond. was enhanced by over three orders of magnitude due to the emergence of I-/S2- exchange, i.e. site-disorder, which led to a sudden decrease of the activation barrier with a concurrent flattening of the energy landscapes. Inspired by this work, two series of elemental substitutions in Li6+xP1-xMxS5I (M = Si and Sn) were investigated in this study and compared to the Ge-analog. A sharp redn. in the activation energy was obsd. at the same M4+/P5+ compn. as previously found in the Ge-analog, suggesting a more general mechanism at play. Furthermore, structural analyses with X-ray and neutron diffraction indicate that similar changes in the Li-sublattice occur despite a significant variation in the size of the substituents, suggesting that in the argyrodites, the lithium substructure is most likely affected by the occurring Li+ - Li+ interactions. This work provides further evidence that the energy landscape of ionic conductors can be tailored by inducing local disorder.
- 22Yubuchi, S.; Uematsu, M.; Hotehama, C.; Sakuda, A.; Hayashi, A.; Tatsumisago, M. An argyrodite sulfide-based superionic conductor synthesized by a liquid-phase technique with tetrahydrofuran and ethanol. J. Mater. Chem. A 2019, 7, 558– 566, DOI: 10.1039/C8TA09477B22https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXit1ehsb7K&md5=631057a4de4a3d024b3c6e84d9b383cfAn argyrodite sulfide-based superionic conductor synthesized by a liquid-phase technique with tetrahydrofuran and ethanolYubuchi, So; Uematsu, Miwa; Hotehama, Chie; Sakuda, Atsushi; Hayashi, Akitoshi; Tatsumisago, MasahiroJournal of Materials Chemistry A: Materials for Energy and Sustainability (2019), 7 (2), 558-566CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)Sulfide-based solid electrolytes with halide elements are essential components of advanced all-solid-state batteries. Argyrodite crystals are viable candidates as solid electrolytes for realizing all-solid-state batteries. However, a simple and effective route for the synthesis of these solid electrolytes is required. Herein, argyrodite Li6PS5Br superionic conductors were synthesized from a homogeneous soln. by a liq.-phase technique. The Li6PS5Br solid electrolyte was prepd. in a shorter synthesis time of one day using THF and ethanol as compared with the solid-phase method. More importantly, of all the sulfide-based solid electrolytes prepd. by liq.-phase techniques, Li6PS5Br showed the highest ionic cond. of 3.1 mS cm-1 at 25 °C. The obtained particle size of 1 μm is suitable for application in all-solid-state cells. Moreover, coating electrode active materials with the solid electrolyte using the precursor soln. led to a large contact area between the electrode and electrolyte and improved the cell performance. In addn., infiltrating a porous electrode with the precursor soln. of the solid electrolyte is suitable for forming homogeneous composite electrodes to improve the cell performance. The all-solid-state cell using the Li6PS5Br fine powder with a high cond. of 1 mS cm-1 or more exhibited a reversible capacity of 150 mA h g-1. This technique is effective for the industrial prodn. of solid electrolytes and is applicable to all-solid-state batteries.
- 23Hibi, Y.; Tanibata, N.; Hayashi, A.; Tatsumisago, M. Preparation of sodium ion conducting Na3PS4-NaI glasses by a mechanochemical technique. Solid State Ionics 2015, 270, 6– 9, DOI: 10.1016/j.ssi.2014.11.02423https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhvF2rtbfO&md5=1e10b715694dd842fc06d669e965eca0Preparation of sodium ion conducting Na3PS4-NaI glasses by a mechanochemical techniqueHibi, Yoshiaki; Tanibata, Naoto; Hayashi, Akitoshi; Tatsumisago, MasahiroSolid State Ionics (2015), 270 (), 6-9CODEN: SSIOD3; ISSN:0167-2738. (Elsevier B.V.)Structures and ionic conductivities of the (100 - x)Na3PS4• xNaI (0 ≤ x (mol%) ≤ 33) glasses and glass-ceramics were investigated. In the XRD patterns, halo patterns were obsd. in the compn. range of 0 ≤ x ≤ 29. The glass-ceramics were prepd. by a heat treatment of the glasses. In the glass-ceramics with NaI, an unknown phase which has not been reported was mainly pptd. The Raman spectra of the glasses and glass-ceramics indicated that all samples included the PS43- units. The conductivities of glasses increased with increasing the NaI content, and the 71Na3PS4•29NaI glass showed the highest cond. of 1.4 × 10-5 S cm-1. The conductivities of the glass-ceramics at all compn. were over 10-4 S cm-1.
- 24Tanibata, N.; Deguchi, M.; Hayashi, A.; Tatsumisago, M. All-Solid-State Na/S Batteries with a Na3PS4 Electrolyte Operating at Room Temperature. Chem. Mater. 2017, 29, 5232– 5238, DOI: 10.1021/acs.chemmater.7b0111624https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXosVyis70%253D&md5=bb8f474e7c6c127e4c3d8ff5c26f0b97All-Solid-State Na/S Batteries with a Na3PS4 Electrolyte Operating at Room TemperatureTanibata, Naoto; Deguchi, Minako; Hayashi, Akitoshi; Tatsumisago, MasahiroChemistry of Materials (2017), 29 (12), 5232-5238CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)Bulk-type all-solid-state Na/S cells, which are expected to have high capacity, be highly safe, and have low material cost, were fabricated using a Na3PS4 glass-ceramic as a solid electrolyte. The sulfur composite electrodes were prepd. by mech. milling of sulfur active material, a conductive additive (acetylene black), and a Na3PS4 glass-ceramic electrolyte. The all-solid-state Na/S cells used the reaction up to the final discharge product of sulfur active material, Na2S, and achieved a high capacity of ∼1100 mAh (g of S)-1 at room temp. The rate of utilization of sulfur active material was ∼2 times higher than that of high-temp.-operating NAS batteries (com. available NAS batteries, Na/sintered β''-alumina/S), where Na2Sx melts with bridging sulfurs contribute to redox in the sulfur electrodes. The open circuit potential curve of the discharge process of the Na/S batteries operating at room temp. was similar to that of the NAS batteries operating at high temps.; X-ray diffraction and XPS measurement indicated that amorphous Na2Sx with a structure similar to the structure of these melts contributed to sulfur redox reaction in the all-solid-state Na/S cells. A galvanostatic intermittent titrn. technique and impedance measurement suggested that the overpotential during the discharge process in the all-solid-state Na/S cells was mainly derived from the sodium diffusion resistance in the solid sulfur active material. The finding would be an effective guide for achieving higher performance for all-solid-state Na/S cells.
- 25Banerjee, A.; Park, K. H.; Heo, J. W.; Nam, Y. J.; Moon, C. K.; Oh, S. M.; Hong, S. T.; Jung, Y. S. Na3SbS4: A Solution Processable Sodium Superionic Conductor for All-Solid-State Sodium-Ion Batteries. Angew. Chem., Int. Ed. 2016, 55, 9634– 9638, DOI: 10.1002/anie.20160415825https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhtFSqurbO&md5=095d79b76c1ff797b5bc2482d0da6066Na3SbS4: A Solution Processable Sodium Superionic Conductor for All-Solid-State Sodium-Ion BatteriesBanerjee, Abhik; Park, Kern Ho; Heo, Jongwook W.; Nam, Young Jin; Moon, Chang Ki; Oh, Seung M.; Hong, Seung-Tae; Jung, Yoon SeokAngewandte Chemie, International Edition (2016), 55 (33), 9634-9638CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)All-solid-state sodium-ion batteries that operate at room temp. are attractive candidates for use in large-scale energy storage systems. However, materials innovation in solid electrolytes is imperative to fulfill multiple requirements, including high cond., functional synthesis protocols for achieving intimate ionic contact with active materials, and air stability. A new, highly conductive (1.1 mS cm-1 at 25°C, Ea=0.20 eV) and dry air stable sodium superionic conductor, tetragonal Na3SbS4, is described. Importantly, Na3SbS4 can be prepd. by scalable soln. processes using methanol or water, and it exhibits high conductivities of 0.1-0.3 mS cm-1. The soln.-processed, highly conductive solidified Na3SbS4 electrolyte coated on an active material (NaCrO2) demonstrates dramatically improved electrochem. performance in all-solid-state batteries.
- 26Moon, C. K.; Lee, H.-J.; Park, K. H.; Kwak, H.; Heo, J. W.; Choi, K.; Yang, H.; Kim, M.-S.; Hong, S.-T.; Lee, J. H. Vacancy-Driven Na+ Superionic Conduction in New Ca-Doped Na3PS4 for All-Solid-State Na-Ion Batteries. ACS Energy Lett. 2018, 3, 2504– 2512, DOI: 10.1021/acsenergylett.8b0147926https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhslantb%252FN&md5=4ddd8daa12a7448a6278656c2a5313bdVacancy-Driven Na+ Superionic Conduction in New Ca-Doped Na3PS4 for All-Solid-State Na-Ion BatteriesMoon, Chang Ki; Lee, Hyun-Jae; Park, Kern Ho; Kwak, Hiram; Heo, Jongwook W.; Choi, Keunsu; Yang, Hyemi; Kim, Maeng-Suk; Hong, Seung-Tae; Lee, Jun Hee; Jung, Yoon SeokACS Energy Letters (2018), 3 (10), 2504-2512CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)Mech. sinterable sulfide Na+ superionic conductors are key to enabling room-temp.-operable all-solid-state Na-ion batteries (ASNBs) for large-scale energy storage applications. To date, few candidates can fulfill the requirement of a high ionic cond. of ≥1 mS cm-1 using abundant, cost-effective, and nontoxic elements. Herein, the development of a new Na+ superionic conductor, Ca-doped cubic Na3PS4, showing a max. cond. of ∼1 mS cm-1 at 25° is described. Complementary analyses using cond. measurement by the a.c. impedance method, 23Na NMR spectroscopy, and d. functional theory calcns. reveal that the aliovalent substitution of Na+ in Na3PS4 with Ca2+ renders a cubic phase with Na vacancies, which increases the activation barriers but drastically enhances Na-ion diffusion. TiS2/Na-Sn ASNBs employing Ca-doped Na3PS4 exhibit a high charge capacity of 200 mA h g-1 at 0.06 C, good cycling performance, and higher rate capability than those employing undoped cubic Na3PS4.
- 27Fuchs, T.; Culver, S. P.; Till, P.; Zeier, W. G. Defect-Mediated Conductivity Enhancements in Na3–xPn1–xWxS4 (Pn = P, Sb) Using Aliovalent Substitutions. ACS Energy Lett. 2020, 5, 146– 151, DOI: 10.1021/acsenergylett.9b0253727https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXitlOnt7nN&md5=0fdea83a3424dd22edab64becbb8541aDefect-Mediated Conductivity Enhancements in Na3-xPn1-xWxS4 (Pn = P, Sb) Using Aliovalent SubstitutionsFuchs, Till; Culver, Sean P.; Till, Paul; Zeier, Wolfgang G.ACS Energy Letters (2020), 5 (1), 146-151CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)The sodium-ion conducting family of Na3PnS4, with Pn = P, Sb, has gained interest for the use in solid-state batteries due to their high ionic cond. However, significant improvements to the cond. have been hampered by the lack of aliovalent dopants that can introduce vacancies into the structure. Inspired by the need for vacancy introduction into Na3PnS4, the solid solns. with WS42- introduction are explored. The effect of the substitution with WS42- for PS43- and SbS43- is monitored using a combination of X-ray diffraction, Raman, and impedance spectroscopy. With increasing vacancy concn., improvements resulting in a very high ionic cond. of 13 ± 3 mS·cm-1 for Na2.9P0.9W0.1S4 and 41 ± 8 mS·cm-1 for Na2.9Sb0.9W0.1S4 can be obsd. This work acts as a stepping-stone toward further engineering of ionic conductors using vacancy injection via aliovalent substituents.
- 28Zhang, Z.; Ramos, E.; Lalere, F.; Assoud, A.; Kaup, K.; Hartman, P.; Nazar, L. Na11Sn2PS12: A New Solid State Sodium Superionic Conductor. Energy Environ. Sci. 2018, 11, 87– 93, DOI: 10.1039/C7EE03083E28https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhvFahtLfP&md5=44d22c10c325f2757a700dadb3e94d04Na11Sn2PS12: a new solid state sodium superionic conductorZhang, Z.; Ramos, E.; Lalere, F.; Assoud, A.; Kaup, K.; Hartman, P.; Nazar, Linda F.Energy & Environmental Science (2018), 11 (1), 87-93CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)We report a new sodium superionic conductor, Na11Sn2PS12, that crystallizes in an unprecedented three-dimensional structure type and exhibits an ionic cond. of 1.4 mS cm-1, with a very low activation energy barrier for Na-ion mobility of 0.25 eV. A combination of structural elucidation via single crystal X-ray diffraction and ab initio mol. dynamics simulations show that Na+-ion conduction pathways flow through equi-energetic sodium-sulfur octahedra interconnected by partial vacancy cross-over sites in all crystallog. dimensions, providing an understanding of the underlying isotropic 3D fast-ion conduction in this material.
- 29Duchardt, M.; Ruschewitz, U.; Adams, S.; Dehnen, S.; Roling, B. Vacancy-Controlled Na+ Superion Conduction in Na11Sn2PS12. Angew. Chem., Int. Ed. 2018, 57, 1351– 1355, DOI: 10.1002/anie.20171276929https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXlt1Oqsw%253D%253D&md5=bbb8f1c8e7a702ca50743a69eba1c793Vacancy-Controlled Na+ Superion Conduction in Na11Sn2PS12Duchardt, Marc; Ruschewitz, Uwe; Adams, Stefan; Dehnen, Stefanie; Roling, BernhardAngewandte Chemie, International Edition (2018), 57 (5), 1351-1355CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)Highly conductive solid electrolytes are crucial to the development of efficient all-solid-state batteries. Meanwhile, the ion conductivities of lithium solid electrolytes match those of liq. electrolytes used in com. Li+ ion batteries. However, concerns about the future availability and the price of lithium made Na+ ion conductors come into the spotlight in recent years. Here we present the superionic conductor Na11Sn2PS12, which possesses a room temp. Na+ cond. close to 4 mS cm-1, thus the highest value known to date for sulfide-based solids. Structure detn. based on synchrotron x-ray powder diffraction data proves the existence of Na+ vacancies. As confirmed by bond valence site energy calcns., the vacancies interconnect ion migration pathways in a 3D manner, hence enabling high Na+ cond. Sodium electrolytes are about to equal the performance of their lithium counterparts.
- 30Smetaczek, S.; Wachter-welzl, A.; Wagner, R.; Rettenwander, D.; Amthauer, G.; Andrejs, L.; Taibl, S. Local Li-ion conductivity changes within Al stabilized Li7La3Zr2O12 and their relationship to three-dimensional variations of the bulk composition. J. Mater. Chem. A 2019, 7, 6818– 6831, DOI: 10.1039/C9TA00356H30https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXjsFShu78%253D&md5=116b3fd2a34716807004400cc2e15f6bLocal Li-ion conductivity changes within Al stabilized Li7La3Zr2O12 and their relationship to three-dimensional variations of the bulk compositionSmetaczek, Stefan; Wachter-Welzl, Andreas; Wagner, Reinhard; Rettenwander, Daniel; Amthauer, Georg; Andrejs, Lukas; Taibl, Stefanie; Limbeck, Andreas; Fleig, JuergenJournal of Materials Chemistry A: Materials for Energy and Sustainability (2019), 7 (12), 6818-6831CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)The attractiveness of cubic Li7La3Zr2O12 (LLZO) based garnets lies in their high ionic cond. and the combination of thermal and electrochem. stability. However, relations between the exact chem. compn. and ionic cond. are still not well understood and samples of very similar compn. and processing may show very different properties. In this contribution, the authors studied Al stabilized LLZO by employing a combination of local cond. measurements and 3-dimensional local chem. anal. using laser ablation inductively coupled plasma optical emission spectroscopy (LA-ICP-OES). These measurements revealed significant cond. variations across some samples, with variations up to almost one order of magnitude, as well as an inhomogeneous elemental distribution of Al and Li, largely along the samples. Surprisingly, neither the local Al content nor the local Li content showed a clear correlation with the local Li-ion cond. Accordingly, an in-depth understanding of the conduction properties of Al stabilized LLZO has to conc. on aspects beyond the simple chem. compn. Yet unknown factors (e.g. O vacancies or local cation site occupancies) seem to have a much higher impact on the ionic cond. than the exact stoichiometry.
- 31Wachter-Welzl, A.; Kirowitz, J.; Wagner, R.; Smetaczek, S.; Brunauer, G.C.; Bonta, M.; Rettenwander, D.; Taibl, S.; Limbeck, A.; Amthauer, G.; Fleig, J. The origin of conductivity variations in Al-stabilized Li7La3Zr2O12 ceramics. Solid State Ionics 2018, 319, 203– 208, DOI: 10.1016/j.ssi.2018.01.03631https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXislSrsL0%253D&md5=f0636fbb282602cfda371415d720f611The origin of conductivity variations in Al-stabilized Li7La3Zr2O12 ceramicsWachter-Welzl, A.; Kirowitz, J.; Wagner, R.; Smetaczek, S.; Brunauer, G. C.; Bonta, M.; Rettenwander, D.; Taibl, S.; Limbeck, A.; Amthauer, G.; Fleig, J.Solid State Ionics (2018), 319 (), 203-208CODEN: SSIOD3; ISSN:0167-2738. (Elsevier B.V.)All-solid state batteries have the ability to bring us closer to a zero-emission society. Such battery systems, however, require a powerful solid Li-ion conductor with high stability and exceptionally high Li-ion cond. Cubic Li7La3Zr2O12 (LLZO) garnets are attractive candidates combining high ionic cond. and thermal as well as electrochem. stability. Since the cubic LLZO polymorph is not stable at room temp., supervalent cations, such as Al3+, are needed to stabilize the highly conductive phase. However, strong variations in cond. values were reported even for very similar Al contents, which is crit. for future battery applications. Therefore, the overall performance of 44 samples with nominally identical compn. (Li6.40Al0.20La3Zr2O12), sintered at two different temps. (1150 °C and 1230 °C, resp.) was analyzed by electrochem. impedance spectroscopy. The aim of this work is to elucidate the origin of the strong variations in cond. reported in literature. This study shows that the effective conductivities of the LLZO samples vary between 2 × 10-5 and 8 × 10-4 S cm-1, which cannot be attributed to obvious differences in sample prepn. Furthermore, the stepwise redn. of the sample vol. and repeated measuring of the impedance revealed cond. variations even within a single sample. Finally, preliminary chem. anal. by laser ablation (LA) - inductively coupled plasma (ICP) - mass spectrometry (MS) identified Al inhomogeneities in LLZO, which may be responsible for cond. variations of nominally equal samples.
- 32Gevorgyan, S. A.; Zubillaga, O.; María, J.; De Seoane, V.; Machado, M.; Parlak, E. A.; Tore, N.; Voroshazi, E.; Aernouts, T.; Müllejans, H. Round robin performance testing of organic photovoltaic devices. Renewable Energy 2014, 63, 376– 387, DOI: 10.1016/j.renene.2013.09.03432https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhvFelu7jN&md5=ce56b80244c12615314e8212b27dca18Round robin performance testing of organic photovoltaic devicesGevorgyan, Suren A.; Zubillaga, Oihana; Vega de Seoane, Jose Maria; Machado, Maider; Parlak, Elif Alturk; Tore, Nesrin; Voroshazi, Eszter; Aernouts, Tom; Mullejans, Harald; Bardizza, Giorgio; Taylor, Nigel; Verhees, Wiljan; Kroon, Jan M.; Morvillo, Pasquale; Minarini, Carla; Roca, Francesco; Castro, Fernando A.; Cros, Stephane; Lechene, Balthazar; Trigo, Juan F.; Guillen, Cecilia; Herrero, Jose; Zimmermann, Birger; Sapkota, Subarna Babu; Veit, Clemens; Wurfel, Uli; Tuladhar, Pabitra S.; Durrant, James R.; Winter, Stefan; Rousu, Sanna; Valimaki, Marja; Hinrichs, Volker; Cowan, Sarah R.; Olson, Dana C.; Sommer-Larsen, Peter; Krebs, Frederik C.Renewable Energy (2014), 63 (), 376-387CODEN: RNENE3; ISSN:0960-1481. (Elsevier Ltd.)This study addresses the issue of poor intercomparability of measurements of org. photovoltaic (OPV) devices among different labs. We present a round robin performance testing of novel OPV devices among 16 labs., organized within the framework of European Research Infrastructure Project (SOPHIA) and European Energy Research Alliance (EERA). Three types of OPVs with different structures, dimensions and encapsulations are studied and compared with ref. Si solar cells certified by accredited labs. The agreement of the measurements of these among different labs. is analyzed by focusing on testing procedures, testing equipment and sample designs. A no. of deviations and pitfalls are revealed and based on the analyses, a set of recommendations are suggested for improving the agreement among the measurements of such OPV technologies.
- 33Bron, P.; Dehnen, S.; Roling, B. Li10Si0.3Sn0.7P2S12 - A low-cost and low-grain-buondary resistance lithium superionic conductor. J. Power Sources 2016, 329, 530– 535, DOI: 10.1016/j.jpowsour.2016.08.11533https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhsVGjs7vM&md5=9798002fa1483e9261d730485701177eLi10Si0.3Sn0.7P2S12 - A low-cost and low-grain-boundary-resistance lithium superionic conductorBron, Philipp; Dehnen, Stefanie; Roling, BernhardJournal of Power Sources (2016), 329 (), 530-535CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)Despite remarkable recent advances in the field of solid electrolytes for lithium ion batteries, there is still considerable room for improvements with respect to ionic cond., cost and electrochem. stability. This study tests systematically how much Sn in the superionic conductor Li10SnP2S12 can be replaced by Si or Al, while retaining its tetragonal structure. For comparison, also the known superionic conductors Li10SnP2S12, Li10GeP2S12, and Li10SiP2S12 are synthesized and characterized with respect to their grain and grain boundary resistances. The results show that due to the negligible grain boundary resistance of the new compd. Li10Si0.3Sn0.7P2S12, its total Li+ ion cond. is only 10-20% lower than that of the expensive superionic conductor Li10GeP2S12 and about four times higher than that of Li10SiP2S12.
- 34Vargas-Barbosa, N. M.; Roling, B. Dynamic ion correlations in solid and liquid electrolytes: how do they affect charge and mass transport. ChemElectroChem 2020, 7, 367– 385, DOI: 10.1002/celc.20190162734https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXit12isr%252FM&md5=4a89619ca70b3bcb82f48c3cbb749609Dynamic Ion Correlations in Solid and Liquid Electrolytes: How Do They Affect Charge and Mass Transport?Vargas-Barbosa, N. M.; Roling, B.ChemElectroChem (2020), 7 (2), 367-385CODEN: CHEMRA; ISSN:2196-0216. (Wiley-VCH Verlag GmbH & Co. KGaA)A review. Solid and liq. electrolytes for electrochem. energy storage and conversion cells, such as batteries, supercapacitors and fuel cells, contain often high concns. of mobile ions. Therefore, the ion dynamics in these electrolytes is characterized by pronounced directional correlations between successive ion movements, which exert a strong influence on charge and mass transport. In this manuscript, we review the relevant transport properties of (i) single-ion conducting solid electrolytes and of (ii) liq. electrolytes with a single type of cations and a single type of anions. All transport quantities are based on Onsager's linear irreversible thermodn. and are defined in the lab. frame of ref., so that they can be easily related to correlations functions of the equil. ion dynamics by means of linear response theory. In the case of single-cation conducting solid electrolytes, we discuss how the complex interplay between cation-cation and cation-lattice interactions leads to a competition between cation self-correlations and distinct-cation correlations. In the case of liq. electrolytes, we describe how cation-cation, anion-anion, and cation-anions correlations influence the various transport quantities, such as total ionic cond., Haven ratio, salt diffusion coeff. and cation transference nos. Moreover, we discuss how, in dil. liq. electrolytes, ion correlations can be governed by ion pair formation. Finally, the competition between cation/anion and cation/polymer chain interactions can lead to neg. cation transference nos. in polymer electrolytes, i. e. to cations migrating towards the pos. electrode. Taken together, these case studies showcase how ion correlations in electrolyte systems can strongly influence the overall efficiency of energy storage and conversion devices due to transport limitations.
Supporting Information
Supporting Information
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsenergylett.9b02764.
Synthesis procedure of all samples and X-ray diffraction results; all experimental measurement conditions of the different data sets along with their statistical analysis; measured impedance spectra and Arrhenius plots as well as the comparison of the transport properties against possible sample preparation and measurement influences (PDF)
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