The DOI matches its Crossref record; 36 of the 36 references it cites were found in a registry or an index.
The Compensation Effect in the Vogel–Tammann–Fulcher (VTF) Equation for Polymer-Based Electrolytes
Abstract
Single-ion conducting polymer electrolytes have been proposed to significantly enhance lithium ion battery performance by eliminating concentration gradients within the cell. Such electrolytes have universally suffered from poor conductivity at low to moderate temperatures. In an attempt to improve conductivity, numerous studies have sought to better understand the fundamental interplay of ion content and segmental motion, with typical analyses relying on a fit of temperature-dependent conductivity data using the Vogel–Tammann–Fulcher (VTF) equation to assist in separating these effects. In this study, we leverage the large accessible composition window of a newly synthesized, single ion conducting polysulfone–poly(ethylene glycol) (PSf- co -PEG) miscible random copolymer to more completely understand the interrelationship of glass transition temperature, ion content, and the polymer’s Li + conductivity. It is demonstrated here that choice of fitting procedure and Vogel temperature plays a crucial role in the observed trends, and importantly, after optimization of the data fitting procedure, a strong positive correlation was observed between the VTF equation prefactor and apparent activation energy for polymers in this electrolyte class. This relationship, known as the compensation effect (among other names) for the related Arrhenius-type behavior of activated processes such as chemical kinetics and diffusion, is shown here to exist in several other polymer electrolyte classes. Given conductivity’s inverse exponential dependence on the apparent activation energy, maximum conductivity within an electrolyte class is achieved in samples where the activation energy is small. For a system in which the compensation effect exists, decreasing activation energy also decreases the prefactor, highlighting the limiting nature of the compensation effect and the importance of escaping from it. Blending of small molecules is shown to break the apparent trend within the PSf- co -PEG system, suggesting a clear route to high transference number, high conductivity electrolytes.
Overview
The claims and statistics of this paper haven’t been checked yet.
Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.
Integrity signals
Registry
Cites
Statistics
Verification
Claims the paper makes
The claims and statistics of this paper haven’t been checked yet.
Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.
Self-check
Percentages, sums and reported differences re-computed from the paper’s own numbers.
The self-check needs the paper’s full text.
Citations
Cites
Challenges for Rechargeable Li Batteries
Goodenough, J. B., & Kim, Y. (2010) · Chemistry of Materials · doi:10.1021/cm901452z · Cited by 10,943
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries
Xu, K. (2004) · Chemical Reviews · doi:10.1021/cr030203g · Cited by 7,437
A review of conduction phenomena in Li-ion batteries
Park, M., Zhang, X., Chung, M., Less, G. B., & Sastry, A. M. (2010) · Journal of Power Sources · doi:10.1016/j.jpowsour.2010.06.060 · Cited by 1,627
Single-ion BAB triblock copolymers as highly efficient electrolytes for lithium-metal batteries
Bouchet, R., Maria, S., Meziane, R., Aboulaich, A., Lienafa, L., Bonnet, J.-P., Phan, T. N. T., Bertin, D., Gigmes, D., Devaux, D., et al. (2013) · Nature Materials · doi:10.1038/nmat3602 · Cited by 1,425
Electrochemical aspects of the generation of ramified metallic electrodeposits
Chazalviel, J.-N. (1990) · Physical Review A · doi:10.1103/physreva.42.7355 · Cited by 1,402
Plating a Dendrite-Free Lithium Anode with a Polymer/Ceramic/Polymer Sandwich Electrolyte
Zhou, W., Wang, S., Li, Y., Xin, S., Manthiram, A., & Goodenough, J. B. (2016) · Journal of the American Chemical Society · doi:10.1021/jacs.6b05341 · Cited by 1,006
Hallinan, D. T., & Balsara, N. P. (2013) · Annual Review of Materials Research · doi:10.1146/annurev-matsci-071312-121705 · Cited by 853
Isokinetic Relationship, Isoequilibrium Relationship, and Enthalpy−Entropy Compensation
Liu, L., & Guo, Q. (2001) · Chemical Reviews · doi:10.1021/cr990416z · Cited by 821
Fundamental water and salt transport properties of polymeric materials
Geise, G. M., Paul, D. R., & Freeman, B. D. (2014) · Progress in Polymer Science · doi:10.1016/j.progpolymsci.2013.07.001 · Cited by 783
Zheng, H., Li, J., Song, X., Liu, G., & Battaglia, V. S. (2012) · Electrochimica Acta · doi:10.1016/j.electacta.2012.03.161 · Cited by 674
The history of polymer electrolytes
ARMAND, M. (1994) · Solid State Ionics · doi:10.1016/0167-2738(94)90419-7 · Cited by 576
The importance of the lithium ion transference number in lithium/polymer cells
Doyle, M., Fuller, T. F., & Newman, J. (1994) · Electrochimica Acta · doi:10.1016/0013-4686(94)85091-7 · Cited by 553
Single-ion polymer electrolytes based on a delocalized polyanion for lithium batteries
Meziane, R., Bonnet, J.-P., Courty, M., Djellab, K., & Armand, M. B. (2011) · Electrochimica Acta · doi:10.1016/j.electacta.2011.03.074 · Cited by 374
Modeling of lithium-ion batteries
Newman, J., Thomas, K. E., Hafezi, H., & Wheeler, D. R. (2003) · Journal of Power Sources · doi:10.1016/s0378-7753(03)00282-9 · Cited by 334
Porcarelli, L., Shaplov, A. S., Bella, F., Nair, J. R., Mecerreyes, D., & Gerbaldi, C. (2016) · ACS Energy Letters · doi:10.1021/acsenergylett.6b00216 · Cited by 312
Origin and consequences of the compensation (Meyer-Neldel) law
Yelon, A., Movaghar, B., & Branz, H. M. (1992) · Physical Review B · doi:10.1103/physrevb.46.12244 · Cited by 307
Devaux, D., Bouchet, R., Glé, D., & Denoyel, R. (2012) · Solid State Ionics · doi:10.1016/j.ssi.2012.09.020 · Cited by 304
Single-Ion Block Copoly(ionic liquid)s as Electrolytes for All-Solid State Lithium Batteries
Porcarelli, L., Shaplov, A. S., Salsamendi, M., Nair, J. R., Vygodskii, Y. S., Mecerreyes, D., & Gerbaldi, C. (2016) · ACS Applied Materials & Interfaces · doi:10.1021/acsami.6b01973 · Cited by 302
Feng, S., Shi, D., Liu, F., et al. (2013) · Electrochimica Acta · doi:10.1016/j.electacta.2013.01.119 · Cited by 278
Wang, F., Hickner, M. A., Ji, Q., Harrison, W., Mecham, J. B., Zawodzinski, T. A., & McGrath, J. E. E. (2001) · Macromolecular Symposia · doi:10.1002/1521-3900(200110)175:1<387::aid-masy387>3.0.co;2-1 · Cited by 254
Multi-excitation entropy: its role in thermodynamics and kinetics
Yelon, A., Movaghar, B., & Crandall, R. S. (2006) · Reports on Progress in Physics · doi:10.1088/0034-4885/69/4/r04 · Cited by 248
Webb, M. A., Jung, Y., Pesko, D. M., Savoie, B. M., Yamamoto, U., Coates, G. W., Balsara, N. P., Wang, Z.-G., & Miller, T. F. (2015) · ACS Central Science · doi:10.1021/acscentsci.5b00195 · Cited by 225
Ion-containing polymers: new energy & clean water
Hickner, M. A. (2010) · Materials Today · doi:10.1016/s1369-7021(10)70082-1 · Cited by 224
Molecular mobility and Li+ conduction in polyester copolymer ionomers based on poly(ethylene oxide)
Fragiadakis, D., Dou, S., Colby, R. H., & Runt, J. (2009) · The Journal of Chemical Physics · doi:10.1063/1.3063659 · Cited by 182
Chintapalli, M., Le, T. N. P., Venkatesan, N. R., Mackay, N. G., Rojas, A. A., Thelen, J. L., Chen, X. C., Devaux, D., & Balsara, N. P. (2016) · Macromolecules · doi:10.1021/acs.macromol.5b02620 · Cited by 168
Inceoglu, S., Rojas, A. A., Devaux, D., Chen, X. C., Stone, G. M., & Balsara, N. P. (2014) · ACS Macro Letters · doi:10.1021/mz5001948 · Cited by 158
Liang, S., Choi, U. H., Liu, W., Runt, J. P., & Colby, R. H. (2012) · Chemistry of Materials · doi:10.1021/cm3005387 · Cited by 150
Rojas, A. A., Ínceoğlu, Ş., Mackay, N. G., Thelen, J. L., Devaux, D., Stone, G. M., & Balsara, N. P. (2015) · Macromolecules · doi:10.1021/acs.macromol.5b01193 · Cited by 131
Self-doped block copolymer electrolytes for solid-state, rechargeable lithium batteries
Sadoway, D. R., Huang, B., Trapa, P. E., Soo, P. P., Bannerjee, P., & Mayes, A. M. (2001) · Journal of Power Sources · doi:10.1016/s0378-7753(01)00642-5 · Cited by 107
Buss, H. G., Chan, S. Y., Lynd, N. A., & McCloskey, B. D. (2017) · ACS Energy Letters · doi:10.1021/acsenergylett.6b00724 · Cited by 91
Self-citation2-Methoxyethyl (methyl) carbonate-based electrolytes for Li-ion batteries
Gu, G.-Y., Bouvier, S., Wu, C., Laura, R., Rzeznik, M., & Abraham, K. (2000) · Electrochimica Acta · doi:10.1016/s0013-4686(00)00394-7 · Cited by 83
Kim, H. W., & Park, H. B. (2011) · Journal of Membrane Science · doi:10.1016/j.memsci.2011.01.053 · Cited by 77
Single ion conductors—polyphosphazenes with sulfonimide functional groups
Allcock, H. R., Welna, D. T., & Maher, A. E. (2006) · Solid State Ionics · doi:10.1016/j.ssi.2006.01.039 · Cited by 72
Temperature dependence of conductivity of mixed-phase composite polymer solid electrolytes
Wieczorek, W. (1992) · Materials Science and Engineering B · doi:10.1016/0921-5107(92)90041-7 · Cited by 71
Chen, Q., Bao, N., Wang, J. H., Tunic, T. R., Liang, S., & Colby, R. H. (2015) · Macromolecules · doi:10.1021/acs.macromol.5b01958 · Cited by 62
Data Analysis with the Vogel−Fulcher−Tammann−Hesse Equation
Mano, J. F., & Pereira, E. N. B. (2004) · The Journal of Physical Chemistry A · doi:10.1021/jp0484433 · Cited by 45
Cited by
Designing polymers for advanced battery chemistries
Lopez, J., Mackanic, D. G., Cui, Y., & Bao, Z. (2019) · Nature Reviews Materials · doi:10.1038/s41578-019-0103-6 · Cited by 894
Promising Routes to a High Li+ Transference Number Electrolyte for Lithium Ion Batteries
Diederichsen, K. M., McShane, E. J., & McCloskey, B. D. (2017) · ACS Energy Letters · doi:10.1021/acsenergylett.7b00792 · Cited by 874
Self-citationZhang, Y., Zhang, R., & Tao, Y. (2023) · Carbohydrate Polymers · doi:10.1016/j.carbpol.2023.121300 · Cited by 27
Metadata
- Authors
- Diederichsen, K. M., Buss, H. G., & McCloskey, B. D.
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2017-05-09
- Volume
- 50
- Issue
- 10
- Pages
- 3831-3840
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W2612753737
- Cited by
- 386
- References
- 36
- FWCI
- 12.31
- Type
- journal article
- Language
- en
- Open access
- closed
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
Are you an author, or do you see a problem with this page? Request a review
Data sources
Bibliographic data: Semantic Scholar, OpenAlex, Crossref.
Contains information from the Semantic Scholar Academic Graph Datasets, made available under the ODC Attribution License (ODC-BY 1.0).
Semantic Scholar’s data is described in: Kinney, R., et al. (2023). The Semantic Scholar Open Data Platform. arXiv:2301.10140.
