Exploiting the paddle-wheel mechanism for the design of fast ion conductors

Zhang, Zhizhen; Nazar, Linda F.

doi:10.1038/s41578-021-00401-0

Cited by 117 publications

(111 citation statements)

References 168 publications

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“…Recently, a "paddle-wheel" mechanism has been proposed to interpret the cation-anion interplay that occurs in some ion conductors. 16 That is, motions of anions in adynamic rotational disorder can assist the surrounded cations to hop in rotor phases. Cations move through the "revolving doors" or "paddle-wheels" formed by the rotation of the translationally static anions.…”

Section: Li-ion Transport Mechanisms In Ceramic Electrolytesmentioning

confidence: 99%

“…Mixing anions is one of the effective ways to tailor the anion framework and the reorientate tendency. 16 When designing highly conductive electrolytes by utilizing the "paddle-wheel" mechanism, it is essential to reduce the order-disorder transition temperature to stabilize the rotor phases at room temperature to realize high ionic conductivity at room temperature. Indeed, superionic conductors have been designed successfully for ambient applications based on such a unique "paddle-wheel" mechanism.…”

Section: Li-ion Transport Mechanisms In Ceramic Electrolytesmentioning

confidence: 99%

“…Indeed, superionic conductors have been designed successfully for ambient applications based on such a unique "paddle-wheel" mechanism. 16 Generally, in Li-ion conducting ceramics, the grain boundaries resistance is much higher than the intragrain resistance. The structure and composition of grain boundaries can be much different from bulk crystals.…”

Section: Li-ion Transport Mechanisms In Ceramic Electrolytesmentioning

confidence: 99%

“…In the cation conduction mechanisms discussed above, cations are transported in a static framework. Recently, a “paddle‐wheel” mechanism has been proposed to interpret the cation–anion interplay that occurs in some ion conductors 16 . That is, motions of anions in adynamic rotational disorder can assist the surrounded cations to hop in rotor phases.…”

Section: Ceramic Electrolytesmentioning

confidence: 99%

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Ionic conductivity and ion transport mechanisms of solid‐state lithium‐ion battery electrolytes: A review

Yang

2022

Energy Science & Engineering

161

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This review article deals with the ionic conductivity of solid-state electrolytes for lithium batteries. It has discussed the mechanisms of ion conduction in ceramics, polymers, and ceramic-polymer composite electrolytes. In ceramic electrolytes, ion transport is accomplished with mobile point defects in a crystal. Li + ions migrate mainly via the vacancy mechanism, interstitial mechanism, or interstitial-substitutional exchange mechanism. In solid polymer electrolytes, Li + ions are transported mainly via the segment motion, ion hopping (Grotthuss mechanism), or vehicle mechanism (mass diffusion). This study has also introduced various electrolyte materials including perovskite oxides, garnet oxides, sodium superionic conductors, phosphates, sulfides, halides, cross-linked polymers, block-copolymers, metal-organic frameworks, covalent organic frameworks, as well as ceramic-polymer composites. In addition, it has highlighted some strategies to improve the ionic conductivity of solid-state electrolytes, such as doping, defect engineering, microstructure tuning, and interface modification.

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Section: Li-ion Transport Mechanisms In Ceramic Electrolytesmentioning

confidence: 99%

Section: Li-ion Transport Mechanisms In Ceramic Electrolytesmentioning

confidence: 99%

Section: Li-ion Transport Mechanisms In Ceramic Electrolytesmentioning

confidence: 99%

Section: Ceramic Electrolytesmentioning

confidence: 99%

See 2 more Smart Citations

Ionic conductivity and ion transport mechanisms of solid‐state lithium‐ion battery electrolytes: A review

Yang

2022

Energy Science & Engineering

161

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“…The vibrations of the host lattice are, however, likely to play a role in the magnitude of 𝐸 A , as they can affect the time-averaged energetic barrier that the mobile ions must overcome. [51][52][53]…”

Section: Figure 4 Vibrational Origin Of the Isotope Effect On Activat...mentioning

confidence: 99%

Relating critical phonon occupation to activation barrier in fast lithium-ion conductors

Agne

Frerichs

Wang

et al. 2022

Preprint

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Phonon-based (vibrational) theories of ion transport are likely key to developing new design strategies for solid-state ionic conductors. However, they are not often utilized because it is difficult to ascertain which vibrational frequencies are important, even in describing fundamental parameters such as the activation barrier. This is perpetuated by the fact that it is difficult to tune vibrational frequencies directly, without changing the chemical structure, in order to study underlying phonon relations. Using isotopic substitution of 6Li for 7Li, we are able to change the mobile ion vibrations in the two exemplary ion conductors Li10SnP2S12 and Li6PS5Cl without altering their structure. Using a combination of nuclear magnetic resonance spectroscopy and ab initio molecular dynamics simulations to characterize temperature-dependent ion transport, it is demonstrated that the isotopic substitution of 6Li for 7Li increases the activation barrier for Li-ion transport. The magnitude of this isotope effect cannot be explained by changes in the zero-point vibrational energy alone. Therefore, we propose that the observed change in the activation barrier is related to the differences in the average critical phonon occupation needed to overcome the activation barrier. Our hypothesis is supported by an analytical model, based on the physics of quantum harmonic oscillators, that gives good agreement with the experimental results. Thus, isotopic substitution provides unique insights into the vibrational perspective and frequency dependence of the activation barrier in fast Li-ion conductors.

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In Situ Cross‐Linked Plastic Crystal Electrolytes for Wide‐Temperature and High‐Energy‐Density Lithium Metal Batteries

Wang

Geng

Zhao

et al. 2022

Adv Funct Materials

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The development of high-energy-density lithium metal batteries has been significantly hampered mainly due to the poor electrolyte-electrode compatibility, narrow operating temperature range, and stringent safety concerns of conventional electrolytes. Here, an in situ cross-linked plastic crystal-based electrolyte (CPCE) with an optimized composition design is proposed. Based on the interaction of succinonitrile (SN) and ethoxylated trimethylolpropane triacrylate (ETPTA) with polar carbonyl groups, CPCE delivers well-tuned energy levels and a concentrated coordination structure, leading to an improved electrochemical window and stable electrodeelectrolyte interface. In addition, the crystallization of SN molecules is also inhibited, ensuring suitable ion migration in bulky CPCE over a wide temperature range. Moreover, both the nonleakage of cross-linked ETPTA and the nonflammability of the plastic crystal electrolyte (PCE) further reinforce the safety of CPCE. As a result, the well-designed CPCE achieves high ion conductivity with a wide electrochemical window (≈5.4 V vs Li + /Li) and a broad operating temperature range (−20 to 100 °C). It also delivers dendrite-free lithium plating with high Coulombic efficiency of up to ≈99.1%. The Cu|CPCE|LiNi 0.8 Co 0.1 Mn 0.1 O 2 anode-free pouch cell exhibits high energy density (≈1520 Wh L −1 ) and high safety during abuse tests. This study paves a new pathway to realize the practical application of high-energy-density lithium metal battery energy storage systems.

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Exploiting the paddle-wheel mechanism for the design of fast ion conductors

Cited by 117 publications

References 168 publications

Ionic conductivity and ion transport mechanisms of solid‐state lithium‐ion battery electrolytes: A review

Ionic conductivity and ion transport mechanisms of solid‐state lithium‐ion battery electrolytes: A review

Relating critical phonon occupation to activation barrier in fast lithium-ion conductors

In Situ Cross‐Linked Plastic Crystal Electrolytes for Wide‐Temperature and High‐Energy‐Density Lithium Metal Batteries

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