Physical aging effects on conductivity in polymer electrolytes

Kumar, Binod; Koka, Sateesh; Rodrigues, Stanley; Nookala, Munichandraiah

doi:10.1016/s0167-2738(02)00610-0

Cited by 22 publications

(12 citation statements)

References 3 publications

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“…Figure 4 shows the time dependencies of the conductivities of the sample within incommensurate phase. The conductivity relaxation may be expressed by the following equation [19];…”

Section: Methodsmentioning

confidence: 99%

Incommensurate phase properties of TlGaSe₂layered crystals

Şentürk

Tumbek

Salehli

et al. 2005

Cryst. Res. Technol.

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The frequency and time dependence of the ac conductivity were measured within incommensurate phase in the frequency range 10 1 -107 Hz and analyzed. The electrical conductivity decreases with decreasing temperature, then saturates in mentioned temperature interval. The ac conductivity is proportional to w s . The value f s decreases with increasing temperature which suggests hopping conduction mechanism. The time dependence of the conductivity exhibited exponential decay. It shows two conductivity relaxations in mentioned temperature interval. Moreover, the characteristic relaxation times decrease with decreasing annealing temperature. The two different relaxation times refer to two different incommensurate ordering in mentioned temperature interval.

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“…Figure 4 shows the time dependencies of the conductivities of the sample within incommensurate phase. The conductivity relaxation may be expressed by the following equation [19];…”

Section: Methodsmentioning

confidence: 99%

Incommensurate phase properties of TlGaSe₂layered crystals

Şentürk

Tumbek

Salehli

et al. 2005

Cryst. Res. Technol.

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“…Due to the effects of the preparation process and electrochemical operation, many SPEs are usually in a non-equilibrium state, in which the free volume and microstructure would evolve with time [ 5 , 6 ]. That is to say, the time-aging may occur in the amorphous polymer and can significantly affect the migration of lithium-ion in the solid electrolyte [ 7 , 8 ]. Subsequently, it would change the distribution of lithium concentration in the active material and lead to cell capacity variation.…”

Section: Introductionmentioning

confidence: 99%

“…As one of the most critical parameters of SPE, the time-dependent conductivity of polymer electrolyte materials has already attracted much attention. As early as 2003, Kumar et al noticed that storage time had greatly affected the ionic conductivity of poly(ethylene oxide) (PEO) based SPE with lithium perchlorate (LiClO 4 ) in the application temperature (0 to 68 °C) [ 7 ]. They show that due to a reduction in the size of the coordinating sphere around the lithium-ion, physical aging enhances the conductive performance of such a composite electrolyte.…”

Section: Introductionmentioning

confidence: 99%

“…It is still an open question whether the ion transport in the aging SPE mainly depends upon the relaxation of polymer cooperative chain segmental motion or not. However, one may reach a consensus that adding a small number of inorganic nanofillers such as Al 2 O 3 [ 7 ], montmorillonite (MMT) clay [ 5 , 9 ], and LiAlO 2 [ 10 ] into the polymer matrix can affect the conductivity of aging electrolyte materials. Meanwhile, the aging rate would be influenced by the nature and loading of ionic salt as well as different types of mixed salts.…”

Section: Introductionmentioning

confidence: 99%

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Modeling and Simulation in Capacity Degradation and Control of All-Solid-State Lithium Battery Based on Time-Aging Polymer Electrolyte

Fang

Fan

et al. 2021

Polymers

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The prediction of electrochemical performance is the basis for long-term service of all-solid-state-battery (ASSB) regarding the time-aging of solid polymer electrolytes. To get insight into the influence mechanism of electrolyte aging on cell fading, we have established a continuum model for quantitatively analyzing the capacity evolution of the lithium battery during the time-aging process. The simulations have unveiled the phenomenon of electrolyte-aging-induced capacity degradation. The effects of discharge rate, operating temperature, and lithium-salt concentration in the electrolyte, as well as the electrolyte thickness, have also been explored in detail. The results have shown that capacity loss of ASSB is controlled by the decrease in the contact area of the electrolyte/electrode interface at the initial aging stage and is subsequently dominated by the mobilities of lithium-ion across the aging electrolyte. Moreover, reducing the discharge rate or increasing the operating temperature can weaken this cell deterioration. Besides, the thinner electrolyte film with acceptable lithium salt content benefits the durability of the ASSB. It has also been found that the negative effect of the aging electrolytes can be relieved if the electrolyte conductivity is kept being above a critical value under the storage and using conditions.

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“…In the first place, it was reported that physical aging could cause a decrease in the size of the coordinating sphere around the cation. As a consequence, the conductive performance of PEO-LiClO 4 enhanced as the storage time increased [ 36 ]. On the other hand, SPEs consisting of poly (acrylonitrile- co -butyl acrylate) and LiTFSI or LiI, as well as a LiTFSI salt mixture, exhibited a dropped conductivity with elapsed time because the continuity of conductivity pathways ground on ion–ion interactions had been damaged to some degree [ 37 ].…”

Section: Introductionmentioning

confidence: 99%

Mechanical Integrity Degradation and Control of All-Solid-State Lithium Battery with Physical Aging Poly (Vinyl Alcohol)-Based Electrolyte

Zhou

et al. 2020

Polymers

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Ensuring the material durability of an electrolyte is a prerequisite for the long-term service of all-solid-state batteries (ASSBs). Herein, to investigate the mechanical integrity of a solid polymer electrolyte (SPE) in an ASSB upon electrochemical operation, we have implemented a sequence of quasi-static uniaxial tension and stress relaxation tests on a lithium perchlorate-doped poly (vinyl alcohol) electrolyte, and then discussed the viscoelastic behavior as well as the strength of SPE film during the physical aging process. On this basis, a continuum electrochemical-mechanical model is established to evaluate the stress evolution and mechanical detriment of aging electrolytes in an ASSB at a discharge state. It is found that the measured elastic modulus, yield stress, and characteristic relaxation time boost with the prolonged aging time. Meanwhile, the shape factor for the classical time-decay equation and the tensile rupture strength are independent of the aging history. Accordingly, the momentary relaxation modulus can be predicted in terms of the time–aging time superposition principle. Furthermore, the peak tensile stress in SPE film for the full discharged ASSB will significantly increase as the aging proceeds due to the stiffening of the electrolyte composite. It may result in the structure failure of the cell system. However, this negative effect can be suppressed by the suggested method, which is given by a 2D map under different lithiation rates and relative thicknesses of the electrolyte. These findings can advance the knowledge of SPE degradation and provide insights into reliable all-solid-state electrochemical device applications.

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Physical aging effects on conductivity in polymer electrolytes

Cited by 22 publications

References 3 publications

Incommensurate phase properties of TlGaSe₂layered crystals

Incommensurate phase properties of TlGaSe₂layered crystals

Modeling and Simulation in Capacity Degradation and Control of All-Solid-State Lithium Battery Based on Time-Aging Polymer Electrolyte

Mechanical Integrity Degradation and Control of All-Solid-State Lithium Battery with Physical Aging Poly (Vinyl Alcohol)-Based Electrolyte

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Physical aging effects on conductivity in polymer electrolytes

Cited by 22 publications

References 3 publications

Incommensurate phase properties of TlGaSe2layered crystals

Incommensurate phase properties of TlGaSe2layered crystals

Modeling and Simulation in Capacity Degradation and Control of All-Solid-State Lithium Battery Based on Time-Aging Polymer Electrolyte

Mechanical Integrity Degradation and Control of All-Solid-State Lithium Battery with Physical Aging Poly (Vinyl Alcohol)-Based Electrolyte

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Product

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Incommensurate phase properties of TlGaSe₂layered crystals

Incommensurate phase properties of TlGaSe₂layered crystals