Recent Advances in Inorganic Solid Electrolytes for Lithium Batteries

Cao, Can; Li, Zhuo-Bin; Wang, Xiaoliang; Zhao, Xingyu; Han, Wei‐Qiang

doi:10.3389/fenrg.2014.00025

Cited by 259 publications

(242 citation statements)

References 99 publications

(92 reference statements)

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“…One of them is called the mixed glass network former effect (MGFE), where the ionic conductivity enhancement is observed when one network former is progressively substituted by another while keeping the total ion concentration constant. 4 MGFE has been investigated in various ternary alkali borophosphate, germanophosphate, and borogermanate glass systems. 5−8 The increase in the ionic conductivity at room temperature was first observed by Magistris et al 9 as a result of the replacement of B 2 O 3 by P 2 O 5 at constant lithium content.…”

Section: Introductionmentioning

confidence: 99%

Lithium-Ion Mobility in Quaternary Boro–Germano–Phosphate Glasses

et al. 2016

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Effect of the structural changes, electrical conductivity, and dielectric properties on the addition of a third glass-former, GeO 2 , to the borophosphate glasses, 40Li 2 O−10B 2 O 3 −(50 − x)P 2 O 5 −xGeO 2 , x = 0−25 mol %, has been studied. Introduction of GeO 2 causes the structural modifications in the glass network, which results in a continuous increase in electrical conductivity. Glasses with low GeO 2 content, up to 10 mol %, show a rapid increase in dc conductivity as a result of the interlinkage of slightly depolymerized phosphate chains and negatively charged [GeO 4 ] − units, which enhances the migration of Li + ions. The Li + ions compensate these delocalized charges connecting both phosphate and germanium units, which results in reduction of both bond effectiveness and binding energy of Li + ions and therefore enables their hop to the next charge-compensating site. For higher GeO 2 content, the dc conductivity increases slightly, tending to approach a maximum in Li + ion mobility caused by the incorporation of GeO 2 units into phosphate network combined with conversion of GeO 4 to GeO 6 units. The strong cross-linkage of germanium and phosphate units creates heteroatomic P−O−Ge bonds responsible for more effectively trapped Li + ions. A close correspondence between dielectric and conductivity parameters at high frequencies indicates that the increase in conductivity indeed is controlled by the modification of structure as a function of GeO 2 addition.

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Section: Introductionmentioning

confidence: 99%

Lithium-Ion Mobility in Quaternary Boro–Germano–Phosphate Glasses

et al. 2016

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“…To understand and ultimately design glasses with increased mobility for chemically strengthening of glass, it is likely important to learn from the experiences in the field of solid electrolytes (Cao et al, 2014). The structural properties are of much importance, hence the following criteria should be FiGUre 7 | Logarithm of the effective diffusion coefficient vs. bond dissociation energy.…”

Section: Discussionmentioning

confidence: 99%

“…The logarithm of the effective diffusion coefficient as a function of the electronic ionic polarizability is given in Figure 8, where Cu + fits into the trend with the alkali ions, while Ag + with relatively high polarizability has an unusually high effective diffusion. High electronic ionic polarizability can be argued to be a positive property on the activation energy of the diffusion as the ions are deformable during the diffusion, a concept that is considered when choosing materials as solid electrolytes taBLe 4 | data collected for understanding trends in the effective diffusion coefficients, following a representation in Vogel (1994 (Cao et al, 2014). As for comparison, the ionic conductivity in aqueous solution as a function of the logarithmic effective diffusion coefficient also gives a similar trend as for the bond dissociation energy (Figure 9).…”

Section: Methodsmentioning

confidence: 99%

Trends in Effective Diffusion Coefficients for Ion-Exchange Strengthening of Soda-Lime-Silicate Glasses

et al. 2017

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Monovalent cations enable efficient ion-exchange processes due to their high mobility in silicate glasses. Numerous properties can be modified in this way, e.g., mechanical, optical, electrical, or chemical performance. In particular, alkali cation exchange has received significant attention, primarily with respect to introducing compressive stress into the surface region of a glass, which increases mechanical durability. However, most of the present applications rely on specifically tailored matrix compositions in which the cation mobility is enhanced. This largely excludes the major area of soda-lime-silicates (SLS) such as are commodity in almost all large-scale applications of glasses. Basic understanding of the relations between structural parameters and the effective diffusion coefficients may help to improve ion-exchanged SLS glass products, on the one hand in terms of obtainable strength and on the other in terms of cost. In the present paper, we discuss the trends in the effective diffusion coefficients when exchanging Na + for various monovalent cations (K + , Cu + , Ag + , Rb + , and Cs + ) by drawing relations to physicochemical properties. Correlations of effective diffusion coefficients were found for the bond dissociation energy and the electronic cation polarizability, indicating that localization and rupture of bonds are of importance for the ion-exchange rate.

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“…As solid electrolytes are not prone to the same flammability hazards as liquid electrolyte batteries are, ASSLIB can offer favorable cycling, longer shelf life, increased packing efficiency, and the use of higher voltage cathodes leading to higher energy density. 3,[8][9][10][11][12][13] Furthermore, solid-state electrolytes have flexible composition, absence of grain boundaries, and a hard surface, which can lead to suppressing side reactions and inhibiting dendritic growth of lithium. 3,8,[14][15][16] As a key component of ASSLIB, solid-state electrolytes should permit high mobility of Li-ions between anode and cathode while blocking conduction of electrons.…”

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confidence: 99%

Effects of Mechanical Strain on Ionic Conductivity in the Interface between LiPON and Ni-Mn Spinel

Thai

Lee

2017

J. Electrochem. Soc.

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We present first-principles calculations to understand ionic conductivity in the interface between lithium phosphorous oxynitride (LiPON) and Ni-Mn spinel (LNM), with emphasis on the effect of mechanical strain. Two LiPON/LNM interfaces, one with and the other without BaTiO 3 (BTO) additive, are modeled as abrupt interfaces to minimize the effects of the space-charge layer formation. It is observed that the interface with BTO additive has higher ionic conductivity than the other. Comparison of structural geometry indicates that the LiPON part of the LiPON/LNM interface is contracted but it recovers with BTO additive, which suggests the relevance of mechanical strain to ionic conductivity in these interfaces and the role of BTO in controlling the mechanical strain. The activation energy barriers of Li-hopping in a bulk LiPON, calculated at different levels of mechanical strain, exhibit a significant increase with compressive strain, supporting the suggested effect of mechanical strain in the interfaces. This result implies that ionic conductivity in the interface between LiPON and cathode can be enhanced by modifying the interface but with appropriate size and distribution of additives. The combination of a metal-oxide cathode and organic liquid electrolytes has become a leading type of Li-ion batteries (LIB) for years.1-3 However, the use of liquid electrolytes constrains the electrochemical performance and lifetime of LIB due to multiples issues, in particular regarding safety. [4][5][6][7] One strategy to rectify these issues is to employ solid electrolytes instead, aiming at all solid-state LIB (ASSLIB). As solid electrolytes are not prone to the same flammability hazards as liquid electrolyte batteries are, ASSLIB can offer favorable cycling, longer shelf life, increased packing efficiency, and the use of higher voltage cathodes leading to higher energy density.3,8-13 Furthermore, solid-state electrolytes have flexible composition, absence of grain boundaries, and a hard surface, which can lead to suppressing side reactions and inhibiting dendritic growth of lithium. 3,8,[14][15][16] As a key component of ASSLIB, solid-state electrolytes should permit high mobility of Li-ions between anode and cathode while blocking conduction of electrons. Lithium phosphorous oxynitride (LiPON) has attracted attention as a promising candidate to satisfy these conditions. 8,14,16,17 As an amorphous material, LiPON has exhibited an acceptable ionic conductivity (∼10 −6 S/cm) compared to crystalline structures 18,19 and negligible electronic conductivity measured around < 10 −14 S/cm. 16,18 In addition, LiPON can be fabricated as a film structure with excellent electrochemical stability up to 5.5 V 3,8,15 and have also been shown to exhibit high cyclability. 8,20 Despite all these advantages, the commercialization of LiPON has been delayed due to relatively slow ionic conduction in the LiPONemployed ASSLIB compared to that of the LIB utilizing liquid electrolytes. Large interfacial resistance has been alleged to be a major fac...

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Recent Advances in Inorganic Solid Electrolytes for Lithium Batteries

Cited by 259 publications

References 99 publications

Lithium-Ion Mobility in Quaternary Boro–Germano–Phosphate Glasses

Lithium-Ion Mobility in Quaternary Boro–Germano–Phosphate Glasses

Trends in Effective Diffusion Coefficients for Ion-Exchange Strengthening of Soda-Lime-Silicate Glasses

Effects of Mechanical Strain on Ionic Conductivity in the Interface between LiPON and Ni-Mn Spinel

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