FEATURES OF PHASE TRANSFORMATIONS IN THE SYNTHESIS OF COMPLEX LITHIUM-CONDUCTING OXIDE MATERIALS

Lithium-ion batteries (LIB`s) are widely used in consumer electronics, mobile phones, personal computers, as well as in hybrid and electric vehicles. Liquid electrolytes, which mainly consist of aprotic organic solvents and lithium-conductive salts, are used for the transfer of lithium ions in LIB`s. However, the application of liquid electrolytes in LIB`s leads to a number of problems, the most significant of which are the risk of battery ignition during operation due to the presence of flammable organic solvents and loss of capacity due to the interaction of liquid electrolyte with electrode materials during cycling. An alternative that can ensure the safety and reliability of lithium batteries is the development of completely solid state batteries (SSB`s). SSB`s are not only inherently safer due to the absence of flammable organic components, but also have the potential to increase significantly the energy density. Instead of a porous separator based on polypropylene saturated with a liquid electrolyte, the SSB`s use a solid electrolyte that acts as an electrical insulator and an ionic conductor at the same time. The use of a compact solid electrolyte, which acts as a physical barrier that prevents the growth of lithium dendrites, also allows using lithium metal as the anode material. It is desirable to use oxide systems as the solid electrolytes for SSB`s, as they are resistant to moisture and atmospheric air. Among the lithium-conducting oxide materials, which exhibit relatively high lithium conductivity at a room temperature and can be used as a solid electrolyte in the completely solid-state batteries, lithium-air batteries and other electrochemical devices, the most promising materials are ones with NASICON, perovskite and garnet-type structures. The phase transformations that occur during the synthesis of complex lithium-conductive oxides, namely Li1.3Al0.3Ti1.7(PO4)3 with the NASICON-type structure, Li0.34La0.56TiO3 with the perovskite-type structure and Li6.5La3Zr1.5Nb0.5O12 with the garnet-type structure by the solid-state reactions method in an air were investigated. The optimal conditions for the synthesis of each of the above-mentioned compounds were determined.

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Aluminum based sulfide solid lithium ionic conductors for all solid state batteries

Nanoscale ◽

10.1039/c4nr00804a ◽

2014 ◽

Vol 6 (12) ◽

pp. 6661-6667 ◽

Cited By ~ 13

Author(s):

S. Amaresh ◽

K. Karthikeyan ◽

K. J. Kim ◽

Y. G. Lee ◽

Y. S. Lee

Keyword(s):

Solid State ◽

Ionic Conductivity ◽

Solid Electrolyte ◽

Organic Liquid ◽

Liquid Electrolyte ◽

Ionic Conductors ◽

Lithium Secondary Batteries ◽

Solid State Batteries ◽

All Solid State Batteries ◽

The Cost

The ionic conductivity of a Li–Al–Ge–P–S based thio-LISICON solid electrolyte is equivalent to that of a conventional organic liquid electrolyte used in lithium secondary batteries. The usage of aluminum brings down the cost of the solid electrolyte making it suitable for commercial solid state batteries.

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Hybrid solid electrolyte with the combination of Li7La3Zr2O12 ceramic and ionic liquid for high voltage pseudo-solid-state Li-ion batteries

Journal of Materials Chemistry A ◽

10.1039/c6ta07268b ◽

2016 ◽

Vol 4 (43) ◽

pp. 17025-17032 ◽

Cited By ~ 35

Author(s):

Hyun Woo Kim ◽

Palanisamy Manikandan ◽

Young Jun Lim ◽

Jin Hong Kim ◽

Sang-cheol Nam ◽

...

Keyword(s):

Ionic Liquid ◽

Solid State ◽

Solid Electrolyte ◽

High Voltage ◽

Liquid Electrolyte ◽

Li Ion Batteries ◽

Ceramic Particles ◽

Ionic Liquid Electrolyte ◽

Safety Aspects ◽

Li Ion

Concerning the safety aspects of high-voltage Li-ion batteries, a pelletized hybrid solid electrolyte (HSE) was prepared by blending Li7La3Zr2O12 (LLZO) ceramic particles and an ionic liquid electrolyte (ILE) for use in pseudo-solid-state Li-ion batteries.

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Feasible Energy Density Pushes of Li-Metal vs. Li-Ion Cells

Applied Sciences ◽

10.3390/app11167592 ◽

2021 ◽

Vol 11 (16) ◽

pp. 7592

Author(s):

Duygu Karabelli ◽

Kai Peter Birke

Keyword(s):

Solid State ◽

Energy Density ◽

Potential Application ◽

Solid Electrolytes ◽

Metal Electrode ◽

Liquid Electrolyte ◽

Trade Off ◽

Liquid Electrolytes ◽

Feasible Option ◽

Li Ion

Li-metal batteries are attracting a lot of attention nowadays. However, they are merely an attempt to enhance energy densities by employing a negative Li-metal electrode. Usually, when a Li-metal cell is charged, a certain amount of sacrificial lithium must be added, because irreversible losses per cycle add up much more unfavourably compared to conventional Li-ion cells. When liquid electrolytes instead of solid ones are used, additional electrolyte must also be added because both the lithium of the positive electrode and the liquid electrolyte are consumed during each cycle. Solid electrolytes may present a clever solution to the issue of saving sacrificial lithium and electrolyte, but their additional intrinsic weight and volume must be considered. This poses the important question of if and how much energy density can be gained in realistic scenarios if a switch from Li-ion to rechargeable Li-metal cells is anticipated. This paper calculates various scenarios assuming typical losses per cycle and reveals future e-mobility as a potential application of Li-metal cells. The paper discusses the trade-off if, considering only the push for energy density, liquid electrolytes can become a feasible option in large Li-metal batteries vs. the solid-state approach. This also includes the important aspect of cost.

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Quasi-solid electrolyte developed on hierarchical rambutan-like γ-AlOOH microspheres with high ionic conductivity for lithium ion batteries

Nanoscale ◽

10.1039/d1nr02046c ◽

2021 ◽

Author(s):

Mengmeng Gao ◽

Xiaolei Wu ◽

Shuhong Yi ◽

Shuwei Sun ◽

Caiyan Yu ◽

...

Keyword(s):

Solid State ◽

Ionic Conductivity ◽

Solid Electrolyte ◽

Lithium Ion Batteries ◽

Lithium Ion ◽

High Ionic Conductivity ◽

Liquid Lithium ◽

Liquid Electrolytes ◽

Solid State Batteries ◽

Solid State Electrolytes

Upgrading liquid electrolytes with all-solid-state electrolytes (ASEs) or quasi-solid-state electrolytes (QSEs) for solid-state batteries (SBs) have emerged not only to address the intrinsic disadvantages of traditional liquid lithium ion batteries,...

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All-Solid-State Lithium Battery Working without an Additional Separator in a Polymeric Electrolyte

Polymers ◽

10.3390/polym10121364 ◽

2018 ◽

Vol 10 (12) ◽

pp. 1364 ◽

Cited By ~ 3

Author(s):

Seonggyu Cho ◽

Shinho Kim ◽

Wonho Kim ◽

Seok Kim ◽

Sungsook Ahn

Keyword(s):

Solid State ◽

Solid Electrolyte ◽

Technology Development ◽

System Development ◽

New Technology ◽

Internal Resistance ◽

Liquid Electrolyte ◽

Ion Conductivity ◽

Li Battery ◽

Li Ion

Considering the safety issues of Li ion batteries, an all-solid-state polymer electrolyte has been one of the promising solutions. Achieving a Li ion conductivity of a solid-state electrolyte comparable to that of a liquid electrolyte (>1 mS/cm) is particularly challenging. Even with characteristic ion conductivity, employment of a polyethylene oxide (PEO) solid electrolyte has not been sufficient due to high crystallinity. In this study, hybrid solid electrolyte (HSE) systems have been designed with Li1.3Al0.3Ti0.7(PO4)3 (LATP), PEO and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). A hybrid solid cathode (HSC) is also designed using LATP, PEO and lithium cobalt oxide (LiCoO2, LCO)—lithium manganese oxide (LiMn2O4, LMO). The designed HSE system has 2.0 × 10−4 S/cm (23 °C) and 1.6 × 10−3 S/cm (55 °C) with a 6.0 V electrochemical stability without an additional separator membrane introduction. In these systems, succinonitrile (SN) has been incorporated as a plasticizer to reduce crystallinity of PEO for practical all-solid Li battery system development. The designed HSC/HSE/Li metal cell in this study operates without any leakage and short-circuits even under the broken cell condition. The designed HSC/HSE/Li metal cell in this study displays an initial charge capacity of 82/62 mAh/g (23 °C) and 123.4/102.7 mAh/g (55 °C). The developed system overcomes typical disadvantages of internal resistance induced by Ti ion reduction. This study contributes to a new technology development of all-solid-state Li battery for commercial product design.

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Solid–electrolyte-interphase design in constrained ensemble for solid-state batteries

Energy & Environmental Science ◽

10.1039/d1ee00754h ◽

2021 ◽

Author(s):

William Fitzhugh ◽

Xi Chen ◽

Yichao Wang ◽

Luhan Ye ◽

Xin Li

Keyword(s):

Solid State ◽

Solid Electrolyte ◽

Solid Electrolyte Interphase ◽

Liquid Electrolyte ◽

Solid State Battery ◽

Solid State Batteries ◽

Solid System

All-solid-state battery is fundamentally different from liquid electrolyte batteries. To design interface stabilities, the solid system must be described by the constrained thermodynamic ensemble rather than the conventional unconstrained ensemble.

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The use of high-resolution FESEM to study solid-state phase transformations and reactions

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100172875 ◽

1994 ◽

Vol 52 ◽

pp. 1028-1029

Author(s):

P. G. Kotula ◽

D. D. Erickson ◽

C. B. Carter

Keyword(s):

Solid State ◽

High Resolution ◽

Phase Transformations ◽

High Efficiency ◽

Sol Gel ◽

Quantitative Information ◽

Solid State Reactions ◽

Critical Dimensions ◽

Backscattered Electrons ◽

Backscattered Electron

High-resolution field-emission-gun scanning electron microscopy (FESEM) has recently emerged as an extremely powerful method for characterizing the micro- or nanostructure of materials. The development of high efficiency backscattered-electron detectors has increased the resolution attainable with backscattered-electrons to almost that attainable with secondary-electrons. This increased resolution allows backscattered-electron imaging to be utilized to study materials once possible only by TEM. In addition to providing quantitative information, such as critical dimensions, SEM is more statistically representative. That is, the amount of material that can be sampled with SEM for a given measurement is many orders of magnitude greater than that with TEM.In the present work, a Hitachi S-900 FESEM (operating at 5kV) equipped with a high-resolution backscattered electron detector, has been used to study the α-Fe2O3 enhanced or seeded solid-state phase transformations of sol-gel alumina and solid-state reactions in the NiO/α-Al2O3 system. In both cases, a thin-film cross-section approach has been developed to facilitate the investigation. Specifically, the FESEM allows transformed- or reaction-layer thicknesses along interfaces that are millimeters in length to be measured with a resolution of better than 10nm.

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Toward a better understanding of chemical and microstructure heterogeneities inherited from solidification and solid state phase transformations in the Ti-48Al-2Cr-2Nb alloy

Matériaux & Techniques ◽

10.1051/mattech:2004005 ◽

2004 ◽

Vol 92 (1-2) ◽

pp. 39-50 ◽

Cited By ~ 5

Author(s):

M. Charpentier ◽

D. Daloz ◽

A. Hazotte ◽

E. Aeby-Gautier

Keyword(s):

Solid State ◽

Phase Transformations

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Rational Design of Quasi Zero-Strain NCM Cathode Materials for Minimizing Volume Change Effects in All-Solid-State Batteries

10.26434/chemrxiv.10000751.v1 ◽

2019 ◽

Author(s):

Florian Strauss ◽

Lea de Biasi ◽

A-Young Kim ◽

Jonas Hertle ◽

Simon Schweidler ◽

...

Keyword(s):

Solid State ◽

Solid Electrolyte ◽

Cathode Materials ◽

Rational Design ◽

Electrode Materials ◽

Cycling Performance ◽

Mechanical Degradation ◽

Volume Changes ◽

Solid State Batteries ◽

All Solid State Batteries

Measures to improve the cycling performance and stability of bulk-type all-solid-state batteries (SSBs) are currently being developed with the goal of substituting conventional Li-ion battery (LIB) technology. As known from liquid electrolyte based LIBs, layered oxide cathode materials undergo volume changes upon (de)lithiation, causing mechanical degradation due to particle fracture, among others. Unlike solid electrolytes, liquid electrolytes are somewhat capable of accommodating morphological changes. In SSBs, the rigidity of the materials used typically leads to adverse contact loss at the interfaces of cathode material and solid electrolyte during cycling. Hence, designing zero- or low-strain electrode materials for application in next-generation SSBs is desirable. In the present work, we report on novel Co-rich NCMs, NCM361 (60% Co) and NCM271 (70% Co), showing minor volume changes up to 4.5 V vs Li+/Li, as determined by operando X-ray diffraction and pressure measurements of LIB pouch and pelletized SSB cells, respectively. Both cathode materials exhibit good cycling performance when incorporated into SSB cells using argyrodite Li6PS5Cl solid electrolyte, albeit their morphology and secondary particle size have not yet been optimized.

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