Effect of oxygen pressure on structure and ionic conductivity of epitaxial Li0.33La0.55TiO3 solid electrolyte thin films produced by pulsed laser deposition

Bharathi, K. Kamala; Tan, Haiyan; Takeuchi, Saya; Meshi, Louisa; Shen, Haoting; Shin, Jongmoon; Takeuchi, Ichiro; Bendersky, Leonid A.

doi:10.1039/c6ra12879c

Cited by 23 publications

(21 citation statements)

References 42 publications

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“…Furthermore, in 1984, Kochergina et al [448] published a report on Li 0.5 La 0.5 TiO 3 . Subsequently, the Li 3x La (2/3)−x (1/3)−2x TiO 3 phase (with 0 < x < 0.16) (LLTO), where denotes a structural vacancy, and its related compounds, have been thoroughly studied by numerous workers [451][452][453][454][455][456][457][458][459][460][461][462][463][464][465][466][467]. Afterwards, in 1987, Belous et al [449] [458] and an E a of 0.40 eV.…”

Section: Perovskite-type Structure Electrolytesmentioning

confidence: 99%

“…Furthermore, in 1984, Kochergina et al [ 448 ] published a report on Li 0.5 La 0.5 TiO 3 . Subsequently, the Li 3 x La (2/3)− x □ (1/3)−2 x TiO 3 phase (with 0 < x < 0.16) (LLTO), where □ denotes a structural vacancy, and its related compounds, have been thoroughly studied by numerous workers [ 451 , 452 , 453 , 454 , 455 , 456 , 457 , 458 , 459 , 460 , 461 , 462 , 463 , 464 , 465 , 466 , 467 ]. Afterwards, in 1987, Belous et al [ 449 ] studied the effect of the Li content on the structure of Li 3 x La (2/3)− x □ (1/3)−2 x TiO 3 (0.04 ≤ x ≤ 0.17) and performed conductivity measurements.…”

Section: Oxide Solid Electrolytesmentioning

confidence: 99%

“…(i) Many efforts have been invested to elucidate the crystal structure and conduction mechanism of Li 3 x La (2/3)− x □ (1/3)−2 x TiO 3 by (a) analyzing the effect of the preparation method: Solid-state [ 458 ], sol–gel [ 461 ], precipitation [ 459 ], electrospinning [ 462 ], and thin film (RF sputtering and PLD) [ 463 ], and reaction conditions, such as temperature and time; (b) investigating the concept of doping, i.e., substitution of La by other lanthanides (Pr, Nd, Sm, Gd, Dy, Y) [ 464 ], using various Li doping contents [ 451 ], or substituting other alkali ions, such as Na + and K + ions, or alkaline-earth ions, such as Sr 2+ and Ba 2+ ions, or Ag + ions at the La sites; (c) in 2000, Mizumoto investigated the conductivity relaxation in various lithium ion conductors with the perovskite-type structure [ 465 ], and (d) considering doping the Ti sites with tri- (e.g., Al 3+ ) [ 466 ], tetra- (e.g., Zr 4+ ), penta- (e.g., Ta 5+ , Nb 5+ ) [ 485 ], and hexavalent ions (e.g., W 6+ ). It was determined that the conduction mechanism of the LLTO compounds varied with the composition, A-site deficiency, Li + and La 3+ ions concentration, and dopants [ 466 ].…”

Section: Oxide Solid Electrolytesmentioning

confidence: 99%

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Sulfide and Oxide Inorganic Solid Electrolytes for All-Solid-State Li Batteries: A Review

et al. 2020

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Energy storage materials are finding increasing applications in our daily lives, for devices such as mobile phones and electric vehicles. Current commercial batteries use flammable liquid electrolytes, which are unsafe, toxic, and environmentally unfriendly with low chemical stability. Recently, solid electrolytes have been extensively studied as alternative electrolytes to address these shortcomings. Herein, we report the early history, synthesis and characterization, mechanical properties, and Li+ ion transport mechanisms of inorganic sulfide and oxide electrolytes. Furthermore, we highlight the importance of the fabrication technology and experimental conditions, such as the effects of pressure and operating parameters, on the electrochemical performance of all-solid-state Li batteries. In particular, we emphasize promising electrolyte systems based on sulfides and argyrodites, such as LiPS5Cl and β-Li3PS4, oxide electrolytes, bare and doped Li7La3Zr2O12 garnet, NASICON-type structures, and perovskite electrolyte materials. Moreover, we discuss the present and future challenges that all-solid-state batteries face for large-scale industrial applications.

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Section: Perovskite-type Structure Electrolytesmentioning

confidence: 99%

Section: Oxide Solid Electrolytesmentioning

confidence: 99%

Section: Oxide Solid Electrolytesmentioning

confidence: 99%

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Sulfide and Oxide Inorganic Solid Electrolytes for All-Solid-State Li Batteries: A Review

et al. 2020

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“…• C. 28 We deposited a-LLTO on interdigitated contacts at 0.2 Torr oxygen, 4 Hz, and ∼2 J /cm 2 at various temperatures expanding the full range from Furusawa et al and Ahn and Yoon. 15,19 The Nyquist plots show a single semicircle and dielectric capacitance tail (Fig.…”

Section: 26mentioning

confidence: 99%

Amorphous Lithium Lanthanum Titanate for Solid-State Microbatteries

Lee

Wang

Xin

et al. 2016

J. Electrochem. Soc.

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Lithium lanthanum titanate (LLTO) is a promising solid state electrolyte for solid state batteries due to its demonstrated high bulk ionic conductivity. However, crystalline LLTO has a relatively low grain boundary conductivity, limiting the overall material conductivity. In this work, we investigate amorphous LLTO (a-LLTO) thin films grown by pulsed laser deposition (PLD). By controlling the background pressure and temperature we are able to optimize the ionic conductivity to 3 × 10 −4 S/cm and electronic conductivity to 5 × 10 −11 S/cm. XRD, TEM, and STEM/EELS analysis confirm that the films are amorphous and indicate that oxygen background gas is necessary during the PLD process to decrease the oxygen vacancy concentration, decreasing the electrical conductivity. Amorphous LLTO is deposited onto high voltage LiNi 0. Next generation lithium-ion batteries will require a broad range of energies to meet the challenges of portable electronic storage from electric vehicles to microelectromechanical systems (MEMS). The cost per Watt-hour of commercial batteries have shown incremental improvement due to better manufacturing design, but drastic increases in energy and power density are needed to satisfy projected demand. 1 Solid-state electrolytes are researched heavily because they have the potential to improve capacity loss, cycle lifetime, operation temperature, and safety. Lithium Phosphorous Oxynitride (LiPON) based thin-film solid-state batteries have excellent cycle life and are currently commercialized.2,3 However, LiPON has a relatively low ionic conductivity (1 × 10 −6 S/cm) and other solid electrolytes have demonstrated conductivity several orders of magnitude higher. 4,5 Lithium lanthanum titanate (LLTO) is a promising solid-state electrolyte due to its high bulk ionic conductivity (∼10 −3 S/cm) at room temperature, negligible electronic conductivity, and high voltage, atmospheric, and temperature stabilities.6-8 Extensive fundamental studies have been carried out to demonstrate this high ionic conductivity, elucidate the crystal structure, and determine the mechanism of lithium ion conduction.9-12 However, there are fundamental impediments to the implementation of crystalline LLTO into an actual device. One key issue is that crystalline LLTO has a relatively low grain boundary ionic conductivity (<10 −5 S/cm), lowering the effective material ionic conductivity. 6 In addition, crystalline LLTO is unstable in contact with lithium metal because lithium will easily insert reducing Ti 4+ to Ti 3+ , thus increasing electronic conductivity. 13,14Fortunately, amorphous LLTO has not only been shown to overcome these barriers, the lower energy constraints of fabricating amorphous LLTO opens up numerous thin film synthesis techniques. Amorphous LLTO thin films have been synthesized by pulsed laser deposition (PLD), RF magnetron sputtering, E-beam evaporation, atomic layer deposition, chemical solution deposition and sol-gel synthesis. [15][16][17][18][19][20][21][22][23][24] Furusawa et al. demonstrated amorphous LL...

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“…In contrast, promising oxide electrolytes (e.g., perovskite La 0. 5 ), and LISI-CON (Li 14 ZnGe 4 O 16 )), [7][8][9] with high chemical stabilities are currently limited by high grain-boundary resistances. Hence a dramatic reduction of the thickness of the solid electrolyte is required to overcome the limited lithium conductivity to enable fast charge-discharge rates.…”

Section: Introductionmentioning

confidence: 99%

Lithium-based vertically aligned nanocomposites for three-dimensional solid-state batteries

Cunha

Huijben

2021

MRS Bulletin

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Planar two-dimensional (2D) solid-state lithium-ion batteries exhibit an undesirable energy versus power balance, which can be dramatically improved by the application of three-dimensional (3D) geometries. Current ceramics-based nanocomposites exhibit limited control of the distribution and orientation of the nanoparticles within the matrix material. However, the tailoring of functionalities by the strong coupling between the two phases and their interfaces, present in epitaxial 3D vertically aligned nanocomposites (VANs), show promising advantages over the conventional 2D planar multilayers. Although a range of epitaxial VANs have been studied in the last decade, lithium-based VANs toward battery applications have remained mostly unexplored. Interestingly, two recent studies by Qi et al. and Cunha et al. demonstrate the unique potential of lithium-based VANs toward the realization of 3D solid-state batteries with enhanced energy storage performance. In this article, we will discuss these promising results as an enhanced current collector within the cathode or as an integrated solid-state cathode-electrolyte composite. Furthermore, we will describe different design configurations that can be applied to realize self-assembled VAN-based complete 3D battery devices.

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Effect of oxygen pressure on structure and ionic conductivity of epitaxial Li_0.33La_0.55TiO₃ solid electrolyte thin films produced by pulsed laser deposition

Abstract: We report on the ionic conductivity of Li0.33La0.55TiO3 (LLTO) epitaxial films grown on the (100) and (111) surfaces of single crystal SrTiO3 (STO) substrates at different oxygen partial pressures (from 1.33 to 26.66 Pa).

Cited by 23 publications

References 42 publications

Sulfide and Oxide Inorganic Solid Electrolytes for All-Solid-State Li Batteries: A Review

Sulfide and Oxide Inorganic Solid Electrolytes for All-Solid-State Li Batteries: A Review

Amorphous Lithium Lanthanum Titanate for Solid-State Microbatteries

Lithium-based vertically aligned nanocomposites for three-dimensional solid-state batteries

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