Ionic conductivity properties of amorphous Li–La–Zr–O solid electrolyte for thin film batteries

Kalita, Dipangkar; Lee, S.H.; Lee, K.S.; Ko, Doo Hyun; Yoon, Young Soo

doi:10.1016/j.ssi.2012.09.011

Cited by 97 publications

(67 citation statements)

References 46 publications

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“…This value is about two orders of magnitude lower than the reported value for bulk Li 7 La 3 Zr 2 O 12 (LLZO) sample; however, it is comparable to the reported garnet LLZO thin film prepared at much higher temperature. 3,12,13 AC impedance analysis at different temperatures for a thin film of Li-La-Zr-O on MgO shows activation energy in the range of 0.6 eV and is found to be consistent with literature. 3 In the next step, Li-La-Zr-O thin film is deposited on the LiCoO 2 pellet to prepare an electrochemical half-cell comprised of an electrode and an electrolyte.…”

Section: Resultssupporting

confidence: 87%

X-ray Photoelectron Spectroscopy and AC Impedance Spectroscopy Studies of Li-La-Zr-O Solid Electrolyte Thin Film/LiCoO₂Cathode Interface for All-Solid-State Li Batteries

Zarabian

Bartolini

Pereira‐Almao

et al. 2017

J. Electrochem. Soc.

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Li ion half-cell electrode-based configuration was prepared by spin-coating using precursor of Li-stuffed garnet with intended composition of Li 7 La 3 Zr 2 O 12 on LiCoO 2 . The main goal of this study was lowering the heat-treatment to 400 • C, which is well below the chemical reaction temperature of these phases. Liquid precursor of the nominal compound was prepared and spin-coated on the top surface of MgO(100) and LiCoO 2 pellets until the appropriate thickness was obtained. Electrochemical impedance spectroscopy (EIS) was used to understand the resistance and capacitance behavior of the electrolyte and electrolyte-electrode interface. The ac impedance of half-cell shows semicircles, corresponding to the response from bulk electrolyte, second phase and interface. The interfacial region between LiCoO 2 and Li-La-Zr-O film was deeply studied with X-ray photoelectron spectroscopy (XPS) depth profile analysis. XPS results show that Co diffuses from the substrate toward the solid electrolyte; Li depletes in the interface region, and moves to the top surface, which changes the electronic structure of Co to a multiplicity of reduced forms. The present study shows that even at 400 • C, the Li-stuffed garnet precursor and LiCoO 2 cathode seem to form reaction products, suggesting that is critical for applications to develop protecting layers between the cathodes and Li-stuffed garnet electrolytes. Switching from an organic polymer-based Li ion electrolyte to a ceramic Li ion electrolyte in conventional Li ion batteries is expected to allow for higher energy density, improve safety and prolong lifetime. These, all-solid-state Li batteries can also be miniaturized, which will streamline the packing design and save cargo space. A solid electrolyte has to have several criteria to be able to use in the Li ion batteries such as high ionic conductivity at room temperature, high Li + ion transference number, chemical stability versus the Li cathodes and the Li anodes during preparation and battery operation, sustainability and economic feasibility.1-3 Although all-solid-state batteries offer lots of advantages over conventional liquid and polymer based batteries, the widespread applications of currently developed solid-state (ceramic) Li ion electrolytes have been postponed by low conductivity and or high reactivity with the electrodes which impede reaching high power density required for electric vehicles. 4,5 Li-stuffed garnet is a promising type of solid electrolyte offering an advantage of very high electrochemical stability window (∼6 V versus Li/Li + for Zr and Ta-based garnets), which opens up the possibility of using alternative cathodes and anodes for high voltage applications. It solely allows Li ions to move, and reduces the chance of capacity fading by unwanted reactions and or self-discharging. It is benign and resistant to Li dendrite electroplating.6-8 Interfacial resistance of Li stuffed garnet with Li metal and LiCoO 2 has been the scope of some recent studies targeting developing high performance battery f...

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Section: Resultssupporting

confidence: 87%

X-ray Photoelectron Spectroscopy and AC Impedance Spectroscopy Studies of Li-La-Zr-O Solid Electrolyte Thin Film/LiCoO₂Cathode Interface for All-Solid-State Li Batteries

Zarabian

Bartolini

Pereira‐Almao

et al. 2017

J. Electrochem. Soc.

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“…The peaks from other secondary phases were not observed. This feature is a advantage over other conventional thin film deposition methods such as sputtering and sol-gel method, because by using these deposition methods, heat treatment such as heating substrate during deposition or post-annealing should be necessary to obtain well crystallized film [24][25][26][27][28][29][30]. However, it should be noted that the absolute value of peak intensity in raw LAGP powder is approximately 10 times larger than that for ADed LAGP film.…”

Section: Resultsmentioning

confidence: 99%

“…Several studies have been carried out for preparing thin film solid electrolyte using RF magnetron sputtering [22][23][24][25], pulsed laser deposition [26,27] and sol-gel methods [28][29][30]. These methods are efficient for fabricating uniform film and controlling the film thickness, but in some cases, it is difficult to control elementary composition.…”

Section: Introductionmentioning

confidence: 99%

Properties of aerosol deposited NASICON-type Li1.5Al0.5Ge1.5(PO4)3 solid electrolyte thin films

Inada

Ishida

Tojo

et al. 2015

Ceramics International

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“…The tetragonally distorted form of LLZO, however, has significantly lower lithium ion conductivity [9,11]. Thin film fabrication of garnet-type LLZO has been explored by either RF sputtering or pulsed laser deposition (PLD), with the reported room temperature ionic conductivity (typically in the range of 10 -7 S/cm) several orders of magnitude lower than that of the bulk materials [12,13]. PLD is a technique known for its ability to preserve the target stoichiometry, but the influence of impurities arising…”

Section: Introductionmentioning

confidence: 99%

Effects of crystallinity and impurities on the electrical conductivity of Li–La–Zr–O thin films

et al. 2015

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We present a study of the fabrication of thin films from a Li 7 La 3 Zr 2 O 12 (LLZO) target using pulsed laser deposition. The effects of substrate temperatures and impurities on electrochemical properties of the films were investigated. The thin films of Li-La-Zr-O were deposited at room temperature and higher temperatures on a variety of substrates.Deposition above 600 °C resulted in a mixture of cubic and tetragonal phases of LLZO, as well as a La 2 Zr 2 O 7 impurity, and resulted in aluminum enrichment at the surface when Al-containing substrates were used. Films deposited at 600 °C exhibited the highest room temperature conductivity, 1.61×10 -6 S/cm. The chemical stability toward metallic lithium was also studied using X-ray photoelectron spectroscopy, which showed that the oxidation state of zirconium remained at +4 following physical contact with heated lithium metal.

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Ionic conductivity properties of amorphous Li–La–Zr–O solid electrolyte for thin film batteries

Cited by 97 publications

References 46 publications

X-ray Photoelectron Spectroscopy and AC Impedance Spectroscopy Studies of Li-La-Zr-O Solid Electrolyte Thin Film/LiCoO₂Cathode Interface for All-Solid-State Li Batteries

X-ray Photoelectron Spectroscopy and AC Impedance Spectroscopy Studies of Li-La-Zr-O Solid Electrolyte Thin Film/LiCoO₂Cathode Interface for All-Solid-State Li Batteries

Properties of aerosol deposited NASICON-type Li1.5Al0.5Ge1.5(PO4)3 solid electrolyte thin films

Effects of crystallinity and impurities on the electrical conductivity of Li–La–Zr–O thin films

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Ionic conductivity properties of amorphous Li–La–Zr–O solid electrolyte for thin film batteries

Cited by 97 publications

References 46 publications

X-ray Photoelectron Spectroscopy and AC Impedance Spectroscopy Studies of Li-La-Zr-O Solid Electrolyte Thin Film/LiCoO2Cathode Interface for All-Solid-State Li Batteries

X-ray Photoelectron Spectroscopy and AC Impedance Spectroscopy Studies of Li-La-Zr-O Solid Electrolyte Thin Film/LiCoO2Cathode Interface for All-Solid-State Li Batteries

Properties of aerosol deposited NASICON-type Li1.5Al0.5Ge1.5(PO4)3 solid electrolyte thin films

Effects of crystallinity and impurities on the electrical conductivity of Li–La–Zr–O thin films

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X-ray Photoelectron Spectroscopy and AC Impedance Spectroscopy Studies of Li-La-Zr-O Solid Electrolyte Thin Film/LiCoO₂Cathode Interface for All-Solid-State Li Batteries

X-ray Photoelectron Spectroscopy and AC Impedance Spectroscopy Studies of Li-La-Zr-O Solid Electrolyte Thin Film/LiCoO₂Cathode Interface for All-Solid-State Li Batteries