Preparation of lithium ion conductive Al-doped Li7La3Zr2O12 thin films by a sol–gel process

Tadanaga, Kiyoharu; Egawa, Hiromi; Hayashi, Akitoshi; Tatsumisago, Masahiro; Mosa, Jadra; Aparicio, Mario; Durán, Alicia

doi:10.1016/j.jpowsour.2014.09.164

Cited by 87 publications

(85 citation statements)

References 25 publications

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“…While undoped and amorphous LLZO thin films exhibit a lithium ion conductivity at room temperature (σ RT ) in the order of 10 −7 S · cm −1 , 6,7 Al-doped LLZO thin films show a lithium ion conductivity in the range of 10 −6 − 10 −5 S · cm −1 . [8][9][10][11] Only one study on cubic LLZO thin films, codoped with Al and Ta, 14 shows a conductivity value that is comparable to values reported for bulk ceramics. However, this value of 1.2 · 10 −4 S · cm −1 is only obtained from an in-plane measurement, 14 while the conductivity measured through the solid electrolyte film is as low as 2.0 · 10 −9 S · cm −1 .…”

mentioning

confidence: 69%

“…16 The only modification made to the setup described in Loho et al 16 is that a porous stainless steel microsieve R200 (Tridelta Siperm GmbH) was used in front of the sample holder to achieve a more uniform gas flow and hence deposition. As precursor materials for the LLZO thin film deposition, 2,2,6,6-tetramethyl-3,5-heptanedionato lithium (LiC 11 4 , Sigma Aldrich, 98%) were premixed inside an Ar-filled glove box (MBraun GmbH) with O 2 -and H 2 Olevels <1 ppm. The Li: La: Zr molar ratio in the precursor mixture was set to 10.5: 3: 2.…”

Section: Methodsmentioning

confidence: 99%

“…by stabilization of the cubic LLZO phase via doping, 4,5 while only a few publications have addressed LLZO thin film deposition at all. [6][7][8][9][10][11][12] The advantage of thin films is that their lithium ion conductivity for the use in an all-solid-state battery does not need to be as high as compared to bulk solid electrolytes, taking into account the electrolyte resistance R:…”

mentioning

confidence: 99%

“…Up to now, pulsed laser deposition (PLD), 6,8,9 sputtering, 7,14 solgel based methods, 10,11 and metal organic chemical vapor deposition (MO-CVD) 12 have been used to deposit LLZO thin films. However, the only report on LLZO thin film fabrication via MO-CVD does not provide any electrochemical characterization of the films.…”

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confidence: 99%

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Garnet-Type Li₇La₃Zr₂O₁₂Solid Electrolyte Thin Films Grown by CO₂-Laser Assisted CVD for All-Solid-State Batteries

Loho

Djenadic

Bruns

et al. 2016

J. Electrochem. Soc.

114

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The detailed characterization of garnet-type Li-ion conducting Li 7 La 3 Zr 2 O 12 (LLZO) solid electrolyte thin films grown by novel CO 2 -laser assisted chemical vapor deposition (LA-CVD) is reported. A deposition process parameter study reveals that an optimal combination of deposition temperature and oxygen partial pressure is essential to obtain high quality tetragonal LLZO thin films. The polycrystalline tetragonal LLZO films grown on platinum have a dense and homogeneous microstructure and are free of cracks. A total lithium ion conductivity of 4.2 · 10 −6 S · cm −1 at room temperature, with an activation energy of 0.50 eV, is achieved. This is the highest total lithium ion conductivity value reported for tetragonal LLZO thin films so far, being about one order of magnitude higher than previously reported values for tetragonal LLZO thin films prepared by sputtering and pulsed laser deposition. The results of this study suggest that the tetragonal LLZO thin films grown by LA-CVD are applicable for the use in all-solid-state thin film lithium ion batteries. Over the last decades a progressive miniaturization of electronic components took place. As a result there is an increasing demand for micro-sized power sources that drives the current research on thin film batteries. Possible applications range from sensors and radiofrequency identification tags to implantable medical devices. For these applications an all-solid-state thin film Li-ion battery is desirable due to considerable advantages such as excellent safety properties and easy integration in microelectronics. Furthermore, the energy density of such an all-solid-state cell can be increased compared to a cell with conventional liquid electrolyte, if the chosen solid electrolyte material is stable toward high voltage cathode materials as well as toward a lithium metal anode. The garnet-type solid electrolyte Li 7 La 3 Zr 2 O 12 (LLZO), first reported in 2007 by Murugan et al., 1 is a material that combines those properties with reasonably high lithium ion conductivity of up to 2.3 · 10 −5 S · cm −1 in its tetragonal 2 and up to 1.2 · 10 −3S · cm −1 in its cubic 3 modification. However, these high conductivity values have so far only been achieved for bulk ceramics, but not for thin films. Apparently, over the last years researchers have focused on the optimization of the lithium ion conductivity in bulk ceramics, e.g. by stabilization of the cubic LLZO phase via doping, 4,5 while only a few publications have addressed LLZO thin film deposition at all. 6-12The advantage of thin films is that their lithium ion conductivity for the use in an all-solid-state battery does not need to be as high as compared to bulk solid electrolytes, taking into account the electrolyte resistance R:where A is the contact area, l is the thickness and σ is the Li-ion conductivity of the solid electrolyte, respectively. For example, in their recent study Liu et al. 13 report on a functioning bulk all-solid-state battery using cubic LLZO as solid electrolyte with ∼ 1 mm thickn...

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mentioning

confidence: 69%

Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Garnet-Type Li₇La₃Zr₂O₁₂Solid Electrolyte Thin Films Grown by CO₂-Laser Assisted CVD for All-Solid-State Batteries

Loho

Djenadic

Bruns

et al. 2016

J. Electrochem. Soc.

114

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“…3 Finally, the thin film is deposited on the LiCoO 2 and the interface chemical reaction between LLZO and LiCoO 2 phases was studied using X-ray photoelectron spectroscopy and AC impedance spectroscopy.…”

Section: 10mentioning

confidence: 99%

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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Chemical Solution Deposition (CSD)

Bäcker¹,

Baumann²,

Brunkahl³

et al. 2019

Digital Encyclopedia of Applied Physics

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Chemical solution deposition (CSD) can offer economic access to large area coatings, which are required to handle significant amounts of energy in innovative applications. CSD represents an umbrella term encompassing various methods such as sol–gel, metallo‐organic decomposition (MOD), and chemical bath deposition (CBD), which are used for the fabrication of functional metal chalcogenide films. These methods are all based on the layer fabrication from precursors dissolved in the liquid phase, which are transformed into the final functional film material by different working principles. The differences are related to the involved chemistry, solvent, temperatures, and heating processes, as described herein. In addition, chemical and physical deposition methods are briefly compared, highlighting their advantages and disadvantages.

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Preparation of lithium ion conductive Al-doped Li7La3Zr2O12 thin films by a sol–gel process

Cited by 87 publications

References 25 publications

Garnet-Type Li₇La₃Zr₂O₁₂Solid Electrolyte Thin Films Grown by CO₂-Laser Assisted CVD for All-Solid-State Batteries

Garnet-Type Li₇La₃Zr₂O₁₂Solid Electrolyte Thin Films Grown by CO₂-Laser Assisted CVD for All-Solid-State 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

Chemical Solution Deposition (CSD)

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Preparation of lithium ion conductive Al-doped Li7La3Zr2O12 thin films by a sol–gel process

Cited by 87 publications

References 25 publications

Garnet-Type Li7La3Zr2O12Solid Electrolyte Thin Films Grown by CO2-Laser Assisted CVD for All-Solid-State Batteries

Garnet-Type Li7La3Zr2O12Solid Electrolyte Thin Films Grown by CO2-Laser Assisted CVD for All-Solid-State 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

Chemical Solution Deposition (CSD)

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Product

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Garnet-Type Li₇La₃Zr₂O₁₂Solid Electrolyte Thin Films Grown by CO₂-Laser Assisted CVD for All-Solid-State Batteries

Garnet-Type Li₇La₃Zr₂O₁₂Solid Electrolyte Thin Films Grown by CO₂-Laser Assisted CVD for All-Solid-State 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