Molecular design effects of alkoxide-derived precursor solution on low-temperature crystallization of cubic garnet type Li ion conductor

Ohno, Tomoya; Padarti, Jeevan Kumar; Hayashi, Yoshimasa; Hirai, Shigeto; Matsuda, Takeshi; Kawaguchi, Takahiko; Sakamoto, Naonori; Wakiya, Naoki; Arai, Takashi; Suzuki, Hisao

doi:10.1016/j.matlet.2020.128747

Cited by 9 publications

(9 citation statements)

References 14 publications

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“…The preparation method was adapted from our previous research, focusing on synthesizing Ta-substituted LLZO using the metal alkoxide route with chemical modification 19) . In this study, we prepared two different precursor solutions: (i) Li The starting reagents for the Hf-LLZO and Hf,W-LLZO precursor solutions, with a concentration of 0.02 M, included Zr(OC 3 H 7 ) 4 (purity 99.9%, Sigma-Aldrich), HfCl 4 (purity 98%, Sigma-Aldrich), WCl 6 (purity ≥99.99%, Sigma-Aldrich), La(NO 3 ) 3 ‧ 6H 2 O (99.999%, Sigma-Aldrich), and metal Li.…”

Section: Methodsmentioning

confidence: 99%

“…In contrast, this study Jeevan kumar PADARTI, Hisao SUZUKI, Takahiko KAWAGUCHI, Naonori SAKAMOTO, Naoki WAKIYA, Shigeto HIRAI and Tomoya OHNO investigates the substitution of Hf in Zr-site using a methodology that includes the use of highly purified Zr alkoxide. Building upon previous research efforts focused on dopants involving Al 18) , Ta 19) , and Mg+Sr 20) , this study specifically explores the feasibility of Hf doping to stabilize the cubic garnet phase.…”

Section: Introductionmentioning

confidence: 99%

“…The methodology involves the chemical modification of Zr alkoxides through a chelation reaction using acetic acid for partial hydrolysis, followed by polycondensation reactions 19) . A notable advantage of this approach is the versatility of precursor solutions applicable for thin-film processing or particle coating for interface modification 21) .…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of Cubic Li7La3Zr2O12 Doped with Hf and W Using Metal Alkoxide Derived Sol-Gel Precursors

PADARTI,

SUZUKI,

KAWAGUCHI

et al. 2024

J. Jpn. Soc. Powder Powder Metallurgy

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This study investigated the viability of Hf and/or W doping in Li 7 La 3 Zr 2 O 12 (LLZO) through an alkoxide derived sol-gel process aimed at stabilizing the ion-conductive cubic garnet phase. Results revealed that Hf doping tends to favor the tetragonal garnet phase, while co-doping with Hf and W effectively stabilizes the cubic garnet structure. This stabilization is attributed to the similar ionic radii of Hf 4+ (0.71 Å) and the slightly smaller W 6+ (0.62 Å) compared to Zr 4+ (0.72 Å), considering charge neutrality. In both doping scenarios, a coexisting Li-deficient pyrochlore phase is observed, likely due to the use of HfCl 4 and WCl 6 as starting reagents in the alkoxide process, which results in reduced Li-coordinated carboxyl sites attached to chelated Zr alkoxide. However, increasing the Li excess content above 30% effectively eliminates the pyrochlore phase, thus stabilizing the cubic garnet phase. Impedance measurements conducted on Hf-doped LLZO and Hf,W co-doped LLZO (with 40% excess Li) sintered ceramics reveal a significant enhancement in bulk ion conductivity, with the Hf,W co-doped LLZO pellet exhibiting two orders of magnitude higher conductivity (1.09 × 10 −4 S cm −1 ). This finding confirms the stability of the cubic phase even with partial substitution of W and with 40% excess Li.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Synthesis of Cubic Li7La3Zr2O12 Doped with Hf and W Using Metal Alkoxide Derived Sol-Gel Precursors

PADARTI,

SUZUKI,

KAWAGUCHI

et al. 2024

J. Jpn. Soc. Powder Powder Metallurgy

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“…Apart from abovementioned techniques, many other synthetic routes, such as solution method, [31,103,104] combinatorial solid-liquid route, [99][100][101][102] and spray pyrolysis, [13,[105][106]115] have also been applied for LLZO synthesis, as summarized in Table 2. Overall, these methods have their own specific advantages and can produce comparable properties to those of solid state reaction.…”

Section: Wet Chemistry Routes and Other Techniquesmentioning

confidence: 99%

Processing and Properties of Garnet‐Type Li₇La₃Zr₂O₁₂ Ceramic Electrolytes

Chen

Wang

et al. 2022

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the limited electrochemical window of liquid organic electrolytes, high-voltage cathode materials and Li metal cannot be incorporated in current battery chemistry, thus making it challenge to further improve the energy density. Moreover, the flammability of liquid electrolytes also poses serious safety concerns of LIBs. Under such context, solid-state battery (SSB) using solid state electrolytes (SSEs) have attracted much attention. SSEs are typically nonflammable with wide electrochemical window and high mechanical strength. These merits allow to employ high-voltage cathodes and the "holy-grail" Li metal anode (≈3860 mAh g −1 ), offering drastic improvements in energy density and safety performance. Owing to these promises, SSB has been intensively studies in recent years.Developing a suitable solid electrolyte is critical to realize SSB technology. Substantial efforts have been made on developing various SSE systems, including NASICON (Na Super Ion Conductor)-type, perovskite-type, Garnet-type Li 7 La 3 Zr 2 O 12 (LLZO), sulfide-based, polymer electrolytes, and composite electrolytes. Among these materials, LLZO possesses high ionic (10 −4 -10 −3 S cm −1 ) and low electronic (σ e < 10 −8 S cm −1 ) conductivities at room temperature, [2,3] good mechanical strength, and good electrochemical stability. As such, it has received tremendous attention since its discovery in 2007. [3] Numerous experimental and computational studies have been conducted over the past decades. LLZO-based SSBs have also been demonstrated through various interface engineering strategies.Various formats of LLZO electrolyte have been studied so far. Based on the properties and processing routes, they can be in general categorized into three types, ceramic bulk/tape-based, thin film-based, and single crystal-based electrolytes (Figure 1 and Table 1). Among them, thin film LLZO processing faces the difficulties of Li loss and impurity phase formation during deposition and annealing (Figure 1a). Successful preparation of dense, uniform, and single phase LLZO films is rarely demonstrated. The reported conductivities of thin film LLZO in most studies are between 10 −8 and 10 −4 S cm −1 , which is far behind its ceramic counterpart. In addition, due to geometric limit (≈µm), the capacity of thin film batteries is low, making them only applicable to microelectronic devices. Single crystal growth also faces many processing-related difficulties (Figure 1b). The LLZO single crystal is mostly for the purposes of mechanistic study in LLZO crystal chemistry, which can be investigated without the interference from microstructural defects. [5] From Garnet-type solid electrolyte Li 7 La 3 Zr 2 O 12 (LLZO) is widely considered as one of the most promising candidates for solid state batteries (SSBs) owing to its high ionic conductivity and good electrochemical stability. Since its discovery in 2007, great progress has been made in terms of crystal chemistry, chemical and electrochemical properties, and battery application. Nonetheless, reliable and controll...

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“…10), 30) We recently reported on molecular-design effects via chemical modification using acetic acid and distilled water for the partial hydrolysis lowered the crystallization temperature of Li 7 La 3 Zr 1.75 Ta 0.25 O 12 (c-LLZTO). 31) We also reported the hydrolysis and polycondensation imprint on tetraethyl orthosilicate (TEOS) in aqueous solution in the presence of an acid catalyst (HCl), which plays an important role in the formation of the amorphous silica shell on the core nanoparticles. 32) This article describes the synthesis of phase-pure mesoporous Li 2 FeSiO 4 /C nanocomposite particles by a modified solgel processing via the alkoxide route.…”

Section: Introductionmentioning

confidence: 99%

Copolymerization effect on the synthesis of Li2FeSiO4/C nanocomposites by chemical solution deposition

Padarti

Jupalli

Iimura

et al. 2022

J. Ceram. Soc. Japan

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Olivine-structured lithium iron silicate is one of the promising cathodes for the development of high energy lithium ion batteries. This article describes the synthesis of phase-pure mesoporous Li 2 FeSiO 4 /C nanocomposite particles by a modified solgel processing via the alkoxide route. Controlled polymerization of Si alkoxide mediated partial hydrolysis in conjunction with copolymerization of Fe precursors chelated with citric acid minimized the formation of impurity phases and lowered the crystallization temperature. This approach resulted in high-purity, mesoporous Li 2 FeSiO 4 /C nanoparticles aggregated in the submicrometer range (382 nm on average) and comprising primary nanocrystallites with an average diameter of 20 nm. The residual carbon appears to be coated on Li 2 FeSiO 4 particles with an average thickness of about 2 nm and resembles a graphenelike surface layer. The material exhibits stable electrochemical performance with a reversible capacity of about 164.5 mAh•g ¹1 at a rate of 0.1 C. The good cycling stability is attributed to synergistic effects in our synthesis mechanism that produces in-situ carbon coated Li 2 FeSiO 4 nanocomposites.

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Molecular design effects of alkoxide-derived precursor solution on low-temperature crystallization of cubic garnet type Li ion conductor

Cited by 9 publications

References 14 publications

Synthesis of Cubic Li<sub>7</sub>La<sub>3</sub>Zr<sub>2</sub>O<sub>12</sub> Doped with Hf and W Using Metal Alkoxide Derived Sol-Gel Precursors

Synthesis of Cubic Li<sub>7</sub>La<sub>3</sub>Zr<sub>2</sub>O<sub>12</sub> Doped with Hf and W Using Metal Alkoxide Derived Sol-Gel Precursors

Processing and Properties of Garnet‐Type Li₇La₃Zr₂O₁₂ Ceramic Electrolytes

Copolymerization effect on the synthesis of Li<sub>2</sub>FeSiO<sub>4</sub>/C nanocomposites by chemical solution deposition

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Molecular design effects of alkoxide-derived precursor solution on low-temperature crystallization of cubic garnet type Li ion conductor

Cited by 9 publications

References 14 publications

Synthesis of Cubic Li<sub>7</sub>La<sub>3</sub>Zr<sub>2</sub>O<sub>12</sub> Doped with Hf and W Using Metal Alkoxide Derived Sol-Gel Precursors

Synthesis of Cubic Li<sub>7</sub>La<sub>3</sub>Zr<sub>2</sub>O<sub>12</sub> Doped with Hf and W Using Metal Alkoxide Derived Sol-Gel Precursors

Processing and Properties of Garnet‐Type Li7La3Zr2O12 Ceramic Electrolytes

Copolymerization effect on the synthesis of Li<sub>2</sub>FeSiO<sub>4</sub>/C nanocomposites by chemical solution deposition

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Processing and Properties of Garnet‐Type Li₇La₃Zr₂O₁₂ Ceramic Electrolytes