Fabrication of a magnesium-ion-conducting magnesium phosphate electrolyte film using atomic layer deposition

Tsuruoka, Tohru; Tsujita, Takuji; Su, Jin; Yu, Ning; Hamamura, Tomofumi; Inatomi, Yuu; Nakura, Kensuke; Terabe, Kazuya

doi:10.35848/1347-4065/ab79e8

Cited by 6 publications

(7 citation statements)

References 31 publications

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“…The activation energy increased from 1.37 to 1.75 eV after ambient temperature rising to 500 °C. This reduced conductivity is attributed to the decomposition of the phosphate matrix by thermal desorption of P atoms at high temperatures (this result was reported in our previous works [24, 38] ). In contrast, the ALD MgPON SSE film showed almost unchanged ionic conductivity after the ambient temperature rose to 500 °C, which suggests that the nitrogen‐incorporated ALD MgPON SSE has higher thermal stability than the ALD MgPO SSE.…”

Section: Resultssupporting

confidence: 77%

Nitrogen Plasma Enhanced Low Temperature Atomic Layer Deposition of Magnesium Phosphorus Oxynitride (MgPON) Solid‐State Electrolytes

Tsuruoka

Tsujita

et al. 2023

Angewandte Chemie

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Solid‐state batteries (SSBs) that use solid electrolytes instead of flammable liquid electrolytes have the potential to generate higher specific capacity and offer better safety. Magnesium (Mg) based SSBs with Mg metal anodes are considered to be one of the most promising energy storage candidates, because it gives high theoretical volumetric capacities of 3830 mAh cm−3. Here, we demonstrate an atomic layer deposition (ALD) process with a double nitrogen plasma process that successfully produces nitrogen‐incorporated magnesium phosphorus oxynitride (MgPON) solid‐state electrolyte (SSE) thin films at a low deposition temperature of 125 °C. The ALD MgPON SSEs exhibit an ionic conductivity of 0.36 and 1.2 μS cm−1 at 450 and 500 °C, respectively. The proposed ALD strategy shows the ability of conformal deposition nitrogen‐doped SSEs on pattered substrates and is attractive for using nitride ion‐conducing films as protective or wetting interlayers in solid‐state Mg and Li batteries.

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Section: Resultssupporting

confidence: 77%

Nitrogen Plasma Enhanced Low Temperature Atomic Layer Deposition of Magnesium Phosphorus Oxynitride (MgPON) Solid‐State Electrolytes

Tsuruoka

Tsujita

et al. 2023

Angewandte Chemie

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“…Table 1 provides the state‐of‐the‐art multivalent SEs and their properties. [ 10–12,32,39,102,112–232 ]…”

Section: Solid‐state Electrolytes (Ses)mentioning

confidence: 99%

“…2+ . Tsuruoka et al [230] reports MgPO thin film SEs by developing alternative Mg-O and P-O sub-cycles at 125-300 °C temperatures. The lower temperature synthesis persuades multi-bonding states for the phosphate matrix with a mixture of metaphosphates and pyrophosphates as well as a disordered matrix for Mg 2+ -ions hopping conduction.…”

Section: Times Larger 𝜎 Mgmentioning

confidence: 99%

Li, Na, K, Mg, Zn, Al, and Ca Anode Interface Chemistries Developed by Solid‐State Electrolytes

Shinde,

Wagh,

Kim

et al. 2023

Advanced Science

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Solid‐state batteries (SSBs) have received significant attention due to their high energy density, reversible cycle life, and safe operations relative to commercial Li‐ion batteries using flammable liquid electrolytes. This review presents the fundamentals, structures, thermodynamics, chemistries, and electrochemical kinetics of desirable solid electrolyte interphase (SEI) required to meet the practical requirements of reversible anodes. Theoretical and experimental insights for metal nucleation, deposition, and stripping for the reversible cycling of metal anodes are provided. Ion transport mechanisms and state‐of‐the‐art solid‐state electrolytes (SEs) are discussed for realizing high‐performance cells. The interface challenges and strategies are also concerned with the integration of SEs, anodes, and cathodes for large‐scale SSBs in terms of physical/chemical contacts, space‐charge layer, interdiffusion, lattice‐mismatch, dendritic growth, chemical reactivity of SEI, current collectors, and thermal instability. The recent innovations for anode interface chemistries developed by SEs are highlighted with monovalent (lithium (Li+), sodium (Na+), potassium (K+)) and multivalent (magnesium (Mg2+), zinc (Zn2+), aluminum (Al3+), calcium (Ca2+)) cation carriers (i.e., lithium‐metal, lithium‐sulfur, sodium‐metal, potassium‐ion, magnesium‐ion, zinc‐metal, aluminum‐ion, and calcium‐ion batteries) compared to those of liquid counterparts.

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“…In 2019, we proposed a plasma-assisted ALD process of a magnesium phosphate film using tris(ethylcyclopentadienyl)magnesium and tris(dimethylamino)phosphine (TDMAP) as the Mg and P precursors, respectively. , Since TDMAP contains nitrogen in its molecular structure, nitrogen incorporation into the phosphate matrix was considered to be advantageous. However, when O 2 plasma was used after TDMAP, nitrogen-free magnesium phosphate films were deposited.…”

Section: Introductionmentioning

confidence: 99%

Effects of Plasma Reactants on Atomic Layer Deposition of Lithium Phosphate and Lithium Phosphorus Oxynitride Electrolyte Films

Tsuruoka,

Mallik,

Tsujita

et al. 2024

Chem. Mater.

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The effects of plasma reactants on the plasmaassisted atomic layer deposition (ALD) of lithium phosphate are investigated in relation to the fabrication of high-quality lithium phosphorus oxynitride (LiPON) thin films for potential use as a solid-state electrolyte (SSE) in both microbatteries and neuromorphic devices. Our ALD processes enable the incorporation of nitrogen into a lithium phosphate matrix, using lithium tertbutoxide and tris(dimethylamino)phosphine as the lithium and phosphorus precursors, respectively, in a deposition temperature window of 220−300 °C. With O 2 plasma, polycrystalline lithium phosphate films, with a relatively well-arranged pyrophosphate, are deposited. Amorphous LiPON films, with a mixture of pyrophosphates and orthophosphates, are obtained when Ar or NH 3 plasma is used. When the NH 3 flow rate increases, the nitrogen composition increases up to ∼13%, while residual carbon is kept below a few percent. For a Li 2.5 PO 1.9 N 0.8 film deposited at 300 °C with NH 3 plasma, the ionic conductivity is measured as 1.65 ± 0.42 × 10 −6 S/cm at 25 °C, with an activation energy of 0.66 eV. This conductivity is the highest value of any ALD LiPON film reported to date. Our ALD processes exhibit a high level of controllability of the molecular structures of the phosphorus oxynitride matrix with high ionic conductivity, which makes them suitable for realizing high-performance Li SSE thin films.

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Fabrication of a magnesium-ion-conducting magnesium phosphate electrolyte film using atomic layer deposition

Cited by 6 publications

References 31 publications

Nitrogen Plasma Enhanced Low Temperature Atomic Layer Deposition of Magnesium Phosphorus Oxynitride (MgPON) Solid‐State Electrolytes

Nitrogen Plasma Enhanced Low Temperature Atomic Layer Deposition of Magnesium Phosphorus Oxynitride (MgPON) Solid‐State Electrolytes

Li, Na, K, Mg, Zn, Al, and Ca Anode Interface Chemistries Developed by Solid‐State Electrolytes

Effects of Plasma Reactants on Atomic Layer Deposition of Lithium Phosphate and Lithium Phosphorus Oxynitride Electrolyte Films

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