Molecular Layer Deposition of Alucone Thin Film on LiCoO<sub>2</sub> to Enable High Voltage Operation

Lidor‐Shalev, Ortal; Leifer, Nicole; Ejgenberg, Michal; Aviv, Hagit; Perelshtein, Ilana; Goobes, Gil; Noked, Malachi; Rosy, .

doi:10.1002/batt.202100152

Cited by 10 publications

(6 citation statements)

References 80 publications

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“…When used as a protective layer, it can effectively improve the cycling stability of Li metal anode. [ 44 ] Alucone thin film (using trimethylaluminum, hydroquinone, and ethylene glycol as the precursors) was coated on LiCoO 2 via MLD to enable high voltage operation [ 45 ] and also deposited on sodium metal to suppress dendritic and mossy Na formation. [ 46 ] In addition, zinc‐based MLD or alternate ALD‐MLD technologies have been successfully explored to deposit thin film for various applications like ultralow thermal conductivity, [ 47 ] peizoresistor, [ 48 ] thermoelectrics, and transparent conductor.…”

Section: Introductionmentioning

confidence: 99%

Molecular‐Layer‐Deposited Zincone Films Induce the Formation of LiF‐Rich Interphase for Lithium Metal Anodes

Chang

Fang

et al. 2023

Advanced Energy Materials

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The poor SEI may also induce the heterogeneous deposition of Li, leading to the formation of notorious dendrites. [11][12][13] The uncontrolled Li dendrites not only consume cyclable Li but also accumulate irreversible "dead lithium" owing to the loss of electric connection. [14][15][16] Coulombic efficiency (CE) is then dramatically reduced. At a fixed loading, the deliverable capacity decays rapidly. In addition, Li dendrites may cause safety issues such as short circuits and catastrophic cell failures, which hinder the practical application of Li metal batteries. [17][18][19] Many studies have reported to suppress the formation of Li dendrites successfully and could address the interface issues appropriately by designing electrolyte rationally, [20][21][22] constructing 3D framework materials, [23,24] developing new electrolyte additive, [25][26][27] modifying currentcollectors, [28,29] and building artificial SEI coating. [30][31][32] These strategies have demonstrated significant progress in stabilizing the SEI. Among the complicated composition of various SEI systems, lithium fluoride (LiF) has been repeatedly reported to play an important role in forming better SEI because LiF has high chemical stability and a low Li + diffusion barrier. [33,34] The formation of LiF in the organic/inorganic hybrid SEI is the key step in building a robust Li metal anode because the SEI will determine the uniformity of Li metal nucleation/growth during the subsequent plating/stripping. [35,36] Building a LiF-rich SEI is an critical approach to controlling Li metal growth uniformity. However, Lithium metal anodes suffer from low Coulombic efficiency and dendritic growth owing to an unstable solid electrolyte interphase (SEI), which limit the practical applications of lithium metal anodes. Here, zincone (ZnHQ) is conformally fabricated on 3D copper nanowires (CuNWs) via a molecular layer deposition (MLD) technology. Upon polarization, the terminal oxygen of ZnHQ serves as a strong nucleophilic agent to attack Li bis(trifluoromethanesulfonyl) imide, yielding a LiF-rich SEI. This SEI facilitates the Li transport, shuts off the electron conduction, and inhibits the growth of lithium dendrites. In addition, the zinc atoms of ZnHQ induce favorable Li deposition owing to their lithiophilicity. These advantages enabled by MLD make the ZnHQ-modified CuNW (CuNW@ZnHQ) an ideal Li metal anode, which demonstrates excellent cyclability. A symmetrical cell of CuNW@ZnHQ shows high cycling stability for more than 7000 h at the current density of 1 mA cm −2 . When pairing with a Ni/ Co/Mn ternary oxide cathode (NCM523), the resultant CuNW@ZnHQ||NCM full cell is cycled for 1000 cycles with a 90% capacity retention at an areal capacity of 3.2 mAh cm −2 . The MLD technology brings new opportunities for next-generation high-energy Li metal batteries.

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Section: Introductionmentioning

confidence: 99%

Molecular‐Layer‐Deposited Zincone Films Induce the Formation of LiF‐Rich Interphase for Lithium Metal Anodes

Chang

Fang

et al. 2023

Advanced Energy Materials

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“…The prototype process is the one with TMA and EG. [ 111,231,287–332 ] However, TMA works very well with many other organics as well. [ 40,46,54,108,109,114,125,148,211–213,218,219,221,226,228,230,234,240,244,245,249,252,255,256,258,260,262,264,267–269,273–277,279–284,325,333–369 ] The bulkier dimethyl aluminum isopropoxide precursor has been successfully used with EG as well.…”

Section: Brief Account Of Ald/mld Processes Developedmentioning

confidence: 99%

“…[ 111,231,287–332 ] However, TMA works very well with many other organics as well. [ 40,46,54,108,109,114,125,148,211–213,218,219,221,226,228,230,234,240,244,245,249,252,255,256,258,260,262,264,267–269,273–277,279–284,325,333–369 ] The bulkier dimethyl aluminum isopropoxide precursor has been successfully used with EG as well. [ 323 ] Different TMA + organic processes have been investigated, e.g., to elucidate the effect of the organic backbone length, i.e., long (1,10‐decanediol) or short (1,6‐hexanediol), on the mechanical properties; indeed, as expected, with the increasing chain length, the stretchability was enhanced.…”

Section: Brief Account Of Ald/mld Processes Developedmentioning

confidence: 99%

Atomic/Molecular Layer Deposition for Designer's Functional Metal–Organic Materials

Multia

Karppinen

2022

Adv Materials Inter

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organic ligands act as bridges between the metal centers to form infinite 1D, 2D, or 3D structures. These materials are often referred to as coordination polymer (CP) [1] or metal-organic framework (MOF) [2] materials; the latter term is used when the metal-organic material is crystalline and highly porous. [3] The research field of CP-and MOF-type materials has grown tremendously over the last two decades. The structural and chemical diversity of these materials has served as a continuous source of scientific excitement; the same diversity has also triggered huge technological interest as these materials possess enormous potential to be tailored for a wide variety of applications ranging from gas capture, storage, and separation to sensing, catalysis, optics, electronics, and energy storage. [4][5][6][7] Most of the targeted application breakthroughs of metal-organics require that these materials can be produced as highquality thin films and coatings, which can be integrated with the other components in the actual device configuration. The possibility to deposit such thin films in an industry-feasible manner on the substrate types needed, would be a major step forward in the field. [8] Traditionally, solvent-based processes such as liquid-phase epitaxy, Langmuir-Blodgett, layer-by-layer, and electrochemical deposition techniques have been used for metal-organic thin films. [9][10][11] These are, however, incompatible with the requirements set by the possible integration of the materials in microelectronics. This is due to corrosion and contamination risks, and the problems in patterning and precise deposition on high-aspect-ratio features. Hence, it is vital to develop solventfree thin-film deposition routes for the metal-organic material family. In the optimal case, these deposition methods should allow conformal coatings on large-area and high-aspect-ratio substrates.The currently strongly emerging ALD/MLD technique is uniquely suited to address the challenge in a scientifically elegant yet industrially feasible way. This technique is derived from the two parent gas-phase thin-film techniques: ALD for inorganic materials (mostly binary metal oxides, sulfides, and nitrides), [12][13][14] and its counterpart MLD for purely organic thin films (e.g., polyimides and polyamides). [15] In both cases, the attractive film growth characteristics are derived from the unique way of separating the different precursor gas pulses. Currently, ALD is the standard thin-film technology in many Atomic layer deposition (ALD) for high-quality conformal inorganic thin films is one of the cornerstones of modern microelectronics, while molecular layer deposition (MLD) is its less-exploited counterpart for purely organic thin films. Currently, the hybrid of these two techniques, i.e., ALD/MLD, is strongly emerging as a state-of-the-art gas-phase route for designer's metal-organic thin films, e.g., for the next-generation energy technologies. The ALD/MLD literature comprises nearly 300 original journal papers covering most of the alkali...

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“…[4][5][6][7][8] While the inorganic component in these hybrid materials typically forms the basis for the desired electrical, optical, magnetic or catalytic functionality, the organic component could bring e.g. mechanical flexibility, 5,9,10 additional structural/chemical tunability [11][12][13][14][15] or even unforeseen bio-or lightbased actions [16][17][18][19] for the hybrid material.…”

Section: Introductionmentioning

confidence: 99%

Low-temperature ALD/MLD growth of alucone and zincone thin films from non-pyrophoric precursors

et al. 2022

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Molecular Layer Deposition of Alucone Thin Film on LiCoO₂ to Enable High Voltage Operation

Cited by 10 publications

References 80 publications

Molecular‐Layer‐Deposited Zincone Films Induce the Formation of LiF‐Rich Interphase for Lithium Metal Anodes

Molecular‐Layer‐Deposited Zincone Films Induce the Formation of LiF‐Rich Interphase for Lithium Metal Anodes

Atomic/Molecular Layer Deposition for Designer's Functional Metal–Organic Materials

Low-temperature ALD/MLD growth of alucone and zincone thin films from non-pyrophoric precursors

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Molecular Layer Deposition of Alucone Thin Film on LiCoO2 to Enable High Voltage Operation

Cited by 10 publications

References 80 publications

Molecular‐Layer‐Deposited Zincone Films Induce the Formation of LiF‐Rich Interphase for Lithium Metal Anodes

Molecular‐Layer‐Deposited Zincone Films Induce the Formation of LiF‐Rich Interphase for Lithium Metal Anodes

Atomic/Molecular Layer Deposition for Designer's Functional Metal–Organic Materials

Low-temperature ALD/MLD growth of alucone and zincone thin films from non-pyrophoric precursors

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Product

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Molecular Layer Deposition of Alucone Thin Film on LiCoO₂ to Enable High Voltage Operation