Electrochemically Active In Situ Crystalline Lithium-Organic Thin Films by ALD/MLD

Abstract

Intercalated metal–organic framework (iMOF) type electrochemically active aromatic metal carboxylates are intriguing material candidates for various energy storage devices and microelectronics. In this work, we grow in situ crystalline thin films of such materials through atomic/molecular layer deposition (ALD/MLD); the remarkable benefit of this approach is the possibility to evaluate their electrochemical properties in a simple cell configuration without any additives. Five organic linkers are investigated in combination with lithium: terephthalic acid (TPA), 3,5-pyridinedicarboxylic acid (PDC), 2,6-naphthalenedicarboxylic acid (NDC), 4,4′-biphenyldicarboxylic acid (BPDC), and 4,4′-azobenzenedicarboxylic acid (AZO). In particular, the electrochemical activity of Li-PDC and the crystal structure of Li-AZO are addressed here for the first time. We believe that the in situ gas-phase thin-film deposition is a crucial requirement to benefit from the iMOF-type electrode materials in, e.g., microelectronics and wearable devices.

Atomic/molecular layer deposition of Ni-terephthalate thin films

“…2b, the GPC value decreases with increasing deposition temperature, in a fashion seen for most of the ALD/MLD processes. 48,49 This diminishing growth rate with increasing temperature is commonly attributed to (i) the tendency of the metal precursor to remain in excess in the porous organic layer more readily at low temperatures, 49 and/or (ii) the tendency of the sticky low-vapor-pressure organic molecule to get incorporated as a kind of reservoir within the growing film at low temperatures; 48,50 in both cases the excess precursors would act as extra reaction sites for the film growth. Despite the strong temperature dependence, the Ni(thd) 2 +TPA process was found to deliver the Ni-TPA films in a highly reproducible manner at each deposition temperature.…”

New Hybrid Organic-Inorganic Thin Films by Molecular Layer Deposition for Rechargeable Batteries

“…Recently, Karppinen and co-workers made encouraging progress on MLD surface chemistry and process development for Li-containing organic-inorganic thin films (Lidicarboxylates), and demonstration of these novel materials as the anode [Li-TPA (Nisula and Karppinen, 2016), Li-PDC, Li-NDC, Li-BPDC, and Li-ZAO (Multia et al, 2020)] and the cathode (Li 2 Q) (Nisula and Karppinen, 2018) in LIBs. For the first time, they reported the MLD recipes for these Lidicarboxylates, by using lithium bis(trimethylsilyl)amide (LiHMDS) as the Li precursor, in combination with five organic linkers, terephthalic acid (TPA), pyridinedicarboxylic acid (PDC), 2,6-naphthalenedicarboxylic acid (NDC), 4,4′biphenydicarboxylic acid (BPDC), and 4,4′azobenzenedicarboxylic acid (AZO) (Figure 1D).…”

“…3D microbatteries allow significantly increased surface area of active materials in the limited footprint as planar thin-film batteries and thus provide high energy and power densities (Figure 1A). However, manufacturing 3D microbatteries has been challenging due to the strict requirements on the uniformity and pinhole-free deposition of the anode, solid electrolyte, and cathode layers on high-surface-area substrates (Oudenhoven et al, 2011;Roberts et al, 2011;Liu et al, 2020), Zhao et al (2021) with permission from The Royal Society of Chemistry); (C) electrochemical performance of MLD-tincone (TDMASn-glycerol) as the anode in LIBs (reproduced from Zhu et al (2020) with permission from The Royal Society of Chemistry); (D) crystal structure of Li-PDC, Li-TPA, Li-NDC, and LiBPDC, with their corresponding organic precursors, and redox reactions mechanisms for Li-TPA and LiZAO (reprinted with permission from Multia et al (2020) Copyright 2020 American Chemical Society); (E) configuration of an all ALD/MLD-made Li 2 Q/LiPON/Cu cell, and Li-ion storage mechanism of Li 2 Q as the cathode (reproduced from Nisula and Karppinen (2018) with permission from The Royal Society of Chemistry); (F) Nyquist plot, Arrhenius plot, and AFM roughness of lithicone by MLD (reproduced from Kazyak et al (2020) with permission from The Royal Society of Chemistry).…”

Low Temperature Deposition of Highly Cyclable Porous Prussian Blue Cathode for Lithium‐Ion Microbattery

“…One widely accepted game changer is that of 3D or porous electrode design with high surface-to-volume ratio, to have interfacial exchanges over an extended surface with better electrolyte accessibility, short ionic diffusion paths, and mass transport kinetics, thereby decoupling the inverse energy/power relationship. [2][3][4][5][6] Various advanced coating techniques like chemical vapor deposition, [7,8] atomic layer deposition (ALD), [9,10] molecular layer deposition, [11] sputtering, [12,13] etc. have been used for conformal coating of active materials on porous structures.…”