Atomic/Molecular Layer Deposition of Lithium Terephthalate Thin Films as High Rate Capability Li-Ion Battery Anodes

Nisula, Mikko; Karppinen, Maarit

doi:10.1021/acs.nanolett.5b04604

Cited by 106 publications

(158 citation statements)

References 26 publications

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“…21 We obtained very recently positive evidence that it is possible to find ALD/MLD fabrication conditions for the in-situ deposition of crystalline metal-organic thin films; our proof-of-theconcept data were for Li-TP and Cu-TP thin films (TP stands for terephthalate). 20,22 Here we introduce a straightforward and readily reproducible ALD/MLD process for the manufacturing of calcium terephthalate (Ca-TP) coordination network thin films from Ca(thd)2 and benzene-1,4-dicarboxylic acid or so-called terephthalic acid (TPA) precursors over a notably wide deposition temperature range; schematics of our ALD/MLD process are shown in Figure 1. Calcium-terephthalate networks have been synthesized in bulk form and demonstrated to be interesting candidates for example for Li-ion battery anode materials; 23 also known is that the Ca-TP materials synthetized in bulk form tend to have DMF and/or H2O molecules in their structures, and thus require high-temperature annealing to obtain the solvent-free product.…”

Section: Introductionmentioning

confidence: 99%

In Situ Atomic/Molecular Layer-by-Layer Deposition of Inorganic–Organic Coordination Network Thin Films from Gaseous Precursors

Ahvenniemi

Karppinen

2016

Chem. Mater.

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Crystalline inorganic-organic coordination network materials possess a property palette highly attractive for a number of frontier applications. In many prospective applications of these materials high-quality thin films would be required. Gas-phase thin-film techniques could potentially provide a number of advantages over the current liquid-phase techniques for depositing such state-of-the-art hybrid thin films. The strongly emerging atomic/molecular layer deposition (ALD/MLD) technique in particular enables the rational fabrication of inorganic-organic thin films in a digital atomic/molecular layer-by-layer manner through successive gas-to-surface reactions of inorganic and organic precursors but the resultant films have been amorphous. Here we demonstrate the in-situ ALD/MLD growth of well-crystalline calcium terephthalate (Ca-TP) coordination network thin films in a wide deposition temperature range. We moreover investigate the water absorption/desorption characteristics of the films and report attractive mechanical properties for both the dry and water-intercalated films.

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Section: Introductionmentioning

confidence: 99%

In Situ Atomic/Molecular Layer-by-Layer Deposition of Inorganic–Organic Coordination Network Thin Films from Gaseous Precursors

Ahvenniemi

Karppinen

2016

Chem. Mater.

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“…Lithium terephthalate (LiTP) has been deposited using Lithd and terephthalic acid as precursors between 200 and 280 • C [102]. This material has been proposed as a possible Li-ion battery anode due to its high theoretical capacity of 300 mAh/g and a low potential of 0.8 V (vs. Li + /Li) [106].…”

Section: Anodesmentioning

confidence: 99%

Metal Fluorides as Lithium-Ion Battery Materials: An Atomic Layer Deposition Perspective

2018

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Lithium-ion batteries are the enabling technology for a variety of modern day devices, including cell phones, laptops and electric vehicles. To answer the energy and voltage demands of future applications, further materials engineering of the battery components is necessary. To that end, metal fluorides could provide interesting new conversion cathode and solid electrolyte materials for future batteries. To be applicable in thin film batteries, metal fluorides should be deposited with a method providing a high level of control over uniformity and conformality on various substrate materials and geometries. Atomic layer deposition (ALD), a method widely used in microelectronics, offers unrivalled film uniformity and conformality, in conjunction with strict control of film composition. In this review, the basics of lithium-ion batteries are shortly introduced, followed by a discussion of metal fluorides as potential lithium-ion battery materials. The basics of ALD are then covered, followed by a review of some conventional lithium-ion battery materials that have been deposited by ALD. Finally, metal fluoride ALD processes reported in the literature are comprehensively reviewed. It is clear that more research on the ALD of fluorides is needed, especially transition metal fluorides, to expand the number of potential battery materials available.

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“…[5] Another class of devices requiring robust, low-profile, and cheap energy solutions is the ubiquitous low-power sensor and signaling systems, which are powered by energy harvested via thermo-, tribo-, or piezoelectric effect [6][7][8] and possibly stored in a supercapacitor [9] or a Li-ion microbattery. [10,11] In the following sections,…”

Section: Introductionmentioning

confidence: 99%

Flexible Thermoelectric ZnO–Organic Superlattices on Cotton Textile Substrates by ALD/MLD

Karttunen

Sarnes

Townsend

et al. 2017

Adv Elect Materials

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we focus on small-scale energy harvesting based on the thermoelectric effect.Thermoelectric materials can be used to convert waste heat to electric energy via Seebeck effect. They are characterized by a dimensionless figure-of-merit ZT = S 2 σT/(κ e + κ L ), where S is the Seebeck coefficient (thermopower), σ the electrical conductivity, T the temperature, and κ e and κ L the electronic and lattice contributions to the thermal conductivity κ. [12] Figure 1 illustrates the basic principle of a conventional thermoelectric (TE) energy conversion device and the concept of a TE generator device combined with a flexible substrate. Furthermore, Figure 1c shows how the ZT value arises from the abovementioned individual components. Alloys of bismuth telluride (Bi 2 Te 3 ) and antimony telluride (Sb 2 Te 3 ) are by far the most widely used TE materials. They show high ZT values for near-room-temperature applications and have been utilized for decades in solid-state refrigeration applications. A major obstacle for the widespread utilization of Bi-Sb-Te based thermoelectrics is the low abundance of tellurium: it is among the rarest elements in the Earth's crust. Furthermore, current thermoelectric generators based on conventional TE materials such as Bi 2 Te 3 are typically inflexible solid-state devices, which would not be convenient for mobile small-scale applications. [12] Consequently, there is a significant interest in producing flexible and efficient TE generator solutions. In particular, a mechanically flexible TE generator solution integrated with light-weight and comfortable textile substrates could be an enabling platform for body-heat-based energy harvesting.Recently Lee et al. fabricated woven-yarn thermoelectric textiles by coating electrospun polyacrylonitrile nanofiber cores with n-type Bi 2 Te 3 and p-type Sb 2 Te 3 and twisting them into flexible yarns. [13] By weaving the TE-coated yarns into textiles, they were able to obtain an output power of up to 8.56 W m −2 for a temperature difference of 200 K in the textile thickness direction. Another recent study on thermoelectric fabrics utilized a completely different type of material solution, where thermoelectric PEDOT:PSS (poly(3,4-ethylenedioxythiophene) polystyrene sulfonate) polymer was used to coat a polyester fabric with a solution-based method. [14] This fabric-TE device was based on p-type PEDOT:PSS only, resulting in a so-called unileg-type device that produced an output power of about 260 µW m −2 for a temperature difference of 75 K.The thermoelectric properties of both pristine ZnO and ZnO-organic superlattice thin films deposited on a cotton textile are investigated. The thin films are fabricated by atomic layer deposition/molecular layer deposition, using hydroquinone as the organic precursor for the superlattices. The resulting thin-film coatings are crystalline, in particular when deposited on a textile substrate with a thin predeposited Al 2 O 3 seed layer. The thermoelectric properties of the ZnO and ZnO-organic superlattice coatings are comp...

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Atomic/Molecular Layer Deposition of Lithium Terephthalate Thin Films as High Rate Capability Li-Ion Battery Anodes

Cited by 106 publications

References 26 publications

In Situ Atomic/Molecular Layer-by-Layer Deposition of Inorganic–Organic Coordination Network Thin Films from Gaseous Precursors

In Situ Atomic/Molecular Layer-by-Layer Deposition of Inorganic–Organic Coordination Network Thin Films from Gaseous Precursors

Metal Fluorides as Lithium-Ion Battery Materials: An Atomic Layer Deposition Perspective

Flexible Thermoelectric ZnO–Organic Superlattices on Cotton Textile Substrates by ALD/MLD

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