Evolution of Hierarchically Layered Cu-Rich Silicide Nanoarchitectures

Amiinu, Ibrahim Saana; Kapuria, Nilotpal; Adegoke, Temilade Esther; Holzinger, Angelika; Geaney, Hugh; Scanlon, Micheál D.; Ryan, Kevin M.

doi:10.1021/acs.cgd.0c00833

Cited by 5 publications

(5 citation statements)

References 38 publications

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“…HRTEM of Si@CuSiNW revealed corresponding d-spacings of ≈0.62 and ≈0.28 nm of the CuSi NW core, in agreement with previous reports on Cu 15 Si 4 . [30,89] Additionally, HRTEM imaging of the Si@SiNW core confirmed Si with a lattice spacing of ≈0.32 nm, in line with previous reports on crystalline Si (Figure S9, Supporting Information). [67,90] The population density of Si NW branches along host Si NWs was found to vary widely, with the ratio of host NWs to NW branches (hNW-bNW) dependent on both the length and diameter of Si NW stems.…”

Section: Resultssupporting

confidence: 89%

A Nanowire Nest Structure Comprising Copper Silicide and Silicon Nanowires for Lithium‐Ion Battery Anodes with High Areal Loading

Collins

Kilian

Geaney

et al. 2021

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expansion during charge (300% when fully lithiated). [9][10][11][12][13] The build-up of mechanical stress through expansion of the active layer causes a loss of electrical contact with the non-expanding current collector, exacerbating capacity fade. Nanostructuring can alleviate mechanical stress build-up through smaller particle sizes, structural porosity and void spaces. [9,10] Nanoparticles (NPs), [14][15][16][17] nanowires (NWs), [18][19][20][21][22][23][24][25] and nanotubes (NTs) [26][27][28][29] are the most widely used morphologies, allowing for structural relaxation through shortened diffusion channels, increased porosity and larger surface area to volume ratios.Cu is the optimal current collector for lithium-ion battery anodes, due to its superior electrical conductivity over stainless steel (SS) and other carbon-based substrates. However, direct growth of Si on Cu yields electrochemically inactive CuSi compounds. [30][31][32] Alternatively, slurry-based Si electrodes suffer from issues of capacity fade as harsh expansion leads to electrical contact loss with the current collector. [33][34][35] Also, issues of capacity fade are heightened for thicker slurry layers, behaving similarly to bulk Si. [36,37] Si composites with graphite have gained huge popularity over recent years, synergistically combining the high lithiation capacity of Si with the low cost, stability, and scalability of carbon. [38][39][40][41][42] Graphite incorporation can alleviate instability issues common with Si-rich electrodes. [43,44] Karuppiah et al. demonstrated impressive long-term stability of slurry-based electrodes of Si NWs directly grown on graphite, retaining 87% capacity after 250 cycles versus Li metal. [44] Similarly, Datta et al. found that Si/graphite stability could be further enhanced through amorphous carbon coating, removing direct contact between Si and the electrolyte, and delivering a stable capacity of 660 mAh g −1 . [45] Slurry-based composites allow for high achievable Si loadings while maintaining anode stability. However, thick slurry layers suffer from poor fast-rate performance and inactive slurry additions negatively impact energy density. [46][47][48][49] The incorporation of Si into metallic or carbonbased frameworks like Mxenes, [50,51] graphene, [52,53] CNTs, [54,55] and CNFs [56,57] has allowed considerable improvements in cell stability, although the continued presence of inactive slurry components increases dead weight. Directly grown electrodes offer a multitude of advantages over slurry-based configurations, however, achieving stable performance of high loading binder-free Si electrodes has historically been difficult.High loading (>1.6 mg cm −2 ) of Si nanowires (NWs) is achieved by seeding the growth from a dense array of Cu 15 Si 4 NWs using tin seeds. A one-pot synthetic approach involves the direct growth of CuSi NWs on Cu foil that acts as a textured surface for Sn adhesion and Si NW nucleation. The high achievable Si NW loading is enabled by the high surface area of CuSi NWs and bolst...

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Section: Resultssupporting

confidence: 89%

A Nanowire Nest Structure Comprising Copper Silicide and Silicon Nanowires for Lithium‐Ion Battery Anodes with High Areal Loading

Collins

Kilian

Geaney

et al. 2021

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“…: 00‐001‐0802), along with Cu, Cu 15 Si 4, and Cu 0.83 Si 0.17 in agreement with the previous reports. [ 10b,11a,13,15 ] The additional reflections of Cu 0.83 Si 0.17 in XRD and absence of this phase in the TEM analysis of nanowire suggest that it only exists in a preformed silicide layer on the Cu foil surface prior to the Cu 15 Si 4 nanowire growth, [ 11a,16 ] and that is the reason it was not identified the HRTEM analysis of NWs (Figure 1j). The Raman spectrum of the Sb@Cu 15 Si 4 NW array shown in Figure S3 (Supporting Information) displays two peaks at 146.3 and 110 cm −1 which are attributed to the A 1g and E g bands of Sb, respectively.…”

Section: Resultsmentioning

confidence: 99%

Directly Deposited Antimony on a Copper Silicide Nanowire Array as a High‐Performance Potassium‐Ion Battery Anode with a Long Cycle Life

Imtiaz

Kapuria

Amiinu

et al. 2022

Adv Funct Materials

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Antimony (Sb) is a promising anode material for potassium-ion batteries (PIBs) due to its high capacity and moderate working potential. Achieving stable electrochemical performance for Sb is hindered by the enormous volume variation that occurs during cycling, causing a significant loss of the active material and disconnection from conventional current collectors (CCs). Herein, the direct growth of a highly dense copper silicide (Cu 15 Si 4 ) nanowire (NW) array from a Cu mesh substrate to form a 3D CC is reported that facilitates the direct deposition of Sb in a core-shell arrangement (Sb@Cu 15 Si 4 NWs). The 3D Cu 15 Si 4 NW array provides a strong anchoring effect for Sb, while the spaces between the NWs act as a buffer zone for Sb expansion/contraction during K-cycling. The binder-free Sb@Cu 15 Si 4 anode displays a stable capacity of 250.2 mAh g −1 at 200 mA g −1 for over 1250 cycles with a capacity drop of ≈0.028% per cycle. Ex situ electron microscopy revealed that the stable performance is due to the complete restructuring of the Sb shell into a porous interconnected network of mechanically robust ligaments. Notably, the 3D Cu 15 Si 4 NW CC is expected to be widely applicable for the development of alloying-type anodes for next-generation energy storage devices.

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“…We have confirmed that no pattern formation is observed when the rate of deposition was increased to 5 Å s −1 . Second, the AFM studies have shown that the total thickness of a particular island was found to be ∼ 150 nm, implying the initial formation of Cu 3 Si layer impedes further diffusion of Cu into the Si which gives the top layer of the islands as pure Cu [18,54].…”

Section: Understanding Growth Behaviourmentioning

confidence: 99%

“…Ordered 2-dimensional (2D) Cu nanostructures on Si(111) have been reported for very low thicknesses by Zang et al [16]. In the recent years, a huge volume of work has been reported on diffusion studies of Cu in Si substrates [17–41]. In most of the studies on the growth of Cu nanostructures on the silicon substrate, the films are deposited at room temperature and post annealed for preparation of nanostructures.…”

Section: Introductionmentioning

confidence: 99%

Understanding substrate-driven growth mechanism of copper silicide nanoforms and their applications

Sen

Kanitkar

Muthe

2023

Materials Science and Technology

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The growth mechanism of various nanoforms of copper/copper silicide on Si substrates with different orientations is reported here. The triangular, square and rectangular copper/copper silicide nanostructures are deposited on silicon substrates with (111), (100) and (110) orientations respectively, by thermal evaporation of metallic copper at different substrate temperatures. Investigations confirm that the nanostructures consist of a pure copper layer on top of a copper silicide layer. The morphology and growth behaviour studies confirmed for the first time that the formation of well-defined structures and shapes are governed by the Si substrate orientation and the surface reconstruction of the Si planes. The copper silicide nanostructures are used in field emission applications and also serve as a template for the growth of carbon nano-fibre.

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Evolution of Hierarchically Layered Cu-Rich Silicide Nanoarchitectures

Cited by 5 publications

References 38 publications

A Nanowire Nest Structure Comprising Copper Silicide and Silicon Nanowires for Lithium‐Ion Battery Anodes with High Areal Loading

A Nanowire Nest Structure Comprising Copper Silicide and Silicon Nanowires for Lithium‐Ion Battery Anodes with High Areal Loading

Directly Deposited Antimony on a Copper Silicide Nanowire Array as a High‐Performance Potassium‐Ion Battery Anode with a Long Cycle Life

Understanding substrate-driven growth mechanism of copper silicide nanoforms and their applications

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