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Energy, Environmental, and Catalysis Applications

Covalently-bonded Si-polymer Nanocomposites Enabled by
Mechanochemical Synthesis as Durable Anode Materials
Wenyue Shi, Hao Bin Wu, Jesse Baucom, Xianyang Li, Shengxiang Ma, Gen Chen, and Yunfeng Lu
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.0c09938 • Publication Date (Web): 05 Aug 2020
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Covalently-bonded Si-polymer Nanocomposites Enabled by Mechanochemical
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Synthesis as Durable Anode Materials
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9 Wenyue Shia, Hao Bin Wuc, Jesse Baucoma, Xianyang Lia, Shengxiang Maa, Gen Chena,b,* and
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11 Yunfeng Lua,*
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14 a Department
15 of Chemical and Biomolecular Engineering, University of California, Los Angeles,
16 Los Angeles, CA 90095, USA
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18 b School of Materials Science and Engineering, Central South University, Changsha, Hunan
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20 410083, China
21 c School of Materials Science and Engineering, Zhejiang University, Hangzhou, Zhejiang 310027,
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23 China
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25 * Corresponding authors: Gen Chen (Email: geenchen@gmail.com), Yunfeng Lu
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27 (luucla@ucla.edu)
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30 KEYWORDS
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33 Silicon/polymer composite; Resilient polymer coating; High-energy ball-milling; Lithium-ion
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35 battery; Silicon anode material;
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ABSTRACT
40 Silicon is one of the most promising anode materials for lithium-ion batteries due to its
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42 high theoretical capacity and low cost. However, significant capacity fading caused by severe
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44 structural degradation during cycling limits its practical implication. To overcome this barrier, we
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design a covalently-bonded nanocomposite of silicon and poly(vinyl alcohol) (Si-PVA) by high-
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47 energy ball-milling of a mixture of micron-sized Si and PVA. The obtained Si nanoparticles are
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49 wrapped by resilient PVA coatings that covalently bonds to the Si particles. In such nanostructure,
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51 the soft PVA coatings can accommodate the volume change of the Si particles during repeated
52 lithiation and delithiation. Simultaneously, as formed covalent bonds enhance the mechanical
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54 strength of the coatings. Due to the significantly improved structural stability, the Si‒PVA
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56 composite delivers a lifespan of 100 cycles with a high capacity of 1526 mAh g‒1. In addition, a
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3 high initial Coulombic efficiency over 86% and an average value of 99.2% in subsequent cycles
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5 can be achieved. This reactive ball milling strategy provide a low-cost and scalable route to
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7 fabricate high performance anode materials.
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12 1. INTRODUCTION
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14 The fast-growing demand for electric vehicles, portable devices and grid-scale energy
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16 storage urges the development of next-generation lithium-ion batteries (LIBs) with higher power
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18 and energy density1–4. Considerable research efforts hence have been devoted to the engineering
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of silicon, a promising anode material with moderate operating potential (0.1~0.4 V) and high
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21 specific capacity (3578 mAh g‒1 for Li3.75Si) in comparison with the current commercial graphite
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23 (0.05 V and 372 mAh g‒1).5–10 Bulk silicon resources are abundant and cost-effective, yet its severe
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25 pulverization and repeated formation of solid-electrolyte interphase (SEI) caused by the huge
26 volume expansion (300%) result in irreversible capacity loss and poor cycling stability.11–13
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28 Therefore, its practical application has been greatly restricted.
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Aiming at improving the structural integrity, a variety of synthetic strategies have been
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32 developed to fabricate silicon nanostructures.14–19 Significantly, special attention has been put into
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34 the protection of silicon with functional coating layers, involving different methods such as
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36 CVD,20–22 heat treatment,14,23–25 sol-gel26,27 and so on.28–31 However, the complexity, inefficiency
37 and high-cost generally impede their large-scale production and adaption. High-energy ball-
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39 milling (HEBM) has been reported as a low-cost, high-yield and scalable method for the efficient
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41 production of silicon nanomaterials, which is feasible for industrial manufacture.32 Different from
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mixing ball-milling, energy can be re-dispersed and transported by HEBM with strong friction and
44 collision. More interestingly, the precedents of organic reactions and synthesis of metal-organic
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46 frameworks demonstrate the feasibility of building chemical bonds through HEBM.33–35 As for
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48 the preparation of Si-based anode materials, HEBM has mostly been engaged in size breaking-
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down alone. With the smaller size benefited from HEBM, nanoporous Si particles can be obtained
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51 with further wet etching process.36,37 Combined with necessary post-processing treatment, robust
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53 chemical connection with protective layers can be constructed.38–41 However, the concept of
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3 reactive high-energy ball-milling (RBM) has rarely been applied for the direct production of
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5 silicon nanocomposites with chemically bonded coating layers.
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Herein, we report polymer-coated silicon nanocomposites with in situ generation of
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9 covalent bonds between Si nanoparticles and poly(vinyl alcohol) (PVA) by a solvent-free, one-pot
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11 and no-post-process RBM method. PVA acts as the resilient component in the composites because
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13 of its high tensile strength and flexibility. The flexible covalently-bonded coating buffers the
14 volume expansion of the silicon during lithiation process, which effectively prevents the particles
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16 from pulverization and maintains the integrity of electrode. The size of Si nanoparticles can be
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18 adjusted by regulating the content of PVA, among which silicon nanoparticles coated by 5% PVA
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deliver the optimal electrochemical properties. A reversible specific capacity of 1526 mAh g‒1 is
21 obtained at 200 mA g‒1 after 100 cycles with loading of 1 mg cm‒2. A high initial Coulombic
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23 efficiency (ICE) over 86% and an average of 99.2% have been achieved.
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28 2. EXPERIMENTAL SECTION
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2.1 Synthesis for PVA Coated Silicon Composite
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33 Silicon (99%, ~325 mesh) and poly(vinyl alcohol) (MW 89,000-98,000, 99% hydrolyzed)
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35 were purchased from Sigma-Aldrich without further purification. Si and different amount of PVA
36 (0, 2 wt%, 5 wt%, 10 wt%) were mixed in the jars with the ball-to-powder ratio of ~12, sealed in
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38 argon atmosphere, and milled by the high-energy ball-miller (Retsch, High Energy Ball Mill Emax)
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40 at 1000 rpm. After 10 h, all powder was collected without further treatment.
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42 2.2 Structural Characterization
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Crystalline structures of the Si-PVA powder were determined by the Rigaku powder X-ray
46 diffractometer (XRD) using Kα radiation (λ = 1.54 Å). Surface morphology and particle sizes
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48 were investigated by scanning electron microscopy (Nova 230 Nano SEM), transmission electron
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50 microscopy (FEI T12 Quick CryoEM and CryoET TEM) and High-resolution transmission
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electron microscopy (FEI Titan S/TEM). Raman spectra was conducted on a Renishaw 2000
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53 System with a He/Ne laser at a wavelength of 633 nm. Infrared spectra experiments were carried
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55 out by a transmission mode on a Jasco 420 Fourier transform infrared (FTIR) spectrophotometer.
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3 Thermogravimetric analysis (TGA) was performed in argon atmosphere by a ramping rate of 10
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5 oC min‒1. Gas sorption measurements were conducted using a Micromeritics ASAP 2020 system
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7 at 77 K. Prior to gas adsorption/desorption measurement, all power was degassed at 120 °C for
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12 h. For X-ray photoelectron spectroscopy (XPS) studies, AXIS Ultra DLD was used for analysis.
10 All the spectra were fitted to Gaussian–Lorentzian functions and a linear-type background using
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12 CasaXPS software. The binding energy values were all calibrated using C 1s peak at 284.5 eV.
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14 2.3 Electrochemical Characterization
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17 The electrochemical performance was evaluated using 2032-type coin cells with the Li foil
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as the counter/reference electrode. The working electrodes were comprised of active materials
20 (Si-PVA composite), acetylene black, and poly(acrylic acid) (PAA) binder with the weight ratio
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22 7:2:1 and were fabricated using a typical slurry method. The mass loading of the active material
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24 was ~1 mg cm−2 for each electrode. The electrolyte was 1 M LiPF6 in a mixture of ethylene
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carbonate (EC)/diethyl carbonate (DEC) with a volume ratio of 1:1 (LP40, BASF), and 5 vol%
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27 fluoroethylene carbonate (FEC, Sigma-Aldrich) was used as an additive. The assembled cells
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29 were galvanostatically cycled between 0.05 and 2 V vs Li+/Li at different current densities using
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31 a LAND battery testing system (China). The specific capacities were calculated based on the total
32 mass of the Si-PVA powder. Cyclic voltammetry (CV) experiments for the first cycles were
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34 performed using the electrochemical station Solartron 1860/1287 with a scan rate of 0.1 mV s−1
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36 from open-circuit voltage (OCV, ∼3 V vs Li/Li+) to 0 and back to 2 V. Electrochemical impedance
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spectroscopy (EIS) data were recorded ranging from 100 kHz to 10 mHz with a voltage amplitude
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44 3. RESULTS AND DISCUSSION
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47 The synthetic strategy is schematically illustrated in Figure 1. The bulk silicon powder
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and PVA without any solvent are sealed in argon atmosphere in a ball-milling jar. Bearing the
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50 impact from the steel balls, the micron-sized silicon is ground into nanoparticles. Simultaneously,
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52 the mechanical energy also triggers the chemical reaction between freshly exposed surface of
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54 silicon nanoparticles and reactive hydroxyl groups of PVA. Due to the low dissociation energy of
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3 O-H bonds42, the hydroxyl groups on PVA cleave and form Si-O-C bonds, generating
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5 nanocomposites of PVA coated silicon nanoparticles with robust chemical bonding.
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26 Figure 1. Schematic diagram of the reactive ball-milling (RBM) process starting with bulk silicon and the
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28 product of poly(vinyl alcohol) (PVA) coated silicon nanoparticles with the covalent bonds between PVA
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and the silicon on the surface.
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33 The samples with different amount of PVA relative to silicon are denoted as RBM Si-
34 2%PVA, RBM Si-5% PVA and RBM Si-5%PVA, respectively. Pure ball-milled Si without
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36 adding PVA is denoted as HEBM Si. The Raman spectrum of crystalline silicon generally contains
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38 one sharp peak at 520 cm‒1, which will redshift in a size-dependent manner.43 Compared to raw
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silicon materials, the characteristic peak of ball-milled silicon-PVA nanocomposite in Raman
41 spectrum shifts from 520 to 504 cm‒1 (Figure 2a) with different content of PVA, indicating the
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43 formation of Si nanocrystals. The corresponding peak of HEBM Si, however, appears at a slightly
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45 higher wavenumber, suggesting a larger particle size than that of the PVA coated silicon.
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47 X-ray diffraction (XRD) patterns presents accordant results (Figure 2b). Increasing the
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49 content of PVA in the composite significantly broadens the widths of diffraction peaks of (111),
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51 (220) and (311) of Si-PVA composites, which directly confirms the reduced crystalline size in the
52 presence of PVA. Due to the turbulent crushing during RBM, the crystalline silicon experiences
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54 a deformation into amorphous structure on the edge of the particles as suggested by the reduced
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56 peak intensity in the XRD patterns, which might benefit the kinetics of lithium ions transport.8 N2
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3 sorption isotherms indicate a rising BET surface area with the addition of PVA due to the reduced
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5 particle size (Figure S1). Starting from micron-size silicon with a BET surface area of only 5.1
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7 m2 g‒1, Si-PVA nanocomposites deliver much enlarged BET surface areas of 11.1, 17.4 and 19.2
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m2 g‒1 for Si-2%PVA, Si-5%PVA and Si-10%PVA, respectively. The different volume of these
10 samples (Figure 2c) with the same weight indicate a reduced tap density and thus a decreasing
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12 particle size. Based on the tap density of Pristine Si, the tap densities of ball-milled powders are
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14 calculated accordingly and presented in Table S1.
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37 Figure 2. Characterizations of bulk silicon, HEBM Si, and RBM Si-PVA nanocomposites. (a) Raman
38 spectrum, (b) XRD pattern, (c) photographs comparing the tap density, TEM images of (d) HEBM Si and
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40 (e) RBM Si-5% PVA and (f) HR-TEM image of RBM Si-5% PVA.
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43 SEM characterizations were carried out to examine the morphology of samples after ball
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45 milling. Owing to the exposure of the high-energy surface of the particles during HEBM, the
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secondary aggregation of the nanoparticles is usually severe and inevitable. Without additional
48 PVA, the finely crushed primary HEBM Si particles naturally aggregate into secondary particles
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50 up to 10 μm, which dispossesses the advantages of nanomaterials and renders a drastic structural
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52 transition during lithiation and delithiation. By forming covalent bonds between the PVA and Si
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particles, the active surface is chemically quenched, which effectively mitigates the formation of
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55 aggregates. The RBM Si-5%PVA primary particles are typically below 200 nm (Figure S2a),
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3 notably smaller than the HEBM Si (Figure S2b). Most of the secondary particles of RBM Si-
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5 5%PVA fall in the range of 0.5-1 μm. TEM images display more distinct differences. The RBM
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7 Si-5% PVA particles are around 200 nm and well-dispersed (Figure 2e). In contrast, the HEBM
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Si appears as an aggregation with size over 2 μm (Figure 2d). The sizes of RBM Si-2%PVA and
10 RBM Si-10%PVA are consistent with the BET results as well (Figure S3). The diffraction spots
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12 corresponding to (111), (220) and (311) lattice planes of polycrystalline silicon can be found in
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14 the SAED pattern (Figure S4). The (111) lattice of silicon with an interplanar spacing 0.32 nm
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can be determined in the HRTEM image (Figure 2f). More importantly, a layer of amorphous
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17 domain is observed around the Si nanocrystals, which may be assigned to the polymer coating
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19 and/or amorphous Si. The Si nanoparticles are effectively separated by the in situ formed polymer
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21 framework and the agglomeration is therefore remarkably suppressed during HEBM. Such unique
22 structure might accommodate the volume change of Si, and also prevent the Si particles from
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24 aggregation upon repeated lithiation/delithiation.
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The formation of covalent bonds between Si and PVA during the ball-milling process is
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28 further supported by the X-ray photoelectron spectroscopy (XPS) profiles. Typical peaks for Si in
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30 Si 2p spectrum located at 99.6, 100.3, 100.9 and 103.5 eV represent Si 2p3/2, Si 2p1/2, Si-O and
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32 SiO2, respectively (Figure 3a).44 All these peaks remain in the spectrum of RBM Si-5%PVA. In
33 addition, a new peak at 102.5 eV corresponding to Si-O-C bonding appears,45 probably due to the
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35 reaction between hydroxyl groups (-OH) from PVA and freshly exposed surface of silicon particles
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37 during RBM (Figure 3b). After the RBM process, the C-H/C-C peak (284.8 eV) from PVA
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polymer chain remains in C 1s spectrum, while the original C-OH peak at 286.3 eV is replaced by
40 a new peak at 286.9 eV for Si-O-C (Figure 3c, d). Consistently, in O 1s spectrum, the Si-O-C peak
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42 (532.2 eV) in RBM Si-5%PVA completely replaces the C-OH peak (533.4 eV) in PVA (Figure
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44 3e, f, and S5).46 These observations imply that hydroxyl groups in PVA have fully reacted with
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silicon during RBM and a layer of Si-O-C coating layer has formed on the surface of silicon. The
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47 FTIR result provides direct evidences of the covalent bonds on the coated silicon particles surface
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49 (Figure 3g). The peak of Si-O-Si stretching around 1150-1200 cm‒1 for HEBM Si 47 also appears
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51 in the spectrum of RBM Si-5%PVA, while the C-O peak in PVA for RBM Si-5%PVA shows up
52 at around 1100 cm‒1. More importantly, the characteristic peak of Si-O-C locates at around 1020
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54 cm‒1. Additionally, the chemical linking between PVA and Si particles after RBM is confirmed
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56 by TGA. Both RBM Si-5%PVA and HEBM Si exhibit extraordinary thermal stability up to 1000
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C, compared to pure PVA with major weight loss occurring at around 250 C (Figure 3h).
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5 Different from extensively reported physical coating/wrapping on the surface of Si nanoparticles,
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7 RBM is capable to achieve in situ generation of covalent bonds, inducing a robust shell to protect
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9 silicon particles. Furthermore, the complete removal of reactive groups in the raw materials might
10 also improve the electrochemical stability.
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31 Figure 3. Characterizations of the chemical structure of the HEBM Si and RBM Si-5%PVA. Si 2p XPS
32 spectra for (a) HEBM Si and (b) RBM Si-5% PVA. C 1s XPS spectra for (c) PVA and (d) RBM Si-5%
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34 PVA. O 1s XPS spectra for (e) PVA and (f) RBM Si-5% PVA. (g) FTIR and (h) TGA for PVA, HEBM Si
35 and RBM Si-5% PVA.
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39 The electrochemical lithiation/delithiation performances of the as-prepared silicon
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particles were investigated in half-cell configurations. Figure 4a displays the CV feature of the
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42 RBM Si-5%PVA for the first four cycles. In the first cycle, the distinctive cathodic peak around
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44 0.05 V reveals the initial formation of LixSi (0x3.75) alloy process. The two anodic peaks at
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46 0.36 V and 0.53 V can be assigned to the phase transformation from high-Li-content to low-Li-
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content LixSi alloys and eventually to amorphous Si. The subsequent scans exhibit similar CV
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49 profiles, with another cathodic peak emerging at 0.18 V. The current increases steadily as the
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51 scans proceed, implying an activation process and formation of stable SEI on the electrode surface.
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53 Besides the well-established lithiation/delithiation peaks, no side reaction was detected, which is
54 attributed to the elimination of reactive groups during RBM process.
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3 Galvanostatic charging/discharging at 0.2 A g‒1 for RBM Si-5%PVA discloses stable
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5 voltage profiles with well-defined charging/discharging plateaus. With the increasing content of
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7 PVA in the active materials, the specific capacity slightly decreases. Meanwhile, stability of the
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electrodes is notably improved, leading to higher capacity retention upon cycling. The initial
10 capacity for bare HEBM Si is 3255 mAh g‒1 with an ICE of only 83.0%, along with fast capacity
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12 fading (Figure 4b). The stability is slightly improved with 2% of PVA. Nonetheless, the RBM
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14 Si-5%PVA electrode exhibits initial specific capacity of around 3000 mAh g‒1 and an ICE of 86.1%
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with negligible capacity loss in the first three cycles (Figure 4c). The RBM Si-10%PVA shows a
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17 similar stability compared with RBM Si-5%PVA while the initial specific capacity drops to 2434
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19 mAh g‒1 due to the higher weight ratio of inactive PVA (Figure S6). Through the PVA coating,
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21 the stability and the ICE of the electrodes are greatly improved with minimal sacrifice on the
22 specific capacity.
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3 Figure 4. Electrochemical characterizations of the RBM Si-PVA anodes. (a) CV for RBM Si-5%PVA
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5 sample. Galvanostatic charging/discharging profiles for (b) HEBM Si and (c) RBM Si-5%PVA. (d) Rate
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7 performance of HEBM Si and RBM Si-5%PVA electrodes with the loading of 1 mg cm‒2. (e) Long-term
8 cycling performances of ball-milled silicon materials at 0.2 A g‒1 with the mass loading of 1 mg cm‒2. (f)
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10 EIS profiles of RBM Si-5%PVA electrode before and after cycling. Inset: magnified EIS profiles of the
11 high frequency region. (g) Fast charging/discharging (3.0 A g‒1) performance of RBM Si-5%PVA electrode
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13 with the mass loading of 1 mg cm‒2.
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16 Figure 4d compares the rate performance of RBM Si-5%PVA and HEBM Si electrodes.
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18 Ranging from 0.15 to 3.0 A g‒1, the capacity of electrode drops stepwise to 801 mAh g‒1 and
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20 recovers to 2234 mAh g‒1 once the current returns to 0.15 A g‒1. Figure 4e shows the galvanostatic
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cycling stability of the ball-milled silicon materials with a loading of 1 mg cm-2 and a current
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23 density of 0.2 A g‒1. In contrast to the drastic capacity fading of HEBM Si, Si-PVA
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25 nanocomposites synthesized through RBM present enhanced stability and higher capacity
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27 retention. It is noteworthy that the RBM Si-5%PVA offers the best improvement. Besides a high
28 ICE of 86.1% as mentioned earlier, the Coulombic efficiency (CE) rapidly reaches over 97% from
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30 the second cycle onwards (Table S2). After being activated in the first 10 cycles, the electrode
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32 steadily becomes stabilized and remains stable for later cycles, with 1526 mAh g‒1 reversible
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specific capacity retained after 100 cycles and an average CE of 99.2%. A substantial capacity
35 loss to 1395 mAh g‒1 occurs in the first 5 cycles for RBM Si-10%PVA electrode, ending up with
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37 a reversible capacity of 798 mAh g‒1 after 100 cycles. We speculate that the severe polymer
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39 solvation and swelling from the higher content of PVA leads to a more significant structural change,
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thus causing the quick capacity fade in the first several cycles. In addition, HEBM Si is simply
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42 stirred and mixed with 5% of PVA to demonstrate the vital role of RBM. Owing to the side
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44 reactions with the electrolytes induced by the reactive groups on PVA, the ICE is hardly over 70 %.
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46 Without the robust chemical interaction to preserve the integrity, the electrode quickly fails. EIS
47 tests were conducted simultaneously at different cycle numbers. The diameters of the semicircles
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49 in the plots were evaluated with the measurement and indicate the charge transfer resistance (Rct)
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51 of the cell.48,49 For fresh electrodes, the resistance first gradually decreases from 316 Ω (HEBM
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Si) to 240 Ω (RBM Si-5%PVA), due to the improved ion transportation kinetics benefited from
54 the reduced particle sizes. However, when the PVA content has reached 10%, the charge transfer
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56 resistance increases back to 340 Ω, indicating the role of non-conductive additive PVA has
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3 overruled the slight size decrease compared to RBM Si-5%PVA (Figure S7). This result provides
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5 another explanation for the superior cell performance with RBM Si-5%PVA. After the first cycle
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7 of galvanostatic charging/discharging for the RBM Si-5%PVA electrode, the impedance reduces
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dramatically to 56 Ω, suggesting the formation of ionic conductive SEI layer. The impedance of
10 the cell continues to decrease until it reaches 21 Ω after the 50th cycle, and remains stable at 21 Ω
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12 to the 100th cycle (Figure 4f). At the beginning of cell cycling, the formation of SEI layers and
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14 improved interfacial contact that can be ascribed to the activation and wetting process significantly
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enhanced the charge transfer capability. Eventually, the Rct maintains constant, revealing a
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17 stabilized SEI layer and mitigated Si pulverization. To strike a balance between the capacity and
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19 stability, RBM Si-5%PVA is preferentially selected for the additional cycling tests. Further
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21 increasing the current density to 3.0 A g‒1, the RBM Si-5%PVA electrode delivers a reversible
22 specific capacity 750 mAh g‒1 after 150 cycles (Figure 4g). Through the covalent linking between
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24 silicon and PVA protective layer by RBM, the electrochemical performances in terms of CE and
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26 cycling stability of the electrode are greatly improved.
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3 Figure 5. (a) Schematic diagram of the lithiation/delithiaion process of the ball-milled silicon materials.
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5 (b-g) Morphology of cycled silicon electrodes. SEM images of (b, c, d) HEBM Si electrodes and (e, f, g)
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RBM Si-5%PVA after (b, e) one, (c, f) five and (d, g) ten cycles, respectively.
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Figure 5a illustrates the working mechanism of the resilient PVA coating that promotes
12 the cycling stability of the silicon electrodes. On the surface of silicon, the flexible polymer PVA
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14 with a linear chain structure can stretch and contract along with the volume expansion and
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16 shrinkage of silicon particles during lithiation and delithiation. Unlike solely physical contact, the
17 stable chemical bonding between the PVA chains and particles surface prevents phase separation
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19 during the volume variation of silicon. The PVA coating acts as a resilient buffer layer to
20
21 accommodate the volume expansion and thus prevents the particles from pulverization. As a result,
22
23
the integrity and thus cycling stability of the electrode would be notably improved. SEM images
24 of cycled electrodes provide a visible demonstration of the improved mechanical stability of Si-
25
26 PVA nanocomposites. After only one cycle of lithiation/delithiation, the surface of HEBM Si
27
28 electrode becomes rough with deep cracks with a typical width of 10.5 μm (Figure 5b). The
29
electrode film continuously breaks down upon cycling (Figure 5c), leading to obvious
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31 disintegration after 10 cycles with almost 20 μm width cracks (Figure 5d). On the other hand, only
32
33 minor crevices typically 2.0 μm in width on the surface of electrode is observed for RBM Si-
34
35 5%PVA (Figure 5e), and the electrode remains generally intact from the 5th to the 10th cycle (Figure
36 5f, g). The RBM Si-10%PVA electrode shows a similar result (Figure S8). With only 5% PVA
37
38 coating, we successfully mitigate the pulverization and thus enhanced the cycling stability of the
39
40 silicon anodes.
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43
44
45 4. CONCLUSIONS
46
47 In conclusion, we successfully developed an efficient RBM strategy for large-scale
48
49 preparation of Si-PVA nanocomposites as anode materials for LIBs by using in situ chemical
50
51 reaction between silicon particles and the hydroxyl groups on PVA chains. The Si-PVA
52
nanocomposite with 5% PVA exhibits a primary size of Si within 200 nm coated by PVA through
53
54 Si-O-C covalent bond on the surface. By varying the weight ratio of PVA, the sizes of the particles
55
56 can be regulated, among which 5% PVA coated silicon particles demonstrate optimal
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3 electrochemical performances. At 0.2 A g‒1, the RBM Si-5%PVA delivers a reversible capacity
4
5 over 1526 mAh g‒1 after 100 cycles, with an ICE over 86.1% and an average CE of 99.2%. Raising
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7 the current to 3.0 A g‒1, a capacity around 800 mAh g‒1 after 150 cycles can be maintained. The
8
9
superior electrochemical performance can be attributed to the following aspects: (1) nanosized Si
10 particles from ball milling greatly shorten the diffusion pathway of Li+, leading to enhanced
11
12 kinetics; (2) polymer coating effectively reduces the size of primary nanoparticles; (3) the resilient
13
14 PVA coating layer with robust covalent bond is adaptive to the volume change of silicon particles.
15
Therefore, the severe pulverization of Si-based anode is effectively alleviated. In addition, the
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17 synthetic strategy features one-pot and solvent-free reaction without post-procedure, as well as
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19 low cost of the raw materials, thus being suitable for industrial manufacturing. Thus, the RBM
20
21 method developed in this work offers a feasible approach to fabricate Si-based anode materials for
22 next-generation LIBs.
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24
25
26
27 ASSOCIATED CONTENT
28
29 Supporting Information
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31
32
The Supporting Information is available free of charge on the ACS
33
34 Publications website at http://pubs.acs.org.
35
36 Supporting information includes materials and electrochemical
37
38 characterizations.
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40
41
42
43 AUTHOR INFORMATION
44
45
46 Corresponding Author
47
48 * E-mail: geenchen@gmail.com, luucla@ucla.edu
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50
51
52
53 Acknowledgement
54
55
56 We are grateful for the support of the UCLA-Dynavolt Research Center.
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