Waste LCD Glass-directed Fabrication of Silicon Particles for Lithium

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Waste LCD Glass-directed Fabrication of Silicon Particles for Lithium Ion Battery Anodes Woohyeon Kang, Jae-Chan Kim, Jun Hong Noh, and Dong-Wan Kim ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.9b02654 • Publication Date (Web): 17 Aug 2019 Downloaded from pubs.acs.org on August 18, 2019

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ACS Sustainable Chemistry & Engineering

Waste LCD Glass-directed Fabrication of Silicon Particles for Lithium Ion Battery Anodes

Woohyeon Kang‡, Jae-Chan Kim‡, Jun Hong Noh, and Dong-Wan Kim*

School of Civil, Environmental and Architectural Engineering, Korea University, 145 Anamro, Seongbuk-gu, Seoul 02841, South Korea

*Corresponding Author Tel.: +82 2 3290 4863; fax: +82 2 3290 5999; E-mail: [email protected]. (D.-W. Kim)

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ACS Sustainable Chemistry & Engineering 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Abstract The rapid increase of waste liquid crystal display (LCD) is becoming a serious problem. Among the constituents of waste LCD panels, glass substrates are not completely recycled and buried in landfills due to the lack of recycling technologies. In order to establish recycling strategy with sustainable process and application, we fabricated silicon (Si) materials into lithium ion battery (LIB) anodes through the magnesiothermic reduction of waste LCD glasses. To synthesize high-quality Si materials, an optimized pre-treatment process is proposed to remove undesirable contents from waste LCD glasses. In the purpose of achieving high areal capacity for practical applications, we conducted facile and cost-effective electrode maturation, which improves the cohesion and adhesion of the Si anodes. The electrochemical measurement results showed that the waste LCD glass derived Si electrodes exhibited high areal and gravimetric capacity of 6.3 mA h cm−2 and 3438 mA h g−1, respectively, in the initial cycle. The electrodes maintained high areal capacity of 3.1 mA h cm−2 during the 100th cycle. This reduced Si materials and electrode-manufacturing process can be a cost-effective and sustainable recycling technology for waste LCD glass management and anode material for LIBs.

Keywords: Waste LCD glass, Magnesiothermic reduction, Silicon, Lithium ion batteries, Anode


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Introduction Worldwide effort to establish a sustainable society has triggered the development of ecofriendly energy production and storage technologies.1,2 In particular, lithium ion battery (LIB) technologies have been dramatically improved since it can be applied to green industries such as electric vehicles and energy storage systems for smart grids.2-4 Despite incredible growth that LIB underwent, commercial LIBs are facing limitations in above-mentioned green industries due to limited energy density of anode materials.1,5,6 To overcome this problem, Si anodes have been intensively studied as the most potential alternative to commercial graphite anodes in LIBs owing to their high theoretical capacity (3579 mA h g−1 for Li3.75Si), low working voltage, and environmental benignity.5,7-9 In line with these trends, various research has been reported fabricating Si anodes using waste materials or biomass in the purpose of fabricating eco-friendly Si anodes.10-14 Liquid crystal displays (LCDs) have been dominating the display market in various applications such as monitors, portable devices, and household.15,16 According to the statistics, global supply of large area LCDs reached 683.5 million units in 2016, and it is predicted that the demand will increase to ~217 million m2 in 2021.16 In conjunction with the tremendous supply and demand of LCDs, considerable amount of waste LCDs are generated, which has become a serious social problem. Liu et al. predicted that the total display area of waste LCDs in China will reach 5539 km2 in 2020.15 Valuable components in waste LCDs, such as indium from indium tin oxide films,17,18 and printed circuit boards are recovered or recycled.19,20 However, waste LCD glass substrates are not completely recycled, thus being incinerated or buried in landfills owing to lack of recycling technologies.21 Some researchers have suggested recycling strategies such as reusing as foamed glasses,21 feed material for ceramic tiles,22,23 glass ceramics,24,25 and aggregate for concretes;26,27 however, none of these are practically



utilized. In order to reduce discarded waste LCD glasses, diversification in recycling methods for waste LCD glasses is required. LCD glass substrates are typical alkaline-earth aluminoborosilicate glasses, which are mainly composed of amorphous SiO2 (~60 wt%), Al2O3, B2O3, CaO, and SrO.28 Regarding high SiO2 content in waste LCD glasses, fabricating them into metallurgical grade Si can be an economically valuable recycling strategy. Metallurgical grade Si can be produced through various methods such as reduction of SiF4,29 chemical vapor deposition of silane,30 and carbothermal reduction (CR) of silica precursor in arc furnace,31 and magnesiothermic reduction (MR). On an industrial scale, MG-Si is synthesized through CR of silica.31,32 However, commercial CR lacks eco-friendliness and sustainability due to extremely high reduction temperature of 2000 °C, which emits a massive amount of CO2 to atmosphere.1,32 MR are usually operated at a relatively low temperature near 600°C, that is suitable reduction method for waste LCD glass in the terms of environment and sustainability issue. Despite these advantages, industrial wastes require intensive energy and time to leach impurities and organic components. The impurities can remain as inert species after MR, which cannot be removed by acid treatment. Therefore, waste LCD glasses require an optimized leaching process to fabricate MG-Si. Herein, we pre-treated waste LCD glasses via a facile process including ball milling and HNO3 treatment to remove impurities such as Al, Ca, Sr, and B contents. Through subsequent MR, waste LCD glass derived Si was successfully synthesized in economical and sustainable manners. In order to establish recycling strategy with sustainable synthesis and application, we fabricated waste LCD glass derived Si into LIB anodes. However, main challenges of Si anodes still remain, such as drastic volume expansion (~300 %) and fracture during lithiation/delithiation. The repeated dramatic volume changes upon cycling lead to the collapse of the electrode integrity, thereby causing rapid capacity fading and low coulombic 4 ACS Paragon Plus Environment

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efficiency.5,33,34 For practical applications, the areal capacity should be around 3.5 mA h cm−2.35 In order to enhance the areal capacity, loading mass of active materials should be increased. However, the volume expansion issue worsens as loading mass increases because stable film thickness is limited by the binder bonding strength, which entangles active material and current collectors during repeated volume change. To overcome this problem, various research on robust binder systems which enable long-term stability of Si electrodes have been proposed.3640

Among these, recently, Hernandez et al. reported the importance of post-treatment and

improved the binding system to improve the mechanical stability of Si electrodes without material modification by nanostructuring or carbon coating. This post-treatment can improve not only the cohesion between Si materials but also adhesion between Si and Cu substrates.40 Herein, we prepared waste LCD glass derived Si anode using carboxylmethyl cellulose (CMC) binder and post-treatment. The fabricated Si anodes delivered a high areal capacity of 3.1 mA h cm−2 in 100th cycle through mechanical reinforcement of the electrode, thereby resulting in moderate capacity fading.

Experimental Materials The collected waste LCD glass scrap were provided by the Institute for Advanced Engineering (Korea) and as-received waste LCD glass were manually crushed, ground, and sieved (through 200 mesh) to obtain fine waste LCD glass powder (WL). Mg powder (99.5 %) was purchased from Hana AMT (Korea) and used for magnesiothermic reduction (MR). All liquid reagents were purchased from SAMCHUN chemical (Korea) and used without further purification.

Preparation of ball-milled WL (bm-WL), HNO3 treated WL (HN-WL), and ball5 ACS Paragon Plus Environment


milled/HNO3 treated WL (bmHN-WL) WL was ball milled and/or HNO3 treated before MR. Ball milling was conducted with WL (5 g) dispersed in deionized water (DIW; 100 mL) at the speed of 180 rpm for 24 h. The ballmilled suspension was filtered by a poly(vinylidene fluoride) membrane (Durapore®, 0.45 µm) using a pressure filtration system. Subsequently, the collected products were freeze dried to obtain bm-WL. HN-WL was fabricated by treating WL (5 g) in 5 M HNO3 (100 mL) at 60 °C for 72 h followed by washing with DIW and freeze drying. The bm-WL was subjected to the same HNO3 treatment and named bmHN-WL.

Fabrication of bm-Si, HN-Si, and bmHN-Si bm-WL (0.5 g) was homogeneously mixed with Mg powder (0.4 g) in a mortar and the mixture was sealed up in a stainless-steel ampoule. The ampoule was heated at 650 °C for 6 h at a heating rate of 5 °C/min. The whole process was conducted under argon atmosphere. Asobtained product was treated with 2 M HCl for 1 h to etch Mg by-products. Subsequently, residual SiO2 was removed by soaking in 5 wt% HF aqueous solution for 1 h. Finally, bm-Si was obtained after washing with DIW several times. HN- and bmHN-Si were fabricated through the same procedure by using HN- and bmHN-WL as SiO2 precursors.

Material characterization Samples were characterized by field-emission scanning electron microscopy equipped with energy dispersive X-ray spectroscopy (SEM-EDX; SU–70, Hitachi, Japan), particle size analysis (PSA; ELSZ-1000, Otsuka Electronics, Japan), wavelength dispersive X-ray fluorescence spectrometry (XRF; ZSX Primus IV, Rigaku), X-ray diffraction (XRD; Ultima III, Rigaku, Japan), X-ray photoelectron spectroscopy (XPS; K-Alpha+, Thermo Fisher Scientific Messtechnik), and transmission electron microscopy equipped with EDX (TEM6 ACS Paragon Plus Environment

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EDX, JEM-2010, JEOL, Japan). Additionally, the composition of bm-WL and WL were analyzed by inductively coupled plasma atomic emission spectrophotometer (ICP-AES; Ultima 2, Jobin Yvon Horiba, Japan). After the HNO3 treatment of bm-WL and WL, the acidic suspension was thoroughly filtered followed by washing with DIW. The filtrate and DIW used for washing were gathered, diluted to 1.9 L, and analyzed by ICP-AES. The leached amount in terms of concentration (wt%) was calculated by dividing the weight (mg) of Al, B, and Ca by a total sample weight of 5 g, based on ICP-AES results.

Electrochemical performance bm-, HN-, and bmHN-Si were used as active materials for working electrodes. For the preparation of an electrode, slurry was prepared by mixing active material (72.6 wt%), super P (10.9 wt%), CMC (7.3 wt%, Mw = ~90,000, Aldrich), citric acid (CA; 6.5 wt%), and potassium hydroxide (KOH, 2.8 wt%) with DIW. The specific amounts of CA and KOH were set to make slurry as a pH 3 buffer solution. Standard electrodes were fabricated by slip casting using the above-mentioned slurry on a copper substrate followed by drying at room temperature for 2 h and additional drying at 70 °C for 12 h. The matured electrodes were prepared by storing the room temperature dried film in a chamber with 99 % relative humidity for 48 h and then drying at 70 °C for 12 h. The electrodes with active material loading mass between 1.5 and 2.0 mg cm−2 were chosen for electrochemical evaluation. Half cells were assembled in an argon-filled glove box using Swagelok-type cell composed of a working electrode, Li foil for counter electrode, glass microfiber separator (GF/F, Whatman), and liquid electrolyte of 1.0 M LiPF6 EC/DMC = 1:1 v/v with 10 vol% FEC additive. Galvanostatic cycler (4300K, Maccor, USA) was used to evaluate the electrochemical properties in the voltage range of 0.01 to 1.5 V (vs. Li/Li+). CV was tested at a 0.1 mV s−1 scan rate in the same voltage range. 7 ACS Paragon Plus Environment


Results and discussion Characterization of WL, bm-WL, HN-WL, and bmHN-WL Figure 1 illustrates the overall process of synthesizing three kinds of Si via MR using pretreated waste LCD glass as a SiO2 precursor. To fabricate highly pure Si, two purification methods were applied to WL before MR. Firstly, waste LCD glasses were manually crushed, ground, and sieved (through 200 mesh) to obtain the white fine powder of WL as shown in Figure 1. Three kinds of raw materials of bm-WL, HN-WL, and bmHN-WL were fabricated to demonstrate the effect of pre-treatment. Subsequently, bm-, HN-, and bmHN-WL were subjected to MR and termed as bm-, HN-, and bmHN-Si, respectively.

Figure 1. Illustration of the procedure to synthesize bm-Si, HN-Si, and bmHN-Si from waste LCD glasses.


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Compositional determination was conducted by XRF and ICP-AES for all WL samples. The XRF results are depicted in Figure 2a with analyte (element) concentration in weight percentage. The detailed XRF results with compound (oxide) and analyte concentrations are shown in Figure S1. WL consists of SiO2 (52.74 wt%), Al2O3 (16.59 wt%), B2O3 (14.03 wt%), CaO (7.03 wt%), and SrO (6.42 wt%) as oxides and Si (23.63 wt%), Al (8.4 wt%), B (4.16 wt%), Ca (4.84 wt%), and Sr (5.24 wt%) as elements (Figure S1a). The XRF results of WL represent chemical composition of LCD glass substrates, which correspond to the chemical composition of alkaline-earth aluminoborosilicate glass.23,28 After ball milling in DIW for 24 h (bm-WL), the Si and Al content of bm-WL increased to 24.32 and 8.62 wt%, respectively, while B, Ca, and Sr content decreased to 3.47, 4.62 and 4.85 wt%, respectively (Figure S1b). Considering that alkaline-earth ions (Ca2+ and Sr2+) and boron ions in alkaline-earth aluminoborosilicate glasses are susceptible to water, these ions at the surface of WL dissolved in water, thus decrease in content.16,41,42 However, impurity removal effect of ball milling in DIW is not strong enough because it could not remove Al3+ and a large amount of Ca2+ and Sr2+. Therefore, HNO3 treatment was conducted to remove Al3+ and alkaline-earth ions in WL. From the XRF results of HN-WL, the Si content increased to 27.29 wt% and that of Al, Ca, and Sr decreased to 7.68, 4.45, and 5.04 wt%, respectively (Figure S1c). It can be assumed that HNO3 treatment contributed to reducing Al content of WL. However, contents of most of the elements slightly decreased because of the extremely large particle size of WL which limits the intrusion depth of HNO3 treatment.43 After HNO3 treatment of WL (HN-WL), B content was not detected because of photon reabsorption that limits analysis depth of light elements (i.e. B) in XRF analysis.44 Since near surface B content of HN-WL was removed by HNO3 treatment, B content could not be detected.



Figure 2. Physical and chemical analysis of WL samples. (a) XRF results of all WL samples in analyte (element) concentration. SEM images of (b) WL, (d) HN-WL, (f) bm-WL, and (h) bmHN-WL. PSA results of (c) WL, (e) HN-WL, (g) bm-WL, and (i) bmHN-WL.

In the investigation of boron content of HN-WL and bmHN-WL, the HNO3 leachate for 5 g of WL and bm-WL were inspected by ICP-AES (Figure S2). As shown in Figure S2, 45.05 mg (0.9 wt%) of Al3+, 20.01 mg (0.4 wt%) of B ions, and 29.77 mg (0.6 wt%) of Ca2+ dissolved into the filtrate of WL. Regarding XRF data of WL, an only small amount of ions were removed due to intrusion depth limitation of by HNO3 treatment. Besides, by subtracting ICP-AES data from XRF data residual B content of HN-WL can be roughly calculated as 3.76 wt%. On the other hand, 446.3 mg (8.9 wt%) of Al3+, 139.5 mg (2.8 wt%) of B ions, and 244.9 mg (4.9


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wt%) of Ca2+ dissolved into the filtrate of bm-WL. Unlike HN-WL, most of Al3+ and Ca2+ are removed by HNO3 treatment which corresponds to the XRF data of bmHN-WL (Figure S1d). Thus, it can be inferred that most of the B ions are removed by size reducing effect of ballmilling and impurity removal via HNO3 treatment. The morphologies and size distribution of WL, bm-, HN-, and bmHN-WL were identified by SEM and PSA (Figure 2b–i). The SEM images in Figure 2b, d, f, and h show that all the WL samples have atypical shapes in common. However, their distribution of particle size varied because of the different pre-treatment processes, and the results are shown in Figure 2c, e, g, and i. WL has a broad size distribution ranging from 300 nm to 9 µm with small bits spread out on the surface of large particles (Figure 2f and h). After HNO3 treatment for 72 h and the subsequent washing process, HN-WL showed narrower size distribution of 400 nm to 5 µm; however, there was no remarkable difference observed in its morphology (Figure 2c and e). Figure 2f–i illustrate the SEM images and PSA results of bm- and bmHN-WL, which underwent the same ball-milling process. They seem to have almost similar morphologies and size distribution of 400 to 550 nm. The size reduction via ball-milling minimized unleached volumes caused by intrusion depth limitation of HNO3 treatment, thereby resulting in the elimination of most elements other than Si. Consequently, by combining ball milling and HNO3 treatment, bmHN-WL showed decreased Al, Ca, and Sr concentrations of 1.35, 0.32, and 0.41 wt%, and increased concentration of 38.98 wt% as an element, and 94.01 wt% as oxide (Figure S1d).

Characterization of bm-Si, HN-Si, and bmHN-Si The reduced Si materials were prepared by MR using WL, bm-, HN-, and bmHN-WL and each sample was termed WL-, bm-, HN-, and bmHN-Si, respectively, depending on the source materials. Figure 3a illustrates the XRD patterns of reduced Si materials. After the MR of WL, 11 ACS Paragon Plus Environment


the XRD pattern of WL-Si showed much lower peak intensity compared to that of the other Si samples because WL-Si had low reduction yield originating from low silica content in the WL precursor. In the enlarged XRD pattern of WL-Si (Figure S3a), several negligible peaks corresponding to Si and impurities were observed. On the contrary, large intense peaks were detected in the XRD patterns of bm-, HN-, and bmHN-Si. The peaks at 28, 47, and 56° were well indexed to the typical patterns of Si (JCPDS #27-1402), indicating the synthesis of highly crystalline Si. However, bm- and HN-Si contained unexpected compounds of MgAl2O4 (JCPDS #21-1152), CaB6 (JCPDS #74-1171), and SrB6 (JCPDS #87-0286). As shown in enlarged XRD patterns in Figure S3b, c, bm- and HN-Si includes similar peaks which are between reference peaks of CaB6 and SrB6. These alkaline-earth metal borides belong to the same crystal structure and space group (cubic, Pm3m) thereby possessing the same miller indices and similar XRD peak locations.45 As a result, it can be assumed that these peaks represent a mixture of CaB6 and SrB6. MgAl2O4, CaB6, and SrB6 are chemically inert; thus, HCl and HF acid treatments could not remove these compounds. On the contrary, XRD patterns of bmHN-Si did not include the peaks of MgAl2O4, CaB6, and SrB6, indicating that most of the impurity ions were leached by ball milling and subsequent HNO3 treatment.


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Figure 3. Morphology and compositional analysis of Si samples. (a) XRD patterns of WL-, bm-, HN-, and bmHN-Si. EDX mapping images of (b) bm-Si, (c) HN-Si, and (d) bmHN-Si.

The morphologies and elemental distribution of reduced Si materials were characterized by SEM images and EDX mapping. The SEM images of bm-, HN-, and bmHN-Si in Figure S4b, e, and h, respectively, show bulky and irregular morphologies, which possess pores or spherical surface traces in common. After MR, Si and Mg by-products (MgO and Mg2Si) coexist in interwoven aggregates. When Mg by-products are etched out by acid treatment, pores and spherical traces are left behind.30 However, owing to particle size difference, macropores and spherical traces are formed in bulk particles (HN-Si), whereas only spherical surface traces are created in smaller particles (bm-Si and bmHN-Si). EDX mapping images in Figure 3b–d depict the distribution of Si, Al, Mg, Ca, and O. Si is represented in green color. MgAl2O4 and CaB6 are indicated in yellow and sky-blue circles, respectively. Impurities and Si particles are randomly distributed in bm- and HN-Si, whereas impurities are seldom observed in bmHN-Si. The specific EDX mapping results and EDX spectra are shown in Figure S4. Since B content 13 ACS Paragon Plus Environment


in Si samples was not able to be detected by EDX mapping, XPS analyses were conducted (Figure S5). As shown in the XPS survey spectra, peaks related to Mg, Ca, Sr, and B are only observed at bm- and HN-Si, while bmHN-Si only have peaks related to Si. Especially, B 1s peak near 187 eV can be observed clearly for bm- and HN-Si, indicating the presence of CaB6 and SrB6. The purity of bmHN-Si was identified by TEM-EDX results shown in Figure S6. bmHNSi includes over 99 wt% of Si with few Al contents, indicating highly pure Si. On the other hand, the inclusion of MgAl2O4, CaB6, and SrB6 in bm- and HN-Si was confirmed by the XRD and EDX analyses. Considering chemical inertness of these impurities, bm- and HN-Si are not suitable materials for LIB anodes.46,47 As a result, highly pure bmHN-Si was successfully synthesized in terms of eco-friendliness via preliminary impurity removal and subsequent MR of WL.

Electrochemical performance In order to establish a recycling strategy with the sustainable application, bmHN-Si was fabricated into anodes for LIBs. The electrochemical performance was measured by lithium ion half-cell test using bmHN-Si as anode materials. All electrodes were fabricated by conventional slip casting technique with CMC binder and a pH 3 buffer solution. Subsequently, Si electrodes were matured in humidity (relative humidity of ~99 %) for 48 h (matured electrode). For the comparison, standard electrodes were fabricated without post-treatment. Figure 4a illustrates how adhesion and cohesion of the Si electrodes are enhanced by the posttreatment of maturation. In standard electrodes, binders are usually coated on the surface of Si particles and the current collector. After the maturation, the coated binder tends to aggregate at Si particle contacts or the particle-current collector interface and forms robust polymer bridges. Numerous CMC chains in a polymer bridge cooperatively endure mechanical stress by mutual 14 ACS Paragon Plus Environment

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friction and disentanglement, thereby enhancing mechanical reinforcement.40

Figure 4. (a) Schematic representation of the maturation procedure and its effects on the electrode. (b) CV curves and (c) galvanostatic charge/discharge curves of matured bmHN-Si 15 ACS Paragon Plus Environment


electrode. (d) Cycling stability performance and (e) rate capability performance of matured bmHN-Si electrode. (f) EIS analysis of matured/standard bmHN-Si electrode.

To demonstrate the reactivity of bmHN-Si, the CV curves of bmHN-Si electrodes were evaluated in the voltage range of 0.01–1.5 V at a 0.1 mV s−1 scan rate. In Figure 4b, most of the peaks correspond to alloying/dealloying peaks of Si. During the initial cathodic process, the only peak near 0 V represents lithiation of crystalline Si to amorphous LixSi.48 During subsequent cycles, two peaks in the charge process at 0.35 and 0.54 V indicate the dealloying of LixSi, and the peak at 0.15 V in the discharge process expresses the alloying of Si with Li.13 The peaks tend to amplify upon cycling due to kinetic activation of Si particles.12 The overall aspects of the CV curves of the bmHN-Si electrodes are almost similar to that of the standard bmHN-Si electrodes (Figure S7a). The result of CV represents stable reaction between waste LCD glass-derived Si and Li in the LIB half-cell system. Figure 4c depicts the galvanostatic charge/discharge curves of the bmHN-Si electrodes at a current density of 0.5 A g−1 between 0.01 and 1.5 V. In the first cycle, tests were conducted at a low current density of 0.1 A g−1. The initial specific capacities of the bmHN-Si electrodes were measured to be 4083 and 3438 mA h g−1 for the discharge and charge processes, respectively. The initial coulombic efficiency exhibited a high value of 84 %. The initial low current density led to the entire reaction of bulky Si materials and stable formation of solid electrolyte interface (SEI) layer, thereby resulting in high initial specific capacity and coulombic efficiency. For the initial cycles, typical plateaus can be observed at approximately 0.1 V (discharge process) and 0.39 V (charge process), which indicate alloying/dealloying reaction between crystalline Si and Li.49,50 In the second cycle, the discharge plateaus were broadened and the charge plateaus were dropped to approximately 0.3 V due to the formation of amorphous LixSi from amorphous Si. The long-term stability of the bmHN-Si electrodes were investigated by galvanostatic 16 ACS Paragon Plus Environment

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cycling test. Figure 4d describes the cycling performance of the bmHN-Si electrodes with a current density of 0.1 A g−1 for the first cycle and 0.5 A g−1 for the rest of the cycles in the voltage range of 0.01–1.5 V. The bmHN-Si electrodes exhibited high reversible specific capacities of 3438 and 2773 mA h g−1 for the first and second cycles, respectively. The bmHNSi electrodes also possess excellent coulombic efficiency, which was maintained over 99 % from the fourth cycle; however, the standard bmHN-Si electrodes showed unstable coulombic efficiency upon cycling. The reversible capacity of the bmHN-Si electrodes was maintained at 1710 mA h g−1 until the 100th cycle owing to the mechanical reinforcement by maturation. On the contrary, the standard bmHN-Si electrodes underwent rapid capacity fading, which reached 298 mA h g−1 at the 100th cycle. These results indicate that capacity retention was improved from 11 to 64 % during the 100 cycles through the electrode maturation process. Many previous studies, which processed Si anodes using various waste materials, focused on synthesis of Si materials via nanostructuring and composite formation with carbon to overcome volume expansion issues of Si anodes. In our study, we fabricated Si materials from waste LCD glass and further applied the facile electrode post-treatment process which enabled reinforced mechanical stability. Even without conductive carbonaceous additives, the cycling performance of bmHN-Si electrodes is comparable to other waste material-derived Si anodes.10-14 (see Table S1 in supporting information) Although the loading mass of the bmHN-Si electrodes was 1.5–2.0 mg cm−2, they provided super-high areal capacities of 6.3 and 5.0 mA h cm−2 for the first and second cycles, respectively (Figure S8). The bmHN-Si electrodes exhibited a high areal capacity of 3.1 mA h cm−2 at the 100th cycle. The outstanding areal capacity of the bmHN-Si electrodes are compared to the previously reported Si anodes in Table S2. Majority of the studies concentrated on nanostructuring and incorporation of conductive materials to enhance the electrochemical performance. On the other hand, some studies on high areal capacity Si electrodes focused on 17 ACS Paragon Plus Environment


the mass loading of active materials. The bmHN-Si electrode has a very common active loading mass of 1.5 mg cm−2 and uses a micro-sized Si without any carbon medium. Nevertheless, the bmHN-Si electrodes exhibited higher areal capacity than recently reported Si electrodes owing to the high reactivity of high-purity Si and stable contact with the current collector provided by maturation upon cycling. The rate performance was evaluated at diverse current densities with five cycles each. The bmHN-Si electrodes exhibited discharge capacities of 2874, 2618, 2416, 2115, 1978, and 1532 mA h g−1 (Figure 4e) at current densities of 0.2, 0.3, 0.5, 0.8, 1, and 2 A g−1, respectively. After another five cycles at the current density of 1 A g−1, the discharge capacity of the bmHN-Si electrodes recovered to 1949 mA h g−1. The standard bmHN-Si electrode showed discharge capacities of 3165, 2802, 2425, 2077, 1746, and 1301 mA h g−1 and recovered to 1665 mA h g−1 at the same current density condition (Figure S7b). The bmHN-Si electrodes exhibited better rate capability owing to the stable kinetics enabled by the improved mechanical stability of the electrode. To understand the enhanced electrochemical performance of the bmHN-Si electrodes, electrochemical impedance spectroscopy (EIS) was performed over the frequency range of 100,000 to 0.1 Hz at the 2nd and 100th discharge states (Figure 4f). The Nyquist plots include semicircles, which indicate SEI resistance (Rs) and charge transfer resistance (Rct). The bmHNSi electrodes possess a single semicircle because a large Rct semicircle overlaps the Rs semicircle. At the second discharge process, Rct of the bmHN-Si electrodes is smaller than that of the standard bmHN-Si electrodes. After the 100th discharge process, the semicircle is divided into two semicircles; however, the bmHN-Si electrodes show much smaller Rct values than standard bmHN-Si electrodes. As Figure 4d in this manuscript, the specific capacity of standard bmHN-Si electrodes was steeply decreased until the 30th cycle. Interestingly, Coulombic efficiency of the standard electrodes was also reduced during the first 30 cycles. The extra18 ACS Paragon Plus Environment

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discharge capacity presented the more consumption of lithium ions for continuous SEI formation, representing that fresh Si surface was continuously exposed in the standard bmHNSi electrodes.51 The stable SEI formation induced the reversible expansion/shrinkage cycle without particle fracturing or elimination from the current collector, which led to lower resistance and stable cycling retention of the bmHN-Si electrodes. This result suggested that maturation process provides a better chance of forming stable SEI compared to the standard electrodes.

In the purpose of understanding the maturation effects on electrodes, XPS analyses were conducted to investigate the surface corrosion of Cu current collector and confirm the existence of Cu-ester bond. Figure 5a, d, g and 5b, e, h describe the Cu 2p and C 1s spectra of bare, standard processed, and maturation processed Cu foils, respectively. Standard/matured Cu foils were prepared by sonicating standard/matured bmHN-Si electrodes in DIW for 10 s followed by vacuum drying. The binding energy of all the spectra was adjusted by setting the binding energy of C-C as 284.6 eV. As shown in Figure 5a, d, and g, Cu 2p3/2 peak is commonly observed for bare, standard, and matured Cu foils at about 932.6–932.8 eV, which corresponds to metallic Cu.52 The shoulder at 933.7 eV representing Cu2+ is very small in the bare Cu foil and gets larger after the standard process.53 However, in the matured Cu foil, the shoulder enlarges and another shoulder at 935.1 eV appears due to the acidic environment during maturation.53 In addition, Cu2+ satellites around 939–946 eV, which were not observed for bare Cu foil, also tend to get stronger after the standard and maturation processes. These results reveal that maturation derived corrosion produces Cu2+ species such as CuO, Cu(OH)2, and Cu(OC(=O)-R)2.40



Figure 5. Surface analyses of Cu foil corrosion. Cu 2p and C 1s XPS spectra of (a, b) bare, (d, e) standard, and (g, h) matured Cu foils. SEM images of (c) bare, (f) standard, and (i) matured Cu foils.

Further investigation on the C 1s spectra was conducted to prove the presence of Cu-ester bonds (Figure 5b, e, h). Three peaks at 284.6, 286.3, and 288.3 eV can be observed in common and these can be indexed as C-C, C-O, and O=C-O, respectively.54 The C 1s spectrum of the bare Cu foil resembles the peaks induced by hydrocarbon contamination.54 Meanwhile, the standard Cu foil has a high C-O and O=C-O contribution to its spectra indicating the existence of CMC residues. The contribution of C-O and O=C-O is high for the matured Cu foil owing 20 ACS Paragon Plus Environment

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to the grafted CMC chains, which form Cu-ester bonds with the current collector. Therefore, it is possible to assume that an acidic binder solution corrodes the surface of a Cu foil, and subsequently, maturation provides an environment for Cu-ester bond formation. Bare, standard processed, and maturation processed Cu foils were examined using their SEM images, and their surface characteristics were compared after corrosion (Figure 5c, f, i, and Figure S9). Before observation, standard/matured Cu foils were prepared by gently washing out the casted slurry of the standard/matured bmHN-Si electrode using a paper wiper. As shown in the SEM image of the bare Cu foil, a smooth surface mainly exists with some crevices. After the standard process, more crevices can be observed; however, a smooth surface still coexists. An extremely rough surface is observed for the matured Cu foil due to sufficient corrosion. Similar results are shown in Figure S9. The bare Cu foil appears glossy because it did not undergo any acidic environment. However, in the standard Cu foil, the glossy surface seems faded due to slight corrosion. After maturation, the corroded surface of the Cu foil can be clearly witnessed because of the color difference. The cracking behaviors of the standard and matured bmHN-Si electrodes after 40 cycles were observed using their SEM images (Figure 6). The cycled electrodes were maintained at 1.5 V for at least 12 h to observe them at a complete delithiated state. Subsequently, the electrodes were immersed in DMC to wash out residual Li-salts and electrolyte and then dried in vacuum for SEM observation. The fibers, which can be seen in Figure 6b and d, are glass fiber separator residues, which could not be completely removed. As shown in Figure 6a and c, no remarkable difference can be found between the pristine standard/matured electrodes. After 40 cycles, two electrodes clearly differ in crack spacing and size of islands. The standard bmHN-Si electrodes exhibited islands with a diameter of ~200 µm and narrow crack spacing, whereas the bmHN-Si electrodes showed islands with a diameter smaller than 100 µm and wide crack spacing. The insets of Figure 6b and d describe the cracking characteristics of the 21 ACS Paragon Plus Environment


two electrodes. In substrates with a thin film coating, the diameter of islands is inversely proportional to the required critical shear stress between the film and substrate for slip to occur.40,55 Moreover, films with high fracture toughness are known to possess wide crack spacing.56 Therefore, matured electrodes have strong cohesion and adhesion cracks in islands with a small diameter and wide crack spacing. The matured electrode, which has wide crack spacing, can take advantage of the volume expansion of Si particles and thus achieve better cycling retention. In contrast, narrow crack spacing and weak adhesion of the standard electrode cannot endure the stress induced by the volume expansion of Si particles, thereby causing decohesion of Si particles, which results in capacity fading.

Figure 6. Investigation on the cracking behaviors of standard and matured bmHN-Si electrodes using SEM images. Pristine (a) standard and (c) matured bmHN-Si electrodes. (b) Standard and (d) matured bmHN-Si electrodes after 40 cycles.

In summary, the bmHN-Si electrodes achieved high areal and gravimetric capacity with 22 ACS Paragon Plus Environment

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high cycling retention owing to post-treatment. The pH 3 buffer solution used for dissolving the binder plays a critical role in the formation of anchoring bonds between the Si-CMC and Cu-CMC interface. The pH 3 environment neutralizes SiO- and COO- into SiOH and COOH, respectively, and these groups can form hydrogen bonds in slurry. During the drying process, this hydrogen bond favors to form ester bonds, which act as robust anchoring bonds between Si particles and CMC.57 In addition, acidic environment maintenance provided by maturation sufficiently corrodes the surface of the Cu current collector, and the carboxyl group in CMC favors to form Cu-ester bonds, thereby improving adhesion. Thus, maturation enables the formation of polymer bridges and two kinds of anchoring bonds, thereby enhancing mechanical reinforcement. The sustainable recycling solution for waste LCD glass should accompany several important techniques such as CO2 reduction and leaching solution processing. When these efforts combined with our work, ultimately, waste LCD glass-derived Si can give the possibility of industrial scale production for lithium-ion battery applications. Nevertheless, we believe that this work provides a new recycling method of waste LCD glass, which use as electrode materials with the practical usable electrochemical performance.

Conclusion In conclusion, Si particles were successfully synthesized by MR of WL with sustainable manners. Before the reduction, the glass powder underwent pre-treatment, which consists of ball milling in DIW and HNO3 treatment. The particle size reduction followed by the increase in surface area due to the ball-milling process and strong leaching effect of HNO3 treatment contributed to sufficient impurity removal. High-purity bmHN-Si was directly used as an



electrode material, which underwent post-treatment in humid atmosphere for 48 h. The matured waste LCD glass derived Si electrodes exhibited excellent areal and gravimetric capacities of 6.3 mA h cm−2 and 3438 mA h g−1, respectively, in the initial cycle. Moreover, their capacity retention was 6 times better than standard Si electrodes after 100 cycles. As a result, various analyses showed that improved electrochemical performance and cycle stability were caused by the reinforced adhesion and cohesion of the Si electrodes. Consequently, this recycling strategy proposes sustainable synthesis and application of Si using waste LCD glasses, thus can be a promising solution for waste LCD glass management.

ASSOCIATED CONTENT Supporting Information. XRF results of WL samples, ICP-AES results of HNO3 leachate for WL and bm-WL, enlarged XRD patterns of Si samples, EDX mapping images of Si samples, XPS results of Si samples, TEM-EDX results of bmHN-Si, CV curves and rate capability performance of standard bmHNSi electrodes, cycling stability results in areal capacity, table comparing Si anodes using waste materials, table comparing Si anodes in areal capacity, images of Cu foils used for electrodes.

AUTHOR INFORMATION Corresponding Author * Tel.: +82 2 3290 4863; fax: +82 2 3290 5999; E-mail: [email protected]. Author Contributions ‡These

authors contributed equally to this work.

ORCID Woohyeon Kang : 0000-0002-1199-9548 24 ACS Paragon Plus Environment

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Jae-Chan Kim : 0000-0003-4034-7685 Jun Hong Noh : 0000-0002-1143-5822 Dong-Wan Kim : 0000-0002-1635-6082 Notes The authors declare no competing financial interest.

ACKNOWLEDGEMENTS This work was supported by the R&D Center for Valuable Recycling (Global-Top R&BD Program) of the Ministry of Environment (Project No.: R2–17_2016002250005). This work was supported by the National Research Foundation of Korea (NRF) Grant funded by the Ministry of Science and ICT (2019R1A2B5B02070203), and by Creative Materials Discovery Program through the National Research Foundation of Korea (NRF) funded by Ministry of Science and ICT (2018M3D1A1058744). This work was supported by a Korea University Grant.

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Abstract Graphic

Synopsis Sustainable and cost-effective fabrication of waste LCD glass derived Si materials as stable anodes for lithium ion batteries.


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Waste LCD Glass-directed Fabrication of Silicon Particles for Lithium

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