MXene Composite Papers for High

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Flexible and Free-standing Silicon/MXene Composite Paper for High-performance Lithium-Ion Batteries Yuan Tian, Yongling An, and Jinkui Feng ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b21893 • Publication Date (Web): 18 Feb 2019 Downloaded from http://pubs.acs.org on February 19, 2019

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ACS Applied Materials & Interfaces

Flexible and Free-Standing Silicon/MXene Composite Paper for High-Performance Lithium-Ion Batteries Yuan Tian, Yongling An, Jinkui Feng* SDU & Rice Joint Center for Carbon Nanomaterials, Key Laboratory for Liquid-Solid Structural Evolution & Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, China. Corresponding author: Jinkui Feng Email: [email protected] Keywords: MXene, silicon, lithium-ion batteries, flexible, free-standing, binder-free anode

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ABSTRACT Silicon has been developed as the exceptionally desirable anode candidate for lithium-ion batteries (LIBs), attributing to its highest theoretical capacity, laigh working potential and abundant resource. However, large volume expansion and poor conductivity hinder its practical application. Herein, we fabricate flexible, free-standing and binder-free silicon/MXene composite papers directly as anodes for LIBs. The Silicon/MXene composite papers are synthesized via covalently anchoring silicon nanospheres on the highly conductive networks based on MXene sheets by vacuum filtration. This unique architecture can accommodate large volume expansion, enhance conductivity of composites, prevent restacking of MXene sheets, offer additional active sites and facilitate efficient ions transport, which exhibits superior electrochemical performance with high capacity of 2118 mAh g-1 at 200 mA g-1 current density after 100 cycles, steady cycling ability of 1672 mAh g-1 at 1000 mA g-1 after 200 cycles , and rate performance of 890 mAh g-1 at 5000 mA g-1. This work may shed lights on the development of silicon-based anodes for LIBs.


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1. INTRODUCTION Lithium-ion batteries (LIBs) with superb stability and high capacity are developed as the most favorable candidates for futural energy storage.1-6 Silicon is one of the most desirable anodes for LIBs, ascribing to its highest specific capacity (3579 mAh g-1 at mild temperature), laigh working potential, coupled with abundant storage in nature.6-10 However, several conundrums hamper its large-scale application in LIBs. The huge volume change of approximately 300% during cycling process produces severe pulverization of the Si, electrical contact between current collectors and Si particles, and continuous increase of solid electrolyte interphase (SEI) layer.3,8,11 Consequently, the Si anodes exhibit poor cycling life and low Coulombic efficiency. To address these failure modes caused by volume expansion, intensive attempts have been devoted into the development of Si anodes with well-designed Si nanostructures (e.g., nanowire,12 nanotube13 and nanoporous structure14). In our previous work, nanoporous Si was synthesized by vacuum distillation method as anodes for LIBs and exhibited enhanced electrochemical performance.14 In view of the sophisticated nanostructure with available surrounding free space and small size, Si anodes composed of nanoscale Si particles can withstand large volume change to avoid strains during lithiation/delithiation process.13 Another crucial challenge of Si anodes in LIBs is its intrinsically poor electrical conductivity and low ionic diffusivity, depressing the rate capability and the power output efficiency.10,15,16 Our group fabricated nanocomposites of porous Si and reduced graphene oxide as anodes for LIBs, delivering improved electrochemical capabilities.15 However, traditional Si-based anodes are typically fabricated by casting slurry containing Si particles, conductive additives, and polymeric binders into Cu foil. The utilization of electrochemically inactive binders and additives leads to a


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significant reduction in absolute anode capacity,18 which inevitably increases the cost of LIBs, limiting the large-scale implementation of Si in LIBs. Recently, self-supported binder-free electrodes have drawn considerable attention due to the ease and flexibility of battery assembly.19-24 Ni et al. have made a significant and characteristic contribution to the field, such as conductive Na2Ti3O7 binder-free electrodes,20 3D self-supported CuO electrodes,22 S-TiO2 self-supported nanotube electrodes,24 and so on. This unique structure can achieve a strong electrical and mechanical contact with high conductive matrix, shorten ions and electrons diffusion distance, realize the flexibility and robust structural integrity of electrodes, eliminate the need for binder and conductive additive, and finally deliver superior electrochemical storage performance.20,22-26 Additionally, as the escalating demand for flexible electronic devices, flexible and freestanding electrodes have excellent prospects for future energy storage materials. MXene, a novel and important family of two-dimension materials, is fabricated by extracting “A” layers from layered carbonitrides or carbides identified as MAX.27-29 Compared with graphene, MXene has a perfect conjunction of graphene oxide’s and graphene characters.28,30 Moreover, Gogotsi et al. proposed that MXene outperforms solution processed graphene membrane with respect to electronic conductivity, and has already been proved to be promising electrode candidates in LIBs.28,31 Among various MXenes, Ti3C2Tx is the most explored MXene due to its high electric conductivity, low ion diffusion barrier, negative surface charge in solutions, low operating voltage, two-dimension nature, mechanically flexibility, and environment friendly.27-29 More importantly, Gogotsi et al.32,33 reported that Ti3C2Tx sheets can be easily fabricated into flexible and additive-free Ti3C2Tx films that display superior


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electrochemical performance. These features make Ti3C2Tx as ideal two-dimension flexible freestanding substrate for energy storage applications. In this work, we fabricate free-standing and flexible Si/MXene composite papers as anodes without binders and additives for LIBs. The Si/MXene composite paper anodes integrate all the merits of both components by covalently anchoring the Si nanospheres on the highly conductive networks based on MXene sheets through vacuum-assisted filtration. MXene sheets act as twodimension support to load the Si nanospheres, which can prevent aggregation and strain of Si particles during the lithation/delithiation process. Besides, MXene sheets also play the part of effective electron conductor and current collector, which can facilitate ion transport during cycling process. Meanwhile, Si nanospheres can isolate MXene sheets to avoid restacking, which preserves the active surfaces. This flexible and free-standing structure can buffer volume expansion, offer additional active sites, and accelerate ions transport. Therefore, the flexible and free-standing Si/MXene composite papers present the improved electrochemical capability. This work is expected to develop a pathway to foster the large-scale application of high energy density Si anodes for LIBs. 2. EXPERIMENTAL SECTION 2.1. Material Preparation 2.1.1. Delamination of MXene: In a typical experiment, concentrated HCl (38 wt%) was appended to 5 mL water forming homogeneous HCl solution. LiF (purchased from Aladdin) was added to above-mentioned HCl solution, and agitated for 0.5 h at 35 °C in a Teflon container. Thereafter, Ti3AlC2 (MAX, 500 mesh) was slowly added to above mixture to prevent overheating, and kept at 35 °C under magnetic stirring for 2 days. Subsequently, abovesynthesized mixture was cleaned using deionized water, and centrifuged for many times until the


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pH of supernatant reached approximately 7. After acidic supernatant was removed, the black slurry-like sediment was collected from 100 mL centrifuge tube. Then, we put deionized water into aforesaid swollen sediment, followed by vigorously shaking with hand for 10 minutes until the sediment was re-dispersed into black suspension. Subsequently, the black suspension was centrifuged for 1 h at 1500 rpm to collect stable dark concentrated supernatant. The supernatant, named as MXene colloidal solution, was mainly composed of Ti3C2Tx with single or few layer flakes. Finally, we determined the concentration of MXene colloidal solution by filtering a certain volume MXene colloidal solution through a polyvinylidene fluoride (PVDF) membrane (0.22 μm in pore size, Φ50 mm in diameter) using Buchner funnel with sand core (Φ40 mm) and measuring the weight of MXene film after being dried. 2.1.2. Fabrication of flexible Si/MXene composite paper: 60 mg commercial spherical silicon nanoparticles (20-60 nm, purchased from Aladdin, denoted as Si nanospheres) were added to 25 mL aforementioned MXene colloidal solution, and stirred for 6 h. Subsequently, 25 mL above-synthesized mixture were vacuum filtrated through a PVDF membrane by using Buchner funnel with sand core. The weight of obtained flexible and free-standing Si/MXene paper (denoted as Si/MXene) were measured after dried at 70 °C for overnight in vacuum condition. Finally, we obtained the Si/MXene electrodes that mass loading of the active materials is approximately 1.1-1.3 mg cm-2 . Eventually, we stored all the samples in glove box stuffed with argon. 2.2 Material Characterization Microstructure of all the products were detected using transmission electron microscope (JEOL, JEM-2100) and field emission scanning electron microscopy (ZEISS, SUPPA 55) operated at an accelerating voltage of 5 kV. Energy dispersive spectrum (EDS) analysis system


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was used to investigated microstructure and element distribution. The crystalline structure was characterized with Rigaku Dmax-rc X-ray diffractometer (Cu Kα) from 5 to 90° at 10° min-1. Raman spectra were recorded to detect structure and composition by a Horiba Jobin Yvon spectrometer using 632 nm Raman pump as excitation source in a spot size of about 1 μm. The X-Ray photoelectron spectroscopy (XPS, Casa 2318PR1-0) by Al Kα X-ray radiation was detected. 2.3 Electrochemical Tests Electrochemical measurements of all the samples were conducted in coin-type 2032 half cells. The above Si/MXene composite papers were used as working electrode, Celgard 2400 microporous membrane was separator, LiPF6 (1 M) in ethylene carbonate/diethyl carbonate (EC/DEC, 1:1, volume ratio) was used as the electrolyte, and lithium foil acted as reference electrode and counter electrode. For comparison, pure Si anodes were fabricated by casting a homogeneous slurry into copper foil and dried at 70 °C for overnight. The slurry was fabricated by blending commercial Si nanospheres, carbon black and polyvinylidene fluoride (PVDF) binder (8:1:1, weight ratio) at room temperature. The coin-type 2032 batteries were set up in glove box stuffed with argon and tested at room temperature. And the water and oxygen content of glove box are both below 1 ppm. Cyclic voltammetry tests (CV) on CHI 660E electrochemical workstation were conducted at 0.1 mV s-1. Electrochemical impedance spectroscopy (EIS) was also detected from 0.01 Hz to 1 MHz on a CHI 660E electrochemical workstation. Moreover, we detected galvanostatic discharge/charge curves between 0.01 and 1 V on a NEWARE galvanostatic programmable battery charger (BTS-5V3A). 3. RESULTS AND DISSCUSION


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The schematic for preparation of flexible and free-standing Si/MXene paper is depicted in Figure 1 (detailed information are given in Experimental Section). Briefly, MXene (Ti3C2Tx) is fabricated by selective etching Al layers of precursor (MAX, Ti3AlC2, Figure S1) using LiF/HCl, and finally delaminates into single or few layer MXene in deionized water to form a dark colloidal solution. Subsequently, commercial pure Si nanospheres were mixed with the abovesynthesized dark MXene colloidal solution at room temperature to form homogeneous mixture. Finally, the flexible free-standing Si/MXene composite paper anodes are fabricated by vacuumassisted filtration. SEM image of MXene shows a graphene-like morphology in Figure S2. The TEM images in Figure S3a reveals the uniform distribution of Si nanospheres that its diameters are from 20 to 60 nm. TEM image in Figure 2a displays that Si nanospheres are equably distributed on the surface of MXene sheets. The corresponding HR-TEM images reveal the existence of MXene and Si with 0.31 nm lattice fringe spacing ascribing to (111) planes (Figure 2b), which coincides with reported literature.8,14 This structure can achieve close electrical contact and robust mechanical support through MXene sheets, thus making it possible to directly utilize flexible free-standing Si/MXene paper as anodes. In fact, the above-synthesized Si/MXene is easily detachable from the filter membranes to obtain a large, flexible and freestanding film, as shown in inset of Figure 2a. The cross-section SEM image of Si/MXene shows that silicon nanospheres are randomly distributed between parallel MXene sheets (Figure 2c), which can facilitate ions transport during cycling process. The elemental distribution of Si/MXene is further detected by electron energy loss spectroscopy (EELS) maps, which is illustrated in the Figure 2d-g. These figures exhibit element distributions of Si, Ti, and C, confirming the uniform distribution of Si nanospheres on MXene sheets. This result is conformable with HRTEM observations and indicates that close contact between Si nanospheres


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and MXene conductive substrate. SEM images and corresponding elemental mapping images in the Figure S4 further verify co-existence of Si and MXene. The structure and crystalline phase are investigated by XRD patterns and Raman spectra. Figure 2h provides XRD patterns of MXene, commercial Si nanospheres, and Si/MXene. XRD pattern of MXene is in accord with previous literature, which exhibits a characteristic peak at approximately 2θ = 6.44° of (002) plane,28 indicating that well delaminated MXene is successfully synthesized. Comparatively, the (002) peak of Ti3AlC2 precursor in Figure S1b is located at 2θ = 9.4°. The XRD pattern of commericial Si nanospheres in Figure 2h(Si) fits well its pure structure (JCPDS no. 27-1402). The XRD pattern of Si/MXene exhibits a combination of MXene with (002) peak and Si with (111), (220), (311), (400), (331) and (422) peaks. Moreover, the (002) peak of MXene in the Si/MXene composite down-shifts to 2θ = 6.09°, indicating an enlarged interlayer spacing based on Bragg's law.28,35 Raman spectra is further performed to explore the composition of Si/MXene. In the Figure 3i, Si/MXene has not only the same peaks as commercial Si nanospheres at 510 cm-1 and from 880 to 983 cm-1, but also the same peaks corresponding to MXene. XRD pattern and Raman spectra further confirm the successful formation of Si/MXene composite paper. The specific surface area of Si/MXene in Figure 2j is about 98 m2 g-1. XPS is further investigated to explore chemical state of elements in MXene and Si/MXene. As illustrated in Figure 2k, C-O, C-F, and -C=O, bonds from the terminations of MXene as well as the C-Ti bonds from Ti3C2 are detected in the high-resolution C 1s spectrum.38 The delaminated MXene sheets have a highly negative potential (-39.5 to -63 mV) and are hydrophilic due to the abundant functional groups.39 Such features make MXene sheets easy to disperse into deionized water and are favorable for the assembly of Si nanoparticles. Comparatively, typical C-Ti bond from Ti3C2 can be observed in high-resolution C 1s spectrum


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of Si/MXene in the Figure 2i, indicating presence of MXene.38 The peak of Si-C bond can be observed in the C 1s spectrum located at 284.3 eV, as shown in Figure 2l. Moreover, Figure 2m demonstrates that Si 2p spectrum are divided into two peaks of Si-C at 99.6 eV and monatomic Si at 98.9 eV.40 This result may imply the formation of an interaction between MXene and Si nanospheres. The Si-C bond formed at the interfaces between MXene and Si nanospheres is favorable to the interfacial electron transfer and structural stability, expecting to obtain improved electrochemical performance of Si/MXene anodes. The above results demonstrate successful fabrication of Si/MXene, which enhances electrical conductivity of Si/MXene and accommodates volume change of Si nanospheres during cycling process. Cyclic voltammetry (CV) measurements were performed to investigate electrochemical lithium storage behaviors of Si/MXene anodes. The charge/discharge measurement is conducted with 2032-coin half cells. Flexible free-standing Si/MXene composite paper is directly used as the working electrode. For comparison, pure Si anodes are also tested at same electrochemical conditions. Figure 3a exhibits the first three CV plots of Si/MXene anodes for LIBs between 0.01 V and 3 V at 0.1 mV s-1. Similar to previous literature, CV profiles of the initial cycle in discharge portion are different with the subsequent cycles.11,41 The broad reduction peak starts at approximately 1.28 V in 1st cycle while disappears in subsequently cycles, which is likely attributed to formation of SEI layer.28,35 The pointy peak at 0.13 V and two apparent oxidation peaks at around 0.33 V and 0.52 V in initial cycle are ascribed to cathodic lithiation of Si to form LixSi and anodic delithiation of LixSi back to Si, respectively.41-43 In the subsequent lithiation scans, a relatively broad reduction peak starting at around 0.29 V attributes to lithiation of Si as well as formation of LixSi.11,43 The oxidation peaks at approximately 0.33 and 0.52 V gradually become strong, and the increscent peak region can be assigned to gradual activation of Si/MXene


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anodes.11,44 The galvanostatic charge/discharge behaviors in first 20 profiles of Si/MXene and pure Si anodes for LIBs at 200 mA g-1 are displayed in Figure 3b and c, respectively. For comparison, pure Si anodes in Figure 3c only have a 2142 mAh g-1 reversible capacity and capacity decreases to 919 mAh g-1 after 20 cycles. However, in Figure 3b, Si/MXene anodes can achieve approximately 2930 mAh g-1 reversible capacity and 71% Coulombic efficiency in first cycle. Besides, the charge/discharge profiles of Si/MXene anodes present better overlap than that of Si anodes in initial 20 cycles, reflecting high reversibility of Si/MXene anodes. Furthermore, as illustrated in Figure S5, the MXene anodes for LIBs after 20 cycles only show capacity of around 52 mAh g-1 at 200 mA g-1 current density, which is far below total capacity of the Si/MXene anodes. This result is in accordant with previous literature.45 Figure 3d compares cycling stability of Si/MXene and pure Si anodes for LIBs at 200 mA g-1. The reversible capacity of Si/MXene anodes is maintained well after 100 cycles while pure Si anodes show fast capacity decaying. The enhanced cycling stability of Si/MXene than pure Si anodes implies that MXene effectively enhances electrical conductivity of Si/MXene anodes and buffers volume expansion of Si nanospheres during cycling process, highlighting unique benefits of MXene in Si/MXene anodes. In the Figure 3e and f, the rate capability of Si/MXene is further explored at increasing current densities. Figure 3e shows that the discharge capacities can achieve 1768, 1501, 1294, 1033, 886 mAh g-1 at varied current densities from 1000, 2000, 3000, 4000 to 5000 mA g-1. Corresponding capacity retention of Si/MXene is maintained at 51.33% even at 5000 mAh g-1. Moreover, when current density is restored to 1000 mA g-1, the capacity of Si/MXene anodes returns to 1670 mAh g-1, exhibiting a 95.33% capacity retention, verifying superior reversibility of Si/MXene anodes during cycling process. Inspired by superior rate capability of Si/MXene anodes, the


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long-term cycling stability is also detected at 1000 mA g-1 current density after first ten cycles activated at 200 mA g-1. As shown in Figure 3g, the capacity is maintained well and Coulombic efficiency is stable after 200 cycles, reflecting steady cycling performance. The ameliorated electrochemical properties of Si/MXene anodes can be attributed to its particular structure design, which improves electrical conductivity of the Si/MXene and alleviate volume expansion of Si nanospheres in Si/MXene anodes during the lithiation/delithiation process. The excellent electrochemical performance of Si/MXene anodes for LIBs are explored, which is illustrated in Figure 4. During lithiation process, this unique configuration can enhance conductivity of Si/MXene, prevent the restacking of MXene sheets, offer additional active sites and facilitate efficient ion transport. And such configuration also can alleviate volume change, which is consistent with result of optical photographs of Si/MXene anodes after 100 cycles (Figure 5b). As a contrast in Figure 5a, serious shedding of active material in pure Si anodes after 100 cycles can be obviously observed, which may cause loose contact between the current collector and the active material, causing fast capacity fading. The EIS is detected to research electrochemical capabilities of Si/MXene anodes for LIBs. Figure 5c exhibits the distinctive Nyquist plots, which is formed of a depressed semicircle in high-medium frequency area because of the charge transfer resistance and the surface impedance, and an inclined line at laigh frequency area corresponding to Li+ diffusion.46,47 The charge resistance of Si/MXene anodes for LIBs after 100 cycles is far lower than pure Si anodes, which is in accord with results of cycling performance (Figure 3c), confirming that special structure can effectively accommodate volume change and improve electrical conductivity of Si/MXene. Therefore, the unique structure design by covalently anchoring Si nanospheres on the two-dimension substrate with highly conductive network based on MXene sheets is favorable to enhance the electrochemical performance.


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4. CONCLUSIONS In summary, free-standing and flexible Si/MXene composite papers have been successfully fabricated. As binder-free anodes for LIBs, Si/MXene composite papers exhibit outstanding lithium storage performance. Highly conductive MXene networks can supply a rigid current collector, enhance the conductivity of Si/MXene, accommodate the large volume expansion, offer additional active sites and facilitates the efficient ions transport. Meanwhile, the Si nanospheres can prevent the re-stack of MXene sheets. This work may pave a novel pathway for large-scale applications of Si anodes for LIBs.

Figure 1. Schematic diagram for the preparation of Si/MXene composite paper.


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Figure 2. Morphological and structural characterization of Si/MXene. a) TEM (inset shows the photograph), b) High-Resolution TEM, c) Cross-sectional SEM image. d-g) EELS maps of e) Si (yellow), f) Ti (red), and g) C (green) elements. h) XRD patterns, i) Raman spectra and j)


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Nitrogen adsorption-desorption isotherm, High-resolution C 1s spectra of (k) MXene and (l) Si/MXene, and (m) High-resolution Si 2p spectra of Si/MXene.


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Figure 3. Electrochemical capability of Si/MXene and pure Si anodes (vs Li+/Li). (a) CV plots of first three cycles for Si/MXene anodes at 0.1 mV s-1 from 0.01 to 3 V. Galvanostatic charge/discharge curves of (b) Si/MXene and (c) pure Si anodes at 200 mA g-1 from 1st to 20th cycles. (d) Cycling stability of Si/MXene and pure Si anodes at 200 mA g-1. (e) Rate ability and (f) corresponding capacity retention of Si/MXene anodes at varied current densities from 1000 to 5000 mA g-1. (g) Long-term cycling capability of Si/MXene anodes at 1000 mAh g-1.


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Figure 4. Lithiation schematics of Si/MXene anodes for LIBs.


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Figure 5. (a-b) The optical photographs and (c) EIS spectra before cycle and after 100 cycles of pure Si and Si/MXene anodes.


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ASSOCIATED CONTENT Supporting Information. The Supporting Information is available free of charge on the ACS Publications website at DOI: Material characterization and electrochemical characterization. AUTHOR INFORMATION Corresponding Authors *E−mail: [email protected] (J. K. Feng) ORCID Yuan Tian: 0000-0003-1242-0216 Yongling An: 0000-0002-2666-3051 Jinkui Feng: 0000-0002-5683-849X Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT We greatly acknowledge the financial support from Shandong Provincial Science and Technology Key Project (2018GGX104002), Shandong Provincial Natural Science Foundation (China, ZR2017MB001), The Young Scholars Program of Shandong University (2016WLJH03), Independent Innovation Foundation of Shandong University, the Project of the Taishan Scholar (No. ts201511004), The State Key Program of National Natural Science of China (Nos. 61633015, 51532005), The National Natural Science Foundation of China (No. 21371108), and 1000 Talent Plan program (No. 31370086963030).


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Table of Contents Graphic


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MXene Composite Papers for High

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