Dual Bond Enhanced Multidimensional Constructed Composite

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Dual Bonds Enhanced Multi-Dimensional Constructed Composite Silicon Anode for High Performance Lithium Ion Batteries Shiqi Liu, Xu Zhang, Pengfei Yan, Renfei Cheng, Yushu Tang, Min Cui, Boya Wang, Liqiang Zhang, Xiaohui Wang, Yuyuan Jiang, Lin Wang, and Haijun Yu ACS Nano, Just Accepted Manuscript • DOI: 10.1021/acsnano.9b02129 • Publication Date (Web): 19 Jul 2019 Downloaded from pubs.acs.org on July 20, 2019

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Dual

Bonds

Enhanced

Multi-Dimensional

Constructed Composite Silicon Anode for High Performance Lithium Ion Batteries Shiqi Liu†, Xu Zhang†, Pengfei Yan‡, Renfei Cheng§, Yushu Tang⊥, Min Cui†, Boya Wang†, Liqiang Zhang⊥, Xiaohui Wang§, Yuyuan Jiang‡, Lin Wang† and Haijun Yu*† †College of Materials Science and Engineering, Key Laboratory of Advanced Functional Materials, Education Ministry of China, Beijing University of Technology, Beijing 100124, P.R. China ‡Institute of Microstructure and Properties of Advanced Materials, Beijing University of Technology, No. 100, Pingleyuan, Chaoyang District, Beijing 100124, P.R. China §Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, P.R. China ⊥ State Key Laboratory of Heavy Oil Processing, Department of Materials Science and Engineering, China University of Petroleum, Beijing Changping 102249, P.R. China.

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ABSTRACT: The development of silicon-based anode materials is important for improving the energy density of current lithium ion batteries. However, there are still strong demands for these materials with better cycle stability and higher reversible capacity. Here, a kind of dual bonds restricted MXene-Si-CNT composite anode materials with enhanced electrochemical performance is reported. These dual bonds have been clearly revealed by X-ray photoelectron spectroscopy technique and also proven by the theoretical calculations with spontaneous reaction energy values (−0.190 eV/atom and −0.429 eV/atom for Ti-Si and C-Si bonds, respectively). The cycle stability of the composites, prepared by a facile ball-milling synthetic method, can obviously be improved because of the existence of these dual bonds and the multi-dimensional constructed architecture. The MXene-Si-CNT composite with 60 wt.% silicon possesses the best overall performance with ~80% capacity retention after 200 cycles and achieves 841 mAh g−1 at 2 A g−1. This approach demonstrates a promising strategy to exploit high-performance anode materials and lessens the immanent negative effect of silicon-based materials. Furthermore, it is significant to extend this method on other anode materials with serious volumetric change problems during cycling process.

KEYWORDS: dual bonds, MXene-Si-CNT, composite anode, binding energy, lithium ion batteries

The development of rechargeable lithium ion batteries (LIBs) has drawn considerable attentions due to the demands of energy-storage systems, portable electronic devices and electric vehicles. LIBs are in full-swing due to their high energy density.1–6 In the large-scale production, applicable preparing methods are the vital concerns. Exploring advanced high performance materials is imperative. There are many promising materials emerging during the advancement of energy-


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storage fields. For cathodes, high energy density electrode materials such as LiNixCoyMnzO2 (NCM), LiNixCoyAlzO2 (NCA) and lithium-manganese-rich layered oxides (LLOs) have already occupied a place in the competitive market.7–11 For anodes, while the graphite anode (372 mAh g−1) has been applied into commercialization, silicon-based anode has shown a prosperous potential in LIBs because of its more impressive theoretical capacity (4212 mAh g−1 for Li4.4Si) and higher energy density than graphite. Accordingly, attentions to energy-storage developments have been paid on Si-based anode materials of high capacities.12,13

Nevertheless, the development of silicon anode has been hindered by its nature such as extreme volume expansion (~300%) during lithiation and delithiation resulting in pulverized particles, vulnerable solid-electrolyte interphase (SEI) films and ruptured electrical contact, all of which lead to the declined drastic capacity and limited cycle life.14,15 To address the congenital deficiencies of silicon anode, three common methods were proposed: (1) constructing nanostructures of Sibased anode including nanosheets, nanotubes, nanowires and porous structures to shorten the electrons transport paths;16–19 (2) compositing Si with other materials such as surface coating with carbon or amorphous TiO2 to improve stability circumstance during charge/discharge process;15,20 (3) designing amorphous Si electrodes, such as constructing hierarchical porous amorphous Si by electrodeposition technology or developing sponge-like amorphous silicon by magnesiothermic reduction to control the volume expansion variety.21,22 substantial problems.

Yet these methods inevitably exist

Sophisticated and ambiguous processes in constituting nanostructure

architecture are usually difficult to accomplish and the cost is too high when using advanced equipment such as the electrostatic spinning machine. Also, silicon-carbon composites hold the most promising hope for the anode materials. However its relatively lower capacity and energy


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density temporarily restrict the development in the smart power grids and devices. In addition, coating techniques are currently not effective in that the uniform coating of layers has not been well established yet.23,24

MXene, one of the most promising and competitive candidates for rechargeable batteries, was applied into rechargeable batteries since Yury Gogotsi et al. synthesized it in 2011.25 To date, numbers of attempts have been implemented to use MXene to prepare composites, including selfassembled structures of SnO2 or TiO2 on MXene, MoS2-on-MXene heterostructures, flexible MXene/Graphene films and so on.26–28 Combining the advantages of high electrical conductivity of MXene-based materials and the high capacity of Si-based materials, the resultant MXene-Si composites are expected to be promising substitutes of Si/C composites, but rarely reported.

Moreover, apart from the physical confinement, chemical binding of active materials in composites is also able to obtain well interacted structures to prevent dislocation of them and thus to improve the battery performance. For example, chemical binding of polysulfides with host materials were realized by Ti-S bonds, O-S bonds and P-S bonds to protect polysulfides from dissolving in the electrolytes to gain higher performances of Li-S batteries.29–33 As for Si-based materials, researchers have developed polymer binders such as poly(acrylic acid)-poly(2hydroxyethyl

acrylate-co-dopamine

methacrylate)

(PAA-P(HEA-co-DMA)),

self-healing

polymers (SHPs) and SHP-polyethylene glycol (PEG) binder by constructing fixed-soft conglomerates and chemical bonds to stabilize low-cost Si-based anodes to acquire higher cycle capabilities.34–36 However, to the best of our knowledge, the employment of multiple chemical


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bonding to synthesize well-interacted Si-based composites as anodes have never been reported. We here propose this strategy to confine silicon particles inside a composite matrix to improve the performances.

Herein, a partial-etched MXene material possessing high electrical conductivity and stable crystalline structure was used to fabricate dual bonds restricted MXene-Si-CNT (MSC) composites with a multi-dimensional constructed architecture to improve anode performances for LIBs.37 Both Ti-Si and C-Si bonds were detected by X-ray photoelectron spectroscopy (XPS) technique and confirmed by the first-principles density function theory (DFT) calculations with −0.190 eV/atom and −0.429 eV/atom spontaneous reaction binding energies, respectively, which can effectively protect the Si-based anode during charge/discharge cycles. MSC composite with a 60 wt.% Si content has shown overall performances, including a reversible capacity of 1260 mAh g−1 for LIBs at the current density 500 mA g−1 with ~80% capacity retention after 200 lithiation/delithiation cycles and rate performances of 841 mAh g−1 at 2 A g−1. The MSC composites not only provide a probable way to construct enhanced electrochemical stable electrodes by introducing multiple chemical bonds but also picture a vision that the accessible and scalable process approaches to the large-scale materials synthesis in industry. RESULTS AND DISCUSSION


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Figure 1. (a) Illustration of the synthesis process of MSC composites; (b) schematic representation of the mechanochemically by ball-milling MXene in the presence of corresponding Si and CNT to produce MSC composites.

The synthesis procedure is schematically demonstrated in Figure 1a. In a typical procedure, MXene, commercial Si and CNT were ball-milled by a planetary ball-mill equipment. After certain periods of ball-milling, homogenous MSC composites were obtained. In this process, tungsten carbide balls provide appropriate energy to starting materials to reinforce them combining into chemical bonds restricted composite (Figure 1b). At the substance interfaces in MSC, Si particles are reactive enough to instantly select Ti atoms from MXene to form Ti-Si and C atoms from CNT to form C-Si bonds. This facile procedure is eco-friendly and suitable for the largescale production.


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Figure 2. XRD patterns of (a) MXene and Si; (b) different revolution speed (200 rpm, 600 rpm, 900 rpm) of ball-milled MSC-60 composites; (c) different proportions of MXene to Si in MSC. The structures of MSC composites were characterized by X-ray diffraction (XRD) technique (Figure 2). XRD patterns of the Si and MXene precursors are shown in Figure 2a. Apart from Si phase (JCPDS No. 27-1402), residual MAX phases emerges in MXene’s pattern due to the incomplete etch, and the characteristic (002) peak of MXene appears at ~9.5°.23,38 Figure 2b and c show XRD patterns obtained under different revolution rates and materials proportions, respectively. Altering contents of MXene and Si individually (named by the contents of silicon as MSC-20, MSC-40, MSC-60 and MSC-80) does not influence the XRD patterns of these composites apart from the peak intensities. During this synthesis process, no other phases are generated in the as-prepared MSC composites. However, once the ball-milling speed up to 600


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(MSC600 rpm) or 900 (MSC900 rpm) rpm, TiSi2 new phases appear in XRD patterns because the very high energy engendered by high speed ball-milling drives the alloy of the raw materials.

Figure 3. SEM images of (a) partial-etched MXene; (b) nano-Si; (c) ball-milled MSC-60 composite; corresponding elemental mapping images (d)-(f) for the distribution of Si, Ti and C elements, respectively.

Morphologies of the raw materials and MSC composites were examined by scanning electron microscopy (SEM) (Figure 3). MXene exhibits thick-layer patterns because a portion of MAX phases remained during etching process. In particular, SEM images of the as-prepared MSC-60 composite (Figure 3c) show appropriate multi-dimensional constructed architecture consisting of MXene, nano-Si (Figure 3b) and CNT. In this architecture, MXene and nano-Si were grounded together and Si nanoparticles were firmly attached onto the surfaces and interlayers of MXene. Meanwhile, CNT twined around MXene-Si aggregates so that they can combine together tightly. At the same time, composites with different proportions of MXene to nano-Si were prepared to explore the impacts of material contents. As we can see from the SEM images (Figure S1a-c), different from the network in Figure 3c, a large amount of crushed aggregates and particles are nonuniformly distributed in these samples. We also synthesized MSCs from starting materials


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including MXene, commercial Si microparticles and CNT with different proportions (Figure S2a), the morphologies of which are shown in SEM in Figure S2b-e and display non-uniform distribution and large-sized grains.

Besides, at ultra-high speeds (Figure S1d and e), the

morphologies of MSC turn into vague and disordered due to the strong milling impact from the high energy. In Figure 3d-f, Si, Ti and C elements disperse homogeneously in those particles as revealed by their characteristic EDX elemental maps, revealing that silicon can be well distributed within MXene and CNT by ball-milling method.

Figure 4. (a) TEM images of the MSC-60 composite consists of MXene, Si and CNT; (b) STEM image of the MSC-60 composite; (c)-(e) are the EDX elemental mapping images of Si, Ti and C elements, respectively.

Transmission electron microscopy (TEM) characterization of the MSC-60 composite has been further performed to reveal the morphology of MXene, Si particles and CNT and their physical contact (Figure 4a). Moreover, the physical integration of components in MSC has been confirmed by scanning transmission electron microscopy (STEM) high-angle annular dark-field (HAADF) imaging (Figure 4b) and EDX mapping results (Figure 4c-e), where silicon particles tightly


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bounded to MXene surface and CNT. Moreover, as for the composite interfaces, Si particles could be observed clearly binding with MXene (Figure S3). It indicates that this MSC composite can be combined with MXene, Si and CNT, which is consistent with SEM results. Multi-dimensional constructed skeleton-like structures provide excellent conductive network for silicon particles in these composites, and electron transfers during charging and discharging processes can be well promoted by this framework. The inactivation phenomena of silicon anodes due to their volume expansion during lithiation/delitiation will be effectively modulated by this multi-dimensional skeleton with appropriate spaces for silicon accommodation, and the electrochemical contacts will also be enhanced by CNT own to its high electron conductivity.39–43 The N2 absorption/desorption measurement (Figure S4) shows the BET surface area of the pristine MSC-60 is 20.48 m² g−1. In the same time, the conductivity of MSC anode material provided by CNTs cannot be ignored. The Raman test of MSC-60 was performed to detect the structure integrity of CNTs after ball milling. As shown in Figure S5a and 5b, the D band is very weak compared with the G band, demonstrating that CNTs in MSC-60 have a low defect density. The absence of structure damage of CNTs from ball milling implies that the conductivity of MSC was not reduced due to the structure-damage effect.


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Figure 5. High-resolution XPS spectra after sputtering with Ar+ ion of (a) Si 2p, (b) Ti 2p3/2 and (c) C 1s in MSC-60 and MS-60, respectively; (d) optimized structure of CNT-Si and MXene-Si units. To further investigate the structural assets of MSC composites, XPS analyses (Figure 5a-c) were carried out on MSC-60 and MXene-Si-60 (MS-60) to figure out the distinctions in the elements and chemical bonds. The characteristic here comes from the exhibits of both Ti-Si and C-Si bonds as revealed by Ti 2p3/2, C 1s and Si 2p core spectra. On one hand, the Si 2p component observed at 99.1 eV and 101.0 eV can be deconvoluted into Si-C and Si-Ti peaks, respectively. On the other hand, in the MSC-60 composites, the Ti 2p3/2 component observed at 453.9 eV can be deconvoluted into Ti-Si peaks, and the C 1s component observed at 283.4 eV can be deconvoluted into C-Si peaks (peak fitting results are shown in Table S1).44–49 The peak at 453.9 eV in Ti 2p3/2 and the peak at 283.4 eV in C 1s spectra of MSC-60 are characteristic Ti-Si and C-Si bonds,


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respectively. Because of the specific elemental compositions of MXene, the origin of Ti-Si bonds could be deducted from Si and MXene. Considering the sources of carbon are diverse, the area of characteristic C-Si peak in Si 2p varies from 41% for MSC-60 to 33% for MS-60, and therefore we can conclude that parts of C-Si bonds are originated from the combination of CNT (CCNT-Si) and MXene (CMXene-Si). Apart from XPS confirmation, the existence of C-Si bonds can also be confirmed the characteristic peak at ~880.7 cm−1 by Fourier-transform infrared spectroscopy (FTIR) analysis (Figure S6).50,51 In addition, while the amount of CNT was kept to be additional 2 wt.% of total mass, the intensity of this C-Si peak is found to increase with the increasing in the amount of Si, further suggesting the existence of CCNT-Si bonds between Si particles and CNT.

To further substantiate the existence Ti-Si and C-Si bonds, we calculated the total energy of MXene, Si, CNT, CNT-Si and MXene-Si to study the binding energy of MXene-Si and CNT-Si. Equation of binding energies are defined as follow ∆Ef =

∆Ef =

EMXene - Si - EMXene - ESi

(1)

n

ECNT - Si - ECNT - ESi

(2)

n

where ΔEf is the binding energy, EMXene, ESi and ECNT are the total energy of MXene, Si and CNT, EMXene-Si and ECNT-Si are the total energy of MXene-Si and CNT-Si composite structures, and n is the number of atoms.


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From Equation (1) and (2), binding energies of MXene-Si and CNT-Si are calculated to be −0.190 eV/atom and −0.429 eV/atom, respectively. Low binding energy with negative values promotes the spontaneous formation and stabilization of MXene-Si and CNT-Si composite structures. During the high energy milling process, atoms with unoccupied orbitals are generated at the surface of starting materials, and atom reconstructions with electron transfers take place in proper MXene-Si or CNT-Si interface. As a result, chemical bonds can be formed at the MXene-Si or CNT-Si interface in this process, and the most stable status of MXene-Si or CNT-Si heterostructure is realized.25,52 Optimized structure units of MXene-Si and CNT-Si binding modes are presented in Figure 5d, demonstrating more clarity of MSC materials at molecular structure level.53

Figure 6. Typical charge/discharge curves at the current density of 500 mA g−1 and at the potential window of 0.01-1.5 V of (a) different ball-milling speeds in MSC-60 composites and (c) different proportions of MSC composites for the second cycle; (b) and (d) are the corresponding cycling capabilities of above materials performances tested at 200 mA g−1 for the 1st cycle and 500 mA g−1 for the following cycles.


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Different ball-milling revolution speeds and different proportions of precursors in MSC were tried synthesize a series of MSC composites to select the best electrochemical performance sample (Figure 6). MSC-60 composite using nano-Si precursor at ball-milling revolution speeds of 200 (MSC-60), 600 (MSC600 rpm) and 900 (MSC900 rpm) rpm was first tested as anodes in LIBs. The cycle performances of the three anodes are shown in Figure 6a, which shows that the capacity and initial Coulombic efficiency (ICE) decrease with the increase of the revolution speed. These phenomena can be ascribed to the effect of high-speed synthetic routes, i.e., the inefficiency of the inhomogeneous morphology and the overmilled structure with alloying phases of the composites to sustain the extreme volume expansion during lithiation and delithiation. The emerging alloying phases are likely electrochemical inertness, leading to the difficulty of the lithiation and delithiation process and thus the failure of the batteries. The electrochemical characterizations of MSC composites were also performed on composites obtained at 200 rpm ball-milling speed, with either different MXene to Si ratios (Figure 6c and d) or different particle sizes of Si (Figure S7). MSC-60 composites deliver the optimal cycle performance, the capacity of MSC-80 declines quickly, and the more durable cycle performances can be obtained with the trends of less silicon proportions added. In particular, MSC-20 anode possesses the most stable cycle life among all four as-prepared samples although the capacity is relatively lower than those of others. It suggests that the higher contents of MXene provide better cycle capability, stabilize the electrode structures, and restrain silicon’s volume expansion and pulverization. Materials prepared from different revolution speed such as 100 rpm, 300 rpm and 400 rpm were also exhibited in Figure S8. However, the MSC anodes prepared from micro-Si exhibit poor cycle capabilities because the silicon microparticles are too large to be stably restricted on the current collectors and also suffer


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from pulverization. Compared with the overall cycle performances of the above samples, MSC60 was chosen as a representative composite to be explored for further electroanalytical techniques.

Figure 7. (a) CV curves of MSC-60 anode at the first three cycles; (b) representative galvanostatic charge-discharge process profiles of MSC-60 at 500 mA g-1 vs. Li+/Li; (c) rate performance at current densities of 100, 200, 500, 1000, 2000 and 100 mA g-1 in the same cut-off voltage; (d) Nyquist plots of the pristine state batteries consisting of MSC-60, MS-60, CNT-Si, the inset presents the equivalent circuit model; (e) cycling capabilities as well as the Coulombic efficiency of different composites.


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The lithiation and delithiation properties of the obtained MSC-60 anode materials have been investigated by the cyclic voltammetry (CV) tests at a scan rate of 0.1 mV s−1 between 0.01 and 1.6 V (vs. Li/Li+), which exhibits typical Si-based materials profile (Figure 7a). In the first cycle, it can be observed that MSC anode shows a sharp reductive peak at around 0.18 V, which demonstrates the formation of a stable solid electrolyte interface (SEI) film.21,23,35 The two oxidation peaks observed at around 0.35 V and 0.53 V represent the delithiation stages of the anode materials, and they also indicate the Li-Si alloying/dealloying stages.16,17 Classic charge/discharge curves (Figure 7b) of MSC for the 1st, 5th, 10th, 50th and 100th cycles display a stable potential profile, and the ICE of MSC-60 is 70.38%, which is larger than common ICEs. Meanwhile, the following CE rapidly increases to ~98% after 10 cycles. It is known that the low initial CE of Sibased materials attributes to the formation of SEI film. With the participation and synergy of MXene and CNT in MSC, the formation of highly conductive SEI film could be facilitated by Ti-Si and C-Si bonding in composites, resulting the lift of the ICE.

The superiority of the MSC-60 composite is also manifested by their superb rate capabilities as shown in Figure 7c. The discharge capacities of MSC-60 anode are 1613, 1514, 1357, 1140 and 841 mAh g−1 at current densities of 100, 200, 500, 1000 and 2000 mA g−1, respectively. When the current density returns back to 100 mA g−1, a discharge specific capacity of 1392 mAh g−1 can be obtained, while the rate performances of MSC600rpm and MSC900 rpm are inferior to MSC-60 (Figure S9). These superior performances of composites including MSC-60, MS-60 and CNT-Si are further supported by Nyquist plots access from electrochemical impedance spectroscopy (EIS)


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measurements. Especially, the total resistances of the above three kinds of materials are proved by the fitted impedance spectra with the equivalent circuit (inset in Figure 7d), which show that the interfacial charge transfer resistance of MSC-60 is the lowest (Table S2).21,44,54 The MSC composite has the lowest resistance, which favors the fast Li+ kinetics and the formation of highly conductive SEI film due to the fast electrons and ions transport. It is probably that the conductive MXene and CNT and the formed Ti-Si and C-Si bonds in MSC facilitate the fast electrons and ions transport.

All electrodes were implemented at 200 mA g−1 for the initial cycle and then for the following cycles at 500 mA g−1 (Figure 7e), and MSC anodes exhibited excellent electrochemical performance. Especially, the MSC-60 delivers the highest initial reversible capacity of 1260 mAh g−1, and presents a high specific capacity of ~1000 mAh g−1 and around 80% capacity retention after 200 cycles. We have also conducted the MSC-60 with 8:1:1 electrode composition, the initial reversible areal capacity is 1301 mAh g−1 at current density of 500 mA g−1 (Figure S10), similar to the electrode with 7:2:1 composition.

As a two-dimensional material, MXene provides

conductive network for zero-dimensional silicon particles to enhance its electrochemical activity and to boost high electrical conductivity of MSC, which ensures the improvement of MSC anode’s rate capabilities. Besides, one-dimensional CNT in MSC bridges and binds Si and MXene together, and augments conducting pathways for individual particles, which guarantees the structure stability and outstanding conductivity.55–57 During charge and discharge stages, MSC’s appropriate multi-dimensional architecture also restrains the volume expansion of silicon, which is beneficial to stabilize the cycle performance, to acquire a higher specific capacity and to obtain high rate capabilities.


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To further explore the role of MXene, Si and CNT played in MSC anode, we performed additional electrochemical tests (Figure 7e) on MS-60 and CNT-Si electrodes. Under the same test condition as above, only after 20 cycles, a sharp capacity fading appears in the following cycles, which reflects that the above mentioned three raw materials are indispensable in the electrode reactions and the excellent cycle stability could not be realized without MXene-Si-CNT triple components construction. It demonstrates that Ti-Si and C-Si bonds emerged in this MSC composite and are beneficial for attenuating volume expansion and pulverization of Si anodes during charging and discharging by the strengthened chemical bonding.29,30 Nevertheless, neither bonding species in MXene-Si (including Ti-Si and CMXene-Si) nor CCNT-Si bonding in CNT and Si alone cannot realize the optimal performance. Comparing MSC and MS, the CCNT-Si bonding between CNT and Si in MSC does not exist while Ti-Si bonds still exists in MS. It demonstrates that this distinct Ti-Si bonding formed in the ball-milling process originates from Ti atoms of MXene with Si. As for CSi bonds, binding ability of carbon source from CNT triumphs that of carbon source from MXene. Thus, both Ti-Si and CCNT-Si dual bonds mediate each other and synergistically affect the attractive performance of MSC anode together. Moreover, we confirmed the maintenance of the dual bonds after 150 cycles by XPS (Figure S11), which showed that the Ti-Si and C-Si bonds emerged at 99.0 eV and 101.0 eV, respectively.58 The appearance of these two peaks approves that the dual chemical bonds are strong enough to endure the electrochemical processes and retain in the matrix of MSC electrodes.


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Figure 8. Different discharge states of MSC composite: (a) pristine state of lithium metal contacted with MSC; the MSC anode under conventional lithiation conditions of (b) −0.5 V potential, (c) −1 V potential and (d) −3 V potential; (e) MSC after withdrawing the lithium metal; the electron diffraction patterns of the MSC composite (f) before reacting, (g) upon reacting with Li metal and (h) after the lithiation reaction.

Finally, we examined the complete lithium alloying process of MSC by an in situ TEM approach to directly capture the dynamic changes. Once the Li2O-covered lithium electrode driven by a piezoceramic manipulator was contacted to the MSC composite, a constant voltage was immediately applied on the sample to launch the lithiation process. The morphology and structural evolution of MSC upon lithiation was recorded in Figure 8a-e, and a real-time movie characterizing the first lithiation process is shown in supplemental material (movie S1). The


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electron diffraction patterns (EDPs) of the MSC taken prior to, upon, and after the lithiation reaction are shown in Figure 8f, g and h, respectively. The pristine composite demonstrates obvious sharp Bragg spots in this EDP (Figure 8f), indicating the existence of Si. As alloying with Li ions, those sharp spots become indistinct, meanwhile some new dim ones are generated. A typical structural transformation of silicon matrixes from Si (JCPDS No. 27-1402) to Li12Si7 (JCPDS No. 40-0942) is supposed to take place in this process (Figure 8g and h). During this lithiation process, MSC composite demonstrated an unobvious volume expansion and the composite did not undergo pulverization during the potential varying. The SEM tests were also performed to evaluate the volume change of the MSC during lithiation (Figure S12). The thickness change between the two electrodes as measured from SEM images is only 18%, a significantly suppressed volume expansion during the electrochemical process. CONCLUSIONS In summary, we have employed MXene, commercial Si nanoparticles and carbon nanotubes to fabricate a dual bond restricted multi-dimensional constructed architecture of MXene-Si-CNT (MSC) triple components composite. As a result, MSC anodes showed superb lithium storage capabilities due to the formation of Ti-Si and C-Si bonds. Owing to these factors, MSC composite with 60 wt.% silicon anodes in LIBs exhibited excellent comprehensive performance with ~80% capacity retention after 200 charge/discharge cycles, a reversible capacity of 1260 mAh g−1 and excellent rate performance with 1034 mAh g−1 at 2 A g−1. With the assists of in situ TEM measurements, the construction of MSC composite to improve performances of commercial Si can be confirmed dynamically. In particular, this composite construction also provides several assets to fulfill the demands of the large-scale production for commercialization. Hence, this study


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provides opportunities to meet the urgent need of energy storage applications and derives more scalable synthetic routes.

EXPERIMENTAL METHODS Synthesis of MXene-Si-CNT (MSC) Composites. In this work, Si powders (Aladdin (100-120 nm), and Alfa Aesar (1-5 μm) for comparison) and carbon nanotubes (CNT, Timesnano, single walled) were purchased and used as received. Partial etched MXene was synthesized according to previous literature with shorter etching time.59 MSC composites were prepared by ball milling of MXene and Si (1:4, 2:3, 3:2 and 4:1 by weight) with additional 2 wt.% CNT in ~20 mL ethanol at 200 rpm for 7 h, in which a tungsten carbide pot and balls were used. The obtained mixtures were dried at 40 ºC in an oven for 10 h to remove ethanol, and then transferred into an argon-filled glove box. Composites prepared with 40 wt.% MXene, 60 wt.% Si without CNT added and prepared at different revolution speeds (600 rpm and 900 rpm) were used for comparison. Structural Characterizations. The structures of the as-prepared composites were investigated by field-emission scanning electron microscopy (FE-SEM) equipped with an energy dispersive X-ray (EDX) spectrometer (FEI QUANTA 650) and scanning transmission electron microscopy (STEM, TITAN G2 60-300). In situ TEM was performed on the TEM (FEI Tecnai F20). X-ray diffraction (XRD) was examined by Bruker D8 Advance diffractometer with a rotating anode generator (Cu Kα1 radiation, λ=1.5406 Å). X-ray photoelectron spectroscopy (XPS, Thermo Fisher Scientific ESCALAB 250Xi) was carried out using Al Kα monochromatic beam (1486.6 eV). Fouriertransform infrared spectroscopy (FTIR, Thermo Fisher Nicolet 380) were collected from 750 to 2000 cm-1.


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Electrochemical Measurements. The working electrodes were prepared by casting slurries consisting of 70 wt.% MSC as the active material, 20 wt.% Super P carbon as the conducting agent and 10 wt.% carboxymethyl cellulose (CMC) as the binder onto Cu foils. After casting, the electrodes were dried at 80 ºC for 12 h in a vacuum oven and then pressed at 10 Mpa in air. The mass loaded amounts of active materials in the electrodes were around 1.20 mg cm−2. The electrodes were then transferred into an argon filled glove box. R2032-type coin half cells (MTI Corporation) were assembled consisting of the prepared working electrodes, Li foil as the negative electrode, a Celgard separator, and 1 M LiPF6 in a 1:1 (v/v) mixture of ethylene carbonate (EC) and diethyl carbonate (DEC) with 2% fluoroethylene carbonate (FEC) as the electrolyte. Galvanostatic measurements were performed on a Land Battery Testing System in the voltage range of 0.01-1.5 V. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were conducted on a Solartron electrochemical workstation. The specific capacity was measured on the basis of the total weight of MXene-Si-CNT composite. Computational Methods. All the calculations were performed using the density functional theory (DFT) method, which is implemented in the Vienna ab initio package (VASP) with a plane wave basis set.60,61 The plane wave expansion of the eigenfunctions was carried out with a cut-off energy of 480.0 eV. All structures were relaxed until the self-consistent force was less than 10−2 eV Å−1 and the difference of the total energy between two consecutive steps was less than 10−5 eV. The van der Waals force scheme was used to describe the interlayer interaction in MXene-Si. We set a 20 Å vacuum layer to simulate the combinative procedure of MXene-Si and CNT-Si. To attenuate the effect of lattice mismatch, 2 × 1 × 2 and 4 × 1 × 1 supercells were used for Si (containing 8 Si atoms) and Ti3C2 (containing 2 Ti3C2 units), respectively. The length of CNT in the model is 4.92 Å.


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ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website at http://pubs.acs.org. Supporting Information Available: More information of MXene-Si-CNT, including Figure S1S12, Table S1-S2 and Movie S1 (PDF) AUTHOR INFORMATION Corresponding Author * E-mail: [email protected]. ORCID Haijun Yu: 0000-0003-0204-9943 Shiqi Liu: 0000-0003-3230-9099 Xu Zhang: 0000-0001-7320-4360 Author Contributions H.J.Y. proposed the project and designed the experiments. S.Q.L. and M.C. synthesized MSC samples and performed the battery tests. R.F.C. and X.H.W. provided MXene samples. P.F.Y. and Y.Y.J. conducted the TEM measurements. X.Z. performed XPS tests and helped analyze the XPS data. B.Y.W. performed the DFT calculations. Y.S.T. and L.Q.Z. conducted the in situ TEM tests. S.Q.L., X.Z. and H.J.Y. wrote and polished the manuscript. L.W. discussed the experimental results. All authors analyzed the data and contributed to the discussion. ACKNOWLEDGMENTS


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S.Q. Liu is grateful for technical assistances from Mr. Guan’erqi Gao, Mr. Xuyang Shen and Ms. Furong Sun in this work. This work was financially supported by the National Natural Science Foundation of China (Grants 51622202, 21603009, and 21875007), the National Key R&D Program of China (Grant No. 2018YFB0104302) and Beijing Natural Science Foundation (B) (KZ201910005002).

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