Metal–Organic Frameworks (MOFs) as Sandwich Coating Cushion for

Nov 16, 2015 - (6) Silicon (Si), one of the most promising anode materials for the next generation LIBs,(7) has been extensively studied in the past f...
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Metal−Organic Frameworks (MOFs) as Sandwich Coating Cushion for Silicon Anode in Lithium Ion Batteries Yuzhen Han, Pengfei Qi, Junwen Zhou, Xiao Feng, Siwu Li, Xiaotao Fu, Jingshu Zhao, Danni Yu, and Bo Wang* Key Laboratory of Cluster Science, Ministry of Education of China, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, School of Chemistry, Beijing Institute of Technology, Beijing 100081, People’s Republic of China S Supporting Information *

ABSTRACT: A novel metal−organic framework (MOF) sandwich coating method (denoted as MOF-SC) is developed for hybrid Li ion battery electrode preparation, in which the MOF films are casted on the surface of a silicon layer and sandwiched between the active silicon and the separator. The obtained electrodes show improved cycling performance. The areal capacity of the cheap and readily available microsized Si treated with MOF-SC can reach 1700 μAh cm−2 at 265 μA cm−2 and maintain at 850 μAh cm−2 after 50 cycles. Beyond the above, the commercial nanosized Si treated by MOF-SC also shows greatly enhanced areal capacity and outstanding cycle stability, 600 μAh cm−2 for 100 cycles without any apparent fading. By virtue of the novel structure prepared by the MOFs, this new MOF-SC structure serves as an efficient protection cushion for the drastic volume change of silicon during charge/ discharge cycles. Furthermore, this MOF layer, with large pore volume and high surface area, can adsorb electrolyte and allow faster diffusion of Li+ as evidenced by decreased impedance and improved rate performance. KEYWORDS: metal−organic frameworks, lithium ion battery, silicon, anode, sandwich coating method

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INTRODUCTION Lithium ion batteries (LIBs) are widely used for energy storage in numerous electronic devices due to their relatively high energy density and power density.1−4 The most representative commercial anode material of LIBs is graphite, but its low theoretical capacity (372 mAh g−1) and inferior rate capability limit its use in many emerging applications, such as electric vehicles (EVs) and large-scale sustainable energy storage systems.5 Hence there is increasing demand in developing advanced electrode materials with higher energy density.6 Silicon (Si), one of the most promising anode materials for the next generation LIBs,7 has been extensively studied in the past few years for its high theoretical capacity, low cost, natural abundance, and environmental benignity. The theoretical capacity of Si is 4200 mAh g−1; one Si atom can at most react with 4.4 lithium atoms to form a Li4.4Si alloy.8 This, however, results in a large volume change of 400%, leading to cracking and pulverization of the electrode upon repeated charging and discharging and rapid capacity fading during the long cycling.9 In addition, the solid electrolyte interphase (SEI) is not stable upon direct exposure of silicon to the electrolyte, causing sustaining consumption of the electrolyte and low Coulombic efficiencies. To address these scientific issues, strategies have been proposed to control the size and structure of Si,10,11 or to protect Si with surface coatings,12 such as carbon13 and metal oxides.14 Although considerable improvements have been made, these methods are sometimes too complicated and time-consuming, and are mainly based on the © XXXX American Chemical Society

design of active silicon; little attention has been paid on the modification of the silicon electrode as a whole by introducing functional layers.15 MOFs16−18 have attracted great research interest in many fields,19−22 such as catalysis,23 gas storage,24 sensing,25 separation,26 etc. The application of MOFs in LIBs is currently a field of increasing attention and we and others have explored the potential of MOFs with some preliminary results in recent years.27 Specifically, MOFs have been introduced to improve the properties of existing cathode and anode materials28 and found use as sulfur hosts in Li−S batteries.29 Furthermore, MOF-derived materials can be directly used as electrode materials and show outstanding performance in lithium storage.30 Because the large pore volume and high surface area of MOFs, they could provide much space and some researchers have also studied their storage of electrolyte,31,32 among which MOFs were used as the solid electrolyte for the LIBs. The pores of the MOFs could be filled with electrolyte to improve the diffusion of Li+ and reduce the impedance of the LIBs.

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RESULTS AND DISCUSSION In this paper, for the first time, a novel metal−organic framework (MOF) sandwich coating method (denoted as Received: August 31, 2015 Accepted: November 16, 2015

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DOI: 10.1021/acsami.5b08109 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

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the simulated ones (Figure S2 in the Supporting Information), indicating the crystallographic purity of the bulk MOF samples. The 200 mesh Si (75 μm) was further ball-milled by a planetary miller at 200 rpm for 6 h to obtain the micro-Si sample. PXRD patterns (Figure S3a in the Supporting Information) show the two main diffraction peaks at 28.5° and 47.4° in the diffraction patterns of Si, which are ascribed to the (111) and (220) facets of Si, respectively. The broadened weak diffraction peak between 10° and 20° of the nano-Si is due to the amorphous substrate. The morphology of the micro-Si particles is not homogeneous with many aggregates; the maximum particle is about 2 μm in size (Figure S4a in the Supporting Information). These multisized Si particles were mixed together, which was proved to be favorable for long charge−discharge cycles.33 The small Si particles can fill the empty space between the large ones, thus shortening the path of the diffusion of Li+ across different Si particles and the electrical connectivity can be also promoted as a result. Figure 2 (also see Figure S3b, in the

MOF-SC) is developed for hybrid Li ion battery electrode preparation, in which the MOF films are casted on the surface of a silicon layer and sandwiched between the active silicon and the separator. The obtained electrodes show improved cycling performance. The areal capacity of the cheap and readily available microsized Si (micro-Si) treated with MOF-SC can reach 1700 μAh cm−2 at 265 μA cm−2 and maintain at 850 μAh cm−2 after 50 cycles. Beyond the above, the commercial nanosized Si (nano-Si) treated by MOF-SC also shows greatly enhanced areal capacity and outstanding cycle stability, 600 μAh cm−2 for 100 cycles without any apparent fading. This new MOF-SC structure serves as an efficient protection cushion for the drastic volume change of Si during charge/discharge cycles. MOFs in the upper coating layer, with large pore volume and high surface area, can effectively adsorb the electrolyte and allow faster diffusion of Li+ as evidenced by decreased impedance and improved rate performance (vide inf ra). The MOF-SC, is shown in Figure 1. First, conductive carbon (Super P) is painted on the surface of Cu foil; second silicon

Figure 2. (a) Sandwich electrode of C/Si/ZIF-8 on the Cu foil (wet). (b) Electrodes coated with different MOFs (ZIF-8, ZIF-67, MIL-53, NH2-MIL-53, MOF-5, HKUST-1). (c,d) SEM images of C/Si/ZIF-8 electrode (cross section) and elemental mapping of the electrode by energy-dispersive X-ray spectroscopy (EDS).

Figure 1. Representative procedure of the coating method, the structure of the sandwich electrode and the possible protection mechanism during cycling. The red arrows represent the diffusion of Li+.

Supporting Information) shows the appearance and SEM images of the electrode prepared by the MOF-SC method. The cross section of the electrode is clearly layered. As evidenced by elemental mapping using EDS, the bottom of the electrode is the Cu foil whereas Si particles are embedded between the Super P layer and the MOF layer; the Zn element is welldispersed on the surface, which is attributed to the thin layer of ZIF-8. This electrode that is prepared by the MOF-SC method is denoted as C/Si/ZIF-8 where C represents super P. The advantages of the present strategy to prepare sandwich electrode in LIBs are exemplified by the improved electrochemical performance. The cycling performance of the C/Si/ ZIF-8 (micro-Si) electrode at a current density of 265 μA cm−2 between the voltage ranges of 0.01−2 V is shown in Figure 3a. In the first discharge, the electrode exhibits a higher capacity than the second one. The small irreversible capacity loss in the first cycle could be caused by the irreversible decomposition of the electrolyte and the formation of SEI layer. The initial discharge and charge capacities are 2046 and 1752 μAh cm−2 for C/Si/ZIF-8, and after 50 cycles the capacity still maintains at 850 μAh cm−2. For the pristine micro-Si, the initial discharge and charge capacities are 1507 and 1331 μAh cm−2, respectively. The electrode shows a sharp fading and the capacity rapidly drops to below 50 μAh cm−2 within 20 cycles.

particles are casted on the conductive carbon; on top of the silicon layer, MOF particles (ZIF-8) are subsequently casted, leading to a sandwiched Si electrode architecture. The electrode was cut into round slices, the diameter is 12 mm. The Si loading of the electrodes (1.13 cm2) is 0.7 mg (micro-Si) and 0.5 mg (nano-Si). We had selected different parts of the electrode and weighed the mass, the electrode is very uniform and the error is less than 0.1 mg. The weight of the MOF on the surface of the electrode is 0.4 mg. This unique arrangement could supply sufficient spaces for the volume change of Si during cycling. The bottom Super P enhances the contact of the silicon with the current collector giving improved electrical conductivity. The upper MOF layer can adsorb and permit fast diffusion of electrolyte into and out-of the Si layer. The MOFs can also reduce the direct exposure of Si to the electrolyte and help to form a stable SEI layer so as to mitigate the capacity fading during cycling. (The detailed experimental procedure is shown in the Experimental Section.) The obtained electrode was fully characterized by PXRD, SEM, AC impedance, and galvanostatic tests. The assynthesized MOFs were characterized by powder X-ray diffraction (PXRD); the patterns are consistent with that of B

DOI: 10.1021/acsami.5b08109 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

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Figure 3. (a) Cycling performances of C/Si/ZIF-8, C/Si/C structure electrode and pure micro-Si. The current density is 265 μA cm−2. (b) Nyquist plots for the micro-Si, C/Si/C and C/Si/ZIF-8 after five cycles under an applied voltage of 0.15 V. (c) Galvanostatic charge−discharge profiles of C/ Si/ZIF-8 at a current density of 265 μA cm−2. C/Si/ZIF-8 denotes the sandwich structure surface coated by ZIF-8.

To understand the unique role of the MOF protection layer, Super P is utilized again on the top of the electrode instead of MOF, denoted as C/Si/C. C/Si/C shows a lower capacity than that of C/Si/ZIF-8 with poorer long cycling stability (Figure 3a). The capacity of C/Si/C fades to 330 μAh cm−2 (50th cycle) from 2360 μAh cm−2 (first cycle), corresponding to a capacity retention rate of 14%, much lower than that of C/Si/ ZIF-8 (42%). From the galvanostatic charge−discharge voltage curves shown in Figure 3c, we can find that the voltage platform is 0.2−0.4 V, attributive to the lithiation and delithiation of silicon, in consistence with the cyclic voltammetry (CV) curves of C/Si/ZIF-8 electrode (Figure S5 in the Supporting Information). AC impedances are shown in Nyquist plots for C/Si/ZIF-8, C/Si/C and the Si powder (Figure 3b). The impedance of C/Si/ZIF-8 associated with the charge-transfer resistance is much lower than that of the C/Si/C and pure Si powder. We postulate the low impedance benefits from the sandwich electrode structure, in conjunction with the enhanced electrical conductivity provided by the Super P at the bottom and the promoted transport of electrolyte by the MOF on the surface. We further evaluated how the thickness of the Si layer affects the performance of the batteries, by comparing three electrodes with different Si thicknesses (50, 100, 150 μm). The results showed that a thinner Si layer would lead to a lower areal capacity but with slower capacity fading (Figure S6 in the Supporting Information). Thus, to achieve the best cycling stability, the thickness of Si layer in the following experiment was 50 μm. We also applied this MOF-SC method to nanosized silicon (nano-Si). The PXRD and SEM observations are shown in Figure S3 and Figure S4b in the Supporting Information. The size of nano-Si is around 50−100 nm with spherical shapes. The electrode preparation procedure was identical to that of micro-Si except for nano-Si was used instead. Cycling

performances are shown in Figure 4. The capacity of C/Si/ ZIF-8 (nano-Si) maintained at 600 μAh cm−2 without any

Figure 4. Cycling performance of the C/Si/ZIF-8 (nano-Si) structure, pure nano-Si and C/Si/C (nano-Si) electrodes. (The current density of the first five cycles is 200 μA cm−2.) C/Si/ZIF-8 (nano-Si) represents the sandwich structure with surface coated by ZIF-8.

apparent decrease for 100 cycles at a current density of 425 μA cm−2. In contrast, the capacity of the pristine nano-Si faded to nearly zero after 50 cycles; C/Si/C (nano-Si) also faded more rapidly than C/Si/ZIF-8 (nano-Si). The voltage curves are shown in Figure S7 in the Supporting Information, and the voltage platform matches that of characteristic silicon. To examine further the stability of the MOF during cycling, ex situ PXRD was used (Figure S8 in the Supporting Information). Before and after cycling, the two diffraction patterns match well, indicating good maintenance of ZIF-8 crystal structures throughout charge/discharge cycles. Ex situ SEM was also utilized to characterize fully the sandwich structure. As shown in Figure S9 in the Supporting Information, ZIF-8 particles are uniformly distributed on the surface of the electrode without obvious change after cycling; the ZIF-8 protection layer is still nicely attached to the Si surface. C

DOI: 10.1021/acsami.5b08109 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

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53 and NH2-MIL-53), or MOFs with small apertures (ZIF-8, ZIF-67) would perform better in improving cycling stability, compared to MOFs with open channels (MOF-5, MOF-199). With the same crystal structure and small open windows (Figure 5b), ZIF-8 and ZIF-67 have the similar electrochemical performance. With the open channels measured around 1 nm, MOF-5 and HKUST-1 (Figure 5a) show inferior retention rates. The Lewis acidic sites in HKUST-1 do not supply additional protection of the silicon particles over the cycles. With the same crystal structure yet additional −NH2 groups (Figure 5c), the capacity retention of Si/NH2-MIL-53 (68%) is very close to that of Si/MIL-53 (72%), which might suggest the key parameter for MOF-SC method is indeed the porosity rather than the additional functional groups on the side chain, i.e., the −NH2 groups. The AC impedance data are shown in Figure S10b in the Supporting Information when coated with different MOFs, the impedances are dramatically lower than that of the pure micro-Si.

We also explored the applicability of the MOF-SC method to several other representative MOFs, ZIF-67, MOF-5, HKUST-1, MIL-53, and NH2-MIL-53. In this system, we coated the electrode with just two layers (bottom Super P layer was omitted), where Si is directly casted on the current collector with the MOF layer on the top of the Si layer. Cycle performances of the micro-Si electrodes coated by different MOFs are shown in Figure S10 in the Supporting Information. The discharge capacities of the sixth cycle as well as the capacity retention over 30 cycles are shown in Figure 5d (also see Table

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CONCLUSION In conclusion, the MOF sandwich coating method, MOF-SC, is employed to prepare the silicon (Si) anodes. The decay rate is reduced when using the MOF-SC structure as an effective protection cushion. The obtained electrodes show excellent cycling performances; the areal capacity of micro-Si MOF sandwich structure, C/Si/ZIF-8, reaches 1700 μAh cm−2 and shows slower decrease over cycles. The areal capacity maintains at 850 μAh cm−2 after 50 cycles and the capacity retention rate is much higher than those of pure Si and the Super P sandwich structure, C/Si/C. The commercial nanosized Si (nano-Si) with the same MOF-SC approach also shows an enhanced performance and its areal capacity maintains at 600 μAh cm−2 without any clear drop for over 100 cycles. We also explored the applicability of MOF-SC method to several other representative MOFs, ZIF-67, MOF-5, HKUST-1, MIL-53, and NH2-MIL-53. These results suggest that flexible MOFs (MIL53 and NH2-MIL-53), or MOFs with small apertures (ZIF-8, ZIF-67) would perform better in improving cycling stability, compared to MOFs with open channels (MOF-5, MOF-199). The novel structure with an upper coating layer of MOFs can be used as a protection “net” or “cushion” for the silicon anode. More importantly, because of the large pore volume and high surface area of MOFs, this porous MOF layer can hold more electrolyte while facilitating fast diffusion of Li + and consequently lower the overall impedance. These preliminary results using the MOF-SC method on various MOF structures show that MOFs might be, in addition to a protection layer, an ideal solid electrolyte material for LIBs. This unique MOF-SC is also very straightforward and easy to operate for future industrial applications. The new method may serve as an alternative approach for the protection of Si and preparation of electrodes. Further mechanism study of these MOF sandwich structure is in process and will be reported timely.

Figure 5. (a−c) Crystal structures of different MOFs (HKUST-1, MOF-5, ZIF-8, ZIF-67, MIL-53, NH2-MIL-53). (d) Capacities of the sixth cycle and capacity retentions of micro-Si and micro-Si coated by different MOFs after 30 cycles. Si/MOF represents the structure with surface coated by different MOFs.

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S1 in the Supporting Information). In all MOFs cases, the capacity retention rates are higher than that of the pristine micro-Si (Figure 5d). Capacity retention rates of Si/ZIF-8 and Si/ZIF-67 are almost identical (65%), whereas those of Si/ MOF-5 (45%) and Si/HKUST-1 (31%) are slightly lower. It is worth noting that even these retention rates are still 2 times higher than that of the pristine micro-Si (14%). The capacity retention of Si/NH2-MIL-53 (68%) is very close to that of Si/ MIL-53 (72%). These results suggest that flexible MOFs (MIL-

EXPERIMENTAL SECTION

Preparation of the Sandwich Electrode. To prepare the anodes, 70 wt % active material (Si), 20 wt % Super P carbon black and 10 wt % sodium alginate binder were mixed in water solution to form a slurry. The conductive slurry was prepared by adding 70 wt % Super P and 30 wt % sodium alginate binder to the water. The MOF slurry was prepared by adding 70 wt % MOF and 30 wt % sodium alginate binder to the water. Because of serious hydrophilia of MOF-5 and HKUST-1, the slurry of the two MOFs were prepared by using D

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ACS Applied Materials & Interfaces the poly(vinylidene fluoride) (PVDF) binder in N-methylpyrrolidinone (NMP) solution. In our solution system, the concentration of the alginate binder is 15 mg/mL. First, the conductive slurry was casted onto copper foil using the applicator. The thickness of the slurry was 50 μm; then the active materials was coated on the surface of the Super P using the same method, the thickness of the Si was adjusted by the applicator (50, 100, 150 μm); next, the MOF slurry was coated on the surface of the Si, the thickness of the MOF layer was 50 μm. Between each coating step, the electrode was placed and dried at room temperature for 10 min to remove the too much water. The procedure of the coating method is showed in Figure S1 in the Supporting Information. The obtained electrode was dried under a vacuum at 120 °C for 12 h. Then the electrode was cut into round slices, the diameter is 12 mm. The Si loading of the electrodes are 0.7 mg (micro-Si) and 0.5 mg (nano-Si). We had selected different parts of the electrode and weighed the mass, the electrode is very uniform and the error is lass than 0.1 mg. The weight of the MOF on the surface of the electrode is 0.4 mg. Coin cells of CR2032 type were constructed inside an argon-filled glovebox using a lithium metal foil as the negative electrode and the composite positive electrode separated by polypropylene microporous separator (Celgard 2400). The electrolyte used was 1 M LiPF6 in ethyl carbonate (EC), diethyl carbonate (DMC), and ethyl methyl carbonate (EMC) (1:1:1 in v/v/ v). Assembled coin cells were allowed to soak overnight and then were charged and discharged between 0.01 and 2.0 V using a Land battery tester at ambient temperature. The electrochemical impedance spectra were measured using a potentiostat (CHI 760E: CH Instrumental Inc.) after 5 cycles. The frequency range was from 10−2 to 105 Hz with an applied voltage of 0.15 V. Synthesis of ZIF-8. ZIF-8 nanocrystals were synthesized through a simple stirred method. 0.297 g of Zn(NO)3·6H2O and 2.6 g of 2methylimidazolate were added in 150 mL of methanol, the solution was stirred for 24 h. The sediment was centrifuged and washed with methanol (50 mL) for three times and dried at 85 °C. Synthesis of ZIF-67. 5 g of Co(NO)3·6H2O and 33 g of 2methylimidazolate were added in 300 mL of water, and the solution was stirred for 8 h. The sediment was centrifuged and washed with water (50 mL) for three times and dried at 85 °C. Synthesis of HKUST-1. Benzenetricarboxylic acid (0.5 g, 2.38 mmol) was mixed in 12 mL of a 1:1:1 mixture of DMF/EtOH/H2O; Cu(OAc)·2H2O (0.86 g, 4.31 mmol) was mixed with 12 mL of the same solvent, and the mixtures were combined with stirring. Then triethylamine (0.5 mL) was added to the reaction mixture, which was stirred for another 23 h. The product was collected by centrifugation and washed with 100 mL of DMF and 50 mL of ethanol, then the blue powder was dried at 85 °C. Synthesis of MOF-5. MOF-5 were synthesized through a simple stirred method. Terephthalic acid (2.5 g) and triethylamine (4 mL) were dissolved in 200 mL of DMF. Zn(OAc)2·2H2O (8.5 g) was dissolved in 250 mL of DMF. Then the zinc salt solution was droped to the former solution, and the mixture was stirred to form a precipitate. The solution was stirred for 2.5 h. Then the product was collected by centrifugation and washed with 100 mL of DMF, and 50 mL of methanol then was dried at 85 °C. Synthesis of MIL-53. Al(NO3)3·9H2O (1.30 g) and BDC (0.288 g) were dissolved in 5 mL of deionized water. The synthesis was carried out in a 20 mL Teflon-lined stainless steel Parr bomb under autogenous pressure for 3 days at 220 °C. After centrifugation and washing with deionized water, the resulting white product was dried at 80 °C. Synthesis of NH2-MIL-53. 0.5 g of AlCl3·6H2O, 0.376 g of NH2− H2BDC, and 5 mL of H2O were added in the Teflon lined autoclave. The reaction was reacted 5 h at 150 °C and cooled to room temperature. The product was collected by centrifugation and washed with 100 mL of H2O and dried at 85 °C. All the products were characterized by PXRD. Treatment of μ-Si. The 200 mesh silicon was purchased from Alibaba (98%). 2 g of silicon was added to the grinding mill, 3 mL of ethanol was added as the dispersion liquid to prevent sinking to the bottom. After ball milling for 6 h, the product was dried at 85 °C. The

1−3 μm Si was obtained. The nano-Si was purchased from Shanghai Chaowei Nano Technology without any treatment before using. The size of the nano-Si was 50−100 nm. Powder X-ray diffraction (PXRD) pattern was analyzed with monochromatized Cu Kα (λ = 1.541 78 Å) incident radiation by a D8 Advance Bruker powder diffractometer operating at 40 kV voltage and 50 mA current.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.5b08109. Procedure of the coating method, PXRD data of different MOFs, PXRD of the nano-Si and micro-Si and the sandwich electrode of C/Si/ZIF-8 on the Cu foil, SEM images of micro-Si and nano-Si, cyclic voltammetry test of C/Si/ZIF-8 electrode, cycling performances of the micro-C/Si/ZIF-8 electrodes with different thickness of Si, galvanostatic charge−discharge profiles of C/Si/ZIF-8 (nano-Si) PXRD of the C/Si/ZIF-8 (nano-Si) electrode before and after cycling, SEM images of the C/Si/ZIF-8 (nano-Si) electrode and SEM images of the electrode after 20 cycles, cycling performance of the micro-Si/ MOFs electrode and pure micro-Si and Nyquist plots for the micro-Si and -Si/MOFs after five cycles under an applied voltage of 0.1 V, and sixth and thirtieth discharge capacities and the decay rates the electrodes (PDF).

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AUTHOR INFORMATION

Corresponding Author

*B. Wang. E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was financially supported by the 973 Program 2013CB834704; Provincial Key Project of China (7131253); the National Natural Science Foundation of China (21471018, 21404010, 21201018); 1000 Plan (Youth).

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REFERENCES

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DOI: 10.1021/acsami.5b08109 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

Research Article

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DOI: 10.1021/acsami.5b08109 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX