This is the pre-peer reviewed version of the following article: Dubal D.P., Jayaramulu K., Sunil J., Kment Š., Gomez-Romero P., Narayana C., Zboril R., Fischer R.A.. Metal–Organic Framework (MOF) Derived Electrodes with Robust and Fast Lithium Storage for Li-Ion Hybrid Capacitors. Advanced Functional Materials, (2019). 29. 1900532: - . 10.1002/adfm.201900532, which has been published in final form at https://dx.doi.org/10.1002/adfm.201900532. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. Advanced Materials Metal Organic Framework (MOF) derived Electrodes with Robust and Fast Lithium Storage for Li-Ion Hybrid Capacitors --Manuscript Draft-- Manuscript Number: adma.201807830 Full Title: Metal Organic Framework (MOF) derived Electrodes with Robust and Fast Lithium Storage for Li-Ion Hybrid Capacitors Article Type: Communication Section/Category: Keywords: MOF-derived Materials, manganese oxide, Li-ion capacitors, Energy Storage, Energy Density. Corresponding Author: Roland A. Fischer Technische Universität München Garching, GERMANY Additional Information: Question Response Please submit a plain text version of your To cover letter here. Dear Editor, We would like to submit our manuscript “Metal Organic Framework (MOF) derived Electrodes with Robust and Fast Lithium Storage for Li-Ion Hybrid Capacitors to Advance Materials as a communication. All authors have read and approved the submitted manuscript. The contents of our manuscript are original and not under consideration for publication elsewhere. Many papers promise electrode materials with energy densities much larger than those of supercapacitors and power densities much greater than those of batteries. However, High energy density AND high power density at the same time, all at a low cost is the real challenge. That is the holy grail of energy storage. Our report delivers precisely that. We are presenting a novel combination featuring simultaneously power density values typical of supercapacitors with energy density values worthy of batteries. This valuable combination has been made possible thanks to the implementation of kinetically-balanced two different Metal Organic Framework (MOF) derived electrodes. A concept most frequently overlooked in hybrid energy storage devices in general and in Lithium-Ion Capacitors (LICs) in particular. Herein, we engineer a well-organized interleaved composite of graphene-like nanosheets decorated with MnO2 nanoparticles (MnO2@C-NS) using manganese- based metal-organic framework (MOF) as a promising anode material for LICs. This uniquely architecture hybrid showed intriguing electrochemical properties including high reversible specific capacity 1054 mAh/g (close to the theoretical capacity of MnO2, 1232 mAh/g) with remarkable rate capability and cyclic stability (90 % over 1000 cycles). Moreover, a novel Li-ion hybrid capacitor (LIHC) is assembled using MnO2@C-NS as anode and MOF derived ultrathin nanoporous carbon nanosheets (derived from other potassium-based metal-organic framework) as cathode materials. The full-cell exhibits ultrahigh specific energy density of 166 Wh/kg at 550 W/kg and maintained to 49.2 Wh/kg even at high specific power density of 3.5 kW/kg as well as long cycling stability (91% over 5000 cycles). The present results already overcome power limits of batteries and energy density limits of Supercapacitors. This is first “Full MOF-derived LIHC” where both anode and cathode are derived from two different MOFs. Both electrodes are different types of easily scalable MOF-derived Powered by Editorial Manager® and ProduXion Manager® from Aries Systems Corporation materials with a great potential for low-cost upon mass production. We believe this report is more than just one step forward to the general use of electrochemical energy storage for EVs and stationary applications. By showing the way through engineering LIHC based on MOF derived hybrid materials, enable new opportunities for designing newly advanced MOF derived electrodes for next- generation energy storage devices. We really look forward to the publication of this thorough work in Advance Materials, which we consider the best suited journal for a status-breaking work like the one you have at hand. Sincerely yours and behalf of all coauthors Prof. Dr. Roland A. Fischer Chair of Inorganic and Metal-Organic Chemistry Technical University of Munich and Prof. Dr. Radek. Zboril Regional Centre of Advanced Technologies and Materials, Faculty of Science, Palacky University. Do you or any of your co-authors have a No. The authors declare no conflict of interest. conflict of interest to declare? Corresponding Author Secondary Information: Corresponding Author's Institution: Technische Universität München Corresponding Author's Secondary Institution: First Author: Roland A. Fischer First Author Secondary Information: Order of Authors: Roland A. Fischer Deepak P. Dubal Kolleboyina Jayaramulu, PhD Sunil Janaky Štěpán Kment Pedro Gomez-Romero, Professor Chandrabhas Narayana, Professor Radek Zbořil Order of Authors Secondary Information: Abstract: Hybrid inorganic-organic porous metal-organic frameworks (MOFs) demonstrated a great promise as ideal electrode materials for energy-related applications viz. Li-ion batteries and Li-ion Capacitors (LICs). Herein, we engineer a well-organized interleaved composite of graphene-like nanosheets decorated with MnO2 nanoparticles (MnO2@C-NS) using manganese-based MOF as a promising anode Powered by Editorial Manager® and ProduXion Manager® from Aries Systems Corporation material for LIHC. This uniquely architecture hybrid showed intriguing electrochemical properties including high reversible specific capacity 1054 mAh/g (close to the theoretical capacity of MnO2, 1232 mAh/g) at 0.1 A/g with remarkable rate capability and cyclic stability (90% over 1000 cycles). Such a remarkable performance might be assigned to the hierarchical porous ultrathin carbon nanosheets and tightly attached MnO2 nanoparticles, which provide structural stability and low contact resistance during repetitive lithiation/delithiation processes. Moreover, a novel Li-ion hybrid capacitor (LIHC) is assembled using MnO2@C-NS as anode and MOF derived ultrathin nanoporous carbon nanosheets (derived from other potassium-based metal- organic framework) as cathode materials. The full-cell exhibits ultrahigh specific energy density of 166 Wh/kg at 550 W/kg and maintained to 49.2 Wh/kg even at high specific power density of 3.5 kW/kg as well as long cycling stability (91% over 5000 cycles). This work shows that engineering MOF derived hybrid materials can significantly impact the Li-ion storage properties. Powered by Editorial Manager® and ProduXion Manager® from Aries Systems Corporation Complete Manuscript DOI: 10.1002/((please add manuscript number)) Article type: Communication 1 2 3 4 Metal Organic Framework (MOF) derived Electrodes with Robust and Fast Lithium Storage 5 for Li-Ion Hybrid Capacitors 6 7 Deepak P. Dubal,1,4*$ Kolleboyina Jayaramulu,2,3*$ Sunil Janaky,5 Štěpán Kment,3 Pedro Gomez- 8 Romero,4 Chandrabhas Narayana,5 Radek Zbořil3* and Roland A. Fischer2* 9 10 11 12 13 1 Dr. D. P. Dubal 14 School of Chemical Engineering, The University of Adelaide, 15 16 Adelaide, South Australia 5005, Australia 17 Email: dubaldeepak2@gmail.com 18 19 2 Dr. K. Jayaramulu, Prof. Dr. R. A. Fischer 20 21 Chair of Inorganic and Metal-Organic Chemistry, Department of Chemistry and Catalysis Research 22 Centre, Technical University of Munich, 85748 Garching, Germany 23 Email: jaya.kolleboyina@tum.de 24 Email: roland.fischer@tum.de 25 26 3 27 Dr. K. Jayaramulu, Dr. S. Kment, Prof. Dr. R. Zboril 28 Regional Centre of Advanced Technologies and Materials, 29 Faculty of Science, Palacky University, Šlechtitelů 27, 783 71, Olomouc, Czech Republic. 30 Email: radek.zboril@upol.cz 31 32 4 33 Dr. D. P. Dubal, Prof. Dr. P. Gomez-Romero 34 Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and the Barcelona Institute of 35 Science and Technology, Campus UAB, Bellaterra 08193, Barcelona, Spain 36 37 5 38 Prof. Dr. C. Narayana, Ms. S. Janaky 39 Chemistry and Physics of Materials Unit, 40 Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR) 41 Jakkur, Bangalore, 560064, India 42 43 $ 44 Both authors contributed equally. 45 46 47 48 Keywords: MOF-derived Materials, manganese oxide, nanoporous carbon, Li-ion capacitors, 49 Energy Storage, Energy Density. 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 Abstract 1 2 3 Hybrid inorganic-organic porous metal-organic frameworks (MOFs) demonstrated a great promise 4 5 as ideal electrode materials for energy-related applications viz. Li-ion batteries and Li-ion 6 7 Capacitors (LICs). Herein, we engineer a well-organized interleaved composite of graphene-like 8 9 nanosheets decorated with MnO2 nanoparticles (MnO2@C-NS) using manganese-based metal- 10 organic framework (MOF) as a promising anode material for LIHC. This uniquely architecture 11 12 hybrid showed intriguing electrochemical properties including high reversible specific capacity 13 14 1054 mAh/g (close to the theoretical capacity of MnO2, 1232 mAh/g) at 0.1 A/g with remarkable 15 16 rate capability and cyclic stability (90 % over 1000 cycles). Such a remarkable performance might 17 18 be assigned to the hierarchical porous ultrathin carbon nanosheets and tightly attached MnO2 19 20 nanoparticles, which provide structural stability and low contact resistance during repetitive 21 lithiation/delithiation processes. Moreover, a novel Li-ion hybrid capacitor (LIHC) is assembled 22 23 using MnO2@C-NS as anode and MOF derived ultrathin nanoporous carbon nanosheets (derived 24 25 from other potassium-based metal-organic framework) as cathode materials. The full-cell exhibits 26 27 ultrahigh specific energy density of 166 Wh/kg at 550 W/kg and maintained to 49.2 Wh/kg even at 28 29 high specific power density of 3.5 kW/kg as well as long cycling stability (91% over 5000 cycles). 30 31 This work shows that engineering MOF derived hybrid materials and introducing conductive carbon 32 nanostructure can significantly impact the Li-ion storage properties, enabling new opportunities for 33 34 designing newly advanced MOF derived electrodes for next-generation energy storage devices. 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 61 62 63 64 65 Introduction 1 A swift advancement in portable electronics, hybrid electric vehicles, and large-scale smart grids 2 3 4 demanding for innovative electrochemical energy storage systems with both high energy and power 5 6 density as well as long cycle life at low cost.1-4 In this context, a new system called “Lithium Ion 7 8 Capacitors (LICs)” is proposed in the beginning of 21st century, which is hybrid arrangement of a 9 10 11 battery-like (as anode) and supercapacitor-like electrodes (as cathode) in organic electrolyte, 12 13 heading to enhance energy and power densities.5-7 It has been hyped that LIC bridges the low 14 15 16 energy density supercapacitors (SCs) and low power Li-ion batteries (LIBs).8-9 This good 17 18 performance of LIC in terms of energy and power density is owed to the coupling effect from the 19 20 21 rapid charging rate of capacitor-type electrode, the large specific capacity of the battery-like 22 23 electrode, and the much wider working potential window of the organic electrolytes.5, 6 So far, 24 25 several hybrid LIC designs have been realized, which are based on an activated carbon (AC) 26 27 28 cathode combined with graphite, Li4Ti5O12, vanadates (Li3VO4, BiVO4 etc.) or metal oxides anode.10- 29 30 16 However, the poor rate capability of graphite, the relatively high redox potential (~1.5 V, vs. 31 32 33 Li/Li+) of Li4Ti5O12 (LTO) and the poor electrical conductivity and cycle stability of metal oxides 34 35 hamper their utilization in high performance LICs. Therefore, it is crucial to explore the novel 36 37 38 anode materials with high rate capability, good cycle stability and low redox potential to achieve 39 40 further improvements for hybrid LICs. 41 42 43 Recently, two-dimensional (2D) porous materials have been successfully applied in newly 44 45 developed energy storage systems due to their large surface area for reaction and interfacial 46 47 transport, and short diffusion paths.17-19 Especially, inorganic-organic hybrid porous materials such 48 49 50 as metal-organic frameworks (MOFs) with high specific surface area and low density have been 51 52 claimed to be promising electrode materials for next-generation LIBs and supercapacitors.19-22 53 54 55 MOFs are building blocks of low cost and cheap metal salts/organic ligands in appropriate 56 57 solvents.23 The metal sites can be ions of transition metals, alkaline earth metals, or lanthanides and 58 59 60 61 62 63 64 65 organic linkers are typically multidentate molecules with N- or O donor atoms (pyridyl, 1 polyamines, carboxylates, and so on). 2 3 4 Several MOFs have been investigated as promising anode materials for LIBs, where metal cations 5 6 in MOFs act as active sites for redox reactions, and open crystal frameworks support effective and 7 8 reversible insertion/extraction for Li ions.24, 25 However, the chemical stability of MOFs suffers 9 10 11 from more severe challenges in the complex electrochemical environment of LIBs. Therefore, the 12 13 thermal, chemical, and structural stabilities of MOFs are in high demand, which are critical to the 14 15 16 cycling performance of LIBs in practical applications. In addition, the electrical conductivity of 17 18 MOFs is important to the practical specific capacity and rate performance. Thus, MOFs with high 19 20 21 electrical conductivity and stability are desirable anode materials for LIBs and LICs. An emerging 22 23 method to engineer high conductivity anode with good electrochemical performance is to develop 24 25 porous transition metal oxides embedded in porous carbon matrices using MOFs as sacrificial 26 27 28 framework precursors. 27-29 For instance, Li et al. 28 prepared micro-cuboid-like carbon-decorated 29 30 iron oxide (C-Fe3O4) from Fe-MOFs precursors and reported a high reversible capacity of 975 31 32 29 33 mAh/g over 50 cycles at 100 mA/g. Yang et al. reported ZnO quantum dots@hierarchically 34 35 porous carbon with high specific capacity of approximately 1200 mAh/g and good cycling stability. 36 37 38 However, best of our knowledge there is no report on the utilization of MOF-derived transition 39 40 metal oxide anode for LICs. 41 42 43 Herein, we engineered hybrid manganese oxide nanoparticles embedded porous graphene-like 44 45 carbon nanosheets (MnO2@C-NS) as a promising anode material for lithium ion hybrid capacitor 46 47 (LIHC) by direct carbonization of a three-dimensional manganese-based MOF [Mn(1,4- 48 49 50 napdc)]n composed with Mn(II) metal ion, 1,4-ndc (ndc= naphthalene dicarboxylate) (Scheme 51 52 S1).30 In this hybrid, graphene-like carbon nanosheets can acts as “flexible confinement” to enwrap 53 54 55 MnO2 particles, which can compensate for the volume change of MnO2 and prevent the detachment 56 57 and agglomeration of pulverized MnO2, thus extending the cycling life of the electrode. Moreover, 58 59 60 lithium-ion hybrid capacitor (LIHC) fabricated with MnO2@C-NS as the anode and MOF-derived 61 62 63 64 65 nanoporous carbon sheets (prepared from other potassium-based metal-organic framework, NPCS) 1 as cathode yields a working potential of 4.0 V and high values of specific energy and power density 2 3 4 as well as long cycle life. This study reveals that MOF based materials can be promising anode and 5 6 cathode materials for highly efficient and robust LIHC or LIBs. 7 8 9 10 11 Results and Discussion 12 13 Here we have used a [Mn(1,4-napdc)]n (1) for preparing a composite of MnO2 nanoparticle and 14 15 16 graphitic carbon support under particular pyrolytic conditions, the detailed experimental procedure is 17 18 provided in supporting information and scheme S1. The structural integrity of as-synthesized MOF 19 20 21 was confirmed by PXRD (Figure S1). In this process, [Mn(1,4-napdc)]n (1) acts as both sacrificial 22 23 carbon matrix and manganese precursor. The resulting hybrid material was further characterized by 24 25 using Raman and XRD techniques to investigate its compositional and structural properties. Raman 26 27 28 spectrum of MnO2@C-NS hybrid (Figure 1a) shows a significant band around 647 cm-1, which 29 30 might correspond to MnO2 31. A slight displacement in MnO2 band position compared to literature 31 32 33 value might be attributed to the interaction of Mn-O with the carbon matrix. Moreover, two 34 35 additional bands can be seen at around 1340 and 1593 cm-1, where the former could be assigned to 36 37 38 sp3 carbon and the later to graphitic (sp2) carbon. In addition, relative intensities of these two bands 39 40 indicate the dominance of sp3 carbon over sp2 carbon, which might be due to the small defects with 41 42 43 graphitic carbon environment include bonding disorders and oxygen functional groups. Figure 1 (b) 44 45 shows the XRD pattern of MnO2@C-NS, where all the peaks are assigned to the β-MnO2 phase 46 47 (JCPDS: 24-0735). No other impurities were found. The composition of the MnO2@C-NS hybrid 48 49 50 was further analyzed by XPS (Figure S3a). The deconvoluted high-resolution C1s signal allows the 51 52 quantitative assignment of two different kinds of carbon atoms. The main peak at 284.7 eV originates 53 54 55 from the sp2 graphitic nature carbon (C–C sp2) and other peak at 289.34 eV indicates the presence of 56 57 C O (Figure 1c). Moreover, core-level Mn3s spectrum exhibits two major peaks at binding energies 58 59 60 61 62 63 64 65 of 89.75 and 84.95 eV with a spin-energy separation of 4.8 eV, indicate the presence of 1 tetravalent Mn species in good agreement with literature reports (Figure 1d).32 2 3 4 Field-emission scanning electron microscopy (FE-SEM) and transmission electron microscopy 5 6 (TEM) studies provided insights into morphological and detailed structural characteristics of 7 8 MnO2@C-NS (Figure S4). The panoramic view with SEM images from different cross-sections 9 10 11 MnO2@C-NS sample are presented in Figure 2 (a-c), suggesting the formation of layer-by-layer 12 13 structure consisting of graphene-like carbon nanosheets decorated with MnO2 nanoparticles. The 14 15 16 TEM image (Figure 2d) reveals that these MnO2 nanoparticles are homogeneously and tightly 17 18 attached to the graphene-like carbons sheets, even after the ultrasonication used to disperse the 19 20 21 MnO2@C-NS hybrid for TEM characterization. It is further clearly seen from Figure 2 (c-e) that 22 23 carbon nanosheets wrap MnO2 nanoparticles, which helps to prevent MnO2 from agglomeration and 24 25 enables a good dispersion of these oxide particles over the carbon support. The high-resolution 26 27 28 TEM image in Figure 2e shows the interfacial structure between graphene-like carbon nanosheets 29 30 and the MnO2 nanoparticles. The well-resolved lattice fringes with an interplanar distance of 0.31 31 32 33 nm is associated to (110) plane of MnO2. Energy-dispersive X-ray spectroscopy elemental mapping 34 35 was used to investigate the distribution of MnO2 particles in the hybrid structure (Figure 2 g, h). It 36 37 38 is revealed the uniform dispersion of the MnO2 particles in the layered structure consisting of 39 40 graphene-like carbon/MnO2 hybrid sheets. It is further interesting to note that the MnO2@CNS 41 42 43 hybrid exhibited the BET and Langmuir surface areas of 45 m2/g and 65 m2/g, respectively with a 44 45 large pore volume of 1.09 cm3/g (Figure S3b). The unique architecture of the interlayered carbon 46 47 nanosheets anchored MnO2 nanoparticles possesses a certain amount of macropores and mesopores 48 49 50 that form an open porous system, and a limited amount of micropores and small mesopores, which 51 52 facilitate electrolyte ion diffusion to active sites with less resistance and tolerate the volume change. 53 54 33 55 56 57 The exceptional architecture of MnO2 nanocrystals incorporated ultrathin carbon nanosheets 58 59 60 (MnO2@C-NS) makes it promise for energy storage applications. Therefore, the electrochemical 61 62 63 64 65 performance of the MnO2@C-NS was investigated as an anode material for LIB. Figure 3 (a) 1 displays initial few CV curves for MnO2@C-NS anode in a potential window of 0.01 to 3.0 V at 1 2 3 4 mV s-1 scan rate. The first cathodic scan shows a peak around 0.52 V, corresponding to the 5 34 6 formation of solid electrolyte interface (SEI) at the electrode surface which disappeared in the 7 8 next subsequent cycle. The sharp peak observed near 0.10 V suggest the reduction of Mn 2+ to Mn0 9 10 35, 36, 11 which shifts to 0.30 V in the next cycle, indicating an irreversible phase transformation that 12 13 leads to the formation of metallic manganese and Li2O. 37 Conversely, in the anodic scan, two peaks 14 15 16 at 1.29 V and 2.1 V indicate two-step electrochemical oxidation reaction. The wide oxidation peak 17 18 at about 1.29 V may be associated to the oxidation of Mn0 to Mn2+ 38 while a very small peak at 2.1 19 20 21 V may be originated from the re-oxidation of Mn(II) to a higher oxidation state promoting from the 22 23 fast Li reaction kinetics and synergistic effects of carbon and MnOx.38, 39 From the second cycle, the 24 25 CV curves tend to overlap, suggesting the excellent cycling stability. 26 27 28 The charge/discharge profiles for MnO2@C-NS unambiguously support the claims made from CV 29 30 curves. Figure 3 (b) displays the first ten charge/discharge curves for the MnO2@C-NS at a current 31 32 33 density of 0.1 A g-1. In the first discharge, a small plateau at around 0.53 V and, a slop thereafter to 34 35 0.01 V is clearly observed, which may be associated to the SEI formation and the reduction of Mn2+ 36 37 38 to Mn0 during Li-insertion, respectively. 40, 41 The initial discharge and charge capacities of the 39 40 MnO2@C-NS were found to be 1546 and 985 mAh/g, respectively with initial Coulombic 41 42 43 efficiency of 63.7 %. The sudden drop in the initial capacity is attributed to the decomposition of 44 45 electrolyte and formation of SEI layer, which normally observed in metallic oxide-based anodes. 42- 46 47 45 Figure 3 (c) shows the rate performance of the MnO2@C-NS at different current densities. 48 49 50 Notably, MnO2@C-NS nanocomposite delivered excellent reversible capacities of 1054 mAh/g and 51 52 323 mAh/g at 0.1 A/g and 20 A/g, respectively. Thus, even at very high current density, the 53 54 55 MnO2@C-NS delivered a reversible capacity of 333 mAh/g, which is still a very substantial value 56 57 (about 86 % of the theoretical capacity of graphite). Moreover, when the current density changed 58 59 60 back to 0.1 A/g after 100 cycles, the MnO2@C-NS nanocomposite could achieve a capacity of 1021 61 62 63 64 65 mAh/g, demonstrating excellent rate capability. The capacity obtained for MnO2@C-NS 1 nanocomposite is significantly higher than previously reported values (see Table S1), which might 2 3 4 be ascribed to the porous structure of MnO2@C-NS electrode, that offers an easy access to 5 6 electrolyte ions and generates large number of electroactive sites, resulting in excellent capacity and 7 8 rate capability.46, 47 9 10 11 The Li-ion charge kinetics of MnO2@C-NS were further characterized by estimating the capacitive 12 13 48 and diffusion-controlled charge contributions to the total charges stored in the electrode. 14 15 16 Generally, the storage mechanism can be revealed by the dependence of the current (i) on the scan 17 18 rate (v) 49: 19 20 21 i  a b (1) 22 23 where a and b are adjustable parameters; b = 0.5 corresponds to the semi-infinite diffusion process, 24 25 26 and b = 1 indicates a capacitive process.50 In this context, the CV curves were recorded at different 27 28 scan rates (from 1 mV/s to 10 mV/s) for MnO2@C-NS electrode (Figure S5). There is a good linear 29 30 relationship between the current and the scan rate with R2 = 0.9967 and 0.9984 for the cathodic and 31 32 33 anodic scans, respectively. In addition, the slope of the corresponding log() vs log(i) plot is b = 34 35 0.68, suggesting the kinetics dominated by diffusion-controlled process (Figure S6a). In order to 36 37 38 calculate, the capacitive charge contribution to the total current response, Equation (1) can be re- 39 40 written as, 41 42 43 i  k1  k 2 1 / 2 (2) 44 45 46 Thus, the current at a fixed potential is equal to the sum of capacitive contribution (k1) and 47 48 diffusion-controlled contribution (k2 1/2 51 ). The constants k1 and k2 can be determined by plotting 49 50 51 i/1/2 versus 1/2 and measuring the slope and the y-axis intercept point of a straight line, 52 53 respectively. As shown in Figure S5, the shaded area (k1v) with the experimental currents, it is 54 55 56 found that about 73 % of the total current of the MnO2@C-NS electrode is contributed by the 57 58 diffusion-controlled process at 1 mVs-1. Figure 3 (d) present the percent contribution of separate 59 60 61 capacitive and diffusion-controlled charge contributions measured at different scan rates. The Li-ion 62 63 64 65 diffusion coefficient in MnO2@C-NS electrode was further estimated by the Randles-Sevick 1 equation 52 2 3 4 i p  2.69  105 n 3 / 2 ADLi1 / 2 1 / 2 C (3) 5 6 7 where ip is current maximum in amps (we considered current value at 3 points), n is number of 8 9 electrons involved in the charge storage, A is electrode area in cm2 (for simplicity we have 10 11 12 considered geometrical area), DLi is diffusion coefficient in cm2/s,  is scan rate in V/s, C is 13 14 concentration of Li-ion in mol/cm3. The diffusion coefficients for MnO2@C-NS calculated at 15 16 17 different points is in the range of 10-9- 10-11 cm2/s for different scan rates (see Figure S6b). The 18 19 diffusion coefficients for MnO2@C-NS increases slowly with scan rate, further confirming the high 20 21 rate capability of the material. Long-term cycling stability is a key parameter in energy storage 22 23 24 systems, which defines the practical suitability of material. The cycling performance of MnO2@C- 25 26 NS was investigated at 0.5 A/g over 1000 cycles and presented in Figure 3 (e). It is evidenced that 27 28 29 the nanocomposite displayed an excellent cycling stability around 90 % retention over 1000 30 31 charge/discharge cycles. Moreover, the Coulombic efficiency of MnO2@C-NS electrode is 32 33 34 remarkably improved after first few charge/discharge cycles and stabilized at around 99 % over 35 36 1000 cycles. This long cycling performance may be attributed to the unique nano-architecture of 37 38 39 MnO2@C-NS where MnO2 nanocrystals are wrapped in the graphene-like carbon nanosheets. In 40 41 such a nanostructure, graphene-like nanosheets not only provides a conducting scaffold for MnO2 42 43 nanocrystals but also offers ion-buffering reservoir to suppress the volume expansion during 44 45 46 charge/discharge cycles while MnO2 nanocrystals deliver high capacity through their faradic charge 47 48 storing mechanism. Thus, the synergic combination of MnO2 nanocrystals and graphene-like carbon 49 50 51 nanosheets together offers high capacity with complementary long-term cycling stability. 52 53 The extraordinary properties of the MnO2@C-NS electrode can be attributed to its unique porous 54 55 56 MnO2 nanocrystals wrapped graphene-like carbon nanosheets architecture, which reduces the mass- 57 58 transfer resistances, and offer high intrinsic conductivity for smoothing electron transport. Thus, 59 60 61 62 63 64 65 such a high Li-ion storage capacity, excellent rate/cycling stabilities and adequate voltage range of 1 MnO2@C-NS make it an excellent candidate as anode for hybrid Li-ion capacitors. 2 3 4 The cathode material: MOF derived nanoporous carbon nanosheets (NPCS) 5 6 To develop high performance cathode materials in LICs, the key is to engineer high surface area, 7 8 tunable pore size and high conductivity carbon materials. Herein, we have prepared controlled 2D 9 10 11 nanoporous carbon sheets (NPCS) by direct carbonization of a specifically selected two- 12 13 13 dimensional potassium-based MOF as described in our previous report. XRD pattern of NPCS 14 15 16 shows characteristic (d002) graphitic peak of carbon materials at around at 24.3 while the two 17 18 intense bands for carbon materials are clearly observed at around 1340 and 1593 cm-1 in Raman 19 20 21 spectrum (Figure S7). Moreover, Raman analysis suggest the existence of small defects in NPCS 22 23 with graphitic carbon environment.53 The TEM image of nanoporous carbon nanosheets (NPCS) 24 25 26 (Figure 4 (a)) reveals the existence of ultrathin nanosheets with a layered structure. The BET 27 28 surface area was determined to be 1292 m2g-1 with a large pore volume of 1.06 cm3g-1 that can 29 30 provide a short ion-transport pathway with a minimized inner-pore resistance. The resulting layered 31 32 33 2D carbon nanostructure provides excellent specific surface area and pore volume that can 34 35 significantly enhance the charges stored at the electrode surface. 36 37 38 The NPCS cathode was initially tested in a Li half-cell between 1.5-4.5 V vs. Li/Li+ and the results 39 40 are displayed in Figure 4 (b-e). The nearly rectangular CV curves with small humps are observed 41 42 43 for NPCS cathode at all the scan rates, indicating major contribution from EDLC with small 44 45 contribution from pseudo-capacitance due to surface oxygen groups (Figure 4b). Moreover, the 46 47 48 linear relationship between current density and scan rates in CV curves confirmed that the 49 50 electrochemical reactions in the NPCS cathode were not diffusion-limited but confined to the 51 52 surface.54 The galvanostatic charge-discharge (GCD) curves of NPCS at different current densities 53 54 55 from 0.1 A/g to 15.6 A/g are presented in Figure S8. The GDC profiles show linear and symmetric 56 57 nature without any plateau and distinct inflection points, confirming the capacitive charge storage 58 59 60 behavior of NPCS electrode. The first discharge capacity of NPCS was 133 mAh/g at a current 61 62 63 64 65 density of 0.1 A/g (Figure 4c), which is comparable to a previously reported cathode [55-57]. The 1 rate capability test suggested remarkably fast Li storage capability in the NPCS cathode (Figure 4d). 2 3 4 Even at high current rate of 15.6 A/g, the NPCS showed a specific capacity of 56.7 mAh/g (42 % of 5 6 initial capacity) and the initial capacity was recovered when the current rate was returned to 0.1 A/g, 7 8 indicating excellent reversibility. It is further interesting to note that, the NPCS cathode exhibits 9 10 11 excellent cycling stability with 86 % capacity retention over 7000 cycles at current density of 2.4 12 13 A/g (see Figure 4 (e)). Upon repeated cycles, the high specific capacity was maintained with a 14 15 16 Coulombic efficiency of 100 %. Thanks to the unique ultrathin graphene-like layered structure of 17 18 NPCS, which offers high surface area and adequate pore volume for high charge storage 19 20 21 capabilities (large Li+ uptake) and long cycling stability. 22 23 Considering all these excellent electrochemical properties of NPCS in LiPF6 electrolyte and its 24 25 complementary electrochemical voltage, NPCS was expected to be a suitable cathode electrode to 26 27 28 be paired with MnO2@C-NS anode in a LIC. 29 30 31 32 33 Li-ion hybrid capacitor (LIHC) based on MnO2@C-NS anode and NPCS cathode 34 35 Although recent advancements in the development of Li-ion capacitors (LICs) using Li-intercalated 36 37 38 materials (e.g. LiCoO2) and activated carbon (AC) electrodes, they still may have some significant 39 40 drawbacks. 5, 6 For example, it is very difficult to fully utilize the overall specific energy density of 41 42 43 such battery electrodes due to the redox reaction kinetics being too slow in LIC systems. This 44 45 inherent difference can diminish the energy storage ability of the electrochemical device especially 46 47 during fast charge-discharge processes compromising their practical applications. This drawback 48 49 50 requires the design of advanced electrodes, which could help offsetting the low charge-transfer 51 52 kinetics intrinsic to redox reactions of battery electrodes. In this context, our MnO2 nanocrystals 53 54 55 wrapped graphene-like carbon nanosheets (MnO2@C-NS) would be promising hybrid anode for 56 57 LIHC where MnO2 nanocrystals reduces the diffusion path of charge-compensating ions and 58 59 60 graphene-like carbon nanosheets provide extra electronic conductivity. In addition, it also provides 61 62 63 64 65 the opportunity to get all-in-one faradaic and capacitive activities displayed in parallel, which might 1 further helps to lessen the kinetic mismatch problem associated to LIHCs. 2 3 4 Herein, we have fabricated LIHC full cell using MnO2@C-NS as anode and highly porous NPCS as 5 6 cathode material by taking advantage of their different working potential windows as shown in 7 8 Figure 3a and 4b. Note that, the masses of the cathode and anode must be adjusted to match the 9 10 11 capacity, due to the specific capacity difference between MnO2@C-NS and NPCS electrodes. We 12 13 thus used an optimized mass ratio of 1:7.6 between the MnO2@C-NS and NPCS electrode. 14 15 16 of specific capacitance and capacity with current density for MnO2@C-NS//NPCS cell. 17 18 Thus, we have provided double hybridization approach, that is, the simultaneous combination of 19 20 21 faradaic and capacitive materials in a single electrode (MnO2@C-NS) and their use in front of a 22 23 capacitive one (NPCS). In effect, this strategy would be equivalent to a combination of faradaic and 24 25 capacitive materials in parallel AND in series, thus improving kinetic aspects as well as larger 26 27 28 voltages and energy densities. The reaction kinetics of LIHC is presented in Figure 5 (a) where Li 29 30 ions rapidly transferred/extracted into/from MnO2@C-NS through surface faradic reactions, while 31 32 33 PF6- anions swiftly adsorbed/desorbed on the porous NPCS cathode during charge/discharge 34 35 processes, respectively. The electrochemical performances of MnO2@C-NS//NPCS LIHC cell was 36 37 38 tested within the voltage range of 0.01-4.0 V. In order to understand the charge storage mechanism, 39 40 the charge/discharge curves of MnO2@C-NS//NPCS cell were recorded at 0.5 A/g with 41 42 43 corresponding potential profiles of cathode (black) and anode (red) with respect to Li-metal (see 44 45 Figure 5 (b)). As expected, the anode and cathode electrodes work in the potential ranges: 0.01 V to 46 47 2.0 V and 2.0 V to 4.0 V (vs Li/Li+), respectively. In MnO2@C-NS hybrid electrode, the graphene- 48 49 50 like carbon nanosheets first charged by electrostatic forces in the initial state (Figure 5b, Region I) 51 52 until the electrode potential reaches the redox reaction potential of the MnO2 nanocrystals. Then 53 54 55 MnO2 nanocrystals charged through the redox reactions while maintaining the potential of the 56 57 hybrid electrode, until the faradaic component (MnO2) reaches its full-charge state (Region II) as 58 59 60 seen in Figure 5 (b). After the full charge of the MnO2, the carbon nanosheets is charged again 61 62 63 64 65 (Region III) until the maximum potential of the hybrid electrode is reached. Thus, the total amount 1 of energy stored in MnO2@C-NS hybrid system is the sum of energy stored in the MnO2 2 3 4 nanocrystals and carbon nanosheets. The hybrid electrode is bound to have improved power 5 6 densities due to the carbon nanosheets, which can also store electrochemical energy by electrostatic 7 8 force, enhances the electron transfer to the MnO2 nanocrystals in the hybrid electrode system, 9 10 11 causing a better charge transfer reaction at high rates. Figure 5 (c) shows GCD curves for LIHC cell 12 13 at different current densities from 0.45 A/g to 2.91 A/g. The shapes of GCD curves at different 14 15 16 current densities exhibit quasi-symmetric triangular-shape, suggesting good combination between 17 18 the hybrid MnO2@C-NS anode and EDLC NPCS cathode. Interestingly, it is further evidenced that 19 20 21 the LIHC cell provide low IR drop, suggesting good electrical conductivity of the materials. The 22 23 variations of specific capacitance and specific capacity with current densities are shown in Figure 5 24 25 (d). The capacity of the full LIHC cell was calculated to be 129 mAh/g, considering total weight of 26 27 28 active materials in both electrodes (mass of active materials in cathode and anode). 29 30 A Ragone plot is the graphical representation of the balance between energy and power density, 31 32 33 which is key for many practical applications. The energy and power density values of MnO 2@C- 34 35 NS//NPCS LIC cell at different current densities were calculated from the GCD curves and 36 37 38 presented in Figure 6 (a). The device is able to achieve a maximum energy density of 166 Wh/kg (at 39 40 a power density of 550 W/kg) and a maximum power density of 3.9 kW/kg (at energy density of 41 42 43 49.3 Wh/kg). The integrated performance (energy density vs. power density) is best compared with 44 45 most reported LICs such as MnO-C//CNS, Li4Ti5O12//TRGO, HC//AC, LTO//AC, C-LTO//AC etc. 46 47 [7, 13, 57-70 and Table S2]. More remarkably, from Figure 6 (b), the LIHC exhibits superior long- 48 49 50 term cycling stability with ~91% capacity retention after 5000 cycles at 1 A/g as well as excellent 51 52 Coulombic efficiency (nearly 98% retained after the cycling test). The initial increase in the 53 54 55 capacity might be attributed to the activation of MnO2@C-NS electrode. 56 57 We have designed an advanced MOF derived MnO2 nanocrystals wrapped graphene-like 58 59 60 carbon nanosheets (MnO2@C-NS) hybrid anode and nanoporous carbon sheets (NPCS) cathode for 61 62 63 64 65 high performance LIC, which can surpass the main intrinsic drawbacks of kinetics and capacity 1 mismatch in such a combined system. Such a high performance of MnO2@C-NS//NPCS LIC might 2 3 4 be ascribed to the following characteristics (Figure 6c): 1) the porosity between graphene-like 5 6 nanosheets in MnO2@C-NS anode facilitates Li ion transport, which offer high capacity and 7 8 excellent rate capability. 2) the interleaved structure of graphene-like nanosheets homogeneously 9 10 11 confine the MnO2 nanoparticles that inhibits the volume change, alleviating the stress of MnO2 12 13 particles, and preventing the detachment and agglomeration of pulverized MnO2 during cycling. 3) 14 15 16 the MOF derived nanoporous carbon nanosheets (NPCS) provides a conductive network, high 17 18 surface area, short diffusion lengths which are optimal for adsorption/desorption of electrolyte ions, 19 20 21 thereby providing both improved energy and power densities. 22 23 Conclusions 24 25 In conclusion, a novel Li-ion hybrid capacitor (LIHC), combining MOF-derived MnO2 26 27 28 nanoparticles decorated graphene-like carbon nanosheets (MnO2@C-NS) anode and ultrathin 29 30 nanoporous carbon nanosheets (NPCS) cathode, is successfully designed and investigated for the 31 32 33 first time. The MnO2@C-NS//NPCS hybrid device exhibits energy densities of 166-49 Wh/kg over 34 35 the power densities from 550 to 3.5 kW/kg, which are considerably higher than the previous reports. 36 37 38 The high-performance of the hybrid system is attributed to both MOF derived graphene-like carbon 39 40 nanosheets-enhanced electrode materials. As-prepared MnO2@C-NS anode achieves both high 41 42 43 specific capacity of 1054 mAh/g at 0.1 A/g and good rate performance with good cycle stability 44 45 (90% over 1000 cycles); meanwhile, the cathode electrode material ultrathin nanoporous carbon 46 47 sheets (NPCS) shows high EDLC specific capacitance as well as rate capability with excellent 48 49 50 stability (86% over 7000 cycles). These combined features make the hybrid supercapacitor exhibit a 51 52 remarkable energy density much higher than the commercial supercapacitors and can even compare 53 54 55 with commercial lithium-ion batteries with improved power density. 56 57 58 59 60 61 62 63 64 65 Supporting Information 1 Supporting Information is available from the Wiley Online Library or from the author. 2 3 4 5 Acknowledgements 6 7 8 K.J. and D.P.D. contributed equally to this work. K.J. is grateful to the Alexander von Humboldt 9 10 (AvH) foundation for a postdoctoral fellowship. D.P.D. acknowledges the support of University of 11 Adelaide, Australia for grant of Research Fellowship (VC Fellow). The authors also gratefully 12 13 acknowledge support by the Catalysis Research Centre at TU Munich and the support from the 14 15 Ministry of Education, Youth and Sports of the Czech Republic (LO1305) and the assistance 16 17 provided by the Research Infrastructure NanoEnviCz, supported by the Ministry of Education, 18 19 Youth and Sports of the Czech Republic under Project No. LM2015073. The authors also gratefully 20 21 acknowledge support by the Catalysis Research Centre at TU Munich and the support by the 22 Operational Programme Research, Development and Education—European Regional Development 23 24 Fund, projects no. CZ.02.1.01/0.0/0.0/15_003/0000416 and CZ.02.1.01/0.0/0.0/16_019/0000754 of 25 26 the Ministry of Education, Youth and Sports of the Czech Republic. M.P. acknowledges the internal 27 28 project IGA_PrF_2018_015 of Palacký University in Olomouc. 29 30 31 Received: ((will be filled in by the editorial staff)) 32 Revised: ((will be filled in by the editorial staff)) 33 Published online: ((will be filled in by the editorial staff)) 34 35 36 37 References 38 39 [1] D. P. Dubal, O. Ayyad, V. Ruiz, P. Gomez-Romero, Chem. Soc. Rev. 2015, 40 41 44, 1777. 42 [2] M. Salanne, B. Rotenberg, K. Naoi, K. Kaneko, P. -L. Taberna, C. P. Grey, 43 44 B. Dunn, P. Simon, Nat. Energy 2016, 1, 16070. 45 [3] K. Naoi, W. Naoi, S. Aoyagi, J. Miyamoto, T. Kamino, Acc. Chem. Res. 46 2013, 46, 1075 47 48 [4] D. P. Dubal, N. R. Chodankar, D. H. Kim, P. Gomez-Romero, Chem. Soc. 49 Rev. 2018, 47, 2065 50 51 [5] K. Naoi, S. Ishimoto, J. Miyamoto, W. Naoi, Energy Environ. Sci. 2012, 5, 52 9363. 53 [6] V. Aravindan, J. Gnanaraj, Y.S. Lee, S. Madhavi, Chem. Rev. 2014, 114, 54 55 11619. 56 [7] D. P. Dubal, P. Gomez-Romero, Mater. 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Commun. 2005, 35 4613-4615. 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 61 62 63 64 65 Figure captions 1 2 3 4 Figure 1 (a and b) Raman spectrum and XRD pattern for MnO2@C-NS nanocomposite, 5 respectively (c, d) Core-level XPS spectra of C1s (C1s spectrum is deconvoluted in three small 6 peaks) and Mn3s for MnO2@C-NS nanocomposite, respectively. 7 8 9 Figure 2 (a-c) FESEM image of MnO2@C-NS nanocomposite at different magnifications, 10 11 suggesting formation of interleaved architecture. (d-e) TEM and HRTEM images of MnO2@C-NS 12 nanocomposite, respectively, suggesting decoration of MnO2 nanoparticles on graphene-like carbon 13 nanosheets (f) STEM image of MnO2@C-NS nanocomposite. (g-h) EDAX mapping of MnO2@C- 14 15 NS nanocomposite with corresponding EDS spectrum, confirming the presence of Mn, O and C 16 without any impurities. 17 18 19 Figure 3 Electrochemical properties of MnO2@C-NS nanocomposite in Li-half cell configuration: 20 (a) First few cyclic voltammetry curves recorded at scan rate of 1 mV/s. (b) Initial ten galvanostatic 21 22 charge/discharge curves measured at 0.1 A/g. (c) Variation of specific capacity with cycling at 23 different current rates. (d) Plot of capacitive charge contribution to total charge at different scan 24 25 rates, (d) Cycling stability and Coulombic efficiency at 0.5 A/g, showing capacity retention of 90 % 26 after 1000 cycles. 27 28 29 Figure 4 (a) HRTEM image of NPCS, showing highly porous, ultrathin interconnected nanosheets 30 network. (b-c) Electrochemical properties of MOF derived nanoporous carbon nanosheets (NPCS) 31 32 electrode in a Li half-cell within the potential range of 1.5 to 4.5 V (vs Li/Li+). (b) Cyclic 33 voltammetry curves at different scanning rates. (c) Galvanostatic charge/discharge curves at current 34 density of 0.1 A/g, (d) Rate capability properties of NPCS at different current densities, (d) Long- 35 36 term cycling stability measured over 7000 cycles at 2.4 A/g. 37 38 39 Figure 5 Electrochemical properties of MnO2@C-NS//NPCS LIHC full cell in voltage range of 40 0.01 to 4 V: (a) schematic illustration of design of unique LIHC. (b) CD curve for MnO2@C- 41 NS//NPCS LIHC cell at current density of 0.5 A/g with corresponding potential distribution across 42 43 MnO2@C-NS anode and NPCS cathode versus Li-foil reference electrode. (c) GCD curves for 44 MnO2@C-NS//NPCS LIHC cell at different current densities, (d) Variation of specific capacitance 45 46 and capacity with current density for MnO2@C-NS//NPCS cell. 47 48 Figure 6 (a) Ragone plot for MnO2@C-NS//NPCS LIC device with comparison of previously 49 50 reported. (b) Capacity retention and Coulombic efficiency of MnO2@C-NS//NPCS LIHC cell over 51 5000 cycles, suggesting excellent cycling stability with >98 % Coulombic efficiency. (c) Schematic 52 53 presentation of charge storing mechanism in MnO2@C-NS hybrid electrode. 54 55 56 57 58 59 60 61 62 63 64 65 1 2 Figure 1 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 61 62 63 64 65 Figure 2 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 61 62 63 64 65 Figure 3 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 61 62 63 64 65 Figure 4 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 61 62 63 64 65 Figure 5 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 61 62 63 64 65 Figure 6 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 61 62 63 64 65 The table of contents 1 Metal-Organic Framework (MOF) derived electrodes for high performance Li-Ion hybrid capacitor: 2 Graphene-like nanosheets wrapped MnO2 anode and Nanoporous carbon nanosheets cathode 3 4 5 6 Keywords MOF-derived elecctrodes, Manganese oxide, Nanoporous carbon, Li-ion capacitors, 7 High energy density. 8 9 10 Deepak P. Dubal,1,4*$ Kolleboyina Jayaramulu,2,3*$ Sunil Janaky,5 Štěpán Kment,3 Pedro Gomez- 11 Romero,4 Chandrabhas Narayana,5 Radek Zbořil3* and Roland A. Fischer2* 12 13 Metal Organic Framework (MOF) derived Electrodes with Robust and Fast Lithium Storage 14 15 for Li-Ion Hybrid Capacitors 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 61 62 63 64 65 Copyright WILEY-VCH Verlag GmbH & Co. KGaA, 69469 Weinheim, Germany, 2016. 1 2 3 Supporting Information 4 5 6 Metal Organic Framework (MOF) derived Electrodes with Robust and Fast Lithium Storage 7 8 for Li-Ion Hybrid Capacitors 9 10 Deepak P. Dubal,1,4*$ Kolleboyina Jayaramulu,2,3*$ Sunil Janaky,5 Štěpán Kment,3 Pedro Gomez- 11 Romero,4 Chandrabhas Narayana,5 Radek Zbořil3* and Roland A. Fischer2* 12 13 14 15 1 16 Dr. D. P. Dubal 17 School of Chemical Engineering, The University of Adelaide, 18 19 Adelaide, South Australia 5005, Australia 20 Email: dubaldeepak2@gmail.com 21 22 2 Dr. K. Jayaramulu, Prof. Dr. R. A. Fischer 23 Chair of Inorganic and Metal-Organic Chemistry, Department of Chemistry and Catalysis Research 24 25 Centre, Technical University of Munich, 85748 Garching, Germany 26 Email: jaya.kolleboyina@tum.de 27 Email: roland.fischer@tum.de 28 29 3 30 Dr. K. Jayaramulu, Dr. S. Kment, Prof. Dr. R. Zboril 31 Regional Centre of Advanced Technologies and Materials, 32 Faculty of Science, Palacky University, Šlechtitelů 27, 783 71, Olomouc, Czech Republic. 33 Email: radek.zboril@upol.cz 34 35 4 36 Dr. D. P. Dubal, Prof. Dr. P. Gomez-Romero 37 Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and the Barcelona Institute of 38 Science and Technology, Campus UAB, Bellaterra 08193, Barcelona, Spain 39 40 5 Prof. Dr. C. Narayana, Ms. S. Janaky 41 42 Chemistry and Physics of Materials Unit, 43 Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR) 44 Jakkur, Bangalore, 560064, India 45 46 $ 47 Both authors contributed equally. 48 49 50 51 52 Keywords: MOF-derived Materials, manganese oxide, nanoporous carbon, Li-ion capacitors, 53 Energy Storage, Energy Density 54 55 56 57 58 59 60 61 62 63 64 65 Experimental and related aspects 1 Materials 2 3 All reagents and solvents were commercially available and used as supplied without further 4 purification. MnCl2·4H2O, 1,4-napthalenedicarboxylate, and KOH were obtained from Sigma- 5 Aldrich. 6 7 8 Synthesis of [Mn(1,4-ndc)]n (1): 9 10 The synthesis procedure of 1 has been described by Kitagawa et al.[1]. Reaction of MnCl2·4H2O (1.0 11 mmol) with 1,4-napdcH2 (1.0 mmol) and KOH (2.0 mmol) in water (10–12 ml) at 180 °C for 72h h 12 resulted in pink colored powder in 40% yield with respect to Mn. 13 14 1. T. K. Maji, W. Kaneko, M. Ohba, S. Kitagawa, Chem. Commun. 2005, 4613-4615. 15 16 17 18 Synthetic procedure for KMOF: 19 Nanocrystals of KMOF were prepared according to a slightly modified procedure from literature. 20 21 (ref) In a 20 ml of Teflon, 1.51 g of BTC, 0.632 g of KNO3, 0.074 g NH4F of were dissolved in 15 22 mL of DMF under sonication. The autoclave was tightly closed and placed in an oven at 120 °C for 23 24 3 days. After cooling to room temperature, the supernatant was decanted and the products were 25 washed three times with DMF, three times with methanol. Methanol as solvent was decanted and 26 replaced once per day during the course of three days. Colorless rod crystals were recovered for 27 28 KMOF in ≥90% yield based on potassium. 29 1. M. K. Kim, V. Jo, D. W. Lee, I.-W. Shim and K. M. Ok, CrystEngComm, 2010, 12, 1481- 30 31 1484 32 33 Preparation of hybrid MnO2@carbon matrix 34 35 The composite material was prepared by the following method. The resultant MOF powder 36 was heat treated in nitrogen flow of 100 ml per minute at 800 oC with a heating rate of 5 oC 37 38 per minute for 6 h to carbonize the mixture. The resultant composite recovered after 39 repetitive washing with ethanol and drying at 60 oC. 40 41 42 Preparation of Nanoporous carbon sheets (NPS-800) from KMOF: 43 The nanoporous carbon sheets were prepared by the following method. . In a typical synthesis, 1 g 44 45 of KMOF-1 prepared at a synthesis temperature of 120 °C. The KMOF-1 heated at 200 °C overnight. 46 The activated KMOF-1 was heat-treated in a nitrogen flow of 100 ml per minute at 450 °C with a heating 47 rate of 5 °C per minute for 6 h to carbonize the mixture. The resultant composite (denoted as NPS-450) 48 49 have potassium-based impurities. Further, NPS-450 composite heat treated in a nitrogen flow of 100 50 mL per minute at various temperature 800 °C with a heating rate of 5 °C per minute for 8h. Finally, 51 52 nanoporous carbon sheets (NPS-800) was recovered after dissolution of the potassium oxide in 5 53 wt% hydrochrloric acid, by filtration, repetitive washing with water/ethanol (1:1) and drying at 54 100 °C. 55 56 57 58 59 60 61 62 63 64 65 Materials characterization 1 The synthesized materials were characterized by different techniques. X-ray diffraction 2 3 (XRD) data of all samples were collected by the X’Pert PRO PANanalytical equipment (Bragg- 4 Brentano geometry with automatic divergence slits, position sensitive detector, continuous mode, 5 6 room temperature, Cu-Kα radiation, Ni filter. The powder samples were dropped onto silicon wafer 7 with grease and measured at the same equipment (5-80°, at a step of 0.0197°, with accumulation 8 time 200 s per step). For Rietveld refinement, FullProf Suite program with VESTA graphical 9 10 interface was used. The X-ray photoelectron spectra (XPS) analyses were obtained by X-ray 11 photoelectron spectroscopy (XPS, SPECS Germany, PHOIBOS 150).The surface morphological 12 13 analyses of samples were carried out using the different techniques such as field-emission scanning 14 electron microscopy (FEI Quanta 650F Environmental SEM) and transmission electron microscopy 15 (Tecnai G2 F20 S-TWIN HR(S) TEM, FEI). The Raman spectrum of respective sample were 16 17 collected through instrument, DXR Raman (Thermo, USA); laser wavelength: 633 nm, laser power 18 on sample: 2mW, exposition time: 5s, 32 spectra were averaged at each spot to obtain one data 19 20 point. Adsorption studies of N2 (77 K) of all samples were carried out using MICROMERITICS 21 analyzer, outgassed at 423 K under high vacuum. 22 23 24 Electrochemical testing 25 Electrodes were prepared by mixing the active material (MnO2@C-NS or nanoporous 26 27 carbon nanosehets NPS-800), Super-P conductive carbon black and polyvinylidene fluoride binder 28 (PVDF) in an N-methyl-2-pyrrolidone (NMP) with 70 %:20 %:10% ratio. The resulting paste was 29 30 uniformly coated onto Al or Cu foil, dried at 100 C for 12 h, and pressed under hydraulic press. 31 The mass loading of MnO2@C-NS and NPS-800 was around 1.5 mg/cm2. Initially, both the 32 materials MnO2@C-NS and NPS-800 were tested with half-cell configuration where the Li metal, 33 34 glass-fiber and a 1 M lithium hexafluorophosphate in a 1:1 mixture of ethylene carbonate and 35 dimethyl carbonate (1:1, EC:DMC) were used as counter electrode, separator and electrolyte, 36 37 respectively. The NPS-800 cathode half-cell was tested within the voltage range from 4.5 to 1.5 V 38 and MnO2@C-NS anode within 3.0 to 0.01 V using a Biologic potentio-galvanostat. Prior to 39 assembling full LIC cell, MnO2@C-NS and NPS-800 were cycled 10 cycles in half-cells at 0.1 A/g, 40 41 and then the cells were disassembled in the glove box and by collecting electrodes, full cell was 42 fabricated and tested within 0.01 to 4 V. The BiVO4 anode was fully discharged up to 0.01 V (vs. 43 44 Li) before used in the full LIC cells. In present investigation, the mass ratio of MnO2@C-NS to 45 NPS-800 O was maintained at 1:5 (1.6 mg of MnO2@C-NS and 7.9 mg of NPS-800). 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 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 Figure S1. Synthesis concept of the step-wise formation of manganese nanoparticles at graphitic 33 34 porous carbon matrix from manganese-based metal-organic framework 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 61 62 63 64 65 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 Figure S2 Powder XRD pattern of 1 (a) simulated pattern; (b) as-synthesized [Mn(1,4-napdc)]n (1) 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 61 62 63 64 65 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 Figure S3 (a) Full XPS spectrum of MnO2@C-NS nanocomposite suggesting the formation of 44 MnO2 and carbon. (b) Nitrogen adsorption/desorption isotherm of MnNDC and MnO2@C-NS. 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 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 Figure S4 (a, b) SEM and (c, d) TEM images of MnO2@C-NS at two different magnification 31 confirming the formation of interleaved composite of graphene-like carbon nanosheets decorated 32 33 with MnO2 nanoparticles. 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 61 62 63 64 65 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 Figure S5 CV curves for MnO2@C-NS at different scan rates with the capacitive contribution to 31 the total current is shown by the shaded region, which suggest increasing trend of capacitive 32 33 contribution with scan rate. 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 61 62 63 64 65 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 Figure S6 (a) Plot of log (current) vs log(scan rate) for anodic and cathodic responses. (b) Li-ion 39 40 diffusion coefficients of MnO2@C-NS electrode at different scan rates. 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 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 Figure S7 (a) XRD, (b) Raman and (c) BET analysis with corresponding pore size distribution 47 48 curve (inset) for MOF-derived nanoporous carbon nanosheets (NPCS), confirming the formation of 49 high surface area with tunable pore size NPCS cathode material. 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 Figure S8 Galvanostatic charge/discharge curves for NPCS cathode in half cell configuration (vs 25 26 Li/Li+) at different current densities. 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 61 62 63 64 65 15 16 17 18 19 20 21 22 Supporting Information Table 1 23 24 Table 1 Comparison of electrochemical properties of carbon based anode materials with present report 25 26 27 Anode Material Reversible capacity (mAh/g) Capacity retention (mAh/g) References 28 29 MnO2@C-NS 1054 at 0.1 A/g 90 % at 0.5 A/g after 1000 cycles Present work 30 31 32 MnO2/carbon nanotube 820 at 200 mA/g 77 % at 200 mA/g after 50 cycles [S1] 33 34 MnO2/ Carbon Nanohorns 565 at 450 mA/g 98 % at 450 mA/g after 60 cycles [S2] 35 36 37 Graphene-Wrapped MnO2- 890 at 0.1 A/g 24% increase after 245 cycles at 0.4 A/g [S3] 38 39 Graphene Nanoribbons 40 41 MnO2/carbon nanotube 500 at 50 mA/g 45 % at 50 mA/g after 16 cycles [S4] 42 43 44 TiO2-C/MnO2 865 at 33.5 mA/g 90 % at 335 mA/g after 100 cycles [S5] 45 46 MnO/C 798 at 200 mA/g 77 % at 200 mA/g after 40 cycles [S6] 47 48 49 Graphene-MnO2 Nanotube 581 at 100 mA/g - [S7] 50 51 Fe-MOF derived C-Fe3O4 975 at 100 mA/g 80 % at 100 mA/g after 50 cycles [S8] 52 53 54 MOF derived ZnO quantum 1200 at 75 mA/g 100 % at 75 mA/g after 50 cycles [S9] 55 56 dots@hierarchically porous carbon 57 58 59 60 61 62 38 63 64 65 15 16 17 18 19 20 21 22 Supporting Information Table 2 23 24 Table 2 Comparison of published electrochemical properties of Li-ion capacitors with our present work 25 26 27 LIC cell Energy density (Wh/kg) Power density (W/kg) Voltage (V) Cycling stability References 28 29 MnO2@C-NS//NPCS 166 at 550 W/kg 3000 at 49 Wh/kg 4.0 91 % after 5000 cycles Present work 30 31 32 N-CNPipes//PRGO 262 at 450 W/kg 9000 at 78 Wh/kg 4.0 89 % after 1000 cycles [S10] 33 34 Li4Ti5O12//AC 67.5 at 490 W/kg 4995 at 33.6 Wh/kg 3.0 85 % after 2000 cycles [S11] 35 36 37 Li3VO4//AC 49.1 at 72.5 W/kg 24.5 at 129.7 Wh/kg 3.5 - [S12] 38 39 Fe3O4-Graphene// 3D 147 at 150 W/kg 2587 at 86 Wh/kg 3.0 70 % after 1000 cycles [S13] 40 41 Graphene 42 43 44 Graphene-VN 162 at 200 W/kg 10000 at 64 Wh/kg 4.0 86% after 1000 cycles [S14] 45 46 //carbon nanorods 47 48 49 CNT/V2O5//AC 25.5 at 40 W/kg 6300 at 6.9 Wh/kg 2.7 80% after 10000 cycles [S15] 50 51 TiO2-B 12.5 at 300 W/kg 1300 at 8 Wh/kg 2.8 1000 cycles [S16] 52 53 54 nanowire//CNT 55 56 TiP2O7//AC 13 at 46 W/kg 370 at 0.2 Wh/kg 3.0 78% after 500 cycles [S17] 57 58 59 BiVO4//PRGO 152 at 384 W/kg 3861 at 42 Wh/kg 4.0 81% after 6000 cycles [S18] 60 61 62 39 63 64 65 15 16 17 18 19 20 21 22 MnO-C//carbon nanosheets 100 at 83 W/kg 33650 at 21 Wh/kg 3.0 70 % after 5000 cycles [S19] 23 24 3D-MnO/CNS//3D-CNS 184 at 83 W/kg 18000 at 83 Wh/kg 3.0 76 % after 5000 cycles [S20] 25 26 27 HC//AC 82 at 100 W/kg 5500 at 45 Wh/kg 2.1 - [S21] 28 29 TiC//PHPNC 101.5 at 450 W/kg 675000 at 23.4 Wh/kg 4.5 82 % after 5000 cycles [S22] 30 31 32 Li-Hard carbon//AC 82 at 100 W/kg 50000 at 1 Wh/kg 2.8 100 % after 40 cycles [S23] 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 61 62 40 63 64 65 References 1 2 [S1] H. 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