Carbon Nanoscrolls for Aluminum Battery - ACS Nano (ACS

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Carbon Nanoscrolls for Aluminum Battery Zhaomeng Liu,† Jue Wang,† Hongbo Ding,† Suhua Chen,† Xinzhi Yu,† and Bingan Lu*,†,‡ †

School of Physics and Electronics, Hunan University, Changsha 410082, China Fujian Strait Research Institute of Industrial Graphene Technologies, Jinjang 362200, China

‡

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ABSTRACT: This design provides a scalable route for in situ synthesizing of special carbon nanoscrolls as the cathode for an aluminum battery. The frizzy architectures are generated by a few graphene layers convoluting into the hollow carbon scroll, possessing rapid electronic transportation channels, superior anion storage capability, and outstanding ability of accommodating a large volume expansion during the cycling process. The electrochemical performance of the carbon nanoscroll cathode is fully tapped, displaying an excellent reversible discharge capacity of 104 mAh g−1 at 1000 mA g−1. After 55 000 cycles, this cathode retains a superior reversible specific capacity of 101.24 mAh g−1 at an ultrafast rate of 50 000 mA g−1, around 100% of the initial capacity, which demonstrates a superior electrochemical performance. In addition, anionic storage capability and structural stability are discussed in detail. The battery capacity under a wide temperature range from −80 to 120 °C is examined. At a low temperature of −25 °C, the battery delivers a discharge capacity of 62.83 mAh g−1 after 10 000 cycles, obtaining a capacity retention near 100%. In addition, it achieves a capacity of 99.5 mAh g−1 after 4000 cycles at a high temperature of 80 °C, with a capacity retention close to 100%. The carbon nanoscrolls possess an outstanding ultrafast charging/variable discharging rate performance surpassing all the batteries previously reported, which are highly promising for being applied in energy storage fields. KEYWORDS: carbon nanoscrolls, aluminum battery, cathode, anion intercalation, ultrafast rechargeable investigated.24−26 However, the high ionic charge density of Al3+ greatly reduces the ionic diffusivity and solvation− desolvation process, which impedes the intercalation/deintercalation of Al3+ ions into/out of the host electrodes.27,28 Most recently, several excellent reviews have described aluminum batteries that are composed of an aluminum foil anode, a graphitic cathode, and an ionic liquid electrolyte of AlCl3/[EMIm]Cl.17,19,23,29 In particular, an interesting approach utilizing graphite as the cathode material for storing anions was described by Dai et al. through taking advantage of the long-range-ordered layered structure of graphite. 30 However, as shown in Figure 1a, commercial graphite, a cathode material that offers a high operating voltage, is easily expanded after the insertion of anions into the lattice, causing pulverization and then deteriorating the cycling stability and reversible capacity.31−33 Considerable efforts have been carried out using three-dimensional graphene (presented in Figure 1b) prepared by chemical vapor deposition to solve this problem, which displays a promising performance for storing AlCl4− and Al2Cl7− anions because of the superior electrical conductivity,

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ecent development of electric energy storage systems has generated an enormous upsurge of interest in energy storage devices because of their inherent advantages, including a long life span and environmental friendliness, which attracts intensive exploration of various rechargeable battery systems (e.g., Li-ion batteries,1−6 Li−S batteries,7,8 and Li−air batteries9,10). However, the increasing lithium depletion has aroused severe concerns over the mass application of lithium-based energy storage devices, fiercely driving the development of rechargeable battery technologies based on highly abundant metals, such as Na,11−13 Mg,14−16 and Al.17−21 Among them, Al-based batteries are ideal for electric energy storage since it can offer considerable advantages, such as the abundance and low cost of Al anodes as well as the ultrahigh electrochemical stability.22 In Al-based batteries, metallic Al is usually employed as the anode, which exhibits a high safety performance because electrodeposition of Al in ionic liquids is fast, smooth, and dendrite-free.23 Therefore, the cathode largely decides the performance of the full battery, which is becoming the core of research on aluminum batteries. To obtain a cathode with a high performance, the cathodes for a “rocking-chair”-type aluminum battery, in which Al3+ ions reversibly shuttle back and forth between the electrolyte and electrodes, have been significantly © XXXX American Chemical Society

Received: May 25, 2018 Accepted: July 26, 2018 Published: July 26, 2018 A

DOI: 10.1021/acsnano.8b03961 ACS Nano XXXX, XXX, XXX−XXX

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Figure 1. Schematic diagram of anion insertion in various carbon materials. (a) Structural change of spherical graphite after anion intercalation. (b) Schematic diagrams of 3D graphene. (c) Illustration of tricontinuous and trihigh design for a desired graphene cathode. (d) Schematic diagram of a carbon nanotube with no anion storage ability. (e) Embedding of anions in the structure of a carbon nanoscroll. (f) Schematic illustration of the fabrication steps for the synthesis of carbon nanoscrolls.

ing the volume expansion. Besides, with the abundance of the C and Fe sources, the synthesis of carbon nanoscrolls is easily achieved at a low cost. To gain more insight into the application of carbon nanoscrolls in aluminum batteries, the frizzy material is investigated as the cathode material under various electrochemical tests with a potential window from 0.4 to 2.3 V. The electrochemical performance of the carbon nanoscroll cathode is fully tapped, demonstrating an excellent reversible discharge capacity of 104 mAh g−1 at 1000 mA g−1. Furthermore, the cathode offers an ultralong cycling stability, delivering a high capacity of about 101.24 mAh g−1 at a current density of 50 000 mA g−1 with a Coulombic efficiency (CE) close to 100% over 55 000 cycles. In addition, the carbon nanoscroll cathode exhibits an outstanding temperature performance (from −80 to 120 °C) in terms of the excellent specific capacity, high Coulombic efficiency, and superior cycle life. More importantly, an excellent cycle performance of carbon nanoscrolls under fast charging and slow discharging is verified (the battery can be fully charged in 6 s and discharged for more than 492 s, and nearly 100% capacity retention is obtained after 6600 cycles with the charge and discharge current at 10 000 and 100 mA g−1, respectively). On the basis of the ultrafast electrochemical performance as well as the low energy consumption and facile fabrication, carbon nanoscrolls are a highly promising electrode material for aluminum batteries and they may serve as an appropriate electrode material for other energy storage devices.56−60

yet it is too expensive to synthesize the material in the industrialized production.34,35 Recently, Gao et al. reported a design by adopting a “trihigh tricontinuous” (3H3C) graphene film as the cathode for aluminum batteries, as illustrated in Figure 1c. It delivered a superior high specific capacity around 120 mAh g−1 as well as an excellent rate capability and cycle life.36 However, the preparation of graphene films could be complicated and highly energy consumptive, which impedes its mass production. Carbon nanotubes (shown in Figure 1d) are not a suitable material for the cathode of an aluminum battery because there is no transportation channel, which leads to a poor capacity.37,38 Therefore, a scalable synthesis of cathode material with a facile preparation and low energy consumption for aluminum batteries is urgently needed.30,39−41 In this study, we report the synthesis of carbon nanoscrolls through a facile method, with carboxymethyl chitosan as the carbon source and ferric trichloride hexahydrate as the catalyst.42−45 The schematic diagram of a carbon nanoscroll is shown in Figure 1e. Several superior reviews have reported the synthesis of carbon nanoscrolls with graphite stripping and graphene automatic crimp methods, which are complicated and difficult to achieve in industrialization.46−50 Herein, a curly carbon architecture, in which the growth of few-layer graphene sheets is catalyzed by the iron cores to convolute a nanoscroll, is formed. A schematic illustration of fabrication steps for the synthesis of carbon nanoscrolls is depicted in Figure 1f. The prepared raw materials were carbonized at 600 °C; then the obtained soft carbon is catalyzed by iron as the temperature rises to 1000 °C, possessing a flaked structure. Due to the continuous catalysis by iron at 1100 °C for 5 h, the flaked carbon rolls up and forms the end-product with a scroll-like structure. This special architecture could endow the carbon nanoscrolls with rapid electron transmission channels along the scroll and superior anion storage capability.40,51−55 It should be pointed out that the volume expansion of carbon nanoscrolls is regulatable when the anions are embedded in the lattice due to this curly structure, which leaves large room for accommodat-

RESULTS AND DISCUSSION As shown in Figure 2a, the facile strategy is able to fabricate 60 g per batch of carbon nanoscrolls easily using the reduced iron atoms as the graphitization catalyst and a stoichiometric amount of carboxymethyl chitosan as the raw material. The diversified morphology of the as-prepared carbon nanoscrolls after a low-temperature annealing process is fully explored. The scanning electron microscope (SEM) images of carbon B


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Figure 2. Morphology and structure of the as-prepared carbon nanoscrolls. (a) Photograph of the final product (about 60 g) of carbon nanoscrolls per batch. (b) SEM image of the intermediate state product presents a frizzy flake-like architecture when the annealing temperature reaches 1000 °C. (c, d) SEM images of the as-prepared carbon nanoscrolls at different magnifications. (e) Typical TEM image of the sample showing the scroll-like structure. (f) High-resolution TEM revealing the scroll is hollow. The IFFT image in the illustration exhibits a single graphene layer. (g) EDS mappings showing the distribution of C and Fe elements. (h) XRD curve of the synthesized carbon nanoscrolls. (i) Raman spectrum of the synthesized carbon nanoscrolls.

nanoscrolls using different magnifications are shown in Figure 2b−d. The image of the intermediate state product in Figure 2b presents a frizzy flake-like architecture when the annealing temperature reaches 1000 °C, which is prepared for further catalysis. Compared to the image of soft carbon in Figure S1, the agglomerations in Figure 2c present dominant scroll-like structures, which indicates a key role of iron catalysis in the formation of such nanostructures. From the inset of Figure 2c, a frizzy scroll structure is supported by the neatly spread carbon nanoscrolls. More interestingly, hollow structures can be observed in Figure 2d, indicating that the carbon nanoscrolls evolve from the iron atoms. From the crosssectional view in the inset of Figure 2d, it is worth mentioning that the opening at the end of the carbon scrolls is visible, which validates the curly structure. This special structure obtained through a simple annealing approach is attributed to the assistance of the iron catalyst, which acts as the core for the in situ growth of the generated carbon material that expands and forms the carbon nanoscrolls. In order to further investigate the morphology, transmission electron microscopy (TEM) was conducted. From the TEM image in Figure 2e, it can be found that a few flaky materials gather together, with part of the carbon nanoscrolls existing on the surface. After

being sonicated for 1 h, the material is fully dispersed with the scroll-like-structured carbon clearly observed in Figure S2. The pictures in Figure S2a,b reveal that the single carbon nanoscroll is successfully produced with a length greater than 5 μm, which agrees with SEM results. To investigate compositions of the frizzy carbon material, various measurements were adopted to analyze the structure and morphology. From Figure 2f and Figure S3, it is suggested that the carbon nanoscrolls consist of single or multilayer carbon sheets that grow from iron cores and then seamlessly wrap into cylindrical scrolls. The overlapped carbon sheets may fold and form multilayer carbon sheets, which conforms to the appearance in Figure S4. The interlamellar spacing of carbon sheets is about 0.377 nm, which is larger than the lattice distance of graphite, possessing a superior anion storage ability. Besides, the pleated carbon nanoscrolls may provide many electron transport channels during the charge/discharge process. The inverse fast Fourier transform image of the carbon material in the illustration of Figure 2f exhibits a lattice spacing similar to that of graphene sheets. Therefore, it is confirmed that this frizzy carbon material is actually formed through folding the graphene sheet and finally generating the long strip carbon nanoscrolls. The elemental energy dispersive spectrometer (EDS) mappings in C


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Figure 3. Cycle performance of as-synthesized carbon nanoscrolls. (a) CV curves of an as-fabricated carbon nanoscroll cathode at the scanning rate of 10 mV s−1. (b) Selected galavanostatic charge−discharge curves in the potential range of 0.4−2.3 V at 10 000 mA g−1. (c) Rate capability of carbon nanoscrolls in the rate range from 5000 to 200 000 mA g−1. (d) Long-term cycle performance of carbon nanoscrolls at 10 000 mA g−1. (e) Long-term cycle performance of carbon nanoscrolls at a current density of 50 000 mA g−1 over 55 000 cycles.

Compared to the XRD curve of soft carbon in Figure S5, the synthesized carbon nanoscrolls exhibit a higher degree of graphitization, which is ascribed to the folding and turbostatic stacking of the graphene sheets. No iron species is observed in the XRD pattern, indicating that the iron element was etched away completely. Raman spectra in Figure 2i display the D band (1368.41 cm−1) and G band (1579.46 cm−1) with a ratio of ID/IG ≈ 0.258 (less than one), suggesting the successful transformation of disordered soft carbon to crystal graphene. In addition, the 2D mode (2676.35 cm−1) of graphene has a ratio of I2D/ID ≈ 2.801, which demonstrates that the synthesized sample has a graphene structure. In a nutshell, this special route achieved the fabrication of carbon nanoscrolls

Figure 2g further confirm that the frizzy structure is composed of carbon element derived from the carboxymethyl chitosan carbonation process. Interestingly, there is no iron element discovered in the illustration, indicating that iron was completely eliminated during the acid leaching process. Considering the curly structure, the carbon nanoscrolls may have a superior electronic conductivity as well as an excellent anion storage ability. From the X-ray diffraction (XRD) pattern in Figure 2h, the obtained carbon nanoscrolls display broad diffraction peaks at around 26.45° and 42.51°, which belong to the (002) and (100) facets of graphitic materials, respectively. It is generally established that an intense (002) peak is associated with an improved degree of graphitization. D


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Figure 4. Morphology and structure of the carbon nanoscrolls obtained from the electrodes being disassembled after finishing a specified cycle at different conditions. The testing state of the electrode in (a) and (b) is being charged to 2.3 V in the first cycle: (a) TEM image of the electrode showing the uniform scroll-like architecture at a full charged state; (b) EDS mappings of the disassembled electrode showing the distribution of C, Cl, and Al elements. The testing state of the electrode in (c) and (d) is being discharged to 0.4 V in the first cycle: (c) TEM image of the electrode showing the uniform scroll-like architecture at a fully discharged state; (d) EDS mappings of the disassembled electrode showing the distribution of C, Cl, and Al elements. (e) Ex-situ X-ray diffraction patterns of carbon nanoscrolls at the rate of 1000 mA g−1 during the second cycling process. The testing state of the electrode in (f)−(h) is cycled at 10 000 mA g−1 for 10 000 times: (f, g) TEM images of the electrode at different magnifications showing the stability of the curly architecture; (h) typical HRTEM image of the electrode showing the frizzy structure with graphitic lattices.

of AlCl4− out of the carbon nanoscroll interlayers. As shown in Figure 3b, the carbon nanoscroll cathode delivers the initial discharge and charge capacities of 100.49 and 101.11 mAh g−1 at a rate of 10 000 mA g−1. The initial Coulombic efficiency is about 99.3%. Encouragingly, the first discharge curve exhibits an average discharge plateau at about 1.45 V, which correlates to the extraction of AlCl4− from the carbon nanoscroll sheets during the cycling process. For the 10 000th cycle, the carbon nanoscroll cathode achieves discharge and charge capacities of 100.54 and 101.01 mAh g−1. In addition, the discharge curve of the 10 000th cycle overlaps with the initial curve, indicating a good reversibility and repeatability. Moreover, the observed charge/discharge behaviors in the first cycle are consistent with the CV results, which indicates that carbon nanoscrolls have a great potential for serving as the cathode material for aluminum batteries. The rate performance of the carbon nanoscroll in aluminum batteries at various current densities is presented in Figure 3c. Notably, the carbon-nanoscroll-based aluminum battery exhibits an excellent rate capability, displaying superior reversible capacities of about 100.01, 99.3, 97.55, 95.78, 93.53, and 88.82 mAh g−1 at increasing discharging current densities of 5000, 10 000, 20 000, 50 000,

through agglomerating the graphene sheets to build a curly structure. The superior electrochemical performance of the carbon nanoscroll cathode for an aluminum battery at room temperature is presented in Figure 3. The AlCl4− storage mechanism of the synthesized carbon nanoscroll is described as follows. Figure S6 illustrates that the curly structure contributes to the superior anion storage ability because of the existence of graphene layers and inner walls. Besides, the long channels crossing the parallel carbon nanoscrolls also supply a more convenient pathway for electron transportation and provide more contact interface between the electrode and electrolyte, which satisfies the rapid exchange of anions during the cycling process. Figure 3a depicts the cyclic voltammetry (CV) curve of the carbon nanoscroll cathode in a pouch battery for the first cycle with a scan rate of 10 mV s−1 between 0.4 and 2.3 V. Obviously, an intensive oxidation peak is located at around 2.05 V during the intercalation process, which is attributed to the insertion of AlCl4− into the interlayer of carbon nanoscrolls. In the deintercalation process, the carbon nanoscroll electrode displays two intensive reduction peaks at about 1.45 and 1.85 V, which are associated with the extraction E


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ACS Nano 100 000, and 200 000 mA g −1 for 200 times. The corresponding Coulombic efficiency is about 97.4%, 98.1%, 98.8%, 99.1%, 99.99%, and 100%, respectively. In addition, the electrode exhibits an outstanding cycle stability with no capacity decay for 200 cycles, which validates that the structure of the carbon nanoscroll can improve the ability of the material to withstand the attack of large current. Moreover, the discharge capacities could recover to their original value as the current densities return to 10 000 mA g−1, indicating a superior high rate recuperability. As depicted in Figure S7, the carbon nanoscroll electrode reveals a good cycling performance, possessing a specific capacity of about 104.3 mAh g−1 and a capacity retention of about 100% after 2500 cycles at a high current density of 1000 mA g−1. Furthermore, the electrochemical performance of a carbon nanoscroll cycled at 10 000 mA g−1 for 19 000 cycles is shown in Figure 3d. It is noticeable that the electrode still delivers a capacity as high as 101.35 mAh g−1 with an equivalent capacity retention of about ∼100%. Remarkably, this charge/discharge process expresses a high Coulombic efficiency around 99% during 19 000 cycles, which is possibly due to the excellent electronic conductivity brought by the frizzy scroll structure. Moreover, as exhibited in Figure 3e, the carbon nanoscrolls deliver an excellent specific capacity of 101.24 mAh g−1 at an ultrahigh current rate of 50 000 mA g−1. A capacity retention of ∼100% was achieved after 55 000 cycles with a stable Coulombic efficiency of 100%. The outstanding cycle stability could be attributed to the agglomeration of the graphene sheets, which builds a curly structure that is beneficial to the electron transport between the electrode material and electrolyte. In addition, at a high Coulombic efficiency of about 100%, the energy density of the carbon nanoscroll as cathode for an aluminum battery is calculated, resulting in a cell-level energy density of 30 Wh kg−1. The energy density of carbon nanoscrolls can be further improved (for example, M. Kovalenko et al. changed the acid condition of the electrolyte and the cathode current collectors, reaching the highest record energy density (65 Wh kg−1) of an aluminum battery).28,61−63 Considering the superior rate and long-term cycling performance, the high Coulombic efficiency, and the extremely high capacity retention, it can be concluded that the cathode material, the carbon nanoscroll, have superior comprehensive advantages for aluminum batteries. The morphology change, elemental distribution, and structural transformation of the prepared material were investigated to achieve a comprehensive understanding of the proposed anion storage mechanism of the carbon nanoscrolls. The aluminum batteries were disassembled in an Ar-filled glovebox after being initially charged to 2.3 V and discharged to 0.4 V at 1000 mA g−1 in the first cycle and then cycled at 10 000 mA g−1 for 10 000 times. The obtained electrodes were rinsed with dimethyl carbonate solution several times and dried in an argon atmosphere for the following analyses, including TEM, EDS, and XRD. Obviously, a well-maintained curly structure of the carbon nanoscroll being charged to 2.3 V is observed from the TEM image in Figure 4a, which demonstrates that the scroll-like structure of the electrode is not damaged during the electrode preparation. Besides, the interwoven carbon nanotube network and electrolyte decomposition products are also found on the surface of the active material. With AlCl4− intercalating in the carbon nanoscrolls, the graphite layer spacing is measured and shown in Figure S8a−c. It is obvious that the graphite lattice spacing is enlarged to 0.394 nm, which proves that the carbon nanoscrolls are fully

charged. The repeated TEM image at 2.3 V in Figure S9 proves that the morphology of the synthesized free-standing electrode is uniform. From the red select region enlarged and presented in Figure 4b, it should be pointed out that the fuscous curves on the surface of the scrolls are hollow, which verifies the proposed curly structure. Furthermore, C, Cl, and Al elements detected in the EDS mappings further confirm that the sample obtained from disassembling the battery primarily consists of carbon with a small quantity of Cl and Al from AlCl4− anions. This finding suggests that AlCl4− anions have inserted into the obtained graphene layers of the scroll-like structure. The peculiar phenomenon that major Cl and Al elements distribute along the path of the carbon nanoscroll walls proves that the special architecture of the carbon nanoscroll has a superior anion storage ability. To further confirm the morphological change of the active material during cycling, a TEM image of the carbon nanoscroll electrode discharged to 0.4 V in the first cycle is demonstrated in Figure 4c. An elongated scroll-like graphene structure consisting of a cannular profile connected by the threadlike carbon nanotube is clearly observed, which demonstrates that the structure of carbon nanoscroll is retained well without being damaged by the electrolyte in the first cycle. A homogeneous distribution of the C, Cl, and Al elements of the sample discharged to 0.4 V is revealed in Figure 4d. Compared with the charged state, the percentage of Cl and Al elements in the electrode under a discharged state is largely reduced, which indicates that AlCl4− anions could depart from the lattice of the carbon nanoscrolls during the discharging process. The structural transformation of the carbon nanoscroll during intercalation/deintercalation of AlCl4− is confirmed by the ex-situ XRD measurement in Figure 4e. Ex-situ XRD patterns of the carbon nanoscroll electrodes after being initially charged to 2.3 V and then discharged to 0.4 V at 1000 mA g−1 were recorded. It is apparent that both samples present diffraction peaks with lower intensity than that of pristine carbon nanoscrolls. Interestingly, after the battery was charged to 2.3 V with a current density of 1000 mA g−1, the (002) peak of the synthesized carbon nanoscroll at 2θ = 26.45° vanished, while two peaks appeared at 23.54° and 28.18°. The formation of the two fresh peaks is attributed to the intercalation of AlCl4−, which leads to highly strained graphene stacking. From the XRD curve of the fully discharged electrode, it is obvious that these two peaks disappear and a special peak emerges at 27.03°, which implies that the anion insertion process undergoes a reversible process in the stacking between the catalytic graphene layers. The (002) peak shifts from 26.45° to 27.03° after the first cycle, which is ascribed to the fact that the adjacent layers are being pushed during the insertion of AlCl4−, and thus the interlayer spacing decreases. The ex-situ XRD results prove that the carbon nanoscroll has a superior structure stability. As a cathode material, the structure stability of carbon nanoscrolls during ultrafast charge/discharge processes is very important. The TEM and high-resolution (HR)TEM images in Figure 4f−h characterize the morphological characteristics of the electrode material after 10 000 cycles. Figure 4f shows some scroll-like materials coexisting with the lathy carbon nanotube on the surface, demonstrating an interactive conductive network. The selected area is enlarged and shown in Figure 4g, from which the special curly structure is preserved after being cycled at a high current rate of 10 000 mA g−1 for 10 000 times. The obtained TEM image in Figure S10 further characterizes the morphology of F


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Figure 5. Comprehensive electrochemical performance of the prepared carbon nanoscroll material. The testing state of the electrode in (a)− (c) is being cycled at a wide range temperature: (a) charge and discharge curves at the temperature range from −25 to 120 °C; (b) cycle performance of the pouch battery at low (−25 °C) and high temperatures (60, 80, 100, and 120 °C), respectively; (c) excellent long cycle performance of the carbon nanoscroll pouch battery at −25 and 80 °C. The testing state of the electrode in (d)−(f) is being cycled at ultrafast charging/variable discharging current densities: (d) charge and discharge curves of carbon nanoscrolls charging at 20 000 mA g−1 and discharging at current densities ranging from 100 to 20 000 mA g−1; (e) fast charge and slow discharge performance of the pouch battery charging at 20 000 mA g−1 and discharging at current densities ranging from 100 to 20 000 mA g−1; (f) excellent long cycle performance of the carbon nanoscroll battery under a high charging current density up to 10 000 mA g−1 and a small discharging current at 100 mA g−1.

enlarged to 0.437 nm, which is attributed to the ultrafast insertion−deinsertion of AlCl4− anions during the charge/ discharge process. Therefore, the folded graphene layers on the scroll-like profile enhance the anions’ storage ability, offering a structural stability during the anions storage process as well supplying plenty of electronic transport channels, which benefits the ultrafast movement of electrons. In particular, the increased lattice space always gives rise to the volume expansion and structure damage to the graphite-like material during the cycling process. Because the structure is composed of curly layers of graphene and a hollow core of the scroll, the synthesized carbon nanoscroll electrode could accommodate more volume expansion and maintain a stable structure. This special structure provides a large hollow scroll as the buffer to tolerate more lattice expansion. The above phenomenon

the electrode, which reveals that the lattice of the carbon material is undamaged and testifies an exceptional stability of the carbon nanoscroll structure even under an extremely high current rate. The lattice of the junction between the carbon nanoscroll and carbon nanotube is clearly observed in Figure 4h (the magnified HRTEM image of the selected area). This rugged construction of carbon nanotubes dispersed on the graphene sheet greatly improves the electronic conductivity of the electrode. Moreover, the graphite-like lattice on the surface of the carbon nanoscroll is spotted, displaying the interplanar crystal spacing of about 0.437, 0.438, and 0.274 nm (the pictures during the distance test are shown in Figure S11), respectively, which affirms the above hypothesis that the graphene sheets fold on the surface. In comparison with the original interplanar spacing, the lattice distance of 0.377 nm is G


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mAh g−1 at a current density of 5000 mA g−1), with a superior Coulombic efficiency of 92.8% and 90.5%, respectively. As shown in Figure 5c, the carbon nanoscroll presents a long-life cycle at 80 °C, which displays a capacity of 99.5 mAh g−1 and a Coulombic efficiency above ∼92.2%. Besides, it shows a 100% capacity retention after 4000 cycles, which is better than the previous reports. The cycle performance of graphene at a low temperature of −25 °C has been intensively studied, delivering a reversible capacity of 62.83 mAh g−1 at 10 000 mA g−1 and a capacity retention of 100% after 10 000 cycles. Hence, the excellent low-temperature performance of the electrode is attributed to the scroll-like structure of the carbon nanoscroll, which tremendously enhances the permeability ability during cycling. In brief, the carbon nanoscroll achieves a superior temperature endurance, which allows the aluminum battery to perform at a wide temperature range. For the practical application of a battery, it is vital to simultaneously achieve a full charge in a very short time (fast charge) and continuous discharge for a long period of time (slow discharge). According to the above superior ultrafast electrochemical performance, it is desirable to evaluate the fast charging and slow discharging stability of the carbon nanoscroll cathode for aluminum batteries at the optimized current density. The typical discharge/charge profiles at the charge current of 20 000 mA g−1 and the descending discharge current densities are shown in Figure 5d. When the discharge current densities are tuned to 10 000 and 5000 mA g−1, it is obvious that both cyclic processes deliver similar discharge capacities of 102.1 and 102.7 mAh g−1, with a high Coulombic efficiency of 101% and 102%, respectively, which is a little higher than the capacity (101.5 mAh g−1) and Coulombic efficiency (99%) at the rate of 20 000 mA g−1. From the above observation, the Coulombic efficiency at the decreased discharge current density is higher than 100%, so it is necessary to optimize the discharge cutoff voltage. As the discharging current densities decrease from 5000 to 2000, 1000, 500, 200, and 100 mA g−1, the discharge cutoff voltages increase from 0.4 to 0.5, 0.6, 0.6, 0.7, and 0.7 V, yielding the stable capacities of 102.6, 101.50, 98.9, 99.96, 96.80, and 98.60 mAh g−1, respectively. The rate performance of the aluminum battery under fast full charge/various long-period discharge is displayed in Figure 5e. The carbon nanoscroll presents a superior cycle performance after more than 100 cycles, with a Coulombic efficiency of 101%, 98.6%, 98.3%, 99.9%, 95.6%, and 98.7% at a discharge rate ranging from 5000 to 2000, 1000, 500, 200, and 100 mA g−1. Moreover, the specific charge/ discharge capacities could recover to their initial value as the charge/discharge current densities return to 20 000 mA g−1, which indicates that the carbon nanoscroll cathode has a superior high rate recuperability and structure stability. The obtained rate performance of the carbon nanoscroll is shown in Figure 5f. Notably, the long-term cycle performance of the carbon nanoscroll cathode was obtained under a high charging current density up to 10 000 mA g−1 and a small discharging current at 100 mA g−1, equivalent to a charging time of 6 s and a discharging time of more than 492 s. This battery reveals an outstanding cycling stability, reaching a retention of about 99% after cycling for 6600 times and a high Coulombic efficiency above 95−99%.

identifies that the curly structure is well reserved after a longterm cycling, expressing an extraordinary stability. By combining ex-situ TEM, XRD, and EDS mapping results, it can be concluded that the obtained carbon nanoscrolls deliver superior electronic transport channels, outstanding anionic storage ability, and excellent structural stability, offering a highly promising candidate for the cathode material of aluminum batteries. In applications, the battery will experience a temperature variation, such as cold in winter and hot in summer. Therefore, the electrochemical performance under a wide operating temperature range and ultrafast charging/discharging current densities is the prime requirement in determining the feasibility of applying carbon nanoscrolls as the cathode for aluminum batteries. As a demonstration, the carbon nanoscroll electrode has successfully powered a light-emitting diode (LED) and presented superior flexibility, as shown in Figure S12. Figure 5a reveals the typical charge−discharge profiles with the temperature varying from −25° to 120 °C, in which the battery survives both an ice-salt bath and 120 °C baking. Even though the initial discharge specific capacity at 0 °C (100.02 mAh g−1) is a little lower than that of battery cycling at 25 °C (101.45 mAh g−1), the sample shows an increasing Coulombic efficiency from 96−98% to 99−100% when the external temperature decreases from room temperature to 0 °C, which proves that an aluminum battery with the carbon nanoscroll cathode could withstand a low-temperature condition (Figure 5b). Likewise, when the experiment temperature decreased from 0 to −25 °C, both the charge and discharge capacities are reduced, while the Coulombic efficiency still remains unchanged, which could be ascribed to the decrement of the conductivity of the electrolyte that results in a little capacity decay but a higher cycle efficiency. As the temperature returns to room temperature, the capacity quickly recovers to 101.5 mAh g−1 at a charge/discharge current of 5000 mA g−1 with a Coulombic efficiency higher than 98%. The sample presents a similar stability when the temperature drops directly from room temperature to −25 °C again. Besides, the specific capacity of the battery at −80 °C is about ∼0 mAh g−1, while it delivers full capacity as the temperature returns to 25 °C. The typical cycle performance is presented in Figure S13. Conversely, the carbon nanoscroll electrode exhibits an increased specific discharge capacity with a decreased Coulombic efficiency at 60 °C in comparison to room temperature (Figure 5b). There is no denying that the temperature increment increases the diffusion and irregular movement of ions. In the meantime, anions scatter when the carbon nanoscroll lattice is enhanced at elevated temperature, which would lead to an electric energy loss, resulting in a lower Coulombic efficiency. Given the drastic decomposition of the electrolyte at elevated temperature, a strategy of optimizing the charge cutoff voltage is adopted to improve the cycling stability as well as enhance the Coulombic efficiency. With the temperature further increasing to 80 °C, this battery reveals a stable discharge capacity (about 95.8 mAh g−1), together with a Coulombic efficiency of about 95.4% in the voltage range of 0.6−2.25 V. It is effective to decrease the charge cutoff voltage from 2.30 to 2.25 V, which reveals a negligible decay in discharge capacity (from 102 to 95.8 mAh g−1) and high enhancement in Coulombic efficiency (from 78% to 95%). Importantly, the cutoff voltage optimization strategy is also valid when the temperature further rises to 100 and 120 °C, exhibiting an acceptable high discharge capacity (94.6 and 88.9

CONCLUSIONS A highly crystalline carbon nanoscroll is successfully synthesized by a facile and scalable method using carboxH


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served as the current collectors for both cathode and anode.35 The diameter of AlCl4− ion is 0.488 nm. The charge/discharge tests were conducted in the potential range of 0.4−2.3 V using a multichannel battery testing system (Neware BTS-53). A CHI660e electrochemical workstation (Chenhua, Shanghai) was used to perform the CV measurements at 10 mV s−1 within the voltage range of 0.4−2.3 V.

ymethyl chitosan and ferric trichloride hexahydrate as the raw materials. The rapid electron transmission channels, the superior anion storage property, and the ability to accommodate a large volume expansion of this scroll-like structure were fully obtained. Interestingly, the aluminum battery with a carbon nanoscroll as the cathode material exhibited an excellent electrochemical performance, including a high capacity, an ultrafast cycle performance, a wide operation temperature endurance ability, and an extraordinary ultrafast charging/variable discharging rate property. Concretely, it delivered an excellent cycling life with a reversible specific capacity of 101.24 mAh g−1 at the ultrafast rate of 50 000 mA g−1, maintaining 100% of the initial capacity after 55 000 cycles. In addition, the long cycle performance of carbon nanoscrolls at −25 and 80 °C was obtained, with discharge capacities of 62.83 and 99.50 mAh g−1 with ∼100% retained capacity, respectively. Furthermore, at a high current charging density up to 10 000 mA g−1 and being slowly discharged at 100 mA g−1, the carbon nanoscroll electrode presented a high capacity retention of about 99% after 6600 cycles with a high Coulombic efficiency above 95−99%. This work not only demonstrates a great impetus of utilizing carbon nanoscrolls as an admirable cathode material for aluminum battery but also innovates a method of designing high-performance electrode materials for energy storage and conversion devices.

ASSOCIATED CONTENT S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsnano.8b03961. Additional information (PDF)

AUTHOR INFORMATION Corresponding Author

*E-mail: [email protected]. ORCID

Bingan Lu: 0000-0002-0075-5898 Notes

The authors declare no competing financial interest.

ACKNOWLEDGMENTS Z.L. and J.W. contributed equally to this work. This work was financially supported by National Natural Science Foundation of China (Nos. 51672078 and 21473052), Hunan University State Key Laboratory of Advanced Design and Manufacturing for Vehicle Body Independent Research Project (No. 71675004), Hunan Youth Talents (2016RS3025), and Foundation of State Key Laboratory of Coal Conversion (Grant No. J17-18-903).

METHODS AND EXPERIMENTAL Synthesis of Carbon Nanoscrolls. To obtain carbon nanoscrolls, a one-step sintering route was used by leveraging iron catalytic carbonizing of soft carbon at a lower roasting temperature. Specific steps are as follows: carboxymethyl chitosan (DS., 80%) and FeCl3· 6H2O (A.R., 98%) with a mass ratio of 2:5 were mixed into distilled water to form a homogeneous colloidal slurry. Then, the moisture was volatilized at 110 °C in a vacuum. The obtained mixture was heated at 600 °C for precarbonization and roasted at 1100 °C for 5 h under an Ar atmosphere and then allowed to cool at a rate of 2 °C min−1. Finally, the synthesized material was immersed in 1 M hydrochloric acid (HCl) for 1 day to eliminate the iron residue, followed by filtering and drying for several times. The acquired powder was carbon nanoscrolls. As a comparison, the material obtained by roasting carboxymethyl chitosan at 1100 °C for 5 h under an Ar atmosphere was named soft carbon. The material obtained by annealing a carboxymethyl chitosan and FeCl3·6H2O mixture at 1000 °C for 5 h under an Ar atmosphere was named as an intermediate state for investigating the synthetic mechanism. Materials Characterizations. Powder XRD (Rint-2000, Rigaku, Cu Kα) was adopted to confirm the crystalline phase of the synthesized carbon nanoscroll. A field emission scanning electron microscope (Hitachi S-4800, 20 kV) was used to characterize the morphology of the material. The detailed morphology changes of the electrodes were characterized by TEM (Titan G2 60-300 with image corrector). EDS mapping analysis was used to deliver the elemental distributions. The Raman spectra (Renishaw 2000 system) were measured in the frequency range of 1000−3000 cm−1. Electrochemical Measurements. The working electrodes were fabricated as follows: 10% conductive agent (carboxylated carbon nanotubes), 10% binder (carboxyl methylated cellulose), and 80% active material (carbon nanoscrolls) were mixed into deionized water to form a slurry. The obtained slurry was spread out on the filter membrane using vacuum extraction. Acetone was used to remove the carrier, and then a free-standing carbon nanoscroll material was acquired. Pouch aluminum batteries were assembled in a dry Ar-filled glovebox, using a piece of free-standing carbon nanoscroll (∼0.1−1 mg) as the cathode, Al foil (∼200 mg) as the anode, and cellulose paper as the separator. The electrolyte was the light yellow ionicliquid electrolyte (AlCl3/[EMIm]Cl = 1.3 by mole), and nickel foils

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