Jindui Honga,
Chunping Chena,
Ampornphan Siriviriyanunb,
Dana-Georgiana Crivoia,
Philip Holdwayc,
Jean-Charles Buffeta and
Dermot O'Hare*a
aChemistry Research Laboratory, Department of Chemistry, University of Oxford, 12 Mansfield Road, Oxford, OX1 3TA, UK. E-mail: dermot.ohare@chem.ox.ac.uk
bSCG Chemicals Co., Ltd., 1 Siam Cement Rd, Bangsue, Bangkok, 10800, Thailand
cDepartment of Materials, University of Oxford, Parks Road, Oxford, OX1 3PH, UK
First published on 10th August 2021
The development of future mobility (e.g. electric vehicles) requires supercapacitors with high voltage and high energy density. Conventional active carbon-based supercapacitors have almost reached their limit of energy density which is still far below the desired performance. Advanced materials, particularly metal hydroxides/oxides with tailored structure are promising supercapacitor electrodes to push the limit of energy density. To date, research has largely focused on evaluation of these materials in aqueous electrolyte, while this may enable high specific capacitance, it results in low working voltage window and poor cycle stability. Herein, we report the development of Ni2Mn-layered double oxides (Ni2Mn-LDOs) as mixed metal oxide-based supercapacitor electrodes for use in an organic electrolyte. Ni2Mn-LDO obtained by calcination of [Ni0.66Mn0.33(OH)2](CO3)0.175·nH2O at 400 °C produced the best performing Ni2Mn-LDOs with high working voltage of 2.5 V and a specific capacitance of 44 F g−1 (at 1 A g−1). We believe the performance of the Ni2Mn-LDOs is related to its unique porous structure, high surface area and the homogeneous mixed metal oxide network. Ni2Mn-LDO outperforms both the single metal oxides (NiO, MnO2) and the equivalent physical mixture of the two oxides. We propose this performance boost arises from synergy between NiO and MnOx due to a more effective homogeneous network of NiO/MnOx domains in the Ni2Mn-LDO. This work clearly shows the advantage of an LDO over the single component metal oxides as well as the physical mixture of mixed metal oxides and highlights the possibilities of development of further mixed metal oxides-based supercapacitors in organic electrolyte using LDH precursors.
To achieve high specific capacitance without sacrificing the operating voltage, power capacity and cycle stability, metal oxide electrodes using organic electrolyte have been developed.7–11 Sugimoto et al. reported that NiO can achieve a wider working voltage and much higher energy density in organic electrolyte than in aqueous electrolyte.9 The composites of NiO/polypyrrole10 and NiO/carbon fibre cloth11 have also been developed to improve the electrochemical performance of NiO. Nesscap patented that MnO2 achieved better specific capacitance in the organic electrolyte with dual salts than that with single salt.12 Despite the above development, the use of mixed metal oxides in organic electrolytes remains relatively unexplored. Due to their complementary properties, mixed metal oxides have shown synergetic effects in many applications (e.g. catalysis,13,14 photocatalysis15 and batteries16,17). Individually, both NiO and MnO2 have been investigated as supercapacitor electrodes, displaying typical surface redox pseudocapacitance9,11 and bulk intercalation pseudocapacitance,18 respectively. We thought it could be highly rewarding to study mixed metal oxides for their potential advanced supercapacitor electrode, particularly in the organic electrolyte.
Layered double hydroxides (LDHs), are a big family of anion layered materials that have positively charged metal hydroxide layers and negatively charged anion interlayers.19–23 Transition metal-LDHs including [Ni0.66Mn0.33(OH)2](CO3)0.175·nH2O (Ni2Mn-LDH) have been widely studied as supercapacitor electrodes using aqueous alkaline electrolyte.24–30 By simple calcination of LDHs, they can be transformed into a unique type of mixed metal oxide often referred as layered double oxides (LDOs). LDOs have found applications in CO2 capture,31 catalysis,32 and batteries.33 LDOs were also developed as advanced supercapacitor electrode materials in aqueous electrolytes thanks to their better conductivity and unique structure.34 Herein, we report the use of Ni2Mn-LDO prepared by calcination of Ni2Mn-LDH as mixed metal oxides-based supercapacitor electrode in TEABF4/acetonitrile. We investigated the performance of Ni2Mn-LDO electrodes prepared at different calcination conditions including calcination temperature, ramping rate and hold time. Control samples including NiO, MnO2 and physical mixtures of NiO and MnO2 were also prepared and evaluated in the same organic electrolyte.
The as-obtained Ni2Mn-LDHs were calcinated in a crucible without lid in a box furnace in static air. The following conditions were investigated: (a) different calcination temperatures (200, 300, 400, 500, 600, 700 and 900 °C) with a fixed ramp rate of 5 °C min−1 and a holding time of 3 h, samples are referred as LDO200, LDO300, LDO400, LDO500, LDO600, LDO700 and LDO900, respectively; (b) different ramp rate (0.5, 5, 10, 30, 50 and 100 °C min−1) at fixed calcination temperatures of 400 °C and a holding time of 3 h; and c) different holding time (0.5, 1, 3, 6, 12 and 24 h) with fixed calcination temperature of 400 °C and a ramp rate of 5 °C min−1. Several control samples were also prepared: NiO was obtained from the calcination of Ni(OH)2 at 400 °C, 5 °C min−1 for 3 h. Commercial MnO2 was used alone and also physically mixed in with the as-synthesised NiO to give a 2:1 Ni:Mn ratio as a further reference sample.
(1) |
To further investigate the steps in LDH to LDO evolution, TGA was carried out for Ni2Mn-LDH to monitor the thermal decomposition of LDH in the temperature range of 45–900 °C. As shown in Fig. 1(c), there are typically three thermal event onsets/mass losses for the LDH at 97, 186 and 240 °C, corresponding to the loss of physisorbed/intercalated water, the metal hydroxide layer dehydroxlyation (oxyhydroxide)-metal oxide conversion and decarbonation, respectively. At 124 °C, there is a 11.1 wt% mass loss from the complete loss of moisture. By 300 °C, a further 13.0 wt% mass loss arising from carbonate decomposition and dehydroxlyation was observed. Combined with the XRD results in Fig. 1(a and b), the most likely transformation sequence with increasing temperature is shown in Fig. 1(d). The data suggests that the LDH converts to NiOOH and Ni–Mn-Ox initially (LDO200) and then transforms to another Ni–Mn-Ox phase at 300 °C (LDO300). At 400 °C, NiO and MnOx form separated nano-domained phases, which upon further heating transform into the mixture of NiO–Ni6MnO8–NiMnO3 from 500 °C until 700 °C. At 900 °C, these mixed metal oxides convert to the mixture of NiO and the spinel phase, NiMn2O4. This rich chemistry of LDH-LDO transformation provides series of LDOs with different phases and crystallinity for the study as supercapacitor electrodes.
Fig. 2 and Fig. S1† show the Ni 2p3/2, Ni 2p1/2 and Mn 2p3/2 XPS spectra for Ni2Mn-LDH and the LDOs (LDO200, LDO300, LDO400, LDO700 and LDO900). Fig. 2(a) shows binding energies at 855.8 and 873.5 eV for the pristine LDH, which corresponding to the Ni2+ 2p3/2 and Ni2+ 2p1/2, respectively.36 The other two binding energies at 861.5 and 879.2 eV are corresponding to satellite peaks of Ni2+. Similar binding energies for Ni 2p are also found in LDO400 (Fig. 2(b)) and LDO300/LDO700/LDO900 (Fig. S1(b–d)†), confirming the oxidation state of Ni remains unchanged in these samples. Fig. S1(a)† shows that the Ni 2p peak of LDO200 is broad and can be deconvoluted into three peaks at 855.7, 858.2 and 862.9 eV, corresponding to Ni2+, Ni3+ and satellite peaks, respectively.36 The above results are consistent with the XRD results in Fig. 1(b) that indicates the presence of NiOOH in LDO200. Fig. 2(c-d) show very broad peaks for Mn (about 12 eV full width at half maximum, FWHM), which are more complicated to analyse due to the multiplet splitting and shakeup features.37 For all samples except LDO200, four main peaks can be fitted at about 641.1, 642.4, 643.7 and 645.6 eV (satellite peak), which suggest the co-existence of Mn2+, Mn3+ and Mn4+.38 Higher oxidation state of Mn were observed in LDO200 (Fig. S1(e)†) which could be the mixing of Mn3+, Mn4+ and even Mn5+. The higher oxidation state of Ni and Mn in LDO200 could be due to the oxidation of dehydrated hydroxides by oxygen from the calcination in air at 200 °C, but it is unclear for now how they are reduced to original chemical status when the calcination temperature is lifted above 200 °C.
To study the effect of morphology, porosity and phases on electrode performance, TEM and BET have been carried out on both LDH and LDOs. Fig. 3(a) shows the platelet-like morphology of Ni2Mn-LDH with platelet diameters about 50–150 nm. A similar morphology is retained in LDO200 (Fig. 3(b)) despite the structural phase change to an LDO. Fig. 3(c and d) show well-distributed mesopores (2–4 nm) in LDO300 and LDO400. These mesopores are known as Kirkendall voids which are formed due to the difference in diffusivities of Ni and Mn atoms.39 As a result, LDO300 and LDO400 have the highest surface area and pore area (Fig. S2(a and b)†). These results demonstrate that LDOs with unique porous structures can be made from a simple and facile calcination method. In comparison, complex methods are typically required to make porous mixed metal oxides involving the synthesis with a template and subsequent template removal.40 Fig. 3(e and f) show that the Kirkendall voids become larger (4–20 nm) in LDO500 and LDO600. At 700 and 900 °C, most of the voids disappear with the particle size becomes larger due to the sintering at higher temperature (Fig. 3(g and h)). The STEM-EDS mapping of LDO400 in Fig. 3(i–l) show that Ni and Mn are well-distributed across the entire sample indicating the homogeneous mixing of NiO and MnOx in LDO400. In addition to the unique porous structure, LDOs have another advantage of intimate homogeneous mixing of two metal oxides, compared to physical mixing.
Fig. 4(a) and Fig. S3† show the cyclic voltammetry (CV) curves of LDH and LDOs in the organic electrolyte. As far as we are aware this is the first electrochemical study of an LDH/LDO in an organic electrolyte. The LDH has a relative narrow potential window (2.0 V) and limited specific capacitance over the potential window investigated. The expansion of the enclosed area within the CV curves of the LDOs indicates the enhanced specific capacitance in LDOs compared to the LDH. Particularly, LDO400 shows the strongest current response due to its highly porous structure and the intimate homogeneous mixing of electrochemically active NiO and MnOx phases. Fig. 4(a) shows a smooth CV curve for LDH in the organic electrolyte (1 M TEABF4 in AN) except for a minor reduction peak at −0.6 V. This indicates its surface-limited storage mechanism. In comparison, the CV response of Ni2Mn-LDH in alkaline aqueous electrolyte shows the typical peak shape of a battery-type storage mechanism.24,41 Fig. 4(b) shows the galvanostatic charge–discharge of LDH and LDO400. From the discharge curve and using eqn (1), the specific capacitance of LDH is calculated to be 3.2 F g−1 while LDO400 can reach 44 F g−1, which is at least 13 times higher than LDH. Both higher specific capacitance and wider working potential in LDO400 will facilitate the development of much higher energy density supercapacitors. Fig. 4(b) shows a smooth charge/discharge curve without an obvious battery-type plateau indicating nearly constant capacitance over the potential range. This is consistent with the CV data. Nyquist plots and the equivalent circuit model were shown in Fig. 4(c). Series resistance (Rs) can be obtained from the intersection of curve with x axis indicates the lower series resistance in LDO400 possibly due to its better compatibility with the organic electrolyte. On the other hand, it seems that the charge transfer resistance (Rct) is lower in Ni2Mn-LDH although the semi-circle is less obvious. Overall, the internal resistance (Rs + Rct) of LDO400 is lower than that of Ni2Mn-LDH. Galvanostatic charge–discharge curves in Fig. 4(d) show that LDOs have similar charge–discharge behaviour but with significantly different capacity. The calculated specific capacitances and measured specific surface area were plotted versus the calcination temperature in Fig. 4(e). A similar trend is found for the effect of calcination temperature on specific capacitance and specific surface area. However, a high surface area does not guarantee the best performance.4 The calcination temperature significantly affects the specific capacitance as it induces the changes of chemical composition, crystallinity, phase fraction, surface area and porous structure within the LDOs. A slow calcination (low ramp rate) of the LDH results in better performance while the effect of calcination holding time is negligible (Fig. S4†). Overall, the optimised conditions are: calcination at 400 °C with ramping rate of 5 °C min−1 and hold time of 3 h. Under the optimal conditions, LDO400 has the best performance due to the intimate mixing of low crystallinity, high surface area, active NiO/MnOx phases with a highly porous structure. We also noted that spinel oxides have been reported as supercapacitor electrodes with high performance in an aqueous electrolyte,42 however, a relative low specific capacitance was found for the spinel containing LDO (900 °C) here which could be due to the different storage mechanism in the organic electrolyte.
To further illustrate the difference between the mixed metal LDO and a simple mixture of metal oxides, control samples of NiO, MnO2 and a physical mixture (in the appropriate ratio) were prepared, evaluated by CV and GCD, and compared with LDO400. The envelop shape of CV in Fig. 4(f) indicates that storage mechanism of NiO is likely to be a fast surface redox pseudocapacitance9,11 which can be described by the eqn (2).
(NiO)surface + TEA+ + e− ↔ (NiO−TEA+)surface | (2) |
This involves fast and reversible redox reactions on the surface of NiO involving the tetraethylammonium cation (TEA+, from the electrolyte salt TEA+BF4−). For MnO2, a pair of redox events is observed with small voltage offset indicating that the storage mechanism involves the intercalation pseudocapacitance4 which can be described by the eqn. (3).18
MnO2 +TEA+ + e− ↔ (MnOO)TEA | (3) |
During the intercalation/deintercalation of TEA+ in the interlayers/tunnels of MnO2, there is reversible redox transition between Mn4+ and Mn3+. The linear dependence of potential on the state of charge in Fig. 4(i) is another characteristic of pseudocapacitive storage mechanism in NiO and MnO2. A higher specific capacitance is found in the physical mixture compared to their parent materials indicating the synergetic effect between NiO and MnO2. This could be due to the combined contribution of fast redox pseudocapacitance of NiO and intercalation pseudocapacitance of MnO2. For LDO400, the specific capacitance is even higher due to the synergic effect between two types of pseudocapacitive storage mechanism, uniform porous structure and a better distribution of NiO/MnOx than in the physical mixture of NiO/MnO2. From Fig. 4(i), the specific capacitances of NiO, MnO2 and physical mixture of NiO and MnO2 are calculated to be 12 F g−1 (2.5 V), 24 F g−1 (2.0 V), 36 F g−1 (2.5 V), respectively, all of which are lower than that of LDO400 (44 F g−1 at 2.5 V). These results clearly show the advantage of LDO over the single component metal oxides as well as the physical mixture of mixed metal oxides.
To illustrate the storage mechanism of LDO400, CV experiments at different scan rates (1–100 mV S−1) were collected and shown in Fig. 5(a and b). According to the power law relationship, eqn (4).43,44
i = aυb | (4) |
To demonstrate that LDO as the high-working voltage electrode, a symmetric two-electrode system using both LDO400 as cathode and anode was evaluated by CV at various voltage windows. Fig. 6 shows quasi-rectangular shapes of CV curves up to 2.5 V. At working voltage of 2.6 V, the discharge CV curve starts to distort slightly at 2.25 V which becomes more significant at the working voltage of 2.8 V indicating the non-reversible structure change of LDO400. These results confirm that LDO400 can operate at high working voltage up to 2.5 V using a symmetric design.
Footnote |
† Electronic supplementary information (ESI) available: Details of chemicals and materials, and characterisation methods. Fig. S1–S4, XPS, BET, pore size distribution of LDH and LDOs, effect of calcination ramping rate and hold time on the specific capacitance. See DOI: 10.1039/d1ra04681k |
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