Simin
Wang‡
a,
Qifei
Guo‡
b,
Haoran
Liu
a,
Longhai
Zhang
a,
Chaofeng
Zhang
a,
Tengfei
Zhou
a,
Quanwei
Ma
a,
Hongbao
Li
*a,
Rui
Wang
a and
Yang
Zheng
*b
aInstitutes of Physical Science and Information Technology, School of Materials Science and Engineering, Leibniz International Joint Research Center of Materials Sciences of Anhui Province, Anhui Province Key Laboratory of Environment-Friendly Polymer Materials, Key Laboratory of Structure and Functional Regulation of Hybrid Material (Ministry of Education), Anhui University, Hefei 230601, China. E-mail: lihb@ahu.edu.cn
bThe State Key Laboratory of Refractories and Metallurgy, Institute of Advanced Materials and Nanotechnology, Wuhan University of Science and Technology, Wuhan 430081, China. E-mail: yzheng@wust.edu.cn
First published on 7th December 2023
Organic small-molecule compounds have become promising cathode materials for high-performance lithium-ion batteries (LIBs) due to their high theoretical capacity, efficient utilization of active sites, low cost, and sustainability. However, severe dissolution and poor electronic conductivity limit their further practical applications. Herein, we have synthesized an insoluble organic small molecule, ferrocenyl-3-(λ1-azazyl) pyrazinyl [2,3-f] [1,10] phenanthrolino-2-amine (FCPD), by grafting ferrocene onto pyrazino[2,3-f] [1,10] phenanthroline-2,3-diamine (PPD). The combination of ferrocene (p-type Fe2+ moiety) and PPD (n-type CN groups) in a bipolar manner endows the target FCPD cathode with an increased theoretical capacity and a wide voltage window. The highly conjugated π–π aromatic skeleton inside enhances FCPD's electron delocalization and promotes strong interaction between FCPD units. Additionally, the mesoporous structure within the FCPD can provide numerous electroactive sites, contact area, and ion diffusion channels. Benefiting from the bipolar feature, aromatic, and mesoporous structure, the FCPD cathode demonstrates a large capacity of 250 mA h g−1 at 0.1 A g−1, a long lifespan of 1000 cycles and a high-rate capability of 151 mA h g−1 at 5 A g−1 along with a wide voltage window (1.2–3.8 V). Additionally, in situ synchrotron FT-IR and ex situ XPS reveal its dual ion storage mechanism in depth. Our findings provide essential insights into exploring the molecular design of advanced organic small molecules.
Organic electrode materials can generally be classified into two categories based on different reaction mechanisms, n-type for cation storage and p-type for anion storage.4,24 Among them, n-type organic cathodes have been extensively studied due to their high capacity. Examples of n-type organic cathodes include carbonyl compounds, imine-carbonyl compounds, imine compounds, and nitroaromatics. However, the low redox potential (<2.8 V vs. Li+/Li) limits their practical applications. On the other hand, p-type organic cathodes offer a higher redox potential (>3 V vs. Li+/Li), but their capacity is often limited. Examples of p-type organic cathodes are triphenylamine derivatives, triphenylphosphine derivatives, organosulfur compounds, and nitronyl nitroxide compounds. To address these limitations, a promising strategy is to combine both n-type and p-type features in a bipolar manner, allowing for simultaneous cation and anion storage. This approach enables the achievement of an ideal potential and capacity. Bipolar organic cathodes, such as PANI, poly-quinone-phenylenediamine, and poly(1,8-diaminonaphthalene), have exhibited remarkable energy storage performance over the past few decades.29 However, their large molecular weight and inactive units often result in low specific capacity. Additionally, the utilization of active sites within their polymer structures is typically inefficient.
In contrast, bipolar organic small-molecule compounds possess multiple redox groups, which can maximize the number of electrons transferred per unit and lead to highly efficient utilization.30 However, issues with dissolution and low electronic conductivity limit their cycling stability and reaction kinetics. Polymerization and the integration of carbonaceous materials are considered powerful methods to address these issues, but significantly increased molecular weight and the inclusion of inactive composite will inevitably weaken their electrochemical performance.31,32 By contrast, increasing the degree of π-conjugation should be considered as an effective method. This can effectively create and strengthen van der Waals interactions between neighboring organic small molecules, leading to a strong intermolecular π–π stacking. The strong π–π interaction can not only maintain the stable structure of small molecules during repeated lithiation/de-lithiation processes but also suppress their severe dissolution by forming aggregates or clusters.33,34 Additionally, the greater delocalization of π electrons in these highly conjugated organic small molecules can enhance electronic conductivity.
In this study, we have designed and synthesized an organic small-molecule cathode by grafting ferrocene onto PPD, which we refer to as FCPD. FCPD possesses a bipolar feature and a high degree of π-conjugation simultaneously due to the p-type moiety (Fe2+), n-type groups (CN), and aromatic structure. The bipolar feature allows both the cation and anion to serve as charge carriers, resulting in a large capacity and a wide redox window. The high degree of π-conjugation facilitates charge transport and interaction between the small-molecule units, leading to fast kinetics and low solubility. As a result, the FCPD cathode exhibited excellent Li+/anion-storage performance. Furthermore, density functional theory (DFT) calculations and in/ex situ spectra characteristics provide a detailed understanding of the Li+/anion-storage mechanism of the FCPD cathode.
Furthermore, XPS analysis revealed the presence of C 1s, N 1s, and Fe 2p in FCPD (Fig. 1c–e). In the Fe 2p spectrum, the characteristic peaks at 708.1 and 720.8 eV correspond to Fe2+, indicating the successful grafting of ferrocene.38 The C 1s spectrum exhibits four peaks at 284.8, 285.7, 287.6, and 291.1 eV, which can be attributed to the CC/C–C, C–N, and CN bonds and the π–π satellite peak, respectively. The N 1s spectrum further shows the characteristic peaks of C–N (400.1 eV) and CN (398.8 eV),3,33,40,41 conforming the existence of these bonds in FCPD. Additionally, the N 1s spectrum contains a peak at 399.3 eV related to the N–H bonds, which should be derived from the amino group in FCPD. Afterward, the solubility of the three small molecules (PPD, FCA, and FCPD) in the organic electrolyte was explored.
As shown in Fig. 1f, PPD and FCA-soaked electrolytes turn deep yellow and brown colors, respectively, indicating their high solubility. In contrast, the FCPD-soaked electrolyte is almost colorless, suggesting that the synthesized FCPD is much less soluble in the electrolyte. In addition, further UV-vis spectra of these soaked electrolytes are collected in Fig. 1g. It is evident that only the FCPD-soaked electrolyte exhibits a spectrum similar to that of the fresh electrolyte, providing further confirmation of its insolubility.2,33 Furthermore, the TGA profiles of PPD, FCA, and FCPD are shown in Fig. 1h, revealing their respective thermal decomposition temperatures of 280, 130, and 260 °C. It should be note that both FCA and FCPD left residuals after annealing at 750 °C, which can be attributed to the oxidation of the ferrocene inside, further validating the successful ferrocene grafting.38,42
Afterwards, the microstructure of these organic materials was observed by SEM and TEM. Interestingly, unlike the irregular morphology of PPD and FCA monomers (Fig. S1a and b†), uniform nanospheres with a smooth surface were observed in FCPD, as displayed in Fig. 2a and b. Fig. 2c confirms the presence of these nanospheres with a diameter of approximately 720 nm, which is well consistent with further TEM image observations (Fig. 2d). Moreover, the corresponding energy-dispersive X-ray spectroscopy mapping images clearly illustrate the uniform distributions of C (purple), N (green), and Fe (red) species on the FCPD nanosphere (Fig. 2e). To examine the porosity of these FCPD nanospheres, N2 adsorption–desorption isotherm was recorded at 77 K. As seen in Fig. 2f, FCPD exhibits a typical IV type feature, indicating the existence of mesopores within the FCPD nanospheres. The pore size distribution curve further confirms the size of mesopores, i.e., ≈3.8 nm (the inset of Fig. 2f). The mesoporous structure in FCPD can significantly increase the contact area with the electrolyte and boost the ion diffusion, which can effectively increase the ion storage capacity and electrochemical kinetics.43,44 Additionally, the Brunauer–Emmett–Teller (BET) surface area can be calculated to be 20.3 m2 g−1.
To understand the molecular structure–property relationship, DFT calculations were performed. Fig. 3a displays the optimized molecule models (PPD, FCA, and FCPD) and corresponding molecular orbital energy levels (LUMO and HOMO). Among them, FCPD exhibits a lower LUMO value of −3.821 eV compared to that of PPD (−2.862 eV) and FCA (−3.508 eV). According to molecular orbital theory, a lower LUMO level corresponds to a higher electron affinity for the organic small molecule.45 Meanwhile, the LUMO–HOMO energy gaps (ΔE) of PPD, FCA, and FCPD were calculated to be 2.086, 1.555, and 1.243 eV, respectively. The narrow gap in FCPD facilitates charge transfer, leading to higher electronic conductivity.46 At the same time, an increase in the DOS for FCPD across the Fermi level (Fig. 3b) verifies the rapid charge transfer as well. In addition, according to the calculated molecular electrostatic potential (Fig. 3c), multiple regions around CN groups show negative values. As is known, these regions are more conducive to capturing the cation (Li+) and can be considered as the possible reactive sites. Therefore, according to the multiple active sites, FCPD will capture more Li ions per unit. In short, the aforementioned narrow gaps, increased DOS, and multiple active centers give the FCPD cathode enhanced electronic conductivity and storage capabilities.19
Fig. 3 (a) The calculated HOMO, LUMO, and (b) density of states for the FCA, PPD, and FCPD models. (c) Electron density distribution of the FCPD models. |
To explore the electrochemical performance of the FCPD cathode, the CV curves of the initial three cycles were collected at a scan rate of 0.1 mV s−1 between 1.2 and 3.8 V (Fig. S2†). Obviously, two pair of redox peaks are observed, one in the low-potential (1.8 and 2.2 V) and the other in the high-potential region (2.3 and 3.2 V). The low-potential redox peaks are attributed to the n-type redox-active unit (CN), while the high-potential redox peaks correspond to the p-type unit (Fe2+). Such a typical bipolar feature helps expand its working potential window and theoretical capacity.
Subsequently, the rate capability of the samples was investigated at different current densities ranging from 0.1 to 5.0 A g−1, as shown in Fig. 4a. The FCPD cathode exhibits high capacities of 250, 231, 213, 194, and 183 mA h g−1 at 0.1, 0.3, 0.5, 1.0, and 3.0 A g−1, respectively. Even at the maximum current value of 5.0 A g−1, it retains a reversible capacity of 151 mA h g−1, which is competitive compared to reported values (Table S1†). Notably, even at various current densities, the corresponding charge/discharge profiles with FCPD still possess the bipolar feature (Fig. S3c†) as compared to PPD and FCA (Fig. S3a and b†), which is well consistent with the dQ/dV profiles (Fig. S3d–f†). FCPD exhibits clear platforms and characteristic peaks, indicative of n-type and p-type reactions, demonstrating remarkable stability and reversibility. When the current density returns to 0.1 A g−1, a capacity of 240 mA h g−1 can be achieved, highlighting its good reversibility. In contrast, PPD and FCA cathodes exhibit fast capacity decay at different current densities, especially at 5.0 A g−1, where only 75 mA h g−1 and 100 mA h g−1 are retained, which can be ascribed to their severe solubility in the electrolyte. Besides, the FCPD cathode shows attractive cycling performance at 0.1 A g−1, as shown in Fig. 4b. Even after 100 cycles, it retains a discharge capacity as high as 249 mA h g−1. The corresponding capacity fading rate is only 1.6% and it maintains an average coulombic efficiency of approximately 100% throughout the cycling. In contrast, PPD and FCA exhibit relatively low capacity and poor coulombic efficiency.
Fig. 4c shows a long-term cycling performance of the FCPD cathode at 5.0 A g−1. Surprisingly, even after continuous 1000 cycles, the FCPD cathode still maintains a capacity as large as 150 mA h g−1, corresponding to a high-capacity retention of 81.9%. This demonstrates its superior stability. To investigate the remarkable cycling stability of FCPD, FT-IR spectroscopy was conducted for different numbers of cycles during its long-term cycling. As depicted in Fig. 4d, even after 100, 500, and 1000 cycles, no significant changes in the characteristic peaks of FCPD are observed in FT-IR spectra. This can be attributed to the cushioning effect of the mesoporous structure in FCPD. Afterward, EIS diagrams for PPD, FCA, and FCPD cathodes were collected to study their kinetics performance. As shown in Fig. S4,†47,48 the semicircle in the high-middle frequency region represents the charge transfer resistance (Rct). Coupled with the proposed equivalent circuit model (inset of Fig. 4e), the FCPD cathode exhibits the lowest Rct (190.3 Ω) compared to those of PPD (212.1 Ω) and FCA (251.1 Ω) (Fig. 4e). More importantly, different from the large fluctuation of Rct for PPD and FCA cathodes during the cycling (20th, 50th, and 100th cycles), the FCPD cathode just shows a slight change. This fast and stable charge transfer ensures that the FCPD cathode has ideal reaction kinetics during repeated lithiation/de-lithiation, which is closely related to its significant cycle and rate behavior.49 Such excellent electrochemical performances can be attributed to its highly conjugated structure, which can significantly increase the intermolecular force, thus suppressing its high solubility in the electrolyte for high cycling stability (the capacity decay rate of FCPD is 18.1% after 1000 cycles at 5.0 A g−1). By comparison, some organic cathode materials without the aromatic conjugated structure usually show rapid capacity decay. For example, the capacity decay rate of azine (N–N-linked diimine)-based polymers (P3)50 is 15% after 200 cycles at 0.13 A g−1; the capacity decay rate of benzo[c]thiophen-1(3H)-thione (DPTTO)51 is 19% after 100 cycles at 0.05 A g−1. Additionally, the resultant FCPD cathode exhibits extended conjugation, which ensures electron delocalization and a low energy gap, leading to high electronic conductivity.
To further reveal the electrochemical kinetics of the FCPD cathode, the Li+ diffusion coefficients (DLi+) at different charge/discharge stages were calculated according to the GITT curves (Fig. S5†) and eqn (1).
(1) |
Subsequently, to understand the fast kinetics of the FCPD cathode, CV curves were collected under various scan rates ranging from 0.1 to 3.0 mV s−1, as shown in Fig. S6.† The relationship between the scan rate (v) and peak current (i) can be described using eqn (2) and (3).
i = avb | (2) |
log(i) = blog(v) + log(a) | (3) |
To reveal the storage mechanism of the FCPD cathode, in situ synchrotron FT-IR characterization was performed in different charge/discharge states. As shown in Fig. 5a–c, the 2nd charge/discharge profiles and corresponding in situ synchrotron FT-IR contour map were recorded. In the discharging process, the characteristic peaks related to the CN bond (1550–1570 cm−1) gradually decrease, accompanied by an increase of C–N bonds at around 1070 cm−1.54 This phenomenon can be ascribed to the Li reaction with CN bonds, which leads to the consumption of CN bonds and the formation of C–N–Li. Besides, the C–SO2–N bond corresponding to the anions (TFSI−) can be observed at around 1300 cm−1,55 which presents the same evolution as for the CN bond, indicating the participation of the anions (TFSI−) in the reaction. Subsequently, a further charging process shows the recovery of these bonds, indicating their high reversibility as active sites in FCPD. In addition, the charge/discharge processes were further investigated by ex situ XPS measurement. As shown in Fig. 5d, a reversible change in peak intensity for Li 1s spectra is observed in the full charge and discharge states, indicating a reversible Li-storage behavior in FCPD. The N 1s spectrum (Fig. 5e) reveals two major peaks associated with the CN and C–N bonds at 398.8 and 400.01 eV, respectively. The CN bonds gradually decrease from the initial state to the full lithiation state, while the C–N bonds increase significantly, suggesting a transformation between CN and C–N bonds.56–58 After charging to 3.8 V, the peak of CN bonds enhances obviously, accompanied by a decrease in the C–N bond peak, demonstrating the revision of the CN bonds from the C–N bonds. These findings further support the results obtained from in situ FT-IR spectra.
Notably, in addition to the reversible Li-storage in FCPD, the anions (TFSI−) can also function as charge carriers for energy storage, just as shown in Fig. 5f. The S 2p spectrum exhibits the characteristic peak of TFSI−, which appears in the charge state and disappears in the discharge state. Further ex situ Raman also shows the characteristic peak of TFSI− at 700–900 cm−1 and its reversible change, providing strong evidence for reversible anion storage in FCPD (Fig. 5h).59 It is well known that, during the charge process, the p-type units are in a positively charged state and interact with the anions.4 It is worth noting that during the charging, Fe2+ of the ferrocene could be oxidized to Fe3+, resulting in a positively charged state. This state has been detected in the Fe 2p spectrum (Fig. 5g). Then, Fe3+ interacts with TFSI− to realize anion storage. Subsequently, Fe3+ would be reduced back to Fe2+ in the discharging process, leading to the recovery of the characteristic peaks of Fe2+. In brief, the CN bonds, severing as n-type active units in FCPD, reversibly participate in lithium storage, while Fe2+ acts as a p-type active unit for reversible TFSI− storage, just as illustrated in Fig. 5i. Finally, the potential application of FCPD was explored by using graphite as the anode to study the performance of graphite//FCPD full cells and pouch batteries (Fig. 6a and d). As depicted in Fig. 6b, the cell exhibits a high capacity of 145 mA h g−1 at 0.1 A g−1 after 100 cycles (based on cathode quality) and can light multiple diodes (Fig. 6c), indicating good cycling performance. In addition, as shown in Fig. 6d, the graphite//FCPD pouch cells can maintain a stable open-circuit voltage of 2.307 V, while being capable of illuminating two diodes continuously (Fig. 6e).
Footnotes |
† Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d3sc05843c |
‡ These authors contributed equally to this work. |
This journal is © The Royal Society of Chemistry 2024 |