Mesoporous Manganese Phosphonate Nanorods as a Prospective

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Cite This: ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

Mesoporous Manganese Phosphonate Nanorods as a Prospective Anode for Lithium-Ion Batteries Peng Mei,†,‡,§ Jaewoo Lee,∥ Malay Pramanik,‡ Abdulmohsen Alshehri,⊥ Jeonghun Kim,# Joel Henzie,‡ Jung Ho Kim,*,∥ and Yusuke Yamauchi*,†,#,¶ †

College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, China International Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan § Department of Nanoscience and Nanoengineering, Faculty of Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo 169-8555, Japan ∥ Australian Institute for Innovative Materials (AIIM), University of Wollongong, Squires Way, North Wollongong, New South Wales 2500, Australia ⊥ Department of Chemistry, King Abdulaziz University, P.O. Box 80203, Jeddah 21589, Saudi Arabia # School of Chemical Engineering & Australian Institute for Bioengineering and Nanotechnology (AIBN), The University of Queensland, Brisbane, Queensland 4072, Australia ¶ Department of Plant & Environmental New Resources, Kyung Hee University, 1732 Deogyeong-daero, Giheunggu, Yongin-si, Gyeonggi-do 446-701, South Korea ‡

S Supporting Information *

ABSTRACT: Mesoporous materials can serve as well-performed electrode candidates for lithium-ion batteries (LIBs). Mesoporous manganese phosphonate (MnP) nanorods are composed of an interconnected network of pores that have high infiltration capacity for electrolyte and less tortuous transport pathways for lithium/electron charge carriers. The mesoporous architecture should also help alleviate stress from volume variation upon lithium intercalation/deintercalation cycles. We used MnP as an LIB anode and observed an initial reversible capacity of 420 mA h g−1 and a modest Coulombic efficiency of 68.7% at a relatively high current density of 144 mA g−1. The reversible capacity stabilizes at 253 mA h g−1 after 100 repetitive cycles, while most of the time, the Coulombic efficiency remains around 100%. The results show that, as a prospective LIB anode, the mesoporous MnP can achieve desirable capacity with decent durability and rate capability. KEYWORDS: mesoporous materials, manganese phosphonates, electrodes, lithium ion batteries, surfactants

1. INTRODUCTION Along with the rapid progress of social modernization and industrialization, the exhaustion of fossil fuels and related degradation of environmental quality (e.g., global warming) have posed a serious threat to the human survival and development throughout the world. To cope with the burgeoning energy demand and rising ecological concerns, it is imperative to find alternative sustainable and eco-friendly energy/power sources.1−3 Lithium-ion batteries (LIBs), using electrochemical reactions to store energy in lightweight devices that achieve high energy densities and long life spans,4,5 have become ubiquitous in portable consumer electronics (e.g., cell phones, laptops, and digital cameras). Eventually, LIBs found applications in larger devices in the fields of health care, defense, aerospace, and now even serve as backup energy supplies in electrical grids.6,7 LIBs can also serve as power supplies for electric vehicles (EVs), helping to reduce petroleum use and cutting greenhouse gas emissions. Although the opportunities for LIBs abound, there are still challenges that © XXXX American Chemical Society

are required to realize the performance requirements of EVs and other demanding applications.8,9 Modern LIB devices consist of four essential components: the cathode, anode, electrolyte, and separator, all of which are collectively responsible for the overall performance.10 Many recent advances in LIBs have been focused on discovering new kinds of electrode materials.11 Achieving high-energy-density LIBs is realizable via developing cathode materials with high operating potential, or by engineering high-capacity cathode/ anode materials.12 As the commercially used anode, graphite still suffers limited lithium storage capability and some unfavorable side reactions with organic solvents. This has inspired researchers to seek new anode materials to replace carbon.13,14 Received: April 2, 2018 Accepted: May 15, 2018

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DOI: 10.1021/acsami.8b05292 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

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ACS Applied Materials & Interfaces A variety of mesoporous/nanoporous materials such as Si,15 Sn,16 alloys (e.g., Sn−Cu and Co−Sn),17,18 metal oxides (e.g., Co3O4 and Fe2O3),19,20 metal chalcogenides (e.g., MoS2 and MoSe 2 ), 21,22 and metal phosphates (e.g., FePO 4 and SnP2O7)23−25 have been examined as electrodes alternative to graphite, demonstrating enhanced lithium storage capacity, durability, and rate performance. This is due in part to the material architecture, which enables abundant active sites, sufficient electrolyte−electrode contact, facile lithium and electron transport, as well as mitigating the negative effects of volume expansion.26,27 Among the various kinds of porous materials, mesoporous metal phosphonates are promising because of the versatile hybrid framework with tunable functionalities, which offer them opportunities in a host of applications.28−30 However, few works have examined metal phosphonates in energy storage devices.31−35 Recently, we reported the synthesis of mesostructured manganese phosphonates (MnPs) and their application in supercapacitor devices.35 In this study, we explore their use as anode materials in LIBs.

2. EXPERIMENTAL SECTION 2.1. Materials. Cetyltrimethylammonium bromide (CTAB), 1hydroxyethane-1,1-diphosphonic acid (HEDP, 60 wt % in H2O), tetramethylammonium hydroxide solution (25 wt % in H2O), and manganese nitrate tetrahydrate (Mn(NO3)2·4H2O, ≥97 wt %) were purchased from Sigma-Aldrich and directly used. 2.2. Synthesis. As described in detail in a previous report,35 a synthetic gel was formed by adding the Mn(NO3)2 solution dropwise to the CTAB/HEDP solution, and the pH was maintained at ∼7. After stirring thoroughly, the synthetic gel was kept in an autoclave at 120 °C for 36 h. Finally, the dried precipitates were extracted with acetone to remove the remaining CTAB.36 The as-synthesized and extracted materials were designated as “as pre MnP” and “MnP”, respectively. For comparison, we have prepared bulk MnP without using the CTAB. 2.3. Characterizations. Scanning electron microscopy (SEM) images were acquired with a Hitachi SU-8000 field emission scanning electron microscope. Transmission electron microscopy (TEM) images were obtained with a JEM-2100F transmission electron microscope. Nitrogen adsorption−desorption measurements were conducted on a BELSORP-mini II apparatus. Powder X-ray diffraction (XRD) patterns were obtained from a Rigaku Rint 2000 diffractometer (Cu Kα radiation source; 40 kV, 40 mA). X-ray photoelectron spectroscopy (XPS) spectra were recorded with a PHI Quantera SXM instrument. The obtained spectra were calibrated by referencing the C 1s line (285 eV). Thermogravimetric analyses (TGAs) were performed on a Hitachi HT-Seiko Instrument at a heating rate of 3 °C min−1 in an atmosphere of N2. 2.4. Electrochemical Measurements. The electrochemical properties were assessed with CR2032 button cells. For the fabrication of the working electrode, active materials (60 wt %) were mixed with Super P carbon (20 wt %) and polyvinylidene fluoride (20 wt %) and then coated on Cu foils. The loading level of the electrodes was fixed at 1.1 mg cm−2. Galvanostatic charge−discharge profiles were acquired in the voltage window of 0.01−2.00 V (vs Li/Li+). Electrochemical impedance spectroscopy (EIS) investigation was performed using a VMP-3 multichannel workstation (Bio-Logic) in the frequency region of 105 to 10−2 Hz.

Figure 1. (a) SEM images of MnP prepared with Mn:P = 5:2 exhibiting the nanorod morphology, (b−d) TEM images of the MnP sample showing the disordered mesostructure, and (e) N 2 adsorption−desorption isotherms of MnP (inset: pore-size distribution curve).

high-resolution TEM images in Figures 1c,d and S1 shows numerous randomly arranged mesopores throughout the specimen. The mean pore diameter estimated by TEM is around 3−4 nm, in accordance with the pore-size distribution analysis (inset in Figure 1e). The preceding data have clearly demonstrated the formation of a disordered mesostructured manganese phosphonate. From crystallographic data (Figure S2) of the MnP prepared with Mn:P = 5:2, it was revealed that the framework is poorly crystallized/amorphous. The first peak at ∼9° is due to cross-linking between the phosphonic and the metallic moieties, as generally reported in metal phosphonate materials.35 The surface elements and oxidation states of the mesostructured MnP were determined by XPS technique. The survey spectrum (Figure 2a) shows the existence of carbon, manganese, phosphorus, and oxygen. The Mn 2p core level spectrum (Figure 2b) has a characteristic doublet pattern (2p3/2 and 2p1/2) arising from spin−orbit coupling. The Mn 2p3/2 peak centered at 641.8 eV and the associated satellite peak at higher binding energy (∼646 eV) indicate the presence of divalent manganese.37 In addition, the Mn 3s line (Figure 2c) exhibits two multiplet-splitting components and the separation (ΔE) is up to 6.09 eV, which is also characteristic of the Mn2+ species.38−40 The intense peak located at 133.0 eV in Figure 2d matches the P 2p energy level of pentavalent tetra-bonded phosphorus.41 The asymmetric O 1s line in Figure 2e contains two overlapping components positioned at 532.6 and 531.4 eV, featuring the oxygen in the C−OH and the phosphonate groups, respectively. The detailed discussions on the mesostructure of the MnP sample and the bonding of the framework have been described in our earlier publication.35 TGA was conducted to quantify the content of CTAB remaining in the MnP material (Figure S3a). Pure CTAB powder starts to decompose at ∼200 °C and completely decomposes before 280 °C (as highlighted in gray region). As for the MnP samples, interestingly, the decomposition

3. RESULTS AND DISCUSSION As shown in the representative SEM images, the MnP sample primarily comprises homogeneous rodlike nanoparticles that are ∼30−40 nm in width (Figure 1a). Further inspections of the microstructure of the MnP samples were conducted by TEM. The overview of the TEM image in Figure 1b further corroborates its uniform nanorod shape. A closer look from the B


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ACS Applied Materials & Interfaces

Figure 3. SEM images of MnP samples prepared at pH = 7 with aging time of 36 h, maintaining different Mn:P ratios: (a) 4:2, (b) 3:2, (c) 2:2, and (d) 1:2.

∼5 wt % of CTAB remained) as the anode for LIB test. Besides, its highest surface area among those of the obtained MnP materials is supposed to significantly contribute to the enhancement of the lithium storage capacity. The initial charge−discharge profiles of the MnP electrode shown in Figure 4a were acquired at 72 mA g−1 in the voltage

Figure 2. XPS spectra of MnP prepared with Mn:P = 5:2: (a) survey spectrum, (b) Mn 2p spectrum, (c) Mn 3s spectrum, (d) P 2p spectrum, and (e) O 1s spectrum.

temperature of the CTAB residue extends to 200−325 °C (as highlighted in pink region), likely caused by the constraints of the hybrid framework. The results show that acetone extraction decreases the residual CTAB in the MnP sample from 35.3 to 5.5 wt %. In pursuit of the desired periodic mesostructured MnP, we have fine-tuned the synthetic parameters including Mn/P ratio, pH, and aging time and characterized the mesostructural ordering by low-angle XRD measurements. The mesostructural evolution has been discussed in detail in our previous report.35 Beyond that, as the initial ratio of Mn/P dropped to lower levels (i.e., Mn:P = 4:2, 3:2, 2:2, and 1:2), the morphology of the MnP sample was transformed from nanorods into nanoplatelets (Figure 3), which might be because of the change of preferred crystal growth orientation. Decreasing the Mn/P ratio is expected to impart more negative charge in the phosphonate frameworks. Based on this fact, the addition of positively charged CTA+ is required to balance the charge across the interface of micelles/precursor. In the case of MnP prepared with Mn:P = 1:2 (i.e., lowest Mn/P ratio), a considerable amount of CTAB still remained after extraction according to TGA (Figure S3b). In addition to this, all the MnP samples prepared with different Mn/P ratios have been examined by nitrogen adsorption−desorption measurements (Figure S4). The MnP samples prepared with Mn:P = 5:2 (i.e., highest Mn/P ratio) had the highest surface area, presumably because of the presence of minimum residual CTAB in the framework. Inspired by the numerous benefits of mesoporous structure and the successful trial of manganese phosphonate for supercapacitors,35 herein, we made a further attempt to use mesoporous MnP as an LIB anode. The residual CTAB may have a negative impact on the lithium intercalation process, so we adopted the MnP sample prepared with Mn:P = 5:2 (merely

Figure 4. (a) First-cycle charge−discharge profiles of MnP anode at 72 mA g−1, (b) cycling performance of MnP anode at 144 mA g−1 in the range of 0.01−2.00 V (vs Li/Li+), (c) rate capability of MnP anode at different current densities, and (d) charge−discharge curves of MnP anode acquired at each rate.

window of 0.01−2.00 V (vs Li/Li+). A distinct discharge plateau at around 0.4 V can be found upon the first discharge process, which could be credited to the characteristic lithium intercalation process within manganese phosphonates. The first discharge capacity of the MnP electrode reaches up to 1117 mA h g−1; however, the subsequent charge capacity immediately comes down to 404 mA h g−1, indicating a relatively low Coulombic efficiency of 36.2%. The irreversible consumption of lithium is most likely because of the solid electrolyte interface (SEI) formation, especially in the case of our mesoporous MnP material with a large void space. The SEI layers, in turn, prevent the electrode surface from unfavorable side reactions over subsequent cycles.42 C


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ACS Applied Materials & Interfaces

Table 1. Comparison of Electrochemical Performance with Several Reported Typical Metal Phosphates as Anode Materials for LIBs samples vanadium phosphate nanoparticles (VPO4/C, VPO4) tin phosphate (Sn3(PO4)2) manganese pyrophosphate nanoplatelets (Mn2P2O7) iron phosphate nanoparticles (variscite FePO4) mesostructured manganese phosphonate nanorods

voltage range (V)

current density (mA g−1)

first discharge capacity (mA h g−1)

cycle numbers

capacity retention (%)

refs

0.01−3.00

20

887.3 (VPO4/C), 548.7 (VPO4)

30

38.7 (VPO4/C), 41.9 (VPO4)

64

0.02−1.20 0.02−0.90 0.01−3.00

20

30

65

50

1070

35

19 59 28 (10th), 15 (35th)

0.00−2.4

61

609

30

30

67

0.01−2.00

72

1117

144

421

To find some clue to the possible electrochemical reaction mechanism, the differential capacity plots of the MnP electrode for the initial two cycles are shown in Figure S5. In the first discharge process, the pronounced reduction peak at ∼0.4 V is most likely because of the SEI formation and other unexpected side reactions as mentioned above. The absence of this peak in the second cycle is actually the evidence of the protective effect of the SEI on the electrode surface. Additionally, a distinct oxidation peak at ∼0.97 V can be observed in the first charge process; however, the corresponding reduction peak (∼0.68 V) in the first discharge process is not so clearly visible because of being overshadowed by its adjacent sharp peak (∼0.4 V). This pair of redox peaks is well-preserved in the subsequent cycle (0.86 V/1.1 V), while the peak positions have some positive shift that may be caused by the formation of defective particles.43 As shown by the XPS analysis, the only Mn species in the pristine MnP sample are Mn(II). On the basis of a previous report describing the Mn(II)-based coordination polymer,44 it is reasonable to infer that the reversible redox peaks obtained in our MnP sample might come from the electron-transfer reaction between the Mn(II)/Mn pair. To evaluate the durability of the MnP sample, long cycling tests were performed at a current density of 144 mA g−1 (Figure 4b). The MnP electrode delivers a reversible capacity of 420 mA h g−1 with modest a Coulombic efficiency of 68.7% for the first cycle. The capacity remained above 80% during the first 20 cycles. Even at the 100th cycle, the MnP material retained a reversible capacity of 253 mA h g−1, representing decent retention of 60%. In addition, the Coulombic efficiency has seen a rapid increase in the early cycles and then stayed around 100% in the following cycles, suggesting that the electrolyte/electrode system is remarkably stable during cycling. For comparison, we have conducted cycling test on a bulk MnP sample (Figure S6). As expected, the bulk electrode delivered much lower capacities than the mesoporous one throughout the cycling. More noticeably, it suffered a lot faster capacity fading (32%) over the first 20 cycles. The rate capability of the MnP electrode is shown in Figure 4c. As the current densities increase, the reversible capacity of the MnP electrode decays gradually from 382 mA h g−1 at 144 mA g−1 to 206 mA h g−1 at a fairly high rate of 1440 mA g−1. More notably, an appreciable reversible capacity of 161 mA h g−1 has been maintained at a fairly high current density (3600 mA g−1). When the rate returns to 144 mA g−1, the MnP electrode is capable of restoring over 85% of initial capacity. Furthermore, the capacity values of MnP become more stable

66

this work 100

88.6 (10th), 74 (30th), 71.6 (35th), 60.2 (100th)

at higher rates, manifesting its prominent cyclic reversibility and stability under high-rate operations. The charge−discharge profiles of the MnP electrode at different current densities are shown in Figure 4d. With increasing rate, the characteristic lithium extraction/insertion plateaus become less obvious but still visible, suggesting that no serious polarization has occurred. The obtained results reveal the remarkable cycling performance and rate capability of our mesostructured MnP material, which can be explained as follows: the mesoporous structure with nanosized dimensions can afford abundant active sites and adequate electrolyte/ electrode contact, plus facile and rapid lithium/electron transport.45−50 Additionally, the ample internal void space can alleviate the severe volume variation upon cycling, which guarantees the long-term cycle stability.51−54 EIS is widely acknowledged as a reliable method to diagnose the battery kinetic process (SEI, charge transfer, and diffusion) within the LIB systems. Figure S7 shows the comparative Nyquist plots of our MnP electrode and its bulk counterpart after the initial formation cycle, both of which comprise two depressed semicircles and one inclined line. In this scenario, the semicircle in the high-frequency range is generally interpreted by the film resistance (Rf) of the SEI layers.55−57 The obviously smaller diameter of the high-frequency semicircle of our MnP electrode reveals its lower Rf than that of the bulk one, reflecting the easier lithium migration through the SEI layers in the former case. The second semicircle at the medium frequency area is normally correlated to the interfacial chargetransfer resistance (Rct).58−60 Likewise, judging by the size of the medium-frequency semicircle, the Rct of our MnP electrode is estimated to be much lower than that of the bulk one, which will significantly facilitate the charge-transfer reaction involved in the current battery system. Furthermore, the slanted tail in the low-frequency range is typically linked to the ion diffusion behavior in the host solid-state phase.61−63 The steeper slope of our MnP electrode is definitely an indication of faster lithium diffusion process, which is favorable in high-rate charge− discharge properties. Apart from carbonaceous material, studies on anode candidates for LIBs so far primarily concentrate on various inorganic materials, including metal oxides, sulfides, phosphates, and so forth. There is rather limited room for the development of new purely inorganic materials, however, because very few metals can exhibit desirable properties and proper potential versus Li/Li+. Table 1 gives a rough comparison of our mesostructured MnP with several reported representative metal phosphates as anode materials for D


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ACS Applied Materials & Interfaces LIBs.64−67 Even tested at a higher rate, the electrochemical properties of our MnP material is considerable regarding capacity and retention. Although the organics within the hybrid framework might cause some adverse effect in regard to the electrochemical reaction, the exquisite mesostructure could facilitate the reversible and stable intercalation/deintercalation of abundant lithium ions in/from the electrode matrix. In this context, mesostructured metal phosphonates could be a promising family of the electrode material for LIBs.

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4. CONCLUSION We described the electrochemical properties of mesoporous manganese phosphonate nanorods as anode materials in LIBs. Thanks to the elaborate mesoporous architecture with nanorod morphology, our mesostructured MnP anode could reversibly accommodate a considerable amount of lithium with decent capacity retention at even high-rate conditions. At the relatively high rate of 144 mA g−1, the mesoporous MnP electrode is capable of delivering a first reversible capacity of 420 mA h g−1 with a decent Coulombic efficiency of 68.7%. Even after the prolonged 100 cycles, a reversible capacity of 253 mA h g−1 can be retained, showing prominent Coulombic efficiency in the latter cycling as well. The results described above reveal the potential of the mesoporous MnP material as a promising anode candidate for LIBs.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.8b05292. TEM image, wide-angle XRD pattern, the selected area electron diffraction pattern, TGA curves, N2 adsorption− desorption isotherms, differential capacity plots, cycling performances, and the Nyquist plots of the mesoporous MnP electrodes (PDF)

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected] (J.H.K). *E-mail: [email protected] (Y.Y.). ORCID

Joel Henzie: 0000-0002-9190-2645 Yusuke Yamauchi: 0000-0001-7854-927X Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the Deanship of Scientific Research (DSR), King Abdulaziz University (grant no. KEP1-130-39), the Australian Research Council (ARC) Future Fellow (grant no. FT150100479), JSPS KAKENHI (grant nos. 17H05393 and 17K19044), and the research funds by Qingdao University of Science and Technology and the Suzuken Memorial Foundation. The authors would like to thank New Innovative Technology (NIT) for helpful suggestions and discussions on materials fabrication.

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REFERENCES

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