Environmentally Sustainable Aluminum-Coordinated Poly

Jan 3, 2018 - Hee Joong Kim†‡, Youngjin Kim§‡, Jimin Shim, Kyung Hwa Jung, Min Soo Jung, Hanseul Kim, Jong-Chan Lee, and Kyu Tae Lee. School of...
1 downloads 16 Views 2MB Size
Subscriber access provided by UNIV OF NEW ENGLAND ARMIDALE

Article

Environmentally Sustainable Aluminiumcoordinated Poly(tetrahydroxybenzoquinone) as a Promising Cathode for Sodium Ion Batteries Hee Joong Kim, Youngjin Kim, Jimin Shim, Kyung Hwa Jung, Min Soo Jung, Hanseul Kim, Jong-Chan Lee, and Kyu Tae Lee ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b13911 • Publication Date (Web): 03 Jan 2018 Downloaded from http://pubs.acs.org on January 4, 2018

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

ACS Applied Materials & Interfaces is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 30 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

Environmentally Sustainable Aluminiumcoordinated Poly(tetrahydroxybenzoquinone) as a Promising Cathode for Sodium Ion Batteries Hee Joong Kim,†,‡ Youngjin Kim,§,‡ Jimin Shim, Kyung Hwa Jung, Min Soo Jung, Hanseul Kim, Jong-Chan Lee*, and Kyu Tae Lee* School of Chemical and Biological Engineering and Institute of Chemical Process, Seoul National University, 599 Gwanak-ro, Gwanak-gu, Seoul 151-742, Republic of Korea, KEYWORDS: Coordination polymer, Organic compound, Benzoquinone, Aluminum, Sodium ion battery, Cathode

ABSTRACT

Na-ion batteries are attractive as an alternative to Li-ion batteries because of their lower cost than Li-ion batteries. Organic compounds have been considered as promising electrode materials due to their environmental friendliness and molecular diversity. Herein, aluminum-coordinated poly(tetrahydroxybenzoquinone) (P(THBQ-Al)), one of the coordination polymers, is introduced for the first time as a promising cathode for Na-ion batteries. P(THBQ-Al) is synthesized

ACS Paragon Plus Environment

1

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 2 of 30

through a facile coordination reaction between benzoquinonedihydroxydiolate (C6O6H22-) and Al3+ as ligands and complex metal-ions, respectively. Tetrahydroxybenzoquinone is environmentally sustainable because it can be obtained from natural resources such as orange peels. Benzoquinonedihydroxydiolate also contributes to delivering high reversible capacity because each benzoquinonedihydroxydiolate unit is capable of two electron reactions through the sodiation of its conjugated carbonyl groups. Electrochemically inactive Al3+ improves the structural stability of P(THBQ-Al) during cycling because of no change in its oxidation state. Moreover, P(THBQ-Al) is thermally stable and insoluble in non-aqueous electrolytes. These result in excellent electrochemical performance including a high reversible capacity of 113 mA h g-1 and stable cycle performance with negligible capacity fading over 100 cycles. Moreover, the reaction mechanism of P(THBQ-Al) is clarified through ex situ XPS and IR analyses, in which the reversible sodiation of C=O into C−O−Na is observed.

INTRODUCTION Na-ion batteries have received much attention as an attractive alternative to Li-ion batteries because they are potentially low in cost per energy.1-5 In addition, the insertion chemistry of Naion batteries is similar to that of Li-ion batteries because both use a monovalent charge carrier, such as Li+ and Na+.6-10 This similarity enabled us to develop various electrode materials for sodium-ion batteries in a short period of time using a database of electrode materials investigated in Li-ion batteries. For example, graphite,11-13 hard carbon,14-17 alloys,18-21 phosphorus,22-25 metal oxides,26-28 polyanion materials,29-31 and organic compounds32-53 have been examined as electrode materials for Na-ion batteries and exhibited promising electrochemical performances. Among them, organic compounds, including organic free radicals,32 organosulfur,33 and organic

ACS Paragon Plus Environment

2

Page 3 of 30 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

carbonyl34-43, 45 compounds have recently been considered promising electrode materials due to their environmental friendliness, molecular diversity, and good electrochemical performance.54-56 In particular, quinone derivatives such as benzoquinone (BQ),44-46 anthraquinone (AQ),47-49 phenanthraquinone (PQ),50-51 naphthoquinone (NQ)52 are attractive as a cathode because of their high theoretical capacity (approximately 600 mA h g−1) and high redox potential. However, many quinone derivatives have challenging issues, including their poor cycle performance due to the dissolution of electrode materials in an electrolyte and low thermal stability.44-47, 54, 57-59 Various strategies have been introduced to improve these poor properties. For example, single organic molecules were incorporated into porous carbons through a π-π interaction between aromatic compounds and carbon.50, 59 However, organic components in the composites were eventually dissolved during cycling, although their initial forms were insoluble. Organic salts and polymers were also investigated because they are intrinsically insoluble in the electrolyte.45 However, most were structurally unstable, thus leading to structural deformation during cycling. This resulted in the degradation of electrode materials. Recently, metal-organic coordination polymers (CPs) including metal-organic frameworks (MOFs) and porous coordination polymers (PCPs) have received considerable attention for the synthesis of supramolecular polymers, nanoparticles, and cross-linked hydrogels.60-65 Coordination-driven polymerization is attractive because of its simple and facile synthesis in which building blocks are easily constructed through coordination between metals and organic ligands. They are also structurally and thermally stable. Moreover, their solubility in nonaqueous solvents is controllable, depending on the types of ligands and complex metal-ions.61 These properties are advantageous for electrode materials in Na-ion batteries. Therefore, we introduce the aluminum-coordinated poly(tetrahydroxybenzoquinone) (P(THBQ-Al)), one of the

ACS Paragon Plus Environment

3

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 4 of 30

coordination polymers, for the first time as a promising cathode material for Na-ion batteries. Benzoquinonedihydroxydiolate (C6O6H22−) and aluminum cation (Al3+) were selected as ligands and complex metal ions, respectively, for the preparation of a coordination polymer. Benzoquinonedihydroxydiolate has a stable phenolic ligand, thus leading to the formation of diverse stable chelating complexes. Benzoquinonedihydroxydiolate is also environmentally friendly and sustainable because it can be obtained from glyoxal or myo-inositol, widely present in natural resources, such as orange peels, grapes, and plant leaves.44,

66

Moreover, each

benzoquinone unit in the polymer is capable of two electron reactions through the sodiation and desodiation of its conjugated carbonyl groups, resulting in a high reversible capacity. Aluminum cation (Al3+) is a complex metal ion that is suitable for electrode materials. Although various metal cations can form coordination polymers with benzoquinonedihydroxydiolate,64,

67

electrochemically inert metal cations that are not involved in the redox reaction are more promising in terms of their structural stability. Specifically, transition metal cations, such as iron, nickel and cobalt are involved in the redox reaction, in which their oxidation states change during charging and discharging.68-71 This causes repetitive breakage and/or the rearrangement of the coordination bonds during cycling, leading to structural deformation. In contrast to the electrochemically active metal cations, the coordination bonds of electrochemically inert metal cations, such as Al3+, are not deformed during charging and discharging because the oxidation state of Al3+ is not changed during cycling. This results in improved structural stability. Owing to these properties of benzoquinonedihydroxydiolate and Al3+ in the coordination polymer, P(THBQ-Al) exhibited excellent electrochemical performance, including a high reversible capacity of 113 mA h g-1 and stable cycle performance with a negligible capacity fading over 100 cycles. Moreover, we clarified the reaction mechanism of P(THBQ-Al) through ex situ XPS

ACS Paragon Plus Environment

4

Page 5 of 30 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

and IR analyses, in which the reversible transition between C=O and C−O−Na was observed during discharging and charging.

EXPERIMENTAL SECTION Materials. Tetrahydroxybenzoquinone (THBQ, >96 %) and aluminum chloride (AlCl3, >98 %) were obtained from Tokyo Chemical Industry (TCI). Poly(vinylidene fluoride) (PVdF), Nmethyl-2-pyrrolidone (NMP) (anhydrous), tetraethylene glycol dimethyl ether (TEGDME, >98 %), sodium perchlorate (NaClO4, >98 %), and sodium hydroxide (NaOH, >98 %) were obtained from Sigma-Aldrich and used without any purification. Conductive carbon black (Super P, Alfa Aesar, A Johnson Matthey Company) was dried at 60 oC in a vacuum over 24 hours before use. Deionized (DI) water with a resistivity of 18.3 mΩ cm was obtained from a water purification system (Synergy, Millipore, USA). Synthesis of Poly(THBQ-Aluminum) (P(THBQ-Al)). 2.32 mmol of AlCl3 (0.31 g) was added to the aqueous solution of THBQ (2.32 mmol, 0.4 g). The mixture was vigorously stirred at room temperature with N2 blowing. After stirring for 10 min, 60 mL of 1 M NaOH solution was added with stirring. A dark-brown solid was precipitated. The filtrated product, P(THBQ-Al), was washed with ethanol, methanol, and acetone, and then dried in a vacuum. Yield: 0.64 g (62.7 %). Electrochemical Characterization. P(THBQ-Al) powders were mixed with carbon black (CB, Super P) and poly(vinylidene fluoride) (PVdF) in NMP in a 6:2:2 weight ratio. The slurry was casted onto an aluminum current collector. The electrodes were dried at 120 oC in a vacuum over 8 hours. In the case of THBQ, electrodes were prepared with a 3:2:5 weight ratio (THBQ: CB: PVdF). The loading amounts of electrode materials were approximately 1 mg cm−2. The electrochemical performance was evaluated using 2032 coin cells with a Na metal anode and 1

ACS Paragon Plus Environment

5

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 6 of 30

M NaClO4 in a TEGDME electrolyte solution. The galvanostatic experiments were performed with the current density of 20 mA g−1 (ca. 0.2 C) at 30 oC. To examine the dissolution of active materials in the electrolyte, 1 mg of active materials was stored in 1 mL of the electrolyte for a week. Material Characterization. Coordination chemistry in P(THBQ-Al) was investigated by X-ray photon electron spectroscopy (XPS, PHI-1600) using Mg Kα (1254.0 eV) as a radiation source. Survey spectrum was collected over a range of 0‒1100 eV, followed by a high resolution scan of the C 1s, O1s, and Al 2p region. The coordination reaction between hydroxyl groups and aluminum cation was confirmed by Fourier-transform infrared spectroscopy (FT-IR, Nicolet 6700, Thermo Scientific). The morphologies of THBQ and P(THBQ-Al) were examined using a field emission scanning electron microscope (FESEM, JSM-6701F, JEOL). The crystal structures and thermal properties of THBQ and P(THBQ-Al) were investigated using powder Xray diffractometry (D8 Advance, Bruker) and thermal gravimetric analysis (TGA, Q-5000 IR, TA Instruments), respectively. TGA was operated at the heating rate of 10 oC min−1 in N2 atmosphere. For ex situ analyses, coin cells were disassembled in an argon-filled glove box. Then, the collected electrodes were washed with dimethyl carbonate (DMC) and sealed in a pouch to inhibit their exposure to ambient air. The sealed pouches were opened just before XPS and FT-IR spectroscopy measurements.

RESULTS AND DISCUSSION Figure 1a demonstrates the facile synthesis of P(THBQ-Al) through a coordination driven selfassembly of phenolic ligand (Tetrahydroxybenzoquinone (THBQ) anion) and metal ion (Al3+ cation). As 1 M NaOH aqueous solution was added to the aqueous solution of THBQ and AlCl3

ACS Paragon Plus Environment

6

Page 7 of 30 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

mixtures, phenol groups in THBQ were deprotonated, forming a benzoquinonedihydroxydiolate (C6O6H22−). The O− with a lone pair in the ligand were then expected to be coordinated with Al3+ through coordination bonds,72-75 leading to the precipitation of P(THBQ-Al) powders. Figure 2a shows the Fourier transform infrared spectroscopy (FT-IR) spectra of THBQ and P(THBQ-Al). As THBQ was converted into P(THBQ-Al), the intensity of hydroxyl vibrational peaks at 3360 and 3544 cm−1 substantially decreased, whereas a new characteristic peak of Al-O bonding at 1508 cm−1 appeared.61 This suggests that THBQ was polymerized into P(THBQ-Al) through the coordination of C6O6H22− and Al3+ ions. The formation of P(THBQ-Al) was further supported by the Al 2p X-ray photoelectron spectroscopy (XPS) spectrum of P(THBQ-Al). As shown in Figure 2b, the Al 2p XPS peak was observed at 74.4 eV, corresponding to the Al-O bonding.76 The XRD patterns of THBQ and P(THBQ-Al) shown in Figure 2c reveal that P(THBQ-Al) is amorphous, whereas THBQ is highly crystalline. In addition, P(THBQ-Al) exhibited improved thermal stability compared to THBQ. As shown in the thermogravimetric analysis (TGA) profiles of THBQ and P(THBQ-Al) in N2 atmosphere, P(THBQ-Al) showed a weight loss at approximately 350 oC, whereas THBQ was decomposed at approximately 250 oC (Figure 2d). The superior thermal stability of P(THBQ-Al) to THBQ is attributable to its stronger Al-O bonding than H-O bonding in THBQ. Figure 2e and 2f show field emission scanning electron microscopy (FE-SEM) images of THBQ and P(THBQ-Al), respectively. While the size of THBQ plates was tens of micrometers, that of agglomerated P(THBQ-Al) powders ranged from hundreds of nanometers to a few micrometers.77

ACS Paragon Plus Environment

7

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 8 of 30

Figure 1. (a) Synthetic scheme and (b) electrochemical reaction mechanism of P(THBQ-Al).

ACS Paragon Plus Environment

8

Page 9 of 30 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

Figure 2. (a) FT-IR spectra of P(THBQ-Al) and THBQ. (b) Al 2p XPS spectrum of P(THBQAl). (c) XRD patterns and (d) TGA analysis of P(THBQ-Al) and THBQ. SEM images of (e) THBQ and (f) P(THBQ-Al). (g) Optical images of TEGDME electrolytes after storing each THBQ and P(THBQ-Al) powder for one week (1 mg mL−1).

ACS Paragon Plus Environment

9

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 10 of 30

The electrochemical performances of THBQ and P(THBQ-Al) electrodes were evaluated in the voltage range from 1.5 to 3 V (vs. Na/Na+) at a specific current of 20 mA g−1 (0.2 C) using a half cell comprising a sodium metal electrode and 1 M NaClO4 in tetraethylene glycol dimethyl ether (TEGDME). Figure 3a and 3b show the voltage profiles of P(THBQ-Al) and THBQ electrodes, respectively. P(THBQ-Al) delivered a high reversible capacity of approximately 113 mA h g−1, whereas THBQ delivered a negligible capacity. The theoretical specific capacity of P(THBQ-Al) is 288 mA h g−1, assuming that six carbonyl groups in the repeating group of P(THBQ-Al) can store 6 Na+ cations through the reaction mechanism shown in Figure 1b. Four plateaus were observed in the voltage profiles of P(THBQ-Al), which is consistent with four reversible redox peaks in the cyclic voltammogram of P(THBQ-Al) (Figure S1). In addition, P(THBQ-Al) exhibited excellent cycle performance, such as a negligible capacity fading over 100 cycles, as shown in Figure 3c. P(THBQ-Al) also showed stable cycle performance at the higher C-rate such as 100 mA g−1 (1 C) (Figure S2). The remarkable difference between P(THBQ-Al) and THBQ in electrochemical performance is attributed to the different solubilities of P(THBQ-Al) and THBQ in the electrolyte.59, 78 After storing THBQ powders in the electrolyte for a week, most THBQ powders disappeared and the color of the electrolyte changed from a transparent color to brown, as shown in Figure 2g. This indicates that THBQ is highly soluble in the electrolyte. In contrast to THBQ, no color change in the electrolyte was observed when P(THBQ-Al) powders were stored for a week. This indicates that P(THBQ-Al) is not soluble in the electrolyte. Moreover, the solubilities of the charged and discharged P(THBQ-Al) electrodes in the electrolyte were further examined through the color change of the electrolyte after storing each electrode for a week. In contrast to the pristine THBQ electrode, no color change in the electrolytes was observed after storing each pristine, charged, and discharged P(THBQ-Al) electrode (Figure 4a). This suggests

ACS Paragon Plus Environment

10

Page 11 of 30 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

Figure 3. Voltage profiles of (a) P(THBQ-Al) and (b) THBQ electrodes. (c) Cycle performance of THBQ and P(THBQ-Al). Numbers in (a) and (b) indicate the cycle number.

ACS Paragon Plus Environment

11

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 12 of 30

Figure 4. (a) Optical images and (b) UV-Vis spectra of TEGDME electrolytes after storing bare THBQ, charged P(THBQ-Al), and discharged P(THBQ-Al) electrodes for one week.

ACS Paragon Plus Environment

12

Page 13 of 30 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

that the sodiated and desodiated forms of P(THBQ-Al) electrodes were also insoluble in the electrolyte. The dissolution behaviors of P(THBQ-Al) and THBQ electrodes were further supported by UV-Vis spectroscopy (Figure 4b). The absorption peak at 310 nm was observed in the UV-Vis spectrum of the supernatant electrolyte for the THBQ electrode, indicating the presence of benzoquinone derivatives dissolved in the electrolyte. However, no UV-Vis absorption peaks were observed for the charged and discharged P(THBQ-Al) electrodes, indicating that negligible amounts of P(THBQ-Al) were dissolved in the electrolyte. Thus, the THBQ electrode was dissolved in the electrolyte during cycling, leading to the loss of active materials. This loss resulted in poor electrochemical performance of THBQ. However, since the solubility of P(THBQ-Al) in the electrolyte is negligible, the loss of active materials in the P(THBQ-Al) electrode during cycling was suppressed. This is further supported by ex situ SEM analysis. The morphology of P(THBQ-Al) powders in the electrode remained unchanged after cycling because P(THBQ-Al) was not dissolved in the electrolyte during cycling, as shown in Figure S3. Therefore, the improved capacity retention of P(THBQ-Al) is attributed to the negligible solubility of P(THBQ-Al) in the electrolyte. To elucidate the electrochemical reaction mechanism of P(THBQ-Al), we performed ex situ XPS analysis. Figure 5b shows the O 1s XPS spectra of the P(THBQ-Al) electrodes collected at various points, as indicated in the corresponding voltage profile (Figure 5a). Each O 1s spectrum was deconvoluted into four peaks, such as a Na auger peak at 537.2 eV, C−O−Na bond at 534.1 eV, C=O bond at 532.6 eV, and Al−O bond at 531.5 eV.79 The peak intensity ratios of C=O and C−O were calculated by integrating the peak areas of C=O and C−O peaks, and their values were displayed in Figure 5c. The relative peak intensity of C=O gradually decreased during discharging (sodiation) and increased again during charging. This suggests that Na+ ions are

ACS Paragon Plus Environment

13

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 14 of 30

Figure 5. (a) Voltage profiles of the P(THBQ-Al) electrode. (b) Ex situ O 1s XPS spectra of the P(THBQ-Al) electrodes and (c) the relative area ratios of C=O and C−O peaks shown in (b). (d) Ex situ C 1s XPS spectra of the P(THBQ-Al) electrodes. The numbers in (b), (c), and (d) represent the P(THBQ-Al) electrodes collected at various points indicated in (a).

ACS Paragon Plus Environment

14

Page 15 of 30 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

inserted into P(THBQ-Al) through the conversion of carbonyl groups (C=O) into sodium phenoxide groups (C−O−Na) during discharging, and vice versa during charging. The same reversible transformation of C=O into C−O−Na during sodiation and desodiation were further supported by the ex situ C 1s XPS spectra (Figure 5d). These results demonstrate that the electrochemical reaction of C=O groups in P(THBQ-Al) is highly reversible during sodiation and desodiation. Moreover, the peak position of Al−O bonding in the ex situ Al 2p XPS spectra was not shifted during sodiation and desodiation, as shown in Figure S4. This suggests that the Al−O coordination bonds in P(THBQ-Al) were not decomposed during sodiation and desodiation because Al3+ was not involved in the redox reaction. The reversible conversion of carbonyl groups (C=O) of P(THBQ-Al) into sodium phenoxide groups (C−O−Na) was also supported by ex situ IR analysis, as shown in Figure 6. The vibration peaks at 1105 and 1242 cm−1 originated from Al−O in the coordination complex and C−F in a PVdF binder, respectively, remained unchanged during sodiation and desodiation. The intensity of C−O peak at 1155 cm−1 and C−O−Na peak at 1530 cm−1 gradually increased and decreased during sodiation and desodiation, respectively. Inversely, the intensity of C=O peak at 1570 cm−1 gradually decreased and increased during sodiation and desodiation, respectively. This is consistent with ex situ XPS analysis.

CONCLUSIONS Amorphous P(THBQ-Al) coordination polymer was investigated for the first time as a cathode material for Na-ion batteries. P(THBQ-Al) was synthesized through a facile coordination-driven self-assembly of benzoquinonedihydroxydiolate (C6O6H22-) and Al3+. P(THBQ-Al) exhibited excellent electrochemical performance, including a high reversible capacity of 113 mA h g−1 and

ACS Paragon Plus Environment

15

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 16 of 30

Figure 6. (a) Voltage profiles of the P(THBQ-Al) electrode. (b) Ex situ FT-IR spectra of the P(THBQ-Al) electrodes. The numbers in (b) represent the P(THBQ-Al) electrodes collected at various points indicated in (a).

ACS Paragon Plus Environment

16

Page 17 of 30 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

stable cycle performance, such as a negligible capacity fading over 100 cycles. Each benzoquinone unit in P(THBQ-Al) is capable of two electron reactions through the sodiation of its conjugated carbonyl groups, thus leading to a high reversible capacity. Moreover, electrochemically inert aluminum cation (Al3+) improved the structural stability of P(THBQ-Al) during cycling. While quinone-based single organic molecules, such as THBQ, were highly soluble in the electrolyte, the coordination polymer of P(THBQ-Al) was insoluble in the electrolyte, resulting in no loss of active materials during cycling. Therefore, the stable cycle performance of P(THBQ-Al) is attributable to its improved structural stability and negligible solubility in the electrolyte. We further clarified the reaction mechanism of P(THBQ-Al) through ex situ XPS and IR analyses. The reversible sodiation of C=O into C−O−Na was observed during cycling. Finally, we believe that coordination polymers are promising as electrode materials for Na-ion batteries because of their facile synthesis and sustainability.

ASSOCIATED CONTENT Supporting Information. The Supporting Information is available free of charge on the ACS Publications web sites. Ex situ SEM images and Al 2p XPS spectra of the P(THBQ-Al) electrodes. Cyclic voltammogram and cycle performance of P(THBQ-Al) (PDF)

AUTHOR INFORMATION Corresponding Authors

ACS Paragon Plus Environment

17

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 18 of 30

*E-mail: [email protected] (J.-C. Lee) *E-mail: [email protected] (K. T. Lee) Present Addresses † H. J. Kim is currently at the Department of Chemical Engineering and Materials Science, University of Minnesota, Twin Cities, 421 Washington Ave. SE, Minneapolis, MN, United States. § Y. Kim is currently at the Chemical Engineering, Materials Science and Engineering Program, Texas Materials Institute, The University of Texas at Austin, Austin, TX, 78712, United States. Author Contributions ‡These authors contributed equally. Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT This research was supported by the National Research Foundation of Korea (NRF) Grant (No. NRF- 2016R1A2B3015956 and NRF-2016R1D1A1A02937104) and the Materials and Components Technology Development Program of MOTIE/KEIT, Republic of Korea [10050477, Development of separator with low thermal shrinkage and electrolyte with high ionic conductivity for Na-ion batteries].

ACS Paragon Plus Environment

18

Page 19 of 30 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

REFERENCES (1) Ellis, B. L.; Nazar, L. F. Sodium and sodium-ion energy storage batteries. Curr. Opin. Solid State Mater. Sci. 2012, 16, 168-177. (2) Hong, S. Y.; Kim, Y.; Park, Y.; Choi, A.; Choi, N. S.; Lee, K. T. Charge carriers in rechargeable batteries: Na ions vs. Li ions. Energy Environ. Sci. 2013, 6, 2067-2081. (3) Kim, S. W.; Seo, D. H.; Ma, X.; Ceder, G.; Kang, K. Electrode materials for rechargeable sodium-ion batteries: potential alternatives to current lithium-ion batteries. Adv. Energy Mater. 2012, 2, 710-721. (4) Slater, M. D.; Kim, D.; Lee, E.; Johnson, C. S. Sodium-Ion Batteries. Adv. Funct. Mater. 2013, 23, 947-958. (5) Zhu, Z.; Chen, J. Review-Advanced Carbon-Supported Organic Electrode Materials for Lithium (Sodium)-Ion Batteries. J. Electrochem. Soc. 2015, 162, A2393-A2405. (6) Zhao, Q.; Lu, Y.; Chen, J. Advanced Organic Electrode Materials for Rechargeable Sodium-Ion Batteries. Adv. Energy Mater. 2017, 7, 1601792. (7) Fang, C.; Huang, Y. H.; Zhang, W. X.; Han, J. T.; Deng, Z.; Cao, Y. L.; Yang, H. X. Routes to High Energy Cathodes of Sodium-Ion Batteries. Adv. Energy Mater. 2016, 6, 1501727. (8) Yabuuchi, N.; Kubota, K.; Dahbi, M.; Komaba, S. Research development on sodium-ion batteries. Chem. Rev. 2014, 114, 11636-11682. (9) Kim, Y.; Ha, K.-H.; Oh, S. M.; Lee, K. T. High-Capacity Anode Materials for Sodium Ion Batteries. Chem. Eur. J. 2014, 20, 11980-11992.

ACS Paragon Plus Environment

19

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 20 of 30

(10) Bommier, C.; Ji, X. Recent Development on Anodes for Na-Ion Batteries. Isr. J. Chem. 2015, 55, 486-507. (11) Jache, B.; Adelhelm, P. Use of Graphite as a Highly Reversible Electrode with Superior Cycle Life for Sodium-Ion Batteries by Making Use of Co-Intercalation Phenomena. Angew. Chem., Int. Ed. 2014, 53, 10169-10173. (12) Kim, H.; Hong, J.; Park, Y. U.; Kim, J.; Hwang, I.; Kang, K. Sodium Storage Behavior in Natural Graphite using Ether-based Electrolyte Systems. Adv. Funct. Mater. 2015, 25, 534-541. (13) Wen, Y.; He, K.; Zhu, Y.; Han, F.; Xu, Y.; Matsuda, I.; Ishii, Y.; Cumings, J.; Wang, C. Expanded graphite as superior anode for sodium-ion batteries. Nat. Commun. 2014, 5, 4033. (14) Kohl, M.; Borrmann, F.; Althues, H.; Kaskel, S. Hard Carbon Anodes and Novel Electrolytes for Long-Cycle-Life Room Temperature Sodium-Sulfur Full Cell Batteries. Adv. Energy Mater. 2016, 6, 1502185 (15) Komaba, S.; Murata, W.; Ishikawa, T.; Yabuuchi, N.; Ozeki, T.; Nakayama, T.; Ogata, A.; Gotoh, K.; Fujiwara, K. Electrochemical Na Insertion and Solid Electrolyte Interphase for HardCarbon Electrodes and Application to Na-Ion Batteries. Adv. Funct. Mater. 2011, 21, 3859-3867. (16) Ponrouch, A.; Goñi, A. R.; Palacín, M. R. High capacity hard carbon anodes for sodium ion batteries in additive free electrolyte. Electrochem. Commun. 2013, 27, 85-88. (17) Li, Z.; Bommier, C.; Chong, Z. S.; Jian, Z.; Surta, T. W.; Wang, X.; Xing, Z.; Neuefeind, J. C.; Stickle, W. F.; Dolgos, M. Mechanism of Na-Ion Storage in Hard Carbon Anodes Revealed by Heteroatom Doping. Adv. Energy Mater. 2017, 1602894.

ACS Paragon Plus Environment

20

Page 21 of 30 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

(18) Kim, Y.; Kim, Y.; Park, Y.; Jo, Y. N.; Kim, Y. J.; Choi, N. S.; Lee, K. T. SnSe alloy as a promising anode material for Na-ion batteries. Chem. Commun. 2015, 51, 50-53. (19) Xu, Y.; Zhu, Y.; Liu, Y.; Wang, C. Electrochemical Performance of Porous Carbon/Tin Composite Anodes for Sodium-Ion and Lithium-Ion Batteries. Adv. Energy Mater. 2013, 3, 128133. (20). Komaba, S.; Matsuura, Y.; Ishikawa, T.; Yabuuchi, N.; Murata, W.; Kuze, S. Redox reaction of Sn-polyacrylate electrodes in aprotic Na cell. Electrochem. Commun. 2012, 21, 6568. (21) Luo, W.; Lorger, S.; Wang, B.; Bommier, C.; Ji, X. Facile synthesis of one-dimensional peapod-like Sb@C submicron-structures. Chem. Commun. 2014, 50, 5435-5437. (22) Kim, Y.; Park, Y.; Choi, A.; Choi, N. S.; Kim, J.; Lee, J.; Ryu, J. H.; Oh, S. M.; Lee, K. T. An Amorphous Red Phosphorus/Carbon Composite as a Promising Anode Material for Sodium Ion Batteries. Adv. Mater. 2013, 25, 3045-3049. (23) Qian, J.; Wu, X.; Cao, Y.; Ai, X.; Yang, H. High Capacity and Rate Capability of Amorphous Phosphorus for Sodium Ion Batteries. Angew. Chem., Int. Ed. 2013, 52, 4633-4636. (24) Yabuuchi, N.; Matsuura, Y.; Ishikawa, T.; Kuze, S.; Son, J.-Y.; Cui, Y.-T.; Oji, H.; Komaba, S. Phosphorus Electrodes in Sodium Cells: Small Volume Expansion by Sodiation and the Surface-Stabilization Mechanism in Aprotic Solvent. ChemElectroChem 2014, 1, 580-589. (25) Kim, Y.; Kim, Y.; Choi, A.; Woo, S.; Mok, D.; Choi, N. S.; Jung, Y. S.; Ryu, J. H.; Oh, S. M.; Lee, K. T. Tin Phosphide as a Promising Anode Material for Na-Ion Batteries. Adv. Mater. 2014, 26, 4139-4144.

ACS Paragon Plus Environment

21

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 22 of 30

(26) Billaud, J.; Clément, R. J.; Armstrong, A. R.; Canales-Vázquez, J.; Rozier, P.; Grey, C. P.; Bruce, P. G. β-NaMnO2: A High-Performance Cathode for Sodium-Ion Batteries. J. Am. Chem. Soc. 2014, 136, 17243-17248. (27) Yabuuchi, N.; Kajiyama, M.; Iwatate, J.; Nishikawa, H.; Hitomi, S.; Okuyama, R.; Usui, R.; Yamada, Y.; Komaba, S. P2-type Nax[Fe1/2Mn1/2]O2 made from earth-abundant elements for rechargeable Na batteries. Nat. Mater. 2012, 11, 512-517. (28) Kwon, M.-S.; Lim, S. G.; Park, Y.; Lee, S.-M.; Chung, K. Y.; Shin, T. J.; Lee, K. T. P2 Orthorhombic Na0.7[Mn1–xLix]O2+y as Cathode Materials for Na-Ion Batteries. ACS Appl. Mater. Interfaces 2017, 9, 14758-14768. (29) Lim, S. Y.; Kim, H.; Chung, J.; Lee, J. H.; Kim, B. G.; Choi, J.-J.; Chung, K. Y.; Cho, W.; Kim, S.-J.; Goddard, W. A.; Jung, Y.; Choi, J. W. Role of intermediate phase for stable cycling of Na7V4(P2O7)4PO4 in sodium ion battery. Proc. Natl. Acad. Sci. U. S. A. 2014, 111, 599-604. (30) Ha, K.-H.; Woo, S. H.; Mok, D.; Choi, N.-S.; Park, Y.; Oh, S. M.; Kim, Y.; Kim, J.; Lee, J.; Nazar, L. F.; Lee, K. T. Na4-αM2+α/2(P2O7)2 (2/3 ≤ α ≤ 7/8, M = Fe, Fe0.5Mn0.5, Mn): A Promising Sodium Ion Cathode for Na-ion Batteries. Adv. Energy Mater. 2013, 3, 770-776. (31) Park, Y.-U.; Seo, D.-H.; Kwon, H.-S.; Kim, B.; Kim, J.; Kim, H.; Kim, I.; Yoo, H.-I.; Kang, K. A New High-Energy Cathode for a Na-Ion Battery with Ultrahigh Stability. J. Am. Chem. Soc. 2013, 135, 13870-13878. (32) Dai, Y.; Zhang, Y. X.; Gao, L.; Xu, G. F.; Xie, J. Y. A Sodium Ion Based Organic Radical Battery. Electrochem. Solid-State Lett. 2010, 13, A22-A24.

ACS Paragon Plus Environment

22

Page 23 of 30 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

(33) Visco, S. J.; Mailhe, C. C.; Dejonghe, L. C.; Armand, M. B. A Novel Class of Organosulfur Electrodes for Energy-Storage. J. Electrochem. Soc. 1989, 136, 661-664. (34) Armand, M.; Grugeon, S.; Vezin, H.; Laruelle, S.; Ribiere, P.; Poizot, P.; Tarascon, J. M. Conjugated dicarboxylate anodes for Li-ion batteries. Nat. Mater. 2009, 8, 120-125. (35) Nokami, T.; Matsuo, T.; Inatomi, Y.; Hojo, N.; Tsukagoshi, T.; Yoshizawa, H.; Shimizu, A.; Kuramoto, H.; Komae, K.; Tsuyama, H. Polymer-bound pyrene-4, 5, 9, 10-tetraone for fastcharge and-discharge lithium-ion batteries with high capacity. J. Am. Chem. Soc. 2012, 134, 19694-19700. (36) Park, Y.; Shin, D. S.; Woo, S. H.; Choi, N. S.; Shin, K. H.; Oh, S. M.; Lee, K. T.; Hong, S. Y. Sodium Terephthalate as an Organic Anode Material for Sodium Ion Batteries. Adv. Mater. 2012, 24, 3562-3567. (37) Hong, J.; Lee, M.; Lee, B.; Seo, D.-H.; Park, C. B.; Kang, K. Biologically inspired pteridine redox centres for rechargeable batteries. Nat. Commun. 2014, 5, 5335. (38) Lee, M.; Hong, J.; Kim, H.; Lim, H.-D.; Cho, S. B.; Kang, K.; Park, C. B. Organic Nanohybrids for Fast and Sustainable Energy Storage. Adv. Mater. 2014, 26, 2558-2565. (39) Luo, W.; Allen, M.; Raju, V.; Ji, X., An Organic Pigment as a High-Performance Cathode for Sodium-Ion Batteries. Adv. Energy Mater. 2014, 4, 1400554. (40) Shimizu, A.; Kuramoto, H.; Tsujii, Y.; Nokami, T.; Inatomi, Y.; Hojo, N.; Suzuki, H.; Yoshida, J.-i. Introduction of two lithiooxycarbonyl groups enhances cyclability of lithium batteries with organic cathode materials. J. Power Sources 2014, 260, 211-217.

ACS Paragon Plus Environment

23

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 24 of 30

(41) Lee, H. H.; Park, Y.; Kim, S. H.; Yeon, S.-H.; Kwak, S. K.; Lee, K. T.; Hong, S. Y. Mechanistic Studies of Transition Metal-Terephthalate Coordination Complexes upon Electrochemical Lithiation and Delithiation. Adv. Funct. Mater. 2015, 25, 4859-4866. (42) Song, Z.; Qian, Y.; Zhang, T.; Otani, M.; Zhou, H. Poly(benzoquinonyl sulfide) as a High-Energy Organic Cathode for Rechargeable Li and Na Batteries. Adv. Sci. 2015, 2, 1500124. (43) Song, Z.; Qian, Y.; Otani, M.; Zhou, H. Stable Li–Organic Batteries with Nafion-Based Sandwich-Type Separators. Adv. Energy Mater. 2016, 6, 1501780. (44) Chen, H. Y.; Armand, M.; Courty, M.; Jiang, M.; Grey, C. P.; Dolhem, F.; Tarascon, J. M.; Poizot, P. Lithium Salt of Tetrahydroxybenzoquinone: Toward the Development of a Sustainable Li-Ion Battery. J. Am. Chem. Soc. 2009, 131, 8984-8988. (45) Song, Z. P.; Qian, Y. M.; Liu, X. Z.; Zhang, T.; Zhu, Y. B.; Yu, H. J.; Otani, M.; Zhou, H. S. A quinone-based oligomeric lithium salt for superior Li-organic batteries. Energy Environ. Sci. 2014, 7, 4077-4086. (46) Lecuyer, M.; Gaubicher, J.; Barres, A. L.; Dolhem, F.; Deschamps, M.; Guyomard, D.; Poizot, P. A rechargeable lithium/quinone battery using a commercial polymer electrolyte. Electrochem. Commun. 2015, 55, 22-25. (47) Liang, Y. L.; Zhang, P.; Yang, S. Q.; Tao, Z. L.; Chen, J. Fused Heteroaromatic Organic Compounds for High-Power Electrodes of Rechargeable Lithium Batteries. Adv. Energy Mater. 2013, 3, 600-605.

ACS Paragon Plus Environment

24

Page 25 of 30 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

(48) Song, Z. P.; Qian, Y. M.; Gordin, M. L.; Tang, D. H.; Xu, T.; Otani, M.; Zhan, H.; Zhou, H. S.; Wang, D. H. Polyanthraquinone as a Reliable Organic Electrode for Stable and Fast Lithium Storage. Angew. Chem., Int. Edit. 2015, 54, 13947-13951. (49) Pan, B. F.; Huang, J. H.; Feng, Z. X.; Zeng, L.; He, M. N.; Zhang, L.; Vaughey, J. T.; Bedzyk, M. J.; Fenter, P.; Zhang, Z. C.; Burrell, A. K.; Liao, C. Polyanthraquinone-Based Organic Cathode for High-Performance Rechargeable Magnesium-Ion Batteries. Adv. Energy Mater. 2016, 6, 1600140. (50) Kwon, M.-S.; Choi, A.; Park, Y.; Cheon, J. Y.; Kang, H.; Jo, Y. N.; Kim, Y.-J.; Hong, S. Y.; Joo, S. H.; Yang, C.; Lee, K. T. Synthesis of Ordered Mesoporous PhenanthrenequinoneCarbon via π-π Interaction-Dependent Vapor Pressure for Rechargeable Batteries. Sci. Rep. 2014, 4, 7404. (51) Jaffe, A.; Saldivar Valdes, A.; Karunadasa, H. I. Quinone-functionalized carbon black cathodes for lithium batteries with high power densities. Chem. Mater. 2015, 27, 3568-3571. (52) Kim, D. J.; Jung, Y. H.; Bharathi, K. K.; Je, S. H.; Kim, D. K.; Coskun, A.; Choi, J. W. An Aqueous Sodium Ion Hybrid Battery Incorporating an Organic Compound and a Prussian Blue Derivative. Adv. Energy Mater. 2014, 4, 1400133. (53) Kim, D. J.; Je, S. H.; Sampath, S.; Choi, J. W.; Coskun, A. Effect of N-substitution in naphthalenediimides on the electrochemical performance of organic rechargeable batteries. RSC Advances 2012, 2, 7968-7970. (54) Song, Z. P.; Zhou, H. S. Towards sustainable and versatile energy storage devices: an overview of organic electrode materials. Energy Environ. Sci. 2013, 6, 2280-2301.

ACS Paragon Plus Environment

25

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 26 of 30

(55) Häupler, B.; Wild, A.; Schubert, U. S. Carbonyls: powerful organic materials for secondary batteries. Adv. Energy Mater. 2015, 5, 1402034 (56) Liang, Y. L.; Tao, Z. L.; Chen, J. Organic Electrode Materials for Rechargeable Lithium Batteries. Adv. Energy Mater. 2012, 2, 742-769. (57) Yokoji, T.; Matsubara, H.; Satoh, M. Rechargeable organic lithium-ion batteries using electron-deficient benzoquinones as positive-electrode materials with high discharge voltages. J. Mater. Chem. A 2014, 2, 19347-19354. (58) Liang, Y. L.; Zhang, P.; Chen, J., Function-oriented design of conjugated carbonyl compound electrodes for high energy lithium batteries. Chem. Sci. 2013, 4, 1330-1337. (59) Kim, H.; Kwon, J. E.; Lee, B. N.; Hong, J.; Lee, M.; Park, S. Y.; Kang, K. High Energy Organic Cathode for Sodium Rechargeable Batteries. Chem. Mater. 2015, 27, 7258-7264. (60) Jung, J. H.; Lee, J. H.; Silverman, J. R.; John, G. Coordination Polymer Gels with Important Environmental and Biological Applications. Chem. Soc. Rev. 2013, 42, 924-936. (61) Zhang, P. F.; Li, H. Y.; Veith, G. M.; Dai, S. Soluble Porous Coordination Polymers by Mechanochemistry: From Metal-Containing Films/Membranes to Active Catalysts for Aerobic Oxidation. Adv. Mater. 2015, 27, 234-239. (62) Shigematsu, A.; Yamada, T.; Kitagawa, H. Selective Separation of Water, Methanol, and Ethanol by a Porous Coordination Polymer Built with a Flexible Tetrahedral Ligand. J. Am. Chem. Soc. 2012, 134, 13145-13147.

ACS Paragon Plus Environment

26

Page 27 of 30 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

(63) Hu, M.; Reboul, J.; Furukawa, S.; Torad, N. L.; Ji, Q. M.; Srinivasu, P.; Ariga, K.; Kitagawa, S.; Yamauchi, Y. Direct Carbonization of Al-Based Porous Coordination Polymer for Synthesis of Nanoporous Carbon. J. Am. Chem. Soc. 2012, 134, 2864-2867. (64) Guo, J. L.; Ping, Y.; Ejima, H.; Alt, K.; Meissner, M.; Richardson, J. J.; Yan, Y.; Peter, K.; von Elverfeldt, D.; Hagemeyer, C. E.; Caruso, F. Engineering Multifunctional Capsules through the Assembly of Metal-Phenolic Networks. Angew. Chem., Int. Ed. 2014, 53, 55465551. (65) Yang, S. J.; Antonietti, M.; Fechler, N. Self-Assembly of Metal Phenolic Mesocrystals and Morphosynthetic Transformation toward Hierarchically Porous Carbons. J. Am. Chem. Soc. 2015, 137, 8269-8273. (66) Clements, R. S.; Darnell, B. Myoinositol Content of Common Foods - Development of a High-Myo-Inositol Diet. Am. J. Clin. Nutr. 1980, 33, 1954-1967. (67) Ejima, H.; Richardson, J. J.; Liang, K.; Best, J. P.; van Koeverden, M. P.; Such, G. K.; Cui, J. W.; Caruso, F. One-Step Assembly of Coordination Complexes for Versatile Film and Particle Engineering. Science 2013, 341, 154-157. (68) Yue, Y. F.; Li, Y. C.; Bi, Z. H.; Veith, G. M.; Bridges, C. A.; Guo, B. K.; Chen, J. H.; Mullins, D. R.; Surwade, S. P.; Mahurin, S. M.; Liu, H. J.; Paranthaman, M. P.; Dai, S. A POMorganic framework anode for Li-ion battery. J. Mater. Chem. A 2015, 3, 22989-22995. (69) Aubrey, M. L.; Long, J. R. A Dual-Ion Battery Cathode via Oxidative Insertion of Anions in a Metal-Organic Framework. J. Am. Chem. Soc. 2015, 137, 13594-13602.

ACS Paragon Plus Environment

27

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 28 of 30

(70) Guo, B. K.; Kong, Q. Y.; Zhu, Y.; Mao, Y.; Wang, Z. X.; Wan, M. X.; Chen, L. Q. Electrochemically Fabricated Polypyrrole-Cobalt-Oxygen Coordination Complex as HighPerformance Lithium-Storage Materials. Chem. Eur. J. 2011, 17, 14878-14884. (71) Han, X. Y.; Yi, F.; Sun, T. L.; Sun, J. T. Synthesis and Electrochemical Performance of Li and Ni 1,4,5,8-naphthalenetetracarboxylates as Anodes for Li-ion Batteries. Electrochem. Commun. 2012, 25, 136-139. (72) Motekaitis, R. J.; Martell, A. E. Complexes of Aluminum(III) with Hydroxy CarboxylicAcids. Inorg. Chem. 1984, 23, 18-23. (73) Bureekaew, S.; Horike, S.; Higuchi, M.; Mizuno, M.; Kawamura, T.; Tanaka, D.; Yanai, N.; Kitagawa, S. One-dimensional Imidazole Aggregate in Aluminium Porous Coordination Polymers with High Proton Conductivity. Nat. Mater. 2009, 8, 831-836. (74) Sikora, F. J.; Mcbride, M. B. Aluminum Complexation by Catechol as Determined by Ultraviolet Spectrophotometry. Environ. Sci. Technol. 1989, 23, 349-356. (75) Senkovska, I.; Hoffmann, F.; Froba, M.; Getzschmann, J.; Bohlmann, W.; Kaskel, S. New Highly Porous Aluminium Based Metal-organic Frameworks: Al(OH)(ndc) (ndc=2,6naphthalene dicarboxylate) and Al(OH)(bpdc) (bpdc=4,4'-biphenyl dicarboxylate). Microporous Mesoporous Mater. 2009, 122, 93-98. (76) Turner, N. H. X-ray photoelectron and Auger electron spectroscopy (Reprinted from Analytical Instrumentation Handbook, Second Edition, Revised and Expanded, pg 863, 1997). Appl. Spectrosc. Rev. 2000, 35, 203-254.

ACS Paragon Plus Environment

28

Page 29 of 30 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

(77) Luo, C.; Huang, R. M.; Kevorkyants, R.; Pavanello, M.; He, H. X.; Wang, C. S. SelfAssembled Organic Nanowires for High Power Density Lithium Ion Batteries. Nano Lett. 2014, 14, 1596-1602. (78) Wu, Y.; Zeng, R.; Nan, J.; Shu, D.; Qiu, Y.; Chou, S.-L. Quinone Electrode Materials for Rechargeable Lithium/Sodium Ion Batteries. Adv. Energy Mater. 2017, 1700278. (79) Pan, B. F.; Huang, J. H.; Feng, Z. X.; Zeng, L.; He, M. N.; Zhang, L.; Vaughey, J. T.; Bedzyk, M. J.; Fenter, P.; Zhang, Z. C.; Burrell, A. K.; Liao, C. Polyanthraquinone-Based Organic Cathode for High-Performance Rechargeable Magnesium-Ion Batteries. Adv. Energy Mater. 2016, 6, 1600140

ACS Paragon Plus Environment

29

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 30 of 30

Table of Contents Graphic

ACS Paragon Plus Environment

30