Polyanthraquinone-TriazineâA Promising Anode Material for High

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Polyanthraquinone-Triazine - A Promising Anode Material for High-Energy Lithium-Ion Battery Hongwei Kang, Huili Liu, Chunxiao Li, Li Sun, Chaofeng Zhang, Hongcai Gao, Jun Yin, Baocheng Yang, Ya You, Ke-Cheng Jiang, Huijin Long, and Sen Xin ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b12888 • Publication Date (Web): 09 Oct 2018 Downloaded from http://pubs.acs.org on October 10, 2018

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ACS Applied Materials & Interfaces

Polyanthraquinone-Triazine - A Promising Anode Material for High-Energy Lithium-Ion Battery Hongwei Kang,† Huili Liu,† Chunxiao Li,‡ Li Sun,† Chaofeng Zhang,*‡ Hongcai Gao,§ Jun Yin,‡ Baocheng Yang,† Ya You,§ Ke-Cheng Jiang∥, Huijin Long∥ and Sen Xin*§ †

Henan Provincial Key Laboratory of Nanocomposites and Applications, Institute of

Nanostructured Functional Materials, Huanghe Science and Technology College, Zhengzhou 450006, China. ‡

School of Chemistry and Chemical Engineering, Hefei University of Technology, Hefei

230009, P. R. China. §

Department of Mechanical Engineering, the University of Texas at Austin, Austin, Texas

78712, USA. ∥

Jiangsu TAFEL New Energy Technology Inc., Nanjing, Jiangsu 211113, P. R. China.

* Corresponding authors. E-mail addresses: [email protected]; [email protected] KEYWORDS: lithium-ion battery, polymer anode, anthraquinone, triazine, storage mechanism

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ABSTRACT: A novel covalent organic framework polymer material that bears conjugated anthraquinone and triazine units in its skeleton has been prepared via a facile one-pot condensation reaction and employed as an anode material for Li-ion batteries. The conjugated units consist of C=N groups, C=O groups and benzene groups, which enable a 17-electron redox reaction with Li per repeating unit and brings a theoretical specific capacity of 1450 mAh g-1. The polymer also shows a large specific surface area and a hierarchically porous structure to trigger interfacial Li storage and contribute to an additional capacity. The highly-conductive conjugated polymer skeleton enables fast electron transport to facilitate the Li storage. In this way, the polymer electrode shows a large specific capacity and favorable cycling and rate performance, making it an appealing anode choice for the next-generation high-energy batteries.


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INTRODUCTION Currently, lithium ion batteries (LIBs) have captured much attention for their superiorities over other rechargeable batteries, such as high energy/power density, long cycle life, and environmental benignity.1-6 To further explore the battery use in emerging fields such as automobiles and grid-level applications, LIBs with higher energy densities are desired.7-9 However, the conventional graphite anode based on intercalation chemistry has a limited theoretical capacity of 372 mA h g-1, making it difficult to boosting the energy output of battery.10-11 In addition, graphite has a intercalation potential very close to the potential for plating of Li metal, which could lead to unfavorable formation of Li dendrites and hampers the safety of battery due to internal shortage.12-13 Thus, it is of great importance to explore anode materials with high theoretical capacity and improved safety.14-17 Organic compounds with Li-storable functional groups, such as the carbonyl group, C=N group and benzene group, are promising electrode materials for LIBs.18-26 Through the reversible multi-electron redox reaction between the functional groups and Li, the compounds are expected to deliver higher specific capacities than graphite. Also, the electrochemical potentials enabling these redox reactions are higher than the plating/stripping potential of Li, which is beneficial for inhibiting the dendrite formation upon cycling. However, the electrode use of small-molecule organic compounds were hindered by some intrinsic problems such as poor conductivity and dissolution of electroactive species into electrolytes.22,

24-26

Aiming at the above challenges,

polymer electrodes offer a feasible solution. While the low solubility of polymers in conventional electrolytes ensures their electrochemical stability in a battery, the Li-storable functional groups, by applying appropriate molecular design, can form a conjugated skeleton to raise the conductivity of charge carriers.21, 23, 25, 27, 28 Moreover, the electrochemical properties (eg., specific capacity, electrochemical potential and even energy storage mechanism) of these



polymers can be precisely modulated by employing various redox-active organic building blocks, such as ketones, carboxylates or amides.29 In case the conjugated polymer can selfassemble into covalent organic frameworks (COF) with ordered two-dimensional or threedimensional porous structure at nanoscale, the polymer is expected to provide more active sites for Li+ diffusion and storage, so that it will exhibit boosted Li storage performance.18, 30-33 In this work, we reported a novel conjugated polymer, polyanthraquinone-triazine (PAT), for anode use in LIBs. The material was synthesized through a facile nucleophilic substitution reaction of 2, 4, 6-trichloro-1, 3, 5-triazine (TCT) by 2, 6-diamino anthraquinone (AQ).34, 35 The conjugated AQ and triazine units facilitates the electron conduction in the polymer, while also forms a porous, crosslinked COF structure with a large specific surface area to provide additional active sites for interfacial Li storage. A detailed discussion has been given to the electrochemical reaction mechanism of PAT with Li, which reveals a complex Li storage chemistry including storage via a 17-electron redox reaction and storage at the electrode|electrolyte interface. The polymer material demonstrates a large reversible capacity and favorable cycling performance, making it a promising anode candidate for the next-generation LIBs.

EXPERIMENTAL SECTION Synthesis of PAT. Under N2 atmosphere, TCT (366 mg, 2.0 mmol), AQ (714 mg, 3.0 mmol) and Na2CO3 (1.06 g, 10.0 mmol) were added into 15 mL of N, N-dimethylformamide (DMF) and were kept at 100 ºC for 20 h, and then kept at 140 °C for another 24 h. The mixture was then cooled down to room temperature and poured into 100 mL of deionized water, and stirred for 30 mins. The precipitate was collected by filtration and washed with deionized water and ethanol. After purification by Soxhlet extraction successively by ethanol, acetonitrile and


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dichloromethane for 2 days, the resultant was dried in vacuum oven at 55 °C for 12 h, obtaining a yellow powdered product (603.5 mg, yield: 70.1%). 1H Nuclear Magnetic Resonance (NMR): (400 MHz, deuterated dimethyl sulfoxide (DMSO-d6)) δ 10.83-10.77 and 6.67-6.53 for N-H, (m, 2H), 8.44-6.83 for aromatic-H (m, 6H);

13

C NMR: (100 MHz, DMSO-d6) δ 182.26, 181.09,

160.46, 154.84, 154.60, 143.61, 143.43 ,135.88, 135.13, 129.68, 129.30, 128.62, 128.48, 128.29, 123.76, 122.95, 121.46, 117.85, 116.98, 116.07, 115.95, 109.78, 109.68. Materials characterization. The morphology of PAT powder was characterized on a fieldemission scanning electron microscope (FE-SEM, Hitachi, S3400N) and a transmission-electron microscope (TEM, Tecnai G2 20 operated at 200kV). The chemical structure of PAT was identified by NMR spectroscopy (400 M NMR spectrometer, Bruker Advance), ultravioletvisible (UV-Vis) absorption spectroscopy (U-4100 UV-Vis-NIR Hitachi spectrometer), Fourier transform infrared (FT-IR) spectrometry (Thermo Scientific Nicolet iS5, wavelength range: 7003500 cm-1) and X-ray powder diffraction (XRD) (Bruker D8 Advance XRD, equipped with a Cu Kα radiation). The porous structure of PAT was studied with N2 adsorption-desorption isotherms collected on a Micromeritics ASAP 2020 instrument at 77 K, after the sample was degassed at 100 °C for 6 h in vacuum. The pore size distribution was calculated by the non-local density functional theory (DFT) method. Electrochemical tests. To prepare the working electrode, PAT was thoroughly mixed with conductive carbon black and binder (polyvinylidene fluoride) at a mass ratio of 60:25:15. Nmethyl-2-pyrrolidone was added during the mixing process, yielding a homogeneous slurry. The slurry was then coated on copper foil (thickness: 20 µm), dried at 60 °C for 24 h under vacuum and finally cut into slices to obtain the working electrode (with the total weight of the electrode material of about 2.2 mg, and the electrode area of 2.0 cm2). The working electrode was paired



with Li metal and assembled into CR2032 coin cells in an argon-filled glove box. 1.0 M LiPF6 dissolved in a mixture of ethylene carbonate and dimethyl carbonate (v:v = 1:1) was used as the electrolyte. Galvanostatic discharge-charge (GDC) test of the cells was performed on an Arbin BT-1 system within the voltage range of 0.01-3 V (all the voltage/potential values are vs. Li+/Li throughout the paper unless otherwisely indicated). The capacity was calculated based on the total mass of the active material. Cyclic voltammogram (CV) measurements were performed on an Autolab PG302N with various scan rates in the potential range of 0.01-3 V. Nyquist plots were also recorded using the Autolab PG302N.

RESULTS AND DISCUSSION As shown in Scheme 1., the polymer was prepared via a Na2CO3-assisted dehydrochlorination reaction. Initially, all the organic substances were dissolved in hot DMF, while a yellow precipitate formed after several hours. It is known that small molecules are easily dissolved in organic electrolyte, hence, purification by soxhlet extraction to remove the small molecules or oligomers is required to enhance the electrochemical stability of the PAT. The purified polymer PAT is not soluble in conventional solvents (such as ethanol, tetrahydrofuran and dichloromethane), yet is soluble in DMSO, making it possible to perform the NMR characterization in DMSO-d6 to study the organic functional groups on PAT. As revealed by 1H NMR (Figure S1), the proportion of aromatic-H and N-H is 6:2, indicating the co-existence of two amino protons (N-H) and six aromatic protons (Ph-H) at the backbones of aminoanthraquinone. The above result indicates successful polymerization of AQ with TCT. The characteristic chemical shifts on 13C NMR (at 182.26, 181.09, 154.8, 154.6 ppm) are assigned to the AQ units,36 while the shift at 160.46 ppm is ascribed to the carbon atoms of triazine.


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Figure S2a shows the SEM image of PAT. It is observed that the as-prepared polymer without purification exhibits a typical anomalous particle-like morphology with the particle size of ca. 1-5 µm. After purification by Soxhlet extraction, the particle sizes distribution of the polymer become homogeneous. Figure S2b shows the TEM result. The particle size of PAT is ca. 100-200 nm, which is consistent with the SEM result. The XRD pattern (Figure S3) of PAT shows diffraction peaks at 11.38º, 15.25º, 26.16º, 27.46º and 30.16º, which correspond to the lattice spacings of 7.81 Å, 5.82 Å, 3.40 Å, 3.26 Å and 2.96 Å, respectively. It should be noted that the three peaks at 20-30º are assigned to the π-π stacking between aromatic rings, which implies that the three anthraquinone units are not in the same plane for the torsional angle of CN-C bonds. The structure of PAT was characterized by UV-Vis absorption spectra and FT-IR. In the UV-Vis spectra (Figure 1a), the maximum absorption wavelength (λmax) of AQ is 394 nm, while the λmax of PAT blue shifts to 380 nm. The above hypsochromic shift phenomenon is likely caused by the reduced intramolecular charge transfer effect when the amino groups are bonded with the electron-deficient triazine core. Compared with AQ, the absorbance of PAT in the near ultraviolet region is also enhanced due to the absorption of triazine units. In the FT-IR spectra (Figure 1b), the peaks at 3422 cm-1 and 3342 cm-1 of PAT are assigned to the asymmetric and symmetric stretching vibrations of N-H in the AQ units. In contrast to the peak of AQ, the peak at 3422 cm-1 of PAT are more intensive (Figure 1b), proving the asymmetric structure caused by substitution of triazine units at anthraquinone backbones. The shoulder peak at 1693 cm-1 of PAT is also enhanced, and the C=O stretch peak shifts towards high energy (from 1627 cm-1 and 1657 cm-1 for AQ to 1629 cm-1 and 1663 cm-1 for PAT, see Figure 1b). The strong absorption peaks at 1570 cm-1 for AQ and 1577 cm-1 for PAT are assigned to anthraquinone rings.37



The porous structure of PAT was investigated by nitrogen absorption-desorption isotherms at 77 K. As shown in Figure 2a, the polymer shows a combined profile which consists of type I adsorption at low pressure (P/P0 < 0.1) and a type H2 hysteresis loop, which indicates the coexistence of micropores and mesopores in the polymer.38, 39 The DFT pore distribution of PAT calculated by the non-local density functional theory (DFT) further reveals concentrated pore sizes at ~1.5 nm and 18.4 nm. The above result proves the COF structure of PAT, which is ascribed to the crosslinked network interconnected by the triazine units. The specific surface area calculated by Brunauer–Emmett–Teller method and the total pore volume (Vtol) calculated by DFT are 140 m2 g−1 and 0.62 cm3 g−1, respectively. The high specific surface area and porous structure of polymer may contribute to significant interfacial Li storage, as will be detailed in the following part. The electrochemical tests of the prepared working electrode of PAT were carried out in a potential range of 0.01-3.0 V vs. Li+/Li. Figure 3a shows the GDC profiles at 200 mA g-1. In the initial discharge process, the PAT electrode shows a small plateau at 2.0 V, which corresponds to the redox reaction between Li and carboxyl group.18, 24 After that, the electrode shows a slopped profile and outputs a high specific capacity of 2550 mAh g-1 (Figure 3a). In the reverse charge process, the electrode delivers a specific capacity of 1305 mA h g-1, corresponding to a Coulombic efficiency of 51% (Figure 3a, b). The low initial Coulombic efficiency is possibly ascribed to the formation of solid electrolyte interface on the electrode surface triggering by side reactions between PAT and electrolyte during the initial discharge process, and is detrimental for the practical anode use of PAT. However, one can expect to mitigate the issue by applying a prelithiation process on the anode, as has been applied to other anode materials such as silicon monoxide.40 In the subsequent cycles, the electrode exhibits slopped GDC profiles without any


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apparent plateaus (Figure 3a), and a steady decay in capacity occurs until the 20th cycle (Figure 3b). After 50 cycles, the polymer electrode stably outputs a reversible capacity of ~820 mAh g-1 and an efficiency >99% (Figure 3b). After 100 cycles, the electrode shows a gradually increased capacity, with 1165 mAh g-1 outputted at the 200th cycle and 1770 mAh g-1 at the 400th cycle, indicating that a slow yet continuous electrochemical activation has occurred during the cycling process. Although the polymer electrode shows a high Li storage voltage, the high specific capacity delivered by PAT offsets the disadvantage on the voltage and renders a high specific energy density. The PAT electrode shows a long cycle life and reasonable rate performance. At a current density of 1 A g-1 (Figure 3c), the polymer electrode delivers a capacity higher than 600 mAh g-1 after 50 cycles. After that, the capacity gradually recovers to 760 mAh g-1 and maintains around the value from the 200th cycle to the 400th cycle. During the cycling process, a stable Coulombic efficiency of nearly 100% is maintained. In the rate performance test (Figure 3d), the PAT electrode is able to deliver a reversible capacity of 540 mAh g-1 upon further increasing the current density to 2 A g-1. The electrochemical performance of PAT is superior to other organic anode materials previously reported in the state-of-the-art pioneer works,31, 41-47 according to the following Table 1. The improved Li storage performance is largely due to high electronic conductivity of PAT, which is further ascribed to fast migration of π electrons along the conjugated polymer skeleton, as will be revealed in the following section. To reveal more factors that influence the electrochemical performance of PAT, we also probed into the Li storage chemistry of the polymer. According to Figure S4, the simplest repeating unit (SRU) of the polymer consists of an AQ segment and a triazine segment. Hence, there are two benzene rings, three C=N groups and two C=O groups in a SRU. According to the



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previous works, Li ions can react with the above groups, with one Li ion per C=N group, one Li ion per C=O group, and six Li ions per benzene ring.18 Therefore, a SRU of PAT can maximumly enable a 17-electron redox reaction with Li, which leads to a theoretical specific capacity of 1450 mAh g-1 (Figure S4). Also, referring to a recent work by Lei et al,18 both the C=N group and benzene rings undergo a gradual electrochemical activation process during repeated (de)lithiation, which reasonably explains the slow but steady capacity ascending during the cycling process. In the light of the large specific surface area of PAT and the reversible specific capacity (1770 mAh g-1) exceeding the theoretical value (1450 mAh g-1) after 400 GDC cycles, it is equally possible for the polymer electrode to show other Li storage chemistry such as interface storage. To verify this point, the CV curves of the PAT electrode at various scan rates (Figure 4a) were collected and analyzed the capacitance contribution of the PAT electrode by separating the diffusion-controlled capacity from the capacitive capacity. The current response (i) at a fixed potential (V) during the CV test can be divided into the contributions from both the capacitancecontrolled process (k1v) and the diffusion-controlled process (k2v1/2) according to the following equation (eq. 1): i (V) = k1v + k2v1/2

(1)

The capacitive contribution (CC) can be calculated from the above eq. 1 (CC = k1v/ i (V)). At a scan rate of 1 mV s-1, the capacitance-controlled process contributes to 22.9% of the total capacity (Figure 4b). As the scan rate increases to 2, 3, 5, and 10 mV s-1, the capacitancecontrolled contribution raises to 27.0%, 31.4%, 37.8%, and 48.1%, respectively (Figure 4c). Since the capacitance-controlled process mainly occurs at the interface between electrode and electrolyte, it is highly possible that the capacity is contributed by both the electrical double-


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layer capacitance due to Li storage at the electrode|electrolyte interface (of mesopores) and the capacity due to storage of quasimetallic Li clusters in the micropores or surface defects of PAT.48-50 In this way, the Li storage in PAT can be described as a complex process that combines a 17-electron redox reaction between Li and double-bond groups (C=C, C=N, and C=O) and the interfacial storage at the mesopore surface (or in the micropores of PAT). It is also noted that, even provided with such complex storage chemistry, the PAT electrode still exhibits favorable structural robustness against Li uptake/release. According to the electrochemical impedance spectroscopic (EIS) study (Figure 4d), the charge transfer resistance (Rct, which is denoted by the diameter of the semicircle in high and intermediate frequency region) shows a slight increase during the 400-cycle GDC process, demonstrating excellent electrochemical stability of PAT towards long-term cycling application. We have also calculated the apparent Li+ diffusion coefficient (DLi+) of the PAT electrode by the Randles-Sevick equation from the CV data in Figure 4a, which is 1.95×10-15 cm2 s-1 according to Figure S5.51, 52 It is admitted that due to the large particle size, the Li+ diffusion in the bulk of the PAT polymer is much slower than that in the nanostructured mesoporous carbon or graphitic carbon.53, 54 The result also explains the slow electrochemical activation process of the PAT electrode, as it also reflects the limited Li+ accessibility of the material. As such, the rate performance of the PAT electrode is mainly contributed by the fast electron transport along the conjugated polymer skeleton, and can be further improved if the Li+ diffusion is facilitated. It is also noted that, the Li+ diffusion rate in PAT is comparable with those obtained from conventional electrode materials such as LiFePO4 or amorphous Si.55, 56 Therefore, with proper nanostructure design or compositing with other highly-conductive components such as graphitic



nanocarbons, it is expected to further improve the Li+ diffusion in PAT, which is beneficial for boosting the electrochemical Li storage performance of the polymer electrode.

CONCLUSION To conclude, a novel COF polymer bearing AQ and triazine units in its skeleton was synthesized and used as anode material for LIBs. The highly-conductive conjugated units and the structural features of the PAT polymer enables fast electron transport, and complex Li storage chemistry that combines a 17-electron redox reaction with a theoretical specific capacity of 1450 mAh g-1 and interfacial storage that provides an additional capacity output. The polymer electrode shows high reversible capacities of 1770 mAh g-1 at 200 mA g-1 and 760 mAh g-1 at 1 A g-1, and maintains a Coulombic efficiency of nearly 100% during cycling. With these advantages, the COF polymer demonstrates its promise as a competitive anode candidate for the next-generation high-energy batteries.57-62

ASSOCIATED CONTENT Supporting Information. 1H and 13C NMR data, XRD pattern, SEM and TEM images of PAT. This material is available free of charge via the Internet at http://pubs.acs.org. AUTHOR INFORMATION Corresponding Author * E-mail: [email protected] (S. X.). * E-mail: [email protected] (C. Zhang). Author Contributions


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The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Notes The authors declare no competing financial interest. ACKNOWLEDGMENT This work is supported by Anhui Province Key Laboratory of Environment-Friendly Polymer Materials and Science -Technology Development Program of Henan Province (182102210403). The authors thank Ms. Juan Rao for her contribution on electrochemical tests.

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Scheme 1. The synthesis route of PAT.


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Figure 1. (a) UV-Vis absorption spectra (in DMF) and (b) FT-IR spectra of AQ (red) and PAT (black).



Figure 2. (a) N2 adsorption–desorption isotherm and (b) pore-size distribution of PAT.


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Figure 3. Electrochemical performance of the PAT electrode, including: (a) GDC profiles at 200 mA g-1, (b) cycling performance at 200 mA g-1, (c) long-term cycling performance at 1 A g-1, and (d) rate capabilities at different current densities.



Figure 4. (a) CV profiles of the PAT electrode collected at different scan rates (1-10 mV s-1) after one discharge-charge cycle, (b) CV profile collected at 1 mV s-1, in which the shaded region indicates the capacitive contribution, (c) capacitive contributions at various scan rates (1, 2, 3, 5, and 10 mV s-1), and (d) EIS spectra collected after the specific number of cycles for the PAT electrode (current density: 200 mA g-1), inset shows the equivalent circuit.


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Table 1. Performance comparison between the previously reported organic anode materials and the PAT material reported in this work. Anode material

Mass ratio of active material/ conductive additive/binder

Reversible capacity (mA·h g-1)

Current density (mA g-1)

Coulombic efficiency (%)

Cycle number

Ref.

Bicarbozole-based covalent organic framework (COF)

5:3:2

628

100

99

400

41

CaC8H4O4

6:3:1

399

20

84

40

42

3,3’-bithiophene polymer

5:4:1

663

500

79.9

1000

43

Terephthalate/Fe metal-organic framework (MOF) @reduced graphene oxide

7:2:1

550

100

N/A

100

44

Biphenyldiaminetriazine COF

Binder free

600

500

82

100

45

Carbazylbenzothiadiazole polymer

6:3:1

404

100

>98

100

46

Triazole-Ag MOF

7:2:1

570

100

>99

100

47

1770

200

>99

400

760

1000

~100%

400

Polyanthraquinonetriazine COF

60:25:15

This work



TOC Figure


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Polyanthraquinone-TriazineâA Promising Anode Material for High

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