Aqueous Lithium-Ion Batteries Using Polyimide-Activated Carbon

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Aqueous Lithium-ion Batteries Using Polyimide-Activated Carbon Composites Anode and Spinel LiMn2O4 Cathode Zhaowei Guo, Long Chen, Yong-Gang Wang, Congxiao Wang, and Yongyao Xia ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.6b02127 • Publication Date (Web): 04 Jan 2017 Downloaded from http://pubs.acs.org on January 10, 2017

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ACS Sustainable Chemistry & Engineering

Aqueous Lithium-ion Batteries Using Polyimide-Activated Carbon Composites Anode and Spinel LiMn2O4 Cathode Zhaowei Guo, Long Chen, Yonggang Wang, Congxiao Wang, and Yongyao Xia ∗ Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Institute of New Energy, iChEm (Collaborative Innovation Center of Chemistry for Energy Materials), Fudan University, Shanghai 200433, People’s Republic of China.

Corresponding author: Yongyao Xia E-mail: [email protected] Tel & Fax: 0086-21-51630318

Abstract Polyimide/activated carbon (PI/AC) composites were prepared by in-situ polymerization

of

1,4,5,8-naphthalenete-tracarboxylic

dianhydride

(NTCDA) and ethylene diamine (EDA) on activated carbon with various mass ratios varying from 50:50 to 70:30. These composites were examined as anode materials in 5M LiNO3 solution in the potential window from -0.75 to 0 V vs. Ag/AgCl. With an optimal composition PI/AC 50:50 in mass ratio, the composite delivers a specific capacity of 1 ACS Paragon Plus Environment


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87 mAh g-1 at the current density of 0.2 A g-1, and it also shows excellent cycling stability and rate capability. A sealed full cell containing PI/AC composite anode and LiMn2O4 cathode delivers a specific capacity of 42mAh g-1 and energy density of 51Wh Kg-1 (based on the total weight of both active materials) at the current density of 0.2 A g-1. The full cell exhibits good cycling stability with a specific capacity of 35 mAh g-1 after 450 cycles, corresponding to a capacity retention of 89%.

Keywords: Aqueous lithium-ion battery; Polyimide; Activated carbon; Composite anode; LiMn2O4

Introduction As one of the most potential stationary power sources for sustainable energies, for instance wind and solar power, the aqueous rechargeable lithium-ion battery (ARLB) has attracted more and more attention from the public.

1-3

The ARLB may not only solve the safety problem due to

inevitable use of highly toxic and flammable organic solvents for lithium-ion batteries, but improve the poor cycling performance associated

with

commercialized

aqueous

rechargeable

batteries

2-4

However,

containing nickel metal-hydride systems and lead-acid.

aqueous electrolyte proposes more requirements on the cathode and anode materials as a result of the narrow electrochemical window.

5-6

Over the past few decades, much more efforts have been made to 2 ACS Paragon Plus Environment

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improve the electrochemical performance of ARLB since its first proposed by Dahn’s group in 1994.

7

Layered LiCoO2, spinel LiMn2O4,

or olivine LiFePO4 was used as the cathode, while V or Ti based oxides and compounds, such as VO2, LiV3O8, LixV2O5, V2O5, TiP2O7 or LiTi2(PO4)3, as the anode for ARLB in most previous research.

8-10

In

spite of plenty of improvements in energy density been achieved during the research of ARLB, the cycling stability is still limited because of the poor stability of anode in aqueous electrolyte, which is derived from side reaction of anode with oxygen and/or water, dissolution of active material in electrolyte, and adverse structural change during charge/discharge process. 10-12 To a large extent, the development process of ARLB systems depends on the electrochemical performance of the anode in aqueous electrolyte. Organic electrode materials have already been examined in organic lithium ion batteries mostly, while they have been implemented in ARLB recently. These materials, especially carbonyl groups conjugated compounds, possess certain advantages of structure diversity, flexibility, tunable redox property and probable high energy density. 13-16 Compared with previously reported anode materials for ARLB, the advantages of a totally distinct redox mechanism 10 and better insolubility in aqueous solution than small molecules

16

are presented by polyimide.

Besides, during the redox process, the framework of polyimide keeps 3 ACS Paragon Plus Environment


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stable. Polyimide has been examined as a potential anode material for ARLB owing to its superior electrochemical performance. 17 As other organic materials, polyimide is a typically poor electrical conductor. Large amounts of conductive additive are inevitable used for polyimide as an anode in ARLB. Song et al developed nanocomposite combining polyimide with functionalized graphene sheet to improve rate performance of polyimide in rechargeable lithium batteries

18

. However,

graphene delivered very low capacity, limiting the capacity of the composite anode. Herein, owing to possessing certain capacity and good electrical conductivity, activated carbon (AC) was intimately mixed with polyimide (synthesized by simple polycondensation reaction from 1,4,5,8-naphthalenete-tracarboxylic dianhydride (NTCDA) and ethylene diamine(EDA)). The PI/AC mass ratio was examined through the comparison of capacity, rate and cycling performance of these composites comprising blended polyimide and activated carbon in a mass ratio varying from 50:50 to 70:30. Afterwards, PI/AC in a 50:50 mass ratio anode was used as anode for ARLB with LiMn2O4 cathode, which was examined as a cathode with good electrochemical performance

19-21

, to

assemble the PI-AC /LiNO3 /LiMn2O4 full cell. The electrochemical property of the full cell was studied in terms of charge/discharge and cycling tests.

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Experimental Materials Synthesis The composites comprising of blended PI and activated carbon were prepared by the above-mentioned method in the mass ratio varying from 50:50 to 70:30. A certain amount of activated carbon was dispersed in the solvent of N-methylpyrrolidone (NMP), followed by stoichiometric NTCDA and EDA added into the suspension. The mixture reacted under reflux at 300℃ for 6 hours. Following being filtrated and washed with ethanol and NMP for several times in turn, the product was dried at 120℃ in air oven for 12 hours. After that, the product was calcined in furnace at 300℃ for 8 hours in nitrogen atmosphere. As a comparison, pure polyimide was also prepared meanwhile by the same process mentioned above. Characterization and electrochemical measurement All samples were characterized by Fourier trans-form infrared spectroscopy (FT-IR) measurements through a NICOLET 6700 FI-TR Spectrometer using KBr pellet. The morphologies of the samples were examined by scanning electron microscopy (SEM, JEOL JSM-6390). Transmission electron microscope (TEM) images were taken using a JEOL JEM-2010 microscope. The PI-containing electrodes were produced by vigorously mixing PI with

activated

carbon,

acetylene

black


(AB),

and

binder


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(polytetrafluoroethylene) (PTFE) in isopropanol in approximately a 60:30:10 mass ratio. The electrode film was vacuum-dried at 80℃ for 10 hours to remove the solvent. Then the electrode film was dried at 120℃ in air oven for 12 hours, followed by pressing the electrode film on stainless steel grid. The typical active material mass loading was about 3 mg cm-2. The cathode electrode consisted of LiMn2O4, acetylene black, and PTFE in an 80:15:5 mass ratio. For the three-electrode cell, the counter electrode was produced with activated carbon, acetylene black, and PTFE in an 85:10:5 mass ratio. Both LiMn2O4 electrode and AC electrode were processed in a similar process. The cyclic voltammetry (CV) tests of all the samples were carried out on CH Instruments electrochemical workstation (CHI 660D). All the electrodes described above were tested in 5M LiNO3 aqueous solution. Ag/AgCl electrode (E=0.1971V vs. SHE) was used as the reference electrode. The CV scan of LiMn2O4 was performed between 0.5 V and 1.05 V vs. Ag/AgCl at a scan rate of 0.5 mV s-1, while that of PI was between -0.85 and -0.1 V vs. Ag/AgCl. Galvanostatic charge-discharge and cycle performance tests were performed between -0.75 and 0 V vs. Ag/AgCl on Hukuto Denko battery charge/discharge system HJ series (Japan) controlled computer with continuous bubbling nitrogen to remove oxygen. The electrochemical performance of the full cell was tested between 0 and 1.75 V at the 6 ACS Paragon Plus Environment

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current density of 0.2 A g-1. Results and discussion Figure 1 shows the FT-IR spectra data collected from as-prepared PI and PI/AC composites. The characteristic absorption peaks at 1702 cm-1, 1671 cm-1 and 771 cm-1 is corresponding to νas (imide C=O), νs (imide C=O), and δ (imide C=O), respectively. The absorption peaks at 1583 cm-1 and 1351 cm-1 can be assigned to naphthalene and ν (imide C–N), respectively. These results from FT-IR are consistent with previous reports. 16 There are no significant differences among SEM images of composites. As is showed in Figure 2a-d, PI agglomerates are approximately varied from a few tenths µm to a fewµm in diameter, and PI/AC composites are a little bigger than pure PI in size. Figure 2e shows the TEM image of pure PI, which is agglomerate together. As observed in Figure 2f and Figure S1, activated carbon is coated by irregular PI. Results of the cyclic voltammetry of PI are presented in Figure 3. As shown in CV curve, both oxidation and reduction processes consist of two continuous steps associated with two electrons transfer respectively. The two redox peaks appear at -0.22V/-0.38V and -0.62V/-0.69V vs. Ag/AgCl, indicating the expected redox reactions at the proper potential. The electrochemical performance results of PI and PI/AC composite in different PI: AC mass ratios anodes are depicted in Figure 4 and Figure 7 ACS Paragon Plus Environment


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5. These data show that capacity, rate and cycling performance is correlated to the PI/AC mass ratio. The charge-discharge profiles of PI and PI/AC composites at different current densities are presented in Figure 4a-d. Without activated carbon included, as Figure 4a shows, PI electrode presents very low specific capacity at even low current density, only 20 mAh g-1 at the current density of 0.2 A g-1, and delivers almost no capacity at the current density of 0.5 A g-1. The delivered specific capacity increases with more activated carbon included in the composites anode. As is observed in Figure 4b, reversible capacity of the composite in a 50:50 PI/AC mass ratio decreases from 88 mAh g-1 to 73 mAh g-1 as the current density increases from 0.1 A g-1 to 2.0 A g-1, with a 17% capacity drop. While reversible specific capacity of the composite in a 60:40 PI/AC mass ratio decreases from 78 mAh g-1 to 53 mAh g-1 under the same current density range, as Figure 4c shows, with a 32% capacity drop. Meanwhile, Figure 4d shows that the composite in a 70:30 PI/AC mass ratio delivers a 47% capacity drop from 80 mAh g-1 to 42 mAh g-1. Figure 4e compares the rate performance of PI and PI/AC composites electrode in a pronounced difference. It is obvious that the PI/AC composite in a 50:50 mass ratio presents the best rate performance and highest capacity among these composites. Theoretically, increasing the relative amount of PI will result in a composite anode of higher energy density, since activated carbon delivers lower capacity than polyimide, 8 ACS Paragon Plus Environment

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which is seemingly not in line with the above results. However, that is because that polyimide cannot deliver its capacity completely with insufficient activated carbon, as the composites in 60:40 and 70:30 mass ratio did. There are no significant differences in cycling stability among PI and PI/AC composites in Figure 5, which shows the cycling performance at the current density of 0.2 A g-1 of PI and PI/AC composites, but different cycling capacity. As Figure 5 shows, PI electrode delivers quite low reversible capacity, about 20 mAh g-1 at the current density of 0.2 A g-1, but excellent cycling performance with little capacity fade. The capacity of the composite in a 50:50 PI/AC mass ratio at the first cycle is 87 mAh g-1. Then it slowly drops to 81 mAh g-1 at the 100th cycle with the capacity retention of 93%. While the capacity of the composite in a 60:40 PI/AC mass ratio delivers the capacity of 70 mAh g-1 at the 95th cycle with the capacity retention of 92%.Within 100 cycles, only 11% capacity drop is observed on the composite in a 70:30 PI/AC mass ratio electrode with the capacity of 67 mAh g-1 at the 100th cycle. Through the comparison of cycling performance of PI/AC composites, the composite in a 50:50 PI/AC mass ratio presents the highest capacity among these three composites with excellent cycling performance. From the above results, it is evident that the composite in a 50:50 PI/AC mass ratio presents the highest capacity, best rate and cycling performance among 9 ACS Paragon Plus Environment


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these composites. Compared with traditional anode materials of ARLB, the composite in a 50:50 PI/AC mass ratio presents higher capacity and better cycling performance, improving the electrochemical performance of ARLB. Considering the capacity, rate and cycling performance, the composite in a 50:50 PI/AC mass ratio was used as anode in concert with cathode LiMn2O4 for ARLB. LiMn2O4 have been regarded as one of the most promising cathode material in ARLB system. Cyclic voltammetry, charge-discharge and cycling tests were carried out in three-electrode cells. The cyclic voltammetry profile at a scan rate of 0.5mV s-1, as is showed in Figure 6a, presents two redox peaks of LiMn2O4 at 0.82V/0.72V and 0.97V/0.86V vs. Ag/AgCl, corresponding to two stages of intercalation/ deintercalation. LiMn2O4 delivers good rate performance and high capacity as shown in Figure 6b and c, with a discharge capacity of 107 mAh g-1 at the current density of 0.1 A g-1 and 92 mAh g-1 at the current density of 0.5 A g-1, namely the capacity retention of 86%. As Figure 6d shows, during the galvanostatic cycling between 0 and 1.05V vs. Ag/AgCl at the current density of 0.2 A g-1, 96% of the initial discharge capacity of 96 mAh g-1 is retained after 100 cycles, with the coulombic efficiency remained at above 97% for the duration of the cycling. All these data demonstrates that LiMn2O4 is a potential cathode material with good rate and cycling performance for ARLB. 10 ACS Paragon Plus Environment

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The mass ratio of LiMn2O4: PI/AC (in a 50:50 mass ratio) is set as 1:1.2 according to the charging capacity of LiMn2O4 and the discharging capacity of PI/AC composite in a 50:50 mass ratio (88:106) of the first cycle. As is observed in Figure 7a, PI-AC/LiNO3/LiMn2O4 full cell shows an average discharging voltage of 1.21V. An initial capacity of 42 mAh g-1 and a specific energy of 51Wh Kg-1 (based on the total weight of both active materials), with a capacity retention of 89% after 450 cycles, are illustrated at the current density of 0.2 A g-1 in Figure 7b. In addition, the coulombic efficiency is above 99% after the initial cycle. The cycling stability of the full cell for ARLB is much superior to traditional ARLB systems. Conclusions In summary, polyimide and activated carbon composites were produced and studied as anode for aqueous rechargeable lithium-ion batteries. Stable structure, low solubility and excellent cycling stability in aqueous solution make polyimide very attractive for use in ARLB. To enhance the poor electrical conductivity, the PI/AC composites in the mass ratio varying from 50:50 to 70:30 were produced by a simple polycondensation reaction between NTCDA and EDA. These PI/AC composites present different capacity, rate and cycling performance. By comparison, the composite in a 50:50 PI/AC mass ratio delivers the highest discharge capacity of 87 mAh g-1at the current density of 0.2 A g-1, 11 ACS Paragon Plus Environment


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the best rate and cycling performance among them, with a capacity retain of 93% after 100 cycles. LiMn2O4 has been examined to be a potential cathode material with good rate and cycling performance for ARLB. A sealed aqueous lithium-ion battery based on PI/AC composite (in a 50:50 mass ratio) anode and LiMn2O4 cathode has been implemented. The PI-AC/LiNO3/LiMn2O4 full cell delivers a special capacity of 42 mAh g-1 and energy density of 51Wh Kg-1 (based on both active materials), with a capacity retention of 89% after 450 cycles at the current density of 0.2 A g-1. The PI-AC/LiMn2O4 ARLB system presents high power density and excellent cycling performance, better than traditional ARLB systems. The PI/AC composite in a 50:50 mass ratio is demonstrated to be a potential anode with superior electrochemical performance for ARLB. Associated Content Supporting Information Information as mentioned in text. TEM of PI/AC composites in a mass ratio of 60:40 and 70:30; Charge-discharge profiles of PI electrode (PI: AB: PTFE= 30:60:10); Cycling profiles of PI electrode (PI: AB: PTFE= 30:60:10). Acknowledgements This work was partially supported by the National Natural Science Foundation of China (No. 21333002), the National Key Research and Development Plan (2016YFB0901503), and Shanghai Science & 12 ACS Paragon Plus Environment

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Technology Committee (13JC1407900). References (1) Wang, G. J.; Zhao, N. H.; Yang, L. C.; Wu, Y. P.; Wu, H. Q.; Holze, R. Characteristics of an aqueous rechargeable lithium battery (ARLB). Electrochim. Acta 2007, 52, 4911-4915. (2) Wang, Y. G.; Yi, J.; Xia, Y. Y. Recent progress in aqueous lithium-ion batteries. Adv. Energy Mater. 2012, 2, 830-840. (3) Wang, Y. H.; Chen, L.; Wang, Y. G.; Xia, Y. Y. Cycling stability of spinel LiMn2O4 with different particle sizes in aqueous electrolyte. Electrochim. Acta 2015, 173, 178-183. (4) Kohler, J.; Makihara, H.; Uegaito, H.; Inoue, H.; Toki, M. LiV3O8: characterization as anode material for an aqueous rechargeable Li-ion battery system. Electrochim. Acta 2000, 46, 59-65. (5) Liu, Z. T.; Qin, X. S.; Xu, H.; Chen, G. H. One-pot synthesis of carbon-coated nanosized LiTi2(PO4)3 as anode materials for aqueous lithium ion batteries. J. Power Sources 2015, 293, 562-569. (6) Suo, L.; Borodin, O.; Gao, T.; Olguin, M.; Ho, J.; Fan, X.; Luo, C.; Wang, C.; Xu, K. “Water-in-salt” electrolyte enables high voltage aqueous Li-ion chemistries. Science 2015, 350, 938-943. (7) Li, W.; Dahn, J. R.; Wainwright, D. Rechargeable lithium batteries 13 ACS Paragon Plus Environment


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Figure Captions Figure 1. FT-IR spectra (KBr pellets) of PI and PI/AC composites. Figure 2. SEM image of (a) PI, (b) PI/AC composite in a 50:50 mass ratio, (c) PI/AC composite in a 60:40 mass ratio and (d) PI/AC composite in a 70:30 mass ratio; TEM image of (e) PI and (f) PI/AC composite in a 50:50 mass ratio. Figure 3. CV profile of PI between -0.85 and -0.1V vs. Ag/AgCl at a scan rate of 0.5mV s-1. Figure 4. Charge-discharge profiles of (a) PI; (b) PI/AC composite in a 50:50 mass ratio; (c) PI/AC composite in a 60:40 mass ratio; (d) PI/AC composite in a 70:30 mass ratio; (e) rate performance of PI and PI/AC composites at different current densities between -0.75 and 0V vs. Ag/AgCl in 5M LiNO3. Figure 5. Cycling performance of PI and PI/AC composites at the current density of 0.2 A g-1 between -0.75 and 0V vs. Ag/AgCl in 5M LiNO3. Figure 6. (a). Cyclic voltammetry profiles of LiMn2O4 at a scan rate of 0.5 mV s-1; (b) charge-discharge profiles of LiMn2O4 at different current densities between 0.5 and 1.05V vs. Ag/AgCl in 5M LiNO3. Figure 7. (a) Charge-discharge profile and (b) cycling profiles of PI-AC/LiNO3/LiMn2O4 full cell at a current density of 0.2 A g-1 between 0 and 1.75V vs. Ag/AgCl in 5M LiNO3.



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Figure 1.


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Figure 2.



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Figure 3.


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Figure 4.



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Figure 5.


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Figure 6.



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Figure 7.


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Table of Content Graphics Title: Aqueous Lithium-ion Battery Using Polyimide-Activated Carbon Composites Anode and Spinel LiMn2O4 Cathode Authors: Zhaowei Guo, Long Chen, Jingyuan Liu, Yonggang Wang, Congxiao Wang, and Yongyao Xia ∗ Synopsis: The aqueous lithium-ion battery based on polyimide-activated carbon composites anode and LiMn2O4 cathode presented great rate and cycling performance.


Aqueous Lithium-Ion Batteries Using Polyimide-Activated Carbon

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