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An Organic Cathode for Potassium Dual Ion Full Battery Ling Fan, Qian Liu, Zhi Xu, and Bingan Lu ACS Energy Lett., Just Accepted Manuscript • Publication Date (Web): 08 Jun 2017 Downloaded from http://pubs.acs.org on June 8, 2017

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ACS Energy Letters

An Organic Cathode for Potassium Dual Ion Full Battery Ling Fan,† Qian Liu, † Zhi Xu,‡ and Bingan Lu†,‡,§* †

School of Physics and Electronics, State Key Laboratory of Advanced Design and

Manufacturing for Vehicle Body, Hunan University, Changsha 410082, P. R. China . ‡

Material Technology Company Limited, Wing Lok Street, Sheung Wan, Hong Kong

999077, People’s Republic of China. §

State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese

Academy of Sciences. *Correspondence to (Lu B.) [email protected]

Abstract Potassium-based dual ion full batteries (PDIBs) were developed with graphite anode, polytriphenylamine (PTPAn) cathode as well as KPF6 based electrolyte. The PDIBs delivered a reversible capacity of 60 mA h g-1 at a median discharge voltage of 3.23 V at 50 mA g-1, with superior rate performance and long term cycling stability over 500 cycles (capacity retention of 75.5%). Unlike the traditional dual ion batteries (DIBs), the operation mechanism of the PDIBs with PTPAn cathode is that the PF6− ions interacted with the Nitrogen atom reversibly in the PTPAn cathode and the K+ ions

were

intercalated/deintercalated

into/from

the

charge/discharge process.

TOC GRAPHICS

ACS Paragon Plus Environment

graphite

anode

during

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The development of large scale electric energy storage systems (EESs) is crucial due to the intermittent and regional features of the renewable energy.1-4 Lithium ion batteries (LIBs), as one of the most effective energy storage devices, have been developed for decades and extensively used in our daily life currently5 despite the fact that the application for large scale EESs is hindered by the limited lithium resources.6 Therefore, more are focusing on the development of alternative ion batteries, including sodium ion batteries (SIBs),7-10 potassium ion batteries (PIBs)11-17 and dual ion batteries (DIBs)18-25 because of their low cost and abundant natural resources. As comparison, the DIBs seem to be more eco-friendly and more cost-effective because of their carbonaceous cathodes instead of the costly and toxic metal compound based cathodes.26-29 Nonetheless, the anions intercalation into traditional graphite cathode requires high voltage and often results in the decomposition of the traditional electrolyte, unless expensive ionic liquid based electrolytes are used.30 Therefore, it is necessary to develop suitable cathode materials for anion storage at relative low voltage. Organic compounds were reported to be used as cathode materials for lithium based DIBs and reduced the operating voltage effectively.31-33 At the same time, the organic materials are known to possess the merits of low cost, large-scale production, renewability, controllable synthetic process.34-36 Poly-triphenylamine (PTPAn), one of the most effective cathode materials for anion storage because of the proper mechanism of PF6− interaction with the Nitrogen atoms in the PTPAn, has been extensively investigated in lithium based dual ion batteries. On the other hand, PIBs (potassium ion batteries) may possess similar energy density as that of LIBs due to their close standard hydrogen potentials: K at -2.93 V vs. E0 and Li at -3.04 V vs. E0.37 Therefore, it is an obvious choice to apply organic compound as electrode material for rechargeable potassium-based dual ion batteries (PDIBs). The oxidation-reduction process of conducting polymer is known to be related to the gain or loss of electrons. For PDIBs, it was proposed for the first time that during oxidation process PTPAn was accounted for the electron loss at the chain, leading to the positively charged N+. During the reduction process, the PTPAn could accept


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electron and the N+ becomes N atom again (electric neutrality). In other words, the positively charged one N+ could interact with one PF6− to form a relative stable compound and absorb one PF6− from the electrolyte during charge process. During discharge process, one N+ will accept one electron to form one N atom and one PF6− will be released and dissolved into the electrolyte again. In order to prove the above proposed mechanism, we developed the PDIBs with PTPAn as cathode, graphite as anode and KPF6 as electrolyte for the first time. The PDIBs could deliver a reversible capacity of 49 mA h g-1 with a median discharge voltage of 3.2 V at the current density of 100 mA g-1. Besides, the PDIBs also exhibited excellent cycling stability over 500 cycles with the capacity retention of 75.5%, corresponding to a capacity decay of 0.049% per cycle. Furthermore, the operation mechanism of the PDIBs was verified: PF6− could interact with the N atom in the PTPAn cathode, while K+ could be intercalate/deintercalate into/from the graphite anode during charge/discharge process. The synthetic process (as shown in Figure S1) revealed that the PTPAn could be facilely synthesized by one-step polymerization of triphenylamine (TPAn). The synthesized PTPAn were characterized with the Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The FTIR in Figure S2 showed the typical chemical bonds of PTPAn. Typically, the peaks located at 1590, 1494, 1328, 1276, 1176, and 820 cm-1 were assigned to the C=C ring stretching, C-C stretching, the C-H bending, C-N stretching, C-H bending, C-C stretching, the C-H bending, C-N stretching, C-H bending and C-H out of plane vibration, respectively. The XRD curve of PTPAn (Figure S3) revealed a broad peak at around 2θ = 20o, consistent with the previously reports.38 A humpy peak located at 2θ = 26o was due to the π-stacking of conductive polymer.39 In addition, XPS measurement was performed (Figure S4a). Two distinct peaks located at 285 and 400 eV were observed, corresponding to the peaks of C1s and N1s, respectively. According to the high-resolution C1s XPS (Figure S4b), two distinct peaks represent bonds of C-C (284.8 eV) and C-N (285.6 eV) could be observed. While the peaks of 400.1 eV and 400.7 eV in the high-resolution N1s XPS (Figure S4c) are correspond to


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the C-N bonds of the PTPAn. Moreover, the nitrogen adsorption/desorption isotherms of the obtained PTPAn was performed (Figure S5). It could be seen that the surface area of the prepared PTPAn is 32 m2 g-1, and the corresponding pore size is 2-5 nm.

Figure 1. (a) The electron exchange of the PTPAn molecule during charge/discharge

process. The proposed mechanism of the PDIBs with a battery configuration of PTPAn cathode| KPF6 (electrolyte)| graphite anode. (b) Charging process. (c) Discharging process.

Figure 1a-c presents the proposed mechanism of the PDIBs with the configuration of PTPAn (cathode)| KPF6 (electrolyte)| graphite (anode). It could be seen that during the charge process (Figure 1a), the K+ in the electrolyte could move to the anode and further intercalate into the graphite to form meta-stable CxK compounds; at the same time, Nitrogen atoms in PTPAn (cathode) would lose electrons to form N+ ions, the PF6− ions in the electrolyte could be captured by the N+ in PTPAn cathode and form a meta-stable compound N+PF6− in the PTPAn of cathode. The amount of the lost electrons from Nitrogen atoms in cathode were equal to the ones accepted at the anode. As comparison, during discharge process, N+ ions in N+


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PF6− compound would accept electrons from the cathode to turn back into electrically natural N atoms. Then, PF6− ions would leave the cathode and dissolve back into the electrolyte. At the same time, negatively charged carbon atoms in CxK compounds would lose electrons to become electrically neutral carbon atoms. The amounts of electrons lost were equal to the amount accepted by the N+ in PTPAn cathode. Then, K+ ions would leave the anode and were dissolved into the electrolyte again. In another word, equal amount of PF6− ions were dissolved into the electrolyte to react with equal amount of K+ ions to form the stable KPF6 again during discharge process (Figure 1b).

Figure 2. The elemental mapping of the electrodes in PDIBs at the state of charged to

4.0 V and discharged to 1.0 V during the initial cycle. (a) The PTPAn cathode at the state of charged to 4.0 V. (b) The PTPAn cathode at the state of discharged to 1.0 V. (c) The graphite anode at the state of charged to 4.0 V. (d) The graphite anode at the state of discharged to 1.0 V. The scale bars in a–d are 200 nm, 300 nm, 200 nm, 400 nm, respectively.


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To verify the above hypothesis about the operation mechanism of the PDIBs, 2032 type of coin cells were assembled with the battery configuration of PTPAn (cathode)| 0.8M KPF6 in ethylene carbonate (EC): diethyl carbonate (DEC) (1:1, v/v) (electrolyte)| graphite (anode). Transmission electron microscope (TEM) and element mapping (Figure 2) were performed to investigate the content of PF6−/K+ in the cathode/anode at the state (charged to 4.0 V and discharged to 1.0 V). It could be seen that the PF6− could be detected in PTPAn cathode when the PDIBs was charged to 4.0 V (Figure 2a), and the corresponding atom ratio of N:F:P is 1:1.63:0.31. As comparison, the corresponding atom ratio of N:F:P was changed to 1:0.1:0.02 when discharged to 1.0 V (Figure 2b). The significant reduce of P and F elements at the state of discharged to 1.0 V indicating that the PF6− were released from the PTPAn during discharge process though a few PF6− ions retained. Meanwhile, the content of K in the graphite anode at the state of charged to 4.0 V and discharged to 1.0 V was further investigated. Figure 2c exhibited the element mapping of graphite anode when charged to 4.0 V. The atom ratio of C:K was 98.5:1.5, indicating the K+ intercalation into the graphite anode during charge process. In contrast, atom ratio of C:K changed to be 99.93:0.07 at the state of discharged to 1.0 V, suggesting the deintercalation of the K+ from the graphite anode during discharge process. In order to further investigate the proper mechanism of the interaction of PTPAn and PF6− during charge/discharge process, XPS was conducted (Figure 3). The full survey XPS spectrum of PTPAn electrode in Figure 3a revealed three peaks, located at around 285, 400 and 534 eV at the pristine state, corresponding to the peaks of C1s, N1s and O1s, respectively. The existence of O1s was assigned to the carboxyl methyl cellulose (CMC) in the PTPAn electrode. In addition, there were three new peaks around 135, 192 and 687 eV when charged to 4.0 V, corresponds to the P 2p, P 2s and F 1s, respectively. The increased elements content of P and F indicated that the PF6− ions had been incorporated into the PTPAn cathode successfully. As contrast, when the PDIBs were discharged to 1.0 V, the XPS peaks of P 2p and P2s disappeared and the F 1s weakened significantly, suggesting the release of the PF6− ions into the electrolyte during discharge process. The phenomenon of increased/decreased P and F


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element during charge/discharge process observed from XPS full survey was consistent with the TEM elemental mapping.

Figure 3. The XPS curves of the PTPAn electrode at different state in the PDIBs half

cells. (a) Full survey XPS. (b-d) High-resolution of N 1s XPS at the state of (b) pristine (c) charged to 4.0 V (d) discharged to 1.0 V.

Furthermore, the high-resolution N1s XPS of PTPAn electrode (Figure 3b) at the pristine state reveals two peaks located at 400 and 400.7 eV, corresponds to the C-N bonds of the PTPAn. When charged to 4.0 V (Figure 3c), the N1s XPS was almost the same as that of the pristine state except for a broad peak located at 402.3 eV, and the high value of 402.3 eV is located at the value of N+ salts. Though there is no report previously about the N1s XPS of the charged PTPAn electrode, we still can conclude that the peak located at 402.3 eV was assigned to the N+ PF6− compound on this occasion. Moreover, when the battery discharged to 1.0 V, the peak located at 402.3 eV was disappeared, indicating the release of PF6− during discharge process. In addition the PDIBs, the PTPAn electrodes were also assembled to sodium dual ion batteries and lithium dual ion batteries. The high resolution N1s XPS of the PTPAn (Figure S6) exhibits similar phenomenon, a peak at 402.3 eV was detected at charged


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state and disappeared at discharged state. At this point, the TEM elemental mappings along with the XPS measurements confirmed our hypothesis about the operation mechanism of the PDIBs.

Figure 4. The electrochemical performance of the PDIBs half cells with the graphite

anode or PTPAn cathode. (a) Cycle stability and (b) Rate performance of graphite anode with voltage range of 0.01-3.0 V. (c) Cycle stability of the PTPAn cathode at 100 mA g-1 with voltage range of 2.0-4.0 V. (d) The typical charge/discharge profiles of the half cells and full cells.

The half cells of the graphite anode and PTPAn cathode were investigated with the configuration of configuration of Potassium foil| 0.8M KPF6 in EC:DEC (1:1, v/v) (electrolyte)| graphite and PTPAn | 0.8M KPF6 in EC:DEC (1:1, v/v) (electrolyte)| Potassium foil, respectively. Figure 4a reveals the cycling stability of the graphite anode at the current density of 100 mA g-1 with voltage of 0.01-3.0 V. The battery could deliver a reversible capacity of 210 mA h g-1 after 70 cycles without obviously capacity decay. Besides, it also exhibits excellent rate performance (Figure 4b) with capacity of 260, 225, 200, 178, 158 and 122 mA h g-1 at the current density of 50, 100, 200, 300, 400, and 500 mA g-1, respectively. Notably, when the current density


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returns to 50 mA g-1, a reversible capacity of 250 mA h g-1 still could be recovered, indicating its superior rate cyclicity. While for the PTPAn cathode, a reversible capacity of 71 mA h g-1 was obtained after 60 cycles at the current density of 100 mA g-1 (Figure 4c). The capacity is below its theoretical capacity, which might be account for the low surface area of the PTPAn, cause the porosity of organic electrode is one of important parameter to its good electrochemical performance.40-41 The typical charge/discharge profiles of the PTPAn or graphite half cells and the PDIBs full cells are shown in Figure 4d.

According to the operation mechanism of the PDIBs, the

charge process of the PTPAn-graphite full cell is corresponds to the charge process of the K-PTPAn half-cell and the discharge process of the K-graphite half-cell, which means the interaction process of PF6−/K+ with PTPAn/graphite; the discharge process of the PTPAn-graphite full cell is corresponds to the discharge process of the K-PTPAn half-cell and the charge process of the K-graphite half-cell, which means the desertion process of PF6−/K+ from PTPAn/graphite. The electrochemical properties of the PTPAn-graphite full cells were investigated with 2032 type cells with the configuration of PTPAn (cathode)| 0.8M KPF6 in EC:DEC (1:1, v/v) (electrolyte)| graphite (anode). Figure 5a presented the typical cyclic voltammetry (CV) curve of the PDIBs at the scan rate of 0.5 mV s-1. Three peaks located at 3.4, 3.85 and 3.99 V were assigned to the different interaction process of PF6−/K+ with PTPAn/graphite during charge process. Besides, three peaks around 3.67, 3.23 and 2.61 V were corresponding to the different desertion process of PF6−/K+ from PTPAn/graphite during discharge process. The typical charge/discharge profile of the PDIBs in Figure 5b exhibited that the charging platform was mainly over 3.5 V, corresponding to the intercalation process of K+ into graphite as well the interaction effect of PF6− into PTPAn. Conversely, one small discharge platform at around 3.65 V along with the long tilted discharge platform (3.5~2.5 V) was observed during discharge process, which was assigned to the release process of K+/PF6− from the graphite/PTPAn electrode and back into the electrolyte. It was worth mentioning that the battery could deliver a discharge capacity of 60 mA g-1 with the median


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discharge voltage of 3.23 V. Moreover, the dQ/dV (Figure 5b insert) calculated from the charge/discharge profile is agree well with the CV curve.

Figure 5. The electrochemical properties of the PDIBs. (a) The CV curve at the scan

rate of 0.5 mV s-1. (b) The typical charge/discharge profile at the current density of 50 mA g-1. Insert, the dQ/dV calculated from the charge/discharge profile. (c) The rate performance at various current densities of 50~300 mA g-1. The long-term cycling stability at the current density of

(d) 50 mA g-1 and (e) 100 mA g-1.


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Figure 5c presents the rate performance of the PDIBs at various current densities of 50~300 mA g-1. The PDIBs could deliver the reversible capacity of 44, 39, 35, 31, and 28 mA h g-1 at the current density of 100, 150, 200, 250, and 300 mA g-1, respectively. In addition, when the current density returned back to 100 mA g-1, a reversible capacity of 40 mA h g-1 could be recovered, indicating the superior capacity recoverability after cycling at high rates. Besides, when a low current density was applied, a high discharge capacity of 60 mA g-1 could be obtained. Moreover, the Coulombic efficiency could be reached to 87%, 91%, 93%, 95%, and 96% at the current density of 100, 150, 200, 250, and 300 mA g-1, respectively. Furthermore, though a low current density of 50 mA g-1 was applied, the Coulombic efficiency is still could reach to around 80%. Similar phenomenon was reported previously in literatures.24, 29, 42 And the corresponding charge/discharge profiles of the PDIBs at various current densities were present in Figure S7. The PDIBs not only exhibited excellent rate performance, but also delivered superior long-term cycling stability. The cycling stability of the PDIBs was performed at the current density of 50 mA g-1 and 100 mA g-1 (Figure 5d and 5e). The PDIBs could deliver a reversible discharge capacity of 52 mA h g-1 after 120 cycles with capacity retention of 89.2%. Notably, when a high current density of 100 mA g-1 was used, the PDIBs could deliver a charge/discharge capacity of 49/52 mA h g-1, corresponding to a Coulombic efficiency of 94%. In addition, after long-term cycling for over 500 cycles, a reversible discharge capacity of 37 mA h g-1 still could be obtained with the capacity retention of 75.5%, corresponding to a capacity decay of 0.049% per cycle. Besides, the Coulombic efficiency was still over 85% even after 500 cycles. The TEM elemental mapping of the PDIBs was further performed after 50 cycles (Figure S8). The atom ratio of N:F:P was 1:2.06:0.36 at the state of charged to 4.0 V (Figure S8a) while the atom ratio turned to be 1:0.17:0.06 when discharged to 1.0 V (Figure S8b).

Furthermore, the content of K in the graphite anode at the state of

charged to 4.0 V (Figure S8c) and discharged to 1.0 V (Figure S8d) after 50 cycles was further investigated. The atom ratio of C:K was 98.76:1.24 and 99.75:0.25 at the state of charged to 4.0 V and discharged to 1.0 V, respectively. The change of atom


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ratio (N:P:F and C:K)

after 50 cycles was similar to that observed in the initial cycle,

indicating that the PTPAn/graphite could reversibly accept the PF6−/K+ even after 50 cycles. In summary, we have developed a potassium based dual ion full cell. The PDIBs exhibited high median discharge voltage of 3.23V and discharge capacity of 60 mA h g-1, superior rate performance and excellent cycling stability over 500 cycles with a capacity retention of 75.5%, corresponding to a capacity decay of 0.049% per cycle. The TEM elemental mappings and XPS measurements revealed that the graphite and N atoms in PTPAn could reversibly accept the K+ and PF6−, respectively during charge/discharge process. This paper may provide guidance for exploring new cathode materials for DIBs besides the graphite intercalation compounds.

ASSOCIATED CONTENT Supporting Information. Experimental methods, synthesis process; FTIR; XRD; XPS; surface area; Elemental mapping after 50 cycles AUTHOR INFORMATION L. Fan and Q. Liu contributed equally to this work. *E-mail: [email protected] Notes The authors declare no competing financial interest. ACKNOWLEDGMENT This work was financially supported by National Natural Science Foundation of China (Nos. 51672078 and 21473052) and Hunan University State Key Laboratory of Advanced Design and Manufacturing for Vehicle Body Independent Research Project (No. 71675004), Hunan Youth Talents (2016RS3025), and Foundation of State Key Laboratory of Coal Conversion (Grant No. J17-18-903). REFERENCES (1) Schon, T. B.; McAllister, B. T.; Li, P. F.; Seferos, D. S. The Rise of Organic Electrode Materials for Energy Storage. Chem. Soc. Rev. 2016, 45, 6345-6404.


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(2) Zhou, H. S. New Energy Storage Devices for Post Lithium-Ion Batteries. Energy Environ. Sci. 2013, 6, 2256-2256. (3) Luo, W.; Shen, F.; Bommier, C.; Zhu, H.; Ji, X.; Hu, L. Na-Ion Battery Anodes: Materials and Electrochemistry. Acc. Chem. Res. 2016, 49, 231-240. (4) Luo, W.; Jian, Z.; Xing, Z.; Wang, W.; Bommier, C.; Lerner, M. M.; Ji, X. Electrochemically Expandable Soft Carbon as Anodes for Na-Ion Batteries. ACS Cent. Sci. 2015, 1, 516-522. (5) Pang, Q.; Kundu, D.; Nazar, L. F. A Graphene-Like Metallic Cathode Host for Long-Life and High-Loading Lithium–Sulfur Batteries. Mater. Horiz. 2016, 3, 130-136. (6) Wang, X.; Fan, L.; Gong, D.; Zhu, J.; Zhang, Q.; Lu, B. Core-Shell Ge@Graphene@TiO2Nanofibers as a High-Capacity and Cycle-Stable Anode for Lithium and Sodium Ion Battery. Adv. Funct. Mater. 2016, 26, 1104-1111. (7) Fan, L.; Lu, B. Reactive Oxygen-Doped 3D Interdigital Carbonaceous Materials for Li and Na Ion Batteries. Small 2016, 12, 2783-2791. (8) Fan, L.; Ma, R. F.; Yang, Y. H.; Chen, S. H.; Lu, B. A. Covalent sulfur for advanced room temperature sodium-sulfur batteries. Nano Energy 2016, 28, 304-310. (9) Sun, J.; Lee, H. W.; Pasta, M.; Yuan, H.; Zheng, G.; Sun, Y.; Li, Y.; Cui, Y. A Phosphorene-Graphene Hybrid Material as a High-Capacity Anode for Sodium-Ion Batteries. Nat. Nanotechnol. 2015, 10, 980-985. (10)Wang, Y. X.; Yang, J.; Chou, S. L.; Liu, H. K.; Zhang, W. X.; Zhao, D.; Dou, S. X. Uniform Yolk-Shell Iron Sulfide-Carbon Nanospheres for Superior Sodium-Iron Sulfide Batteries. Nat. Commun. 2015, 6, 8689. (11) Jian, Z.; Luo, W.; Ji, X. Carbon Electrodes for K-Ion Batteries. J. Am. Chem. Soc. 2015, 137, 11566-11569. (12) Share, K.; Cohn, A. P.; Carter, R.; Rogers, B.; Pint, C. L. Role of Nitrogen Doped Graphene for Improved High Capacity Potassium Ion Battery Anodes. Acs Nano 2016, 10, 9738-9744. (13) Su, D.; McDonagh, A.; Qiao, S. Z.; Wang, G. High-Capacity Aqueous Potassium-Ion Batteries for Large-Scale Energy Storage. Adv. Mater. 2017, 29, 1604007. (14) Wang, X.; Xu, X.; Niu, C.; Meng, J.; Huang, M.; Liu, X.; Liu, Z.; Mai, L. Earth Abundant Fe/Mn-Based Layered Oxide Interconnected Nanowires for Advanced K-Ion Full Batteries. Nano Lett. 2017, 17, 544-550. (15) Xue, L.; Li, Y.; Gao, H.; Zhou, W.; Lu, X.; Kaveevivitchai, W.; Manthiram, A.; Goodenough, J. B. Low-Cost High-Energy Potassium Cathode. J. Am. Chem. Soc. 2017, 139, 2164-2167. (16) Zhang, C. L.; Xu, Y.; Zhou, M.; Liang, L. Y.; Dong, H. S.; Wu, M. H.; Yang, Y.; Lei, Y. Potassium Prussian Blue Nanoparticles: A Low-Cost Cathode Material for Potassium-Ion Batteries. Adv. Funct. Mater. 2017, 27, 1604307. (17) He, G.; Nazar, L. F. Crystallite Size Control of Prussian White Analogues for Nonaqueous Potassium-Ion Batteries. ACS Energy Lett. 2017, 1122-1127. (18) Ishihara, T.; Yokoyama, Y.; Kozono, F.; Hayashi, H. Intercalation of PF6− Anion into Graphitic Carbon with Nano Pore for Dual Carbon Cell with High Capacity. J.


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Power Sources 2011, 196, 6956-6959. (19) Qi, X.; Blizanac, B.; DuPasquier, A.; Meister, P.; Placke, T.; Oljaca, M.; Li, J.; Winter, M. Investigation of PF6(-) and TFSI(-) Anion Intercalation into Graphitized Carbon Blacks and Its Influence on High Voltage Lithium Ion Batteries. Phys. Chem. Chem. Phys. 2014, 16, 25306-25313. (20) Read, J. A.; Cresce, A. V.; Ervin, M. H.; Xu, K. Dual-Graphite Chemistry Enabled by a High Boltage Electrolyte. Energy Environ. Sci. 2014, 7, 617-620. (21) Syzdek, J.; Marcinek, M.; Kostecki, R. Electrochemical Activity of Carbon Blacks in LiPF6− Based Organic Electrolytes. J. Power Sources 2014, 245, 739-744. (22) Read, J. A. In-Situ Studies on the Electrochemical Intercalation of Hexafluorophosphate Anion in Graphite with Selective Cointercalation of Solvent. J. Phys. Chem. C 2015, 119, 8438-8446. (23) Deunf, É.; Jiménez, P.; Guyomard, D.; Dolhem, F.; Poizot, P. A Dual–Ion Battery using Diamino–Rubicene as Anion–Inserting Positive Electrode Material. Electrochem. Commun. 2016, 72, 64-68. (24) Fan, L.; Liu, Q.; Chen, S.; Xu, Z.; Lu, B. Soft Carbon as Anode for High-Performance Sodium-Based Dual Ion Full Battery. Adv. Energy Mater. 2017, 7, 1602778. (25) Fan, L.; Liu, Q.; Chen, S., Lin, K.; Xu, Z.; Lu, B. Potassium-Based Dual Ion Battery with Dual-Graphite Electrode. Small 2017, DOI: 10.1002/smll.201701011. (26) Shi, X.; Zhang, W.; Wang, J.; Zheng, W.; Huang, K.; Zhang, H.; Feng, S.; Chen, H. (EMIm)+(PF6)−Ionic Liquid Unlocks Optimum Energy/Power Density for Architecture of Nanocarbon-Based Dual-Ion Battery. Adv. Energy Mater. 2016, 6, 1601378. (27) Tong, X.; Zhang, F.; Ji, B.; Sheng, M.; Tang, Y. Carbon-Coated Porous Aluminum Foil Anode for High-Rate, Long-Term Cycling Stability, and High Energy Density Dual-Ion Batteries. Adv. Mater. 2016, 28, 9979-9985. (28) Zhang, F.; Ji, B.; Tong, X.; Sheng, M.; Zhang, X.; Lee, C.-S.; Tang, Y. A Dual-Ion Battery Constructed with Aluminum Foil Anode and Mesocarbon Microbead Cathode via an Alloying/Intercalation Process in an Ionic Liquid Electrolyte. Adv. Mater. Interfaces 2016, 3, 1600605. (29) Zhang, X. L.; Tang, Y. B.; Zhang, F.; Lee, C. S. A Novel Aluminum-Graphite Dual-Ion Battery. Adv. Energy Mater. 2016, 6, 1502588. (30) Rodriguez-Perez, I. A.; Jian, Z. L.; Waldenmaier, P. K.; Palmisano, J. W.; Chandrabose, R. S.; Wang, X. F.; Lerner, M. M.; Carter, R. G.; Ji, X. L. A Hydrocarbon Cathode for Dual-Ion Batteries. ACS Energy Lett. 2016, 1, 719-723. (31) 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. (32) Peng, Z.; Yi, X.; Liu, Z.; Shang, J.; Wang, D. Triphenylamine-Based Metal-Organic Frameworks as Cathode Materials in Lithium-Ion Batteries with Coexistence of Redox Active Sites, High Working Voltage, and High Rate Stability. ACS Appl. Mater. Interfaces 2016, 8, 14578-14585. (33) Su, C.; Zhu, X. G.; Xu, L. H.; Zhou, N. N.; He, H. H.; Zhang, C. Organic Polytriphenylamine Derivative-Based Cathode with Tailored Potential and Its


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ACS Energy Letters

Electrochemical Performances. Electrochim. Acta 2016, 196, 440-449. (34) Liang, Y. L.; Tao, Z. L.; Chen, J. Organic Electrode Materials for Rechargeable Lithium Batteries. Adv. Energy Mater. 2012, 2, 742-769. (35) 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. (36) Su, C.; Yang, F.; Ji, L. L.; Xu, L. H.; Zhang, C. Polytriphenylamine Derivative with High Free Radical Density as the Novel Organic Cathode for Lithium Ion Batteries. J. Mater. Chem. A 2014, 2, 20083-20088. (37) Zhang, W.; Mao, J.; Li, S.; Chen, Z.; Guo, Z. Phosphorus-Based Alloy Materials for Advanced Potassium-Ion Battery Anode. J. Am. Chem. Soc. 2017, 139, 3316-3319. (38) Ni, W.; Cheng, J. L.; Li, X. D.; Gu, G. F.; Huang, L.; Guan, Q.; Yuan, D. M.; Wang, B. Polymeric Cathode Materials of Electroactive Conducting Poly(triphenylamine) with Optimized Structures for Potential Organic Pseudo-Capacitors with Higher Cut-off Voltage and Energy Density. RSC Adv. 2015, 5, 9221-9227. (39) Fan, L.; Cui, R. L.; Jiang, L. H.; Zou, Y. P.; Li, Y. F.; Qian, D. A New Small Molecule with Indolone Chromophore as the Electron Accepting Unit for Efficient Organic Solar Cells. Dyes Pigm. 2015, 113, 458-464. (40) Zhang, C.; Yang, X.; Ren, W.; Wang, Y.; Su, F.; Jiang, J.-X. Microporous Organic Polymer-Based Lithium Ion Batteries with Improved Rate Performance and Energy Density. J. Power Sources 2016, 317, 49-56. (41) Zhang, Y.; Wang, J.; Riduan, S. N. Strategies Toward Improving the Performance of Organic Electrodes in Rechargeable Lithium (Sodium) Batteries. J. Mater. Chem. A 2016, 4, 14902-14914. (42) Ji, B.; Zhang, F.; Song, X.; Tang, Y. A Novel Potassium-Ion-Based Dual-Ion Battery. Adv. Mater. 2017, DOI: 10.1002/adma.201700519.


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