Iodine Battery Redox Chemistry in Ionic

Subscriber access provided by University of Florida | Smathers Libraries

Letter

Rechargeable Aluminum/Iodine Battery Redox Chemistry in Ionic Liquid Electrolyte Huajun Tian, Shunlong Zhang, Zhen Meng, Wei He, and Wei-Qiang Han ACS Energy Lett., Just Accepted Manuscript • Publication Date (Web): 24 Apr 2017 Downloaded from http://pubs.acs.org on April 24, 2017

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 Energy Letters 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 17

Rechargeable Aluminum/Iodine Battery Redox Chemistry in Ionic Liquid Electrolyte Huajun Tian*,†, ,Shunlong Zhang†,‡, , Zhen Meng†, Wei He†, Wei-Qiang Han*,†,‡,§ ⊥

⊥

†

Ningbo Institute of Materials Technology & Engineering, Chinese Academy of Sciences, Ningbo 315200, China ‡ School of Physical Science and Technology, Shanghai Tech University, Shanghai 201210, China § Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, China

Corresponding Author *E-mail: [email protected]; [email protected]

Abstract: Rechargeable aluminum ion batteries (RABs) have attracted much attention due to their high charge density, low cost and low flammability. However, the traditional cathodes used in RABs had limited intercalation ability of Al3+ ion, leading to a low capacity. We report for the first time a rechargeable aluminum/iodine (Al/I2) battery. The unique conversion reaction mechanism of the Al/I2 battery chemistry

avoids

the

cathode

material

disintegration

during

repeatedly

charge/discharge process, and this system successfully suppresses the shuttle of dissolved polyiodide in ionic liquid because of the hydrogen-bonding interaction, resulting in a robust rechargeable RABs system. The rechargeable Al/I2 battery based on the I3−/I− redox chemistry demonstrates highly reversible in Al3+ ion storage, providing a high capacity of > 200 mAhg-1 at 0.2 C, and high stability for even over 150 cycles at 1 C. This work provides a new insight in designing RABs system based on redox chemistry. TOC graphic

q * p * * * * l jk * **

e

o

n

m

0.8 0.7 0.6

50 0 200

0.8 1.0 1.2 1.4 1.6

*i h * 150 g * f * 100 e * d 50 *c * *b a 0.6 0.7 0.8 0.9 *1.0 isch

100 Capacity(mAh/g)

150

200

ge ar

50

Voltage(V)

1.1

q p o n m l k j i h g f e d c b a

* * * * * * * * * * * * * * * * *

Intensity(a.u.)

100

arg

150

0.9

Ch

200

1.0 Capacity(m Ah/g)

Voltage(V)

1.1

D

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 Energy Letters

80

120

160 -1

Raman shift (cm )

ACS Paragon Plus Environment

200

ACS Energy Letters 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

The “beyond Li-ion” batteries (Mg2+, Al3+, Ca2+, Zn2+ multivalent ions batteries) have attracted much attention due to their low cost, environmental friendliness, and high charge density.1-9 Rechargeable aluminum ion batteries (RABs) have been considered one of the most promising next-generation rechargeable battery because Al is the most abundant metal element in earth’s crust, and it can provide a remarkable volumetric capacity (8.05 Ahcm-3), which is four times higher than that of lithium. However, two major bottlenecks have hindered the development of RABs, including: (i) The difficulty to design proper electrolyte with wide electrochemical stability window, which can enable Al deposition/stripping highly reversible; (ii) Only a limited number of cathode materials can reversibly intercalate and de-intercalate Al3+ ion due to its difficult intercalation and the disintegration of traditional cathodes materials during the charge/discharge process. Graphite, one of the carbon-based materials, which was chosen to be a cathode for RABs for the first time by Michel Armand, has been proved to be a suitable candidate due to its effective electrochemical intercalation AlCl4- within graphite.10 Vatsala Rani et al. employed fluorinated natural graphite as cathode in RABs, providing a stable performance (>40 cycles) but only delivered a low operating voltage (～0.5V).11 Recently, Lin et al. used a three dimensional (3D) graphitic foam as cathode for RABs, showing a ～2 V operating voltage. However, despite the high working voltage, graphitic foam/Al battery cannot satisfy the demand of high energy density application because of its low capacity (～60 mAh/g).12 Therefore, it is urgent to find a high capacity cathode in RABs with high safety and long cycle life to meet the increasing demand of energy storage and conversion system. As a high capacity of cathode material, iodine (211 mAh g-1) has been proved a promising candidate in Li/I2, 13-15 Zn/I2, 16 Mg/I217-18 batteries. A rechargeable Al/I2 battery is highly attractive because its high energy density (～240 Wh/kg (total electrode)), reasonable theoretical operating voltage (～1.2 V) and low cost (See Calculation section). Xue firstly reported a primary Al/I2 battery and a dye-sensitized solar cell (DSSC) combination based on AlI3 electrolyte.19 Unfortunately, this Al/I2 primary ACS Paragon Plus Environment

Page 2 of 17

Page 3 of 17 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 Energy Letters

battery cannot be rechargeable. To be best of our knowledge, a rechargeable Al/I2 battery has not been reported mainly due to the obstacle of finding an appropriate iodine-based cathode and highly reversible Al deposition/stripping electrolyte. Herein, we report for the first time a rechargeable Al/I2 battery using PVP-I2 complex as cathode and room temperature ionic liquid as electrolyte. The hydrogen bonds existed between the PVP and iodine element guarantee the conversion reaction of I3−/I− redox pair in the cathode highly reversible, and effectively mitigates the shuttle effect of polyiodide towards the Al anode. The iodine-based cathode undergoes a conversion reaction mechanism in the Al/I2 battery as illustrated in Figure 1a, prompting a kind of novel redox chemistry in RABs system design. The Al/I2 battery was assembled by coupling a PVP-I2 complex cathode disk, a glass fiber separator and an Al foil anode into a Swagelok cell instead of coin cell. The electrolyte was made by mixing AlCl3 with 1-ethyl-3-methylimidazolium chloride (EMIC) in an atomic ratio of 1.3:1. In order to be free of continuous corrosion caused by this ionic liquid electrolyte, the Swagelok cell adopted Inconel alloy as current collector to resist the corrosive electrolyte rather than stainless steel as current collector, which ensures kinetic stability of the cell system.

20

The

deposition/striping process of the electrolyte was measured by coin cell and a Coulombic efficiency of close to 100% can be obtained (Figure S1), indicating that the Al deposition/striping process was highly reversible. The average diameter of typical PVP-I2 particles as shown in Figure S2 was around 50～120µm. In order to improve the electron transfer ability of the PVP-I2 cathode, the composites of PVP-I2 and Ketjenblack (KB) were ball milled for a half hour. After that, the smaller particles of active materials were obtained (Figure S3). More importantly, the PVP-I2 and conductive KB could be mixed homogenously (Figure S3) by ball milling method in order to improve the active materials utilization. The charge/discharge profile of Al/I2 battery shown in Figure 2a, displayed the typical voltage profile at a constant charge and discharge current density of 1/5 C with a single discharge plateau of ～0.74 V and charge plateau (～1.01 V). The discharge capacity of Al/I2 battery could reach 203.2mAhg-1(based on the mass of iodine) corresponding ACS Paragon Plus Environment


to an I2 utilization of ~91.6%. The cell can provide an energy density of > 150 Wh/kg (Figure 1b) at 0.2 C. Based on the total mass of PVP-I2 cathode, the overall capacity can reach 110.3 mAhg-1 by increasing the iodine content in PVP-I2 cathode. Taking the total mass of cathode and anode Al into consideration, it also could reach up to 71.7 Wh/kg (Figure S4). Having an advantage over lead-acid (40 Wh/kg), Ni–Cd(40 Wh/kg) and Ni-MH(50 Wh/kg) in energy density, but it is a bit lower compared with the lithium battery. 21 Further work on achieving high energy density of rechargeable Al/I2 battery is still ongoing. The Coulombic efficiency of the cell was 94.7%. To understand the reaction mechanism, The Al3+ ion storage of PVP-I2 electrode was investigated by cyclic voltammetry (CV). The CV of Al/I2 battery was scanned at a low rate of 0.1 mV/s (Figure 2b), and a major single cathodic peak at ～0.71V in first curve could be observed, while, a single anodic peak at ～1.05V could be observed. Combined with the chemical formula of PVP-I2 (Figure S5), the single peak could be corresponded to the I3−/I− redox couple. The Al/I2 battery showed a good electrochemical stability in the potential range at 0.2C (Figure 2c and 2d), showing a good cycling performance with a high capacity of 189.0 mAhg-1 even after 35 cycles. In contrast, we characterized the performance using the iodine as cathode in RABs (Figure S6). The process of preparing iodine cathode was the same with that of the PVP-I2 cathode. The discharge plateau of iodine cathode disappeared quickly after 2nd cycle. This following sloping profile in Figure S6 could be ascribed to the capacitive storage of the conductive KB in the cathode (Figure S7). The capacity fading of only iodine cathode could be attributed that the iodine had high solution in the electrolyte (Figure S8), resulting in severely uncontrollable shuttle effect and then resulted in a quick capacity degradation. This shuttle effect of the polyiodide is very similar to that of sulfur in Li/S chemistry.22-27 Therefore, the polyiodide shuttle effect can also be substantially prevented through host and electrolyte optimization. Further work on improving the physical/chemical properties of the host for better iodine utilization and absorbability of polyiodide is still ongoing. Moreover, Figure 2e showed the rate capability of PVP-I2 cathode in Al/I2 cell at different current rates. The capacity of the PVP-I2 cathode obtained at 0.2C, 0.5C and 1C are 207, 160.8 and ACS Paragon Plus Environment

Page 4 of 17

Page 5 of 17 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 Energy Letters

79.2 mAhg-1, respectively. After reducing the current density back to 0.5C, the capacity increased to 132.9 mAhg-1 again, indicating the excellent rate performance of this RABs system. The long cycling stability of Al/I2 battery was shown in Figure 2f, indicating a stable electrochemical performance even after >150 cycles at 1C. In order to verify the effective suppression of the shuttle effect of polyiodide for the hydrogen-bonding interaction existed in PVP-I2 complex, we did the solubility measurement as shown in Figure S8. The results indicated that the PVP-I2 would be easily saturated (2.4 g/100 mL). We also assembled a Li/PVP-I2 battery (Figure 3a), which could provide an obvious discharge plateau (～3.0V), which was a typical discharge voltage plateau of Li-I2 battery and it had a high Columbic efficiency (98.5%). The results of Li/PVP-I2 indicated that the unique hydrogen-bonding interaction of PVP-I2 could effectively hinder the shuttle effect of polyiodide. In order furtherly confirmed that the hydrogen-bonding interaction existed in PVP-I2 cathode, the Fourier transform infrared spectroscopy (FT-IR) was investigated as shown in Figure 3b. The FT-IR confirmed that a sharp peak at 3437 cm-1, which was attributed to OH stretching,

28

was observed in PVP sample, and this peak of PVP-I2 is widely

broadened and shifted to lower wavenumber at 3420 cm-1, indicating an interaction of hydrogen bonding between iodine species and PVP.29 Meanwhile, the exceptional bonding capability of PVP host to polyiodide is confirmed by color difference recorded using digital photographs (Figure S8). Even after 120h, the PVP-I2 particles are basically immiscible with the ionic liquid electrolyte, and the color of electrolyte shows no clear change from 15 min to 120h. The above experimental results and the structure of PVP-I2 (Figure S5) confirmed our hypothesis that this unique cathode successfully suppresses the shuttle effect of dissolved polyiodide in electrolyte because of the hydrogen-bonding interaction, resulting in a robust rechargeable RABs system. Figure 3c shows the high loading (> 1.5mg/cm2) PVP-I2 cathodes electrochemical performance. The high loading PVP-I2 cathode also exhibited a Al3+ ion storage behavior. However, the capacity would decrease with the increase of active materials ACS Paragon Plus Environment


loading (Figure 3c and Figure S9). When the loading of active material iodine is 200 mAh/g, corresponding to an energy density of > 150 Wh/kg(based on the mass of iodine) (Figure 1b) at 0.2 C, and excellent stability even after 150 cycles at 1C, which is one of the best RABs (Supplementary Table 1). The low cost, safe and unique rechargeable Al/I2 battery makes it a promising candidate for rechargeable multivalent metal ion battery.


Page 8 of 17

Page 9 of 17 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 Energy Letters

Acknowledgements This work is financially supported by the National Natural Science Foundation of China (Grant No. 51504234 and No. 51371186), Zhejiang Provincial Natural Science Foundation of China (Grant No. LY16E040001), the “Strategic Priority Research Program” of the Chinese Project Academy of Science (Grant No. XDA09010201), the Ningbo 3315 International Team of Advanced Energy Storage Materials, Zhejiang Province Key Science and Technology Innovation Team (Grant No. 2013TD16).

Supporting Information Available: This file includes experimental details and characterization of the materials, supplementary figures S1-S15, supplementary table 1

Notes Author Contributions ⊥These authors contributed equally. The authors declare no competing financial interest



References

(1) Aurbach, D.; Lu, Z.; Schechter, A.; Gofer, Y.; Gizbar, H.; Turgeman, R.; Cohen, Y.; Moshkovich, M.; Levi, E. Prototype Systems for Rechargeable Magnesium Batteries. Nature 2000, 407, 724-727. (2) See, K. A.; Chapman, K. W.; Zhu, L. Y.; Wiaderek, K. M.; Borkiewicz, O. J.; Barile, C. J.; Chupas, P. J.; Gewirth, A. A. The Interplay of Al and Mg Speciation in Advanced Mg Battery Electrolyte Solutions. J Am Chem Soc 2016, 138, 328-337. (3) Tutusaus, O.; Mohtadi, R.; Arthur, T. S.; Mizuno, F.; Nelson, E. G.; Sevryugina, Y. V. An Efficient Halogen-Free Electrolyte for Use in Rechargeable Magnesium Batteries. Angew Chem Int Edit 2015, 54, 7900-7904. (4) Chusid, O.; Gofer, Y.; Gizbar, H.; Vestfrid, Y.; Levi, E.; Aurbach, D.; Riech, I. Solid-state Rechargeable Magnesium Batteries. Adv Mater 2003, 15, 627-630. (5) Muldoon, J.; Bucur, C. B.; Gregory, T. Quest for Nonaqueous Multivalent Secondary Batteries: Magnesium and Beyond. Chem Rev 2014, 114, 11683-11720. (6) Jayaprakash, N.; Das, S. K.; Archer, L. A. The Rechargeable Aluminum-ion Battery. Chem Commun 2011, 47, 12610-12612. (7) Elia, G. A.; Marquardt, K.; Hoeppner, K.; Fantini, S.; Lin, R. Y.; Knipping, E.; Peters, W.; Drillet, J. F.; Passerini, S.; Hahn, R. An Overview and Future Perspectives of Aluminum Batteries. Adv Mater 2016, 28, 7564-7579. (8) Ponrouch, A.; Frontera, C.; Barde, F.; Palacin, M. R. Towards a Calcium-based Rechargeable Battery. Nat Mater 2016, 15, 169-173. (9) Zhang, N.; Cheng, F. Y.; Liu, Y. C.; Zhao, Q.; Lei, K. X.; Chen, C. C.; Liu, X. S.; Chen, J. Cation-Deficient Spinel ZnMn2O4 Cathode in Zn(CF3SO3) Electrolyte for Rechargeable Aqueous Zn-Ion Battery. J Am Chem Soc 2016, 138, 12894-12901. (10) Fouletier, M.; Armand, M., Electrochemical Method for Characterization of Graphite-Aluminium Chloride Intercalation Compounds. Carbon 1979, 17, 427-429. (11) Rani, J. V.; Kanakaiah, V.; Dadmal, T.; Rao, M. S.; Bhavanarushi, S. Fluorinated Natural Graphite Cathode for Rechargeable Ionic Liquid Based Aluminum-Ion Battery. J Electrochem Soc 2013, 160, A1781-A1784. (12) Lin, M. C.; Gong, M.; Lu, B. G.; Wu, Y. P.; Wang, D. Y.; Guan, M. Y.; Angell, M.; Chen, C. X.; Yang, J.; Hwang, B. J.; et al. An Ultrafast Rechargeable Aluminium-ion Battery. Nature 2015, 520, 325-328. (13) Zhao, Q.; Lu, Y. Y.; Zhu, Z. Q.; Tao, Z. L.; Chen, J. Rechargeable Lithium-Iodine Batteries with Iodine/Nanoporous Carbon Cathode. Nano Lett 2015, 15, 5982-5987. (14) Wang, Y. L.; Sun, Q. L.; Zhao, Q. Q.; Cao, J. S.; Ye, S. H. Rechargeable Lithium/iodine Battery with Superior High-rate Capability by Using Iodine-carbon Composite As Cathode. Energ Environ Sci 2011, 4, 3947-3950. (15) Yu, M. Z.; McCulloch, W. D.; Beauchamp, D. R.; Huang, Z. J.; Ren, X. D.; Wu, Y. Y. Aqueous Lithium-Iodine Solar Flow Battery for the Simultaneous Conversion and Storage of Solar Energy. J Am Chem Soc 2015, 137, 8332-8335. (16) Li, B.; Nie, Z. M.; Vijayakumar, M.; Li, G. S.; Liu, J.; Sprenkle, V.; Wang, W. Ambipolar Zinc-polyiodide Electrolyte for a High-energy Density Aqueous Redox Flow Battery. Nat Commun


Page 10 of 17

Page 11 of 17 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 Energy Letters

2015, 6, 6303-6310. (17) Bertasi, F.; Sepehr, F.; Pagot, G.; Paddison, S. J.; Di Noto, V. Toward a Magnesium-Iodine Battery. Adv Funct Mater 2016, 26, 4860-4865. (18) Tian, H.; Gao, T.; Li, X.; Wang, X.; Luo, C.; Fan, X.; Yang, C.; Suo, L.; Ma, Z.; Han, W.; Wang, C. High Power Rechargeable Magnesium/iodine Battery Chemistry. Nat Commun 2017, 8, 14083-14090. (19) Xue, B. F.; Fu, Z. W.; Li, H.; Liu, X. Z.; Cheng, S. C.; Yao, J.; Li, D. M.; Chen, L. Q.; Meng, Q. B. Cheap and Environmentally Benign Electrochemical Energy Storage and Conversion Devices Based on AlI3 Electrolytes. J Am Chem Soc 2006, 128, 8720-8721. (20) Gao, T.; Li, X.; Wang, X.; Hu, J.; Han, F.; Fan, X.; Suo, L.; Pearse, A. J.; Lee, S. B.; Rubloff, G. W. A Rechargeable Al/S Battery with an Ionic‐Liquid Electrolyte. Angewandte Chemie 2016, 55, 9898-9901. (21) Girishkumar, G.; Mccloskey, B.; Luntz, A. C.; Swanson, S.; Wilcke, W. Lithium−Air Battery: Promise and Challenges. Journal of Physical Chemistry Letters 2010, 1, 2193-2203. (22) Liang, X.; Hart, C.; Pang, Q.; Garsuch, A.; Weiss, T.; Nazar, L. F. A highly Efficient Polysulfide Mediator for Lithium-sulfur Batteries. Nat Commun 2015, 6, 5682-5689. (23) Chen, J. Z.; Han, K. S.; Henderson, W. A.; Lau, K. C.; Vijayakumar, M.; Dzwiniel, T.; Pan, H. L.; Curtiss, L. A.; Xiao, J.; Mueller, K. T.; et al. Restricting the Solubility of Polysulfides in Li-S Batteries Via Electrolyte Salt Selection. Advanced Energy Materials 2016, 6 , 1600160-1600165. (24) Park, K.; Cho, J. H.; Jang, J.-H.; Yu, B.-C.; De La Hoz, A. T.; Miller, K. M.; Ellison, C. J.; Goodenough, J. B. Trapping Lithium Polysulfides of a Li–S Battery by Forming Lithium Bonds in a Polymer Matrix. Energy Environ. Sci. 2015, 8, 2389-2395. (25) Wang, L.; Liu, J.; Yuan, S.; Wang, Y.; Xia, Y. To Mitigate Self-discharge of Lithium–sulfur Batteries by Optimizing Ionic Liquid Electrolytes. Energy Environ. Sci. 2016, 9, 224-231. (26) Kim, J. H.; Seo, J.; Choi, J.; Shin, D.; Carter, M.; Jeon, Y.; Wang, C.; Hu, L.; Paik, U. Synergistic Ultrathin

Functional

Polymer-Coated

Carbon

Nanotube

Interlayer

for

High

Performance

Lithium-Sulfur Batteries. ACS Appl Mater Interfaces 2016, 8, 20092-20099. (27) Zhang, S. S.; Tran, D. T.; Zhang, Z. Poly(acrylic acid) Gel as a Polysulphide Blocking Layer for High-performance Lithium/sulphur Battery. J. Mater. Chem. A 2014, 2, 18288-18292. (28) Sadeghi, F.; Ashofteh, M.; Homayouni, A.; Abbaspour, M.; Nokhodchi, A.; Garekani, H. A. Antisolvent Precipitation Technique: A Very Promising Approach to Crystallize Curcumin in Presence of Polyvinyl Pyrrolidon for Solubility and Dissolution Enhancement. Colloids and surfaces. B, Biointerfaces 2016, 147, 258-264. (29) Pažout, R.; Housková, J.; Dušek, M.; Maixner, J.; Kačer, P. Platinum Precursor of Anticancer Drug: a Structure Fixed by Long Intermolecular N–H···I and C–H···I Hydrogen Bonds. Structural Chemistry 2011, 22, 1325-1330. (30) Jung, N.; Crowther, A. C.; Kim, N.; Kim, P.; Brus, L. Raman Enhancement on Graphene: Adsorbed and Intercalated Molecular Species. Acs Nano 2010, 4, 7005-7013. (31) And, S. B. S.; Gellene, G. I. Ab Initio Calculations of the Ground Electronic States of Polyiodide Anions. Journal of Physical Chemistry A 1997, 101, 2192-2197. (32) Štangar, U. L. i.; Orel, B.; Vuk, A. S. u.; Sagon, G.; Colomban, P.; Stathatos, E.; Lianos, P. In Situ Resonance Raman Microspectroscopy of a Solid-State Dye-Sensitized Photoelectrochemical Cell. J Electrochem Soc 2002, 149 , E413-E423. (33) Sherwood, P. M. A. X-ray photoelectron Spectroscopic Studies of Some Iodine Compounds. Journal of the Chemical Society Faraday Transactions 1976, 72, 1805-1820.



(34) John F. Moulder;William F. Stickie, P. E. S., ;Kenneth D. Bomben. . Physical Electronics,Inc. 1992, 54-55. (35) Wang, H.; Gu, S.; Ying, B.; Shi, C.; Feng, W.; Wu, C. High-Voltage and Noncorrosive Ionic Liquid Electrolyte Used in Rechargeable Aluminum Battery. Acs Applied Materials & Interfaces 2016, 8, 27444-27448. (36) Wang, H.; Gu, S.; Bai, Y.; Chen, S.; Zhu, N.; Wu, C.; Wu, F. Anion-effects on Electrochemical Properties of Ionic Liquid Electrolytes for Rechargeable Aluminum Batteries. J. Mater. Chem. A 2015, 3, 22677-22686. (37) Wang, S.; Yu, Z.; Tu, J.; Wang, J.; Tian, D.; Liu, Y.; Jiao, S. A Novel Aluminum-Ion Battery: Al/AlCl3-[EMIm]Cl/Ni3S2@Graphene. Advanced Energy Materials 2016, 6, 1600137-1600146.


Page 12 of 17

Page 13 of 17 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 Energy Letters

(a)

Figure 1. Schematic illustration of the rechargeable Al/I2 battery. (a) Schematic of rechargeable Al/I2 batteries; (b)The capacity and voltage of the iodine cathode compared to reported rechargeable non-aqueous aluminum batteries (RABs) cathodes.


Voltage(V)

(a)

1.1

(b)

1.0 0.9 0.8 0.7 0.6 50

150

0.06 0.04 0.02 0.00 1 st 2 nd 3 rd 4 th 5 th

-0.02 -0.04 -0.06 0.5

200

0.6

0.7

0.8

0.9

1.0

1.1

1.2

3+ Voltage（ V vs.Al /Al）

Capacity(mAh/g)

(c) Current(mA) Voltage(V)

100

Page 14 of 17

1.2

1.3

1.0 0.8 0.6 0.02 0.00 -0.02 0

30

60

90

120

150

180

100 300 80 60

200 Iodine loading:1.2mg/cm2

Current density:0.2 C

20

Electrolyte: ionic liquid electrolyte(EMIC:AlCl3=1:1.3)

0 5

10

15

20

25

30

35

350 300

100

250

80

200

60

150 100

0.5C

0.2C

40

0.5C

1C

20

50 0

Cycle number

5

10

15

20

Cycle number

(f)

1C

100

200

80 60

100

40 20

0

30

60

90 Cycle number

120

150

Figure 2. (a) A typical galvanostatic charge/discharge curve of Al/I2 battery with PVP-I2 cathode and ionic liquid electrolyte; (b)Cyclic Voltammogram of the Al/I2 battery; (c)Charge and discharge voltage profiles of the Al/I2 battery in 180h; (d)Cycling performance of Al/I2 battery at 0.2C; (e)Rate capability of Al/I2 battery; (f) Cycling performance of Al/I2 battery at 1C.


Coulombic Efficiency

100

40

Capacity(mAh/g)

(e)

400


Capacity(mAh/g)

(d)


Test time(hour)

Capacity(mAh/g)

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

Current( mA/cm 2 )

ACS Energy Letters

Page 15 of 17 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 Energy Letters

Figure 3.(a)The typical charge/discharge curve of the PVP-I2/KB cathode in Li/I2 battery (Cathode: PVP-I2/KB; Anode: Li metal; Electrolyte: 1M LiTFSI in DME-DOL(1:1) with 1% LiNO3; Current density: C/5); (b) FT-IR spectra of PVP and PVP-I2 samples; (c) The discharge curves of PVP-I2 cathode with different iodine loading at 0.2C; (d) Discharge and charge profile of a typical rechargeable Al/I2 cell during the first cycle at the voltage range of 1.1-0.6V. The marked points are chosen to test the Raman spectra; (e) Raman of the corresponding point in Figure 3d of the rechargeable Al/I2 cell.



(a)

I 3d

Page 16 of 17

(b)

fresh PVP-I2

619.6 eV

Al 2p

Al Discharge 0.6 V

74.6 eV

Al Charge 1.1 V 618.6 eV

Discharge 0.6 V

77 Charge 1.0 V

632

628

624

74.75 eV

619.4 eV

620

616

Binding Energy(eV)

76

75

74

73

72

Binding Energy(eV) (c)

Al Discharge 0.6 V

632

628

624

I 3d

620

616

Binding Energy(eV)

Figure 4. X-ray photoelectron spectroscopy (XPS) study of the cathode and anode. (a) High resolution I 3d spectra of the PVP-I2 cathode; (b) High resolution Al 2p spectra of Al anode; (c) High resolution I 3d spectra of Al anode.


Page 17 of 17

(a) 1.1

50°C

(b)

dQ/dV

Voltage(V)

0.208 V

50°C 30°C

1.0 0.9 0.8 0.7

0.271 V

0.6 50

100

150

200

0.6

0.7

0.8

Capacity(mAh/g)

(c) 500

10 mV

6

10 -0.01Hz

0.9

1.0

1.1

Voltage(V)

(d) 1200

Z''(b) fitting result

Al/EMIC-AlCl3/Al

400

Al/EMIC-AlCl3/PVP-I2 cathode 10 mV

1000

0.6Hz

Z'' (b) (ohm)

Z'' (b) (ohm)

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 Energy Letters

300 200 100

6

10 -0.01Hz

800 600

0.6Hz

Z''(b) fitting result

400 200 0

0 0

200

400

600

800

1000

1200

0

200 400 600 800 1000 1200 1400 1600

Z' (a) (ohm)

Z' (a) (ohm)

Figure 5. (a) A typical galvanostatic charge/discharge curve of Al/I2 battery at temperature of 50 ºC; (b) dQ/dV curve of Al/I2 battery at temperature of 30 ºC and 50 ºC; (c) Electrochemical Impedance Spectrum (EIS) of Al/Al symmetrical cell; (d) EIS of the Al/I2 battery.


Iodine Battery Redox Chemistry in Ionic

Recommend Documents