Electrochemical Performance of Sb4O5Cl2 as a New Anode Material

Subscriber access provided by Washington University | Libraries

Energy, Environmental, and Catalysis Applications

Electrochemical Performance of Sb4O5Cl2 as a new Anode Material in aqueous Chloride Ion Battery Xiaoqiao Hu, Fuming Chen, Shaofeng Wang, Qiang Ru, Benli Chu, Chengyan Wei, Yumeng Shi, Zhicheng Ye, Yanxu Chu, Xianhua Hou, and Linfeng Sun ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b21652 • Publication Date (Web): 11 Feb 2019 Downloaded from http://pubs.acs.org on February 11, 2019

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 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 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.

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

ACS Applied Materials & Interfaces

Electrochemical Performance of Sb4O5Cl2 as a new Anode Material in aqueous Chloride Ion Battery Xiaoqiao Hua, Fuming Chena*, Shaofeng Wanga, Qiang Rua, Benli Chua, Chengyan Weib, Yumeng Shic, Zhicheng Yed, Yanxu Chud, Xianhua Houa*, Linfeng Sune* a Guangdong Provincial Key Laboratory of Quantum Engineering and Quantum Materials, Guangdong Engineering Technology Research Center of Efficient Green Energy and Environment Protection Materials, School of Physics and Telecommunication Engineering, South China Normal University, Guangzhou 510006, China b Guangdong Zhaoqing Institute of Quality Inspection & Metrology, Zhaoqing, 526070, China c College of Optoelectronic Engineering, Shenzhen University, Shenzhen China, 518060 d Huizhou Dongjiang Veolia Environmental Services Co., Ltd, Huizhou, China, 516323 e Department of Energy Science, Sungkyunkwan University, Suwon, Korea 16419 Email: [email protected]; [email protected]; [email protected]

Keywords: Chloride ion battery; Sb4O5Cl2; Energy storage device; chloride ion electrochemistry; aqueous battery

Abstract: Chloride ion battery is considered as the promising electrochemical system due to its high energy density in theory. However, aqueous chloride ion redox materials are limitedly reported owing to its instability or dissolution in aqueous electrolyte. Here, we synthetize a new electrochemical chloride ion material, Sb4O5Cl2, investigate its electrochemical performance in aqueous NaCl electrolyte, and assemble into aqueous chloride ion battery with silver as cathode. During the battery charge process, Sb4O5Cl2 anode electrochemically releases the chloride ions, which captured by Ag cathode with the formation of silver chloride while the discharging reverses the process. The battery demonstrates favorable electrochemical performance. With current density of 600 mA g-1, the battery discharge capacity of 34.6 mAh g-1 can 1 / 16

ACS Paragon Plus Environment

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

be maintained for 50 cycles. This work is greatly significant for the development of anion electrochemical energy storage.

The demand of energy-related resources is increasing with the growing population. The electrochemical energy storage system with high energy density, reliability, sustainability, safety, and environment friendliness is also required for the actual application. A mass of research works in the electrochemical energy storage have been majorly focused on the cation transfer such as lithium ion battery1-10, sodium ion battery11, 12, hydrogen fuel cells etc13. Sodium-ion batteries have recently been paid to the great research interests owing to the prominent merits like the low cost, natural abundance and the suitable redox potential and the better performance than that of their lithium-ion capacitor counterparts14-18. In particular, the research focused on the anionic transfer is very rare. The anion electrochemistry as energy storage device has attracted a lot of attention because of the transportation property of negative ions19, 20. Chloride ion battery system has been considered as a promising electrochemical system owing to its theoretical capacity up to 2500 mAh g-1 for selected couples of electrochemical electrodes and rich natural source21, which is comparable to main stream advanced energy storage technologies like Li–S22-24, and Li-O225-28. In the pioneer works, chloride containing chemicals in organic solvents or ionic liquids was chosen as the 2 / 16


Page 2 of 16

Page 3 of 16 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


electrolytes of chloride ion battery29-34. Searching for appropriate electrode materials in aqueous condition is a challenge due to materials instability or dissolution in electrolyte. Very few materials are suitable. Based on the previous reports, only two materials, BiOCl and silver, are suitable for water-based chloride ion battery system35, where the aqueous NaCl was used as electrolyte with silver cathode and BiOCl anode. In this work, Sb4O5Cl2 was synthesized because the synthesis cost is lower compared with other materials, and its behavior of chloride ion electrochemistry was investigated. The water-based chloride shuttle battery was assembled in salt water electrolyte and silver was chosen as cathode. The reaction mechanisms and electrochemical performance were analyzed

using

the

cyclic

voltammetry

and

electrochemical

charge/discharge process. With the current density of 600 mA g−1 applied the battery discharge capacity is 41.0 mAh g-1 at the 10th cycle, and is maintained at 34.6 mAh g-1 after cycle 50. The water-based rechargeable chloride ion battery will contribute greatly to salty water battery and seawater desalination.

Results and discussion The characterization of the scanning electron microscopy and X-ray diffraction was conducted for our synthesized Sb4O5Cl2 and Ag, as demonstrated in Fig. 1. The particle size of the as-synthesized Sb4O5Cl2 is 3 / 16



only few micron meters. All the peaks in XRD spectra are assigned to Sb4O5Cl2 in Figure 1b, and there are no additional peaks. Figure 1c shows the SEM of silver nanoparticles, well embedded inside carbon nanotubes matrix. Ag particles can be separated adequately to reduce agglomeration of Ag particles; in addition, the electrical conductivity can be increased. The entire XRD pattern can be well indexed to the silver as displayed in Figure 1d. These results confirmed that Sb4O5Cl2 and silver particles were successfully synthesized.

Figure 2 shows the schematic for the Sb4O5Cl2/Ag aqueous rechargeable processes in chloride ion battery. During battery charge as displayed in Figure 2a, the chloride ions are released to electrolyte from Sb4O5Cl2 anode and are captured by Ag electrode with the formation of AgCl. The equilibrium electrons transfer from Ag to Sb4O5Cl2 in the external electrical circuit. The discharging process reverses ion movement as demonstrated in Figure 2b. At this process, chloride ions will escape from the positive electrode with the recovery of silver and be inserted back into negative electrode. At the same time electrons move towards the reverse direction.

In order to better understand the electrochemical reaction mechanism, the cyclic voltammetry test was conducted with Sb4O5Cl2 working electrode, 4 / 16


Page 4 of 16

Page 5 of 16 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


platinum grid counter, and Ag/AgCl reference electrode in 1M NaCl salt electrolyte. The scan rate is 0.8 mV s-1 in this process and the results are shown in Figure 3a. The major peaks at -0.13 V and 0.16 V are assigned to electrode oxidation and the corresponding peaks of reduction are located at -0.87 V and -0.23 V. There are two obvious overlapping reduction peaks close to -0.87 V. Hence, Sb4O5Cl2 is suitable as a negative electrode. At the 1st cycle, the peaks of reduction are at -1.17 V and -0.37 V, which could indicate the formation of solid electrolyte interphase film. The purpose is to find new materials Sb4O5Cl2, and to show that Sb4O5Cl2 can be applied in water system chloride ion batteries. Based on the CV testing results, it can be seen from the performance analysis that Sb4O5Cl2 meets the requirements in the water based chloride ion electrochemistry. Ag is an appropriate positive electrode material for water-system chloride ion batteries, as shown in Figure 3b. It presents the two-electrode CV with Sb4O5Cl2 as anode, Ag cathode, and NaCl salt solution as electrolyte. The scan rate is controlled at 0.8 mV s-1. During the testing, no distinct hydrogen and oxygen evolution can be observed. At the 1st cycle, a major cathodic peak is located at 1.18 V and a tiny irreversible peak at 0.33 V that disappears in the subsequent cycles. The reason is due to minor impurities reaction during the 1st cycle. From the 2nd circle, CV curves demonstrate one pair of broad redox peaks, assigned to chloride ion extraction/insertion at electrodes. The cathodic peaks at 5 / 16



Page 6 of 16

1.06 V are caused by chloride ions insertion to silver from Sb4O5Cl2 with the formation of AgCl. The reaction equations can be described as following Eqs. (1) and (2) during the charging process: Positive electrode:

Ag + Cl- → AgCl + e-

(1)

During the charge process, silver is oxidized to form AgCl with the 150% volume expansion. During the discharge process, the silver recovery causes a 39.9% volume shrink. Negative electrode: Sb4O5Cl2+xe→Sb4O5Cl2-x + xCl-

(2)

The peak of reduction is located at 0.13 V, and it is characteristic of the transfer of chloride ions from positive electrode to negative electrode. The overall reaction of the Sb4O5Cl2/Ag system can be expressed as follows: xAg + Sb4O5Cl2 → xAgCl + Sb4O5Cl2-x

(3)

The x refers the number of transferred chloride ions during charging/discharging process. Figure 4 demonstrates the typical cycle capability of Sb4O5Cl2/Ag electrodes system with the applied current density of 600 mA g-1. For this system, Ag was used in extra amount and the mass of active Sb4O5Cl2 was around 1.0 mg. The specific capacity of Sb4O5Cl2/Ag electrodes battery is obtained based on the weight of Sb4O5Cl2. At the 1st cycle, the Sb4O5Cl2/Ag battery produced a high charging capacity up to 292.6 mAh g-1, and it kept decayed during cycling. After 10 cycles, the capacity 6 / 16


Page 7 of 16 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


dropped to 41.0 mAh g-1. The cause of this phenomenon is that SEI layer could be formed on the electrode material surface. The SEI film is an electron insulator and chloride ion conductor, which leading to the capacity fading. Some side-reactions from impure content of electrode material or electrolyte are irreversible as observed in the CV tests, causing capacity decay at the initial cycles. During charge process, the chloride ions are escaped from Sb4O5Cl2 while captured by Ag electrode. During the discharge process, the chloride ions moved in a reverse way. After 5 cycles, the discharge profile shows a stable capacity. With the increased cycling, the discharge capacity is stable and shows good cycle performance with little fading. At the 50th cycle, the discharging capacity is maintained at 34.6 mAh g-1. Although the capacity is low, it is promising to be a good candidate based on the theoretical prediction, and further optimized investigation will be conducted to improve the capacity. The prepared Ag electrodes surface is relatively smooth as shown in Figure 1(c). However, after 50 times cycles, the rectangular-shape can be found at the cathode as shown in Figure S1, consistent with the previous report36. This morphological transformation could be assigned partly to the oxidative etching of silver at the surface by the chloride ion and the oxygen dissolved in the salt water. In summary, a new Sb4O5Cl2 material was synthetized and its chloride ion electrochemical behavior was investigated in water-based NaCl salt 7 / 16



electrolyte. The Sb4O5Cl2 material was assembled for a chloride ion battery with silver as cathode in the water- based electrolyte with 1M NaCl. The chloride ions can be electrochemically released at Sb4O5Cl2 side and captured at the silver cathode with the AgCl formation during the charge. The discharge reverses the charge transfer process, confirmed by electrochemical CV and the charge/discharge behavior. During a cyclic stability test with current density of 600 mA g-1, the 34.6 mAh g-1 of specific discharge capacity can be achieved after 50 cycles. The electrodes show excellent cycle performance with little fading. The results show that chloride ions can be reversibly reacted at the two electrodes through redox reaction. The current water-based chloride shuttle battery can be assembled and tested in ambient. This technology will significantly contribute to future renewable energy storage and battery desalination.

Acknowledgments This project was supported by South China Normal University. F.C. thanks the support from Outstanding Young Scholar Project (8S0256), and the Scientific and Technological Plan of Guangdong Province (2018A050506078). This work is supported by the Project of Blue Fire Plan (Nos CXZJHZ201708 and CXZJHZ201709). This work was supported by the union project of National Natural Science Foundation of 8 / 16


Page 8 of 16

Page 9 of 16 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


China and Guangdong Province (U1601214), the Scientific and Technological

Plan

of

Guangdong

Province

(2017B090901027,

2018B050502010), the Scientific and Technological Plan of Guangzhou City (201607010322), LanDun information security technology open fund (LD20170210), the Innovation Project of Graduate School of South China Normal University (2017LKXM077 ） and the General topics of extracurricular scientific research of South China Normal University (18WDGB04). Y.S. acknowledges the support from the Key Project of Department of Education of Guangdong Province (2016KZDXM008).

Reference 1.

Du, M.;

Rui, K.;

Chang, Y.;

Zhang, Y.;

Ma, Z.;

Sun, W.;

Yan, Q.;

Zhu, J.; Huang, W.,

Carbon Necklace Incorporated Electroactive Reservoir Constructing Flexible Papers for Advanced Lithium–Ion Batteries. Small 2018, 14, 1702770. 2.

Li, D.;

Xie, X.;

Wang, D.;

Rui, K.;

Ma, Z.;

Xie, L.;

Liu, J.;

Zhang, Y.;

Chen, R.;

Yan, Y.;

Lin, H.;

Zhu, J.; Huang, W., Flexible Phosphorus Doped Carbon Nanosheets/nanofibers: Electrospun

Preparation and Enhanced Li-storage Properties as Free-standing Anodes for Lithium Ion Batteries. J Power Sources 2018, 384, 27-33. 3.

Zhang, Y.;

Zhou, Q.;

Zhu, J.;

Yan, Q.;

Dou, S. X.; Sun, W., Nanostructured Metal

Chalcogenides for Energy Storage and Electrocatalysis. Adv. Funct. Mater. 2017, 27, 1702317. 4.

Wang, Q.;

Rui, K.;

Zhang, C.;

Ma, Z.;

Xu, J.;

Sun, W.;

Zhang, W.;

Zhu, J.; Huang, W.,

Interlayer-Expanded Metal Sulfides on Graphene Triggered by a Molecularly Self-Promoting Process for Enhanced Lithium Ion Storage. ACS Appl. Mater. Interfaces 2017, 9, 40317-40323. 5.

Sawicki, M.; Shaw, L. L., Advances and Challenges of Sodium Ion Batteries as Post Lithium Ion

Batteries. RSC Adv. 2015, 5, 53129-53154. 6.

Etacheri, V.;

Seisenbaeva, G. A.;

Caruthers, J.;

Daniel, G.;

Nedelec, J.-M.;

Kessler, V. G.;

Pol, V. G., Ordered Network of Interconnected SnO2Nanoparticles for Excellent Lithium-Ion Storage. Adv. Energy Mater. 2015, 5, 1401289. 7.

Wu, J.;

Rui, X.;

Wang, C.;

Pei, W.-B.;

Lau, R.;

Yan, Q.; Zhang, Q., Nanostructured

Conjugated Ladder Polymers for Stable and Fast Lithium Storage Anodes with High-Capacity. Adv. Energy Mater. 2015, 5, 1402189. 8.

Gu, P. Y.;

Zhao, Y.;

Xie, J.;

Binte Ali, N.;

Nie, L.;

Xu, Z. J.; Zhang, Q., Improving the

Performance of Lithium-Sulfur Batteries by Employing Polyimide Particles as Hosting Matrixes. ACS Appl. Mater. Interfaces 2016, 8, 7464-7470. 9.

Xie, J.;

Wang, Z.;

Xu, Z. J.; Zhang, Q., Toward a High-Performance All-Plastic Full Battery with 9 / 16



Page 10 of 16

a'Single Organic Polymer as Both Cathode and Anode. Adv. Energy Mater. 2018, 8, 1703509. 10. Xie, J.;

Gu, P.; Zhang, Q., Nanostructured Conjugated Polymers: Toward High-Performance

Organic Electrodes for Rechargeable Batteries. ACS Energy Lett. 2017, 2, 1985-1996. 11. Zhang, D.;

Shi, W.-j.;

Yan, Y.-w.;

Xu, S.-d.;

Chen, L.;

Wang, X.-m.; Liu, S.-b., Fast and

Scalable Synthesis of Durable Na0.44MnO2 Cathode Material via an Oxalate Precursor Method for Na-ion Batteries. Electrochim. Acta 2017, 258, 1035-1043. 12. Nithya, C.; Gopukumar, S., Sodium Ion Batteries: a Newer Electrochemical Storage. Wiley Interdiscip. Rev.: Energy Environ. 2015, 4, 253-278. 13. Steele, B. C. H.; Heinzel, A., Materials for Fuel-cell Technologies. Nature 2001, 414, 345-352. 14. Kim, S.-W.;

Seo, D.-H.;

Ma, X.;

Ceder, G.; Kang, K., Electrode Materials for Rechargeable

Sodium-Ion Batteries: Potential Alternatives to Current Lithium-Ion Batteries. Adv. Energy Mater. 2012, 2, 710-721. 15. Kundu, D.;

Talaie, E.;

Duffort, V.; Nazar, L. F., The emerging chemistry of sodium ion batteries

for electrochemical energy storage. Angew. Chem., Int. Ed. Engl. 2015, 54, 3431-3448. 16. Kong, F.;

Lv, L.;

Gu, Y.;

Tao, S.;

Jiang, X.;

Qian, B.; Gao, L., Nano-sized FeSe2 anchored on

reduced graphene oxide as a promising anode material for lithium-ion and sodium-ion batteries. J. Mater. Sci. 2018, 54, 4225-4235. 17. Yabuuchi, N.;

Kubota, K.;

Dahbi, M.; Komaba, S., Research development on sodium-ion

batteries. Chem. Rev. 2014, 114, 11636-11682. 18. Slater, M. D.;

Kim, D.;

Lee, E.; Johnson, C. S., Sodium-Ion Batteries. Adv. Funct. Mater. 2013,

23, 947-958. 19. Anji Reddy, M.; Fichtner, M., Batteries Based on Fluoride Shuttle. J. Mater. Chem. 2011, 21, 17059-17062. 20. Davis, V. K.; Webb, M. A.; N. G.;

Bates, C. M.;

Billings, K. J.;

Hightower, A.;

Omichi, K.;

Chou, N. H.;

Rosenberg, D.;

Savoie, B. M.; Alayoglu, S.;

Ahmed, M.;

Momčilović, N.;

McKenney, R. K.;

Brooks, C. J.;

Xu, Q.;

Wolf, W. J.;

Darolles, I. M.;

Miller, T. F.;

Nair,

Grubbs, R. H.;

Jones, S. C., Room-temperature cycling of metal fluoride electrodes: Liquid electrolytes for high-energy fluoride ion cells. Science 2018, 362, 1144-1148. 21. Zhao, X.;

Ren, S.;

Bruns, M.; Fichtner, M., Chloride Ion Battery: A New Member in the

Rechargeable Battery Family. J. Power Sources 2014, 245, 706-711. 22. Zhang, H.;

Gao, Q.;

Qian, W.;

Xiao, H.;

Li, Z.;

Ma, L.; Tian, X., Binary Hierarchical Porous

Graphene/Pyrolytic Carbon Nanocomposite Matrix Loaded with Sulfur as a High-Performance Li-S Battery Cathode. ACS Appl. Mater. Interfaces 2018, 10, 18726-18733. 23. Liu, Y.;

Feng, G.;

Guo, X.;

Wu, Z.;

Chen, Y.;

Xiang, W.;

Li, J.; Zhong, B., Employing MnO

as Multifunctional Polysulfide Reservoirs for Enhanced-Performance Li-S Batteries. J. Alloys Compd. 2018, 748, 100-110. 24. Yin, Y.-X.;

Xin, S.;

Guo, Y.-G.; Wan, L.-J., Lithium–Sulfur Batteries: Electrochemistry, Materials,

and Prospects. Angew. Chem., Int. Ed. 2013, 52, 13186-13200. 25. Kim, D. Y.;

Jin, X.;

Lee, C. H.;

Kim, D. W.;

Suk, J.;

Shon, J. K.;

Kim, J. M.; Kang, Y.,

Improved electrochemical performance of ordered mesoporous carbon by incorporating macropores for Li‒O 2 battery cathode. Carbon 2018, 133, 118-126. 26. Zhu, J.;

Metzger, M.;

Antonietti, M.; Fellinger, T.-P., Vertically Aligned Two-Dimensional

Graphene-Metal Hydroxide Hybrid Arrays for Li–O2 Batteries. ACS Appl. Mater. Interfaces 2016, 8, 26041-26050. 10 / 16


Page 11 of 16 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


27. Huang, X.; Zeng, Z.;

Yu, H.;

Liu, D.;

Tan, H.;

Ding, J.;

Zhu, J.;

Zhang, W.;

Zhang, Q.;

Wang, C.;

Srinivasan, M.;

Zhang, J.;

Ajayan, P. M.;

Wang, Y.;

Lv, Y.;

Hng, H. H.; Yan, Q.,

Carbon Nanotube ‐ Encapsulated Noble Metal Nanoparticle Hybrid as a Cathode Material for Li ‐ Oxygen Batteries. Adv. Funct. Mater. 2014, 24, 6516-6523. 28. Zhang, W.;

Zhu, J.;

Ang, H.;

Zeng, Y.;

Xiao, N.;

Gao, Y.;

Liu, W.;

Hng, H. H.; Yan, Q.,

Binder-free Graphene Foams for O2 Electrodes of Li-O2 Batteries. Nanoscale 2013, 5 (20), 9651-9658. 29. Zhao, X.;

Li, Q.;

Yu, T.;

Yang, M.;

Fink, K.; Shen, X., Carbon Incorporation Effects and

Reaction Mechanism of FeOCl Cathode Materials for Chloride Ion Batteries. Sci. Rep. 2016, 6, 19448. 30. Gao, P.;

Reddy, M. A.;

Chakravadhanula, V. S. K.;

Mu, X.;

Clemens, O.;

Diemant, T.;

Zhang, L.;

Zhao-Karger, Z.;

Behm, R. J.; Fichtner, M., VOCl as a Cathode for

Rechargeable Chloride Ion Batteries. Angew. Chem., Int. Ed. 2016, 55, 4285-4290. 31. Zhao, X.;

Li, Q.;

Zhao-Karger, Z.;

Gao, P.;

Fink, K.;

Shen, X.; Fichtner, M., Magnesium

Anode for Chloride Ion Batteries. ACS Appl. Mater. Interfaces 2014, 6, 10997-11000. 32. Gao, P.;

Zhao, X.;

Zhao-Karger, Z.;

Diemant, T.;

Behm, R. J.; Fichtner, M., Vanadium

Oxychloride/Magnesium Electrode Systems for Chloride Ion Batteries. ACS Appl. Mater. Interfaces 2014, 6, 22430-22435. 33. Zhao, X.;

Zhao-Karger, Z.;

Wang, D.; Fichtner, M., Metal Oxychlorides as Cathode Materials

for Chloride Ion Batteries. Angew. Chem., Int. Ed. 2013, 52, 13621-13624. 34. Silambarasan, K.; Joseph, J., Redox-polysilsesquioxane film as a new chloride storage electrode for desalination battery. Energy Technology 2019, accepted, 10.1002/ente.201800601. 35. Chen, F.;

Leong, Z. Y.; Yang, H. Y., An Aqueous Rechargeable Chloride Ion Battery. Energy

Storage Mater. 2017, 7, 189-194. 36. Kim, K.;

Hwang, S. M.;

Park, J.-S.;

Han, J.;

Kim, J.; Kim, Y., Highly improved voltage

efficiency of seawater battery by use of chloride ion capturing electrode. J. Power Sources 2016, 313, 46-50.

11 / 16



Figures:

Figure 1. The SEM images (a) and XRD pattern (b) of the prepared Sb4O5Cl2 electrode material; The SEM images (c) and XRD pattern (d) of the prepared Ag electrode material

12 / 16


Page 12 of 16

Page 13 of 16 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


Figure 2. Schematic representation of the aqueous chloride ions rechargeable battery process during charge process (a) and discharge process (b)

13 / 16



Figure 3. (a) The three-electrode CV curves of Sb4O5Cl2 in aqueous electrolyte with 1 M NaCl, Sb4O5Cl2 working electrode, Pt counter electrode, standard Ag/AgCl reference electrode, (b) two-electrode CV curves of Sb4O5Cl2/Ag system in aqueous electrolyte with 1 M NaCl.

14 / 16


Page 14 of 16

Page 15 of 16 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


Figure 4. (a) The charge/discharge curves of Sb4O5Cl2/Ag battery system in water-based electrolyte with 1 M NaCl and (b) cycling performance. The specific capacity is obtained based on Sb4O5Cl2 weight and Ag is extra amount.

15 / 16



The table of contents entry: A new electrochemical chloride ion material, Sb4O5Cl2, was synthetized and its electrochemical performance was investigated in aqueous NaCl electrolyte, and the aqueous chloride ion battery demonstrated 34.6 mAh g-1 discharge capacity after 50 cycles with silver as cathode. KEYWORDS: Chloride ion battery; Sb4O5Cl2; Energy storage device; chloride ion electrochemistry; aqueous battery Xiaoqiao Hu, Fuming Chen, Shaofeng Wang, Qiang Ru, Benli Chu, Chengyan Wei, Yumeng Shi, Zhicheng Ye, Yanxu Chu, Xianhua Hou, Linfeng Sun Electrochemical Performance of Sb4O5Cl2 as a new Anode Material in aqueous Chloride Ion Battery

Column Title: X. Hu et al.

16 / 16


Page 16 of 16

Electrochemical Performance of Sb4O5Cl2 as a New Anode Material

Recommend Documents