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A novel rechargeable iodide ion battery with zinc and copper anodes
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A novel rechargeable iodide ion battery with zinc and copper anodes Hang Li, Mingqiang Li *, Xiaojie Zhou, Tong Li School of Energy and Power Engineering, Dalian University of Technology, Dalian, 116024, China
H I G H L I G H T S
� An iodide-ion battery based on an iodide ion intercalated carbon material. � The cycle life of battery is more than 10000 times. � Zinc and copper are stable as the anode of the battery. � The electrolyte solvent is ethylene glycol. A R T I C L E I N F O
A B S T R A C T
Keywords: Rechargeable iodide ion battery Ethylene glycol Carbon black Zinc foil
In recent years, metal ion batteries have been developed rapidly and have been made great progress, but nonmetal ion batteries have rarely been reported. In our work, carbon black (cb) is used as cathode material for iodine-ion battery. The electrolyte uses ethylene glycol as a solvent and exhibits exceptional stability, and has been experimentally proven to have high cycle stability when zinc and copper are used as anodes for iodide-ion battery. When the zinc foil is used as the negative electrode, the specific capacity is 83 mA h gcb1 at charge current density of 1 A g 1, and the specific capacity does not attenuated after 10000 cycles. Under the same conditions, when the copper foil is used as negative electrode, the average specific capacity is 92 mA h gcb1, and the specific capacity is 50 mA h gcb1 after about 4000 cycles. After X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) characterization tests, it is verified that the iodide-ion is intercalated in the carbon material instead of the redox reaction during the charging and dis charging process.
1. Introduction In recent years, metal ion batteries have been gained widespread attention due to the demand for large-scale energy storage and the safety and cost of commercial lithium batteries [1]. For example, monovalent (K, Na) and multivalent (Mg, Ca, Zn, Al) elements cations have been made excellent progress [2–10]. However, there are few reports on non-metallic anion batteries. Fluoride-ion battery is a kind of promising new battery chemical material with an energy density ten times that of lithium batteries [11]. Unlike lithium-ion batteries, fluoride-ion batte ries do not pose a safety risk caused by overheating, and the environ mental impact that may be caused when fluoride in battery is extracted is much less than that to be caused during lithium and cobalt extraction. Fluoride-ion batteries are still in the initial stage of researches, and there is still a lack of in-depth research on positive and negative active ma terials, structural design, electrolyte selection and conductivity selection
of fluoride-ion batteries. In particular, current fluorine-ion batteries have poor kinetic conditions, with low operating current, high the operating temperature and poor cycle performance, making it difficult to be practically applied [12–14]. But it enables people to better explore non-metallic anion batteries. Halogens were previously explored for energy storage in Al–Cl2, Zn–Br2, Li–I2, Al–I2, Mg–I2, Na–I2 and Mg–Br2 systems [15–21]. As a main group of iodine and fluorine, it is non-toxic, environmentally friendly, and abundant in the ocean with theoretically high capacity (211 mA h g 1). Currently, it has been widely used in lithium iodine, aluminum iodine batteries, zinc iodine flow batteries [22] and super capacitors [23], showing excellent performance. However, all these batteries are produced through a redox reaction of iodide ions, and an iodide-ion battery to be produced by the principle of iodide ion inter calation has not been reported yet. So far, several carbon sources, including porous carbon, have been
* Corresponding author. E-mail address: [email protected] (M. Li). https://doi.org/10.1016/j.jpowsour.2019.227511 Received 30 July 2019; Received in revised form 20 November 2019; Accepted 26 November 2019 0378-7753/© 2019 Elsevier B.V. All rights reserved.
Please cite this article as: Hang Li, Journal of Power Sources, https://doi.org/10.1016/j.jpowsour.2019.227511
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Fig. 1. (a) Schematic of iodine-ion battery. Herein, carbon black serves as cathode, Zinc foil/Copper foil severs as anode and 1.5 m KI Ethylene glycol solution is used as electrolyte. (b) Taking zinc foil as negative electrode as an example, the reaction mechanism of the negative electrode of the iodide-ion battery during the charging and discharging process.
developed for lithium iodine batteries. Some of these carbon-based materials have also been proven to be useful for intercalation of io dide ions [24]. However, their work mainly focused on doping carbon materials to enhance the iodine loading of carbon electrode, and they could be used for different batteries (Li–I2, Na–I2) to improve battery performance, but iodide battery was not discussed separately. The electrolyte and anode materials with iodide were mainly illustrated in our work, and these materials were not reported before. Meanwhile, it was found that carbon black showed excellent performance for iodide-ion battery and that anode materials played a vital role in iodide-ion battery. Different anode materials will exhibit different open-circuit voltages. Among a number of metal materials, it was found that these two kinds of metal materials, zinc foil and copper foil, could be used as negative electrode of iodide-ion battery, and both of them showed better cycle performance. The principle of iodide-ion battery is shown in Fig. 1. In Fig. 1 (a), the intercalation mechanism of iodide ion can be clearly seen in the positive electrode during charge and discharge. In Fig. 1 (b), zinc foil is used as an example to explain po tassium. This effect of ions in the negative electrode shows that potas sium ions accumulate around the zinc during charging, and then they attract the outer electrons of the zinc, causing these electrons to shift. When the zinc foil is used as the negative electrode of the iodide ion battery, the reaction formula is as shown in (1).
Anode:Zn2þ þ 2e ⇌ZnE0 ¼ 0:763V vs: SHE Cathode:2CI þ 2e ⇌2C þ 2I E0 ¼ 0:5355V vs: SHE Overall:Zn þ 2CI⇌Zn2þ þ 2C þ 2I E0 ¼ 1:285V vs: SHE
(1)
It is also challenging to select electrolyte system for iodide-ion bat tery. The water-based electrolyte is cheap and environmentally friendly. However, electrode sheets will be corroded due to the hydrogen evo lution and oxygen evolution of water, thus reduce the cycle life of the iodide-ion battery will be reduced. Therefore, KI is used in ethylene glycol with high solubility characteristics, and potassium iodide elec trolyte is further used in ethylene glycol system, so as to effectively avoid hydrogen evolution and oxygen evolution, and iodide-ion battery shows better stability. It provides a better direction for exploring and devel oping other ion battery organic electro-electrolyte. 2. Experimental methods 2.1. Material Zinc foil, Cooper foil (thickness of 100 μm) and Stainless steel foil (thickness of 50 μm) were purchased from Sinopharm Chemical Reagent Co Ltd. Polyvinylidene fluoride (PVDF) was purchased from Shandong West Asia Chemical Industry Co Ltd. Carbon black was purchased from 2
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Fig. 2. Performance of iodide-ion battery with different metal anodes. (a) Typical galvanostatic charge/discharge curves for zinc foil as negative electrode at 1 A g¡1 between 0.4 and 1.23 V of the cell. (b) Midpoint charge/discharge voltage of different cycles when zinc foil is used as negative electrode. (c) Typical galvanostatic charge/discharge curves for copper foil as negative electrode at 1 A g¡1 between 0.4 and 0.63 V of the cell. (d) Midpoint charge/ discharge voltage of different cycles when the copper foil is used as negative electrode. When zinc foil (e) and copper foil (f) are used as negative electrode of the iodide-ion battery, the electrolyte of the electrolyte was replaced by K2SO4 instead of KI. (g) The battery performance when the magnesium sheet is selected as the negative electrode of the iodide-ion battery. (h) Charge and discharge curve of zinc-ion hybrid supercapacitor. (i) Charge and discharge curves of copper-based hybrid supercapacitors.
Tianjin Tianyi Century Chemical Technology Co Ltd. Ethylene glycol and N-Methyl pyrrolidone (NMP) were purchased from Tianjin Damao Chemical Reagent Factory.
vacuum dried at 60 � C for 12 h. Galvanostatic charge/discharge per formances were conducted on a battery test system (Neware BTS 4000). 3. Results and discussion
2.2. Material characterization
Fig. 2 (a) shows the charge-discharge curve of an iodide-ion battery with zinc as negative electrode. The electrolyte concentration was 1.5 m KI, and the solvent was ethylene glycol. It can be seen that the opencircuit voltage of the battery is 1.23 V. The reaction equation (1) of the iodide battery can be obtained according to the standard potential of iodine and zinc. During battery charging and discharging, carbon black only acts as an intercalation material for iodide ions and is not involved in the re action. In order to verify that iodide ions play a leading role in the charging and discharging process, we compared the open circuit volt ages of different metal as anode materials. Fig. 2 (c) shows the charge and discharge curve of the battery with the copper foil as negative electrode. It can be seen that the open-circuit voltage of the battery is 0.61 V. Similarly, the reaction equation of the battery is also obtained based on the standard potential of copper and iodine. It should be noted, that the redox process between Cu2þ and Cuþ is controlled by rate, while Cuþ exists in reversible equilibrium with Cu0 at the electrode surface based on galvanostatic measurement [25].
Powder XRD patterns were collected on a X-ray diffractometer (D/ Max 2400, Japan) with Cu Kα radiation (λ ¼ 0.15406 nm). XPS was tested on a Thermo ESCALAB XIþ equipped with a hemispherical analyzer. Fourier transform infrared spectroscopy (FT-IR) spectrum was recorded with a NICOLET 6700 FT-IR Spectrometer using KBr pellets. 2.3. Electrochemical measurements Electrochemical measurements were performed with soft pack bat tery. The full cells were assembled using the carbon black composite as cathode, a zinc metal foil or copper foil as anode, a polyolefin micro porous membrane as separator, and formulating 1.5 m KI with ethylene glycol as electrolyte. The working electrode was fabricated by carbon black, and the binder (Polyvinylidene fluoride, PVDF) in a weight ratio of acetylene black/PVDF ¼ 80:20, with N-Methyl pyrrolidone (NMP) as solvent. It was ground into a slurry in an agate grinding crucible, coated on a surface of a stainless steel foil board (3 cm � 3 cm), and then 3
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Fig. 3. (a) Cycle life of zinc foil as anode of iodide-ion battery. (b) Cycle life of copper foil as anode of iodide-ion battery. (c) Cycle life of iodide-ion battery of waterbased electrolyte when zinc foil is used as negative electrode. (d) The zinc foil is used as negative electrode, the electrolyte solution with different concentrations in the ethylene glycol system, and the specific capacity of the iodide-ion battery when overcharged and overcharged.
Meanwhile, rate is found to be usually restricted by Cu2þ to Cuþ charge transfer reaction at a higher current density [26]. Therefore, the mutual transformation between Cu2þ and Cuþ was only studied, while that between Cuþ and Cu0 was not comprehensively discussed. Anode:Cuþ ⇌Cu2þ þ e E0 ¼ 0:153V vs: SHE Cathode:CI þ e ⇌C þ I E0 ¼ 0:5355V vs: SHE Overall:Cuþ þ CI⇌Cu2þ þ C þ I E0 ¼ 0:688V vs: SHE
K2SO4 instead of KI. Zinc foil and copper foil as negative electrodes, respectively. The charging current density was 1 A g 1, and the discharge current density was 0.4 A g 1. The charge-discharge curve of the zinc foil as the negative electrode of the battery is as shown in Fig. 2 (e). It can be seen that even with low current density discharge, there was no discharge platform and the specific capacity was close to zero. The copper sheet was also similar to negative electrode, as shown in Fig. 2 (f), indicating that the Kþ did not affect the above experiment, thus it was confirmed that the dominant role in the KI electrolyte is iodide ion. Fig. 2 (g) showed the specific capacity of different cycles when the magnesium sheet was used as negative electrode of the iodideion battery and the electrolyte was also 1.5 m KI of the ethylene glycol system. It can be clearly observed that when the magnesium sheet was used as negative electrode, the performance decayed very rapidly, which was mainly because the complicated chemical nature of magne sium, and its failure to formulate a stable kinetic system with the elec trolyte resulted in the serious deterioration of battery performance. Under the same conditions, we used aluminum foil, nickel foil, iron foil, stainless steel foil and tin foil as anode materials for iodide-ion battery, and found that they had no performance which indicated that it was also crucial to select anode materials for iodide-ion battery. Besides, the zinc and copper metals are abundant in natural reserves and cheap, so they are of great practical significance for the application of iodide-ion battery. In order to study the effect of negative metal ions on iodide-ion battery, we used zinc foil as a negative electrode as an example to study the role of zinc ions in the charging and discharging process of iodide-ion battery. As shown in Fig. 2 (h), we replaced the electrolyte with 2 m ZnSO4 and assembled it into a zinc ion hybrid supercapacitor [27]. Compared with the previous 1.5 m KI electrolyte, the zinc ion hybrid supercapacitor had no discharge platform as could be clearly observed, which is the most obviously different from iodide-ion battery [28,29]. It showed that when zinc foil was used as negative electrode of
(2)
Although the open-circuit voltage of different metal negative batte ries has not reached the theoretical value, the open-circuit voltage that is actually measured is very close to the theoretical value. This error is caused by a variety of factors, but it is completely acceptable. The charging and open-circuit voltages for different cycles were also studied, and it was found that the voltage fluctuated as the reaction progressed. As shown in Fig. 2 (b), when zinc was used as negative electrode, the charging voltage was around 1.8 V at the beginning of the cycle. It was because the electrode material was not sufficiently acti vated at the beginning, and the ion channel was blocked, resulting in a large internal resistance of the battery. It can be seen that as the cycle progressed, the charging voltage became lower and lower, and the corresponding open circuit voltage was getting closer to the theoretical value. Starting from 350 cycles, the charging voltage and open-circuit voltage of the battery were close to the theoretical value, and the bat tery also exhibited a stable charge and discharge state. As shown in Fig. 2 (a), there was a stable discharge platform near 1.2 V, and the capacity was 83 mA h gcb1. When copper foil is used as the negative electrode, the results were similar. As shown in Fig. 2 (d), the charging voltage and the open-circuit voltage were high at the beginning due to large internal resistance of the battery. The battery charging and dis charging state was stable after 150 cycles, getting close to theoretical values. As can be seen from Fig. 2 (c), the battery discharge was stable in the range of 0.4–0.65 V, and the capacity reached 92 mA h gcb1. In order to test whether Kþ has an effect on the experiment, we used 4
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Fig. 4. (a) The survey XPS spectrum and the high-resolution XPS spectrum of (b) I3d (c) C1s (d) O1s. XRD of (e) and IR spectra of (f) of positive carbon when iodideion battery is fully charged and discharged. (g) IR spectra of zinc metal anodes when iodide-ion battery is fully charged and discharged.
Fig. 3 (c), the specific capacity of the battery dropped to 44 mA h gcb1 after only 2000 cycles, indicating that the hydrogen evolution and ox ygen evolution of water during the charging and discharging process would seriously affect the cycle life of the iodide-ion battery. It also proves that when ethylene glycol was used as the solvent in the elec trolyte, iodide-ion battery would be more stable, which was an impor tant breakthrough. Fig. 3 (b) shows that when the copper foil was used as the negative electrode of the iodide ion battery, the specific capacity of the iodide-ion battery gradually increased in the first 2000 cycles. After 3850 cycles, the specific capacity dropped to 50 mA h gcb1, showing that the electrolyte of the ethylene glycol system can adapt to different metal negative electrodes. This finding is of universal significance for the iodide-ion battery. In order to compare the effect of electrolytes with different concentrations of ethylene glycol on the specific capacity of iodide-ion battery, we used zinc foil as the anode of iodide-ion battery as an example. The electrolyte concentration was studied separately under the condition of overcharge and over-discharge of iodide-ion battery. The specific capacities of the iodide-ion battery for 0.5 m, 1 m, 1.5 m KI were shown in Fig. 3 (d). It was found that 1.5 m KI had the best per formance and that the maximum discharge specific capacity reached 175 mA h gcb1. In order to verify the intercalation of iodide ions in the positive carbon material, we performed a XPS test. Fig. 4 shows the XPS spectrum of the cathode after the charging is completed when zinc foil is used as anode. Fig. 4 (a) shows the existence of I3d, C1s, and O1s. And in Fig. 4 (b), two obvious I3d peaks located at 619.3 and 631.0 eV can be considered to I3d5/2 and I3d3/2 states [33,34], respectively. The signal of
the iodide-ion battery, iodide ion played a dominant role, and a small number of zinc ions would not affect the iodide battery. The reaction mechanism of zinc ions during charge and discharge is shown in Fig. 1 (b). Kþ accumulates around the zinc during charging. Meanwhile, the surrounding Kþ attracts the extranuclear electrons of zinc, which showed positive divalent state (Zn2þ). During discharging, the potas sium ions were far away from zinc, and the electrons were reset, then Zn2þ become Zn. In addition, as shown in Fig. 4 (g), when iodide-ion battery was fully charged and discharged, we performed IR character ization of the zinc negative electrode. It can be observed that the metal zinc anode did not change during complete charge and discharge, con firming that the zinc anode was not excessively involved. As shown in Fig. 2 (i), in order to verify the role of copper ions in the iodide-ion battery, we replaced the 1.5 m KI with 1.5 m CuSO4 to form a copper-based hybrid supercapacitor without a discharge platform similar to the zinc-ion hybrid supercapacitor [30–32]. The results indi cated that when the copper foil was used as the negative electrode of the iodide-ion battery, iodide still played a dominant role. The reaction mechanism of copper foil during charging and discharging was exactly the same as that of zinc foil. The reaction mechanism of zinc foil has been discussed in detail in Fig. 1 (b) and will not be repeated here. Fig. 3 (a) shows the cycle life of the iodide battery when the zinc foil is used as the negative electrode of the iodide-ion battery and the elec trolyte is 1.5 m KI (ethylene glycol system). It can be seen that after 10000 cycles, the capacity retention rate of the iodide battery was almost 100%. Under the same conditions, the ethylene glycol was replaced by water to make a water-based iodide-ion battery. As shown in 5
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I3d5/2 can be further divided into a C–I peak of 619.3 eV and a C–Iþ-C peak of 619.9 eV [35], which is correlated with the intercalation of io dide ions during charge and discharge. The spectrum of C1s is shown in Fig. 4 (c). The above analysis was also verified by the C–I peak at 285.2 eV. In addition, the peak of 287.6 eV, 284.6 eV can be attributed to – O, graphitic carbon, respectively [36,37]. It indicates that iodide C– ions are inserted into the carbon material during the charging process and combine with carbon atoms to form a C–I bond. The spectrum of O1s is shown in Fig. 4 (d). The peak of 531.3 eV and – O, which is consistent with Fig. 4 (c). 532.2 eV can be attributed to C– The XRD spectrum is shown in Fig. 4 (e). Drum peaks of amorphous carbon between 20� and 27� can be clearly observed during charging and discharging [38,39]. The difference is that when the charge is completed, the peak of the amorphous carbon appears to be more gradual and broader than that when the discharge is completed. It is because when the charging is completed, iodide ion and carbon material are sufficiently combined to affect the characterization of the carbon peak. FT-IR analysis was further carried out to verify the conversion of iodine ion during reaction. As shown in Fig. 4 (f), after charge and discharge were completed, several peaks appeared in the spectrum. The peak at 1650 cm 1,1550 cm 1,885 cm 1 could be ascribed to the – O, C– – C, C–O–C, respectively [40,41]. Peaks stretching vibration of C– at 1350 and 1465 cm 1 could be ascribed to the bending vibration of CH2, while those at 2853, 2926 cm 1 could be assigned to the stretching vibration of CH2. The difference is that the peak value of δ(CH) after charging is significantly weaker than that after discharge, indicating that CH2 group is replaced by another group during charging, and iodide ions and carbon are likely to form a new bond. In addition, the presence – O and C–O–C can be observed upon completion of charging. The of C– – O peak is weakened and a new C– – C bond is formed when discharge C– is completed. It indicates that carbon atoms and other groups of the electrolyte form new chemical bonds during charging, and that the above bonds break and transfer during discharging, and the remaining – C bonds. carbon atoms themselves are combined together to form C–
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4. Conclusion In our work, we firstly proposed an iodide-ion battery and used carbon black as the positive electrode material of iodide-ion battery. It is found that two stable metal anode materials, zinc foil and copper foil showed good performance and cycle stability. Meanwhile, ethylene glycol non-aqueous system was used as electrolyte, and the results showed that it had more remarkable cycle stability than the electrolyte of the water system. It provides a new direction for exploring highly stable electrolytes for ion batteries. It is undeniable that our work is also drawing on many people’s experience, and many problems need to be solved in the iodide battery. It is firmly believed that if everyone works together, this project will become more and more perfect. Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. References [1] J.B. Goodenough, Y. Kim, Challenges for rechargeable Li batteries, Chem. Mater. 22 (2010) 587–603, https://doi.org/10.1021/cm901452z. [2] L.W. Jiang, et al., Building aqueous K-ion batteries for energy storage, Nat. Energy 4 (2019) 495–503, https://doi.org/10.1038/s41560-019-0388-0. [3] Y.Y. Wang, et al., TiO2-Coated interlayer-expanded MoSe2/Phosphorus doped carbon nanospheres for ultrafast and ultralong cycling sodium storage, Adv. Sci. 6 (2019). ARTN 180122210.1002/advs.201801222. [4] X. Ji, et al., Water-activated VOPO4 for magnesium ion batteries, Nano Lett. 18 (2018) 6441–6448, https://doi.org/10.1021/acs.nanolett.8b02854.
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Short communication
A novel rechargeable iodide ion battery with zinc and copper anodes Hang Li, Mingqiang Li *, Xiaojie Zhou, Tong Li School of Energy and Power Engineering, Dalian University of Technology, Dalian, 116024, China
H I G H L I G H T S
� An iodide-ion battery based on an iodide ion intercalated carbon material. � The cycle life of battery is more than 10000 times. � Zinc and copper are stable as the anode of the battery. � The electrolyte solvent is ethylene glycol. A R T I C L E I N F O
A B S T R A C T
Keywords: Rechargeable iodide ion battery Ethylene glycol Carbon black Zinc foil
In recent years, metal ion batteries have been developed rapidly and have been made great progress, but nonmetal ion batteries have rarely been reported. In our work, carbon black (cb) is used as cathode material for iodine-ion battery. The electrolyte uses ethylene glycol as a solvent and exhibits exceptional stability, and has been experimentally proven to have high cycle stability when zinc and copper are used as anodes for iodide-ion battery. When the zinc foil is used as the negative electrode, the specific capacity is 83 mA h gcb1 at charge current density of 1 A g 1, and the specific capacity does not attenuated after 10000 cycles. Under the same conditions, when the copper foil is used as negative electrode, the average specific capacity is 92 mA h gcb1, and the specific capacity is 50 mA h gcb1 after about 4000 cycles. After X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) characterization tests, it is verified that the iodide-ion is intercalated in the carbon material instead of the redox reaction during the charging and dis charging process.
1. Introduction In recent years, metal ion batteries have been gained widespread attention due to the demand for large-scale energy storage and the safety and cost of commercial lithium batteries [1]. For example, monovalent (K, Na) and multivalent (Mg, Ca, Zn, Al) elements cations have been made excellent progress [2–10]. However, there are few reports on non-metallic anion batteries. Fluoride-ion battery is a kind of promising new battery chemical material with an energy density ten times that of lithium batteries [11]. Unlike lithium-ion batteries, fluoride-ion batte ries do not pose a safety risk caused by overheating, and the environ mental impact that may be caused when fluoride in battery is extracted is much less than that to be caused during lithium and cobalt extraction. Fluoride-ion batteries are still in the initial stage of researches, and there is still a lack of in-depth research on positive and negative active ma terials, structural design, electrolyte selection and conductivity selection
of fluoride-ion batteries. In particular, current fluorine-ion batteries have poor kinetic conditions, with low operating current, high the operating temperature and poor cycle performance, making it difficult to be practically applied [12–14]. But it enables people to better explore non-metallic anion batteries. Halogens were previously explored for energy storage in Al–Cl2, Zn–Br2, Li–I2, Al–I2, Mg–I2, Na–I2 and Mg–Br2 systems [15–21]. As a main group of iodine and fluorine, it is non-toxic, environmentally friendly, and abundant in the ocean with theoretically high capacity (211 mA h g 1). Currently, it has been widely used in lithium iodine, aluminum iodine batteries, zinc iodine flow batteries [22] and super capacitors [23], showing excellent performance. However, all these batteries are produced through a redox reaction of iodide ions, and an iodide-ion battery to be produced by the principle of iodide ion inter calation has not been reported yet. So far, several carbon sources, including porous carbon, have been
* Corresponding author. E-mail address: [email protected] (M. Li). https://doi.org/10.1016/j.jpowsour.2019.227511 Received 30 July 2019; Received in revised form 20 November 2019; Accepted 26 November 2019 0378-7753/© 2019 Elsevier B.V. All rights reserved.
Please cite this article as: Hang Li, Journal of Power Sources, https://doi.org/10.1016/j.jpowsour.2019.227511
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Fig. 1. (a) Schematic of iodine-ion battery. Herein, carbon black serves as cathode, Zinc foil/Copper foil severs as anode and 1.5 m KI Ethylene glycol solution is used as electrolyte. (b) Taking zinc foil as negative electrode as an example, the reaction mechanism of the negative electrode of the iodide-ion battery during the charging and discharging process.
developed for lithium iodine batteries. Some of these carbon-based materials have also been proven to be useful for intercalation of io dide ions [24]. However, their work mainly focused on doping carbon materials to enhance the iodine loading of carbon electrode, and they could be used for different batteries (Li–I2, Na–I2) to improve battery performance, but iodide battery was not discussed separately. The electrolyte and anode materials with iodide were mainly illustrated in our work, and these materials were not reported before. Meanwhile, it was found that carbon black showed excellent performance for iodide-ion battery and that anode materials played a vital role in iodide-ion battery. Different anode materials will exhibit different open-circuit voltages. Among a number of metal materials, it was found that these two kinds of metal materials, zinc foil and copper foil, could be used as negative electrode of iodide-ion battery, and both of them showed better cycle performance. The principle of iodide-ion battery is shown in Fig. 1. In Fig. 1 (a), the intercalation mechanism of iodide ion can be clearly seen in the positive electrode during charge and discharge. In Fig. 1 (b), zinc foil is used as an example to explain po tassium. This effect of ions in the negative electrode shows that potas sium ions accumulate around the zinc during charging, and then they attract the outer electrons of the zinc, causing these electrons to shift. When the zinc foil is used as the negative electrode of the iodide ion battery, the reaction formula is as shown in (1).
Anode:Zn2þ þ 2e ⇌ZnE0 ¼ 0:763V vs: SHE Cathode:2CI þ 2e ⇌2C þ 2I E0 ¼ 0:5355V vs: SHE Overall:Zn þ 2CI⇌Zn2þ þ 2C þ 2I E0 ¼ 1:285V vs: SHE
(1)
It is also challenging to select electrolyte system for iodide-ion bat tery. The water-based electrolyte is cheap and environmentally friendly. However, electrode sheets will be corroded due to the hydrogen evo lution and oxygen evolution of water, thus reduce the cycle life of the iodide-ion battery will be reduced. Therefore, KI is used in ethylene glycol with high solubility characteristics, and potassium iodide elec trolyte is further used in ethylene glycol system, so as to effectively avoid hydrogen evolution and oxygen evolution, and iodide-ion battery shows better stability. It provides a better direction for exploring and devel oping other ion battery organic electro-electrolyte. 2. Experimental methods 2.1. Material Zinc foil, Cooper foil (thickness of 100 μm) and Stainless steel foil (thickness of 50 μm) were purchased from Sinopharm Chemical Reagent Co Ltd. Polyvinylidene fluoride (PVDF) was purchased from Shandong West Asia Chemical Industry Co Ltd. Carbon black was purchased from 2
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Fig. 2. Performance of iodide-ion battery with different metal anodes. (a) Typical galvanostatic charge/discharge curves for zinc foil as negative electrode at 1 A g¡1 between 0.4 and 1.23 V of the cell. (b) Midpoint charge/discharge voltage of different cycles when zinc foil is used as negative electrode. (c) Typical galvanostatic charge/discharge curves for copper foil as negative electrode at 1 A g¡1 between 0.4 and 0.63 V of the cell. (d) Midpoint charge/ discharge voltage of different cycles when the copper foil is used as negative electrode. When zinc foil (e) and copper foil (f) are used as negative electrode of the iodide-ion battery, the electrolyte of the electrolyte was replaced by K2SO4 instead of KI. (g) The battery performance when the magnesium sheet is selected as the negative electrode of the iodide-ion battery. (h) Charge and discharge curve of zinc-ion hybrid supercapacitor. (i) Charge and discharge curves of copper-based hybrid supercapacitors.
Tianjin Tianyi Century Chemical Technology Co Ltd. Ethylene glycol and N-Methyl pyrrolidone (NMP) were purchased from Tianjin Damao Chemical Reagent Factory.
vacuum dried at 60 � C for 12 h. Galvanostatic charge/discharge per formances were conducted on a battery test system (Neware BTS 4000). 3. Results and discussion
2.2. Material characterization
Fig. 2 (a) shows the charge-discharge curve of an iodide-ion battery with zinc as negative electrode. The electrolyte concentration was 1.5 m KI, and the solvent was ethylene glycol. It can be seen that the opencircuit voltage of the battery is 1.23 V. The reaction equation (1) of the iodide battery can be obtained according to the standard potential of iodine and zinc. During battery charging and discharging, carbon black only acts as an intercalation material for iodide ions and is not involved in the re action. In order to verify that iodide ions play a leading role in the charging and discharging process, we compared the open circuit volt ages of different metal as anode materials. Fig. 2 (c) shows the charge and discharge curve of the battery with the copper foil as negative electrode. It can be seen that the open-circuit voltage of the battery is 0.61 V. Similarly, the reaction equation of the battery is also obtained based on the standard potential of copper and iodine. It should be noted, that the redox process between Cu2þ and Cuþ is controlled by rate, while Cuþ exists in reversible equilibrium with Cu0 at the electrode surface based on galvanostatic measurement [25].
Powder XRD patterns were collected on a X-ray diffractometer (D/ Max 2400, Japan) with Cu Kα radiation (λ ¼ 0.15406 nm). XPS was tested on a Thermo ESCALAB XIþ equipped with a hemispherical analyzer. Fourier transform infrared spectroscopy (FT-IR) spectrum was recorded with a NICOLET 6700 FT-IR Spectrometer using KBr pellets. 2.3. Electrochemical measurements Electrochemical measurements were performed with soft pack bat tery. The full cells were assembled using the carbon black composite as cathode, a zinc metal foil or copper foil as anode, a polyolefin micro porous membrane as separator, and formulating 1.5 m KI with ethylene glycol as electrolyte. The working electrode was fabricated by carbon black, and the binder (Polyvinylidene fluoride, PVDF) in a weight ratio of acetylene black/PVDF ¼ 80:20, with N-Methyl pyrrolidone (NMP) as solvent. It was ground into a slurry in an agate grinding crucible, coated on a surface of a stainless steel foil board (3 cm � 3 cm), and then 3
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Fig. 3. (a) Cycle life of zinc foil as anode of iodide-ion battery. (b) Cycle life of copper foil as anode of iodide-ion battery. (c) Cycle life of iodide-ion battery of waterbased electrolyte when zinc foil is used as negative electrode. (d) The zinc foil is used as negative electrode, the electrolyte solution with different concentrations in the ethylene glycol system, and the specific capacity of the iodide-ion battery when overcharged and overcharged.
Meanwhile, rate is found to be usually restricted by Cu2þ to Cuþ charge transfer reaction at a higher current density [26]. Therefore, the mutual transformation between Cu2þ and Cuþ was only studied, while that between Cuþ and Cu0 was not comprehensively discussed. Anode:Cuþ ⇌Cu2þ þ e E0 ¼ 0:153V vs: SHE Cathode:CI þ e ⇌C þ I E0 ¼ 0:5355V vs: SHE Overall:Cuþ þ CI⇌Cu2þ þ C þ I E0 ¼ 0:688V vs: SHE
K2SO4 instead of KI. Zinc foil and copper foil as negative electrodes, respectively. The charging current density was 1 A g 1, and the discharge current density was 0.4 A g 1. The charge-discharge curve of the zinc foil as the negative electrode of the battery is as shown in Fig. 2 (e). It can be seen that even with low current density discharge, there was no discharge platform and the specific capacity was close to zero. The copper sheet was also similar to negative electrode, as shown in Fig. 2 (f), indicating that the Kþ did not affect the above experiment, thus it was confirmed that the dominant role in the KI electrolyte is iodide ion. Fig. 2 (g) showed the specific capacity of different cycles when the magnesium sheet was used as negative electrode of the iodideion battery and the electrolyte was also 1.5 m KI of the ethylene glycol system. It can be clearly observed that when the magnesium sheet was used as negative electrode, the performance decayed very rapidly, which was mainly because the complicated chemical nature of magne sium, and its failure to formulate a stable kinetic system with the elec trolyte resulted in the serious deterioration of battery performance. Under the same conditions, we used aluminum foil, nickel foil, iron foil, stainless steel foil and tin foil as anode materials for iodide-ion battery, and found that they had no performance which indicated that it was also crucial to select anode materials for iodide-ion battery. Besides, the zinc and copper metals are abundant in natural reserves and cheap, so they are of great practical significance for the application of iodide-ion battery. In order to study the effect of negative metal ions on iodide-ion battery, we used zinc foil as a negative electrode as an example to study the role of zinc ions in the charging and discharging process of iodide-ion battery. As shown in Fig. 2 (h), we replaced the electrolyte with 2 m ZnSO4 and assembled it into a zinc ion hybrid supercapacitor [27]. Compared with the previous 1.5 m KI electrolyte, the zinc ion hybrid supercapacitor had no discharge platform as could be clearly observed, which is the most obviously different from iodide-ion battery [28,29]. It showed that when zinc foil was used as negative electrode of
(2)
Although the open-circuit voltage of different metal negative batte ries has not reached the theoretical value, the open-circuit voltage that is actually measured is very close to the theoretical value. This error is caused by a variety of factors, but it is completely acceptable. The charging and open-circuit voltages for different cycles were also studied, and it was found that the voltage fluctuated as the reaction progressed. As shown in Fig. 2 (b), when zinc was used as negative electrode, the charging voltage was around 1.8 V at the beginning of the cycle. It was because the electrode material was not sufficiently acti vated at the beginning, and the ion channel was blocked, resulting in a large internal resistance of the battery. It can be seen that as the cycle progressed, the charging voltage became lower and lower, and the corresponding open circuit voltage was getting closer to the theoretical value. Starting from 350 cycles, the charging voltage and open-circuit voltage of the battery were close to the theoretical value, and the bat tery also exhibited a stable charge and discharge state. As shown in Fig. 2 (a), there was a stable discharge platform near 1.2 V, and the capacity was 83 mA h gcb1. When copper foil is used as the negative electrode, the results were similar. As shown in Fig. 2 (d), the charging voltage and the open-circuit voltage were high at the beginning due to large internal resistance of the battery. The battery charging and dis charging state was stable after 150 cycles, getting close to theoretical values. As can be seen from Fig. 2 (c), the battery discharge was stable in the range of 0.4–0.65 V, and the capacity reached 92 mA h gcb1. In order to test whether Kþ has an effect on the experiment, we used 4
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Fig. 4. (a) The survey XPS spectrum and the high-resolution XPS spectrum of (b) I3d (c) C1s (d) O1s. XRD of (e) and IR spectra of (f) of positive carbon when iodideion battery is fully charged and discharged. (g) IR spectra of zinc metal anodes when iodide-ion battery is fully charged and discharged.
Fig. 3 (c), the specific capacity of the battery dropped to 44 mA h gcb1 after only 2000 cycles, indicating that the hydrogen evolution and ox ygen evolution of water during the charging and discharging process would seriously affect the cycle life of the iodide-ion battery. It also proves that when ethylene glycol was used as the solvent in the elec trolyte, iodide-ion battery would be more stable, which was an impor tant breakthrough. Fig. 3 (b) shows that when the copper foil was used as the negative electrode of the iodide ion battery, the specific capacity of the iodide-ion battery gradually increased in the first 2000 cycles. After 3850 cycles, the specific capacity dropped to 50 mA h gcb1, showing that the electrolyte of the ethylene glycol system can adapt to different metal negative electrodes. This finding is of universal significance for the iodide-ion battery. In order to compare the effect of electrolytes with different concentrations of ethylene glycol on the specific capacity of iodide-ion battery, we used zinc foil as the anode of iodide-ion battery as an example. The electrolyte concentration was studied separately under the condition of overcharge and over-discharge of iodide-ion battery. The specific capacities of the iodide-ion battery for 0.5 m, 1 m, 1.5 m KI were shown in Fig. 3 (d). It was found that 1.5 m KI had the best per formance and that the maximum discharge specific capacity reached 175 mA h gcb1. In order to verify the intercalation of iodide ions in the positive carbon material, we performed a XPS test. Fig. 4 shows the XPS spectrum of the cathode after the charging is completed when zinc foil is used as anode. Fig. 4 (a) shows the existence of I3d, C1s, and O1s. And in Fig. 4 (b), two obvious I3d peaks located at 619.3 and 631.0 eV can be considered to I3d5/2 and I3d3/2 states [33,34], respectively. The signal of
the iodide-ion battery, iodide ion played a dominant role, and a small number of zinc ions would not affect the iodide battery. The reaction mechanism of zinc ions during charge and discharge is shown in Fig. 1 (b). Kþ accumulates around the zinc during charging. Meanwhile, the surrounding Kþ attracts the extranuclear electrons of zinc, which showed positive divalent state (Zn2þ). During discharging, the potas sium ions were far away from zinc, and the electrons were reset, then Zn2þ become Zn. In addition, as shown in Fig. 4 (g), when iodide-ion battery was fully charged and discharged, we performed IR character ization of the zinc negative electrode. It can be observed that the metal zinc anode did not change during complete charge and discharge, con firming that the zinc anode was not excessively involved. As shown in Fig. 2 (i), in order to verify the role of copper ions in the iodide-ion battery, we replaced the 1.5 m KI with 1.5 m CuSO4 to form a copper-based hybrid supercapacitor without a discharge platform similar to the zinc-ion hybrid supercapacitor [30–32]. The results indi cated that when the copper foil was used as the negative electrode of the iodide-ion battery, iodide still played a dominant role. The reaction mechanism of copper foil during charging and discharging was exactly the same as that of zinc foil. The reaction mechanism of zinc foil has been discussed in detail in Fig. 1 (b) and will not be repeated here. Fig. 3 (a) shows the cycle life of the iodide battery when the zinc foil is used as the negative electrode of the iodide-ion battery and the elec trolyte is 1.5 m KI (ethylene glycol system). It can be seen that after 10000 cycles, the capacity retention rate of the iodide battery was almost 100%. Under the same conditions, the ethylene glycol was replaced by water to make a water-based iodide-ion battery. As shown in 5
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I3d5/2 can be further divided into a C–I peak of 619.3 eV and a C–Iþ-C peak of 619.9 eV [35], which is correlated with the intercalation of io dide ions during charge and discharge. The spectrum of C1s is shown in Fig. 4 (c). The above analysis was also verified by the C–I peak at 285.2 eV. In addition, the peak of 287.6 eV, 284.6 eV can be attributed to – O, graphitic carbon, respectively [36,37]. It indicates that iodide C– ions are inserted into the carbon material during the charging process and combine with carbon atoms to form a C–I bond. The spectrum of O1s is shown in Fig. 4 (d). The peak of 531.3 eV and – O, which is consistent with Fig. 4 (c). 532.2 eV can be attributed to C– The XRD spectrum is shown in Fig. 4 (e). Drum peaks of amorphous carbon between 20� and 27� can be clearly observed during charging and discharging [38,39]. The difference is that when the charge is completed, the peak of the amorphous carbon appears to be more gradual and broader than that when the discharge is completed. It is because when the charging is completed, iodide ion and carbon material are sufficiently combined to affect the characterization of the carbon peak. FT-IR analysis was further carried out to verify the conversion of iodine ion during reaction. As shown in Fig. 4 (f), after charge and discharge were completed, several peaks appeared in the spectrum. The peak at 1650 cm 1,1550 cm 1,885 cm 1 could be ascribed to the – O, C– – C, C–O–C, respectively [40,41]. Peaks stretching vibration of C– at 1350 and 1465 cm 1 could be ascribed to the bending vibration of CH2, while those at 2853, 2926 cm 1 could be assigned to the stretching vibration of CH2. The difference is that the peak value of δ(CH) after charging is significantly weaker than that after discharge, indicating that CH2 group is replaced by another group during charging, and iodide ions and carbon are likely to form a new bond. In addition, the presence – O and C–O–C can be observed upon completion of charging. The of C– – O peak is weakened and a new C– – C bond is formed when discharge C– is completed. It indicates that carbon atoms and other groups of the electrolyte form new chemical bonds during charging, and that the above bonds break and transfer during discharging, and the remaining – C bonds. carbon atoms themselves are combined together to form C–
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4. Conclusion In our work, we firstly proposed an iodide-ion battery and used carbon black as the positive electrode material of iodide-ion battery. It is found that two stable metal anode materials, zinc foil and copper foil showed good performance and cycle stability. Meanwhile, ethylene glycol non-aqueous system was used as electrolyte, and the results showed that it had more remarkable cycle stability than the electrolyte of the water system. It provides a new direction for exploring highly stable electrolytes for ion batteries. It is undeniable that our work is also drawing on many people’s experience, and many problems need to be solved in the iodide battery. It is firmly believed that if everyone works together, this project will become more and more perfect. Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. References [1] J.B. Goodenough, Y. Kim, Challenges for rechargeable Li batteries, Chem. Mater. 22 (2010) 587–603, https://doi.org/10.1021/cm901452z. [2] L.W. Jiang, et al., Building aqueous K-ion batteries for energy storage, Nat. Energy 4 (2019) 495–503, https://doi.org/10.1038/s41560-019-0388-0. [3] Y.Y. Wang, et al., TiO2-Coated interlayer-expanded MoSe2/Phosphorus doped carbon nanospheres for ultrafast and ultralong cycling sodium storage, Adv. Sci. 6 (2019). ARTN 180122210.1002/advs.201801222. [4] X. Ji, et al., Water-activated VOPO4 for magnesium ion batteries, Nano Lett. 18 (2018) 6441–6448, https://doi.org/10.1021/acs.nanolett.8b02854.
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