The electrochemical properties of iodine cathode in a novel rechargeable hydrogen ion supercapattery system with molybdenum trioxide as anode
Graphical abstract
Introduction
Rechargeable batteries play a very important role in energy storage, especially in wind and solar renewable and clean energy. Researchers are working to develop battery devices that are environmentally friendly, safe and affordable for large-scale applications [1], [2], [3]. Lithium-ion batteries (LIBs) are widely applied in daily life because of their high capacity and superior cycling performance. However, the organic electrolyte in LIBs does not conform to the concept of environmental protection and green development, and also poses a certain threat to safe use [4], [5], [6], [7]. Therefore, there is an urgent need to develop eco-friendly, secure, inexpensive and durable batteries.
Aqueous rechargeable batteries have been widely reported in recent years due to their low-cost, non-flammable water-based electrolytes [8,9], such as Aluminum-ion battery [10,11], Magnesium-ion battery [12], Zinc-ion battery [13,14], Calcium-ion battery [15] and so on. Nevertheless, the larger charge carrier size of these batteries impedes the kinetics of electronic transport. Hence, the hydrogen ion battery with hydrogen ion (H+) as the charge carrier is considered as the promising alternative to the metal ion battery accounting for its small ion radius, wide availability, and negligible cost [16], [17], [18]. In fact, there have been recent reports of hydrogen ion batteries, but the current development of this technology is limited by the choices of the available cathode and anode electrodes [19], [20], [21]. The ideal anode materials must be able to accept H+, and the ion insertion potential needs to be high enough to avoid hydrogen evolution reaction (HER), while exploring the suitable cathode that matches the anode electrode well is still a confusing challenge [22], [23], [24].
So far, it has been proved that hydrogen ions can be reversibly inserted into 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) in acidic electrolyte, delivering a specific capacity of 85 mAh g−1 at 1 A g−1 [25]. However, organic electrodes have a certain degree of dissolution during ion insertion, so some two-dimensional layered materials, such as rGO [26] and Ti3C2Tx [27], are also used as anode electrodes for hydrogen ion batteries. Nevertheless, these two-dimensional materials have a lower hydrogen storage capacity, so many insoluble inorganic oxides, such as MoO3 [28] and WO3 [29,30], have attracted the attention of researchers due to the superior stability and good energy storage. Furthermore, MoO3 has been proved to be a promising anode electrode for many rechargeable batteries [31,32]. For example, Wu and co-workers [33] reported the MoO3 nanosheet arrays as the anode for the Li- and Na-ion batteries, showing excellent cycling stability and high specific capacity (1780 mAh g−1 at 0.1 mA cm−2). Furthermore, MoO3 can also be applied to the anode electrode for hydrogen ion batteries. It has been reported that H+ can insert into MoO3 electrode with a high capacity of 235 mAh g−1 at 5 C [34].
In terms of the choices of cathode materials in the hydrogen ion battery, certain Turnbull's blue analogues (TBAs) and Prussian blue analogues (PBAs) are also confirmed to act as cathodes, such as CuFe-TBA and NiFe-TBA [35]. Whereas, according to the reports [36], the capacities of CuFe-TBA and NiFe-TBA are 95 mAh g−1 and 65 mAh g−1, which are far from satisfying the practical application. In addition, PBAs are also acted as the cathodic host to load iodine due to their enough porosity and continuous micropore channels. For example, Ma and co-workers [37] assembled the Co [Co1/4Fe3/4(CN)6]/I2//Zn battery, which exhibited a superior rate performance with the high capacity of 151.4 mAh g−1 at 20 A g−1. Furthermore, iodine is also used in lithium-ion [38], [39], [40] and sodium-ion [41] batteries. Carbon materials, such as active carbon fiber cloth and carbon paper, are also the ideal materials for iodine loading, which could applied in Zinc ion batteries (ZIBs) (Zn/Zn2+, I−/I) [42]. However, when the charging voltage is higher than 1.6 V in ZIBs, Zn(IO3)2 and ZnO will be generated, leading to the produce of the irreversible capacity [43]. Moreover, iodine is also widely used as cathode material in other rechargeable aqueous batteries due to the redox of itself and abundance of valence states [44]. For instance, Tian and co-workers [45] reported a Mg/I2 battery delivering the high capacity of 140 mAh g−1 at 1 C. Nevertheless, because iodine has a certain volatileness, which leads to the poor rate capability, some polymers are often combined with iodine, such as polyacrylonitrile (PAN) and polyaniline (PANI) are developed to improve the stability and performance [46]. Heteroatomic doping, therefore, may be a way for solving the stability problem.
Although so far, there has been no report that iodine can be used as the cathode electrode material for hydrogen ion batteries, and water-based hydrogen ion batteries formed by matching MoO3 anode electrode are also a blank in research, but they are theoretically feasible to some extent. Supercapattery, also called as supercapacitor-battery hybrid device, has been announced as a new term to signify a vast range of devices that exploit both capacitive and non-capacitive Faradaic charge storage mechanisms at either the electrode material level. As a new type of energy storage device, it combines the advantages of supercapacitor and battery, such as superior rate performance, long cycle life, better temperature characteristics, etc., and has been studied a lot recently [47,48].
Herein, we firstly assembled the novel hydrogen ion supercapattery with iodine as the cathode and MoO3 as the anode, and the H3PO4 (9.5 M) was acted as the electrolyte. The schematic illustration of the novel hydrogen ion supercapattery was shown in Fig. 1. The novel supercapattery showed not only the high capacity characteristics of batteries, but also the excellent rate performance and cycle stability of supercapacitors. NP-CP substrate shows stronger adsorption to I2/I−, but poor to IO3−. The cyclic stability of the I2-NP-CP electrode decreased due to the diffusion of IO3− into electrolyte and thus Nafion resin was used to modify the electrode. The supercapattery exhibits superior rate capability at different current densities ranging from 1 A g−1 to 20 A g−1, and the electrochemical performance of this supercapattery shows that the electrodes remain 124.3 mAh g−1 after 500 cycles at the current density of 15 A g−1, accounting for 93.2 % of the initial capacity. This novel supercapattery system has a certain guiding significance for the future research of hydrogen ion batteries, and heteroatom doping and Nafion modification also provide a new idea for improving the rate performance and cycle stability of rechargeable batteries.
Section snippets
Materials
All the chemicals used in the experiment are analytically pure. Aniline, phytic acid, Ammonium Molybdate Tetrahydrate and Iodine were purchased from Shanghai McLean Biochemical Technology Co., Ltd. Ammonium persulfate, phosphoric acid and nitric acid were provided by Sinopharm Chemical Reagent Co. Ltd. Carbon paper was purchased from Shanghai Hesen Electric Co., Ltd.
Preparation of carbon paper substrates doped with N and P heteroatoms
The solution A was obtained by mixing 0.6 mL aniline and 3 mL phytic acid to form 15 mL aqueous solution with de-ionized (DI)
Results and discussion
The supercapattery was composed of I2-NP-CP cathode electrode and MoO3 anode electrode, 9.5 M H3PO4 was used as the electrolyte. As shown in Fig. 1, when the supercapattery charges, the I2 is oxidized to the higher valence state of IO3− in the cathode electrode, while H+ is embedded into the MoO3 electrode to form HxMoO3 in the anode. Furthermore, when the supercapattery discharges, the IO3− is reduced to I− in the positive electrode, and the H+ is stripped from HxMoO3 to form MoO3 in the
Conclusions
In summary, we have successfully demonstrated that iodine could be used as the cathode electrode for hydrogen ion supercapattery, and that the anode electrode of molybdenum trioxide could be well matched to assemble the I2-NP-CP//MoO3 supercapatteries. Notably, NP-CP shows stronger adsorption to I2/I−, but poor to IO3−. The cyclic stability of the I2-NP-CP electrode decreased due to the diffusion of IO3− into electrolyte. Therefore, Nafion resin is used to modify the electrode to improve the
Authors' statement
The authors certify that this manuscript is original, has not been published previously, and is not currently submitted for review to any other journals elsewhere. The submission is approved by all authors and explicitly by the responsible authorities where the work was carried out. Also, if the submission could be accepted, it will not be published elsewhere in the same form, in English or in any other language, without the written consent of the Publisher.
Shangbin Sang
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.
Acknowledgement
This work was financially supported by the science and technology innovation Program of Hunan Province (No. 2020RC1001), the Fundamental Research Funds for the Central Universities of Central South University (No. 2019zzts445), the Hunan Provincial Science and Technology Plan Project, China (No. 2017TP1001), Natural Science Foundation of Hunan Province (2019JJ50794, 2020JJ4681) .
References (53)
- et al.
A novel dual-graphite aluminum-ion battery
Energy Storage Mater.
(2018) - et al.
Li3-xNaxV2(PO4)3 (0≤x≤3): possible anode materials for rechargeable lithium-ion batteries
Electrochim. Acta
(2016) - et al.
Investigating FeVO4 as a cathode material for aqueous aluminum-ion battery
J. Power Sources
(2019) - et al.
Al3+ ion intercalation in MoO3 for aqueous aluminum-ion battery
J. Power Sources
(2019) - et al.
Inclusion complexation enhanced cycling performance of iodine/carbon composites for lithium–iodine battery
J. Power Sources
(2020) - et al.
Amino-rich surface-modified MXene as anode for hybrid aqueous proton supercapacitors with superior volumetric capacity
J. Power Sources
(2021) - et al.
Superior rate performance of Li3V2(PO4)3 co-modified by Fe-doping and rGO-incorporation
RSC Adv.
(2016) - et al.
Electrochemical and structural investigation of calcium substituted monoclinic Li3V2(PO4)3 anode materials for Li-ion batteries
Adv. Energy Mater.
(2019) - et al.
Electrochemical and structural investigation of the mechanism of irreversibility in Li3V2(PO4)3 cathodes
J. Phys. Chem. C
(2016) - et al.
Structural impact of Zn-insertion into monoclinic V2(PO4)3: implications for Zn-ion batteries
J. Mater. Chem. A
(2019)
Long-life aqueous H+/K+ dual-cation batteries based on dipyridophenazine//hexacyanoferrate electrodes
ACS Appl. Energy Mater.
Recent progress of rechargeable batteries using mild aqueous electrolytes
Small Methods
Reversible Al3+ ion insertion into tungsten trioxide (WO3) for aqueous aluminum-ion batteries
Dalton Trans.
The pitfalls in nonaqueous electrochemistry of Al-ion and Al dual-ion batteries
Adv. Energy Mater.
Advances in rechargeable Mg batteries
J. Mater. Chem. A
A novel dendrite-free Mn2+/Zn2+ hybrid battery with 2.3 V voltage window and 11000-cycle lifespan
Adv. Energy Mater.
Proton inserted manganese dioxides as a reversible cathode for aqueous Zn-ion batteries
ACS Appl. Energy Mater.
Enlisting potential cathode materials for rechargeable Ca batteries
Chem. Mater.
High power and energy density aqueous proton battery operated at −90°C
Adv. Funct. Mater.
A high-rate aqueous proton battery delivering power below −78°C via an unfrozen phosphoric acid
Adv. Energy Mater.
Solid-state proton battery operated at ultralow temperature
ACS Energy Lett.
A novel electrochemical hydrogen storage-based proton battery for renewable energy storage
Energies
Rocking-chair proton batteries with conducting redox polymer active materials and protic ionic liquid electrolytes
ACS Appl. Mater. Interfaces
An ultralow temperature aqueous battery with proton chemistry
Angew. Chem. Int. Ed.
Vanadium hexacyanoferrate as high-capacity cathode for fast proton storage
Chem. Commun.
A rechargeable aqueous proton battery based on a dipyridophenazine anode and an indium hexacyanoferrate cathode
Chem. Commun.
Cited by (5)
Iodine conversion chemistry in aqueous batteries: Challenges, strategies, and perspectives
2023, Energy Storage MaterialsCitation Excerpt :Therefore, compositing iodine with a host substance is a rational tactic to enhance the thermal stability and electrical conductivity of active materials, along with suppressing the shuttle effect of polyiodides. Typically, four methods can load iodine into host materials, i.e., melt-diffusion method [75], vapor-adsorption method [69], solution-adsorption method [26], and electrochemical deposition [44,76,77]. With consideration of iodine uptake capability and electrical conductivity, carbon-based scaffolds, conductive polymers, ordered porous framework materials, MXenes, and other iodine-based CTCs have emerged as promising host materials for AISBs.
Advanced cathodes for aqueous Zn batteries beyond Zn<sup>2+</sup> intercalation
2024, Chemical Society ReviewsA twelve-electron conversion iodine cathode enabled by interhalogen chemistry in aqueous solution
2023, Nature Communications