A high-power aqueous rechargeable Fe-I2 battery
Introduction
The increasing attention to inexhaustible solar energy calls for advanced energy storage techniques [1]. Regarding the challenges afflicting power stations for solar energy storage, the power density, safety as well as cost of the batteries are more of a concern than their energy density [2]. In addition, due to the fluctuation of output current density of solar cell which results from the variation of solar radiation, the batteries should be able to adapt to the random changes of current densities at wide range [3]. The present lithium-ion batteries with organic electrolyte suffer from limited rate capability, high cost and thermal runaway, which dictate against their practical applications in this field [4]. Therefore, increasing interest is stimulated in the quest for safe and low-cost energy storage devices using aqueous electrolyte and earth-abundant elements [5,6].
Among the various options, Fe batteries are of particularly interest because of the following benefits which include: the promise of achieving two-electron transfer at a single redox center, thus delivering a large specific and volumetric energy density (Table S1, Supporting Information); the Fe metal is stable in wide pH range aqueous solution implying the possibility of employing metal iron as anode, which competitive in energy density; inexpensive and non-toxicity [7]. These aforementioned merits have fueled interests in flow battery and batteries based on Fe2+ topotactic intercalation [[8], [9], [10]]. Recently, enthusiasm for utilizing iodine as cathode materials is sparked by the high theoretical specific capacity (211 mAh g-1), fast reaction kinetics, the abundance in the ocean and its eco-friendly nature [[11], [12], [13], [14]]. We herein propose an Fe-I2 battery combines an iron metal anode and iodine composite cathode in aqueous electrolyte. However, several major obstacles should be addressed before its utilization: 1) the formation of Fe dendrites during repeated cycles usually leads to battery failure [15], 2) the disproportion reaction of I2 in alkaline solution and possible Fe corrosion in acidic solution both result in performance fading, 3) the shuttle effects of iodine species in aqueous solution undoubtedly deteriorates the capacity retention [16].
In this work, modified Fe anode and I2/Nitrogen-doped hierarchically porous carbon (N-HPC) composite cathode in aqueous electrolyte have been adopted to address the challenges in Fe-I2 batteries (Fig. 1a). The ascorbic acid is used as additive which suppresses undesired Fe dendrite growth. The N-HPC framework gives a well suppression to deleterious shuttling of iodine species. Compared with other metal-I2 batteries (Fig. 1b, Table S2, Supporting Information), the present Fe-I2 battery demonstrates obvious cost and safety merits with competitive theoretical capacity. Interestingly, the obtained Fe-I2 battery features a high rate performance with an appealing power density of ~1300 W kg-1 at energy density of 120 Wh kg-1. Moreover, the resultant Fe-I2 battery can be directly charged by solar cell with a stable cycle performance and high energy utilization efficiency.
Section snippets
Preparation of I2/N-HPC composite
The N-HPC was prepared according to previously described protocol [17]. Briefly, N-acetyl-d-glucosamine (≥99%, aladdin) was thoroughly mixed in an Agatha mortar with potassium oxalate monohydrate (≥99%, aladdin) and calcium carbonate (Shanghai Songjiang Corp., d ~ 200 nm) at a weight ratio of 1:1:1. The obtained mixture was then heated to 750 °C (3 °C min-1) under an argon gas flow and for 1 h. The product was then washed with diluted HCl and deionized water until pH = 7. Afterward, the
Results and discussion
To evaluate the iodine loading capacity of N-HPC host, the composite cathode is carefully analyzed. Fig. 2a shows the thermogravimetric analysis curves. The slight mass loss of N-HPC stems from the evaporation of water in pores and decomposition of edge doping element [18], and the I2 content in the composite is determined ≈ 40 wt%, which is higher than most of reported iodine hosts [[19], [20], [21], [22]]. However, the hierarchical I2/N-HPC composite demonstrates a smooth surface. The
Conclusions
In summary, we have demonstrated an aqueous rechargeable Fe-I2 battery with high rate and durable cycle performance. The battery is composed of iron metal modified with ascorbic acid as anode, I2/N-HPC composite as cathode, and a mild ferrous salt electrolyte. The nitrogen doping in HPC can not only promote redox of iodine, but also avoid shuttle effect because its well confinement to iodine species. The modification of ascorbic acid to Fe anode is able to effectively alleviate the dendrite
CRediT authorship contribution statement
Chong Bai: Writing - original draft, Data curation, Formal analysis. Huijie Jin: Methodology. Zongshuai Gong: Methodology. Xizheng Liu: Writing - original draft. Zhihao Yuan: Writing - original draft, Supervision, Project administration.
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.
Acknowledgements
This work was financially supported by the National Natural Science Foundation of China (No. U1804255) and the National Key R&D Program of China (2017YFA0700104).
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