Elsevier

Energy Storage Materials

Volume 28, June 2020, Pages 247-254
Energy Storage Materials

A high-power aqueous rechargeable Fe-I2 battery

https://doi.org/10.1016/j.ensm.2020.03.010Get rights and content

Highlights

  • An aqueous Fe-I2 battery is enabled by coordination of functional electrode substrate and electrode architecture.

  • The battery shows excellent rate performance in a wide current range of 500–5000 ​mA ​g-1

  • The battery delivers well producible solar-charge capability when connected with commercial solar cells.

Abstract

Aqueous Fe-I2 rechargeable batteries are highly desirable for large-scale energy storage because of their intrinsic safety, cost effective, and wide abundance of iron and iodine. However, their development suffers from Fe dendrite growth and severe shuttle effect during cycling. Herein, we demonstrate a high-performance Fe-I2 rechargeable battery using metal iron as anode, iodine/hierarchically porous carbon composite as cathode and an eco-friendly aqueous electrolyte. The anode modified with ascorbic acid effectively suppresses the formation of iron dendrite, while the cathode doped with nitrogen greatly reduces the shuttle of iodine species. The battery operates a reversible redox reaction of FeI2/I2 pair with fast kinetics. A capacity ~190 ​mAh g-1 at current densities up to 5000 ​mA ​g-1 and excellent cycle stability of 100% after 550 cycles at 2000 ​mA ​g-1 are obtained. The battery achieves superior power density of ~1300 ​W ​kg-1 at 120 ​Wh kg-1 and high energy density of 130 ​Wh kg-1 at 356 ​W ​kg-1. Our study shows great promise for high-performance rechargeable batteries with low-cost, eco-friendliness and high safety.

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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