Elsevier

Chemical Engineering Journal

Volume 363, 1 May 2019, Pages 285-291
Chemical Engineering Journal

Ni3(BO3)2 as anode material with high capacity and excellent rate performance for sodium-ion batteries

https://doi.org/10.1016/j.cej.2019.01.089Get rights and content

Highlights

  • Ni3(BO3)2 micron-rods were synthesized using a simple solid phase method.

  • Ni3(BO3)2 is first used as anode material for sodium-ion batteries.

  • Ni3(BO3)2 shows specific capacity as high as 428.9 mA h g−1at 200 mA g−1.

  • Ni3(BO3)2 exhibits excellent rate capability of 304.4 mA h g−1 at 2 A g−1.

Abstract

In this paper, Ni3(BO3)2 was synthesized via a simple solid-state reaction method and used as anode materials for sodium-ion batteries for the first time. The Ni3(BO3)2 exhibits a desodiation capacity of 428.9 mA h g−1 at 200 mA g−1 and a high capacity of 304.4 mA h g−1 even at 2000 mA g−1. The resulting material also shows a good cycling stability with a capacity retention of 85.4% over 50 cycles. In-situ X-ray diffraction analysis reveals the phase transition behavior of Ni3(BO3)2 in the first discharge process. Kinetics analysis reveals that the high-performance sodium storage is dominated by pseudocapacitance, especially at the high rate. These highlights indicate that Ni3(BO3)2 would have hopeful prospects as an anode material for sodium-ion batteries.

Introduction

Resource rich, low price and the similar electrochemical storage mechanism to lithium are the decisive factors to develop sodium-ion batteries (SIBs) [1], [2], [3]. In recent years, considerable efforts have been devoted to the research of anode materials for SIBs, such as carbonaceous materials, titanium-based oxide compounds, transition metal oxides (or sulfides) and alloying-type materials [6], [7], [8], [9], [10], [11], [12], [13], [14]. It is generally accepted that graphite as a common anode material for lithium-ion batteries (LIBs) and potassium-ion batteries (KIBs) [4], [5], but not properly intercalate sodium ions. Hard carbon with a great degree of sodium reversible intercalation has been intensive researched, but the low intercalation potential poses a potential safety hazard [6], [7]. Titanium-based oxides possess reasonable operation voltage, nontoxicity and low-cost, as another type anode material, its capacity still needs to be improved [8], [9], [10], [11], [12]. Transition metal oxides (or sulfides) and alloying-type materials have superiority in capacity, while the rapid capacity fading problem needs to be solved [13], [14].

Boron can form borates with most metals in the periodic table of the elements, and several or even dozens of borates can be formed with the same element [15], [16]. These diverse structures will lead to rich chemical properties. In recent decades, various borate materials, such as Ni3B2O6, Fe3BO6, FeBO3, Cr3BO6, VBO3 and Co2B2O5, have been used as electrode materials for lithium-ion batteries [17], [18], [19], [20], [21], [22], [23]. Most recently studies showed that some borates materials used in LIBs also have certain sodium storage capacity [24], [25]. Fe3BO6 was first reported as promising anode materials for SIBs by Tian et al. [26]. It shows an average potential about 1.4 V versus Na+/Na during the charge process and a high specific capacity of 444.4 mA h g−1 at 400 mA g−1. Gu’s group also reported that N-doped Zn3B2O6 delivered a capacity of 295.6 mA h g−1 for SIBs at 50 mA g−1 [27]. The VBO3 also has been investigated as anode for SIBs [21] but the capacity is only about 32.2 mA h g−1.

In this paper, homogeneous micron-rods of Ni3(BO3)2 were synthesized by a facile solid-reaction method. This material was for the first time evaluated as an anode for SIBs. Also, the sodium-ion storage mechanism was studied by the in-situ XRD analysis and kinetics analysis.

Section snippets

Materials synthesis

All chemicals with analytical grade were obtained from Macklin Company and were used without further purification. Ni3(BO3)2 materials were synthesized via a typical solid-state method. Stoichiometric proportions of Ni(NO3)2·6H2O and H3BO3 powder (molar ratio: Ni:B = 3:2) were added into mortar and grind sufficiently to get a homogenous mixture. Then the mixture was heated at 750 °C for 4 h. Finally, the Ni3(BO3)2 products were obtained after being washed with hot de-ionized water for several

Results and discussion

To identify the phase structure of the Ni3(BO3)2, the XRD diffractograms of the product were analyzed and showed a typical XRD pattern of the Ni3(BO3)2 (Fig. 1(a)). All the observed diffraction peaks can be indexed as the orthorhombic structured Ni3(BO3)2 with the Pnmn space group (JCPDS card 75–1809) [28], [29], [30], which shows that no impurity peaks had been detected. And the calculated lattice parameters are calculated to be a = 5.397 Å, b = 8.301 Å, and c = 4.460 Å. As can be seen from

Conclusions

In conclusion, a novel Ni3(BO3)2 µm-rods were successfully prepared via a simple high temperature solid phase method. As an electrode material for SIBs, the Ni3(BO3)2 electrode possesses high reversible capacity of 428.9 mA h g−1 at 200 mA g−1. Even at a remarkable high current density of 2000 mA g−1, the specific capacity of Ni3(BO3)2 materials still reached 304.4 mA h g−1, which shows excellent rate capability. In-situ XRD measurements demonstrated the phase evolution behavior of Ni3(BO3)2

Acknowledgments

This work was supported by the National Natural Science Foundation of China (No: 21673136) and the national key research and development Program of China (2016YFB0901500).

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