Key Takeaways & Executive Findings
- •• A novel NRP/Ti3C2 nanocomposite is synthesized via a facile chemical precipitation method, achieving uniform dispersion of red phosphorus nanoparticles on Ti3C2 nanosheets. • The Ti3C2 matrix effectively mitigates volume expansion and enhances electronic conductivity, leading to improved cycling stability and rate capability for sodium-ion storage. • The NRP/Ti3C2 anode delivers a high reversible capacity of ~862 mAh·g−1 at 0.1 A·g−1 and retains 525.2 mAh·g−1 after 100 cycles, demonstrating excellent long-term performance. • A free-standing NRP/Ti3C2 electrode is fabricated, achieving an areal capacity of ~2.21 mAh·cm−2, offering a promising pathway for high-energy-density sodium-ion batteries.
Abstract
Red phosphorus (RP) has been recognized as a promising anode candidate for sodium-ion batteries (SIBs) due to its high theoretical capacity and natural abundance. However, the electrochemical performance of RP is restricted by the critical issues of the large volume variation upon cycling and the low intrinsic electronic conductivity. Herein, a nanocomposite with the structure of well-dispersed RP nanoparticles intimately attached to the surface of two-dimensional Ti3C2 nanosheets (NRP/Ti3C2) is prepared by a facile chemical precipitation method. The introduction of Ti3C2 nanosheets can effectively prevent the RP nano-grains/clusters from agglomeration and growth in the synthesis process. Besides, the flexible Ti3C2 sheets can not only function as the mechanical support for accommodating the volume change of RP upon Na+ uptake/release process, but also provide an efficient conductive network for electron transportation. Moreover, the shortened ions diffusion distance enabled by the nano feature of RP further favors the electrode reaction kinetics. When employed as anode for SIBs, the synthesized NRP/Ti3C2 composite exhibits a reversible capacity of ~862 and 576 mAh·g−1 at 0.1 and 0.5 A·g−1, respectively, as well as a maintained capacity of 525.2 mAh·g−1 after 100 cycles at 0.1 A·g−1. In addition, the fabricated free-standing NRP/Ti3C2 electrode with a capacity of ~2.21 mAh·cm−2 and stable electrochemical cycling provides a valid guide toward high-performance RP-based anodes for realizing SIBs with high energy density.
1. Introduction
Sodium-ion batteries (SIBs), as significant electrochemical energy storage devices, hold great potential to serve as a supplement or replacement to lithium-ion batteries (LIBs) for supporting large-scale energy storage applications due to the abundance of Na resources and the similar working mechanism [1–3]. As the key component of SIBs, electrode materials largely determine the electrochemical properties of SIBs. For the negative electrode, graphite, the commonly commercialized anode material for LIBs, has been so far inhibited from being used in SIBs because of the thermodynamic instability of binary Na-intercalation graphite compounds [4]. Therefore, considerable efforts have been devoted to developing anode materials with high capacity, excellent cycling stability, and low cost to promote the practical applications of SIBs.
Up to date, in search of advanced anode materials, carbonaceous (hard carbon, soft carbon), alloying, conversion, and mixed alloying-conversion type materials have been proposed [5–8]. For example, benefitting from the provided higher Na+ storage capacity than that of graphite, the properly low working voltage, and the large source of raw materials, hard carbon (non-graphitizable carbon) with a hybrid structure consisting of amorphous nanodomains and graphite-like microcrystallites with random orientations, shows great promise and has already been applied in SIBs launched by several companies dedicated to promoting SIBs industrialization [9–11]. However, it is undeniable that the drawbacks of the unsatisfactory sodium storage capacity and low initial Coulombic efficiency of hard carbon are not conducive to the development of high energy density SIBs [12–14]. Among the alloying-type high-capacity anodes, red phosphorus (RP) has attracted much attention as a most promising candidate (high theoretical specific capacity: ~2596 mAh·g−1; moderately low discharge voltage: ~0.4 V versus Na+/Na) for pairing with high-energy cathodes to enable the SIBs with high energy density [15–17].
Unfortunately, RP suffers from the critical issues of huge volume change during cycling (>300%) and inferior intrinsic electronic conductivity (1×10−14 S·cm−1), in which the former leads to severe particle pulverization, the loss of electrical contact, the unstable surface solid–electrolyte interphase (SEI), and thus the poor cycling stability accompanying with the low Coulombic efficiency [18–19], while the latter restricts the electrode reaction kinetics and rate-capability. To address the aforementioned issues, typical effective strategies have been employed, including particle nanosizing to withstand the large (de)sodiation strain without fracture and shorten the ions/electrons diffusion distance.
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Yuxuan Gao, Chenglong Ma, Yu Zhang, Jin Bai, Zihang Zhu, Jie Wang, Hailei Zhao (2025). Red phosphorus/Ti3C2 MXene nanocomposite and flexible free-standing electrode for sodium-ion storage. Int. Journal of Minerals, Metallurgy and Materials (矿物冶金与材料学报). https://doi.org/10.1007/s12613-025-3091-0
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Frequently Asked Questions
What is the main challenge of using red phosphorus as an anode material for sodium-ion batteries?
Red phosphorus suffers from huge volume changes during cycling (>300%) and low intrinsic electronic conductivity (1×10−14 S·cm−1), leading to particle pulverization, loss of electrical contact, unstable SEI, and poor cycling stability.
How does the Ti3C2 MXene improve the performance of red phosphorus anodes?
Ti3C2 nanosheets act as a mechanical support to accommodate volume changes, provide an efficient conductive network for electron transport, and prevent agglomeration of RP nanoparticles, thereby enhancing cycling stability and rate capability.
What are the key electrochemical performance metrics of the NRP/Ti3C2 composite?
The composite delivers a reversible capacity of ~862 mAh·g−1 at 0.1 A·g−1 and 576 mAh·g−1 at 0.5 A·g−1, with a maintained capacity of 525.2 mAh·g−1 after 100 cycles at 0.1 A·g−1.
What is the significance of the free-standing NRP/Ti3C2 electrode?
The free-standing electrode achieves an areal capacity of ~2.21 mAh·cm−2 and stable cycling, demonstrating its potential for high-energy-density sodium-ion batteries without the need for a current collector.
What method was used to synthesize the NRP/Ti3C2 nanocomposite?
The nanocomposite was prepared by a facile chemical precipitation method, which ensures well-dispersed RP nanoparticles intimately attached to the Ti3C2 nanosheets.
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