Elsevier

Energy Storage Materials

Volume 34, January 2021, Pages 436-460
Energy Storage Materials

Recent progress of phosphorus composite anodes for sodium/potassium ion batteries

https://doi.org/10.1016/j.ensm.2020.10.003Get rights and content

Abstract

Developing highly efficient energy storage technologies is of great significance as the strong support for the utilization of renewable and sustainable energy. Sodium-ion batteries (SIBs) and potassium-ion batteries (KIBs) have attracted considerable attentions as the new generation metal-ion batteries due to the abundance natural reserve and cost-effective merits of Na and K. Phosphorus is viewed as a promising candidate among various anode materials while its poor cycling stability and sluggish electrochemical reaction dynamics caused by huge volume variation and inherently low electronic conductivity greatly limit its practical use for energy storage devices. Compositing by introducing a suitable second component has been proposed as an effective strategy to potentially resolve those issues. Herein, the research progress of phosphorus composite anodes for SIBs/KIBs is reviewed. We firstly summarized the primary modulation methods of anode materials with the working mechanisms of red/black phosphorus (RP/BP) for SIBs/KIBs introduced. The compositing strategies and materials were then reviewed for RP and BP separately from carbonaceous, metallic and organic polymer substrates, respectively. Finally, the challenges and opportunities of RP/BP composites in the development of SIBs/KIBs were presented with the hope to provide some inspirations for the design and fabrication of advanced SIBs/KIBs energy storage systems.

Introduction

With the exhaustion of fossil fuel and strengthening of greenhouse effect, the global energy crisis is becoming one of the focused issues that urgently need to be addressed for human being. Sustainable and renewable energy sources, including solar energy, wind, tidal power, hydropower, etc. are attracting tremendous interests as the potential alternative to the traditional fossil fuel. However, the geographical distribution and intermittent nature of these new-generation energy resources make them difficult to be utilized directly without weather/climate disturbing. Effective energy storage technologies (EST) should be developed for saving and transporting the produced energy from those resources [1], [2], [3], [4]. Among different available EST forms, rechargeable battery-based electrochemical energy storage is extensively investigated and developed for large scale applications in the past decades due to its intrinsic advantages of high specific capacity, ultra-long cycle life, sustainable energy supply, low cost and environment-friendliness [5], [6], [7], [8]. As the representative of alkali metal-ion batteries family, lithium ion batteries (LIBs) has been successfully commercialized in 1991 and continuously improved in the past 10 years) [9,10]. However, the natural reserve deficient and growing cost of the upstream raw materials are increasingly retarding their practical applications for the economic and sustainable energy storage [11,12]. SIBs and KIBs with some similar operational mechanisms to LIBs but natural elements abundance and potential cost advantages have attracted significant attention [13,14]. For example, the low redox potential of Na/Na+(−2.71 V) and K/K+(−2.93 V) vs standard hydrogen electrode (SHE) (Eo) are close to Li (−3.04 vs Eo) [15,16]. Besides, since sodium and potassium do not form alloy with aluminum, aluminum foil can be used as current collector in the anode, which may further reduce the production costs [4,17,18]. It is reported that compared with LIBs, the cost percentage of current collector is 5% lower based on using aluminum foil for SIBs [19]. Furthermore, the Stokes radius in propylene carbonate (PC) are in the order of Li+(4.8 Å) > Na+ (4.6 Å) > K+ (3.6 Å), which indicated superior ionic conductivities of Na+ and K+ than that of Li+ in electrolyte [20]. The smaller Stokes radius gives rise to lower activation energy of ionic diffusion and higher mobility of Na+and K+ compared with Li+ in electrolytes [21,22]. Some other chemical indexes for Na+ and K+ including lower desolvation energy barrier and smaller cohesive energy/metal-O formation energy than Li+ also signify the feasibility of SIBs and KIBs as the promising alternatives to LIBs [23].

The key factors to evaluate the power supply performances of batteries include energy storage density, power density, cycling stability and rate capability, which are strongly dependent on the electrode materials [24,25]. Although some good anode materials have been reported [26,27], exploring high-capacity and long cycling life anode electrodes for SIBs/KIBs is still in its infancy [28], [29], [30]. The direct use of well-developed LIBs anode materials for SIBs and KIBs has been proved to be infeasible. For example, graphite that has been commercialized in LIBs exhibits a poor sodium storage capacity of only 35 mAh g−1 based on computational studies [31], which cannot host the electrochemical insertion of Na+[32]. As reported, the formation energies of Na and graphite compounds are positive, while other alkali metals (i.e. Li and K) are negative by density functional theory (DFT) calculations. Therefore, the Na-graphite compounds are thermodynamically unstable, leading to low sodium capacity [33,34]. In addition, the high solvation energy of Na tends to promote the reversible cointercalation. Therefore, it is possible for Na insertion into graphite with decent capacity under special conditions of electrolytes [35], [36], [37], [38]. Meanwhile, their larger ion dimensions (Na+: 1.02 Å, K+: 1.38 Å vs. Li: 0.76 Å) are more likely to cause powdering and shedding of anode materials [15], which also significantly weaken the electrochemical performance of anodes for SIBs and KIBs. For example, when using graphite materials for KIBs with conventional electrolytes, the graphite intercalation compound produce up to ~60% interlayer swelling, resulting in highly irreversible structural degradation and poor cyclability due to larger K+ radius [39], [40], [41]. Currently, the state-of-art anode materials for SIBs and KIBs mainly include carbon material [42,43], Ti-based compounds [44], [45], [46], Sn-based compounds [47], [48], [49], Sb-based compounds [50], [51], [52] and phosphorus [17,[53], [54], [55]. Among them, phosphorus (especially RP and BP) that has the merits of extremely high theoretical specific capacity (~2596 Ma h g−1), low storage voltage, abundant raw material reserves and low cost, is viewed as the rising star of anode materials for high performance batteries. Meanwhile, the issues including its intrinsic low electronic conductivity and huge volume expansion during cycling also needs to be addressed for the development of long-life and fast SIBs/KIBs [56,57]. The modulated strategies including defect engineering, nano-structuralization, morphology control, compositing, etc., were primarily performed to improve the electrochemical performance of general anode materials for alkali-metal ion batteries (Fig. 1). The defects with vacancies, heteroatom doping, and substitutional impurities can modulate the electronic structure of active materials and change their physicochemical properties (for example, electrical conductivity and wettability of electrode materials), thus leading to the enhancement of electrochemical performance [58,59]. Elaborate engineering of defects can increase the energy storage and active sites by adsorbing or anchoring more external ions and species in the electrolyte, promote the ion diffusion and electron transfer by tuning the intercalation/deintercalation in the materials, and maintain the structural stability for improving the cycling performance [60,61]. The enhancement of electrochemical performance for SIBs and KIBs can be achieved through the enlargement of the active role of defect engineering. Nano-structuralization to downsize the materials into nano-dimension can effectively relieve the volume expansion and powdering of the electrode material during charging/discharging [62,63]. When the material is controlled at the nanometer size, the diffusion path of ions can be significantly shortened with the increased contact for intimate electrode-electrolyte interface built-up, which favorably decrease the energy barrier for intercalation/deintercalation and smooth the transfer of guest ions into the host materials [64], [65], [66], [67]. However, nano-structuralization is not always beneficial since the high surface area may also result in the large SEI formation in the first cycle, which is irreversible and will lead to low initial Coulombic efficiency (ICE). Therefore, rational optimization of the electrode structure is required. The morphology of active materials is also closely related to the electrochemical performance of rechargeable batteries. The structure composed of different building blocks and pores at multidimensional levels shows different specific surface area (SSA) and interconnected porous networks, both of which are considered as key factors to affect the mass diffusion and transfer of electrons and guest ions as well as energy storage density [68], [69], [70]. Tuning the morphology of electrode materials can optimize their structural integrity during electrochemical process and enhance the accessibility to the energy storage sites as well as electron transport kinetics [71,72]. Other than the three strategies aforementioned that are more focused on the intrinsic structural improvement of electrode material itself, compositing is the strategy to combine the features from different components and take the advantages of their synergistic effects for minimizing the drawbacks of individual materials while offering the overall high functionality and performances that the single component cannot provide [73,74]. By controlling the component materials and heterostructure fabrication, the favorable physicochemical properties can be tailed to meet the requirements for specific applications [75,76].

In fact, multi-trials have confirmed the potential with single-phase phosphorus to solve these issues is still low in the current stage, while the integration of other components for heterostructure construction (“compositing”), which has been demonstrated as an effective strategy in other energy related fields [77], is viewed as a promising method to achieve the breakthrough for the fabrication of phosphorus-based high performance anodes for SIBs/KIBs. Carbonaceous materials including activated carbon, carbon nanotube, graphene, etc., that serve as the conductive matrix to scaffold phosphorus can enhance electrical conductivity and form three-dimensional network structure with tunable porous structure and high SSA for alleviating the volume expansion of active materials [42,78]. In recent years, metal as well as its compounds and conductive polymer were also increasingly developed to form the heterostructure with phosphorus to enlarge the candidate of composited anodes considering the carbonaceous based composites still have some limitations in the practical applications [79,80]. Metal and its compounds with high mechanical strength [81] and electrical conductivity [82,83] can ensure the stability of solid electrolyte interface (SEI) and ultrafast electrode transport [84]. Conductive polymer integration is also attractive owing to the versatile functionalization of this class of compounds [85], [86], [87].

We believe compositing phosphorus with heterostructure built-up will be a key and promising strategy to solve its electrochemical drawbacks for the use in alkali-metal batteries. To rationally fabricate phosphorus-based anode materials for SIBs and KIBs with ultra-long cycle life and high rate capability, it is paramount to summarize their current state-of-the-art research progress from the aspect of compositing for understanding the fundamental design guideline and challenges. Despite some excellent reviews about the phosphorus-based materials for SIBs were reported [88], [89], [90], these reviews are primarily focused on the introduction of elemental phosphorus, metal phosphide and phosphorus-carbon materials. To the best of our knowledge, there is still no detailed review for systematically discussing the phosphorus composited anode (PCA) materials and their design strategies for both SIBs and KIBs. Herein, in addition to concentrate on the recent development of PCA, this review also analyzes their working principles and challenges for both SIBs and KIBs in detail, with the aim to draw a roadmap of current material engineering tactic and build up the inherent relationship and regularity for the rational design of high performance electrode materials for broad new-generation alkali-metal batteries.

Section snippets

Working principle and challenges for phosphorus materials

Phosphorus is a non-metallic element with three main allotropes, namely white, red and black phosphorus [91]. The molecular structure of white phosphorus (WP) is highly symmetrical with a tetrahedral structure and weak intermolecular interactions but large bonding strain [92], which leads to its chemical un-stability for easily oxidation under air. Meanwhile, its flammable property also raised safety concern for the applications of batteries [93]. However, it always serves as the starting

Red phosphorus composite anodes for SIBs and KIBs

Building up the heterostructure to form composite is viewed as an attractive method to improve the electrochemical performance of anode materials by taking the advantages from both components. To resolve the low electrical conductivity and huge volume expansion of RP, the conductive matrix was always added to increase the transfer rate of electrons through the anode and stabilize the electrode from sever pulverization. Combining with various types of carbonaceous materials was widely reported

Black phosphorus composite anodes for SIBs and KIBs

As the least reactive phosphorus allotrope, BP with an orthogonal structure that is similar to graphite can be transformed from other allotropes under high temperature and pressure. Compared with RP, the higher bulk electrical conductivity of BP combined with large interlayer spacing (0.52 nm) and reasonable density endows it the high potential for using as anodes for SIBs and KIBs [103,192,193]. However, the huge anisotropic volume expansions, which is around 0%, 92% and 160% along the [100],

Summary and outlook

As one of the materials with highest theoretical capacities for SIBs and KIBs, phosphorus is viewed as a highly promising anode choice for alkali metal-ion batteries. However, its low electrical conductivity and large volume expansion during electrochemical process strongly retard its practical applications for energy storage devices. Among different modulation strategies, compositing with the rational design for phosphorus compositing built-up is an effective way to develop high performance

Declaration of competing interest

The authors declare no conflict of interest.

Acknowledgements

This work is supported by the National Natural Science Foundation of China (51904059, 51902045), LiaoNing Revitalization Talents Program (XLYC1807123), and Fundamental Research Funds for the Central Universities (N2002005, N182505036, N182503030).

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