Phosphorus-Based Anode Materials for Sodium-Ion and Lithium-Ion Batteries

Phosphorus-based anodes have emerged as promising candidates for next-generation alkali-ion batteries, offering exceptionally high theoretical capacities owing to alloying reactions with lithium or sodium. Among phosphorus allotropes, red phosphorus and black phosphorus (including few-layer phosphorene) feature prominently. Red phosphorus is abundant and cost-effective but suffers from severe volumetric expansion (up to 490 %) and poor intrinsic conductivity. Black phosphorus and phosphorene combine high capacity with layered structures that facilitate ion transport, yet they face mechanical degradation and unstable interphases during cycling. To tackle these challenges, research has focused on composite architectures—embedding phosphorus into conductive carbon matrices, nano-structuring via electrospinning or templated pores, and creating heterostructures with two-dimensional materials such as MXenes. Computational modelling and operando characterisation are shedding light on the (de)sodiation and lithiation mechanisms, guiding the design of robust electrodes. The development of phosphorus anodes underpins efforts to improve energy density, reduce reliance on scarce lithium, and harness the wide availability of sodium for grid-scale storage.

Research from Nature Portfolio

One study demonstrated that red phosphorus impregnated into carbon nanofibres exhibits “liquid-like” malleability upon sodiation, revealed by in situ transmission electron microscopy and chemo-mechanical modelling. Encapsulation within carbon fibres effectively buffers volume changes and suppresses side reactions, enabling stable cycling in sodium-ion cells. Another investigation explored the influence of different conductive additives on red phosphorus composites. It was found that commercial Ketjen Black reduces electrode resistance and enhances cycling stability, suggesting a low-cost route to improve alloying-anode performance. In the lithium-ion context, a red phosphorus–decorated electrospun carbon mat was prepared via a simple dropcasting step. The resulting binder-free, self-standing anode combined nano-confined phosphorus particles with a highly porous carbon network, delivering high reversible capacity and excellent rate capability over extended cycles.

Phosphorus-Based Anode Materials for Sodium-Ion and Lithium-Ion Batteries publication trend

The graph below shows the total number of articles in phosphorus-based anode materials for sodium-ion and lithium-ion batteries across all publications each year (not limited to Nature Index journals).

Technical terms

Anode: The negative electrode in a rechargeable battery where alkali ions are inserted during charging.

Alloying–dealloying: Reversible chemical reaction in which phosphorus forms LiₓP or NaₓP phases during (de)insertion of lithium or sodium ions.

Solid electrolyte interphase (SEI): A passivation layer formed on the anode surface that affects ion transport and cycle life.

Electrospinning: A fibre-forming technique that produces continuous nanofibres by applying a high-voltage electric field to a polymer solution or melt.

MXene: Two-dimensional transition metal carbides or nitrides with high conductivity and surface functionality, used to form composites with phosphorus materials.

References

1. Textured Asymmetric Membrane Electrode Assemblies of Piezoelectric Phosphorene and Ti3C2Tx MXene Heterostructures for Enhanced Electrochemical Stability and Kinetics in LIBs. Nano-Micro Letters (2024).
2. Red-phosphorus-impregnated carbon nanofibers for sodium-ion batteries and liquefaction of red phosphorus. Nature Communications (2020).
3. Phosphorus‐Based Composites as Anode Materials for Advanced Alkali Metal Ion Batteries. Advanced Functional Materials (2020).
4. Phosphorus‐Based Anodes for Fast Charging Lithium‐Ion Batteries: Challenges and Opportunities. Small Science (2022).
5. Influence of Conductive additives on the stability of red phosphorus-carbon anodes for sodium-ion batteries. Scientific Reports (2019).
6. Red phosphorus decorated electrospun carbon anodes for high efficiency lithium ion batteries. Scientific Reports (2020).
7. Black Phosphorus Degradation during Intercalation and Alloying in Batteries. ACS Nano (2023).