The high‐entropy materials (HEM) have attracted increasing attention in catalysis and energy storage due to their large configurational entropy and multiunique properties. However, it is failed in alloying‐type anode due to their Li‐inactive transition‐metal compositions. Herein, inspired by high‐entropy concept, the Li‐active elements instead of transition‐metal ones are introduced for metal‐phosphorus synthesis. Interestingly, a new ZnxGeyCuzSiwP2 solid solution is successfully synthesized as proof of concept, which is first verified to cubic system in F‐43m. More specially, such ZnxGeyCuzSiwP2 possesses wide‐range tunable region from 9911 to 4466, in which the Zn0.5Ge0.5Cu0.5Si0.5P2 accounts for the highest configurational entropy. When served as anode, ZnxGeyCuzSiwP2 delivers large capacity (>1500 mAh g−1) and suitable plateau (≈0.5 V) for energy storage, breaking the conventional view that HEM is helpless for alloying anode due to its transition‐metal compositions. Among them, the Zn0.5Ge0.5Cu0.5Si0.5P2 exhibits the highest initial coulombic efficiency (ICE) (93%), Li‐diffusivity (1.11 × 10−10), lowest volume‐expansion (34.5%), and best rate performances (551 mAh g−1 at 6400 mA g−1) owing to its largest configurational entropy. Possible mechanism reveals the high entropy stabilization enables good accommodation of volume change and fast electronic transportation, thus supporting superior cyclability and rate performances. This large configurational entropy strategy in metal‐phosphorus solid solution may open new avenues to develop other high‐entropy materials for advanced energy storage.

The layered GeP shows great advantages for high-energy Li-ion batteries (LIBs) owing to its large capacity and suitable plateau. However, the morphology of GeP nanosheets is difficult to obtain since recent GeP is always synthesized by a high-energy ball-milled method, resulting in serious amorphous features and failure of smart morphology design for flexible devices. Herein, ultra-thin GeP nanosheets are successfully prepared in a large scale by first synthesizing single-crystal GeP via a typical flux method following a fast electrochemical exfoliation. Compared to traditional ultrasonic or mechanical stripping, such electrochemical exfoliation shows a much higher stripping efficiency and quality to meet the large-scale requirement for battery applications. When served as an anode for LIBs, these GeP nanosheets deliver a large capacity (1150 mA h/g) and superior cyclability (>500 cycles) and rate performance (346 mA h/g at 2000 mA/g) for energy storage. More importantly, benefitting from intrinsic layered structural flexibility, these GeP nanosheets enable self-assembling with reduced graphene oxide (RGO) and carbon nanotubes (CNTs) toward free-standing electrode fabrication without a binder and conductive agent. Consequently, a sandwich-like GeP@RGO@CNT hybrid electrode is well-designed, enabling a high capacity (870 mA h/g) and good performances for LIBs as well. This fast exfoliation of GeP nanosheets and free-standing electrode construction can be easily extended to other layered materials toward advanced energy storage.

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