Supramolecular self-assembly synthesis of hemoglobin-like amorphous CoP@N, P-doped carbon composites enable ultralong stable cycling under high-current density for lithium-ion battery anodes

Abstract

Cobalt phosphide (CoP) has been emerging as alternative lithium-ion batteries (LIBs) anode in view of the outstanding thermodynamic stability and high theoretical capacity. However, the lithium storage behaviors were impeded by poor cycling and rate performance induced by huge volumetric changes of CoP anodes during Li+ intercalation/deintercalation and the poor reaction kinetics caused by low electronic conductivity. Herein, the uniquely designed hemoglobin-like composites consisting of CoP nanoparticles coated by N, P-doped carbon shell (CoP@PNC) were prepared via a supramolecular self-assembly method, followed by the facile heat treatment process, which presented the amorphous phase. Based on the synergistic effects of rational nano/microstructure, double heterogeneous elements doped carbon substrate and amorphous phase, the transport paths of Li+ and e− were shortened, the electronic conductivity was enhanced, the volumetric changes were effectively alleviated, resulting in outstanding electrochemical performance when applied as anode electrodes. The CoP@PNC electrodes deliver a capacity of 806.8 mAh g−1 after 100 cycles at 0.1 A g−1 and 523.9 mAh g−1 after 3000 cycles at 2.0 A g−1. Furthermore, pseudo-capacitance behavior dominates the storage mechanism of CoP@PNC electrodes based on the quantitative kinetic analysis result that a high ratio of 66% in total capacity at 0.5 mV−1. This work illuminates the route to effectively relieve the huge volumetric changes to improve the electrochemical performance of transition metal phosphide and promote their practical application steps as electrodes for high energy density batteries.

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Advanced Composites and Hybrid Materials (2023) 6:23
https://doi.org/10.1007/s42114-022-00607-y
RESEARCH
Supramolecular self‑assembly synthesis ofhemoglobin‑like
amorphous CoP@N, P‑doped carbon composites enable ultralong
stable cycling underhigh‑current density forlithium‑ion battery
anodes
QinMu1· RuilinLiu1· HideoKimura1· JinchengLi1· HuiyuJiang1· XiaoyuZhang1,2,3· ZhipengYu1· XueqinSun1·
HassanAlgadi4· ZhanhuGuo5· WeiDu1· ChuanxinHou1
Received: 9 November 2022 / Revised: 6 December 2022 / Accepted: 16 December 2022 / Published online: 26 December 2022
© The Author(s), under exclusive licence to Springer Nature Switzerland AG 2022
Abstract
Cobalt phosphide (CoP) has been emerging as alternative lithium-ion batteries (LIBs) anode in view of the outstanding
thermodynamic stability and high theoretical capacity. However, the lithium storage behaviors were impeded by poor cycling
and rate performance induced by huge volumetric changes of CoP anodes during Li+ intercalation/deintercalation and the
poor reaction kinetics caused by low electronic conductivity. Herein, the uniquely designed hemoglobin-like composites
consisting of CoP nanoparticles coated by N, P-doped carbon shell (CoP@PNC) were prepared via a supramolecular self-
assembly method, followed by the facile heat treatment process, which presented the amorphous phase. Based on the syner-
gistic effects of rational nano/microstructure, double heterogeneous elements doped carbon substrate and amorphous phase,
the transport paths of Li+ and e− were shortened, the electronic conductivity was enhanced, the volumetric changes were
effectively alleviated, resulting in outstanding electrochemical performance when applied as anode electrodes. The CoP@
PNC electrodes deliver a capacity of 806.8 mAh g−1 after 100 cycles at 0.1 A g−1 and 523.9 mAh g−1 after 3000 cycles at
2.0 A g−1. Furthermore, pseudo-capacitance behavior dominates the storage mechanism of CoP@PNC electrodes based on
the quantitative kinetic analysis result that a high ratio of 66% in total capacity at 0.5 mV−1. This work illuminates the route
to effectively relieve the huge volumetric changes to improve the electrochemical performance of transition metal phosphide
and promote their practical application steps as electrodes for high energy density batteries.
Keywords Lithium ion battery· Transition metal phosphide· Amorphous phase
1 Introduction
The aggravating environmental concerns and persistently
increasing energy demands have provoked humans excited
nerves to pursue new types of energy conversion equipment
for the utilization of novel and recyclable energy resources
[1–7], which promotes lithium-ion batteries (LIBs) to the
wide commercial application due its proven multi-advantages
[8–10]. Extensive attention has been paid to anode materials
in terms of the commercial graphite electrode that cannot
* Zhipeng Yu
yuzhipeng861207@163.com
* Zhanhu Guo
zhanhu.guo@northumbria.ac.uk
* Wei Du
duwei@ytu.edu.cn
* Chuanxin Hou
chuanxin210@ytu.edu.cn
1 School ofEnvironmental andMaterial Engineering,
Yantai University, No. 30 Qingquan Road, Shandong,
Yantai264005, China
2 Shandong Laboratory ofYantai Advanced Materials
andGreen Manufacturing, Shandong, Yantai264005, China
3 College ofMaterials Science andEngineering, Taiyuan
University ofScience andTechnology, Shanxi,
Taiyuan030024, China
4 Department ofElectrical Engineering, Faculty
ofEngineering, Najran University, Najran11001,
SaudiArabia
5 Mechanical andConstruction Engineering, Faculty
ofEngineering andEnvironment, Northumbria University,
NewcastleUponTyneNE18ST, UK
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