Advanced Energy Materials
·
2023
·Vol. 14
·期 7
·2302761
·
IF 27.8
Jian Zhou,Chunxian Xing,Jiawei Huang,Yucheng Zhang,Guowei Li,Long Chen,Shuqiang Tao,Zhuoli Yang,Guangren Wang,Linfeng Fei
Lithium-ion batteries (LIBs) with LiFePO 4 (LFP) cathode materials have occupied a significant market share in state-of-the-art power storage systems and electric vehicles, yet the approaching “retiring wave” of these LIBs should be appropriately treated (i.e., recycling of spent LIBs). Current recycling strategies of degraded LFP materials largely direct on leaching of lithium elements, leaving the leached FePO 4 residual as a waste. Inspiringly, LiMn x Fe 1− x PO 4 material is considered one of the potential candidates for next-generation cathode materials because of its high electrochemical performance, extraordinary stability, and low cost. Herein, the direct upcycling of leached FePO 4 toward LiMn 0.25 Fe 0.75 PO 4 (LMFP) cathode material is demonstrated via a green, simple, and scalable mechanochemical pathway. The product features a gradient-doping of Mn, as well as a uniform carbon coating for LMFP particles. As a result, the LMFP cathode material delivers superior electrochemical performance; the capacity (161.3 mA h g −1 at 0.1 C), rate capability (90.1 mA h g −1 at 5 C), cycling stability (95.6% capacity retention after 800 cycles at 1 C), and energy density (≈15% increase as compared to LFP) are almost comparable with those of fresh materials. The as-established upcycling protocol offers a favorable reuse method for leached FePO 4 materials.
研究领域:
材料科学
·
储能技术
·
可持续化学
·
电池回收
·
电化学
✓ 已验证
DOI
高影响因子
GREEN CHEMISTRY
·
2025
·
IF 9.2
Fan Xiao,Lehan Zhu,Zhangjun Wu,Haotian Zhu,Juan Xia,Jiannan Zhu,Zeheng Yang,Weixin Zhang
Lithium iron phosphate (LiFePO4, LFP) and lithium manganese oxide (LiMn2O4, LMO) batteries dominate the energy storage market due to their superior safety, thermal stability, and cost-effectiveness compared to nickel-cobalt-manganese (NCM) oxide-based systems. However, the imminent retirement of these batteries necessitates sustainable recycling methods. Conventional hydrometallurgical and pyrometallurgical processes hold a dominant position in the present lithium recovery industry, but generate low-value by-products such as FePO4 and MnO2, majority of which are discarded, causing issues of resources waste and environment pollution. Herein, we propose a upcycling protocol to transform these FePO4 and MnO2 residues into LiMnxFe1-xPO4, a promising cathode material renowned for its high operating voltage, enhanced energy density, and structural robustness. Specifically, the recovered FePO4 and MnO2 were mixed with lithium and carbon sources in designed molar ratios and then subjected to solid-state reaction at high temperatures to produce LiMnxFe1-xPO4. The synthesized LiMn0.3Fe0.7PO4/C cathode material with a homogeneous carbon coating exhibits remarkable electrochemical performance with a large specific capacity of 164.44 mAh·g-1 at 0.1 C, high rate capability (121.73 mAh·g-1 at 10 C) and great cycling stability (97.46% capacity retention after 500 cycles at 1 C). Notably, the regenerated cathode material after Mn doping delivers about 20% greater energy density than the regenerated LFP. This work establishes a scalable and eco-efficient methodology for closed-loop battery recycling, successfully addressing critical challenges in resource utilization and high-value material synthesis for advanced energy storage systems.
研究领域:
材料科学
·
储能技术
·
可持续化学
·
电化学
·
电池回收
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2026
·
IF 9.6
Xuejie Zhang,Huijie Zhang,Yanyang Jia,Guihua Liu,Aijia Wei,Yongguang Zhang,Jingde Li
Innovatively proposed Mg 2+ & Ti 4+ co-doped to efficiently suppress Mn 3+ -induced Jahn-Teller distortion and stabilize LMFP's olivine framework. • In-situ characterizations combined with DFT calculations clarify the intrinsic mechanism of co-doped regulating LMFP's crystal/electronic structures. • Co-doped significantly boosts LMFP's electronic conductivity and capacitive contribution, realizing superior high-rate performance and structural reversibility. • Co-doped LMFP@C-MT reduces Mn dissolution by alleviating Jahn-Teller distortion, further enhancing the cathode's structural and electrochemical stability. LiMn x Fe 1-x PO 4 (LMFP) cathodes are considered promising candidates for next-generation lithium-ion (Li + ) batteries due to their high safety, low cost, environmental benignity, and relatively high energy density. However, they suffer from severe Jahn-Teller distortion and sluggish Li + kinetics, leading to poor structural stability and rate performance. Herein, a synergistic Mg 2+ and Ti 4+ co-doping strategy is proposed to concurrently regulate the crystal structure and electronic properties of LMFP. Structural and electrochemical analyses show that Mg 2+ and Ti 4+ effectively suppress Mn 3+ -induced Jahn-Teller distortion. This helps stabilize the olivine framework while causing a small shrinkage in the crystal lattice, thereby improving Li + diffusion capability. In situ XRD reveals that un-doped lithium manganese iron phosphate (LMFP@C) undergoes a distinct phase transition during the high-voltage plateau, as evidenced by peak splitting, whereas Mg 2+ and Ti 4+ co-doped lithium manganese iron phosphate (LMFP@C-MT) exhibits a continuous peak shift, indicative of a solid-solution reaction with improved structural reversibility. Density functional theory (DFT) calculations further demonstrate that Mg 2+ lowers the Li + migration energy barrier, while Ti 4+ stabilizes the Mn electronic structure near the Fermi level. This synergistic effect suppresses Jahn-Teller distortion, thereby enhancing both structural stability and electrochemical kinetics. This enables the LMFP@C-MT cathode to deliver a high initial capacity of 158.35 mAh g −1 at 0.2C, along with outstanding cycling stability, retaining 91.39% capacity after 500 cycles at 1C. This work both presents an effective structural modification strategy and supplies theoretical guidance for the development of high-performance LMFP-based cathode materials. The LMFP@C-MT synthesized by the high-temperature solid-state method suppresses the Jahn–Teller distortion induced by Mn 3+ and stabilizes the lattice. Combined with the ordered carbon coating, it enhances the charge transfer kinetics, thereby achieving excellent structural reversibility and electrochemical performance. Download: Download high-res image (196KB) Download: Download full-size image
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Energy Storage Materials
·
2025
·
IF 20.2
Cheng Cheng,Wei Mao,Xuan Cao,Kaijun Xu,Shaochun Tang
With the retirement of a large number of lithium-ion batteries, how to efficiently recycle cathodes, especially for spent LiFePO 4 (S-LFP) olivine materials with low content of valuable elements, has become a research focus. Moreover, upcycling S-LFP to high-voltage olivine LiMn x Fe 1-x PO 4 (LMFP) is crucial for advancing next-generation cathode materials. Herein, this study proposes a solvothermal upcycling strategy that achieves complete elemental recovery and converts S-LFP into high-voltage LMFP. The resulting LMFP exhibits a uniform elemental distribution, attributed to the atomic-level miscibility of Fe and Mn. As a result, the regenerated LMn 0.5 Fe 0.5 PO 4 exhibits remarkable cycle stability with 83.8 % capacity retention after 2500 cycles at 5 C and a 40 % improvement in energy density (561 Wh kg -1 ) over that of S-LFP (402 Wh kg -1 ). This study presents an effective, direct upcycling route for the large-scale production of next-generation, high-performance olivine cathode materials while achieving sustainable reutilization of S-LFP through closed-loop life cycle management.
研究领域:
材料科学
·
储能
·
电化学
·
可持续化学
·
电池回收
✓ 已验证
产品关联
DOI
高影响因子
Journal of Energy Storage
·
2023
·
IF 9.4
Hongying Hou,Meng Ye,Jian Lan,Xiaohua Yu,Ju Rong,Yanpeng Jia,Yixuan Wang,Xianxi Liu
The waste materials may result in the environment pollution and the rapid consumption of the non-renewable natural resources if they aren't reasonably recycled in time. LiMn x Fe 1-x PO 4 can combine the advantages of good rate capability of LiFePO 4 and high voltage of LiMnPO 4 , thus attracting more attentions. Herein, LiMn x Fe 1-x PO 4 /C (x = 0, 0.05, 0.1 and 0.2) powders are prepared from three wastes (spent Li foil, expired manganese gluconate and rust) by FePO 4 process. The results show that LiMn x Fe 1-x PO 4 /C (x = 0, 0.05, 0.1 and 0.2) powders appear as the irregular particles with 100–300 nm in size, and Mn 2+ partly substituted at Fe 2+ site. Especially, optimal 10 % Mn 2+ -doping improves the voltage plateau and energy density of LiFePO 4 /C. In detail, LiMn 0.1 Fe 0.9 PO 4 /C cathode delivers the specific discharge capacity of 159.3 mAh/g at 0.2C and 137.7 mAh/g at 1.0C, higher than those of LiFePO 4 /C cathode, LiMn 0.05 Fe 0.95 PO 4 /C cathode and LiMn 0.2 Fe 0.8 PO 4 /C cathode due to high diffusion coefficient (8.36 × 10 −14 cm 2 /s) and wider ionic diffusion channels of LiMn 0.1 Fe 0.9 PO 4 /C. The capacity retention rate of LiMn 0.1 Fe 0.9 PO 4 /C remains 91.0 % even after 500 cycles at 1.0C. Seemingly, optimal 10 % Mn 2+ -doping can indeed improve the reversible capacity and cyclic performance of LiFePO 4 cathode mainly due to lower charge transfer impedance and widen Li ion diffusion channel.
研究领域:
材料科学
·
能源技术
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）