ACS Applied Materials & Interfaces
·
2023
·
IF 9.5
Lianqi Zhao,Pu Yan,Tianying Liu,Xingzhi Wang,Zeyu Wang,Cong Wu,Wenda Bao,Haiyin Zhu,Yue Zhang,Jin Xie
High-voltage lithium cobalt oxide (LiCoO2) has the highest volumetric energy density among commercial cathode materials in lithium-ion batteries due to its high working voltage and compacted density. However, under high voltage (4.6 V), the capacity of LiCoO2 fades rapidly due to parasitic reactions of high-valent cobalt with the electrolyte and the loss of lattice oxygen at the interface. In this study, we report a temperature-driven anisotropic doping phenomenon of Mg2+ that results in surface-populated Mg2+ doping to the side of the (003) plane of LiCoO2. Mg2+ dopants enter the Li+ sites, lower the valence state of Co ions with less hybridization between the O 2p and Co 3d orbitals, promote the formation of surface Li+/Co2+ anti-sites, and suppress lattice oxygen loss on the surface. As a result, the modified LiCoO2 demonstrates excellent cycling performance under 4.6 V, reaching an energy density of 911.2 Wh/kg at 0.1C and retaining 92.7% (184.3 mAh g–1) of its capacity after 100 cycles at 1C. Our results highlight a promising avenue for enhancing the electrochemical performance of LiCoO2 by anisotropic surface doping with Mg2+.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
PubMed
高影响因子
ACS Nano
·
2024
·
IF 15.8
Miao Chang,Fangyuan Cheng,Wen Zhang,Mengyi Liao,Qing Li,Chun Fang,Jiantao Han
Surface engineering is sought to stabilize nickel-rich layered oxide cathodes in high-energy-density lithium-ion batteries, which suffer from severe surface oxygen loss and rapid structure degradation, especially during deep delithiation at high voltages or high temperatures. Here, we propose a well-designed oxygen-constraining strategy to address the crisis of oxygen evolution. By integrating a La, Fe gradient diffusion layer and a LaFeO3 coating into the Ni-rich layered particles, along with incorporating an antioxidant binder into the electrodes, three progressive lines of defense are constructed: immobilizing the lattice oxygen at the subsurface, blocking the released oxygen at the interface, and capturing the residual singlet oxygen on the external surface. As a result, effective surface passivation, mitigated bulk and surface degradation, suppressed side reactions, and enhanced electrochemical performance are achieved, far beyond conventional single surface modification. The Ni-rich layered oxide cathodes with integrated oxygen-constraining modifications demonstrate impressive cycling stability in both half-cells and full cells, achieving stable long-term cycling even at a high cutoff voltage of 4.7 V and a high temperature of 45 °C. This work provides a multilevel oxygen-constraining strategy, which can be extended to various layered oxide cathodes involving oxygen release challenges, providing an effective path for the development of high-energy-density lithium-ion batteries.
研究领域:
材料科学
·
电化学
·
能源存储技术
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Applied Energy Materials
·
2025
·
IF 5.5
Guofeng Jia,Hongrun Qiu,Jiaqi Meng,Long Li,Shiyu Yang,Lijuan Zhang,Jianwei Li,Fayan Zhu,Min Wang
The conventional P2-type cathode material suffers from irreversible structural degradation, lattice-oxygen release, and severe capacity fading at the high-charge state during cycling. This study systematically investigates the failure mechanisms associated with the structural evolution and oxygen loss of LiNi0.5Mn0.5O2 in the high-charge state while also revealing the positive impact of Cr doping. Cr substitution in the lithium layer increases the proportion of lattice-oxygen content, lowers the oxygen activation plateau during the first cycle, and restrains structural degradation during cycling. These improvements are attributed to the high degree of delocalized Mn–O bonds caused by robust Cr–O covalency. As a result, an extraordinarily stable voltage (decay rate <0.76 mV per cycle) and a high capacity-retention rate are achieved. Insights into the structural stability of LiNi0.5Mn0.5O2 in a high-charge state provide valuable guidance for designing and optimizing Co-free layered cathode materials with enhanced performance.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
·
2024
·
IF 4.1
Yunqin Yang,QiuMing Liang,Tianwei Lei,Huan He,Tianquan Liang
The capacity of Co-free Li-rich Mn-based layered oxide decreases rapidly due to the irreversible lattice oxygen lose and the crystal structure change. The sodium modified cathode materials are synthesized via the sol–gel method and the electrochemical properties are investigated. Specifically, the first discharge capacity of Li 1.18 Na 0.02 Mn 0.54 Ni 0.26 O 2 is 150.5 mAh·g −1 at 2C, demonstrating a capacity preservation rate of 94.1 % after 100 cycles. And the diffusion coefficient of Li 1.18 Na 0.02 Mn 0.54 Ni 0.26 O 2 is 1.2152 × 10 -15 , which is better than 1.3798 × 10 -16 of the undoped material. This work demonstrates that appropriate Na + doping can stabilize the crystal structure, increase the lithium layer spacing and reduce the irrevocable escape of lattice oxygen within material.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2025
·
IF 6.3
Xinwei Xie,Yaoliang Huang,Li Xu,Guangyu Luo,Haifeng Liu,Xinlong Zhang,Jinyue Yang,Junze Lei,Xiaoyuan Yu
O3-type Ni/Mn-based transition metal oxides have garnered significant interest as cathode materials for sodium-ion batteries (SIBs) due to their high specific capacity and abundant resources. However, their commercialization application has been impeded by rapid capacity fading owing to structural degradation, gas evolution, irreversible phase transitions during charge/discharge cycling. Herein, The Zr 4 + /F - dual-doped strategy is developed to boost the Na-storage performance of Ni/Mn-based O3-NaNi 0.3 Fe 0.1 Mn 0.47 Cu 0.1 Zr 0.03 O 2-x F x (NFMCZF-x) layered oxide cathode material prepared by high temperature calcination method. Structural and electrochemical analyses reveal that Zr⁴⁺ doping expands Na⁺-layer spacing and F⁻ doping strengthens transition metal-oxygen bonds. These synergistic effects of Zr 4+ /F - dual-doping is benefit to suppressing O3↔P3 phase transitions, Jahn-Teller distortion and irreversible oxygen redox. Thus, the optimized NFMCZF-0.03 cathode delivers high specific capacity (178 mAh g −1 at 0.1 C) and excellent cycling stability (72 % capacity retention after 100 cycles at 1.0 C). This study establishes dual doping as an effective strategy for developing Ni/Mn-based layered oxide as high-performance cathodes for SIBs.
✓ 已验证
产品关联
DOI
高影响因子
Advanced Composites and Hybrid Materials
·
2025
·Vol. 8
·期 4
·286
·
IF 21.8
Mao Gaoqiang,Lu Jingfan,Cai Haiyan,Yu Wanjing,Tong Hui,Guo Xueyi,Zeng Leiying,Jiang Long
Increasing the operating voltage can significantly increase the energy density of LiCoO 2 , but it is accompanied by severe structural damage and interface degradation. Especially at a high voltage above 4.5 V, LiCoO 2 faces severe challenges, such as irreversible phase transition, lattice oxygen loss, and electrode–electrolyte interface evolution. Herein, a high-voltage LiCoO 2 cathode material with bulk doping and surface coating synergistic modification was designed and prepared. The doped Mg 2+ ions entered the lithium layers as pillars, stabilizing the layered framework. Meanwhile, Li 1.3 La 0.3 Ti 1.7 (PO 4 ) 3 was uniformly coated on the surface of LiCoO 2 , which is beneficial for suppressing Co 3+/2+ ion leaching and interface side reactions during cycling. Furthermore, Li 1.3 La 0.3 Ti 1.7 (PO 4 ) 3 is a fast ion conductor, which facilitates the rapid transport of lithium ions on the surface of the cathode material. Owing to the synergistic effect of Mg 2+ ion doping and Li 1.3 La 0.3 Ti 1.7 (PO 4 ) 3 coating, the orbitals of Co 3d and O 2p in LiCoO 2 crystal are changed, and the irreversible phase transition and oxygen loss are inhibited. The modified material exhibited an excellent electrochemical performance. A discharge capacity of 175.5 mAh·g −1 at 10 C rate, as well as a capacity retention of 90.14% after 200 cycles at 1 C rate, was achieved in the modified material. This work supplies a new method for developing high-voltage oxide cathodes through bulk and interfacial modification.
研究领域:
材料科学
·
电化学
·
储能技术
·
锂离子电池
·
正极材料
✓ 已验证
产品关联
DOI
高影响因子
Energy Storage Materials
·
2024
·
IF 18.9
Yi Liu,Xiang Wu,Hui Feng,Guozhong Lu,Ying Jiang,Xiaobing Lou,Chao Li,Ming Shen,Fushan Geng,Bingwen Hu
Cation-disordered rock-salts (DRX) emerge as an intriguing class of high-capacity cathode materials , garnering significant attention in the development of advanced energy-storage systems. Fluorination strategies have been raised to regulate redox and structure for better DRX electrochemical performance . However, research on the interfacial processes during fluorinated DRX cycling remains limited. Here, we evaluate a highly fluorinated DRX, Li 2 Mn 2/3 Nb 1/3 O 2 F (LMNOF), in different electrolytes to correlate its cycling performance with distinct interfacial evolutions. During cycling in the carbonate-based electrolyte, a thick Mn-containing CEI forms on the LMNOF surface, leading to gradual capacity decay. Intriguingly, the addition of fluoroethylene carbonate (FEC) would bring about surface oxygen loss, Mn-ion dissolution and formation of a fluorinated surface layer by reacting with the LMNOF surface, which critically deteriorate the cycling performance. In comparison, the ether-based electrolyte is compatible with the LMNOF surface, resulting in a more favorable cycling stability. This work sheds light on the interfacial deterioration mechanism of LMNOF cathode in traditional carbonate-based electrolyte, emphasizing the importance of using advanced non-reactive electrolytes to enhance DRX performance.
研究领域:
材料化学
·
电化学
·
能源存储
·
锂离子电池
·
界面科学
·
固态化学
·
先进电池材料
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Pengju Zhang,Jinglin Mu,Mingyu Xie,Tianyu Xue,Minghui Ding,Zhen Zhou,Junying Weng,Pengfei Zhou
Activating anionic redox reactions (ARR) in P2-type layered oxide cathodes has drawn great attention as a promising strategy to break through the bottleneck of their energy density limit. However, irreversible lattice oxygen loss and detrimental structure distortion associated with ARR are still challenges, resulting in severe capacity fading and sluggish reaction kinetics. Herein, we designed a novel P2-Na 0.67 Li 0.15 Mg 0.1 Mn 0.75 O 2 (NLMOMg0.1) sphere as a cathode for sodium-ion batteries (SIBs), leveraging the synergistic effect of Li/Mg co-doping and a LiPO 2 F 2 film-forming additive to enhance the reversibility and reaction kinetics of ARR. The Li/Mg co-doping effectively activates ARR and reduces the Mn 3+ ratio, weakening the Jahn-Teller effect and and minimizing structure distortion. The LiPO 2 F 2 film-forming additive in the electrolyte can form a stable cathode-electrolyte interphase film on the surface of NLMOMg0.1, significantly suppressing side reactions between the electrode and electrolyte and thereby preventing irreversible lattice oxygen loss. Impressively, NLMOMg0.1 with 0.2 wt% LiPO 2 F 2 additive attains a high capacity of 159.1mAh g −1 and an outstanding retention rate of 97.1 % at 0.5C after 300 cycles. In-situ X-ray diffraction (XRD) experiments confirm the excellent structural stability, and in-situ differential electrochemical mass spectrometry (DEMS) and in-situ optical microscope tests demonstrate the inhibition of lattice oxygen loss during the cycling process. This study provides practical guidelines for designing layered oxide cathode materials for SIBs with high stability and dynamics.
研究领域:
材料科学
·
电化学
·
储能技术
·
纳米技术
✓ 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）