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Journal of Materials Chemistry A · 2023 ·Vol. 11 ·期 6 ·2979-2984 · IF 11.9

Stabilizing lattice oxygen and interface chemistry of Ni-rich and Co-poor cathodes for high-energy lithium-ion batteries

Wu Wei,Zhihong Wang,Liyun Yao,Hao Jiang,Chunzhong Li

Development of Ni-rich and Co-poor cathodes (Ni ≥ 80%, Co ≤ 5%) is indispensable for the next-generation lithium-ion batteries (LIBs) owing to the serious impact of scarce resources and fragile supply chain of cobalt, but they suffer from a more prominent lattice oxygen emission with serious Li/Ni intermixing as well as worsening crystal and interface structure. Herein, CeO2−x-coated LiNi0.9Co0.045Mn0.045Al0.01O2 has been demonstrated to stabilize lattice oxygen by the well-dispersed Al–O bonds and the reversible oxygen-storage protective layer. The in situ DEMS and ex situ spectral analyses verified the negligible O2 and CO2 emission, even charging to 4.4 V, and the formation of stable cathode–electrolyte interfacial membrane. The as-obtained cathode exhibited a reversible specific capacity as high as 223 mA h g−1 at 0.1C and 140 mA h g−1 even at 10C with 96.7% capacity retention at 1C after 100 cycles in a coin-type half-cell. About 90.1% capacity retention could still be obtained at 1C in a pouch-type full-cell after 300 cycles. This work provides a viable cathode for durable LIBs by stabilizing the lattice oxygen of Ni-rich and Co-poor cathodes.

研究领域: 电化学 · 材料科学 · 能源存储 · 锂离子电池 · 固态化学 · 表面科学 · 电极材料
✓ 已验证 DOI 高影响因子
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Green Chemical Engineering · 2024 ·Vol. 7 ·期 1 ·51-60 · IF 9.1

High-performance single crystal Ni-rich cathode with regulated lattice and interface constructed by separated lithiation and crystallization calcination

Siqi Chen,Xin Zhou,Shuo Wang,Ping Zhang,Wenbin Wu,Xiaohong Liu,Guilin Feng,Bin Zhang,Wangyan Xing,Meihua Zuo,Ping Zhang,Wei Xiang

Incorporating high valence dopants, such as W 6+ and Mo 6+ has been verified to be effective for tuning the microstructure and grain boundary of polycrystal Ni-rich cathode. However, the hindered consolidation of primary particles induced by dopants during lithiation calcination limits the utilization of those dopants to crystalize single-crystal Ni-rich cathodes with stabilized lattice and surface. Herein, high performance single crystal LiNi 0.84 Co 0.11 Mn 0.05 O 2 cathode with Al 3+ and W 6+ regulated lattice and boundary phase was construed based on commercial process with two-step calcination process containing separated lithiation and crystallization. The introduction of appropriate amount of Al 3+ in the first lithiation calcination of 6 h endows the bulk of crystalline with enhanced lattice stability, while the incorporation of W 6+ with stoichiometrical LiOH in the secondary crystallization calcination of 6 h renders uniformly distributed surface layer without hampering the growth of single-crystal. With the Al 3+ doped bulk lattice, W 6+ doped subsurface region and hetero-epitaxially grown Li 2 WO 4 , the cathode infused by two-step calcination exhibits high discharge capacity, rate performance, and cycling stability. Specifically, the modified LiNi 0.84 Co 0.11 Mn 0.05 O 2 exhibits exceptional capacity retention, maintaining 88.98% of its initial capacity after 200 cycles at a rate of 1 C within a voltage window of 2.7–4.3 V at a temperature of 25 °C in half-cell. This performance is markedly superior to the capacity retention of 72.96% observed for pristine cathode. Even when subjected to a stringent test after 200 cycles at the same rate, the modified cathode sustains an impressive capacity retention of 82.41% at an elevated cut-off voltage of 4.5 V and a temperature of 30 °C.

研究领域: 材料科学 · 电化学 · 能源存储 · 无机化学 · 固体化学
✓ 已验证 DOI 高影响因子
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JOURNAL OF POWER SOURCES · 2024 · IF 8.1

Study on the influence of different manganese sources on the formation of P2/β Bi-phase cathode materials for sodium ion batteries

Yixuan Zhang,Guo-Qiang Liu,Danlei Qiao,Jiaguan Chen,Qiang Sun,Lei Wen

This work focuses on the effect of the of Mn 3+ /Mn 4+ ratio in the reactants on the structure and electrochemical properties of NaMn 0.9 Cu 0.1 O 2 cathode materials for sodium-ion batteries. By systematically varying the manganese valence states in the reactants, we observed a phase transition from the β-phase to the P2-phase with increasing Mn 3+ concentrations in the reactants, contrary to the expected favorability of the β-phase at higher Mn 3+ levels. This finding suggests a complex interplay between the valence states of the reactants and phase formation mechanisms, which needs further investigation. Additionally, electrochemical testing indicated that the phase composition significantly impacts the electrochemical performance of the material. Specifically, the M0 sample, possessing the optimal P2/β ratio, exhibited excellent electrochemical performances, achieving a high initial discharge capacity of 155.1 mA h g −1 and remains 88.1 % after 40 cycles. These results emphasize the importance of precursor selection and valence management in the development of high-performance cathode materials for sodium-ion batteries.

研究领域: 材料科学 · 电化学 · 能源存储 · 无机化学 · 固态化学
✓ 已验证 DOI 高影响因子
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CHINESE JOURNAL OF ANALYTICAL CHEMISTRY · 2022 ·Vol. 50 ·期 7 ·100101 · IF 1.193

Boosting the performances of water-processable LiNi0.5Co0.2Mn0.3O2 cathode with conventional white latex as binder ingredient

Ranehipura Dewage Lahiru SANDARUWAN,Bo-Yu WANG,Suwanda Arachchige Don Rumesh MADHUSANKA,Shun-Chao MA,Hong-Yu WANG

Transition to aqueous electrode fabrication of lithium ion batteries (LIBs) with green binder is certainly profitable and imperative in terms of economic benefit and environmental wellness. However, aqueous processing of cathode in LIB, especially the ternary LiNi x Co y Mn z O 2 (NCM), is still problematic and novel water-soluble binder should be developed to boost the electrochemical performances of cathode. In this regard, commercially available white latex (WL), cooperating with CMC (carboxymethyl cellulose), is employed as water-processable binder mixture for manufacturing NCM cathode. Interestingly, the prepared NCM cathode assisted by WL/CMC mixture exhibits improved electrochemical performances including better initial reversible capacity of 161.7 mAh g −1 at 0.5 C current density, long-term cyclability with a reversible capacity of 155 mAh g −1 along with high-capacity retention of around 96% after cycling 200 times, and even excellent rate capability, which are superior to those of the conventional counterpart base on polyvinylidene fluoride (PVdF). Moreover, the NCM|graphite full cell, which is absolutely based on this novel WL binder, also demonstrates the outstanding electrochemical behaviors.

研究领域: 电化学 · 能源材料 · 锂电池技术 · 高分子材料科学
✓ 已验证 DOI 高影响因子
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ELECTROCHIMICA ACTA · 2021 · IF 6.901

Design of LiAlO2 mosaic structure for preparing high nickel-based LiNi0.88Co0.07Al0.05O2 cathode material by simple hydrolysis method

J. LUO,J.X. Liu,F.M. Xiao,L. Huang,W.C. Li,R.H. Tang,Q. Zhou,Y. Wang

In order to restrain the capacity decay of nickel-rich materials for lithium-ion batteries (LIBs) in advanced energy applications, a Ni-rich cathode (LiNi 0.88 Co 0.07 Al 0.05 O 2 , LANCA) with high-rate capability and cycle life was designed and prepared by coating γ-LiAlO 2 and doping Al 3+ on the surface and inside of the secondary particles, respectively. Specifically, the γ-LiAlO 2 -coated and Al 3+ -doped LANCA samples were synthesized by a simple strategy of pre-coating Ni 0.88 Co 0.07 Al 0.05 (OH) 2 , based on aluminum isopropoxide hydrolysis combined with a post-sintering lithiation process. With the γ-LiAlO 2 and Al 3+ , the capacity retention ratio of the cathode is tremendously improved from 61.7 to 83.6% at 1 C rate after 100 cycles. Even at a heavy current density of 10 C for the LANCA cathode, a high reversible capacity of 154.4 mA h g − 1 can be acquired, which amount to the 82.5% capacity retention at 0.2 C. Detailed morphology and structure observation shows that the side reaction at the electrolyte-cathode interface was suppressed, the structural degradation and intergranular cracking were suppressed, while the diffusion of Li + and conductivity were improved. Therefore, this ingenious structural design has certain reference significance for the development and commercialization of high-performance cathode materials for electric power.

研究领域: 材料科学 · 电化学 · 能源存储 · 无机化学 · 固态化学
✓ 已验证 DOI 高影响因子
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Nano Energy · 2014 · IF 10.211

Hierarchical mesoporous Li2Mn0.5Fe0.5SiO4 and Li2Mn0.5Fe0.5SiO4/C assembled by nanoparticles or nanoplates as a cathode material for lithium-ion batteries

Xiaolei Jiang,Huayun Xu,Jing Liu,Jian Yang,Hongzhi Mao,Yitai Qian

Hierarchical mesoporous Li 2 Mn 0.5 Fe 0.5 SiO 4 consisted of nanoparticles or nanoplates has been successfully synthesized for the first time by a hydrothermal method . Their carbon-coated composites are obtained by a heat treatment in the presence of citric acid. These composites were characterized by powder X-ray diffractometry, scanning and transmission electron microscopy , Raman spectroscopy , and thermogravimetric analysis . The lithium storage capacity and cycling performance of the optimized Li 2 Mn 0.5 Fe 0.5 SiO 4 /C composite are greatly enhanced when tested as a cathode material in lithium-ion batteries (LIBs). It exhibits a discharge capacity of 125   mAh   g −1 after 60 cycles at a rate of 0.1   C. This superior electrochemical property could be ascribed to high purity and mesoporous structure of Li 2 Mn 0.5 Fe 0.5 SiO 4 , which greatly enhances the electronic conductivity as well as the diffusion coefficient of lithium ions .

研究领域: 材料科学 · 电化学 · 能源存储 · 纳米材料 · 固体化学
✓ 已验证 DOI 高影响因子
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International Journal of Electrochemical Science · 2023 ·Vol. 12 ·期 8 ·6930-6939 · IF 1.5

Enhanced Electrochemical Performance of LiFePO4 as Cathode for Lithium Ion Battery by Codoping with Titanium and Nitrogen

Wei Su,Kaiqi Xu,Guobin Zhong,Zengfu Wei,Chao Wang,Yuezhong Meng

Titanium and nitrogen codoped LiFePO 4 was synthesized via a simple solid state reaction using TiN as the dopant source. The morphology, structure, valence state and electrochemical performance of all the samples were investigated and compared with the undoped LiFePO 4 . The results showed that the codoped samples maintained an olivine structure with modified lattice parameters and exhibited a prominent improved electrochemical performance. Among all the codoped samples, LiFe 0.94 Ti 0.04 PO 4-σ N 0.04 showed the best rate capability of 108.1 mAh g -1 even at a high rate of 5 C and exhibited a capacity retention of about 94% after 100 cycles at 1 C.

研究领域: 材料科学 · 电化学 · 能源存储 · 无机化学 · 固态化学
✓ 已验证 DOI 高影响因子
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JOURNAL OF ALLOYS AND COMPOUNDS · 2023 · IF 6.2

Improving the electrochemical performance of Li-rich manganese-based cathode materials by surface treatment with triethylamine

Ao Li,Binfang He,Guangchao Jin,Dongmei Liu,Jingbo Chen

Li-rich manganese-based cathode material is expected to be extremely promising for next-generation lithium-ion batteries due to its high specific capacity derived from additional anion redox behavior and low cost of the main element manganese. However, the irreversible release of lattice oxygen results in poor structural stability and inferior electrochemical performances , such as low initial Coulomb efficiency, irreversible capacity decay and serious voltage decay, which limits its commercialization. Herein, a simple strategy to improve the structural stability and electrochemical performances by one-step treatment with triethylamine (TEA) at moderate temperature is reported. TEA was used as a surface treatment reagent to prepare the modified Li-rich manganese-based cathode materials with oxygen vacancies and local structural distortion on the surface. The presence of surface distortion layer and oxygen vacancies inhibits irreversible oxygen release. The result exhibits that initial Coulomb efficiency, rate performance and initial discharge specific capacities are improved. After 100 cycles at a current density of 1 C, the specific capacity of the surface-treated material is 204.3 mAh g -1 (172.6 mAh g -1 for the pristine material), with a capacity retention of 81.26%. Even at a high current density of 10 C, the discharge specific capacity of 139.4 mAh g -1 is still achieved, demonstrating the excellent electrochemical performance. This study provides a simple and effective strategy for constructing special surface structures on Li-rich manganese-based materials to achieve high performance.

研究领域: 材料科学 · 电化学 · 能源存储 · 锂离子电池 · 固态化学
✓ 已验证 DOI 高影响因子
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IONICS · 2019 ·Vol. 25 ·期 10 ·4567-4576 · IF 2.289

Surface modification of Li1.2Mn0.54Ni0.13Co0.13O2 via an ionic conductive LiV3O8 as a cathode material for Li-ion batteries

Xu Chun-Sheng,Yu Hai-Tao,Guo Chen-Feng,Xie Ying,Ren Ning,Yi Ting-Feng,Zhang Guo-Xu

To improve the stability and performance of the cathode materials, an ionic conductor layer was coated successfully on the surface of Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 (LMNC) microspheres. The structural analysis confirmed that LiV 3 O 8 coating did not change the basic structure of LMNC, and all obtained materials are solid solutions with a good-layered structure and a good crystallinity. The microscopy measurement showed that the thickness of the coating layer for the LV-3 sample is about 2.5 nm. This appropriate layer is helpful for improving the surface stability of LMNC and the diffusion of lithium, leading to an obvious enhancement of the electrochemical performance. Our result confirmed that the average discharge specific capacities for LV-3 sample at 0.1 C, 0.2 C, 0.5 C, 1 C, and 3 C are respectively 265.9, 219.1, 188.0, 156.3, and 121.5 mAh g −1 , which are much larger than the values of other samples. After 50 cycles at a 1 C rate, the capacity retentions for different samples are 60.7%, 74.0%, 87.6%, and 70.4%, indicating that LV-3 sample exhibits the best performance. Furthermore, EIS measurements showed that the diffusion coefficient for LV-3 sample is calculated to be 1.26 × 10 −15  cm 2  s −1 , which is also the largest value among all considered samples. Our experiments identified that coating an ionic conductive layer on the cathode material surface will significantly improve their rate capacity and cycling stability.

研究领域: 材料科学 · 电化学 · 能源存储 · 无机化学 · 固态离子学
✓ 已验证 DOI 高影响因子
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CERAMICS INTERNATIONAL · 2019 ·Vol. 45 ·期 8 ·10633-10639 · IF 3.45

Improved cycling performance of CeO2-inlaid Li-rich cathode materials for lithium-ion battery

Guorong Hu,Zhichen Xue,Zhongyuan Luo,Zhongdong Peng,Yanbing Cao,Weigang Wang,Yuexi Zeng,Yong Huang,Yong Tao,Tianfan Li,Zhiyong Zhang,Ke Du

The Li-rich cathode material for long cycle performance and long-term storage performance is a challenge for next-generation lithium-ion batteries due to the rapid capacity degradation over cycling and the formation of residual lithium on the surface during long-term storage. Herein, an elevated performance of Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 materials via CeO 2 inlay is reported, which was prepared from Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 by sol-gel inlay with CeO 2 . It was proved by scanning electron microscopy, high-resolution transmission electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy that cerium oxide cladding not only covered the surface of the material but also diffused into the interior of the material change crystal structure. Cerium oxide on the cladding not only reduces the material's contact with water and carbon dioxide in the air, but also prevents the material from being corroded by electrolyte during electrochemical test. The position of the transition metal atom is replaced Ce atoms, which increases the unit cell volume and the stability of the Li-rich material during the cycling. The results show that the storage property and the electrochemical cycling property of the material have been improved obviously. The CeO 2 inlaid lithium rich material discharged 204.6 mAh/g for the first time at the current of 1C, and 164.4 mAh/g after 150 charge and discharge cycles with corresponding capacity retention rate of 80.35%, compared with the retention rate of 57.26% for pristine Li-rich material capacity. After being stored in humid air for 40 days, the CeO 2 inlaid lithium-rich material showed better electrochemical performance than the pristine one. It is powerfully demonstrated that the CeO 2 inlay strategy here holds huge promise for surface modification of electrode materials for lithium-ion batteries.

研究领域: 材料科学 · 电化学 · 锂离子电池 · 能源存储 · 无机非金属材料
✓ 已验证 DOI 高影响因子
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Journal of Energy Chemistry · 2016 ·Vol. 26 ·期 3 ·481-487 · IF 2.322

Amorphous Zr(OH)4 coated LiNi0.915Co0.075Al0.01O2 cathode material with enhanced electrochemical performance for lithium ion batteries

Zhen Zhang,Pengfei Zhou,Huanju Meng,Chengcheng Chen,Fangyi Cheng,Zhanliang Tao,Jun Chen

LiNi 0.915 Co 0.075 Al 0.01 O 2 (NCA) with Zr(OH) 4 coating is demonstrated as high performance cathode material for lithium ion batteries (LIBs). The coated materials are synthesized via a simple dry coating method of NCA with Zr(OH) 4 powders, and then characterized with scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Experimental results show that amorphous Zr(OH) 4 powders have been successfully coated on the surface of spherical NCA particles, exhibiting improved electrochemical performance . 0.50   wt% Zr(OH) 4 coated NCA delivers a capacity of 197.6   mAh/g at the first cycle and 154.3   mAh/g after 100 cycles with a capacity retention of 78.1% at 1 C rate. In comparison, the pure NCA shows a capacity of 194.6   mAh/g at the first cycle and 142.5   mAh/g after 100 cycles with a capacity retention of 73.2% at 1 C rate. Electrochemical impedance spectroscopy (EIS) results show that the coated material exhibits a lower resistance, indicating that the coating layer can efficiently suppress transition metals dissolution and decrease the side reactions at the surface between the electrode and electrolyte. Therefore, surface coating with amorphous Zr(OH) 4 is a simple and useful method to enhance the electrochemical performance of NCA-based materials for the cathode of LIBs.

研究领域: 电化学 · 材料科学 · 能源存储 · 电池技术 · 无机非金属材料 · 固态化学
✓ 已验证 DOI 高影响因子
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CERAMICS INTERNATIONAL · 2024 ·Vol. 50 ·期 14 ·24995-25004 · IF 5.1

Synthesis of ultrathin carbon layer-coated LiNiPO4 nanoparticles by solvothermal method

Zhiyi Li,Haili Sun,Wei Wei,Fengxia Liu,Xiaofei Xu,Zhijun Liu

The emerging market of high-power lithium-ion batteries (LIBs) highlights the importance of developing high-voltage cathodes. Lithium nickel phosphate (LiNiPO 4 ) with the highest theoretical discharge potential (∼5.1V) has attracted increasing attention due to its stable olivine structure. In this study, ultrathin carbon layer-coated LiNiPO 4 was synthesized using oleylamine-assisted solvothermal method under different solvothermal times, and the effect of solvothermal time (1h–18h) on LiNiPO 4 samples is fully investigated. X-ray diffraction (XRD) shows that high-purity LiNiPO 4 materials can be prepared after calcination of the solvothermal product under N 2 , but adding part of H 2 to the calcination atmosphere will lead to the generation of impurities in the target product. As the solvothermal time increases, the product will agglomerate and grow, the particle size will increase, and the morphology will change from nanoparticle to rodlike structure. After the high-temperature calcination step, the oleylamine is completely carbonized, and a conductive carbon layer is successfully coated on the LiNiPO 4 with the thickness of 2 nm. As the solvothermal time increases, the graphitization degree of oleylamine increases after carbonization. The existence of the carbon layer and the increase in the degree of graphitization are beneficial to improving the electrical conductivity and Li-ion diffusion rate of LiNiPO 4 . The initial discharge capacity of LNP@C-12h product prepared with 12 h solvothermal time is 35 mA h g −1 at 0.1 C. Rietveld analysis shows that the anti-site defect concentration of the LNP@C material is 1.07 %, and the proportion increases to 2.83 % after several cycles. This work provides a positive contribution to the synthesis and modification of high-voltage LiNiPO 4 materials and explains the electrochemical performance degradation of LiNiPO 4 from the perspective of increasing the concentration of anti-site defects.

研究领域: 材料科学 · 电化学 · 纳米科技 · 能源存储 · 锂离子电池
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