CERAMICS INTERNATIONAL
·
2023
·
IF 5.2
Zhi Yang,Jian Zhang,Bingxue Wu,Xin Zhao,Xuanlin Lu,Yicheng Zhao,Yongdan Li
The oxygen reduction reaction at the cathode is an essential process for protonic ceramic fuel cells . Composite cathode materials are commonly used towards the multiple requirements including high surface oxygen activity as well as sufficient electronic and ionic conductivities . In this study, a cobalt-free composite cathode composed of a perovskite La 0.6 Sr 0.4 FeO 3-δ phase and a Ruddlesden-Popper La 1.2 Sr 0.8 NiO 4+δ phase is synthesized with a self-assembly technology. The cathode process is mainly controlled by (I) the reduction of adsorbed oxygen atom to O − on the surface and (II) the migration of O − from the surface into the lattice. The former benefits from the high electrical conductivity of La 0.6 Sr 0.4 FeO 3-δ , and the latter is accelerated by La 1.2 Sr 0.8 NiO 4+δ attributed to its superior oxygen activity. The one-pot synthesized composite cathode shows an enhanced synergistic effect due to the uniform distribution of the two phases at the nanoscale. The cathode shows the lowest polarization resistances of 0.055 and 0.095 Ω cm 2 at 700 °C in oxygen and air, respectively. The results show that self-assembled La 0.6 Sr 0.4 FeO 3-δ -La 1.2 Sr 0.8 NiO 4+δ nanocomposite is a promising cathode material for protonic ceramic fuel cells.
研究领域:
材料科学
·
能源科学
✓ 已验证
DOI
高影响因子
INTERNATIONAL JOURNAL OF ENERGY RESEARCH
·
2022
·Vol. 46
·期 15
·22782-22794
·
IF 4.672
Zhijun Liu,Yegui Fang,Jianxin Wang,Chensheng Ma,Youkun Tao,Jing Shao
Summary The development of a cobalt-free cathode with long-term stability and high electrochemical activity is important for constructing low-cost and robust solid oxide fuel cells (SOFCs). Here, we report performance enhancement of a cobalt-free cathode achieved by valence regulation of the ferrite-based perovskite. Utilizing co-doping of high valence niobium with low valence nickel, we developed a cathode material La 0.8 Sr 0.2 Fe 0.8 Ni 0.15 Nb 0.05 O 3−δ that allowed representing adequate conductivity of 214 S cm −1 at 700°C, decent thermal compatibility with thermal expansion coefficient being 12 × 10 −6 K −1 , superior electrochemical properties manifested by area-specific resistance of 0.06 Ω cm 2 and peak power density of 760 mW cm −2 at 800°C, and excellent discharge durability of over 480 h at a current density of 460 mA cm −2 under 750°C. This significantly enhanced performance originates from a proper regulation of the electronic structure rendered by synergistic effects induced by the co-doping of the high valence niobium with low valence nickel into the B sites of the ferrite perovskite. Such a regulation enables an optimized compromise among the oxygen vacancies, electronic mobility, oxygen adsorption and dissociation, and strontium segregation.
研究领域:
材料科学
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能源科学
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产品关联
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2025
·
IF 6.3
Yu Zhou,Tianke Ye,Nengchu Xia,Wanbing Guan,Jun Yang,Liangzhu Zhu,Yunfang Gao,Anqi Wu,Jianxin Wang
In this study, a series of cobalt-free spinels Ni 1+x Mn 2-x O 4 (x = 0, 0.2, 0.4, 0.6) were prepared by the solid-liquid composite method. After preparing them into full-cell tests, it was found that Ni 1.4 Mn 1.6 O 4 (NMO) exhibited the best performance when x = 0.4, and subsequent in-depth research was focused on NMO. NMO has good thermal expansion matching with the electrolyte layer below 700 ℃, as well as excellent mixed ionic-electronic conductivity. When employed as a cathode material in an solid oxide fuel cell (SOFC), the cell achieves a discharge power density of 1150.25 mW cm −2 at 800 ℃. However, as the oxygen ion conduction rate decreases with decreasing temperature, the power densities at medium and low temperatures are significantly lower, with only 248.97 mW cm −2 at 650 ℃ and 33.55 mW cm −2 at 600 ℃. The combination of NMO with the electrolyte material 8YSZ results in a significant increase in power density at 650 °C and 600 °C, achieving 330.21 mW cm −2 and 157.81 mW cm −2 , respectively. An SOFC with NMO-YSZ64 as the cathode demonstrates excellent long-term stability, and the voltage degradation rate is less than 1 % after 110 hours of galvanostatic discharge at 650 °C and 200 mA cm −2 . SEM analysis reveals that the microstructure of the cell remains intact after prolonged discharge and has good adhesion at the cathode-electrolyte interface. These results suggest that Ni 1.4 Mn 1.6 O 4 and its composite cathodes are highly promising cathode materials.
研究领域:
材料科学
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能源技术
✓ 已验证
产品关联
DOI
高影响因子
Journal of Energy Storage
·
2025
·
IF 9.8
Zhiwen Wang,Zhenping Qiu,Chaojie Zhao,Zheng Pan,Guangxia Wang,Yue Guo
As demand for high-energy-density batteries grows, cobalt-free ultra-high‑nickel cathodes like LiNiO₂ are poised to revolutionize next-generation energy storage solutions. However, their practical use is hindered by structural degradation caused by phase transitions, oxygen loss, and detrimental interfacial reactions triggered by the strong oxidizing nature of Ni 4+ formed under high voltage, which together lead to rapid capacity degradation and poor cycling stability. To overcome these challenges, effective doping strategies are crucial. This study systematically examines the potential of Mn and Al doping to enhance the stability of LiNiO₂ using in situ XRD, TEM, XPS, and electrochemical testing. The results show that, while both Mn and Al doping enhance structural stability and cycling performance, they operate through different mechanisms. In particular, 4 mol% Al doping remarkably suppresses c-axis expansion, enhances phase transition reversibility, and achieves capacity retention of 84.8 % after 100 cycles at 1C. In contrast, LiNiO₂ exhibits good tolerance toward Mn doping up to 10 mol%, which helps mitigate structural degradation; however, the capacity retention remains moderate at 80.3 %. While Al doping primarily enhances electrochemical performance, Mn doping contributes to preserving the structural integrity of the cathode at higher concentrations. Our study reveals their complementary roles, providing a strategy to address structural challenges and advance sustainable cobalt-free energy storage solutions.
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产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2024
·
IF 8.1
Chenxiao Wang,Kui Liu,Yinghao Wu,Guangjun Zhang,Xuelian Li,Jiaxin Wu,Ruili Sun,Ting Chen,Lang Xu,Shaorong Wang
A-site doping with Ca 2+ , Sr 2+ for the cobalt-free BaFeO 3-δ -based cathode materials for proton-conducting ceramic fuel cells (PCFCs) is studied. The composite Ba 0·8 Ca 0·2 FeO 3-δ (BCF0.2)-BaZr 0.1 Ce 0·7 Y 0.1 Yb 0.1 O 3-δ (BZCYYb) and Ba 0·8 Sr 0·2 FeO 3-δ (BSF0.2)-BZCYYb electrode show polarization resistance (R p ) of 0.156 Ω cm 2 and 0.308 Ω cm 2 at 700 °C, respectively. It is found that the Ca or Sr doping not only benefits oxygen vacancy formation and ion migration but also optimizes the surface oxygen reduction reaction (ORR) process. The density functional theory (DFT) calculations show that the Gibbs energies of *OOH and *OH intermediates are decreased, indicating an enhanced surface ORR. The PCFC with BCF0.2-BZCYYb composite cathode achieves the maximum power density of 299.75 mW cm −2 at 700 °C and shows good stability at 650 °C for 65 h under a constant voltage of 0.75 V. These findings suggest that the BCF0.2-BZCYYb has the potential to serve as cobalt-free cathode materials for PCFCs.
研究领域:
材料科学
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能源科学
✓ 已验证
DOI
高影响因子
CERAMICS INTERNATIONAL
·
2015
·
IF 2.605
Xinbo Mao,Wenbao Wang,Guilin Ma
A novel cobalt-free double-perovskite oxide NdBaFe 1.9 Nb 0.1 O 5+ δ (NBFNb10) was prepared by a solid-state reaction method and investigated as a suitable cathode material for intermediate temperature solid oxide fuel cells (IT-SOFCs). It was discovered that partial substitution of Nb for Fe-site further enhanced the electrical conductivity of NdBaFe 2 O 5+ δ (NBF). The NBFNb10 exhibited the highest conductivity of 109 S cm −1 at 300–800 °C in air, and showed good chemical compatibility with the BaZr 0.1 Ce 0.7 Y 0.2 O 3− α (BZCY) electrolyte. A single cell with the NBFNb10–BZCY composite cathode and NiO–BZCY composite anode-supported BZCY electrolyte membrane (ca. 30 μm thickness) was fabricated and tested at 500–700 °C using H 2 as fuel and air as oxidant. The peak power density and the interfacial polarization resistance ( R p ) were 392 mW cm −2 and 0.14 Ω cm 2 at 700 °C, respectively.
研究领域:
材料科学
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能源科学
✓ 已验证
产品关联
DOI
高影响因子
IONICS
·
2024
·Vol. 30
·期 6
·3157-3169
·
IF 2.4
Liu Sining,Yan Xin,Tian Xinru,Li Sinan,Luo Shao-hua
To meet the development needs of high-performance and low-cost lithium-ion batteries, lithium-rich Co-free manganese-based cathode materials have become the primary choice for future power batteries based on the advantages of low cost and improved battery performance. Herein, Li 1.2 Mn 0.6 Ni 0.2 O 2 is prepared by the high-temperature solid-state method. The impacts of calcination temperature, holding time, and heating rate on the microstructure and properties of cathode materials are systematically studied via orthogonal experiments. Results revealed that Li 1.2 Mn 0.6 Ni 0.2 O 2 prepared by the high-temperature solid-state method at a calcination temperature of 900 °C, holding time of 12 h, and heating rate of 15 °C/min is ideal, with a smaller particle size and uniform particle distribution and a lower agglomeration degree, and the initial discharge specific capacity reaches 148.4 mAh·g −1 at 0.1 C. The discharge specific capacity of 102.8 mAh·g −1 is still maintained after 100 charge–discharge cycles. Among the various factors, holding time has the greatest influence on the lithium-rich Co-free manganese-based cathode material. The crystallinity, electrochemical properties, and microstructure of the material prepared at 12 h were considerably better than those prepared under other conditions. Test findings show that with a small particle size and uniform distribution, the synthesized cathode material has better rate and cycle performances.
研究领域:
材料科学
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电化学
·
能源存储技术
✓ 已验证
产品关联
DOI
高影响因子
Materials Today Energy
·
2024
·
IF 9
Bao Zhang,Heng Wen,Keyi Xian,Na Lu,Chao Zheng,Zhiming Xiao,Xinyou He,Long Ye,Jiexi Wang,Lei Ming,Chunhui Wang,Xing Ou
Ultrahigh nickel cobalt-free layered oxide cathode is considered to be one of the most promising lithium-ion cathode materials due to its high specific capacity and low price. Unfortunately, high nickel cathode materials have problems such as high cation mixing, thermal stability and structure instability, and how to address these problems has been the direction of researchers. Introducing heteroatoms into bulk phase is an essential and effective method for dealing with the above issues. In this paper, the comprehensively reinforced crystal and framework structure has been obtained in LiNi 0.9 Mn 0.1 O 2 (NM-WMM) cathode material by the synchronously doping of W 6+ , Mg 2+ and Mo 6+ . Thanks to the pillar function of all the doping elements and robust metal-O bond of W 6+ and Mo 6+ , the structural and chemical stability of the designed materials have been effectively strengthened, contributing to enhance their cycling performance and high-temperature properties, and optimize the reaction kinetics synchronously. As expected, NM-WMM materials deliver a prominent capacity retention rate at both 25 °C (91 %, 200 cycles, 1 C) and 50 °C (93.9 %, 100 cycles, 1 C). This proves that the multi-element doping modification strategy is beneficial to improve the cyclic performance and thermal stability of Ni-rich Co-free cathode materials.
研究领域:
材料科学
·
电化学
·
能源存储
·
固态化学
·
电池技术
✓ 已验证
DOI
高影响因子
Journal of Energy Storage
·
2025
·
IF 9.8
Hongrun Qiu,Jianwei Li,Li Han,Guangqin Zhu,Min Lei,Xinhe Yang,Guofeng Jia,Min Wang
Cobalt-free manganese-based layered oxides such as LiNi 0.5 Mn 0.5 O 2 are promising cathodes for next-generation high-energy-density lithium-ion batteries owing to their high theoretical capacity. However, their structural instability in highly delithiated states leads to considerable degradation of both the surface and bulk phases during cycling, limiting their applicability. To address this structural instability, a “pinning” and “pillaring” strategy via titanium doping is proposed herein. Titanium ions act as “pillars” in highly delithiated states in the bulk structure, enhancing phase transition reversibility during cycling. In situ and ex situ X-ray diffraction analyses confirm that Titanium doping stabilizes the bulk structure within 3.0–4.8 V at room temperature. X-ray photoelectron spectroscopy reveals that Titanium ions form a “cationic barrier” at the surface, anchoring lattice oxygen and suppressing undesired phase transformations. This dual mechanism endows the 3 % Titanium-doped material with excellent cycling stability. It exhibits an initial discharge capacity of 157.7 mA h g −1 at C/2 and retains 83.45 % of this capacity after 120 cycles. This represents a 24.17 % increase in initial capacity and a 41.30 % improvement in capacity retention compared to those of undoped LiNi 0.5 Mn 0.5 O 2 . The voltage decay rate of the doped material also reduces to 1.64 mV per cycle, indicating a 90.24 % improvement. The proposed approach is a viable strategy for advancing Cobalt-free manganese-based layered oxides for use in high-energy-density lithium-ion batteries.
研究领域:
材料科学
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电化学
·
能源存储
·
锂离子电池
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固态化学
·
表面科学
·
功能材料
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2022
·
IF 4.326
Zhanying Chang,Yiming Zhang,Wei He,Jin Wang,Hongfei Zheng,Baihua Qu,Xinghui Wang,Qingshui Xie,Dong-Liang Peng
Li-rich layered oxides (LLOs) are supposed to be the most competitive cathode materials for lithium-ion batteries (LIBs), because of the high theoretical specific capacities (>250 mAh g–1). However, there are some inherent inferiorities, such as the low initial Coulombic efficiency (ICE) and the rapid capacity/voltage decay, that hinder the large-scale commercial applications of LLOs. Herein, we successfully obtained spinel-coated and phosphate-doped Co-free Li-rich layered oxides (Co-free LLOs) by cotreatment methods, using weakly acidic and alkalinity (NH4H2PO4 solution), which could effectively improve the electrochemical performance. The spinel coating could not only accelerate the movement of Li+ but also restrain O2 release, while the doping PO43– could inhibit the transition-metal (TM) migration between the oxygen octahedral site and the oxygen tetrahedral site. The optimized Co-free LLOs cathode treated with 3% NH4H2PO4 solution could deliver a high ICE of 88% and a high discharge capacity up to 159.5 mAh g–1 after 500 cycles at 1C (1C = 250 mA g–1). Moreover, the voltage fading decreases from 0.64 mV to 0.32 mV per cycle during cycling. This work provides new insights for developing high-performance Co-free LLOs cathode materials.
研究领域:
材料科学
·
电化学
·
能源存储
·
无机化学
·
功能材料
✓ 已验证
DOI
高影响因子
JOURNAL OF POWER SOURCES
·
2024
·
IF 8.1
Shihang Guo,Lin Wang,Chenyang Xue,Sumei Lin,Tingxuan Yi,Yuwen Zhu,Donglin Han
Protonic ceramic cells (PCCs) can convert the energy between electricity and fuels efficiently, and are attracting increasing attention. However, the development of PCCs is restricted by the lack of proper positrode materials. In this work, we report a Co-free system with a nominal composition of BaCe 0.2 Fe 0.8 O 3-δ , which is composed of a Fe-rich matrix phase decorated with Ce-rich nanoparticles. The performance of such a dual-phase positrode system is further improved by doping Zn and/or Ni to increase bulk and surficial concentration of oxygen vacancies. The hydration reaction and surficial adsorption of oxygen species are thereby promoted, benefitting the oxygen reduction reaction. The Ni and Zn co-doped composition Ba(Ce 0.2 Fe 0.8 ) 0.85 (Ni 0.5 Zn 0.5 ) 0.15 O 3-δ exhibits lower polarization resistance than the pristine and singly doped systems, enabling the fuel cells to show high peak power densities of 400, 721, and 828 mW cm −2 at 550, 600, and 650 °C, respectively.
研究领域:
材料科学
·
电化学
·
能源材料
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2025
·
IF 6.3
Yujia Nie,Jingxiong Liu,Youdong Chen,Han Chen,Wei Zhou
Direct ammonia proton ceramic fuel cells (DA-PCFCs) have garnered significant attention in the clean energy sector as a promising technology for achieving carbon-free and efficient energy conversion. The cathode material, as a key component of this system, possesses intrinsic properties that significantly impact the overall performance of the DA-PCFCs. To address the characteristics of ammonia fuel systems, this study synthesized a novel cobalt-free double perovskite cathode material, PrBaFe 2 O 6-δ (PBF), via the sol-gel method. Systematic characterization revealed that PBF not only exhibited a stable cubic perovskite structure, but also synergistically enhanced the oxygen reduction reaction through the combination of mixed Fe ion valence states and abundant surface oxygen vacancies. Furthermore, the thermal expansion coefficient of PBF exhibited better compatibility with the electrolyte than cobalt-containing cathodes. These properties provided a robust foundation for the favorable performance of DA-PCFCs. Electrochemical tests demonstrated that the cell with the PBF cathode achieved a peak power density of 379 mW·cm −2 at 700 °C, with a 67.4 % power retention rate under H 2 fuel conditions. Notably, the performance degradation rate of the cell was only 0.06 % h −1 after 100 h of constant current discharge, indicating excellent operational stability. This study presented an effective strategy to the development of cathodes for DA-PCFCs.
研究领域:
能源材料
·
燃料电池
·
电化学
·
材料科学
·
清洁能源技术
✓ 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）