Journal of Cleaner Production
·
2024
·
IF 9.7
Jiaqun Zou,Bingen Yuan,Chuanxi Zhao,Jianxin Wang,Haoqi Qiu,Jiaxin Dang,Qin Wang,He Miao,Jinliang Yuan
Cobalt (Co) is widely used in energy storage and conversion devices, although its content on our planet is not adequate. Therefore, recycling Co from the spent Co-enriched materials is indispensable. Co-based perovskites , which contain abundant Co, are extensively utilized in solid oxide fuel cells, three-way catalysts, and oxygen-permeable membranes, and the recovery of Co from the spent Co-based perovskites is necessary to meet the long-term requirement of Co. In this work, a facile and universal thermal reduction method (750 °C and N 2 atmosphere) is employed to convert the spent cobalt-based perovskites into high-performance bifunctional oxygen catalysts for zinc-air batteries (ZABs), achieving high-efficient Co recovery and re-utilization. At high temperatures, melamine and dopamine hydrochloride are transformed into carbon nanotubes , C 3 N 4 and reducing gases (such as NH 3 and H 2 ). Simultaneously, the metal elements in the spent Co-based perovskites (SrNb 0.1 Co 0.7 Fe 0.2 O 3 ,SNCF) are converted into nano-scale alloy particles and metal nitrides . Then, the phase structures, micromorphology, and element valences of the obtained multiphase oxygen catalyst (SNCF–Ni-PM) are characterized by X-ray diffraction, scanning/transmission electron microscopy, and X-ray photoelectron spectroscopy, respectively. The electrochemical properties , including oxygen catalytic activities and stability, of SNCF-Ni-PM are measured by linear sweep voltammetry , chronopotentiometry, chronoamperometry, and cyclic voltammetry methods. Considering the practical applications, the aqueous and solid-state ZABs are assembled and measured. The results demonstrate that the multiphase SNCF-Ni-PM mainly includes carbon nanotubes, C 3 N 4 nanosheets , and FeNiN or CoFe nanoparticles . Moreover, SNCF-Ni-PM exhibits excellent bifunctional oxygen catalytic activity, with an oxygen evolution reaction (OER) potential at 10 mA cm −2 of 1.51 V and an oxygen reduction reaction (ORR) half-wave potential of 0.77 V, outperforming most of the reported oxygen catalysts. Using SNCF-Ni-PM, the aqueous and solid-state ZABs can achieve high power densities of 295.9 and 228.4 mW cm −2 , respectively, being superior to most ZABs. In addition, the aqueous ZAB with SNCF-Ni-PM can operate stably for 300 h with a slight degradation. This work provides a feasible method for effectively recycling Co from the spent Co-based perovskites.
研究领域:
材料科学
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能源化学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2022
·
IF 24.319
Zhe Xu,Yijie Wu,Xin Wang,Qiuyi Ji,Taozhu Li,Huan He,Haiou Song,Shaogui Yang,Shiyin Li,Shicheng Yan,Limin Zhang,Zhigang Zou
Oxygen vacancy (V O ) is attracting extensive interest in heterogeneous peroxymonosulfate (PMS) activation, but its role remains elusive for water treatment. Herein, we constructed V O -tuned cobalt-based perovskite LaCoO 3 -V O , achieving superior activity (0.335 min −1 ) than LaCoO 3 (0.124 min −1 ) for iohexol degradation. Nevertheless, V O did not directly serve as reactive sites, indicated by prohibited contaminant degradation via targeted poisoning of cobalt sites. Systemic electrochemical and spectroscopic measurements illustrate facile transformation of cobalt ions, increased charge density of depletion layer and low transfer resistance are attributed to V O manipulation. DFT calculations suggest reactant HSO 5 − is prone to attach defect site for elongated O-O bond. Experimental and theoretical results reveal the contributions of V O include adjusting PMS adsorption configuration, weakening lattice restraining of cobalt ions, reducing reaction barrier and optimizing electronic structures on perovskites. Our work attempts to understand energetic and kinetic factors of deficiency strategy for rational PMS-based degradation.
研究领域:
环境科学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
Nanoscale
·
2022
·Vol. 14
·期 28
·10118-10124
·
IF 8.307
Ruigan Hu,Mengyuan Zhao,He Miao,Fuyue Liu,Jiaqun Zou,Chunfei Zhang,Qin Wang,Ziqi Tian,Qiuju Zhang,Jinliang Yuan
As a potential oxygen evolution reaction (OER) catalyst, Co-based perovskites have received intensive attention. However, Sr readily accumulates on their surface, and makes them inert toward the OER. Herein, we propose a simple but versatile electrochemical reduction method to reconstruct the active surface of Co-based perovskites within a few seconds. By this method, Sr rapidly precipitates from Co-based perovskites, accompanied by the introduction of Sr and oxygen vacancies. After reconstruction, the electrochemical active surface areas of Co-based perovskites greatly increase, and the OER overpotential of the optimized SrNb0.1Co0.7Fe0.2O3−δ (ER-SNCF-20s) reaches 278 mV at 10 mA cm−2. This can be explained by the decrease of overpotentials at the rate-determining step. Using ER-SNCF-20s, the splitting voltage of alkaline natural seawater can reach 1.56 V at 10 mA cm−2, and remains steady for 300 h. This effort offers a feasible method for reconstructing the active surface of Co-based perovskites.
研究领域:
材料科学
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电化学
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可再生能源
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Small
·
2024
·
IF 13
Shuxiong Wang,Xiaoxin Zhang,Yu Chen,Fan Fan,Chang Jiang,Yongkang Xiang,Xiao Xiao,Yuan Fang,Abdullah N. Alodhayb,Jianhui Li,Jijie Huang,Yifei Sun,Zhou Chen
Lowering the thermal expansion coefficient (TEC) and promoting the catalytic activity of cobalt-based perovskite air electrodes is crucial for efficient solid oxide cells (SOCs) devices. However, the co-achievement of both merits has usually been largely compromised in most scenarios. Herein, a dual-doping strategy to manipulate the properties of perovskite cobaltate electrocatalyst is reported in which a high valence element of Ta 5+ is incorporated into B-site to significantly suppress the dynamic reduction of Co 4+ species and reduces the TEC value from PrBaCo 2 O 5+δ (PBC, 17.8 × 10 ⁻6 K −1 ) to PrBaCo 1.96 Ta 0.04 O 5+δ (PBCT, 12.5 × 10⁻ 6 K −1 ) and suppresses the oxygen loss in SOCs operation condition, revealing the improved structural stability. Meanwhile, the Ca 2+ is doped into A-site of Ta-incorporated candidate, further decreasing the covalency of Co─O bonds and facilitating the formation of oxygen vacancies, benefiting the oxygen exchange kinetics and leading to a low polarization resistance of 0.026 Ω cm 2 (800 °C) in as-prepared PrBa 0.8 Ca 0.2 Co 1.96 Ta 0.04 O 5+δ (PBCCT) electrode. The cell with PBCTT demonstrates remarkable robustness during a 50 h thermal cycling test (25 cycles). Moreover, it delivers a high current density of 1.44 A cm⁻ 2 (1.6 V, 800 °C), as well as attractive durability over 100 h for pure CO 2 electrolysis.
研究领域:
材料科学
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电化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
MATERIALS CHEMISTRY AND PHYSICS
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2022
·
IF 4.778
Na Lei,Yin Qiao,Guanfu Liu,Renhao Xu,Guohua Jiang,Muslum Demir,Pianpian Ma
Cobalt-based perovskite SrCo 0.875 Nb 0.125 O 3 is an advantageous electrode material for supercapacitors . However, the particle form of SrCo 0.875 Nb 0.125 O 3 is not conducive to the electrochemical behavior. Based on this, surface MnO 2 modified SrCo 0.875 Nb 0.125 O 3 on carbon cloth (MnO 2 @SrCo 0.875 Nb 0.125 O 3 @CC) has been prepared as supercapacitor electrode. The dandelion-like morphology of MnO 2 significantly increases the specific surface area and inhibits the grain agglomeration of SrCo 0.875 Nb 0.125 O 3 , thus promoting the ion diffusion during the electrochemical process. As a result, the electrochemical performance of the composite is significantly optimized due to the synergistic effect of SrCo 0.875 Nb 0.125 O 3 and MnO 2 . The MnO 2 @SrCo 0.875 Nb 0.125 O 3 @CC electrode yields an ultra-high specific capacitance of 2066.0 mF cm −2 at 2 mA cm −2 current density. Compared with SrCo 0.875 Nb 0.125 O 3 @CC electrode and MnO 2 @CC electrode, this work provides a much improved performance. Besides, an asymmetric supercapacitor composed of MnO 2 @ SrCo 0.875 Nb 0.125 O 3 @CC as positive electrode and CuS@CC as negative electrode exhibits a voltage window of 1.8 V and a specific capacitance of 114.6 mF cm −2 when the current density is 3 mA cm −2 . A high energy density of 51.57 μ Wh cm −2 is achieved at a power density of 4.86 mW cm −2 for the device.
研究领域:
材料科学
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电化学
✓ 已验证
产品关联
DOI
高影响因子
SOLID STATE IONICS
·
2023
·
IF 3.2
Jinghe Bai,Defeng Zhou,Leilei Niu,Ruyi Chen,Xiaofei Zhu,Ning Wang,Qingwen Liang,Wenfu Yan
The development of cathode materials with high oxygen reduction reaction (ORR) activity and stability in intermediate temperature (IT) environments is a key factor in the commercialization of solid oxide fuel cells (SOFC). In this paper, the ORR activity of the cathode is improved by doping high-valent Sc 3+ ions at the B-site of the Sr 0.5 La 0.5 Co 0.8 Cu 0.2-x Sc x O 3–δ (x = 0, 0.02, 0.04), in which Sr 0.5 La 0.5 Co 0.8 Cu 0.18 Sc 0.02 O 3–δ (SLCCS2) shows the best electrochemical performance , and the area-specific resistance of SLCCS2 at 700 °C is only 0.047 Ω cm 2 , much lower than the 0.087 Ω cm 2 of Sr 0.5 La 0.5 Co 0.8 Cu 0.2 O 3–δ (SLCC), and the peak power density of SLCCS2 reached 1.098 W cm −2 , which is 1.84 times that of SLCC (0.598 W cm −2 ). In addition, SLCCS2 effectively reduces the thermal expansion coefficient , improves thermal matching with traditional electrolytes, and overcomes the problem of insufficient long-term SOFC stability caused by the high thermal expansion coefficient of Co-based perovskite to a certain extent. SLCCS2 also exhibits excellent CO 2 tolerance. Considering comprehensively, SLCCS2 is expected to become an IT-SOFC cathode material with development potential.
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
ACS Sustainable Chemistry & Engineering
·
2025
·
IF 7.3
Zhe Zhang,Sigeng Chen,Chuangang Yao,Haixia Zhang,Wanning Liu,Xiaoshi Lang,Kedi Cai
This study introduces a novel strategy for enhancing the performance of SrCo0.9Ta0.1O3 (SCT) perovskite oxides as cathodes by disrupting the periodic arrangement of lattice oxygen through anionic fluorine doping. The partial substitution of oxygen with F in SrCo0.9Ta0.1O3–xFx (SCTFx) generates oxygen vacancies to maintain charge neutrality. Comprehensive characterizations revealed that F doping weakens the metal–oxygen bond strength, promoting oxygen release from the lattice. This, in turn, significantly increases oxygen mobility and enhances surface adsorption/dissociation kinetics, ultimately boosting the electrochemical performance. Among the investigated compositions, SCTF2 (x = 0.2) exhibited the best oxygen reduction reaction (ORR) activity, characterized by a minimal polarization resistance (Rp) of 0.029 Ω cm2 and a peak power density (PPD) of 0.93 W cm–2 at 800 °C. Beyond the ORR performance, F doping also conferred improved chemical stability, effectively suppressing Sr segregation under CO2-containing atmospheres, a critical factor for long-term operation. The SCTF2 material also demonstrates exceptional CO2 electrolysis performance, achieving a current density of 2.21 A cm–2 at 1.5 V and 800 °C, exceeding the performance of many reported solid oxide electrolysis cells (SOECs). These findings underscore the effectiveness of F doping as a means of manipulating the electrochemical catalytic activity and stability of perovskite cathodes, offering a viable pathway toward the development of advanced solid oxide fuel cell and electrolysis cell technologies.
研究领域:
材料科学
·
电化学
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能源技术
·
无机化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Chuangang Yao,Baixi Xia,Haixia Zhang,Haocong Wang,Wenwen Zhang,Qiuhui Guo,Yubo Jiang,Xiaoshi Lang,Kedi Cai
Cathode materials with high catalytic performance and CO 2 tolerance are essential for advancing the large-scale commercialization of solid oxide fuel cells (SOFCs). This study systematically investigates the impact of fluoride incorporation on the physical characteristics and electrochemical behavior of Pr 0.4 Sr 0.6 CoO 3- δ (PSC) perovskite cathode. The results demonstrate that fluoride incorporation significantly decreases the coefficient of thermal expansion, thereby improving the thermal matching between the cathode and electrolyte materials. Additionally, the introduction of fluoride promotes the formation of oxygen vacancies, which facilitates the oxygen adsorption and dissociation processes, thereby improving the oxygen reduction reaction (ORR) kinetics. Furthermore, fluoride incorporation improves the chemical stability of the material by reducing the surface segregation of Sr, thereby greatly enhancing its CO 2 tolerance. The results reveal that fluoride incorporation markedly lowers the polarization resistance (Rp) and improves ORR catalytic activity and output performance. At 800 ℃, fluoride incorporation reduces the Rp from 0.053 to 0.031 Ω cm 2 , representing a reduction of 41.5 %, while increasing the maximum power density to 1.18 W cm −2 , which is 42.7 % higher than that of the undoped PSC. These findings indicate that fluoride incorporation is an effective strategy for significantly enhancing the electrochemical performance and stability of cobalt-based perovskites, providing a promising approach for the development of high-performance cathodes for SOFCs.
研究领域:
材料科学
·
电化学
·
能源材料
·
燃料电池
✓ 已验证
产品关联
DOI
高影响因子
Nanoscale
·
2021
·Vol. 13
·期 47
·20299-20308
·
IF 7.79
Zhishan Li,Meilan Peng,Yingru Zhao,Jianhui Li,Yifei Sun
The mismatch of thermal expansion coefficients (TECs) between cobalt-containing perovskite air electrodes and electrolytes is a great challenge for the development of thermo-mechanically durable solid oxide cells (SOCs). In this work, we propose a facile design principle to directly grow highly dispersed Co reactive sites onto ion-conducting scaffolds and confine the dimension of active centres within nanoscale. As a representative, the Co-socketed BaCe0.7Zr0.2Y0.1O3−δ perovskite (denoted as R-BCZY-Co) was constructed via a consecutive sol–gel and in situ exsolution approach. Combined XRD, H2-TPR, SEM and TEM results confirm the emergence of Co nanoparticles on a BCZY matrix without the segregation of a secondary Co-rich phase. The symmetric half-cell measurement suggests that R-BCZY-Co air electrode with the optimal Co content of 10 mol% exhibits a 7-fold promoted oxygen activation performance with a polarization resistance of ∼0.17 Ω cm2 at 750 °C. The TEC mismatch between fabricated R-BCZY-Co electrodes and BCZY electrolytes is minimized down to only ∼11.4%, which is significantly lower than that of other representative counterparts. Moreover, the detailed XPS result proves that the architecture of exsolved Co on BCZY possesses a higher concentration of surface oxygen vacancy, which further benefits the kinetics of ion diffusion and oxygen absorption.
研究领域:
材料科学
·
电化学
·
固态化学
·
能源材料
✓ 已验证
DOI
高影响因子
Nature Communications
·
2019
·Vol. 10
·期 1
·1-8
·
IF 11.878
Guan Daqin,Zhou Jing,Huang Yu-Cheng,Dong Chung-Li,Wang Jian-Qiang,Zhou Wei,Shao Zongping
Facile and reliable screening of cost-effective, high-performance and scalable electrocatalysts is key for energy conversion technologies such as water splitting. ABO 3- δ perovskites, with rich constitutions and structures, have never been designed via activity descriptors for critical hydrogen evolution reaction (HER). Here, we apply coordination rationales to introduce A-site ionic electronegativity (AIE) as an efficient unifying descriptor to predict the HER activities of 13 cobalt-based perovskites. Compared with A-site structural or thermodynamic parameter, AIE endows the HER activity with the best volcano trend. (Gd 0.5 La 0.5 )BaCo 2 O 5.5+ δ predicted from an AIE value of ~2.33 exceeds the state-of-the-art Pt/C catalyst in electrode activity and stability. X-ray absorption and computational studies reveal that the peak HER activities at a moderate AIE value of ~2.33 can be associated with the optimal electronic states of active B-sites via inductive effect in perovskite structure (~200 nm depth), including Co valence, Co-O bond covalency, band gap and O 2 p -band position.
研究领域:
材料科学
·
电化学
·
催化
·
能量转换
✓ 已验证
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）