The preparation of LiNi_(0.8)Co_(0.2)O_2 was discussed by the multiply sintering method for solid reaction, in which the sintered material was smashed, ground and pelletted between two successive sintering steps. The...The preparation of LiNi_(0.8)Co_(0.2)O_2 was discussed by the multiply sintering method for solid reaction, in which the sintered material was smashed, ground and pelletted between two successive sintering steps. The optimum technological condition was obtained through orthogonal experiments by L_9(3~4) and DTA analysis. The result indicates that the factors of effecting the electrochemical properties of synthesized LiNi_(0.8)Co_(0.2)O_2 are molar ratio of Li/Ni/Co, oxygen pressure, homothermal time, the final sintering temperature in turn according to its importance. The oxygen pressure is reviewed independently and the technological condition is further optimized. With the same method, rare earth element Ce was studied as substitute element of Co and the cathode material of LiNi_(0.95)Ce_(0.05)O_2 with excellent electrochemical properties was prepared. The electrochemical testing results of LiNi_(0.8)Co_(0.2)O_2 and LiNi_(0.95)Ce_(0.05)O_2 experimental batteries show that discharge capacities of them reach 165 and 148 mAh·g^(-1) respectively and the persistence is more than 9 h at 3.7 V.展开更多
The commercialized lithium secondary cells need the electrode materials with high speeific capacity, lower pollution and lower price. Certain industrial materials ( NiSO_4, CoSO_4 , LiOH·H_2O)were used to synthes...The commercialized lithium secondary cells need the electrode materials with high speeific capacity, lower pollution and lower price. Certain industrial materials ( NiSO_4, CoSO_4 , LiOH·H_2O)were used to synthesize Ni_(0.8)Co_(0.2)(OH)_2 of a stratified structure, when various synthesis conditions such as pH, reaction temperature et al. were controlled strictly. After LiOH·H_2O and Ni_(0.8)Co_(0.2) (OH)_2were calcinated in air atmosphere, LiNi_(0.8)Co_(0.2)O_2 positive electrode materials with good layered crystal structure was obtained. Tests showed that the optimal calcination temperature in air atmosphere was about at 720℃ and LiNi_(0.8)Co_(0.2)O_2 synthesized in the above conditions had good electrochemical properties and a low cost. The first specific: discharge capacity of the material was 186 mAh/g, and the specific discharge capacity was 175 mAh/g after 50 cycles at a 0.2C rate, between 3.0～4.2 V with a discharge deterioration ratio of 0.22% each cycle. Tests showed that LiNi_(0.8)Co_(0.2)O_2 positive electrode materials was a promising candidate to replace the commereialized LiCoO_2 for lithium secondary batteries.展开更多
Oxygen anion redox reaction provides a high theoretical capacity for Li-rich manganese-based cathodes.However,irreversible surface oxygen release often results in further oxygen loss and exacerbates the decomposition ...Oxygen anion redox reaction provides a high theoretical capacity for Li-rich manganese-based cathodes.However,irreversible surface oxygen release often results in further oxygen loss and exacerbates the decomposition of the electrolyte,which could reduce the capacity contribution from the anionic redox and produce more acidic substances to corrode the surface of the material.In this paper,the surface oxygen release is suppressed by moderating oxygen anion redox activity via constructing chemical bonds between M(M=Fe and La)in LaFeO_(3)and surface oxygen anions of Li_(1.2)Mn_(0.6)Ni_(0.2)O_(2).The constructed interface layer stabilizes the surface lattice oxygen and retards the electrolyte from being attacked by the nucleophilic oxygen generated in the process of oxygen release,as evidenced by Differential Electrochemical Mass Spectrometry(DEMS)and X-ray Photoelectron Spectroscopy(XPS)detections.Moreover,in the charge and discharge process,the formed FeF_(3),located at the cathode electrolyte interfacial layer,is conducive to the stability of the cathode surface.The modified Li_(1.2)Mn_(0.6)Ni_(0.2)O_(2)electrode with 3 wt%LaFeO_(13)exhibits a high specific capacity of 189.5 mA h g-at 1C(200 mA g^(-1))after 150 cycles with capacity retentions of 96.6%,and 112.6 mA h g^(-1)(84.7%)at 5C after 200 cycles higher than the pristine sample.This study provides a rational design chemical bonding method to suppress the oxygen release from the cathode surface and enhance cyclic stability.展开更多
为进一步提高动力电池正极材料锰酸锂(LiMn_2O_4)的循环稳定性,通过溶胶-凝胶法用快离子导体La_(0.8)Sr_(0.2)MnO_3作为包覆材料对LiMn_2O_4进行表面修饰,探讨了不同包覆量对复合材料电化学性能的影响。采用X射线衍射仪(XRD)、场发射扫...为进一步提高动力电池正极材料锰酸锂(LiMn_2O_4)的循环稳定性,通过溶胶-凝胶法用快离子导体La_(0.8)Sr_(0.2)MnO_3作为包覆材料对LiMn_2O_4进行表面修饰,探讨了不同包覆量对复合材料电化学性能的影响。采用X射线衍射仪(XRD)、场发射扫描电镜(FESEM)和透射电子显微镜(TEM)对样品的微观结构以及形貌进行表征。结果表明:La_(0.8)Sr_(0.2)MnO_3的包覆并没有改变LiMn_2O_4晶体结构及空间构型;相比纯的LiMn_2O_4样品,La_(0.8)Sr_(0.2)MnO_3包覆后的样品颗粒表面较为粗糙;涂层为薄膜状结构,均匀且完全包覆在LiMn_2O_4颗粒的表面。利用电化学测试方法测试其电化学性能,测试结果表明,当La_(0.8)Sr_(0.2)MnO_3包覆量为5%时,具有较好的电化学性能,首次放电比容量为127.4 m A·h/g(0.1 C),25℃循环400次后容量保持率为91.2%,55℃循环100次后容量保持率为91.1%;与未经表面修饰的样品相比,其首次放电比容量为119.1 m A·h/g(0.1 C),400次的容量保持率为61.9%,100次容量保持率为77.9%,La_(0.8)Sr_(0.2)MnO_3包覆后的样品的电化学性能尤其是循环性能得到明显的提高。展开更多
Combustion catalyst La_(0.8)Sr_(0.2)CoO_3 (LSC) is expected to possess relatively high activity for the oxidation of carbon monoxide and many hydrocarbons. If γ-Al_2O_3 is used as its support, cobalt ions can easily ...Combustion catalyst La_(0.8)Sr_(0.2)CoO_3 (LSC) is expected to possess relatively high activity for the oxidation of carbon monoxide and many hydrocarbons. If γ-Al_2O_3 is used as its support, cobalt ions can easily react with γ-Al_2O_3 at not very high temperature to form spinel CoAl_2O_4 or spinel-like, which decreases the activity of the combustion catalyst. In this paper, MgAl_2O_4 and CaAl_2O_4 were pre-coated on γ-Al_2O_3 by impregnation respectively, which formed compound support for LSC. It is shown that, when MgAl_2O_4 layer is covered on the surface of MgAl_2O_4 by impregnation, the entering of cobalt ions into γ-Al_2O_3 lattice is restrained, then LSC formed on the surface of MgAl_2O_4, which leads to a good catalytic activity of xylene complete oxidation. But the layer of MgAl_2O_4 should be thick enough to reach 30% (mass fraction) MgO in the support due to large size particle of MgAl_2O_4 crystalline. If polyvinyl alcohol (PVA) is added into the impregnation solution adequately, MgAl_2O_4 particles formed on the surface of γ-Al_2O_3 are getting smaller, and less amount of MgAl_2O_4 is needed to cover up the surface of γ-Al_2O_3. If CaAl_2O_4 layer substituted for MgAl_2O_4, more closed cover is obtained in virtue of fine particles of CaAl_2O_4. The activity examination shows that smaller particles of MgAl_2O_4 or CaAl_2O_4 can be more effective to hinder cobalt ions entering the lattice of γ-Al_2O_3, and better activities will be obtained.展开更多
Perovskite oxide La_(0.6)Ca_(0.4)Fe_(0.8)Ni_(0.2)O_(3-δ)(LCFN)has been used in symmetric solid oxide cells(SSOCs)to obtain good electrochemical performance in both fuel cells(SOFCs)and electrolysis cells(SOECs)modes....Perovskite oxide La_(0.6)Ca_(0.4)Fe_(0.8)Ni_(0.2)O_(3-δ)(LCFN)has been used in symmetric solid oxide cells(SSOCs)to obtain good electrochemical performance in both fuel cells(SOFCs)and electrolysis cells(SOECs)modes.However,its structural stability still faces challenges and the electrocatalytic activity also needs to be further improved.Herein,tungsten-doped La_(0.6)Ca_(0.4)Fe_(0.7)Ni_(0.2)W_(0.1)0_(3-δ)(LCFNW)perovskite oxide material was synthesized which exhibits good structural stability under H_(2)and superior electrochemical performance as an electrode for SSOCs.In SOFCs mode,the cell achieved the maximum power density of 0.58 W·cm^(-2)with wet H_(2)as fuel at 850℃.In SOECs mode,the current density can reach 1.81 A·cm^(-2)for pure CO_(2)electrolysis at 2 V.Moreover,the SSOCs exhibits outstanding long-term stability in both SOFCs and SOECs modes,proving that doping W in perovskite oxide is an effective strategy to enhance the catalytic activity and stability of the electrode.The LCFNW material developed in this work shows promising prospect as an electrode candidate for SSOCs.展开更多
文摘The preparation of LiNi_(0.8)Co_(0.2)O_2 was discussed by the multiply sintering method for solid reaction, in which the sintered material was smashed, ground and pelletted between two successive sintering steps. The optimum technological condition was obtained through orthogonal experiments by L_9(3~4) and DTA analysis. The result indicates that the factors of effecting the electrochemical properties of synthesized LiNi_(0.8)Co_(0.2)O_2 are molar ratio of Li/Ni/Co, oxygen pressure, homothermal time, the final sintering temperature in turn according to its importance. The oxygen pressure is reviewed independently and the technological condition is further optimized. With the same method, rare earth element Ce was studied as substitute element of Co and the cathode material of LiNi_(0.95)Ce_(0.05)O_2 with excellent electrochemical properties was prepared. The electrochemical testing results of LiNi_(0.8)Co_(0.2)O_2 and LiNi_(0.95)Ce_(0.05)O_2 experimental batteries show that discharge capacities of them reach 165 and 148 mAh·g^(-1) respectively and the persistence is more than 9 h at 3.7 V.
文摘The commercialized lithium secondary cells need the electrode materials with high speeific capacity, lower pollution and lower price. Certain industrial materials ( NiSO_4, CoSO_4 , LiOH·H_2O)were used to synthesize Ni_(0.8)Co_(0.2)(OH)_2 of a stratified structure, when various synthesis conditions such as pH, reaction temperature et al. were controlled strictly. After LiOH·H_2O and Ni_(0.8)Co_(0.2) (OH)_2were calcinated in air atmosphere, LiNi_(0.8)Co_(0.2)O_2 positive electrode materials with good layered crystal structure was obtained. Tests showed that the optimal calcination temperature in air atmosphere was about at 720℃ and LiNi_(0.8)Co_(0.2)O_2 synthesized in the above conditions had good electrochemical properties and a low cost. The first specific: discharge capacity of the material was 186 mAh/g, and the specific discharge capacity was 175 mAh/g after 50 cycles at a 0.2C rate, between 3.0～4.2 V with a discharge deterioration ratio of 0.22% each cycle. Tests showed that LiNi_(0.8)Co_(0.2)O_2 positive electrode materials was a promising candidate to replace the commereialized LiCoO_2 for lithium secondary batteries.
基金supported by the National Natural Science Foundation of China(22175070,22293041,51902081,and 21871106)Key Fund in Hebei Province Department of Education China(ZD2022042)。
文摘Oxygen anion redox reaction provides a high theoretical capacity for Li-rich manganese-based cathodes.However,irreversible surface oxygen release often results in further oxygen loss and exacerbates the decomposition of the electrolyte,which could reduce the capacity contribution from the anionic redox and produce more acidic substances to corrode the surface of the material.In this paper,the surface oxygen release is suppressed by moderating oxygen anion redox activity via constructing chemical bonds between M(M=Fe and La)in LaFeO_(3)and surface oxygen anions of Li_(1.2)Mn_(0.6)Ni_(0.2)O_(2).The constructed interface layer stabilizes the surface lattice oxygen and retards the electrolyte from being attacked by the nucleophilic oxygen generated in the process of oxygen release,as evidenced by Differential Electrochemical Mass Spectrometry(DEMS)and X-ray Photoelectron Spectroscopy(XPS)detections.Moreover,in the charge and discharge process,the formed FeF_(3),located at the cathode electrolyte interfacial layer,is conducive to the stability of the cathode surface.The modified Li_(1.2)Mn_(0.6)Ni_(0.2)O_(2)electrode with 3 wt%LaFeO_(13)exhibits a high specific capacity of 189.5 mA h g-at 1C(200 mA g^(-1))after 150 cycles with capacity retentions of 96.6%,and 112.6 mA h g^(-1)(84.7%)at 5C after 200 cycles higher than the pristine sample.This study provides a rational design chemical bonding method to suppress the oxygen release from the cathode surface and enhance cyclic stability.
文摘为进一步提高动力电池正极材料锰酸锂(LiMn_2O_4)的循环稳定性,通过溶胶-凝胶法用快离子导体La_(0.8)Sr_(0.2)MnO_3作为包覆材料对LiMn_2O_4进行表面修饰,探讨了不同包覆量对复合材料电化学性能的影响。采用X射线衍射仪(XRD)、场发射扫描电镜(FESEM)和透射电子显微镜(TEM)对样品的微观结构以及形貌进行表征。结果表明:La_(0.8)Sr_(0.2)MnO_3的包覆并没有改变LiMn_2O_4晶体结构及空间构型;相比纯的LiMn_2O_4样品,La_(0.8)Sr_(0.2)MnO_3包覆后的样品颗粒表面较为粗糙;涂层为薄膜状结构,均匀且完全包覆在LiMn_2O_4颗粒的表面。利用电化学测试方法测试其电化学性能,测试结果表明,当La_(0.8)Sr_(0.2)MnO_3包覆量为5%时,具有较好的电化学性能,首次放电比容量为127.4 m A·h/g(0.1 C),25℃循环400次后容量保持率为91.2%,55℃循环100次后容量保持率为91.1%;与未经表面修饰的样品相比,其首次放电比容量为119.1 m A·h/g(0.1 C),400次的容量保持率为61.9%,100次容量保持率为77.9%,La_(0.8)Sr_(0.2)MnO_3包覆后的样品的电化学性能尤其是循环性能得到明显的提高。
文摘Combustion catalyst La_(0.8)Sr_(0.2)CoO_3 (LSC) is expected to possess relatively high activity for the oxidation of carbon monoxide and many hydrocarbons. If γ-Al_2O_3 is used as its support, cobalt ions can easily react with γ-Al_2O_3 at not very high temperature to form spinel CoAl_2O_4 or spinel-like, which decreases the activity of the combustion catalyst. In this paper, MgAl_2O_4 and CaAl_2O_4 were pre-coated on γ-Al_2O_3 by impregnation respectively, which formed compound support for LSC. It is shown that, when MgAl_2O_4 layer is covered on the surface of MgAl_2O_4 by impregnation, the entering of cobalt ions into γ-Al_2O_3 lattice is restrained, then LSC formed on the surface of MgAl_2O_4, which leads to a good catalytic activity of xylene complete oxidation. But the layer of MgAl_2O_4 should be thick enough to reach 30% (mass fraction) MgO in the support due to large size particle of MgAl_2O_4 crystalline. If polyvinyl alcohol (PVA) is added into the impregnation solution adequately, MgAl_2O_4 particles formed on the surface of γ-Al_2O_3 are getting smaller, and less amount of MgAl_2O_4 is needed to cover up the surface of γ-Al_2O_3. If CaAl_2O_4 layer substituted for MgAl_2O_4, more closed cover is obtained in virtue of fine particles of CaAl_2O_4. The activity examination shows that smaller particles of MgAl_2O_4 or CaAl_2O_4 can be more effective to hinder cobalt ions entering the lattice of γ-Al_2O_3, and better activities will be obtained.
基金financial support from National Key R&D Program for Young Scientists(2021YFA1501900)National Natural Science Foundation of China(52272257)+4 种基金Material Science and Engineering Discipline Guidance Fund of China University of Mining and Technology(CUMTMS202203)Foundation of State Key Laboratory of Clean and Efficient Coal Utilization,Taiyuan University of Technology(Grant No.SKL2022008)the Jiangsu Provincial Shuangchuang Doctor Program(JSSCBS20211224)Young Elite Scientists Sponsorship Program by(CAST2022QNRC001)the Open Sharing Fund for the Large-scale Instruments(DYGX-2021026)and Equipments of China University of Mining and Technology(CUMT)Analytical for sample characterizations assistance。
文摘Perovskite oxide La_(0.6)Ca_(0.4)Fe_(0.8)Ni_(0.2)O_(3-δ)(LCFN)has been used in symmetric solid oxide cells(SSOCs)to obtain good electrochemical performance in both fuel cells(SOFCs)and electrolysis cells(SOECs)modes.However,its structural stability still faces challenges and the electrocatalytic activity also needs to be further improved.Herein,tungsten-doped La_(0.6)Ca_(0.4)Fe_(0.7)Ni_(0.2)W_(0.1)0_(3-δ)(LCFNW)perovskite oxide material was synthesized which exhibits good structural stability under H_(2)and superior electrochemical performance as an electrode for SSOCs.In SOFCs mode,the cell achieved the maximum power density of 0.58 W·cm^(-2)with wet H_(2)as fuel at 850℃.In SOECs mode,the current density can reach 1.81 A·cm^(-2)for pure CO_(2)electrolysis at 2 V.Moreover,the SSOCs exhibits outstanding long-term stability in both SOFCs and SOECs modes,proving that doping W in perovskite oxide is an effective strategy to enhance the catalytic activity and stability of the electrode.The LCFNW material developed in this work shows promising prospect as an electrode candidate for SSOCs.
