LiMn_(2)O_(4)(LMO)electrochemical lithium-ion pump has gained widespread attention due to its green,high efficiency,and low energy consumption in selectively extracting lithium from brine.However,collapse of crystal s...LiMn_(2)O_(4)(LMO)electrochemical lithium-ion pump has gained widespread attention due to its green,high efficiency,and low energy consumption in selectively extracting lithium from brine.However,collapse of crystal structure and loss of lithium extraction capacity caused by Mn dissolution loss limits its industrialized application.Hence,a multifunctional coating was developed by depositing amorphous AlPO_(4)on the surface of LMO using sol-gel method.The characterization and electrochemical performance test provided insights into the mechanism of Li^(+)embedment and de-embedment and revealed that multifunctional AlPO_(4)can reconstruct the physical and chemical state of LMO surface to improve the interface hydrophilicity,promote the transport of Li^(+),strengthen cycle stability.Remarkably,after 20 cycles,the capacity retention rate of 0.5AP-LMO reached 93.6%with only 0.147%Mn dissolution loss.The average Li^(+)release capacity of 0.5AP-LMO//Ag system in simulated brine is 28.77 mg/(g h),which is 90.4%higher than LMO.Encouragingly,even in the more complex Zabuye real brine,0.5AP-LMO//Ag can still maintain excellent lithium extraction performance.These results indicate that the 0.5AP-LMO//Ag lithium-ion pump shows promising potential as a Li^(+)selective extraction system.展开更多
Novel graphitic carbon nitride(g-C_(3)N_(4))nanosheet/Bi_(5)O_(7)Br/NH_(2)-MIL-88B(Fe)photocatalysts(denoted as GCN-NSh/Bi_(5)O_(7)Br/FeMOF,in which MOF is metal–organic framework)with double S-scheme heterojunctions...Novel graphitic carbon nitride(g-C_(3)N_(4))nanosheet/Bi_(5)O_(7)Br/NH_(2)-MIL-88B(Fe)photocatalysts(denoted as GCN-NSh/Bi_(5)O_(7)Br/FeMOF,in which MOF is metal–organic framework)with double S-scheme heterojunctions were synthesized by a facile solvothermal route.The resultant materials were examined by X-ray photoelectron spectrometer(XPS),X-ray diffraction(XRD),scanning electron microscopy(SEM),energy dispersive X-ray spectroscopy(EDX),transmission electron microscopy(TEM),high-resolution transmission electron microscopy(HRTEM),photoluminescence spectroscopy(PL),Fourier transform infrared spectroscopy(FT-IR),UV-Vis diffuse reflection spectroscopy(UV-vis DRS),photocurrent density,electrochemical impedance spectroscopy(EIS),and Brunauer–Emmett–Teller(BET)analyses.After the integration of Fe-MOF with GCN-NSh/Bi_(5)O_(7)Br,the removal constant of tetracycline over the optimal GCN-NSh/Bi_(5)O_(7)Br/Fe-MOF(15wt%)nanocomposite was promoted 33 times compared with that of the pristine GCN.The GCN-NSh/Bi_(5)O_(7)Br/Fe-MOF(15wt%)nanocomposite showed superior photoactivity to azithromycin,metronidazole,and cephalexin removal that was 36.4,20.2,and 14.6 times higher than that of pure GCN,respectively.Radical quenching tests showed that·O_(2)-and h+mainly contributed to the elimination reaction.In addition,the nanocomposite maintained excellent activity after 4 successive cycles.Based on the developed n–n heterojunctions among n-GCN-NSh,n-Bi_(5)O_(7)Br,and n-Fe-MOF semiconductors,the double S-scheme charge transfer mechanism was proposed for the destruction of the selected antibiotics.展开更多
The spinel lithium manganese oxide cathode materials were prepared by adipic acid-assisted sol-gel method at 350～900 ℃ in air. The effects of water content of solution, molar ratio between metal ion and adipic acid,...The spinel lithium manganese oxide cathode materials were prepared by adipic acid-assisted sol-gel method at 350～900 ℃ in air. The effects of water content of solution, molar ratio between metal ion and adipic acid, cooling rate, synthesis temperature and particle sizes on structure and electrochemical performance of LiMn_2O_4 are investigated by X-ray diffraction (XRD), and cyclic voltammetry (CV). The result shows that the structure and electrochemical performance of LiMn_2O_4 are greatly affected by synthesis condition, and the optimal synthesis condition is determined. Charge-discharge test reveals that the particle size and cooling rate have significant effects on the electrochemical performance of LiMn_2O_4 cathode materials.展开更多
电控离子交换(Electrochemically switched ion exchange,ESIX)系统内对电极具有保持溶液电中性、增强提锂效果且使系统形成闭合回路的关键作用。在ESIX技术盐湖提锂过程中人们主要关注锂离子捕获电极,关于对电极的研究较少。而本文研...电控离子交换(Electrochemically switched ion exchange,ESIX)系统内对电极具有保持溶液电中性、增强提锂效果且使系统形成闭合回路的关键作用。在ESIX技术盐湖提锂过程中人们主要关注锂离子捕获电极,关于对电极的研究较少。而本文研究了不同类型对电极对ESIX系统提锂性能的影响。分别采用聚吡咯/导电炭黑/聚偏二氟乙烯(PPy/C/PVDF)、活性炭/导电炭黑/聚偏二氟乙烯(AC/C/PVDF)和石墨板电极作为ESIX系统中锰酸锂/导电炭黑/聚偏二氟乙烯(LiMn_(2)O_(4)/C/PVDF)提锂膜电极的对电极,考察了这3种ESIX系统在氯化物型高镁锂比模拟卤水(Mg/Li~50)中的提锂性能。结果表明,当PPy/C/PVDF作为对电极时可有效吸附卤水中Cl^(-),且ESIX系统提锂性能最优,Li^(+)吸附量为13.9 mg/g;当PPy/C/PVDF电极湿膜厚度增加至1 mm时,ESIX系统对Li^(+)的提取率可达44.2%,Li^(+)/Mg^(2+)分离因子可达56.82。因此,针对不同的阴离子型盐湖卤水设计匹配的对电极对ESIX技术在盐湖提锂领域的发展具有重要的理论指导意义。展开更多
The present commercial spinel LiMn_(2)O_(4) delivers only 90 m Ah/g–115 m Ah/g,far lower than the theoretical specific capacity.It degrades fast caused by the Jahn–Teller effect,Mn dissolution and related side react...The present commercial spinel LiMn_(2)O_(4) delivers only 90 m Ah/g–115 m Ah/g,far lower than the theoretical specific capacity.It degrades fast caused by the Jahn–Teller effect,Mn dissolution and related side reactions that consume Li inventory.In this work,Zr doping is employed to improve the structural stability and electrochemical performance of spinel LiMn_(2)O_(4).Li_(1.06)Mn_(1.94-x)Zr_xO_4(x=0,0.01,0.02,0.04)have been successfully synthesized by a simple solid-state reaction method and evaluated as cathode for lithium ion batteries(LIB).Li_(1.06)Mn_(1.92)Zr_(0.02)O_4 is superior cathode material with a high capacity of 122 m Ah/g at 1-C rate;long cycle stability,98.39%retention after 100 cycles at 1-C rate,excellent high rate performance 107.1 m Ah/g at 10-C rate,and high temperature performance 97.39%retention after 60 cycles.These are thought to be related to Zr doping effectively stabilizing the spinel LiMn_(2)O_(4),by forming stronger Zr–O bonds in the octahedron,suppressing the Jahn–Teller effect,thus improving electrochemical performance.展开更多
通过共沉淀法合成了CuCr_(2)O_(4)黑色颜料。研究了沉淀剂(即尿素、氨水、氢氧化钠)对相组成和颜色性能的影响。同时,计算了以氨水和氢氧化钠为沉淀剂时CuCr_(2)O_(4)的结晶动力学和结晶机制。结果表明,由于两种离子(Cu^(2+)和Cr^(3+))...通过共沉淀法合成了CuCr_(2)O_(4)黑色颜料。研究了沉淀剂(即尿素、氨水、氢氧化钠)对相组成和颜色性能的影响。同时,计算了以氨水和氢氧化钠为沉淀剂时CuCr_(2)O_(4)的结晶动力学和结晶机制。结果表明,由于两种离子(Cu^(2+)和Cr^(3+))的溶解度不同,沉淀过程的最佳pH值为7.5;由于产物中存在Cr2O3,尿素不适合作为沉淀剂。氨水作为沉淀剂时,CuCr_(2)O_(4)结晶的活化能为120.2 k J/mol,氢氧化钠作为沉淀剂时为141.3 k J/mol。CuCr_(2)O_(4)的结晶过程涉及成核和三维生长。较小的结晶活化能得到的CuCr_(2)O_(4)颗粒细小,分散均匀,呈色性能更优异。展开更多
通过溶胶凝胶法制备出LiMn_2O_4和LiMn_(1.92)Mg_(0.08)O_(3.84)Br_(0.16)锂离子电池正极材料,并用XRD、SEM、XPS、充放电测试和CV对其结构、形貌、化学成份以及电化学性能进行了研究。结果表明,Mg、Br的掺杂未改变LiMn_2O_4的结构。在0...通过溶胶凝胶法制备出LiMn_2O_4和LiMn_(1.92)Mg_(0.08)O_(3.84)Br_(0.16)锂离子电池正极材料,并用XRD、SEM、XPS、充放电测试和CV对其结构、形貌、化学成份以及电化学性能进行了研究。结果表明,Mg、Br的掺杂未改变LiMn_2O_4的结构。在0.5 C倍率下,LiMn_(1.92)Mg_(0.08)O_(3.84)Br_(0.16)的放电比容量为119 m Ah/g,与LiMn_2O_4相比,其首次放电比容量提高了3.6%,循环100次后,Li Mn1.92Mg0.08O3.84Br0.16的容量保持率高达86.9%。在5 C倍率下,LiMn_(1.92)Mg_(0.08)O_(3.84)Br_(0.16)的放电比容量为91.1 m Ah/g,比LiMn_2O_4提高了24.1%。实验表明,Mg、Br共同掺杂提高了LiMn_2O_4的放电比容量,并明显改善其循环稳定性和倍率性能,从而获得了较好的综合电化学性能。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
基金supported by the National Natural Science Foundation of China(21908082,22278426,and 22178154)the Jiangsu Funding Program for Excellent Postdoctoral Talent(2022ZB629)+1 种基金the Natural Science Foundation of Jiangsu Province(BK20221367)the China Postdoctoral Science Foundation(2021M701472)。
文摘LiMn_(2)O_(4)(LMO)electrochemical lithium-ion pump has gained widespread attention due to its green,high efficiency,and low energy consumption in selectively extracting lithium from brine.However,collapse of crystal structure and loss of lithium extraction capacity caused by Mn dissolution loss limits its industrialized application.Hence,a multifunctional coating was developed by depositing amorphous AlPO_(4)on the surface of LMO using sol-gel method.The characterization and electrochemical performance test provided insights into the mechanism of Li^(+)embedment and de-embedment and revealed that multifunctional AlPO_(4)can reconstruct the physical and chemical state of LMO surface to improve the interface hydrophilicity,promote the transport of Li^(+),strengthen cycle stability.Remarkably,after 20 cycles,the capacity retention rate of 0.5AP-LMO reached 93.6%with only 0.147%Mn dissolution loss.The average Li^(+)release capacity of 0.5AP-LMO//Ag system in simulated brine is 28.77 mg/(g h),which is 90.4%higher than LMO.Encouragingly,even in the more complex Zabuye real brine,0.5AP-LMO//Ag can still maintain excellent lithium extraction performance.These results indicate that the 0.5AP-LMO//Ag lithium-ion pump shows promising potential as a Li^(+)selective extraction system.
文摘Novel graphitic carbon nitride(g-C_(3)N_(4))nanosheet/Bi_(5)O_(7)Br/NH_(2)-MIL-88B(Fe)photocatalysts(denoted as GCN-NSh/Bi_(5)O_(7)Br/FeMOF,in which MOF is metal–organic framework)with double S-scheme heterojunctions were synthesized by a facile solvothermal route.The resultant materials were examined by X-ray photoelectron spectrometer(XPS),X-ray diffraction(XRD),scanning electron microscopy(SEM),energy dispersive X-ray spectroscopy(EDX),transmission electron microscopy(TEM),high-resolution transmission electron microscopy(HRTEM),photoluminescence spectroscopy(PL),Fourier transform infrared spectroscopy(FT-IR),UV-Vis diffuse reflection spectroscopy(UV-vis DRS),photocurrent density,electrochemical impedance spectroscopy(EIS),and Brunauer–Emmett–Teller(BET)analyses.After the integration of Fe-MOF with GCN-NSh/Bi_(5)O_(7)Br,the removal constant of tetracycline over the optimal GCN-NSh/Bi_(5)O_(7)Br/Fe-MOF(15wt%)nanocomposite was promoted 33 times compared with that of the pristine GCN.The GCN-NSh/Bi_(5)O_(7)Br/Fe-MOF(15wt%)nanocomposite showed superior photoactivity to azithromycin,metronidazole,and cephalexin removal that was 36.4,20.2,and 14.6 times higher than that of pure GCN,respectively.Radical quenching tests showed that·O_(2)-and h+mainly contributed to the elimination reaction.In addition,the nanocomposite maintained excellent activity after 4 successive cycles.Based on the developed n–n heterojunctions among n-GCN-NSh,n-Bi_(5)O_(7)Br,and n-Fe-MOF semiconductors,the double S-scheme charge transfer mechanism was proposed for the destruction of the selected antibiotics.
文摘The spinel lithium manganese oxide cathode materials were prepared by adipic acid-assisted sol-gel method at 350～900 ℃ in air. The effects of water content of solution, molar ratio between metal ion and adipic acid, cooling rate, synthesis temperature and particle sizes on structure and electrochemical performance of LiMn_2O_4 are investigated by X-ray diffraction (XRD), and cyclic voltammetry (CV). The result shows that the structure and electrochemical performance of LiMn_2O_4 are greatly affected by synthesis condition, and the optimal synthesis condition is determined. Charge-discharge test reveals that the particle size and cooling rate have significant effects on the electrochemical performance of LiMn_2O_4 cathode materials.
基金research on high power flexible battery in all sea depth(Grant No.2020-XXXX-XX-246-00)。
文摘The present commercial spinel LiMn_(2)O_(4) delivers only 90 m Ah/g–115 m Ah/g,far lower than the theoretical specific capacity.It degrades fast caused by the Jahn–Teller effect,Mn dissolution and related side reactions that consume Li inventory.In this work,Zr doping is employed to improve the structural stability and electrochemical performance of spinel LiMn_(2)O_(4).Li_(1.06)Mn_(1.94-x)Zr_xO_4(x=0,0.01,0.02,0.04)have been successfully synthesized by a simple solid-state reaction method and evaluated as cathode for lithium ion batteries(LIB).Li_(1.06)Mn_(1.92)Zr_(0.02)O_4 is superior cathode material with a high capacity of 122 m Ah/g at 1-C rate;long cycle stability,98.39%retention after 100 cycles at 1-C rate,excellent high rate performance 107.1 m Ah/g at 10-C rate,and high temperature performance 97.39%retention after 60 cycles.These are thought to be related to Zr doping effectively stabilizing the spinel LiMn_(2)O_(4),by forming stronger Zr–O bonds in the octahedron,suppressing the Jahn–Teller effect,thus improving electrochemical performance.
文摘通过共沉淀法合成了CuCr_(2)O_(4)黑色颜料。研究了沉淀剂(即尿素、氨水、氢氧化钠)对相组成和颜色性能的影响。同时,计算了以氨水和氢氧化钠为沉淀剂时CuCr_(2)O_(4)的结晶动力学和结晶机制。结果表明,由于两种离子(Cu^(2+)和Cr^(3+))的溶解度不同,沉淀过程的最佳pH值为7.5;由于产物中存在Cr2O3,尿素不适合作为沉淀剂。氨水作为沉淀剂时,CuCr_(2)O_(4)结晶的活化能为120.2 k J/mol,氢氧化钠作为沉淀剂时为141.3 k J/mol。CuCr_(2)O_(4)的结晶过程涉及成核和三维生长。较小的结晶活化能得到的CuCr_(2)O_(4)颗粒细小,分散均匀,呈色性能更优异。
文摘通过溶胶凝胶法制备出LiMn_2O_4和LiMn_(1.92)Mg_(0.08)O_(3.84)Br_(0.16)锂离子电池正极材料,并用XRD、SEM、XPS、充放电测试和CV对其结构、形貌、化学成份以及电化学性能进行了研究。结果表明,Mg、Br的掺杂未改变LiMn_2O_4的结构。在0.5 C倍率下,LiMn_(1.92)Mg_(0.08)O_(3.84)Br_(0.16)的放电比容量为119 m Ah/g,与LiMn_2O_4相比,其首次放电比容量提高了3.6%,循环100次后,Li Mn1.92Mg0.08O3.84Br0.16的容量保持率高达86.9%。在5 C倍率下,LiMn_(1.92)Mg_(0.08)O_(3.84)Br_(0.16)的放电比容量为91.1 m Ah/g,比LiMn_2O_4提高了24.1%。实验表明,Mg、Br共同掺杂提高了LiMn_2O_4的放电比容量,并明显改善其循环稳定性和倍率性能,从而获得了较好的综合电化学性能。
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。
