Owing to the high specific capacity and high voltage,Ni-rich(LiNi0.8Co0.1Mn0.1O2,LNCM811)cathode has been considered as one of the most promising candidate cathode materials for next generation lithium ion batteries,w...Owing to the high specific capacity and high voltage,Ni-rich(LiNi0.8Co0.1Mn0.1O2,LNCM811)cathode has been considered as one of the most promising candidate cathode materials for next generation lithium ion batteries,whereas severe capacity fading greatly hinders its practical application.Notably,the compatibility of Ni-rich materials with LiBF4-containing electrolyte has not yet been realized.Herein,1 M LiPF6-based electrolyte with introducing 2 M LiBF4 is proposed to dramatically improve the cyclic stability of high voltage LNCM811/Li half-cell.Addition of high concentrated LiBF4 improves the moisture stability of electrolyte,which hinders the generation of harmful by-product HF,resulting in improved interfacial stability of LNCM811.Lithium plating/stripping reaction of Li/Li symmetric cell confirms that the enhanced cyclic stability is ascribed to the improved interfacial stability of LNCM811 instead of lithium electrode.Morphology and composition characterization results reveal that LiBF4 participates in the CEI film-forming reaction,resulting in suppressed oxidation of electrolyte and interfacial structural destruction of LNCM811.展开更多
In order to obtain high power density,energy density and safe energy storage lithium ion batteries(LIB)to meet growing demand for electronic products,oxide cathodes have been widely explored in all-solidstate lithium ...In order to obtain high power density,energy density and safe energy storage lithium ion batteries(LIB)to meet growing demand for electronic products,oxide cathodes have been widely explored in all-solidstate lithium batteries(ASSLB)using sulfide solid electrolyte.However,the electrochemical performances are still not satisfactory,due to the high interfacial resistance caused by severe interfacial instability between sulfide solid electrolyte and oxide cathode,especially Ni-rich oxide cathodes,in charge-discharge process.Ni-rich LiNi0.8Co0.1Mn0.1O2(NCM811)material at present is one of the most key cathode candidates to achieve the high energy density up to 300 Wh kg^-1 in liquid LIB,but rarely investigated in ASSLB using sulfide electrolyte.To design the stable interface between NCM811 and sulfide electrolyte should be extremely necessary.In this work,in view of our previous work,LiNbO3 coating with about 1 wt% content is adopted to improve the interfacial stability and the electrochemical performances of NCM811 cathode in ASSLB using Li10GeP2S12 solid electrolyte.Consequently,LiNbO3-coated NCM811 cathode displays the higher discharge capacity and rate performance than the reported oxide electrodes in ASSLB using sulfide solid electrolyte to our knowledge.展开更多
采用共沉淀高温固相反应法合成锂离子电池正极材料LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2(811),通过掺入Li、Mg和Al元素,并采用SEM、XRD、电化学测试,研究掺杂对材料晶体结构和电化学性能影响规律.实验结果表明:共沉淀过程中三价金属离子(Mn^(...采用共沉淀高温固相反应法合成锂离子电池正极材料LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2(811),通过掺入Li、Mg和Al元素,并采用SEM、XRD、电化学测试,研究掺杂对材料晶体结构和电化学性能影响规律.实验结果表明:共沉淀过程中三价金属离子(Mn^(3+)、Al^(3+))出现会促使少量α-Ni(OH)2形成,而Li^+、Mg^(2+)和Al^(3+)均溶入晶格无杂相析出.高温融锂反应中,三种掺杂元素显著削弱Ni^(2+)出现数量,抑制Ni^(2+)混排进入Li^+格位,大幅提升811基体可逆容量;Mg^(2+)、Al^(3+)掺杂进一步增强基体晶格稳定性,改善其循环性能;Li^+-Al^(3+)共掺杂使之达到最佳:首次充电效率ICE超过90%,0.2C倍率下50次循环容量达195.8 m Ah/g、容量保持率为96.2%.展开更多
Lithium-ion batteries(LIBs)featuring a Ni-rich cathode exhibit increased specific capacity,but the establishment of a stable interphase through the implementation of a functional electrolyte strategy remains challengi...Lithium-ion batteries(LIBs)featuring a Ni-rich cathode exhibit increased specific capacity,but the establishment of a stable interphase through the implementation of a functional electrolyte strategy remains challenging.Especially when the battery is operated under high temperature,the trace water present in the electrolyte will accelerate the hydrolysis of the electrolyte and the resulting HF will further erode the interphase.In order to enhance the long-term cycling performance of graphite/LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)LIBs,herein,Tolylene-2,4-diisocyanate(TDI)additive containing lone-pair electrons is employed to formulate a novel bifunctional electrolyte aimed at eliminating H_(2)O/HF generated at elevated temperature.After 1000 cycles at 25℃,the battery incorporating the TDI-containing electrolyte exhibits an impressive capacity retention of 94%at 1 C.In contrast,the battery utilizing the blank electrolyte has a lower capacity retention of only 78%.Furthermore,after undergoing 550 cycles at 1 C under45℃,the inclusion of TDI results in a notable enhancement of capacity,increasing it from 68%to 80%.This indicates TDI has a favorable influence on the cycling performance of LIBs,especially at elevated temperatures.The analysis of the film formation mechanism suggests that the lone pair of electrons of the isocyanate group in TDI play a crucial role in inhibiting the generation of H_(2)O and HF,which leads to the formation of a thin and dense interphase.The existence of this interphase is thought to substantially enhance the cycling performance of the LIBs.This work not only improves the performance of graphite/NCM811 batteries at room temperature and high temperature by eliminating H_(2)O/HF but also presents a novel strategy for advancing functional electrolyte development.展开更多
基金supported by the National Natural Science Foundation of China(21573080)the Guangdong Program for Support of Top-notch Young Professionals(2015TQ01N870)+1 种基金Distinguished Young Scholar(2017B030306013)the Science and Technology Planning Project of Guangdong Province(Grant no.2017B090901020)
文摘Owing to the high specific capacity and high voltage,Ni-rich(LiNi0.8Co0.1Mn0.1O2,LNCM811)cathode has been considered as one of the most promising candidate cathode materials for next generation lithium ion batteries,whereas severe capacity fading greatly hinders its practical application.Notably,the compatibility of Ni-rich materials with LiBF4-containing electrolyte has not yet been realized.Herein,1 M LiPF6-based electrolyte with introducing 2 M LiBF4 is proposed to dramatically improve the cyclic stability of high voltage LNCM811/Li half-cell.Addition of high concentrated LiBF4 improves the moisture stability of electrolyte,which hinders the generation of harmful by-product HF,resulting in improved interfacial stability of LNCM811.Lithium plating/stripping reaction of Li/Li symmetric cell confirms that the enhanced cyclic stability is ascribed to the improved interfacial stability of LNCM811 instead of lithium electrode.Morphology and composition characterization results reveal that LiBF4 participates in the CEI film-forming reaction,resulting in suppressed oxidation of electrolyte and interfacial structural destruction of LNCM811.
基金financially supported partly by the National Key Research and Development Program of China (2018YFB0104302)NSFC (21503148)Major Programs of the Innovation Driven Plan of Guilin (No. 20160203)
文摘In order to obtain high power density,energy density and safe energy storage lithium ion batteries(LIB)to meet growing demand for electronic products,oxide cathodes have been widely explored in all-solidstate lithium batteries(ASSLB)using sulfide solid electrolyte.However,the electrochemical performances are still not satisfactory,due to the high interfacial resistance caused by severe interfacial instability between sulfide solid electrolyte and oxide cathode,especially Ni-rich oxide cathodes,in charge-discharge process.Ni-rich LiNi0.8Co0.1Mn0.1O2(NCM811)material at present is one of the most key cathode candidates to achieve the high energy density up to 300 Wh kg^-1 in liquid LIB,but rarely investigated in ASSLB using sulfide electrolyte.To design the stable interface between NCM811 and sulfide electrolyte should be extremely necessary.In this work,in view of our previous work,LiNbO3 coating with about 1 wt% content is adopted to improve the interfacial stability and the electrochemical performances of NCM811 cathode in ASSLB using Li10GeP2S12 solid electrolyte.Consequently,LiNbO3-coated NCM811 cathode displays the higher discharge capacity and rate performance than the reported oxide electrodes in ASSLB using sulfide solid electrolyte to our knowledge.
文摘采用共沉淀高温固相反应法合成锂离子电池正极材料LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2(811),通过掺入Li、Mg和Al元素,并采用SEM、XRD、电化学测试,研究掺杂对材料晶体结构和电化学性能影响规律.实验结果表明:共沉淀过程中三价金属离子(Mn^(3+)、Al^(3+))出现会促使少量α-Ni(OH)2形成,而Li^+、Mg^(2+)和Al^(3+)均溶入晶格无杂相析出.高温融锂反应中,三种掺杂元素显著削弱Ni^(2+)出现数量,抑制Ni^(2+)混排进入Li^+格位,大幅提升811基体可逆容量;Mg^(2+)、Al^(3+)掺杂进一步增强基体晶格稳定性,改善其循环性能;Li^+-Al^(3+)共掺杂使之达到最佳:首次充电效率ICE超过90%,0.2C倍率下50次循环容量达195.8 m Ah/g、容量保持率为96.2%.
基金financially supported by the Scientific and Technological Plan Projects of Guangzhou City(202103040001),P.R.Chinathe Project of Science and Technology Department of Henan Province(222102240074)the Key Research Programs of Higher Education Institutions of Henan Province(24B150009)。
文摘Lithium-ion batteries(LIBs)featuring a Ni-rich cathode exhibit increased specific capacity,but the establishment of a stable interphase through the implementation of a functional electrolyte strategy remains challenging.Especially when the battery is operated under high temperature,the trace water present in the electrolyte will accelerate the hydrolysis of the electrolyte and the resulting HF will further erode the interphase.In order to enhance the long-term cycling performance of graphite/LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)LIBs,herein,Tolylene-2,4-diisocyanate(TDI)additive containing lone-pair electrons is employed to formulate a novel bifunctional electrolyte aimed at eliminating H_(2)O/HF generated at elevated temperature.After 1000 cycles at 25℃,the battery incorporating the TDI-containing electrolyte exhibits an impressive capacity retention of 94%at 1 C.In contrast,the battery utilizing the blank electrolyte has a lower capacity retention of only 78%.Furthermore,after undergoing 550 cycles at 1 C under45℃,the inclusion of TDI results in a notable enhancement of capacity,increasing it from 68%to 80%.This indicates TDI has a favorable influence on the cycling performance of LIBs,especially at elevated temperatures.The analysis of the film formation mechanism suggests that the lone pair of electrons of the isocyanate group in TDI play a crucial role in inhibiting the generation of H_(2)O and HF,which leads to the formation of a thin and dense interphase.The existence of this interphase is thought to substantially enhance the cycling performance of the LIBs.This work not only improves the performance of graphite/NCM811 batteries at room temperature and high temperature by eliminating H_(2)O/HF but also presents a novel strategy for advancing functional electrolyte development.
