Ni-rich layered oxide with Ni molar content larger than 90%was regarded as an extremely promising candidate for cathode material applied in lithium-ion batteries owing to the significant discharging capacity and low c...Ni-rich layered oxide with Ni molar content larger than 90%was regarded as an extremely promising candidate for cathode material applied in lithium-ion batteries owing to the significant discharging capacity and low cost.Nevertheless,rigorous cycling attenuation resulted from the crystal structure collapse and unstable particles interface deeply restrained the commercial application.In the work,LiNi_(0.90)Co_(0.05)Mn_(0.05)O_(2) was modified by Ta5+doping and Li_(2)MnO_(3) covering,which was aimed to enhance the structure stability,defend the electrolyte attacking and promote Li+migration during cycling.The material characterization demonstrated the cathodes after Ta5+doping delivered the larger cell lattice parameters and higher cation ordering,which was helpful to improve the rate property and discharge capacity at low temperature.The Li_(2)MnO_(3) layer was tightly adhered on the outside of LiNi_(0.90)Co_(0.05)Mn_(0.05)O_(2),which could effectively relieve the electrolyte attacking and sustain the particle morphology integrity.As a result,2 wt%Li_(2)MnO_(3) coated Li(Ni_(0.90)Co_(0.05)Mn_(0.05))_(0.98)Ta_(0.02)O_(2) exhibited the outstanding discharge capacity of 150.2 mAh g^(−1) at 10.0 large current density and 140.6 mAh g^(−1) at−30℃ as well as the remarkable capacity retention of 93.1%after 300 cycles.Meanwhile,the pouch full batteries obtained by 2 wt%Li_(2)MnO_(3) coated Li(Ni_(0.90)Co_(0.05)Mn_(0.05))_(0.98)Ta_(0.02)O_(2) also showed the more stable storage capability,cyclic property in comparison with bare LiNi_(0.90)Co_(0.05)Mn_(0.05)O_(2).展开更多
氟是废旧锂电池回收难以回避的典型杂质元素,其迁移转化行为复杂,制约了高品质正极材料的可控再生制备.本研究通过揭示废旧锂电池在热解、浸出及高镍LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)材料再生过程中氟的迁移转化规律,为氟的定向调控...氟是废旧锂电池回收难以回避的典型杂质元素,其迁移转化行为复杂,制约了高品质正极材料的可控再生制备.本研究通过揭示废旧锂电池在热解、浸出及高镍LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)材料再生过程中氟的迁移转化规律,为氟的定向调控及材料的可控再生制备奠定理论基础实验结果表明:热解过程中部分氟(45.71%)以气态热解产物的形式释放到大气中,而另一部分氟(52.34%)则向废三元材料的晶格内发生迁移,并随着湿法浸出溶解到镍钴锰的浸出液中.浸出液中少量的氟会在共沉淀制备前驱体过程中迁移到Ni_(0.9)Co_(0.05)Mn_(0.05)(OH)2前驱体材料,并随着配锂烧结掺杂到再生LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)材料表面.进一步通过调控氟含量发现,当浸出液中氟浓度控制在0.30 g L^(-1)时,引入到再生LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)材料中的氟不仅不会引起不利相变,而且能够稳定材料结构,从而有效提升再生高镍材料的循环稳定性(1 C电流密度下循环100圈的容量保持率高达95.7%).因此,本研究不仅揭示了废旧锂电池回收过程中氟的迁移转化行为,而且可控再生制备了高性能氟掺杂高镍LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)正极材料,为废旧锂离子电池回收过程中氟的调控提供了理论依据.展开更多
基金supported by the Natural Science Research Projects of Colleges and Universities in Jiangsu Province (grant No.24KJA430012)the Open Project Program of Key Laboratories of Fine Chemicals and Surfactants in Sichuan Provincial Universities (grant No.SCFY2203).
文摘Ni-rich layered oxide with Ni molar content larger than 90%was regarded as an extremely promising candidate for cathode material applied in lithium-ion batteries owing to the significant discharging capacity and low cost.Nevertheless,rigorous cycling attenuation resulted from the crystal structure collapse and unstable particles interface deeply restrained the commercial application.In the work,LiNi_(0.90)Co_(0.05)Mn_(0.05)O_(2) was modified by Ta5+doping and Li_(2)MnO_(3) covering,which was aimed to enhance the structure stability,defend the electrolyte attacking and promote Li+migration during cycling.The material characterization demonstrated the cathodes after Ta5+doping delivered the larger cell lattice parameters and higher cation ordering,which was helpful to improve the rate property and discharge capacity at low temperature.The Li_(2)MnO_(3) layer was tightly adhered on the outside of LiNi_(0.90)Co_(0.05)Mn_(0.05)O_(2),which could effectively relieve the electrolyte attacking and sustain the particle morphology integrity.As a result,2 wt%Li_(2)MnO_(3) coated Li(Ni_(0.90)Co_(0.05)Mn_(0.05))_(0.98)Ta_(0.02)O_(2) exhibited the outstanding discharge capacity of 150.2 mAh g^(−1) at 10.0 large current density and 140.6 mAh g^(−1) at−30℃ as well as the remarkable capacity retention of 93.1%after 300 cycles.Meanwhile,the pouch full batteries obtained by 2 wt%Li_(2)MnO_(3) coated Li(Ni_(0.90)Co_(0.05)Mn_(0.05))_(0.98)Ta_(0.02)O_(2) also showed the more stable storage capability,cyclic property in comparison with bare LiNi_(0.90)Co_(0.05)Mn_(0.05)O_(2).
基金supported by the National Natural Science Foundation of China (51904340)the Natural Science Foundation of Hunan (2021JJ2020066)+1 种基金the National Key Research and Development Program (2019YFC1907801, 2019YFC1907803 and 2019YFC1907804)the Central South University Innovation-Driven Research Programme (2023CXQD009)。
文摘氟是废旧锂电池回收难以回避的典型杂质元素,其迁移转化行为复杂,制约了高品质正极材料的可控再生制备.本研究通过揭示废旧锂电池在热解、浸出及高镍LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)材料再生过程中氟的迁移转化规律,为氟的定向调控及材料的可控再生制备奠定理论基础实验结果表明:热解过程中部分氟(45.71%)以气态热解产物的形式释放到大气中,而另一部分氟(52.34%)则向废三元材料的晶格内发生迁移,并随着湿法浸出溶解到镍钴锰的浸出液中.浸出液中少量的氟会在共沉淀制备前驱体过程中迁移到Ni_(0.9)Co_(0.05)Mn_(0.05)(OH)2前驱体材料,并随着配锂烧结掺杂到再生LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)材料表面.进一步通过调控氟含量发现,当浸出液中氟浓度控制在0.30 g L^(-1)时,引入到再生LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)材料中的氟不仅不会引起不利相变,而且能够稳定材料结构,从而有效提升再生高镍材料的循环稳定性(1 C电流密度下循环100圈的容量保持率高达95.7%).因此,本研究不仅揭示了废旧锂电池回收过程中氟的迁移转化行为,而且可控再生制备了高性能氟掺杂高镍LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)正极材料,为废旧锂离子电池回收过程中氟的调控提供了理论依据.
