It is challenging to efficiently and economically recycle many lithium-ion batteries(LIBs)because of the low valuation of commodity metals and materials,such as LiFePO_(4).There are millions of tons of spent LIBs wher...It is challenging to efficiently and economically recycle many lithium-ion batteries(LIBs)because of the low valuation of commodity metals and materials,such as LiFePO_(4).There are millions of tons of spent LIBs where the barrier to recycling is economical,and to make recycling more feasible,it is required that the value of the processed recycled material exceeds the value of raw commodity materials.The presented research illustrates improved profitability and economics for recycling spent LIBs by utilizing the surplus energy in lithiated graphite to drive the preparation of organolithiums to add value to the recycled lithium materials.This study methodology demonstrates that the surplus energy of lithiated graphite obtained from spent LIBs can be utilized to prepare high-value organolithiums,thereby significantly improving the economic profitability of LIB recycling.Organolithiums(R-O-Li and R-Li)were prepared using alkyl alcohol(R-OH)and alkyl bromide(R-Br)as substrates,where R includes varying hindered alkyl hydrocarbons.The organolithiums extracted from per kilogram of recycled LIBs can increase the economic value between$29.5 and$226.5 kg^(−1) cell.The value of the organolithiums is at least 5.4 times the total theoretical value of spent materials,improving the profitability of recycling LIBs over traditional pyrometallurgical($0.86 kg^(−1) cell),hydrometallurgical($1.00 kg^(−1) cell),and physical direct recycling methods($5.40 kg^(−1) cell).展开更多
Owing to their high theoretical specific capacity and low cost, lithium- and manganese-rich layered oxide (LMR) cathode materials are receiving increasing attention for application in lithium-ion batteries. However, p...Owing to their high theoretical specific capacity and low cost, lithium- and manganese-rich layered oxide (LMR) cathode materials are receiving increasing attention for application in lithium-ion batteries. However, poor lithium ion and electron transport kinetics plus side effects of anion and cation redox reactions hamper power performance and stability of the LMRs. In this study, LMR Li_(1.2)Mn_(0.6)Ni_(0.2)O_(2) was modified by phosphorus (P)-doping to increase Li+ conductivity in the bulk material. This was achieved by increasing the interlayer spacing of the lithium layer, electron transport and structural stability, resulting in improvement of the rate and safety performance. P^(5+) doping increased the distance between the (003) crystal planes from ~0.474 nm to 0.488 nm and enhanced the structural stability by forming strong covalent bonds with oxygen atoms, resulting in an improved rate performance (capacity retention from 38% to 50% at 0.05 C to 5 C) and thermal stability (50% heat release compared with pristine material). First-principles calculations showed the P-doping makes the transfer of excited electrons from the valence band to conduction band easier and P can form a strong covalent bond helping to stabilize material structure. Furthermore, the solid-state electrolyte modified P5+ doped LMR showed an improved cycle performance for up to 200 cycles with capacity retention of 90.5% and enhanced initial coulombic efficiency from 68.5% (pristine) or 81.7% (P-doped LMR) to 88.7%.展开更多
基金National Natural Science Foundation of China,Grant/Award Number:51232005Key-Area Research and Development Program of Guangdong Province,Grant/Award Number:2020B090919003+1 种基金Joint Fund of the National Natural Science Foundation of China,Grant/Award Number:U1401243Shenzhen Technical Plan Project,Grant/Award Number:CYJ20170412170911187。
文摘It is challenging to efficiently and economically recycle many lithium-ion batteries(LIBs)because of the low valuation of commodity metals and materials,such as LiFePO_(4).There are millions of tons of spent LIBs where the barrier to recycling is economical,and to make recycling more feasible,it is required that the value of the processed recycled material exceeds the value of raw commodity materials.The presented research illustrates improved profitability and economics for recycling spent LIBs by utilizing the surplus energy in lithiated graphite to drive the preparation of organolithiums to add value to the recycled lithium materials.This study methodology demonstrates that the surplus energy of lithiated graphite obtained from spent LIBs can be utilized to prepare high-value organolithiums,thereby significantly improving the economic profitability of LIB recycling.Organolithiums(R-O-Li and R-Li)were prepared using alkyl alcohol(R-OH)and alkyl bromide(R-Br)as substrates,where R includes varying hindered alkyl hydrocarbons.The organolithiums extracted from per kilogram of recycled LIBs can increase the economic value between$29.5 and$226.5 kg^(−1) cell.The value of the organolithiums is at least 5.4 times the total theoretical value of spent materials,improving the profitability of recycling LIBs over traditional pyrometallurgical($0.86 kg^(−1) cell),hydrometallurgical($1.00 kg^(−1) cell),and physical direct recycling methods($5.40 kg^(−1) cell).
基金This work was supported by the National Natural Science Foundation of China(U1564205)the Project of Construction of Innovative Teams and Teacher Career Development for Universities and Colleges under the Beijing Municipality(IDHT20180508).Naser Tavajohi acknowledges financial support from the Kempe Foundation.
文摘Owing to their high theoretical specific capacity and low cost, lithium- and manganese-rich layered oxide (LMR) cathode materials are receiving increasing attention for application in lithium-ion batteries. However, poor lithium ion and electron transport kinetics plus side effects of anion and cation redox reactions hamper power performance and stability of the LMRs. In this study, LMR Li_(1.2)Mn_(0.6)Ni_(0.2)O_(2) was modified by phosphorus (P)-doping to increase Li+ conductivity in the bulk material. This was achieved by increasing the interlayer spacing of the lithium layer, electron transport and structural stability, resulting in improvement of the rate and safety performance. P^(5+) doping increased the distance between the (003) crystal planes from ~0.474 nm to 0.488 nm and enhanced the structural stability by forming strong covalent bonds with oxygen atoms, resulting in an improved rate performance (capacity retention from 38% to 50% at 0.05 C to 5 C) and thermal stability (50% heat release compared with pristine material). First-principles calculations showed the P-doping makes the transfer of excited electrons from the valence band to conduction band easier and P can form a strong covalent bond helping to stabilize material structure. Furthermore, the solid-state electrolyte modified P5+ doped LMR showed an improved cycle performance for up to 200 cycles with capacity retention of 90.5% and enhanced initial coulombic efficiency from 68.5% (pristine) or 81.7% (P-doped LMR) to 88.7%.