Upcycling of spent LiCoO<sub>2</sub> cathodes via nickel‐ and manganese‐doping

Zhang, Nianji; Deng, Wenjing; Xu, Zhengming; Wang, Xiaolei

doi:10.1002/cey2.231

Cited by 48 publications

(31 citation statements)

References 43 publications

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“…Furthermore, cathode surface modification or doping for enhanced cycling performance can also be embedded into the upcycling category. [28] For instance, spent LCO can be relithiated and doped with Mg to Mg-recovery LCO so that their cycling stability at high voltage can be improved and even exceed that of new cathode materials. [29] Excessive Dependency on Manual Labor with Safety Concerns: One of the major challenges with direct recycling methods is that the highly repetitive procedures, especially mechanical disassembly, which relies heavily on manual labor.…”

Section: Challenges and Opportunities In Direct Lib Recyclingmentioning

confidence: 99%

Section: Global Challenges and Opportunities Ahead In The Lib Recyclingmentioning

confidence: 99%

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Current Challenges in Efficient Lithium‐Ion Batteries’ Recycling: A Perspective

Gupta

et al. 2022

Global Challenges

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power density, [1] especially for electronic devices, electric vehicles (EVs), and grid storage systems. As a result, the global market of LIBs is expected to follow a rapid upward trend, projected to reach US$56 billion by 2024. [1c] The primary growth will be triggered by the massive EV production, which is expected to reach $253 million by 2030. [1c] The rising LIB utilization has increased the demand for critical raw materials such as lithium (Li), nickel (Ni), and cobalt (Co). However, most of these essential materials are regulated by specific countries. More than half of cobalt ore is mined in the Democratic Republic of Congo and refined in China, and about 80% of lithium is controlled by Australia and Chile. [2] This uneven distribution of raw materials and production areas has raised concerns about the global supply chain. As a result, lithium and cobalt prices are rising and fluctuating, and in the meantime, the geopolitics could lead to a monopoly of raw material supply by local governments. [3] Therefore, from a sustainability perspective, it is essential to establish a secondary supply of critical materials recovered from spent LIBs (from EVs, stationary storage batteries, and home appliances) and from the manufacturing wastes (trimming, end products, off-spec products, etc.) to mitigate the severity of this potential shortage.On the other hand, since LIBs can usually be used for 10 years on average, [3,4] the amount of spent LIBs is expected to reach more than 5 million tons by 2030. [5] The main components of LIBs are cathode materials (LiNi x Co y Mn z O 2 (0 < x, y, z <1, x + y + z = 1, known as NCM), LiCoO 2 (LCO), LiFePO 4 (LFP), etc.), anode materials (graphite), current collectors (aluminum (Al) and copper (Cu)), electrolyte salts such as lithium hexafluorophosphate (LiPF 6 ), organic solvents (ethylene carbonate (EC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), etc.). All these different components contain hazardous materials and result in metal, dust, organic, and fluorine contaminations. [6] Landfilling or incineration can harm ecosystems. For example, once the electrode materials enter the environment, metal ions from the cathode, carbon dust from the anode, strong alkali, and heavy metal ions from the electrolyte may cause severe environmental pollutions, hazards, etc., including raising the pH value of the soil, [7] and producing the toxic gases (HF, HCl, etc.). In addition, the metals and electrolytes in batteries can harm human health. For example, the cobalt may get into the human body via underground water and other channels, causing Li-ion battery (LIB) recycling has become an urgent need with rapid prospering of the electric vehicle (EV) industry, which has caused a shortage of material resources and led to an increasing amount of retired batteries. However, the global LIB recycling effort is hampered by various factors such as insufficient logistics, regulation, and technology readiness. Here, the challenges associated with LIB recycling...

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Section: Challenges and Opportunities In Direct Lib Recyclingmentioning

confidence: 99%

Section: Global Challenges and Opportunities Ahead In The Lib Recyclingmentioning

confidence: 99%

Current Challenges in Efficient Lithium‐Ion Batteries’ Recycling: A Perspective

Gupta

et al. 2022

Global Challenges

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“…If these spent batteries are not handled properly, it will not only cause an enormous waste of resources but also have a significant impact on the environment. [ 5 ] Since the cathode materials have the highest cost in battery components (its cost accounts for about 40% of the total cost of LIBs), it makes more sense to recycle the cathode than the other parts. The traditional methods of large‐scale treatment of spent cathodes in LIBs are hydrometallurgy and pyrometallurgy, but both methods are not suitable for large‐scale regeneration of batteries.…”

Section: Introductionmentioning

confidence: 99%

Long‐Life Regenerated LiFePO₄ from Spent Cathode by Elevating the d‐Band Center of Fe

et al. 2022

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A large amount of spent LiFePO4 (LFP) has been produced in recent years because it is one of the most widely used cathode materials for electric vehicles. The traditional hydrometallurgical and pyrometallurgical recycling methods are doubted because of the economic and environmental benefits; the direct regeneration method is considered a promising way to recycle spent LFP. However, the performance of regenerated LFP by direct recycling is not ideal due to the migration of Fe ions during cycling and irreversible phase transition caused by sluggish Li+ diffusion. The key to addressing the challenge is to immobilize Fe atoms in the lattice and improve the Li+ migration capability during cycling. In this work, spent LFP is regenerated by using environmentally friendly ethanol, and its cycling stability is promoted by elevating the d‐band center of Fe atoms via construction of a heterogeneous interface between LFP and nitrogen‐doped carbon. The FeO bonding is strengthened and the migration of Fe ions during cycling is suppressed due to the elevated d‐band center. The Li+ diffusion kinetics in the regenerated LFP are improved, leading to an excellent reversibility of the phase transition. Therefore, the regenerated LFP exhibits an ultrastable cycling performance at a high rate of 10 C with ≈80% capacity retention after 1000 cycles.

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“…63 Nickel and manganese acetates (Mn : Ni = 3 : 1) in DI water, 3.0 M LiOH and 3.0 M KOH, hydrothermally treated at 190 1C for 16 h, 900 1C for 4 h in air Ni-Mn co-doped LCO 3.0-4.5 V vs.Li + /Li, 1C = 140 mA h g À1 160.23 mA h g À1 at 1C, capacity retention rate of 91.2% after 100 cycles at 1C NCM523 59 The spent cathode material, LiOH, NiO, MnO 2 and NH 4 H 2 PO 4 were dissolved in deionized (DI) water, 450 1C for 5 h, and then heated to 850 1C and kept for 15 h under O 2 atmosphere 3 , NaF, and Li 1Àx FePO 4 were ball-milled under an Ar atmosphere at a speed of 300 rpm for 10 h, pre-sintered at 350 1C under Ar atmosphere for 4 h, ball-milled again for 20 h at a speed of 600 rpm, and then heated for 10 h at 700 1C in an Ar atmosphere. Carbon-coated Na 2 FePO 4 F 2-4.2 V vs. Na + /Na, 1C = 124 mA h g À1 116.3 mA h g À1 at 0.1C LCO 65 Li 2 CO 3 , n(Li) : n(Co) = 1 : 1, 800 1C, Al 2 O 3 and the regenerated LCO and in a mole ratio of n(Al) : n(Co) = 0.01 : 1, 800 1C for 5 h in air Al 2 O 3 -coated LCO 3-4.2 V vs. Li + /Li, 20 mA g À1 136.8 mA h g À1 , 90.1% capacity retention after 1000 cycles at 20 mA g À1 4 1.6-4.2 V vs. Na + /Na 163.2 mA h g À1 over 50 cycles at 100 mA g À1 , 176.3 mA h g À1 at 20 mA g À1 LMO 68 Mn(CH 3 COO) 2 Á4H 2 O and LiOHÁH 2 O, 700 1C for 15 h in air Li/Mn disordered LMO 1-4.7 V vs. Li + /Li, 1C = 148 mA h g À1 207.8 mA h g À1 after the activation cycles at 0.1C (1C = 148 mA h g À1 ), 196.1 mA h g À1 after 60 cycles at 1C, corresponding to a capacity retention of 94.37%.…”

mentioning

confidence: 99%