Balancing the Components of Biomass and the Reactivity of Pyrolysis Gas: Biomass-Assisted Recycling of Spent LiCoO2 Batteries.

Waste biomass is one of the promising feedstocks to supply syngas that can be used as fuels, chemicals, reductants, etc. However, the relationship between the component of biomass and the constituent of pyrolysis gas remains unclear. Here, we study the pyrolysis behaviors of various biomasses and reveal the relationship between the biomass components and gas compositions. Further, different pyrolysis gases are applied for the reduction of spent lithium cobalt oxide (LiCoO2) below 500 °C. The pyrolysis gas with a higher concentration of CO has a higher reductivity to convert LiCoO2 to CoO and Li2CO3 with a conversion rate close to 100% in 1 h at 500 °C. The biomass rich in cellulose and with a lower content of lignin tends to produce pyrolysis gas with a high concentration of CO, which comes from the deliberate breakdown of carboxyl, carbonyl, ether, and ester linkages. Moreover, LiCoO2 exerts catalytic functions over the deoxygenation and enhancement of oxygenates and single-ring aromatics. Overall, this paper offers a tailored approach to regulating biomass pyrolysis gases, enabling highly efficient battery recycling and syngas production.

Recovery of valuable metals from spent lithium-ion batteries through biomass pyrolysis gas-induced reduction.

The development of spent lithium-ion batteries (LIBs) recycling technologies can effectively alleviate environmental pressure and conserve metal resources. We propose a win-win strategy for pyrolysis gas reduction by lignocellulosic biomass, ensuring gas-induced reduction by spatial isolation of biomass and lithium transition metal oxides (LiTMOX (TM = Ni, Co, Mn)), and avoiding the separation of solid carbon and TMOX (TM = Ni, Co, Mn). In the spent LiCoO2 batteries, the lithium recovery efficiency reaches 99.99% and purity reaches 98.3% at 500 °C. In addition, biomass pyrolysis gas reduction is also applicable to treat spent LiMn2O4 and LiNi0.6Co0.2Mn0.2O2 batteries. Thermodynamic analysis verifies that CO dominates the gas reduction recovery process. DFT calculation indicates that the gas reduction induces the collapse of the oxygen framework of LiTMOX (TM = Ni, Co, Mn). Everbatt-based economic and environmental analysis illustrates that this is an environment-friendly and energy-saving method.

An economic, self-supporting, robust and durable LiFe5O8 anode for sulfamethoxazole degradation.

Electrochemically activating peroxydisulfate (PDS) to degrade organic pollutants is one of the most attractive advanced oxidation processes (AOPs) to address environmental issues, but the high cost, poor stability, and low degradation efficiency of the anode materials hinder their application. Herein, an economic, self-supporting, robust, and durable LiFe5O8 on Fe substrate (Fe@LFO) anode is reported to degrade sulfamethoxazole (SMX). When PDS is electrochemically activated by the Fe@LFO anode, the degradation rate of SMX is significantly improved. It is found that hydroxyl radicals (•OH), superoxide radical (O2•-), singlet oxygen (1O2), Fe(Ⅳ), activated PDS (PDS*), and direct electron transfer (DET) reactions synergistically contribute to the degradation of SMX, which can realize the degradation of SMX in four possible routes: cleavage of the isoxazole ring, hydroxylation of the benzene ring, oxidation of the aniline group, and cleavage of the S-N bond, as evidenced by a series of tests of radicals quenching, electron paramagnetic resonance (EPR), linear sweep voltammetry (LSV) and liquid chromatograph mass spectrometer (LC-MS). Furthermore, Fe@LFO has good structural stability, excellent cyclability and low degradation cost, demonstrating its great potential for practical applications. This work contributes to a stable and effective anode material in the field of AOPs.

NaOH-assisted low-temperature roasting to recover spent LiFePO4 batteries.

Decreasing the operating temperature of pyrometallurgical methods for recycling spent lithium-ion batteries (LIBs) is key to reducing energy consumption and cost. Herein, a NaOH-assisted low-temperature roasting approach is proposed to recover spent LiFePO4. During roasting, NaOH acts as an oxidizing agent to oxidize Fe (II) to Fe3O4 at 150°C, thus collapsing its stable olivine structure while PO43- capturing Li+ and Na+ to form Li2NaPO4 and LiNa5(PO4)2. The obtained Fe3O4 is then separated, and the resulting Li salt can be further recovered as Li3PO4 with a Li recovery efficiency of 96.7 % and a purity of 99.9 %. Economic and environmental analysis based on the EverBatt model shows that this low-temperature strategy reduces energy consumption and greenhouse gas (GHG) emissions, thus increasing the potential profit. Overall, NaOH-assisted low-temperature roasting is a prospective strategy that broadens the application of NaOH as an oxidant and opens up a new avenue for decreasing the temperature of recovering spent LiFePO4 by pyrometallurgy.