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The utilization of biomass-assisted pyrolysis in the recycling of spent lithium-ion batteries has emerged as a promising and reliable process. This article furnishes theoretical underpinnings and analytical insights into this method, showcasing sawdust pyrolysis reduction as an efficient means to recycle spent LiMn2O4 and LiNi0.6Co0.2Mn0.2O2 batteries. Through advanced thermogravimetry-gas chromatography-mass spectrometry analysis complemented by traditional thermodynamic demonstration, the synergistic effects of biomass pyrolysis reduction are elucidated, with minor autodecomposition and major carbothermal and gasthermal reduction pathways identified. The controlled manipulation of transition metals has demonstrated the capability to modulate surface pyrolysis gas catalytic reactions and facilitate the preparation of composite materials with diverse morphologies. Optimization of process conditions has culminated in recovery efficiency exceeding 99.0 % for LiMn2O4 and 99.5 % for LiNi0.6Co0.2Mn0.2O2. Economic and environmental analyses underscore the advantages of biomass reduction and recycling for these two types of spent LIBs: low energy consumption, environmental compatibility, and high economic viability.
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The disposal and management of waste lithium-ion batteries (LIBs) and low-density polyethylene (LDPE) plastics pose significant environmental challenges. Here we show a synergistic pyrolysis approach that employs spent lithium transition metal oxides and waste LDPE plastics in one sealed reactor to achieve the separation of Li and transition metal. Additionally, we demonstrate the preparation of nanoscale NiCo alloy@carbon nanotubes (CNTs) through co-pyrolysis of LiNi0.6Co0.2Mn0.2O2 and LDPE. The NiCo alloy@CNTs exhibits excellent catalytic activity (Eonset = ~0.85 V) and the selectivity (~90%) for H2O2 production through the electrochemical reduction of oxygen. This can be attributed to the NiCo nanoalloy core and the presence of CNTs with abundant oxygen-containing functional groups (e.g., -COOH and C-O-C), as confirmed by density function theory calculations. Overall, this work presents a straightforward and green approach for valorizing and upcycling various waste LIBs and LDPE plastics.
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Reactive metals hydrolysis offers significant advantages for hydrogen storage and production. However, the regeneration of common reactive metals (e.g., Mg, Al, etc.) is energy-intensive and produces unwanted byproducts such as CO2 and Cl2. Herein, we employ Zn as a reactive mediator that can be easily regenerated by electrolysis of ZnO in an alkaline solution with a Faradaic efficiency of >99.9 %. H2 is produced in the same electrolyte by constructing a Zn-H2O hydrolysis battery consisting of a Zn anode and a Raney-Ni cathode to unlock the Zn-H2O reaction. The entire two-step water splitting reaction with a net energy efficiency of 70.4 % at 80 °C and 50â mA cm-2. Additionally, the Zn-H2O system can be charged using renewable energy to produce H2 on demand and runs for 600 cycles only sacrificing 3.76 % energy efficiency. DFT calculations reveal that the desorption of H* on Raney-Ni (-0.30â eV) is closer to zero compared with that on Zn (-0.87â eV), indicating a faster desorption of H* at low overpotential. Further, a 24â Ah electrolyzer is demonstrated to produce H2 with a net energy efficiency of 65.5 %, which holds promise for its real application.
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Silicon nanotubes (SNTs) have been considered as promising anode materials for lithium-ion batteries (LIBs). However, the reported strategies for preparing SNTs generally have special requirements for either expensive templates or complex catalysts. It is necessary to explore a cost-effective and efficient approach for the preparation of high-performance SNTs. In this work, a biphasic transformation strategy involving "solid-state reduction" and "dissolution-deposition" in molten salts is developed to prepare SNTs using montmorillonite as a precursor. The rod-like intermediate of silicon-aluminum-calcium is initially reduced in solid state, which then triggers the continuous dissolution and deposition of calcium silicate in the inner space of the intermediate to form a hollow structure during the subsequent reduction process. The transition from solid to liquid is crucial for improving the kinetics of deoxygenation and induces the self-assembly of SNTs during electrolysis. When the obtained SNTs is used as anode materials for LIBs, they exhibit a high capacity of 2791 mAh g-1 at 0.2 A g-1, excellent rate capability of 1427 mA h g-1 at 2 A g-1, and stable cycling performance with a capacity of 2045 mAh g-1 after 200 cycles at 0.5 A g-1. This work provides a self-assembling, controllable, and cost-effective approach for fabricating SNTs.
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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.
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Suministros de Energía Eléctrica , Pirólisis , Biomasa , Lignina/química , Reciclaje , GasesRESUMEN
The anode stability is critical for efficient and reliable seawater electrolyzers. Herein, a NiFe-based film catalyst was prepared by anodic oxidation to serve as a model electrode, which exhibited a satisfactory oxygen evolution performance in simulated alkaline seawater (1 M KOH + 0.5 M NaCl) with an overpotential of 348 mV at 100 mA cm-2 and a long-term stability of over 100 h. After that, the effects of the current density and bulk pH of the electrolyte on its stability were evaluated. It was found that the electrode stability was sensitive to electrolysis conditions, failing at 20 mA cm-2 in 0.1 M KOH + 0.5 M NaCl but over 500 mA cm-2 in 0.5 M KOH + 0.5 M NaCl. The electrode dissolved, and some precipitates immediately formed at the region very close to the electrode surface during the electrolysis. This can be ascribed to the pH difference between the electrode/electrolyte interface and the bulk electrolyte under anodic polarization. In other words, the microzone acidification accelerates the corrosion of the electrode by Cl-, thus affecting the electrode stability. The operational performances of the electrode under different electrolysis conditions were classified to further analyze the degradation behavior, which resulted in three regions corresponding to the stable oxygen evolution, violent dissolution-precipitation, and complete passivation processes, respectively. Thereby increasing the bulk pH could alleviate the microzone acidification and improve the stability of the anode at high current densities. Overall, this study provides new insights into understanding the degradation mechanism of NiFe-based catalysts and offers electrolyte engineering strategies for the application of anodes.
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Boosting the hydrogen evolution reaction (HER) activity of α-MoB2 at large current densities and in pH-universal medium is significant for efficient hydrogen production. In this work, Co2 B/MoB2 heterostructured nanoclusters are prepared by molten-salt electrolysis (MSE) and then used as a HER catalyst. The composition, structure, and morphology of Co2 B/MoB2 can be modulated by altering the stoichiometries of raw materials and synthesis temperatures. Impressively, the obtained Co2 B/MoB2 at optimized conditions exhibits a low overpotential of 297 and 304 mV at 500 mA cm-2 in 0.5 m H2 SO4 and 1 m KOH, respectively. Moreover, the Co2 B/MoB2 catalyst possesses a long-term catalytic stability of over 190 h in both acidic and alkaline medium. The excellent HER performance is due to the modified electronic structure at the Co2 B/MoB2 heterointerface where electrons are accumulated at the Mo sites to strengthen the H adsorption. Density functional theory (DFT) calculations reveal that the formation of the Co2 B/MoB2 heterointerface decreases the H adsorption and H2 O dissociation free energies, contributing to the boosted HER intrinsic catalytic activity of Co2 B/MoB2 . Overall, this work provides an experimental and theoretical paradigm for the design of efficient pH-universal boride heterostructure electrocatalysts.
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The interface interaction between deposited carbon and metallic electrode substrates in tuning the growth of CO2-derived products (e.g., amorphous carbon, graphite, carbide) is mostly unexplored for the high-temperature molten-salt electrolysis of CO2. Herein, the carbon deposition on different transition-metal cathodes was performed to reveal the role of substrate materials in the growth of cathodic products. At the initial stage of electrolysis, transition metals (e.g., Cr, Fe, Ni, and Co) that exhibit appropriate carbon-binding ability (in range of -30 to 60 kJ mol-1) allow carbon diffusing into and then dissociating from metal to form graphite, as the carbon-binding ability can be determined by the Gibbs free energy of formation of metallic carbides. The catalytic cathodes showing super strong (e.g., Ti, V, Mo, and W) or weak (e.g., Cu) carbon-binding ability produce stable carbides or amorphous carbon, respectively. However, the subsequent deposited carbon is immune to the catalysis of the substrate, forming amorphous carbon nanoparticles and nanofibers on the surface of carbides and graphite, respectively. This paper not only highlights the role of the catalytic cathodes for carbon deposition, but also offers a material selection principle for the controllable growth of CO2-derived products in molten salts.
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Improving cycling stability while maintaining a high initial Coulombic efficiency (ICE) of the antimony (Sb) anode is always a trade-off for the design of electrodes of sodium-ion batteries (SIBs). Herein, we prepare a carbon-free Sb8Bi1 anode with an ICE of 87.1% at 0.1 A g-1 by a one-step electrochemical reduction of Sb2O3 and Bi2O3 in alkaline solutions. The improved ICE of the Sb8Bi1 anode is due to the alloying of bismuth (Bi) that prevents irreversible interfacial reactions during the sodiation process. Unlike carbon buffers, the use of Bi will reduce the number of side reactions between the carbon buffer and sodium. Moreover, Bi2O3 can promote the reduction of Sb2O3 and reduce the particle size of Sb from â¼20 µm to below 300 nm. The electrolytic products can be modulated by controlling the cell voltages and electrolysis time. The electrolytic Sb8Bi1 anode delivered a capacity of 625 mAh g-1 after 200 cycles with an ICE of 87.1% at 0.1 A g-1 and even 625 mAh g-1 at 1 A g-1 over 100 cycles. Hence, alloying Bi into Sb is an effective way to make a long-lasting Sb anode while maintaining a high Coulombic efficiency.
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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.
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Aqueous Zn metal batteries are attractive as safe and low-cost energy storage systems. At present, due to the narrow window of the aqueous electrolyte and the strong reliance of the Zn2+ ion intercalated reaction on the host structure, the current intercalated cathode materials exhibit restricted energy densities. In contrast, cathode materials with conversion reactions can promise higher energy densities. Especially, the recently reported conversion-type cathode materials that function in nonalkaline electrolytes have garnered increasing attention. This is because the use of nonalkaline electrolytes can prevent the occurrence of side reactions encountered in alkaline electrolytes and thereby enhance cycling stability. However, there is a lack of comprehensive review on the reaction mechanisms, progress, challenges, and solutions to these cathode materials. In this review, four kinds of conversion-type cathode materials including MnO2 , halogen materials (Br2 and I2 ), chalcogenide materials (O2 , S, Se, and Te), and Cu-based compounds (CuI, Cu2 O, Cu2 S, CuO, CuS, and CuSe) are reviewed. First, the reaction mechanisms and battery structures of these materials are introduced. Second, the fundamental problems and their corresponding solutions are discussed in detail in each material. Finally, future directions and efforts for the development of conversion-type cathode materials for aqueous Zn batteries are proposed.
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Spent lithium-ion batteries (LIBs) and benzene-containing polymers (BCPs) are two major pollutants that cause serious environmental burdens. Herein, spent LIBs and BCPs are copyrolyzed in a sealed reactor to generate Li2CO3, metals, and/or metal oxides without emitting toxic benzene-based gases. The use of a closed reactor allows the sufficient reduction reaction between the BCP-derived polycyclic aromatic hydrocarbon (PAH) gases and lithium transition metal oxides, achieving the Li recovery efficiencies of 98.3, 99.9, and 97.5% for LiCoO2, LiMn2O4, and LiNi0.6Co0.2Mn0.2O2, respectively. More importantly, the thermal decomposition of PAHs (e.g., phenol and benzene) is further catalyzed by the in situ generated Co, Ni, and MnO2 particles, which forms metal/carbon composites and thus prevent the emissions of toxic gases. Overall, the copyrolysis in a closed system paves a green way to synergistically recycle spent LIBs and handle waste BCPs.
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Benceno , Litio , Plásticos , Compuestos de Manganeso , Óxidos , Metales , Suministros de Energía Eléctrica , Reciclaje , PolímerosRESUMEN
High-temperature molten-salt electrolyzers play a central role in metals, materials and chemicals production for their merit of favorable kinetics. However, a low-cost, long-lasting, and efficient high-temperature oxygen evolution reaction (HT-OER) electrode remains a big challenge. Here we report an iron-base electrode with an in situ formed lithium ferrite scale that provides enhanced stability and catalytic activity in both high-temperature molten carbonate and chloride salts. The finding is stemmed from a discovery of the ionic potential-stability relationship and a basicity modulation principle of oxide films in molten salt. Using the iron-base electrode, we build a kiloampere-scale molten carbonate electrolyzer to efficiently convert CO2 to carbon and oxygen. More broadly, the design principles lay the foundations for exploring cheap, Earth-abundant, and long-lasting HT-OER electrodes for electrochemical devices with molten carbonate and chloride electrolytes.
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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 (â¢OH), superoxide radical (O2â¢-), singlet oxygen (1O2), Fe(â £), 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.
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Sulfametoxazol , Contaminantes Químicos del Agua , Sulfametoxazol/química , Contaminantes Químicos del Agua/análisis , Oxidación-Reducción , Radical Hidroxilo/química , ElectrodosRESUMEN
Large anthropogenic inputs of N and P alter the nutrient cycle and exacerbate global eutrophication problems in aquatic ecosystems. This study in Lake Datong, China, investigates the remediation mechanism of multiple remediation technique combinations (dredging, adsorbent amendment, and planting aquatic vegetation) on sediment N and P loads based on two high-resolution sampling techniques (HR-Peeper and DGT) and P sequential extraction procedures. The results showed that high temperature and low dissolved oxygen considerably enhanced pore water dissolved reactive P (DRP) and NH4+ concentrations attributable to abundant Fe-P and organic matter content in the sediment. Fe reduction is critical for regulating pore water DRP release and promoting N removal. Overall, for Lake Datong, combining multiple remediation techniques is more effective in controlling sediment P loads (pore water DRP, P fluxes, forms of P, and labile P), from a long-term perspective, than a single remediation. Lanthanum-modified bentonite (LMB) inactivation treatment can transfer mobile P in the surface sediment into more refractory forms over time, thereby reducing the risk of sediment labile P release. However, it is difficult to effectively remediate internal P loads owing to inappropriate dredging depths and low biomass of aquatic vegetation. Future lake restoration practices should optimize the selection of different remediation technique combinations based on internal N and P pollution characteristics, while reducing external wastewater input. These results are important for understanding the remediation mechanisms of internal N and P and provide suggestions for sediment management of shallow eutrophic lakes.
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Fósforo , Contaminantes Químicos del Agua , Fósforo/análisis , Lagos , Nitrógeno/análisis , Ecosistema , Sedimentos Geológicos , Contaminantes Químicos del Agua/análisis , China , Eutrofización , AguaRESUMEN
Herein, we engineered the cobalt core size and carbon shell thickness of Co@C by molten salt electrolysis (MSE) to investigate the enhanced essence of decreasing core size as well as the shell thickness dependence-mediated transition of catalytic mechanisms. We found that the reaction activation energy (RAE) of Co@C/peroxymonosulfate (PMS) systems was intimately dependent on the core sizes for sulfamethoxazole (SMX) degradation. The smaller core size of 26 nm provided a lower RAE of 13.39 kJ mol-1. In addition, increasing carbon shell thicknesses of Co@C altered the catalytic mechanisms from a radical pathway of SO4â¢- and â¢OH to to a non-radical pathway of 1O2 and electron-transfer process (ETP), which were verified by experimental results and density functional theory (DFT) calculations. Interestingly, increasing carbon shell thicknesses promoted the charge transfer between Co metal slab and carbon shell, increased the adsorption energy of PMS molecule on the Co@C slab, and decreased the length of OO, which favoured the occurrence of non-free radical processes.
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Carbono , Peróxidos , Sulfametoxazol , CatálisisRESUMEN
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.
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Traditional sulfide metallurgy produces harmful sulfur dioxide and is energy intensive. To this end, we develop an anode electrolysis approach in molten salt by which sulfide is electrochemically split into sulfur gas at a graphite inert anode while releasing metal ions that diffuse toward and are deposited at the cathode. The anodic splitting dictates the "sulfide-to-metal ion and sulfur gas" conversion that makes the reaction recur continuously. Using this approach, Cu2S is converted to sulfur gas and Cu in molten LiCl-KCl at 500 °C with a current efficiency of 99% and energy consumption of 0.420 kWh/kg-Cu (only considering the electricity for electrolysis). Besides Cu2S, the anode electrolysis can extract Cu from Cu matte that is an intermediate product from the traditional sulfide smelting process. More broadly, Fe, Ni, Pb, and Sb are extracted from FeS, CuFeS2, NiS, PbS, and Sb2S3, providing a general electrochemical method for sulfide metallurgy.
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Electrólisis , Sulfuros , Electrodos , Electrólisis/métodos , Grafito , Metales/síntesis química , Sulfuros/química , Azufre/químicaRESUMEN
Silicon (Si) is a promising negative electrode material for lithium-ion batteries (LIBs), but the poor cycling stability hinders their practical application. Developing favorable Si nanomaterials is expected to improve their cyclability. Herein, a controllable and facile electrolysis route to prepare Si nanotubes (SNTs), Si nanowires (SNWs), and Si nanoparticles (SNPs) from halloysite clay (Al2(OH)4Si2O5·nH2O) is developed. It is found that HCl-etching temperature and electrolysis potential play key roles in controlling the morphologies of Si. After being HCl-etched at 80 or 90 °C, halloysite clay can be reduced into Si nanotubes at a suitable potential of -1.45 V or Si nanowires at a wide potential from -1.40 to -1.60 V, respectively, while Si nanoparticles can be only obtained at a more negative potential of -1.60 V without HCl-etching. The different morphologies of Si are associated with the change of reduction kinetics after HCl-etching. Besides, when serving as negative electrode materials for LIBs, Si nanotubes exhibit better Li storage performance than Si nanoparticles and Si nanowires, showing a capacity of 3044 mAh g-1 at 0.20 A g-1 and 1033 mAh g-1 after 1000 cycles at 1 A g-1. This work provides a controllable approach for the synthesis of Si nanomaterials for LIBs.
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Despite the vital roles of Co nanoparticles catalytic oxidation in the Fenton-like system for eliminating pollutants, contributions of Co phases are typically overlooked. Herein, a biphase Co@C core-shell catalyst was synthesized by the electrochemical co-reduction of CaCO3 and Co3O4 in molten carbonate. Unlike the traditional pyrolysis method that is performed over 700 °C, the electrolysis was deployed at 450 °C, at which biphase structures, i.e., face-centered cubic (FCC) and hexagonal close-packed (HCP) structures, can be obtained. The biphase Co@C shows excellent catalytic oxidation performance of diethyl phthalate (DEP) with a high turnover frequency value (TOF, 28.14 min-1) and low catalyst dosage (4 mg L-1). Furthermore, density functional theory (DFT) calculations confirm that the synergistic catalytic effect of biphase Co@C is the enhancement for the breaking of the peroxide O-O bond and the charge transfer from catalysts to PMS molecule for the activation. Moreover, the results of radicals quenching experiments and electron paramagnetic resonance (EPR) tests confirm that SO4â¢-, â¢OH, O2â¢-, and 1O2 co-degrade DEP. Remarkably, 100% removals of three model contaminants, including DEP, sulfamethoxazole (SMX) and 2,4-dichlorophen (2,4-DCP), were achieved, either in pure water or actual river water. This paper provides an electrochemical pathway to leverage the phase of catalysts and thereby mediate their catalytic capability for remediating refractory organic contaminants.