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Lithium-ion batteries (LIBs), in which lithium ions function as charge carriers, are considered the most competitive energy storage devices due to their high energy and power density. However, battery materials, especially with high capacity undergo side reactions and changes that result in capacity decay and safety issues. A deep understanding of the reactions that cause changes in the battery's internal components and the mechanisms of those reactions is needed to build safer and better batteries. This review focuses on the processes of battery failures, with voltage and temperature as the underlying factors. Voltage-induced failures result from anode interfacial reactions, current collector corrosion, cathode interfacial reactions, overcharge, and overdischarge, while temperature-induced failure mechanisms include SEI decomposition, separator damage, and interfacial reactions between electrodes and electrolytes. The review also presents protective strategies for controlling these reactions. As a result, the reader is offered a comprehensive overview of the safety features and failure mechanisms of various LIB components.

Lithium-ion batteries (LIBs), in which lithium ions function as charge carriers, are considered the most competitive energy storage devices due to their high energy and power density. However, battery materials, especially with high capacity undergo side reactions and changes that result in capacity decay and safety issues. A deep understanding of the reactions that cause changes in the battery's internal components and the mechanisms of those reactions is needed to build safer and better batteries. This review focuses on the processes of battery failures, with voltage and temperature as the underlying factors. Voltage-induced failures result from anode interfacial reactions, current collector corrosion, cathode interfacial reactions, overcharge, and overdischarge, while temperature-induced failure mechanisms include SEI decomposition, separator damage, and interfacial reactions between electrodes and electrolytes. The review also presents protective strategies for controlling these reactions. As a result, the reader is offered a comprehensive overview of the safety features and failure mechanisms of various LIB components.

Molecular understanding of the solid-liquid interface is challenging but essential to elucidate the role of the environment on the kinetics of electrochemical reactions. Alkali metal cations (M+), as a vital component at the interface, are found to be necessary for the initiation of carbon dioxide reduction reaction (CO2RR) on coinage metals, and the activity and selectivity of CO2RR could be further enhanced with the cation changing from Li+ to Cs+, while the underlying mechanisms are not well understood. Herein, using ab initio molecular dynamics simulations with explicit solvation and enhanced sampling methods, we systematically investigate the role of M+ in CO2RR on Cu surface. A monotonically decreasing CO2 activation barrier is obtained from Li+ to Cs+, which is attributed to the different coordination abilities of M+ with *CO2. Furthermore, we show that the competing hydrogen evolution reaction must be considered simultaneously to understand the crucial role of alkali metal cations in CO2RR on Cu surfaces, where H+ is repelled from the interface and constrained by M+. Our results provide significant insights into the design of electrochemical environments and highlight the importance of explicitly including the solvation and competing reactions in theoretical simulations of CO2RR.

Lithium-ion batteries (LIBs), in which lithium ions function as charge carriers, are considered the most competitive energy storage devices due to their high energy and power density. However, battery materials, especially with high capacity undergo side reactions and changes that result in capacity decay and safety issues. A deep understanding of the reactions that cause changes in the battery's internal components and the mechanisms of those reactions is needed to build safer and better batteries. This review focuses on the processes of battery failures, with voltage and temperature as the underlying factors. Voltage-induced failures result from anode interfacial reactions, current collector corrosion, cathode interfacial reactions, overcharge, and overdischarge, while temperature-induced failure mechanisms include SEI decomposition, separator damage, and interfacial reactions between electrodes and electrolytes. The review also presents protective strategies for controlling these reactions. As a result, the reader is offered a comprehensive overview of the safety features and failure mechanisms of various LIB components.

Lithium-ion batteries (LIBs), in which lithium ions function as charge carriers, are considered the most competitive energy storage devices due to their high energy and power density. However, battery materials, especially with high capacity undergo side reactions and changes that result in capacity decay and safety issues. A deep understanding of the reactions that cause changes in the battery's internal components and the mechanisms of those reactions is needed to build safer and better batteries. This review focuses on the processes of battery failures, with voltage and temperature as the underlying factors. Voltage-induced failures result from anode interfacial reactions, current collector corrosion, cathode interfacial reactions, overcharge, and overdischarge, while temperature-induced failure mechanisms include SEI decomposition, separator damage, and interfacial reactions between electrodes and electrolytes. The review also presents protective strategies for controlling these reactions. As a result, the reader is offered a comprehensive overview of the safety features and failure mechanisms of various LIB components.

The lithium hexafluorophosphate (LiPF6) in spent lithium-ion batteries (LIBs) is a potentially valuable resource and a significant environmental pollutant. Unfortunately, most of the LiPF6 in a spent LIB is difficult to extract because the electrolyte is strongly adsorbed by the cathode, anode, and separator. Storing extracted electrolyte is also challenging because it contains LiPF6, which promotes the decomposition of the solvent. Here we show that electrolytes in spent LIBs can be collected by a less polar solvent dimethyl carbonate (DMC) wash, and LiPF6 can be concentrated by simple aqueous extraction by lowering ethylene carbonate (EC) content in the recycled electrolyte. Due to the similar dielectric constant of EC and water, reducing the content of EC in LIB electrolytes, or even eliminating it, facilitates the separation of water and electrolyte, thus enabling the lithium salts in the electrolyte to be separated from the organic solvent. The lithium salt extracting efficiency achieved in this way can be as high as 99.8%, and fluorine and phosphorus of LiPF6 can be fixed in the form of stable metal fluoride and phosphate by hydrothermal method. The same strategy can be used in industrial waste electrolyte recycling by diluting the waste with DMC and extracting the resulting solution with water. This work thus reveals a new route for waste electrolyte treatment and will also support the development of advanced EC-free electrolytes for high-performance, safe, and easily recyclable LIBs.

Recycling lithium-ion batteries (LIBs) is fundamental for resource recovery, reducing energy consumption, decreasing emissions, and minimizing environmental risks. The inherited properties of materials and design are not commonly attributed to the complexity of recycling LIBs and their effects on the recycling process. The state-of-the-art battery recycling methodology consequently suffers from poor recycling efficiency and high consumption from issues with the cathode and the binder material. As a feasibility study, high-energy-density cathode material LiFeMnPO4 with a water-soluble polyacrylic acid (PAA) binder is extracted with dilute hydrochloric acid at room temperature under oxidant-free conditions. The cathode is wholly leached with high purity and is suitable for reuse. The cathode is easily separated from its constituent materials and reduces material and energy consumption during recycling by 20% and 7%, respectively. This strategy is utilized to fabricate recyclable-oriented LiFeMnPO4/graphite LIBs with a PAA binder and carbon paper current collector. Finally, the limitation of the solubility of the binder is discussed in terms of recycling. This research hopefully provides guidance for recycling-oriented design for the circular economy of the LIB industry.

Sodium-ion batteries (SIBs) are promising electrical power sources complementary to lithium-ion batteries (LIBs) and could be crucial in future electric vehicles and energy storage systems. Spent LIBs and SIBs both face many of the same environmental and economic challenges in their recycling, but SIB recycling has a much higher economic barrier. Although LIB recycling can be profitable by recovering high-valued metals of lithium and cobalt, the lower material valuation of spent SIBs diminishes profitability and may hinder industrial recycling. Pre-emptive strategies to facilitate recycling spent SIBs should be made during the early commercialization stage to ensure that SIBs are designed for ease of recycling, low operation costs and optimum efficiency. This Perspective article summarizes the material components of SIBs, discusses strategies for their recycling and outlines the associated challenges and future outlook of SIB recycling. The insights presented should aid scientists and engineers in creating a circular economy for the SIB industry.

Electrolyte optimization by solvent molecule design has been recognized as an effective approach for stabilizing lithium (Li) metal batteries. However, the coordination pattern of Li+ with solvent molecules has been sparsely considered. Here, we report an electrolyte design strategy based on bi/tridentate chelation of Li+ and solvent to tune the solvation structure. As a proof of concept, a novel solvent with multi oxygen coordination sites is demonstrated to facilitate the formation of an anion-aggregated solvation shell, enhancing the interfacial stability and de-solvation kinetics. As a result, the as-developed electrolyte exhibits ultra-stable cycling over 1400 h in symmetric cells with 50 ?m-thin Li foils. When paired with high-loading LiFePO4, full cells maintain 92% capacity over 500 cycles and deliver improved electrochemical performances over a wide temperature range from -10 °C to 60 °C. Furthermore, the concept is validated in a pouch cell (570 mAh), achieving a capacity retention of 99.5% after 100 cycles. This brand-new insight on electrolyte engineering provides guidelines for practical high-performance Li metal batteries. This article is protected by copyright. All rights reserved

The lithium hexafluorophosphate (LiPF6) in spent lithium-ion batteries (LIBs) is a potentially valuable resource and a significant environmental pollutant. Unfortunately, most of the LiPF6 in a spent LIB is difficult to extract because the electrolyte is strongly adsorbed by the cathode, anode, and separator. Storing extracted electrolyte is also challenging because it contains LiPF6, which promotes the decomposition of the solvent. Here we show that electrolytes in spent LIBs can be collected by a less polar solvent dimethyl carbonate (DMC) wash, and LiPF6 can be concentrated by simple aqueous extraction by lowering ethylene carbonate (EC) content in the recycled electrolyte. Due to the similar dielectric constant of EC and water, reducing the content of EC in LIB electrolytes, or even eliminating it, facilitates the separation of water and electrolyte, thus enabling the lithium salts in the electrolyte to be separated from the organic solvent. The lithium salt extracting efficiency achieved in this way can be as high as 99.8%, and fluorine and phosphorus of LiPF6 can be fixed in the form of stable metal fluoride and phosphate by hydrothermal method. The same strategy can be used in industrial waste electrolyte recycling by diluting the waste with DMC and extracting the resulting solution with water. This work thus reveals a new route for waste electrolyte treatment and will also support the development of advanced EC-free electrolytes for high-performance, safe, and easily recyclable LIBs.

Recycling lithium-ion batteries (LIBs) is fundamental for resource recovery, reducing energy consumption, decreasing emissions, and minimizing environmental risks. The inherited properties of materials and design are not commonly attributed to the complexity of recycling LIBs and their effects on the recycling process. The state-of-the-art battery recycling methodology consequently suffers from poor recycling efficiency and high consumption from issues with the cathode and the binder material. As a feasibility study, high-energy-density cathode material LiFeMnPO4 with a water-soluble polyacrylic acid (PAA) binder is extracted with dilute hydrochloric acid at room temperature under oxidant-free conditions. The cathode is wholly leached with high purity and is suitable for reuse. The cathode is easily separated from its constituent materials and reduces material and energy consumption during recycling by 20% and 7%, respectively. This strategy is utilized to fabricate recyclable-oriented LiFeMnPO4/graphite LIBs with a PAA binder and carbon paper current collector. Finally, the limitation of the solubility of the binder is discussed in terms of recycling. This research hopefully provides guidance for recycling-oriented design for the circular economy of the LIB industry.

The lithium hexafluorophosphate (LiPF6) in spent lithium-ion batteries (LIBs) is a potentially valuable resource and a significant environmental pollutant. Unfortunately, most of the LiPF6 in a spent LIB is difficult to extract because the electrolyte is strongly adsorbed by the cathode, anode, and separator. Storing extracted electrolyte is also challenging because it contains LiPF6, which promotes the decomposition of the solvent. Here we show that electrolytes in spent LIBs can be collected by a less polar solvent dimethyl carbonate (DMC) wash, and LiPF6 can be concentrated by simple aqueous extraction by lowering ethylene carbonate (EC) content in the recycled electrolyte. Due to the similar dielectric constant of EC and water, reducing the content of EC in LIB electrolytes, or even eliminating it, facilitates the separation of water and electrolyte, thus enabling the lithium salts in the electrolyte to be separated from the organic solvent. The lithium salt extracting efficiency achieved in this way can be as high as 99.8%, and fluorine and phosphorus of LiPF6 can be fixed in the form of stable metal fluoride and phosphate by hydrothermal method. The same strategy can be used in industrial waste electrolyte recycling by diluting the waste with DMC and extracting the resulting solution with water. This work thus reveals a new route for waste electrolyte treatment and will also support the development of advanced EC-free electrolytes for high-performance, safe, and easily recyclable LIBs.

Recycling lithium-ion batteries (LIBs) is fundamental for resource recovery, reducing energy consumption, decreasing emissions, and minimizing environmental risks. The inherited properties of materials and design are not commonly attributed to the complexity of recycling LIBs and their effects on the recycling process. The state-of-the-art battery recycling methodology consequently suffers from poor recycling efficiency and high consumption from issues with the cathode and the binder material. As a feasibility study, high-energy-density cathode material LiFeMnPO4 with a water-soluble polyacrylic acid (PAA) binder is extracted with dilute hydrochloric acid at room temperature under oxidant-free conditions. The cathode is wholly leached with high purity and is suitable for reuse. The cathode is easily separated from its constituent materials and reduces material and energy consumption during recycling by 20% and 7%, respectively. This strategy is utilized to fabricate recyclable-oriented LiFeMnPO4/graphite LIBs with a PAA binder and carbon paper current collector. Finally, the limitation of the solubility of the binder is discussed in terms of recycling. This research hopefully provides guidance for recycling-oriented design for the circular economy of the LIB industry.

Lithium iron phosphate batteries (LFP), widely used as power sources, are forecasted to reach the terawatt-hour scale, inevitably leading to battery waste and expediating the urgency for effective recycling processes for LFP. The modern recycling methodologies based on material recovery face significant economic, environmental, and energy consumption challenges. This research attempts to resolve these challenges by providing direct cathode regeneration based on the principles of an external short-circuit to replenish lithium lost in the spent cathode with lithiated materials (LiC6, Li metal). Given that most active lithium loss in the cathode is caused by the growth of the solid electrolyte interphase rather than structural damage, restoring the lost lithium can revitalize a spent cathode battery’s electrochemical performance to a near-original state. The lithium loss in LFP cathodes ranging from 20% to 80% was renewed by supplementing lithium. Relithiation of 10Ah commercial LFP spent cathode showed revitalized electrochemical performance. Compared to the modern recycling methods, direct cathode regeneration improves the economic benefits of recycling by 33%, decreases energy consumption by 48%, and reduces carbon emissions by 62%. Direct cathode regeneration provides a scaffold for the next generation of recycling methods to improve recycling efficiency while reducing their environmental footprint.

Lithium iron phosphate batteries (LFP), widely used as power sources, are forecasted to reach the terawatt-hour scale, inevitably leading to battery waste and expediating the urgency for effective recycling processes for LFP. The modern recycling methodologies based on material recovery face significant economic, environmental, and energy consumption challenges. This research attempts to resolve these challenges by providing direct cathode regeneration based on the principles of an external short-circuit to replenish lithium lost in the spent cathode with lithiated materials (LiC6, Li metal). Given that most active lithium loss in the cathode is caused by the growth of the solid electrolyte interphase rather than structural damage, restoring the lost lithium can revitalize a spent cathode battery’s electrochemical performance to a near-original state. The lithium loss in LFP cathodes ranging from 20% to 80% was renewed by supplementing lithium. Relithiation of 10Ah commercial LFP spent cathode showed revitalized electrochemical performance. Compared to the modern recycling methods, direct cathode regeneration improves the economic benefits of recycling by 33%, decreases energy consumption by 48%, and reduces carbon emissions by 62%. Direct cathode regeneration provides a scaffold for the next generation of recycling methods to improve recycling efficiency while reducing their environmental footprint.

The lithium hexafluorophosphate (LiPF6) in spent lithium-ion batteries (LIBs) is a potentially valuable resource and a significant environmental pollutant. Unfortunately, most of the LiPF6 in a spent LIB is difficult to extract because the electrolyte is strongly adsorbed by the cathode, anode, and separator. Storing extracted electrolyte is also challenging because it contains LiPF6, which promotes the decomposition of the solvent. Here we show that electrolytes in spent LIBs can be collected by a less polar solvent dimethyl carbonate (DMC) wash, and LiPF6 can be concentrated by simple aqueous extraction by lowering ethylene carbonate (EC) content in the recycled electrolyte. Due to the similar dielectric constant of EC and water, reducing the content of EC in LIB electrolytes, or even eliminating it, facilitates the separation of water and electrolyte, thus enabling the lithium salts in the electrolyte to be separated from the organic solvent. The lithium salt extracting efficiency achieved in this way can be as high as 99.8%, and fluorine and phosphorus of LiPF6 can be fixed in the form of stable metal fluoride and phosphate by hydrothermal method. The same strategy can be used in industrial waste electrolyte recycling by diluting the waste with DMC and extracting the resulting solution with water. This work thus reveals a new route for waste electrolyte treatment and will also support the development of advanced EC-free electrolytes for high-performance, safe, and easily recyclable LIBs.

Recycling lithium-ion batteries (LIBs) is fundamental for resource recovery, reducing energy consumption, decreasing emissions, and minimizing environmental risks. The inherited properties of materials and design are not commonly attributed to the complexity of recycling LIBs and their effects on the recycling process. The state-of-the-art battery recycling methodology consequently suffers from poor recycling efficiency and high consumption from issues with the cathode and the binder material. As a feasibility study, high-energy-density cathode material LiFeMnPO4 with a water-soluble polyacrylic acid (PAA) binder is extracted with dilute hydrochloric acid at room temperature under oxidant-free conditions. The cathode is wholly leached with high purity and is suitable for reuse. The cathode is easily separated from its constituent materials and reduces material and energy consumption during recycling by 20% and 7%, respectively. This strategy is utilized to fabricate recyclable-oriented LiFeMnPO4/graphite LIBs with a PAA binder and carbon paper current collector. Finally, the limitation of the solubility of the binder is discussed in terms of recycling. This research hopefully provides guidance for recycling-oriented design for the circular economy of the LIB industry.

The development of efficient oxygen evolution reaction (OER) electrocatalysts is of vital importance for acidic water decomposition. Currently, the rutile structured RuO2 is considered to be the best candidate and has been studied widely. However, the state-of-the-art rutile RuO2 still suffers from unsatisfactory activity and stability, while other crystalline structures of Ru-based oxides are seldom reported as OER electrocatalysts. The present work, for the first time, successfully synthesizes orthorhombic (Ru, Mn)2O3 electrocatalyst through cation exchange. The orthorhombic (Ru, Mn)2O3 particles exhibit the outstanding electrocatalysis performance as OER electrocatalyst, showing an ultralow overpotential of 168 mV at 10 mA cm-2 in acidic water and good stability in 40 h of OER. The outstanding electrocatalysis performance is attributed to the distinct Ru d-band structure together with the larger surface density of Ru active site, which reduces the free energy of the rate-limiting step during OER.

The lithium hexafluorophosphate (LiPF6) in spent lithium-ion batteries (LIBs) is a potentially valuable resource and a significant environmental pollutant. Unfortunately, most of the LiPF6 in a spent LIB is difficult to extract because the electrolyte is strongly adsorbed by the cathode, anode, and separator. Storing extracted electrolyte is also challenging because it contains LiPF6, which promotes the decomposition of the solvent. Here we show that electrolytes in spent LIBs can be collected by a less polar solvent dimethyl carbonate (DMC) wash, and LiPF6 can be concentrated by simple aqueous extraction by lowering ethylene carbonate (EC) content in the recycled electrolyte. Due to the similar dielectric constant of EC and water, reducing the content of EC in LIB electrolytes, or even eliminating it, facilitates the separation of water and electrolyte, thus enabling the lithium salts in the electrolyte to be separated from the organic solvent. The lithium salt extracting efficiency achieved in this way can be as high as 99.8%, and fluorine and phosphorus of LiPF6 can be fixed in the form of stable metal fluoride and phosphate by hydrothermal method. The same strategy can be used in industrial waste electrolyte recycling by diluting the waste with DMC and extracting the resulting solution with water. This work thus reveals a new route for waste electrolyte treatment and will also support the development of advanced EC-free electrolytes for high-performance, safe, and easily recyclable LIBs.

Recycling lithium-ion batteries (LIBs) is fundamental for resource recovery, reducing energy consumption, decreasing emissions, and minimizing environmental risks. The inherited properties of materials and design are not commonly attributed to the complexity of recycling LIBs and their effects on the recycling process. The state-of-the-art battery recycling methodology consequently suffers from poor recycling efficiency and high consumption from issues with the cathode and the binder material. As a feasibility study, high-energy-density cathode material LiFeMnPO4 with a water-soluble polyacrylic acid (PAA) binder is extracted with dilute hydrochloric acid at room temperature under oxidant-free conditions. The cathode is wholly leached with high purity and is suitable for reuse. The cathode is easily separated from its constituent materials and reduces material and energy consumption during recycling by 20% and 7%, respectively. This strategy is utilized to fabricate recyclable-oriented LiFeMnPO4/graphite LIBs with a PAA binder and carbon paper current collector. Finally, the limitation of the solubility of the binder is discussed in terms of recycling. This research hopefully provides guidance for recycling-oriented design for the circular economy of the LIB industry.

New methods for recycling lithium-ion batteries (LIBs) are needed because traditional recycling methods are based on battery pulverization, which requires pre-treatment of tedious and non-eco-friendly discharging and results in low efficiency and high waste generation in post-treatment. Separating the components of recycled LIB cells followed by reuse or conversion of individual components could minimize material cross-contamination while avoiding excessive consumption of energy and chemicals. However, disposing of charged LIB cells is hazardous due to the high reactivity of lithiated graphite towards cathode materials and air, and the toxicity and flammability of the electrolytes. Here we demonstrate that the disassembly of charged jellyroll LIB cells in water with a single main step reveals no emissions from the cells and near perfect recycling efficiencies that exceed the targets of the US Department of Energy and Batteries Europe. The precise non-destructive mechanical method separates the components from jellyroll cell in water, avoiding both uncontrollable reactions from the anode and burning of the electrolyte, while allowing only a limited fraction of the anode lithium to react with water. Recycling in this way allows the recovery of materials with a value of ∼7.14 $ kg−1 cell, which is higher than that of physical separation (∼5.40 $ kg−1 cell) and much greater than the overall revenue achieved using element extraction methods (<1.00 $ kg−1 cell). The precise separation method could thus facilitate the establishment of a circular economy within the LIB industry and build a strong bridge between academia and the battery recycling industry.

Understanding thermal transport across metal/semiconductor interfaces is crucial for the heat dissipation of electronics. The dominant heat carriers in non-metals, phonons, are thought to transport elastically across most interfaces, except for a few extreme cases where the two materials that formed the interface are highly dissimilar with a large difference in Debye temperature. In this work, we show that even for two materials with similar Debye temperatures (Al/Si, Al/GaN), a substantial portion of phonons will transport inelastically across their interfaces at high temperatures, significantly enhancing interface thermal conductance. Moreover, we find that interface sharpness strongly affects phonon transport process. For atomically sharp interfaces, phonons are allowed to transport inelastically and interface thermal conductance linearly increases at high temperatures. With a diffuse interface, inelastic phonon transport diminishes. Our results provide new insights on phonon transport across interfaces and open up opportunities for engineering interface thermal conductance specifically for materials of relevance to microelectronics.

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 LiFePO4. 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).

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 LiFePO4. 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).

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 LiFePO4. 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).

Developing highly active and durable electrocatalysts for acidic oxygen evolution reaction remains a great challenge due to the sluggish kinetics of the four-electron transfer reaction and severe catalyst dissolution. Here we report an electrochemical lithium intercalation method to improve both the activity and stability of RuO2 for acidic oxygen evolution reaction. The lithium intercalates into the lattice interstices of RuO2, donates electrons and distorts the local structure. Therefore, the Ru valence state is lowered with formation of stable Li-O-Ru local structure, and the Ru–O covalency is weakened, which suppresses the dissolution of Ru, resulting in greatly enhanced durability. Meanwhile, the inherent lattice strain results in the surface structural distortion of LixRuO2 and activates the dangling O atom near the Ru active site as a proton acceptor, which stabilizes the OOH* and dramatically enhances the activity. This work provides an effective strategy to develop highly efficient catalyst towards water splitting. © 2022, The Author(s).

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 LiFePO4. 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).

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 LiFePO4. 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).

[EN]The energy content increase is of paramount importance for the development of future Li-based batteries. Here, the authors propose a gel polymer electrolyte in combination with a positive electrode comprising of a Li-rich oxide active material and graphite to produce a high-energy Li metal cell. The current Li-based battery technology is limited in terms of energy contents. Therefore, several approaches are considered to improve the energy density of these energy storage devices. Here, we report the combination of a heteroatom-based gel polymer electrolyte with a hybrid cathode comprising of a Li-rich oxide active material and graphite conductive agent to produce a high-energy "shuttle-relay" Li metal battery, where additional capacity is generated from the electrolyte's anion shuttling at high voltages. The gel polymer electrolyte, prepared via in situ polymerization in an all-fluorinated electrolyte, shows adequate ionic conductivity (around 2 mS cm(-1) at 25 degrees C), oxidation stability (up to 5.5 V vs Li/Li+), compatibility with Li metal and safety aspects (i.e., non-flammability). The polymeric electrolyte allows for a reversible insertion of hexafluorophosphate anions into the conductive graphite (i.e., dual-ion mechanism) after the removal of Li ions from Li-rich oxide (i.e., rocking-chair mechanism).

[EN]The energy content increase is of paramount importance for the development of future Li-based batteries. Here, the authors propose a gel polymer electrolyte in combination with a positive electrode comprising of a Li-rich oxide active material and graphite to produce a high-energy Li metal cell. The current Li-based battery technology is limited in terms of energy contents. Therefore, several approaches are considered to improve the energy density of these energy storage devices. Here, we report the combination of a heteroatom-based gel polymer electrolyte with a hybrid cathode comprising of a Li-rich oxide active material and graphite conductive agent to produce a high-energy "shuttle-relay" Li metal battery, where additional capacity is generated from the electrolyte's anion shuttling at high voltages. The gel polymer electrolyte, prepared via in situ polymerization in an all-fluorinated electrolyte, shows adequate ionic conductivity (around 2 mS cm(-1) at 25 degrees C), oxidation stability (up to 5.5 V vs Li/Li+), compatibility with Li metal and safety aspects (i.e., non-flammability). The polymeric electrolyte allows for a reversible insertion of hexafluorophosphate anions into the conductive graphite (i.e., dual-ion mechanism) after the removal of Li ions from Li-rich oxide (i.e., rocking-chair mechanism).

[EN]The energy content increase is of paramount importance for the development of future Li-based batteries. Here, the authors propose a gel polymer electrolyte in combination with a positive electrode comprising of a Li-rich oxide active material and graphite to produce a high-energy Li metal cell. The current Li-based battery technology is limited in terms of energy contents. Therefore, several approaches are considered to improve the energy density of these energy storage devices. Here, we report the combination of a heteroatom-based gel polymer electrolyte with a hybrid cathode comprising of a Li-rich oxide active material and graphite conductive agent to produce a high-energy "shuttle-relay" Li metal battery, where additional capacity is generated from the electrolyte's anion shuttling at high voltages. The gel polymer electrolyte, prepared via in situ polymerization in an all-fluorinated electrolyte, shows adequate ionic conductivity (around 2 mS cm(-1) at 25 degrees C), oxidation stability (up to 5.5 V vs Li/Li+), compatibility with Li metal and safety aspects (i.e., non-flammability). The polymeric electrolyte allows for a reversible insertion of hexafluorophosphate anions into the conductive graphite (i.e., dual-ion mechanism) after the removal of Li ions from Li-rich oxide (i.e., rocking-chair mechanism).

Understanding the temperature dependence of phase transitions occurred in electrode materials is crucial for improving the low-temperature performance of Li-ion batteries. In this work, we find an unusual temperature dependence in the phase transition of TiO2 nanoparticles on dynamic Li+ intercalation, with a decrease in temperature resulting in the formation of a supersaturated solid solution phase. Kinetic analyses reveal that Li redistribution is facilitated at high temperature while limited at low temperature. This difference manifests as a thermodynamically-controlled phase separation at high temperature and a kinetically-controlled formation of a supersaturated solid solution phase at low temperature. Facilitating the phase separation by enhancing the interfacial kinetics proves effective to improve the low-temperature performance. This study provides a comprehensive and in-depth understanding of the temperature dependence of the lithiation-induced phase transition, which has important implications for the development of the next generation of all-climate rechargeable batteries. © 2020

Understanding the temperature dependence of phase transitions occurred in electrode materials is crucial for improving the low-temperature performance of Li-ion batteries. In this work, we find an unusual temperature dependence in the phase transition of TiO2 nanoparticles on dynamic Li+ intercalation, with a decrease in temperature resulting in the formation of a supersaturated solid solution phase. Kinetic analyses reveal that Li redistribution is facilitated at high temperature while limited at low temperature. This difference manifests as a thermodynamically-controlled phase separation at high temperature and a kinetically-controlled formation of a supersaturated solid solution phase at low temperature. Facilitating the phase separation by enhancing the interfacial kinetics proves effective to improve the low-temperature performance. This study provides a comprehensive and in-depth understanding of the temperature dependence of the lithiation-induced phase transition, which has important implications for the development of the next generation of all-climate rechargeable batteries. © 2020

Metallic lithium is a promising anode to increase the energy density of rechargeable lithium batteries. Despite extensive efforts, detrimental reactivity of lithium metal with electrolytes and uncontrolled dendrite growth remain challenging interconnected issues hindering highly reversible Li-metal batteries. Herein, we report a rationally designed amide-based electrolyte based on the desired interface products. This amide electrolyte achieves a high average Coulombic efficiency during cycling, resulting in an outstanding capacity retention with a 3.5 mAh cm−2 high-mass-loaded LiNi0.8Co0.1Mn0.1O2 cathode. The interface reactions with the amide electrolyte lead to the predicted solid electrolyte interface species, having favorable properties such as high ionic conductivity and high stability. Operando monitoring the lithium spatial distribution reveals that the highly reversible behavior is related to denser deposition as well as top-down stripping, which decreases the formation of porous deposits and inactive lithium, providing new insights for the development of interface chemistries for metal batteries., RST/Storage of Electrochemical Energy, RST/Technici Pool

Understanding the temperature dependence of phase transitions occurred in electrode materials is crucial for improving the low-temperature performance of Li-ion batteries. In this work, we find an unusual temperature dependence in the phase transition of TiO2 nanoparticles on dynamic Li+ intercalation, with a decrease in temperature resulting in the formation of a supersaturated solid solution phase. Kinetic analyses reveal that Li redistribution is facilitated at high temperature while limited at low temperature. This difference manifests as a thermodynamically-controlled phase separation at high temperature and a kinetically-controlled formation of a supersaturated solid solution phase at low temperature. Facilitating the phase separation by enhancing the interfacial kinetics proves effective to improve the low-temperature performance. This study provides a comprehensive and in-depth understanding of the temperature dependence of the lithiation-induced phase transition, which has important implications for the development of the next generation of all-climate rechargeable batteries. © 2020

Metallic lithium is a promising anode to increase the energy density of rechargeable lithium batteries. Despite extensive efforts, detrimental reactivity of lithium metal with electrolytes and uncontrolled dendrite growth remain challenging interconnected issues hindering highly reversible Li-metal batteries. Herein, we report a rationally designed amide-based electrolyte based on the desired interface products. This amide electrolyte achieves a high average Coulombic efficiency during cycling, resulting in an outstanding capacity retention with a 3.5 mAh cm−2 high-mass-loaded LiNi0.8Co0.1Mn0.1O2 cathode. The interface reactions with the amide electrolyte lead to the predicted solid electrolyte interface species, having favorable properties such as high ionic conductivity and high stability. Operando monitoring the lithium spatial distribution reveals that the highly reversible behavior is related to denser deposition as well as top-down stripping, which decreases the formation of porous deposits and inactive lithium, providing new insights for the development of interface chemistries for metal batteries., RST/Storage of Electrochemical Energy, RST/Technici Pool

Transition metal oxides hold great promise as high-energy anodes in next-generation lithium-ion batteries. However, owing to the inherent limitations of low electronic/ionic conductivities and dramatic volume change during charge/discharge, it is still challenging to fabricate practically viable compacted and thick TMO anodes with satisfactory electrochemical performance. Herein, with mesoporous cobalt–boride nanoflakes serving as multifunctional bridges in ZnCo 2 O 4 micro-/nanospheres, a compacted ZnCo 2 O 4 /Co–B hybrid structure is constructed. Co–B nanoflakes not only bridge ZnCo 2 O 4 nanoparticles and function as anchors for ZnCo 2 O 4 micro-/nanospheres to suppress the severe volume fluctuation, they also work as effective electron conduction bridges to promote fast electron transportation. More importantly, they serve as Li + transfer bridges to provide significantly boosted Li + diffusivity, evidenced from both experimental kinetics analysis and density functional theory calculations. The mesopores within Co–B nanoflakes help overcome the large Li + diffusion barriers across 2D interfaces. As a result, the ZnCo 2 O 4 /Co–B electrode delivers high gravimetric/volumetric/areal capacities of 995 mAh g −1 /1450 mAh cm −3 /5.10 mAh cm −2 , respectively, with robust rate capability and long-term cyclability. The distinct interfacial design strategy provides a new direction for designing compacted conversion-type anodes with superior lithium storage kinetics and stability for practical applications. © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Highly conductive carbon microspheres (CMSs) with a hierarchical porous structure are prepared by electrospraying polystyrene/polyvinylpyrrolidine (PS/PVP) solution containing Ketjen carbon black (KB) nanoparticles. The branched KB particles serve as the structural skeleton to support CMSs while the hybrid polymer precursor forms multiscale pores upon pyrolysis. The CMSs possessing an extremely large pore volume of 2.08 cm3 g−1 and a large specific surface area of 756 m2 g−1 are melt-infiltrated with sulfur to form sulfur/CMS composite cathode for lithium-sulfur batteries. The cathode delivers a remarkable initial capacity of 1006 mAh g−1 at 1 C with high retention of 67.5% after 1000 cycles, and an initial capacity of 728 mAh g−1 at 2 C with high retention of 68.5% after 2000 cycles. The excellent electrochemical performance is attributed to the distinct functional and structural features of CMS framework: namely, microscale grain size, closely packed KB particles, large pore volume and hierarchical pore size, as well as superior conductive framework, which in turn suppress the shuttling of dissoluble polysulfides and boost the utilization of encapsulated sulfur. The above findings may offer insights into designing new carbon frameworks for other types of high performance rechargeable batteries.

Highly conductive carbon microspheres (CMSs) with a hierarchical porous structure are prepared by electrospraying polystyrene/polyvinylpyrrolidine (PS/PVP) solution containing Ketjen carbon black (KB) nanoparticles. The branched KB particles serve as the structural skeleton to support CMSs while the hybrid polymer precursor forms multiscale pores upon pyrolysis. The CMSs possessing an extremely large pore volume of 2.08 cm3 g−1 and a large specific surface area of 756 m2 g−1 are melt-infiltrated with sulfur to form sulfur/CMS composite cathode for lithium-sulfur batteries. The cathode delivers a remarkable initial capacity of 1006 mAh g−1 at 1 C with high retention of 67.5% after 1000 cycles, and an initial capacity of 728 mAh g−1 at 2 C with high retention of 68.5% after 2000 cycles. The excellent electrochemical performance is attributed to the distinct functional and structural features of CMS framework: namely, microscale grain size, closely packed KB particles, large pore volume and hierarchical pore size, as well as superior conductive framework, which in turn suppress the shuttling of dissoluble polysulfides and boost the utilization of encapsulated sulfur. The above findings may offer insights into designing new carbon frameworks for other types of high performance rechargeable batteries.

Transition metal oxides hold great promise as high-energy anodes in next-generation lithium-ion batteries. However, owing to the inherent limitations of low electronic/ionic conductivities and dramatic volume change during charge/discharge, it is still challenging to fabricate practically viable compacted and thick TMO anodes with satisfactory electrochemical performance. Herein, with mesoporous cobalt–boride nanoflakes serving as multifunctional bridges in ZnCo 2 O 4 micro-/nanospheres, a compacted ZnCo 2 O 4 /Co–B hybrid structure is constructed. Co–B nanoflakes not only bridge ZnCo 2 O 4 nanoparticles and function as anchors for ZnCo 2 O 4 micro-/nanospheres to suppress the severe volume fluctuation, they also work as effective electron conduction bridges to promote fast electron transportation. More importantly, they serve as Li + transfer bridges to provide significantly boosted Li + diffusivity, evidenced from both experimental kinetics analysis and density functional theory calculations. The mesopores within Co–B nanoflakes help overcome the large Li + diffusion barriers across 2D interfaces. As a result, the ZnCo 2 O 4 /Co–B electrode delivers high gravimetric/volumetric/areal capacities of 995 mAh g −1 /1450 mAh cm −3 /5.10 mAh cm −2 , respectively, with robust rate capability and long-term cyclability. The distinct interfacial design strategy provides a new direction for designing compacted conversion-type anodes with superior lithium storage kinetics and stability for practical applications. © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

It is a huge challenge for high-tap-density electrodes to achieve high volumetric energy density but without compromising the ionic transportation. Herein, we prepared compact Li4Ti5O12 (LTO) microspheres consisting of densely packed primary nanoparticles. The real space distribution of lithium ions inside the compact LTO was revealed by using scanning transmission electron microscopy with electron energy loss spectroscopy (STEM-EELS) to identify the function of grain boundaries for lithium ion transportation during lithiation. The as-prepared LTO microspheres possess a high tap density (1.23 g cm-3) and an ultra-small specific surface area (2.40 m2 g-1). Impressively, the compact LTO microspheres present excellent electrochemical performance. At high rates of 5C, 10C and 20C, the LTO microspheres show a specific capacity of 146.6, 138.2 and 111 mA h g-1, respectively. The capacity retention remains at 97.8% at 5C after 500 cycles. The STEM-EELS results indicate that the lithiation reaction of LTO is firstly initiated at grain boundaries during the high rate lithiation process and then diffuses to the bulk area. The abundant grain boundaries in compact LTO microspheres can form a highly efficient conductive network to preferentially transport the ions, which contributes to high volumetric and gravimetric energy density simultaneously., Accepted Author Manuscript, RST/Fundamental Aspects of Materials and Energy, RST/Storage of Electrochemical Energy

Highly conductive carbon microspheres (CMSs) with a hierarchical porous structure are prepared by electrospraying polystyrene/polyvinylpyrrolidine (PS/PVP) solution containing Ketjen carbon black (KB) nanoparticles. The branched KB particles serve as the structural skeleton to support CMSs while the hybrid polymer precursor forms multiscale pores upon pyrolysis. The CMSs possessing an extremely large pore volume of 2.08 cm3 g−1 and a large specific surface area of 756 m2 g−1 are melt-infiltrated with sulfur to form sulfur/CMS composite cathode for lithium-sulfur batteries. The cathode delivers a remarkable initial capacity of 1006 mAh g−1 at 1 C with high retention of 67.5% after 1000 cycles, and an initial capacity of 728 mAh g−1 at 2 C with high retention of 68.5% after 2000 cycles. The excellent electrochemical performance is attributed to the distinct functional and structural features of CMS framework: namely, microscale grain size, closely packed KB particles, large pore volume and hierarchical pore size, as well as superior conductive framework, which in turn suppress the shuttling of dissoluble polysulfides and boost the utilization of encapsulated sulfur. The above findings may offer insights into designing new carbon frameworks for other types of high performance rechargeable batteries.

Transition metal oxides hold great promise as high-energy anodes in next-generation lithium-ion batteries. However, owing to the inherent limitations of low electronic/ionic conductivities and dramatic volume change during charge/discharge, it is still challenging to fabricate practically viable compacted and thick TMO anodes with satisfactory electrochemical performance. Herein, with mesoporous cobalt–boride nanoflakes serving as multifunctional bridges in ZnCo 2 O 4 micro-/nanospheres, a compacted ZnCo 2 O 4 /Co–B hybrid structure is constructed. Co–B nanoflakes not only bridge ZnCo 2 O 4 nanoparticles and function as anchors for ZnCo 2 O 4 micro-/nanospheres to suppress the severe volume fluctuation, they also work as effective electron conduction bridges to promote fast electron transportation. More importantly, they serve as Li + transfer bridges to provide significantly boosted Li + diffusivity, evidenced from both experimental kinetics analysis and density functional theory calculations. The mesopores within Co–B nanoflakes help overcome the large Li + diffusion barriers across 2D interfaces. As a result, the ZnCo 2 O 4 /Co–B electrode delivers high gravimetric/volumetric/areal capacities of 995 mAh g −1 /1450 mAh cm −3 /5.10 mAh cm −2 , respectively, with robust rate capability and long-term cyclability. The distinct interfacial design strategy provides a new direction for designing compacted conversion-type anodes with superior lithium storage kinetics and stability for practical applications. © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

It is a huge challenge for high-tap-density electrodes to achieve high volumetric energy density but without compromising the ionic transportation. Herein, we prepared compact Li4Ti5O12 (LTO) microspheres consisting of densely packed primary nanoparticles. The real space distribution of lithium ions inside the compact LTO was revealed by using scanning transmission electron microscopy with electron energy loss spectroscopy (STEM-EELS) to identify the function of grain boundaries for lithium ion transportation during lithiation. The as-prepared LTO microspheres possess a high tap density (1.23 g cm-3) and an ultra-small specific surface area (2.40 m2 g-1). Impressively, the compact LTO microspheres present excellent electrochemical performance. At high rates of 5C, 10C and 20C, the LTO microspheres show a specific capacity of 146.6, 138.2 and 111 mA h g-1, respectively. The capacity retention remains at 97.8% at 5C after 500 cycles. The STEM-EELS results indicate that the lithiation reaction of LTO is firstly initiated at grain boundaries during the high rate lithiation process and then diffuses to the bulk area. The abundant grain boundaries in compact LTO microspheres can form a highly efficient conductive network to preferentially transport the ions, which contributes to high volumetric and gravimetric energy density simultaneously., Accepted Author Manuscript, RST/Fundamental Aspects of Materials and Energy, RST/Storage of Electrochemical Energy

Tin and its compounds hold promise for the development of high-capacity anode materials that could replace graphitic carbon used in current lithium-ion batteries. However, the introduced porosity in current electrode designs to buffer the volume changes of active materials during cycling does not afford high volumetric performance. Here, we show a strategy leveraging a sulfur sacrificial agent for controlled utility of void space in a tin oxide/graphene composite anode. In a typical synthesis using the capillary drying of graphene hydrogels, sulfur is employed with hard tin oxide nanoparticles inside the contraction hydrogels. The resultant graphene-caged tin oxide delivers an ultrahigh volumetric capacity of 2123 mAh cm–3 together with good cycling stability. Our results suggest not only a conversion-type composite anode that allows for good electrochemical characteristics, but also a general synthetic means to engineering the packing density of graphene nanosheets for high energy storage capabilities in small volumes.

Uncontrollable dendrite growth hinders the direct use of a lithium metal anode in batteries, even though it has the highest energy density of all anode materials. Achieving uniform lithium deposition is the key to solving this problem, but it is hard to be realized on a planar electrode surface. In this study, a thin lithiophilic layer consisting of vertically aligned CuO nanosheets directly grown on a planar Cu current collector is prepared by a simple wet chemical reaction. The lithiophilic nature of the CuO nanosheets reduces the polarization of the electrode, ensuring uniform Li nucleation and continuous smooth Li plating, which is difficult to realize on the normally used lithiophobic Cu current collector surface. The integration of the grown CuO arrays and the Cu current collector guarantees good electron transfer, and moreover, the vertically aligned channels between the CuO nanosheets guarantee fast ion diffusion and reduce the local current density. As a result, a high Columbic efficiency of 94% for 180 cycles at a current density of 1 mA cm−2 and a prolonged lifespan of a symmetrical cell (700 h at 0.5 mA cm−2) can be easily achieved, showing a simple but effective way to realize Li metal-based anode stabilization. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

The development of lithium (Li) metal anodes Li metal batteries faces huge challenges such as uncontrolled Li dendrite growth and large volume change during Li plating/stripping, resulting in severe capacity decay and high safety hazards. A 3D porous copper (Cu) current collector as a host for Li deposition can effectively settle these problems. However, constructing a uniform and compact 3D porous Cu structure is still an enormous challenge. Herein, an electrochemical etching method for Cu–Zinc (Zn) alloy is reported to precisely engrave a 3D Cu structure with uniform, smooth, and compact porous network. Such a continuous structure endows 3D Cu excellent mechanical properties and high electrical conductivity. The uniform and smooth pores with a large internal surface area ensures well dispersed current density for homogeneous Li metal deposition and accommodation. A smooth and stable solid electrolyte interphase is formed and meanwhile Li dendrites and dead Li are effectively suppressed. The Li metal anode conceived 3D Cu current collector can stably cycle for 400 h under an Li plating/stripping capacity of 1 mA h cm−2 and a current density of 1 mA cm−2. The Li@3D Cu\\LiFePO4 full cells present excellent cycling and rate performances. The electrochemical dealloying is a robust method to construct 3D Cu current collectors for dendrite-free Li metal anodes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

An in-depth understanding of (de)lithiation induced phase transition in electrode materials is crucial to grasp their structure-property relationships and provide guidance to the design of more desirable electrodes. By operando synchrotron XRD (SXRD) measurement and Density Functional Theory (DFT) based calculations, we discover a reversible first-order phase transition for the first time during (de)lithiation of CeO2 nanoparticles. The LixCeO2 compound phase is identified to possess the same fluorite crystal structure with FM3M space group as that of the pristine CeO2 nanoparticles. The SXRD determined lattice constant of the LixCeO2 compound phase is 0.551 nm, larger than that of 0.541 nm of the pristine CeO2 phase. The DFT calculations further reveal that the Li induced redistribution of electrons causes the increase in the Ce-O covalent bonding, the shuffling of Ce and O atoms, and the jump expansion of lattice constant, thereby resulting in the first-order phase transition. Discovering the new phase transition throws light upon the reaction between lithium and CeO2, and provides opportunities to the further investigation of properties and potential applications of LixCeO2. © 2016 American Chemical Society.