Title: A Long‐Cycle‐Life Lithium–CO2 Battery with Carbon Neutrality
Lithium–CO2 batteries are attractive energy‐storage systems for fulfilling the demand of future large‐scale applications such as electric vehicles due to their high specific energy density. However, a major challenge with Li–CO2 batteries is to attain reversible formation and decomposition of the Li2CO3 and carbon discharge products. A fully reversible Li–CO2 battery is developed with overall carbon neutrality using MoS2 nanoflakes as a cathode catalyst combined with an ionic liquid/dimethyl sulfoxide electrolyte. This combination of materials produces a multicomponent composite (Li2CO3/C) product. The battery shows a superior long cycle life of 500 for a fixed 500 mAh g−1 capacity per cycle, far exceeding the best cycling stability reported in Li–CO2 batteries. The long cycle life demonstrates that chemical transformations, making and breaking covalent C-O bonds can be used in energy‐storage systems. Theoretical calculations are used to deduce a mechanism for the reversible discharge/charge processes and explain how the carbon interface with Li2CO3 provides the electronic conduction needed for the oxidation of Li2CO3 and carbon to generate the CO2 on charge. This achievement paves the way for the use of CO2 in advanced energy‐storage systems. more »« less
Wang, Jianda; Powell, Matthew; Alcala, Ryan; Fetrow, Christopher; Zhou, Xiao-Dong; Wei, Shuya
(, Journal of the Electrochemical Society)
Doron Aurbach
(Ed.)
Rechargeable Li-CO2 batteries have emerged as promising candidates for next generation batteries due to their low cost, high theoretical capacity, and ability to capture the greenhouse gas CO2. However, these batteries still face challenges such as slow reaction kinetic and short cycle performance due to the accumulation of discharge products. To address this issue, it is necessary to design and develop high efficiency electrocatalysts that can improve CO2 reduction reaction. In this study, we report the use of NiMn2O4 electrocatalysts combined with multiwall carbon nanotubes as a cathode material in the Li-CO2 batteries. This combination proved effective in decomposing discharge products and enhancing cycle performance. The battery shows stable discharge–charge cycles for at least 30 cycles with a high limited capacity of 1000 mAh/g at current density of 100 mA/g. Furthermore, the battery with the NiMn2O4@CNT catalyst exhibits a reversible discharge capacity of 2636 mAh/g. To gain a better understanding of the reaction mechanism of Li-CO2 batteries, spectroscopies and microscopies were employed to identify the chemical composition of the discharge products. This work paves a pathway to increase cycle performance in metal-CO2 batteries, which could have significant implications for energy storage and the reduction of greenhouse gas emissions.
Sina Rastegar, Zahra Hemmat
(, ACS applied materials interfaces)
null
(Ed.)
Redox mediators (RMs) are solution-based additives that have been extensively used to reduce the charge potential and increase the energy efficiency of Li–oxygen (Li–O2) batteries. However, in the presence of RMs, achieving a long cycle-life operation of Li–O2 batteries at a high current rate is still a major challenge. In this study, we discover a novel synergy among InX3 (X = I and Br) bifunctional RMs, molybdenum disulfide (MoS2) nanoflakes as the air electrode, dimethyl sulfoxide/ionic liquid hybrid electrolyte, and LiTFSI as a salt to achieve long cycle-life operations of Li–O2 batteries in a dry air environment at high charge–discharge rates. Our results indicate that batteries with InI3 operate up to 450 cycles with a current density of 0.5 A g–1 and 217 cycles with a current density of 1 A g–1 at a fixed capacity of 1 A h g–1. Batteries with InBr3 operate up to 600 cycles with a current density of 1 A g–1. These batteries can also operate at a higher charge rate of 2 A g–1 up to 200 cycles (for InBr3) and 160 cycles (for InI3). Our experimental and computational results reveal that while X3– is the source of the redox mediator, LiX at the MoS2 cathode, In3+ reacts on the lithium anode side to form a protective layer on the surface, thus acting as an effective bifunctional RM in a dry air environment. This evidence for a simultaneous improvement in the current rates and cycle life of a battery in a dry air atmosphere opens a new direction for research for advanced energy storage systems.
Wang, Jianda; Powell, Matthew; Alcala, Ryan; Fetrow, Christopher; Zhou, Xiao-Dong; Wei, Shuya
(, Journal of The Electrochemical Society)
Rechargeable Li-CO2batteries have emerged as promising candidates for next generation batteries due to their low cost, high theoretical capacity, and ability to capture the greenhouse gas CO2. However, these batteries still face challenges such as slow reaction kinetic and short cycle performance due to the accumulation of discharge products. To address this issue, it is necessary to design and develop high efficiency electrocatalysts that can improve CO2reduction reaction. In this study, we report the use of NiMn2O4electrocatalysts combined with multiwall carbon nanotubes as a cathode material in the Li-CO2batteries. This combination proved effective in decomposing discharge products and enhancing cycle performance. The battery shows stable discharge–charge cycles for at least 30 cycles with a high limited capacity of 1000 mAh g−1at current density of 100 mA g−1. Furthermore, the battery with the NiMn2O4@CNT catalyst exhibits a reversible discharge capacity of 2636 mAh g−1. To gain a better understanding of the reaction mechanism of Li-CO2batteries, spectroscopies and microscopies were employed to identify the chemical composition of the discharge products. This work paves a pathway to increase cycle performance in metal-CO2batteries, which could have significant implications for energy storage and the reduction of greenhouse gas emissions.
Yu, Mingliang; Li, Bo; Wang, Jing; Xu, Yaobin; Zhang, Nan; Jung, Min Soo; Xue, Zhichen; Cho, Yukio; Kim, Min-Jae; Feng, Guangxia; et al
(, ChemRxiv)
Amidst the rapid expansion of the electric vehicle industry, the need for alternative battery technologies that balance economic viability with sustainability has never been more critical. Here, we report that common lithium salts of Li2CO3 and Li2SO4 are transformed into cathode active mass in Li-ion batteries by ball milling to form a composite with Cu2S. The optimal composite cathode comprising Li2CO3, Li2SO4, and Cu2S, with a practical active mass loading of 12.5-13.0 mg/cm2, demonstrates a reversible capacity of 247 mAh/g based on the total mass of Cu2S and the lithium salts, a specific energy of 716 Wh/kg, and a stable cycle life. This cathode chemistry rivals layered oxide cathodes of Li-ion batteries in energy density but at substantially reduced cost and ecological footprint. Mechanistic investigations reveal that in the composite Li2CO3 serves as the primary active mass, Li2SO4 enhances kinetic properties and reversibility, and Cu2S stabilizes the resulting anionic radicals for reversibility as a binding agent. Our findings pave the way for directly using precursor lithium salts as cathodes for Li-ion batteries to meet the ever-increasing market demands sustainably.
Conventional lithium-ion batteries are unable to meet the increasing demands for high-energy storage systems, because of their limited theoretical capacity. 1 In recent years, intensive attention has been paid to enhancing battery energy storage capability to satisfy the increasing energy demand in modern society and reduce the average energy capacity cost. Among the candidates for next generation high energy storage systems, the lithium sulfur battery is especially attractive because of its high theoretical specific energy (around 2600 W h kg-1) and potential cost reduction. In addition, sulfur is a cost effective and environmentally friendly material due to its abundance and low-toxicity. 2 Despite all of these advantages, the practical application of lithium sulfur batteries to date has been hindered by a series of obstacles, including low active material loading, poor cycle life, and sluggish sulfur conversion kinetics. 3 Achieving high mass loading cathode in the traditional 2D planar thick electrode has been challenged. The high distorsion of the traditional planar thick electrodes for ion/electron transfer leads to the limited utilization of active materials and high resistance, which eventually results in restricted energy density and accelerated electrode failure. 4 Furthermore, of the electrolyte to pores in the cathode and utilization ratio of active materials. Catalysts such as MnO 2 and Co dopants were employed to accelerate the sulfur conversion reaction during the charge and discharge process. 5 However, catalysts based on transition metals suffer from poor electronic conductivity. Other catalysts such as transition metal dopants are also limited due to the increased process complexities. . In addition, the severe shuttle effects in Li-S batteries may lead to fast failures of the battery. Constructing a protection layer on the separator for limiting the transmission of soluble polysulfides is considered an effective way to eliminate the shuttle phenomenon. However, the soluble sulfides still can largely dissolve around the cathode side causing the sluggish reaction condition for sulfur conversion. 5 To mitigate the issues above, herein we demonstrate a novel sulfur electrode design strategy enabled by additive manufacturing and oxidative vapor deposition (oCVD). Specifically, the electrode is strategically designed into a hierarchal hollow structure via stereolithography technique to increase sulfur usage. The active material concentration loaded to the battery cathode is controlled precisely during 3D printing by adjusting the number of printed layers. Owing to its freedom in geometry and structure, the suggested design is expected to improve the Li ions and electron transport rate considerably, and hence, the battery power density. The printed cathode is sintered at 700 °C at N 2 atmosphere to achieve carbonization of the cathode during which intrinsic carbon defects (e.g., pentagon carbon) as catalytic defect sites are in-situ generated on the cathode. The intrinsic carbon defects equipped with adequate electronic conductivity. The sintered 3D cathode is then transferred to the oCVD chamber for depositing a thin PEDOT layer as a protection layer to restrict dissolutions of sulfur compounds in the cathode. Density functional theory calculation reveals the electronic state variance between the structures with and without defects, the structure with defects demonstrates the higher kinetic condition for sulfur conversion. To further identify the favorable reaction dynamic process, the in-situ XRD is used to characterize the transformation between soluble and insoluble polysulfides, which is the main barrier in the charge and discharge process of Li-S batteries. The results show the oCVD coated 3D printed sulfur cathode exhibits a much higher kinetic process for sulfur conversion, which benefits from the highly tailored hierarchal hollow structure and the defects engineering on the cathode. Further, the oCVD coated 3D printed sulfur cathode also demonstrates higher stability during long cycling enabled by the oCVD PEDOT protection layer, which is verified by an absorption energy calculation of polysulfides at PEDOT. Such modeling and analysis help to elucidate the fundamental mechanisms that govern cathode performance and degradation in Li-S batteries. The current study also provides design strategies for the sulfur cathode as well as selection approaches to novel battery systems. References: Bhargav, A., (2020). Lithium-Sulfur Batteries: Attaining the Critical Metrics. Joule 4 , 285-291. Chung, S.-H., (2018). Progress on the Critical Parameters for Lithium–Sulfur Batteries to be Practically Viable. Advanced Functional Materials 28 , 1801188. Peng, H.-J.,(2017). Review on High-Loading and High-Energy Lithium–Sulfur Batteries. Advanced Energy Materials 7 , 1700260. Chu, T., (2021). 3D printing‐enabled advanced electrode architecture design. Carbon Energy 3 , 424-439. Shi, Z., (2021). Defect Engineering for Expediting Li–S Chemistry: Strategies, Mechanisms, and Perspectives. Advanced Energy Materials 11 . Figure 1
Alireza Ahmadiparidari, Robert E. A Long‐Cycle‐Life Lithium–CO2 Battery with Carbon Neutrality. Retrieved from https://par.nsf.gov/biblio/10113966. Advanced materials .
Alireza Ahmadiparidari, Robert E. A Long‐Cycle‐Life Lithium–CO2 Battery with Carbon Neutrality. Advanced materials, (). Retrieved from https://par.nsf.gov/biblio/10113966.
Alireza Ahmadiparidari, Robert E.
"A Long‐Cycle‐Life Lithium–CO2 Battery with Carbon Neutrality". Advanced materials (). Country unknown/Code not available. https://par.nsf.gov/biblio/10113966.
@article{osti_10113966,
place = {Country unknown/Code not available},
title = {A Long‐Cycle‐Life Lithium–CO2 Battery with Carbon Neutrality},
url = {https://par.nsf.gov/biblio/10113966},
abstractNote = {Lithium–CO2 batteries are attractive energy‐storage systems for fulfilling the demand of future large‐scale applications such as electric vehicles due to their high specific energy density. However, a major challenge with Li–CO2 batteries is to attain reversible formation and decomposition of the Li2CO3 and carbon discharge products. A fully reversible Li–CO2 battery is developed with overall carbon neutrality using MoS2 nanoflakes as a cathode catalyst combined with an ionic liquid/dimethyl sulfoxide electrolyte. This combination of materials produces a multicomponent composite (Li2CO3/C) product. The battery shows a superior long cycle life of 500 for a fixed 500 mAh g−1 capacity per cycle, far exceeding the best cycling stability reported in Li–CO2 batteries. The long cycle life demonstrates that chemical transformations, making and breaking covalent C-O bonds can be used in energy‐storage systems. Theoretical calculations are used to deduce a mechanism for the reversible discharge/charge processes and explain how the carbon interface with Li2CO3 provides the electronic conduction needed for the oxidation of Li2CO3 and carbon to generate the CO2 on charge. This achievement paves the way for the use of CO2 in advanced energy‐storage systems.},
journal = {Advanced materials},
author = {Alireza Ahmadiparidari, Robert E},
}
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