Journal articles on the topic 'Li metal free full cell'
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1
Sun, Ju, Jiaxing Liang, Junnan Liu, Wenyan Shi, Neeraj Sharma, Wei Lv, Ruitao Lv, Quan-Hong Yang, Rose Amal, and Da-Wei Wang. "Towards a reliable Li-metal-free LiNO3-free Li-ion polysulphide full cell via parallel interface engineering." Energy & Environmental Science 11, no. 9 (2018): 2509–20. http://dx.doi.org/10.1039/c8ee00937f.
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Chen, Jie, Bin He, Zexiao Cheng, Zhixiang Rao, Danqi He, Dezhong Liu, Xiang Li, Lixia Yuan, Yunhui Huang, and Zhen Li. "Reactivating Dead Li by Shuttle Effect for High-Performance Anode-Free Li Metal Batteries." Journal of The Electrochemical Society 168, no. 12 (December 1, 2021): 120535. http://dx.doi.org/10.1149/1945-7111/ac42a5.
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Anode-free Li metal batteries are considered the ultimate configuration for next-generation high energy-density Li-based batteries due to the elimination of excess Li metal. However, the limited Li source aggravates issues such as dendrite growth and “dead” Li formation. Any Li loss caused by the SEI formation and dead Li has a great influence on the performance of the full cell. Here, we introduce LiI with shuttle effect to suppress the Li dendrites and reactivate the dead Li in the anode-free LiFePO4 (LFP) ∣Cu full cells. During cycling, the iodine transforms between I− and I3 −, and a chemical reactions occur spontaneously between I3 − and Li dendrites or dead Li. The generated Li+ in the electrolyte remains active in the following cycling. The anode-free LFP∣Cu cells deliver an initial discharge capacity of 139 mAh g−1 and maintain capacities of 100 mAh g−1 with a capacity retention of 72% after 100 cycles. Both the anode-free LFP∣Cu coin cells and pouch cells with LiI additive show much-improved performances. This work provides a new strategy for high-performance anode-free Li metal batteries.
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Weldeyohannes, Haile Hisho, Wei-Nien Su, and Bing-Joe Hwang. "Regulating Lithium Metal Deposition for Safe Cell Operation and to Extend Cyclic Performance of an Anode-Free Lithium Metal Battery." ECS Meeting Abstracts MA2022-01, no. 2 (July 7, 2022): 426. http://dx.doi.org/10.1149/ma2022-012426mtgabs.
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Using the ideal Lithium metal (Li) as an anode material for Lithium metal batteries (LMBs) displays considerable potential in enlightening energy density and power density than conventional lithium-ion batteries (LIBs). Nevertheless, the low Coulombic efficiency, significant volume changes during operation, which reduces electrode mechanical stability, and Lithium (Li) dendrites formed and growth from nonuniform Li deposition during cell operation causes safety issues and limits potential uses of Li as an anode material for LMBs. Recently, anode free (Lithium free) lithium metal batteries (AFLMBs) protocol have got great attention due to their higher energy density, reduces cell weight, costs effectiveness, easy fabrication, and safety during the process of cell manufacture. Nevertheless, in AFLMBs, the uncontrolled plating of lithium on bare copper foil imposes a more severe lithium dendrite growth. Hence, planning proper design on an anode current collector which is appropriate for AFLMBs is essential. Herein, we handle the growth of lithium dendrite by guiding lithium metal deposition site to the backside of the gold-sputtered perforated polyimide film (PI@Au), which used as an anode current collector. Hence, metallic lithium (Li) starts to plate on the modified PI@Au surface, and sequentially, growth of Li takes place in the direction away from the separator face (ASF). This backside deposition and growth approach allow the battery to operate safely, even when lithium dendrite exists. . Surprisingly, the dendrite-free surface on the separator-facing side (SF) of PI@Au anode reveals significantly improved cycling stability. As a result PI@Au//Li cell (2 mAh/cm2 and 0.5 mA/cm2) offers stable cycling performance for 1400 h without significant voltage polarization. Conversely, Cu//Li cell cycling with results higher voltage hysteresis and face short-circuit below 600 h at same working conditions. Besides, PI@Au//LFP anode-free full cell configuration maintained 20 % capacity retention (CR) with average Coulombic efficiency of 98.7 % after 340 cycles (0.5 mA/cm2). On the contrary, the Cu//LFP full cell runs only for 165 cycles under the same value of CR. Guiding the plating of Li to the backside of perforated polyimide film insights into an innovative technique for developing ultra-safe AFLMBs and also proves the viability of the electrical insulator substrates as anode current collectors by improving their conductivity and lithiophilicity.
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Wang, Li-Min, Xiao-Kuan Ban, Zong-Zi Jin, Ran-Ran Peng, Chu-Sheng Chen, and Chun-Hua Chen. "In situ coating of a lithiophilic interphase on a biporous Cu scaffold with vertical microchannels for dendrite-free Li metal batteries." Journal of Materials Chemistry A 9, no. 23 (2021): 13642–52. http://dx.doi.org/10.1039/d1ta03037j.
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Copper oxide is coated in situ on a phase inversion-derived Cu scaffold for Li metal anodes, which exhibit a low nucleation overpotential, high coulombic efficiency and a long lifespan. The scaffold-Li//NCM full cell exhibits good cycling stability.
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Zhou, Chengtian, and Venkataraman Thangadurai. "Electrolyte Design for Anode-Free Lithium Metal Batteries." ECS Meeting Abstracts MA2022-01, no. 2 (July 7, 2022): 199. http://dx.doi.org/10.1149/ma2022-012199mtgabs.
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Current lithium-ion batteries (LIBs) are approaching their energy density limits and thus may not keep up with the ever-increasing demand for higher specific energy density in today’s energy storage and power applications. Anode-free lithium metal batteries (AFLMBs) utilize the full theoretical capacity of Li metal anode (3860 mAh g-1, ten times higher than lithiated graphite) and offer lower cost and better safety than cells with Li excess. However, due to the low efficiency of Li deposition and stripping, AFLMBs suffer from rapid capacity loss. In this presentation, we will discuss a unique coin cell configuration design with high compression for AFLMBs. The high pressure leads to more stable cycling performance, providing a more accurate assessment of AFLMBs.1 A carbonate-glyme hybrid electrolyte for AFLMB is demonstrated with a capacity retention of 73% for 50 cycles. The hybrid electrolyte possesses a unique solvation structure, where diglyme solvates both Li-ions and film-forming additive, while carbonates dilute the mixture, enabling facile ion migrations.2 C. Zhou, A. J. Samson, M. A. Garakani, and V. Thangadurai, J. Electrochem. Soc., 168, 060532 (2021). C. Zhou et al., Energy Storage Mater., 42, 295–306 (2021) https://doi.org/10.1016/j.ensm.2021.07.043.
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Chen, Jie, Linna Dai, Pei Hu, and Zhen Li. "Facile One-Step Heat Treatment of Cu Foil for Stable Anode-Free Li Metal Batteries." Molecules 28, no. 2 (January 5, 2023): 548. http://dx.doi.org/10.3390/molecules28020548.
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The anode-free lithium metal battery (AFLMB) is attractive for its ultimate high energy density. However, the poor cycling lifespan caused by the unstable anode interphase and the continuous Li consumption severely limits its practical application. Here, facile one-step heat treatment of the Cu foil current collectors before the cell assembly is proposed to improve the anode interphase during the cycling. After heat treatment of the Cu foil, homogeneous Li deposition is achieved during cycling because of the smoother surface morphology and enhanced lithiophilicity of the heat-treated Cu foil. In addition, Li2O-riched SEI is obtained after the Li deposition due to the generated Cu2O on the heat-treated Cu foil. The stable anode SEI can be successfully established and the Li consumption can be slowed down. Therefore, the cycling stability of the heat-treated Cu foil electrode is greatly improved in the Li|Cu half-cell and the symmetric cell. Moreover, the corresponding LFP|Cu anode-free full cell shows a much-improved capacity retention of 62% after 100 cycles, compared to that of 43% in the cell with the commercial Cu foil. This kind of facile but effective modification of current collectors can be directly applied in the anode-free batteries, which are assembled without Li pre-deposition on the anode.
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Ma, Yu Hong. "Reinforced Hydrophobic Molecular Layer Promoting Waterproof Lithium for High-Performance Lithium-Metal Batteries." Key Engineering Materials 939 (January 25, 2023): 117–22. http://dx.doi.org/10.4028/p-lm3si4.
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The employment of lithium (Li) metal is crucial to sustainable Li metal batteries (LMBs) with realistically high energy density. The management and usage of Li in reality, however, remain high challenge due to the desirable of obtaining an undamaged Li structure arising from the indispensable in extenuating strongly environmental dependence of Li during stored procedure and minimizing the Li depletion and pulverization on long-term cycles. Herein, we impair the molecular hydrogen bonding cooperation between lithium and water molecules on the surface of Li to demonstrate an achievement of environmental independent and durable Li via integrating a reinforced molecular hydrophobic interface on the surface of Li. As a result, the molecular hydrophobic interface modified Li metal can exhibit dendrite-free Li deposition and achieve stable operation for 200 cycles in Li-S full cell at a current of 1 C.
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Wang, Kang, Derong Liu, Ping Yu, Hongyu Gong, Xiaoping Jiang, Meng Gao, and Dongwei Li. "Highly Lithiophilic Three-Dimension Framework of Vertical CuO Nanorod Arrays Decorated Carbon Cloth for Dendrite-Free Li Metal Anode." Batteries 9, no. 2 (February 10, 2023): 127. http://dx.doi.org/10.3390/batteries9020127.
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An Li metal anode has been proposed as a promising candidate for high energy density electrode material. However, the direct use of Li metal can lead to uncontrollable dendrite growth and massive volume expansion, which generates severe safety hazards and hinders practical application. Herein, we developed a novel Li anode by thermal infusion into three-dimensional (3D) carbon cloth (CC) modified with lithiophilic CuO nanorod arrays (denoted as Li@CuO−CC). The 3D CC offers sufficient space for Li storage and adequate electrolyte/electrode contact for fast charge transfer. The uniformly distributed CuO nanorod arrays can improve the lithiophilicity of CC and redistribute the Li-ion flux on the substrate, leading to uniform Li stripping/plating behavior. As a result, the Li@CuO−CC electrode exhibits a dendrite-free feature and superior cycling performance over 1000 h with low overpotential (12 mV) at a current density of 1 mA cm−2 in the symmetrical cell without significant fluctuations. When coupled with an LiFePO4 cathode, the full cell displays high specific capacity (133.8 mAh g−1 at 1 C), outstanding rate performance, and cycle stability (78.7% capacity retention after 600 cycles at 1 C). This work opens a new approach for the development of construction of an advanced anode for Li metal batteries.
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Shi, Qiuwei, Yiren Zhong, Min Wu, Hongzhi Wang, and Hailiang Wang. "High-capacity rechargeable batteries based on deeply cyclable lithium metal anodes." Proceedings of the National Academy of Sciences 115, no. 22 (May 14, 2018): 5676–80. http://dx.doi.org/10.1073/pnas.1803634115.
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Discovering new chemistry and materials to enable rechargeable batteries with higher capacity and energy density is of paramount importance. While Li metal is the ultimate choice of a battery anode, its low efficiency is still yet to be overcome. Many strategies have been developed to improve the reversibility and cycle life of Li metal electrodes. However, almost all of the results are limited to shallow cycling conditions (e.g., 1 mAh cm−2) and thus inefficient utilization (<1%). Here we achieve Li metal electrodes that can be deeply cycled at high capacities of 10 and 20 mAh cm−2 with average Coulombic efficiency >98% in a commercial LiPF6/carbonate electrolyte. The high performance is enabled by slow release of LiNO3 into the electrolyte and its subsequent decomposition to form a Li3N and lithium oxynitrides (LiNxOy)-containing protective layer which renders reversible, dendrite-free, and highly dense Li metal deposition. Using the developed Li metal electrodes, we construct a Li-MoS3 full cell with the anode and cathode materials in a close-to-stoichiometric amount ratio. In terms of both capacity and energy, normalized to either the electrode area or the total mass of the electrode materials, our cell significantly outperforms other laboratory-scale battery cells as well as the state-of-the-art Li ion batteries on the market.
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Park, Se Hwan, Dayoung Jun, Gyu Hyeon Lee, Seong Gyu Lee, Ji Eun Jung, and Yun Jung Lee. "Designing the 3D Porous Anode Based on Pore Size Dependent Li Deposition Behavior for Reversible Li Metal-Free Solid-State-Batteries." ECS Meeting Abstracts MA2022-02, no. 4 (October 9, 2022): 470. http://dx.doi.org/10.1149/ma2022-024470mtgabs.
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Li metal-based all-solid-state batteries (ASSBs) can potentially combine the high energy of Li metal anodes and the safety of ASSBs. Among Li metal-based ASSBs, lithium-free or anodeless ASSBs are considered optimal battery configurations because of their higher energy density and economic advantages attributed to the absence of Li metal during the battery assembly process. Despite the extensive interest in Li-free ASSBs, they continue to suffer from low Coulombic efficiency and poor cycle performance. One reason for this inferior performance is the unstable interface between the current collector and solid electrolyte (SE), which can eventually lead to inhomogeneous Li deposition, dendritic Li growth, and internal short circuits. Various approaches including 3D porous anodes have been proposed to control the Li deposition behavior and improve the reversibility of anodeless ASSBs; however, there is no clarity on the mechanism and conditions for determining the Li deposition behavior in this emerging system. In this study, we systematically investigate the Li deposition behavior depending on the pore size of 3D anode and successfully demonstrate the strategy to obtain a highly reversible 3D porous anode for Li-free ASSBs. We found that more Li deposits could be accommodated within the pores of the anode with a smaller pore size using stacked Ni particles as the Li-hosting porous anode; this implies that the Li movement into the anode occurs via diffusional Coble creep. We proposed the modification of the Ni surface with carbon coating and Ag nanoparticle decoration (Ni_C_Ag particles) to further improve the Li storage capacity of the Ni-based 3D anode and, thereby, secure the interfacial contact between the 3D Ni anode and SE. The resulting Ni_C_Ag 3D anode successfully accommodated the entire Li deposit of 2 mAh cm−2 within the porous architecture without the separation of the anode/SE interface. We clarified the improved Li storage capacity of the Ni_C_Ag anode as follows. (1) C and especially Ag electrochemically react with Li ions above 0 V; thus, Li ions can be transported to 3D Ni_C_Ag porous anode before Li deposition at the SE/anode interface at < 0 V. Further, the high Li ion diffusion coefficient of lithiated carbon and Li-Ag alloy can further reduce Li ions within the pores of the 3D anode; therefore, Li deposition can occur within the porous 3D Ni anode. (2) Lithiophilic C and Ag facilitated the movement of Li via diffusional Coble creep. In particular, Ag with solid solubility in Li (Li(Ag)) can significantly enhance Li adatom mobility because of the identical structure of Li(Ag) with pure Li. (3) Li(Ag) is widely known to lower the energy barrier for Li nucleation. With the significantly reduced nucleation overpotential and interfacial resistance, the Ni_C_Ag anode showed high reversibility in Li deposition and stripping. The Ni_C_Ag anode could be cycled for more than 60 and 100 cycles with Li3PS4 and Li6PS5Cl0.5Br0.5 SE in half cells with a capacity limit of 2 mAh cm−2 and a current density of 0.5 mA cm− 2maintaining the CE of 97.9% and 96.9 %, respectively. Further, the synergistic effects of the stable anode/SE interface and reduced nucleation energy barrier enable stable NCM full-cell cycling at a room temperature of 30 °C. The NCM811 cathode/Ni_C_Ag anode full cell in the Li-free configuration showed an initial areal discharge capacity of 2 mAh cm−2, and it operated stably with a CE of 99.47% for 100 cycles. Figure 1
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Liu, Qingsong, Yue Wang, Jian Zhang, Jianquan Liang, Shuaifeng Lou, Ge Zhu, Hanwen An, et al. "Effective electron–ion percolation network enabled by in situ lithiation for dendrite-free Li metal battery." Applied Physics Letters 121, no. 15 (October 10, 2022): 153901. http://dx.doi.org/10.1063/5.0108998.
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The development of a lithium metal anode has been hindered by the problem of lithium dendrites. The fast and homogeneous ion transport to achieve even lithium plating is challenging but still remains elusive. Improving the single conduction of ions or electrons is not enough to achieve dendrite-free and long life Li–metal composite electrodes. Herein, we use in situ lithiation and electroplating methods to construct an effective mixed electron–ion percolation network composite anode. The mixed ion–electron conductive framework can build a stable interface that provides nucleation sites for Li plating. At the same time, the 3D percolation network composed of 3D nanosheets can facilitate the fast transport of ions and electrons, enabling uniform lithium plating inside the skeleton. As a result, the composite anodes exhibit a stable dendrite-free Li stripping/plating process with low overpotential. Furthermore, the full cell using the composite anode coupled with the LiFePO4 cathode displays high cycle stability with a capacity retention rate of about 100% after 500 cycles. The present strategy of the mixed ion–electron conductive skeleton could further promote the development of the next-generation lithium metal anode.
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Shin, GeunHyeong, EunAe Cho, Hyeonmuk Kang, Taehee Kim, GyuSeong Hwang, and Junho Lee. "Metal Nitrate Embedded Polymeric Interlayer for Improving Cycling Stability of Li Metal Anode." ECS Meeting Abstracts MA2022-01, no. 2 (July 7, 2022): 262. http://dx.doi.org/10.1149/ma2022-012262mtgabs.
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Among secondary batteries using lithium, the use of lithium metal anodes for high capacity has become a hot topic. However, in lithium metal anodes, there is a major problem of dendritic growth and research are actively underway to address the issue. And it is reported that it is possible to improve the stability of Li metal anode by facilitating the movement of lithium ions through various additives to suppress dendritic growth and to make robust and stable SEI layer. To address the issue of dendritic growth of Li, using cesium nitrate is selected to improve the stability of the anode based on a mechanism by which a nitrogen-rich compounds lithiophilic to transport Li ion uniformly are formed in the SEI layer. And also the cesium element induces an cation electrostatic shielding effect while lithium metal is deposited and grown in the anode. In addition, since metal nitrates have very low solubility in carbonate-based electrolytes, polymer nanofiber-interlayer is synthesized by electrospinning to support metal nitrate and supply nitrate continuously and stably, while interlayer does not interfere with the movement of lithium ions through the nanofiber layer. In summary, a metal nitrate embedded polymer nanofiber layer is synthesized through an electrospinning method, then stabilization of a lithium surface and stability of a lithium metal anode are obtained by using an intermediate layer, and a relationship between an additive and SEI formation is identified at a limited solubility in carbonate electrolytes. The study result demonstrates that the lifetime of symmetric Li-Li cells and full cell with LCO cathodes improved greatly. And the deposition morphology of Li become dendrite-free and more uniform.
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Fang, Yongjin, Song Lin Zhang, Zhi-Peng Wu, Deyan Luan, and Xiong Wen (David) Lou. "A highly stable lithium metal anode enabled by Ag nanoparticle–embedded nitrogen-doped carbon macroporous fibers." Science Advances 7, no. 21 (May 2021): eabg3626. http://dx.doi.org/10.1126/sciadv.abg3626.
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Lithium metal has been considered as an ideal anode candidate for future high energy density lithium batteries. Herein, we develop a three-dimensional (3D) hybrid host consisting of Ag nanoparticle–embedded nitrogen-doped carbon macroporous fibers (denoted as Ag@CMFs) with selective nucleation and targeted deposition of Li. The 3D macroporous framework can inhibit the formation of dendritic Li by capturing metallic Li in the matrix as well as reducing local current density, the lithiophilic nitrogen-doped carbons act as homogeneous nucleation sites owing to the small nucleation barrier, and the Ag nanoparticles improve the Li nucleation and growth behavior with the reversible solid solution–based alloying reaction. As a result, the Ag@CMF composite enables a dendrite-free Li plating/stripping behavior with high Coulombic efficiency for more than 500 cycles. When this anode is coupled with a commercial LiFePO4 cathode, the assembled full cell manifests high rate capability and stable cycling life.
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Weeks, Jason Alexander. "Camphene-Assisted Fabrication of Free-Standing Lithium-Ion Battery Electrode Composites." ECS Meeting Abstracts MA2022-02, no. 7 (October 9, 2022): 2414. http://dx.doi.org/10.1149/ma2022-0272414mtgabs.
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Free-standing electrode (FSE) architectures hold the potential to dramatically increase the gravimetric and volumetric energy density of LIBs by eliminating the parasitic dead weight and volume associated with traditional metal foil current collectors, however current FSE fabrication methods suffer from insufficient mechanical stability, electrochemical performance, or industrial adoptability. Here, we demonstrate a scalable camphene-assisted fabrication method that allows simultaneous casting and templating of FSEs comprised of common LIB materials with performance superior to foil-cast counterparts. These porous, lightweight, and robust electrodes simultaneously enable enhanced rate performance by improving mass and ion transport within the percolating conductive carbon pore network and eliminating current collectors for efficient and stable Li+ storage (> 1000 cycle in half-cells) at increased gravimetric and areal energy densities. Compared to conventional foil-cast counterparts, the camphene-derived electrodes exhibit ~1.5x enhanced gravimetric energy density, increased rate capability, and improved capacity retention in coin-cell configurations. A full cell with free-standing anode and cathode cycled for over 250 cycles with greater than 80% capacity retention at an areal capacity of 0.73 mAh/cm2. This active-material-agnostic electrode fabrication method holds potential to tailor the morphology of flexible, current-collector-free electrodes to optimize LIBs for high power or high energy density Li+ storage and is applicable to other electrochemical technologies and advanced manufacturing methods.
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Amici, Julia, Claudia Torchio, Daniele Versaci, Davide Dessantis, Andrea Marchisio, Fabrizio Caldera, Federico Bella, Carlotta Francia, and Silvia Bodoardo. "Nanosponge-Based Composite Gel Polymer Electrolyte for Safer Li-O2 Batteries." Polymers 13, no. 10 (May 17, 2021): 1625. http://dx.doi.org/10.3390/polym13101625.
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Li-O2 batteries represent a promising rechargeable battery candidate to answer the energy challenges our world is facing, thanks to their ultrahigh theoretical energy density. However, the poor cycling stability of the Li-O2 system and, overall, important safety issues due to the formation of Li dendrites, combined with the use of organic liquid electrolytes and O2 cross-over, inhibit their practical applications. As a solution to these various issues, we propose a composite gel polymer electrolyte consisting of a highly cross-linked polymer matrix, containing a dextrin-based nanosponge and activated with a liquid electrolyte. The polymer matrix, easily obtained by thermally activated one pot free radical polymerization in bulk, allows to limit dendrite nucleation and growth thanks to its cross-linked structure. At the same time, the nanosponge limits the O2 cross-over and avoids the formation of crystalline domains in the polymer matrix, which, combined with the liquid electrolyte, allows a good ionic conductivity at room temperature. Such a composite gel polymer electrolyte, tested in a cell containing Li metal as anode and a simple commercial gas diffusion layer, without any catalyst, as cathode demonstrates a full capacity of 5.05 mAh cm−2 as well as improved reversibility upon cycling, compared to a cell containing liquid electrolyte.
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Xu, Zhixiao, and Xiaolei Wang. "3D Heteroatom-Doped Carbon for Lithium/Zinc Metal Anodes." ECS Meeting Abstracts MA2022-01, no. 7 (July 7, 2022): 661. http://dx.doi.org/10.1149/ma2022-017661mtgabs.
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With the advance of portable electronics and electric vehicles, graphite-based lithium-ion batteries with moderate energy densities can not meet the ever-increasing energy demand which calls for high-energy anode materials.[1] Among candidates, lithium metal has been regarded as the ultimate anode for rechargeable batteries because of its highest theoretical specific capacity (3860 mA h g−1) and lowest electrochemical potential (−3.040 V vs SHE).[1] Unfortunately, only primary lithium metal batteries (LMBs) but no rechargeable ones have been commercialized due to the low Coulombic efficiency (CE) and dendritic growth during Li plating/stripping, resulting in short cycle life and safety concerns. Recently, it has been clarified that LMBs failure majorly occur because of low CE, active Li consumption or electrolytes depletion and the low CE is largely caused by “dead” Li formation, which is associated with Li deposition morphology.[2] As such, it is of great significance to develop methods to regulate the Li plating/stripping behavior and minimize the generation of inactive Li deposits for practical application of LMBs. Many strategies have been proposed to improve CE, inhibit Li dendrites, and extend cycle life, including Li host design,[3] electrolyte engineering,[4] separator modification,[5] and artificial solid electrolyte interphase (SEI) construction.[6] In this work, we report the large-area coating of polymer-derived N,O-codoped vertically aligned carbon sheet arrays on commercial Cu foil current collector (NOCA@Cu) as the efficient 3D host toward safe and dendrite-free LMBs through polymer interfacial self-assembly and morphology-preserved carbonization.[7] Interestingly, it is found that the different orientation mode, vertical or horizontal, of polymer layers on the Cu surface will have a huge influence on heteroatom dopants and topological defects of derived carbon. The optimized NOCA@Cu delivers excellent performance with a high CE of 91–93% and long life up to 600 cycles in the carbonate electrolyte as well as 98.5% CE and stable cycling up to 1300 h in ether electrolyte, much better than horizontal carbon film-coated Cu and pristine Cu. On the other hand, aqueous zinc metal-based energy devices show great promise for large-scale energy storage due to the advantage of Zn metals including high theoretical capacity (gravimetric: 820 mAh g−1), suitable redox potential (−0.764 V vs. SHE), high safety, cost effectiveness, and eco-friendliness.[8] However, similar to Li metal, Zn metal also shows poor reversibility of deposition/dissolution.[9] This poor reversibility is mainly caused by the low CE and dendritic growth of Zn metal accompanied by side reactions from metal corrosion and hydrogen evolution due to water decomposition. [10] Hence, it is significant to develop dendrite-free Zn metal anodes with high CE for rechargeable devices, which unfortunately is still challenging as with Li metal anodes. Similar strategies have been proposed to tackle the issues, such as host construction,[11] interfacial protection,[12] and electrolyte engineering.[13] Despite the progress, most of reported Zn anode only experienced low depth of discharge (DOD, <1%),[14] which will considerably lower cell-level energy densities. As such, construction of Zn hosts, e.g., carbon-rich nanomaterials, to regulate the plating/stripping of Zn metal anode under high DOD is important to achieve high cell-level energy densities. As potential carbon hosts, 3D carbons with highly exposed surface area and hierarchically oriented building blocks could homogenize ionic flux, decrease local current densities, and guide Zn deposition in a unique way.[15] In this work, we firstly regulate heteroatom-doped 3D carbon host for high-DOD Zn metal chemistry, including Coulombic efficiency, deposition morphology, and full cell applications. DFT calculations reveal that among oxygen/nitrogen dopants the ether (C-O), carboxylic (-O-C=O-) and pyrrolic N groups show strong binding with Zn, making them favorable heterogeneous nucleation sites for zinc growth. Accordingly, monomers enriched with those O/N groups were rationally selected and corresponding polymers were prepared via controlled self-assembly and converted to carbon with different morphologies and sizes. Among carbon hosts, carbon flowers (Cflower) enable best performance with high CE values of 97~99% at current densities of 0.5~10 mA cm-2, surpassing other structured hosts. Reference [1] Chem. Rev. 2017, 117, 10403. [2] Nature 2019, 572, 511. [3] Carbon Energy 2021, 1. [4] Adv. Energy Mater. 2017, 7, 1602011. [5] ACS Nano 2017, 11, 6114. [6] Nat. Nanotechnol. 2014, 9, 618. [7] Adv. Funct. Mater. 2021, 31, 2102354. [8] Chem. Rev. 2020, 120, 7795. [9] Angew. Chem. Int. Ed. 2020, 59, 13180. [10] ACS Energy Lett. 2020, 5, 3569. [11] Adv. Mater. 2020, 32, 1906803. [12] Adv. Energy Mater. 2018, 8, 1801090. [13] Nat. Mater. 2018, 17, 543. [14] Adv. Mater. 2019, 0, 1900668. [15] Electrochem. Energ. Rev. 2021, 4, 269.
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Teppor, Patrick, Rutha Jäger, Meelis Härmas, Jaan Aruväli, Olga Volobujeva, Miriam Koppel, and Enn Lust. "Bifunctional Platinum-Free Mixed Metal Oxygen Electrocatalysts Based on Naturally Abundant Peat." ECS Meeting Abstracts MA2022-01, no. 35 (July 7, 2022): 1484. http://dx.doi.org/10.1149/ma2022-01351484mtgabs.
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A functioning hydrogen economy requires efficient ways of producing and utilizing hydrogen via electrolyzers and fuel cells. The commercialization of these devices is well underway but their considerable capital costs still inhibit faster adoption by society1,2. One pathway towards more inexpensive devices is by tackling their respective bottlenecks, the oxygen evolution and reduction reactions, which currently require catalyst materials comprised of scarce precious metals. Intensive research is being conducted to introduce and develop suitable replacements for these catalysts. In this field, non-platinum group metal (NPGM) type catalysts have gained significant attention2,3. We present several NPGM-type oxygen electrocatalysts synthesized by modifying peat-derived carbon with nitrogen and different combinations of transition metals (Fe, Co, Ni). The obtained catalysts were characterized with various methods to elucidate their structure-reactivity relations. Namely, SEM-EDS was used to confirm that the modification of peat-derived carbon was successful. Additionally, the various metal alloy species found in the catalysts were identified via X-ray diffraction analysis. The excellent bifunctional electrocatalytic activity of the peat-based materials towards oxygen evolution and reduction was confirmed with rotating disc electrode measurements conducted in a 0.1 M KOH solution. Correlations between the physical and electrochemical properties of the catalysts were established and analyzed. Acknowledgments This work was supported by the EU through the European Regional Development Fund under projects TK141 “Advanced materials and high-technology devices for energy recuperation systems” (2014-2020.4.01.15-0011), NAMUR “Nanomaterials - research and applications” (3.2.0304.12-0397), PRG676 “Development of express analysis methods for micro-mesoporous materials for Estonian peat derived carbon supercapacitors” (01.01.2020–31.12.2024) and PUT1581 (1.01.2017–31.12.2020). References E4tech, 2021, The Fuel Cell Industry Review 2020. C. Lei, S. Lyu, J. Si, B. Yang, Z. Li, L. Lei, Z. Wen, G. Wu, Y. Hou, ChemCatChem 2019, 11, 5855. L. Osmieri, J. Park, D. Cullen, P. Zelenay, D. Myers, K. Neyerlin, Curr Opin Electrochem 2021, 25, 100627. Figure 1
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He, Jiarui, and Arumugam Manthiram. "3D CoSe@C Aerogel as a Host for Dendrite‐Free Lithium‐Metal Anode and Efficient Sulfur Cathode in Li–S Full Cells." Advanced Energy Materials 10, no. 41 (September 22, 2020): 2002654. http://dx.doi.org/10.1002/aenm.202002654.
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Ratso, Sander, Peter Robert Walke, Valdek Mikli, Jānis Ločs, Krišjānis Šmits, Virgīnija Vītola, Andris Sutka, and Ivar Kruusenberg. "CO2 Turned into a Nitrogen Doped Carbon Catalyst for the Fuel Cell and Metal-Air Battery Applications." ECS Meeting Abstracts MA2022-01, no. 35 (July 7, 2022): 1515. http://dx.doi.org/10.1149/ma2022-01351515mtgabs.
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Metal-free catalysts based on nitrogen-doped carbon are among the most promising replacements for Pt-based materials on polymer electrolyte membrane fuel cell (PEMFC) cathodes due to their inherent stability (lack of metal atoms bypasses most of the degradation mechanisms encountered in metal-based non-precious metal catalysts). However, the production of carbon nanostructures that have suitable oxygen reduction reaction (ORR) activities for fuel cell cathode use can create massive amounts of CO2 as a by-product, which counteracts the environmental friendliness of fuel cells. Here, we demonstrate a new method for creating ORR catalysts directly from CO2, which can produce a catalyst with a negative carbon footprint instead of a positive one. Via a fused Li-K carbonate eutectic mixture or pure Li2CO3, CO2 was split into gaseous oxygen and solid carbon, which was then doped with nitrogen using a pyrolysis process with the presence of dicyandiamide and polyvinylpyrrolidone. A thorough physico-chemical characterization of the catalyst materials is presented alongside their electrocatalytic properties for the ORR. The reasons for the properties of the resulting carbon depending on the electrolyte mixture for CO2 electrolysis and deposition temperature are explored. The best performing material had ORR activity nearing that of Pt/C, showing the potential that this method has for creating competitive catalysts while remaining environmentally benign [1]. References Ratso, S.; Walke, P. R.; Mikli, V.; Ločs, J.; Šmits, K.; Vītola, V.; Šutka, A.; Kruusenberg, I. CO2 Turned into a Nitrogen Doped Carbon Catalyst for Fuel Cells and Metal–Air Battery Applications. Green Chem. 2021, 23 (12), 4435–4445. https://doi.org/10.1039/D1GC00659B. Figure 1
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Shim, Jinha, Woowon Chung, and Jin Ho Bang. "Mn Interdiffusion Mobility Controlled By Simple Drying Process for Cobalt Free Core-Shell Ni Rich Cathode Material in Lithium Ion Batteries." ECS Meeting Abstracts MA2022-02, no. 7 (October 9, 2022): 2413. http://dx.doi.org/10.1149/ma2022-0272413mtgabs.
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Lithium-ion batteries (LIBs) become an essential part of many portable devices and even electric vehicles than ever before. Among the various cathode materials, Ni rich layered cathode material has big attention because it has higher specific capacity and energy density. However, at a delithiated state, unstable Ni4+ leads to oxygen release and structural degradation and as a result, irreversible phase transition from R3m to electrochemical inactive Fm3m is observed. So, various strategy is applying to overcome this limitation like three-component system (NCM) or surface coating. However, NCM still cannot solve that problem perfectly and surface coating makes a problem like reducing specific capacity caused by insulating coating material (Al2O3, MnO2...etc) And also, this day, Co free structure of Ni rich cathode material has received more great attention as an alternative to NCM because of its hazardous toxicity and increasing price of Co. At this perspective, many studies have demonstrated Core-Shell or FCG (Full Concentration Gradient) structure can make better structural stability without Co metal than surface coating, which has insulated coating materials. In addition, core shell structure is easier to control the composition than FCG structure. However, in Core-Shell structure, interdiffusion of shell metal to core deteriorate the stability of Core-Shell material, so it needs very delicate heat treatment. And generally, to prevent interdiffusion from traditional core-shell structure, lower synthesis temperature or high valence metal dopant would be needed and that leads lower initial specific capacity or additional doped metal. So, we prevent the Mn interdiffusion by changing valence state of Mn in precursor through simple convection drying process not vacuum drying without decreasing synthesis temperature and additional dopant. Atomic interdiffusion in layered metal oxide structures follows the atomic migration through octahedral and tetrahedral sites. In case of various stated Mn, higher valence state Mn has higher energy barrier to migrate between each Oh and Td sites. Based on this theory, surface Mn rich shell can be oxidized easily under convection oven drying and highly oxidized Mn will be remained better than lower state Mn during high temperature calcination. These more remained Mn in shell can protect the particle surface from electrolyte attack and also higher valence state Mn makes slightly more Ni2+ due to thermodynamic stability and charge balance of Mn on the surface. And that Ni2+ in Li slab (Cation mixing) acts as a pillar to suppress irreversible phase transition of Ni rich materials. Through this surface passivation, phase transition (layered to rock salt ) propagation surface to bulk can be blocked. Furthermore, mechanical pulverization of secondary particle is also prevented because of less permeating electrolyte into bulk structure. Therefore, Li ion diffusion will not be sluggish after cycling as observed by GITT. In addition, more clear Ni rich core assure high specific capacity and faster electrochemical reaction kinetic without severe capacity fading. And also, in Full cell test (using graphite as anode), convection oven dried sample has better structure stability and that means our strategy for core-shell LiNi0.97Mn0.03O2 sample can be good candidate to alternate conventional cathode active material for Lithium ion battery practically. As prepared materials, atomic distribution was observed by EDS and XPS analysis. This study suggests useless of vacuum drying and more cost effective way to prepare Co free Core Shell LiNi0.97Mn0.03O2 cathode material for Lithium Ion Batteries.
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Elsaesser, Patrick, Philipp Veh, Severin Vierrath, Matthias Breitwieser, and Anna Fischer. "MOF-Derived Fe-Zn-N-C Catalysts for Precious Metal Free Cathodes Showing High Performance in Anion-Exchange Membrane Fuel Cells." ECS Meeting Abstracts MA2022-01, no. 35 (July 7, 2022): 1482. http://dx.doi.org/10.1149/ma2022-01351482mtgabs.
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Hydrogen technologies such as low-temperature fuel cells are, besides batteries, the most promising technologies for mobility and transport applications. Currently, Proton Exchange Membrane Fuel Cells (PEMFCs) are, in terms of low-temperature fuel cells, the state-of-the-art technology achieving high power densities and reasonable stabilities. With the recent development and increasing availability of stable and performant hydroxide conductive ionomers, Anion Exchange Membrane Fuel Cells (AEMFCs) have gained increasing interest in recent years as they combine the advantages of PEMFCs, like low-temperature operation and high-power density with the low component costs of alkaline fuel cells.1,2 Especially the possibility of replacing the expensive Pt-based electrocatalysts used in PEMFCs with cheaper electrocatalysts like nickel-based materials for the anode and iron-based materials for the cathode could significantly decrease the fuel cell costs.1,3,4 Although the oxygen reduction reaction (ORR) at the cathode is favored in alkaline media compared to acidic media, the ORR is still a challenging reaction in AEMFCs.5,6 Over the last decades, various materials were investigated in order to replace the expensive Pt electrocatalysts at the cathode. Among these materials, iron- and nitrogen-doped carbons (Fe-N-C) with molecular iron sites (Fe-Nx) show comparable catalytic activities to Pt and decent stabilities.7–9 Fe-N-C catalysts can be obtained by co-pyrolysis of Fe- N-, and C-sources and subsequential acid leaching. One way to achieve Fe-N-C catalysts with high dispersion of Fe-Nx sites is by using Fe-doped metal-organic frameworks (Fe-MOFs) as precursors. These combine the presence of pre-coordinated Fe-Nx motives as well as high porosity and high specific surface area.10 To produce Fe-N-C catalysts, we synthesized Fe-, and Zn-doped MOFs (Fe-Zn-MOF) as multicomponent Fe-, Zn-, N-, and C-precursors and pyrolyzed them in the presence of additional nitrogen sources at high temperatures. The resulting Fe-Zn-N-C catalysts revealed high dispersion of Fe and Zn, high specific surface areas (400-600 m2/g), and high porosity as revealed by XRD, EDX, HAADF STEM, and N2 physisorption. Depending on the pre-treatment of the Fe-Zn-MOF, the Fe content of the resulting Fe-N-C catalyst could be varied. Benefiting from the high Fe-dispersion and the high specific surface areas, the best performing Fe-Zn-N-C catalyst with high Fe content shows high activity towards the ORR in alkaline media (0.1 mol/L KOH) as demonstrated by RDE measurements featuring a high half-wave potential (0.87 V vs. RHE) and high mass activity (47 mA/mgcat) and thereby outperforming a commercial 50 wt.% Pt/C catalyst in terms of half-wave potential (0.83 V vs. RHE). To investigate the performance of the Fe-Zn-N-C catalysts in AEMFCs, membrane electrode assemblies (MEAs) were prepared with the synthesized Fe-Zn-N-C catalysts at the cathode, a commercial PtRu/C catalyst (40 wt.% Pt, 20 wt.% Ru on carbon black, AlfaAesar) at the anode, and a commercial ionomer as membrane and catalyst layer ionomer. The AEMFC with the best performing Fe-Zn-N-C catalyst revealed a high peak power density of 850 mW/cm², which is among the highest reported peak power densities for non-precious metal cathode catalysts in combination with a commercially available anion exchange ionomer. 1 D. R. Dekel, J. Power Sources, 2018, 375, 158–169. 2 R. O’Hayre, S.-W. Cha, W. Colella and F. B. Prinz, Fuel Cell Fundamentals, John Wiley & Sons, Inc, Hoboken, NJ, USA, 2016. 3 X. Ge, A. Sumboja, D. Wuu, T. An, B. Li, F. W. T. Goh, T. S. A. Hor, Y. Zong and Z. Liu, ACS Catal., 2015, 5, 4643–4667. 4 E. S. Davydova, S. Mukerjee, F. Jaouen and D. R. Dekel, ACS Catal., 2018, 8, 6665–6690. 5 M. Hren, M. Božič, D. Fakin, K. S. Kleinschek and S. Gorgieva, Sustain. Energy Fuels, 2021, 5, 604–637. 6 N. Ramaswamy and S. Mukerjee, Adv. Phys. Chem., 2012, 2012, 1–17. 7 X. Ren, B. Liu, X. Liang, Y. Wang, Q. Lv and A. Liu, J. Electrochem. Soc., 2021, 168, 044521. 8 L. Osmieri, L. Pezzolato and S. Specchia, Curr. Opin. Electrochem., 2018, 9, 240–256. 9 M. M. Hossen, K. Artyushkova, P. Atanassov and A. Serov, J. Power Sources, 2018, 375, 214–221. 10 C. Li, D. H. Zhao, H. L. Long and M. Li, Rare Met., 2021, 40, 2657–2689.
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Kim, Jung-Hyun. "(Invited) Non-Conventional, Multimodal Strategies to Create Synergistic Effects on Electrode-Electrolyte Interphase Stabilities in Lithium-Ion Batteries." ECS Meeting Abstracts MA2022-02, no. 1 (October 9, 2022): 33. http://dx.doi.org/10.1149/ma2022-02133mtgabs.
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Ni- or Mn-rich cathode materials have attracted great interest for electric vehicle (EV) applications due to their high gravimetric and volumetric energy densities and low- or cobalt-free compositions. For example, Ni-rich LiNi1-xCox/2Mnx/2O2 (NMC) layered cathodes can deliver > 200 mAh/g when they operate at above 4.3 Vvs.Li. Cobalt-free LiNi0.5Mn1.5O4 (LNMO) spinel operates at around 4.75 Vvs.Li and delivers an excellent rate capability due to three-dimensional Li-diffusion pathways in its lattice. However, due to lack of high-voltage stabilities of conventional, carbonate-based electrolytes, such high-voltage operation (> 4.3 Vvs.Li) led to unwanted electrolyte oxidation and simultaneous parasitic reactions occurring at CEI. Different types of cathodes have their own failure mechanisms which are often associated with side reactions occurring at solid-electrolyte interphase (SEI) on graphite anodes. This was possible because the reaction by-products from CEI could migrate and attack SEI layers on anodes. To address the high-voltage related issues, various approaches have been proposed such as tuning chemical compositions of cathode active materials, surface modification of cathodes or anodes, and stabilizing the CEI or SEI using electrolyte additives. In literature, however, there was no single solution that can resolve all the complex issues occurring in the high-voltage battery cells. For example, coated layers on active materials are prone to fail during long-term cycling due to mechanical failure (e.g., crack and pulverization) of active materials. In addition, not only active materials but carbon conductors (e.g., acetylene black) inside a cathode leads to the electrolyte oxidation, prompted by its high electronic conductivity and large surface area. Considering that such parasitic reactions originate from CEI and propagate to anode SEI, there is a dire need of multimodal strategies that can create synergistic effect on stabilizing the electrode-electrolyte interphases in cell level. In this presentation, I will introduce non-conventional strategies that can effectively enhance electrode-electrolyte interphase stabilities and improve full-cell (i.e., using graphite anodes) performances. First, formation of self-healing CEI on cathode active materials will be demonstrated. The interface of LNMO spinel oxide will be passivated by Ti-enriched shell via sacrificial transition metal dissolutions and suppress the side reactions occurring at CEI. Second, a strategy for passivating both cathode active materials and carbon black conductor by using functional binders will be demonstrated. Since the binder coating will be performed in-situ during a slurry preparation, no extra process will be required while implementing this approach to a cell manufacturing. Finally, solid-electrolyte implemented NMC or LNMO cathodes will be demonstrated as an effective approach to stabilize the high-voltage performance by offering good Li-ion conduction pathways at CEI layer. Improvement mechanism of each approach will be also presented based on physical and electrochemical characterization data. Electrochemical impedance spectroscopy (EIS) revealed a suppression of CEI interfacial resistance during cycling, suggesting the enhanced stability of the multifunctional CEI. Various microscopy and spectroscopy data acquired from cycle-aged CEI and graphite SEI will be corelated to the cell performance data and identify the CEI property-performance relationship. These unique multifunction CEI strategies will be applicable to various cathode materials for the next-generation Li-ion batteries. Figure 1
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Liu, Di-Jia. "(Invited) Understanding the Electrocatalytic Mechanisms of Oxygen and Carbon Dioxide Reduction Reactions." ECS Meeting Abstracts MA2022-01, no. 35 (July 7, 2022): 1468. http://dx.doi.org/10.1149/ma2022-01351468mtgabs.
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Oxygen reduction reaction (ORR) is one of the most important reactions in the field of electrocatalysis today. ORR represents a key cathodic reaction in hydrogen fuel cell, which typically needs to be promoted by the platinum group metals (PGMs), particularly Pt. The high cost of Pt adds significant barrier to the widespread implementation of the fuel cell technology. During the last two decades, substantially amount of effort has been invested in searching for low-cost replacements, or PGM-free catalysts for ORR. Although significant progress has been made, such catalysts still face major challenge in durability. By adding small amount of Pt over PGM-free catalytic substrate, we have found that both activity and stability will be significantly improved through synergistic interaction. [1] To better define synergistic effect in ORR catalysis, however, requires a carefully designed experiment that can separates multiple factors during the catalyst synthesis that can potentially influence the overall activity. In this report, we will discuss our recent study in understanding of the ORR catalysis synergy between Pt/PGM-free components in rationally designed catalyst systems. Another fast developing area of electrocatalysis is CO2 reduction reaction (CO2RR), which promises to electrochemically convert CO2 to fuels and chemicals using renewable electricity. While CO2RR via 2-electron transfer, such as the conversion to CO or formate, has been proven high selective with fast kinetics, conversions to C2+ chemicals require significantly stronger binding between the catalytic site and CO2 to complete multiple electron transfers (8 to 16) and C-C bond coupling steps, therefore are more challenging. More recently, we develop a new amalgamated lithium metal (ALM) synthesis method to preparing highly selective and active CO2RR catalyst for C2+ chemicals such as ethanol production. [2] In this presentation, we will discuss the hypothesis driven CO2RR catalyst design, combined with the mechanistic study for preparing effective catalysts. We will also share some critical insight on CO2RR mechanism through advanced structural characterization and computational modelling. Acknowledgement: This work is supported by U. S. Department of Energy, Hydrogen and Fuel Cell Technologies Office through Office of Energy Efficiency and Renewable Energy and by Office of Science, U.S. Department of Energy under Contract DE-AC02-06CH11357. [1] L. Chong, J. Wen, J. Kubal, F. G. Sen, J. Zou, J. Greeley, M. Chan, H. Barkholtz, W. Ding, and D.-J. Liu, “Ultralow-loading Platinum-Cobalt Fuel Cell Catalysts Derived from Imidazolate Frameworks,” Science (2018) 362, 1276 [2] “Highly selective electrocatalytic CO2 reduction to ethanol by metallic clusters dynamically formed from atomically dispersed copper” Haiping Xu, Dominic Rebollar, Haiying He, Lina Chong, Yuzi Liu, Cong Liu, Cheng-Jun Sun, Tao Li, John V. Muntean, Randall E. Winans, Di-Jia Liu and Tao Xu, (2020) Nature Energy, 5, 623–632
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Tok, Guelen Ceren, Leonhard Reinschlüssel, Anne Berger, and Hubert Andreas Gasteiger. "Spatially Resolved Operando X-Ray Absorption Spectroscopy in NCA/Graphite to Quantify the Potential-Dependent Transition Metal Dissolution and Its Effect on Capacity Fading." ECS Meeting Abstracts MA2022-01, no. 2 (July 7, 2022): 172. http://dx.doi.org/10.1149/ma2022-012172mtgabs.
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Layered transition metal oxides like NCAs (LiNixCoyAlzO2, with x+y+z=1) and NCMs (LiNixCoyMnzO2, with x+y+z=1) are used as cathode active materials (CAMs) for high energy Li-ion batteries due to their high capacity. However, at high upper cut-off potentials, those CAMs suffer from structural instabilities, resulting in severe capacity fading and thus limiting the accessible capacity that can be obtained. Possible causes for the capacity fade at high cut-off potentials and high state-of-charge (SOC) include the (electro)chemical oxidation of the electrolyte oxidation and transition metal (TM) dissolution from the CAM surface.1 Furthermore, layered TM-oxides are known to release lattice oxygen from the near-surface region at high SOC (i.e., at ≈80% SOC when referenced to the total amount of lithium), resulting in reactive oxygen species that induce electrolyte oxidation and HF formation.2 This release of lattice oxygen results in a surface reconstruction from the pristine layered structure to a more resistive spinel- or rocksalt-like structure, thereby inducing an impedance build-up on the cathode. Diffusion of dissolved transition metals to the anode and their subsequent deposition on the anode active material particles can also have a severe effect on cell aging, as the accumulation of metal species on the graphite anode has shown to catalyze the degradation of the protective anode solid/electrolyte interphase (SEI), eventually resulting in the loss of active lithium and in an anode impedance growth. Since the dissolution of manganese is considered to have the most detrimental effect on the anode SEI compared to cobalt and nickel,3 manganese-free NCAs (e.g., LiNi0.8Co0.15Al0.05O2) might have an advantage over manganese-containing NCMs. In this study, we will examine the potential-dependent dissolution of Ni and Co in NCA/graphite cells using operando XAS, and compare it to the potential-dependent dissolution of Ni, Co, and Mn from LiNi0.6Co0.2Mn0.2O2 (NMC622) that we had determined previously by operando XAS.4 Owing to the specially designed geometry of the operando XAS cell,5 we can spectroscopically access and independently investigate the concentration and oxidation state of transition metals, both dissolved in the electrolyte and deposited within the graphite anode. This is illustrated for an NCA/graphite cell in Figure 1. We will also examine the effect of lattice oxygen release from NCA on the NCA/graphite full-cell performance by applying different techniques: We employ a three-electrode Swagelok® type T-cell with a gold wire micro reference electrode (µ-GWRE)6 to quantify the anode and the cathode impedance over the course of 100 cycles as a function of the upper cutoff voltage. In addition, on-line electrochemical mass spectrometry (OEMS)7 is applied to detect the onset SOC for the release of lattice oxygen. From these comparisons, we aim to get a detailed understanding about the influence of transition metal dissolution from NCA on capacity fade and cycle life. References: J. A. Gilbert, I. A. Shkrob, and D. P. Abraham, Journal of The Electrochemical Society, 164 (2), A389-A399 (2017). R. Jung, M. Metzger, F. Maglia, C. Stinner, and H. A. Gasteiger, Journal of The Electrochemical Society, 164 (7), A1361-A1377 (2017). S. Solchenbach, G. Hong, A. T. S. Freiberg, R. Jung, and H. A. Gasteiger, Journal of The Electrochemical Society, 165 (14), A3304-A3312 (2018). R. Jung, F. Linsenmann, R. Thomas, J. Wandt, S. Solchenbach, F. Maglia, C. Stinner, M. Tromp, and H. A. Gasteiger, Journal of The Electrochemical Society, 166 (2), A378-A389 (2019). J. Wandt, A. Freiberg, R. Thomas, Y. Gorlin, A. Siebel, R. Jung, H. A. Gasteiger, and M. Tromp, Journal of Materials Chemistry A, 4 (47), 18300-18305 (2016). S. Solchenbach, D. Pritzl, E. J. Y. Kong, J. Landesfeind, and H. A. Gasteiger, Journal of The Electrochemical Society, 163 (10), A2265-A2272 (2016). N. Tsiouvaras, S. Meini, I. Buchberger, and H. A. Gasteiger, Journal of The Electrochemical Society, 160 (3), A471-A477 (2013). Figure 1
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Kumar, Kavita, Tristan Asset, Plamen Atanassov, Frederic Jaouen, Laetitia Dubau, and Frederic Maillard. "Unravelling the Influence of Oxygen on the Degradation Mechanisms of Fe-N-C Oxygen Reduction Reaction Catalysts." ECS Meeting Abstracts MA2022-01, no. 49 (July 7, 2022): 2070. http://dx.doi.org/10.1149/ma2022-01492070mtgabs.
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Pyrolyzed iron-nitrogen-carbon materials (Fe-N-C) comprising mostly atomic Fe-Nx moieties are the most mature class of noble metal free catalysts for the oxygen reduction reaction (ORR) in acidic media. Such catalysts show excellent performance in proton exchange membrane fuel cell (PEMFC), approaching that of platinum-based catalysts. [1] However, an important performance loss is observed during operation, in conditions mimicking those of a PEMFC. [2] To shed fundamental light onto the degradation mechanisms at stake, two different Fe-N-C materials were prepared, one using a metal organic framework (MOF) and the other a sacrificial support method (SSM), and are labelled Fe-N-C_MOF and Fe-N-C_SSM, respectively. These materials were characterized before and after two different accelerated stress tests (ASTs: 10 k cycles, 0.6-1.0 V vs. RHE, 3s-3s, 0.1 M H2SO4, 80°C) under Ar or O2 atmosphere. Stronger degradation and higher ORR mass activity loss were observed when the AST is performed in O2 vs. Ar-saturated acidic electrolyte. For AST under Ar condition, physicochemical characterisations revealed a demetallation process and the eventual occurrence of a clustering mechanism whereas for AST performed in O2 atmosphere, a decrease of the Fe content and the formation of Fe oxide particles was observed (Figure 1). Keywords: Electrocatalysis, Fe-N-C, Oxygen Reduction Reaction, Durability, PEMFC Acknowledgements These studies were financed by the French National Research Agency in the frame of the CAT2CAT (grant number n°ANR-16-CE05-0007) and the ANIMA (grant number n°ANR-19-CE05-0039) projects. References [1] E. Proietti, F. Jaouen, M. Lefèvre, N. Larouche, J. Tian, J. Herranz, J. P. Dodelet, Nat. Commun. 2011, 2, 416. [2] Y. Shao, J. P. Dodelet, G. Wu, P. Zelenay, Adv. Mater. 2019, 21, 1807615. [3] K. Kumar, T. Asset, X. Li, Y. Liu, X. Yan, Y. Chen, M. Mermoux, X. Pan, P. Atanassov, F. Maillard, L. Dubau, ACS Catal. 2021, 11, 484-494. [4] K. Kumar, P. Gairola, M. Lions, N. Ranjbar-Sahraie, M. Mermoux, L. Dubau, A. Zitolo, F. Jaouen, F. Maillard, ACS Catal. 2018, 8, 11264-11276. [5] K. Kumar, L. Dubau, M. Mermoux, J. Li, A. Zitolo, J. Nelayah, F. Jaouen, F. Maillard, Angew. Chem. 2020, 132, 3261-3269. Figure 1
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Wang, Xiaoping, Magali Ferrandon, Jaehyung Park, Evan C. Wegener, A. Jeremy Kropf, and Deborah J. Myers. "Optimization of Synthesis Variables Towards Improved Activity and Stability of Fe-N-C PGM-Free Catalysts." ECS Meeting Abstracts MA2022-01, no. 35 (July 7, 2022): 1447. http://dx.doi.org/10.1149/ma2022-01351447mtgabs.
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Materials in the Fe-N-C family are the most promising platinum group metal-free (PGM-free) catalysts for the oxygen reduction reaction (ORR) in polymer electrolyte fuel cells (PEFCs).1-3 Although significant progress has been made in recent years in improving both the ORR activity and durability of the Fe-N-C catalysts, further improvements are needed, especially in long-term performance durability in hydrogen-air PEFCs, to enable their use in applications such as propulsion power for light-duty vehicles.3 The most active ORR catalysts in the Fe-N-C family were synthesized by heat treating iron salts or other iron-containing compounds with zinc-based zeolitic imidazolate frameworks (ZIFs) and/or phenanthroline (as carbon and nitrogen sources), or by heat treating iron-substituted ZIFs. For this family of PGM-free materials, it has been shown that many synthesis variables, such as the metal and carbon-nitrogen macrocycle content, the heat treatment temperature, atmosphere, and temperature profile all affect the activity and durability of the resulting catalysts.4-7 Optimization of these variables and testing the resulting catalyst properties is not a trivial task, and only a limited portion of the composite composition and temperature space has been explored for this family of catalysts. To accelerate optimization of the synthesis variables to obtain improved ORR activity and stability for the Fe-N-C catalysts, high-throughput synthesis and characterization methods were developed and utilized. An automation platform, a multi-port ball-mill, and parallel fixed bed reactors in Argonne’s High-throughput Research Laboratory were used to rapidly synthesize the PGM-free catalysts with systematically-varied synthesis conditions. A multi-channel flow double electrode (m-CFDE) cell and other cells were designed and constructed for the simultaneous testing the ORR activity and stability of the multiple catalysts synthesized. The ORR activity and stability of the catalysts were correlated with their Fe speciation, as determined using Fe K-edge X-ray absorption spectroscopy (XAFS), electrochemically-determined surface areas, and other variables, which is beneficial for the further improved catalyst activity and stability. References B. Pivovar, Nature Catalysis, 2 (2019) 562. S. Thompson and D. Papageorgopoulos, Nature Catalysis, 2 (2019) 558. L. Osmieri, J. Park, D.A. Cullen, P. Zelenay, D.J. Myers, and K.C. Neyerlin, Curr. Opin. Electrochem., 25 (2021) 100627. X. Wang, H. Zhang, H. Lin, S. Gupta, C. Wang, Z. Tao, H. Fu, T. Wang, J. Zheng, G. Wu, and X. Li, Nano Energy, 25 (2016) 110. H. Zhang, S. Hwang, M. Wang, Z. Feng, S. Karakalos, L. Luo, Z. Qiao, X. Xie, C. Wang, D. Su, Y. Shao, and G. Wu, J. Am. Chem. Soc., 139 (2017) 14143-14149. E. Proietti, F. Jaouen, M. Lefevre, N. Larouche, J. Tian, J. Herranz, and J.-P. Dodelet, Nature Comm. 2 (2011) 1. A. Zitolo, V. Goellner, V. Armel, M.-T. Sougrati, T. Mineva, L. Stievano, E. Fonda, and F. Jaouen, Nature Materials, 14 (2015) 937. This work was supported by the U.S. Department of Energy (DOE), Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office (HFTO) under the auspices of the Electrocatalysis Consortium (ElectroCat). This work utilized the resources of the Advanced Photon Source, a U.S. DOE Office of Science user facility operated by Argonne National Laboratory for DOE Office and was authored by Argonne, a U.S. Department of Energy (DOE) Office of Science laboratory operated for DOE by UChicago Argonne, LLC under contract no. DE-AC02-06CH11357.
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Zhou, Haitao, Xuehang Wang, and De Chen. "Li-Metal-Free Prelithiation of Si-Based Negative Electrodes for Full Li-Ion Batteries." ChemSusChem 8, no. 16 (July 20, 2015): 2737–44. http://dx.doi.org/10.1002/cssc.201500287.
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Zhao, Chen-Zi, Peng-Yu Chen, Rui Zhang, Xiang Chen, Bo-Quan Li, Xue-Qiang Zhang, Xin-Bing Cheng, and Qiang Zhang. "An ion redistributor for dendrite-free lithium metal anodes." Science Advances 4, no. 11 (November 2018): eaat3446. http://dx.doi.org/10.1126/sciadv.aat3446.
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Lithium (Li) metal anodes have attracted considerable interest due to their ultrahigh theoretical gravimetric capacity and very low redox potential. However, the issues of nonuniform lithium deposits (dendritic Li) during cycling are hindering the practical applications of Li metal batteries. Herein, we propose a concept of ion redistributors to eliminate dendrites by redistributing Li ions with Al-doped Li6.75La3Zr1.75Ta0.25O12 (LLZTO) coated polypropylene (PP) separators. The LLZTO with three-dimensional ion channels can act as a redistributor to regulate the movement of Li ions, delivering a uniform Li ion distribution for dendrite-free Li deposition. The standard deviation of ion concentration beneath the LLZTO composite separator is 13 times less than that beneath the routine PP separator. A Coulombic efficiency larger than 98% over 450 cycles is achieved in a Li | Cu cell with the LLZTO-coated separator. This approach enables a high specific capacity of 140 mAh g−1 for LiFePO4 | Li pouch cells and prolonged cycle life span of 800 hours for Li | Li pouch cells, respectively. This strategy is facile and efficient in regulating Li-ion deposition by separator modifications and is a universal method to protect alkali metal anodes in rechargeable batteries.
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Zhang, Ji-Guang, Xia Cao, Phung M.-L. LE, Yan Jin, Ju-Myung Kim, and Wu Xu. "Development of Anode-Free Metal Batteries." ECS Meeting Abstracts MA2022-01, no. 1 (July 7, 2022): 36. http://dx.doi.org/10.1149/ma2022-01136mtgabs.
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Ever increasing need for electrical vehicles (EVs) continually pushes the boundary of high-density energy storage systems. To date, the state of the art of lithium (Li) ion batteries (LIBs) consisting of graphite anode and high voltage Li intercalation cathodes cannot satisfy the energy demand from these applications. By replacing graphite anode with Li metal anode (LMA), specific energy density of Li metal batteries (LMBs) can increase by more than 50% because LMA has a much higher specific capacity (3820 mAh g-1) than that of graphite (372 mAh g-1). To further increase the energy density of Li batteries, the concept of “anode-free” Li batteries (AFLBs) has been explored. Similar approach can also be used in “anode-free” sodium (Na) batteries (AFSBs) to further improve their energy densities. In this work, we will report our recent work on the development of AFLBs and AFSBs. The common challenges in these batteries will be analyzed and compared first. Several approaches, including development of novel electrolytes, substrate treatment, optimization of testing protocol and environment conditions, have been adopted to increase the cycle life of these batteries. At last, future perspective and application of anode-fee metal batteries will be discussed. References Niu, C.; Liu, D.; Lochala, J. A.; Anderson, C. S.; Cao, X.; Gross, M. E.; Xu, W.; Zhang, J.-G.; Whittingham, M. S.; Xiao, J.; Liu, J., Balancing interfacial reactions to achieve long cycle life in high-energy lithium metal batteries. Nature Energy 2021. Zhang, J.-G., Anode-less. Nature Energy 2019, 4 (8), 637-638. Pereira, N.; Amatucci, G. G.; Whittingham, M. S.; Hamlen, R., Lithium–titanium disulfide rechargeable cell performance after 35 years of storage. Journal of Power Sources 2015, 280, 18-22. Boyle, D. T.; Huang, W.; Wang, H.; Li, Y.; Chen, H.; Yu, Z.; Zhang, W.; Bao, Z.; Cui, Y., Corrosion of lithium metal anodes during calendar ageing and its microscopic origins. Nature Energy 2021.
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Cosby, Monty R., Gia M. Carignan, Zhuo Li, Corey M. Efaw, Charles C. Dickerson, Liang Yin, Yang Ren, Bin Li, Eric J. Dufek, and Peter G. Khalifah. "Operando Synchrotron Studies of Inhomogeneity during Anode-Free Plating of Li Metal in Pouch Cell Batteries." Journal of The Electrochemical Society 169, no. 2 (February 1, 2022): 020571. http://dx.doi.org/10.1149/1945-7111/ac5345.
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Operando synchrotron X-ray diffraction (XRD) studies have not previously been used to directly characterize Li metal in standard batteries due to the extremely weak scattering from Li atoms. In this work, it is demonstrated the stripping and plating of Li metal can be effectively quantified during battery cycling in appropriately designed synchrotron XRD experiments that utilize an anode-free battery configuration in which a Li-containing cathode material of LiNi0.6Mn0.2Co0.2O2 (NMC622) is paired with a bare anode current collector consisting of either Cu metal (Cu/NMC) or Mo metal (Mo/NMC). In this configuration, it is possible to probe local variations in the deposition and stripping of Li metal with sufficient spatial sensitivity to map the inhomogeneity in pouch cells and to follow these processes with sufficient time resolution to track state-of-charge-dependent variations in the rate of Li usage at a single point. For the Cu/NMC and Mo/NMC batteries, it was observed that the initial plating of Li occurred in a very homogeneous manner but that severe macroscopic inhomogeneity arose on a mm-scale during the subsequent stripping of Li, contrasting with the conventional wisdom that the greatest challenges in Li metal batteries are associated with Li deposition.
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Zhang, Hanguang, and Piotr Zelenay. "Platinum Group Metal-Free ORR Catalysts for Anion Exchange Membrane Fuel Cells." ECS Meeting Abstracts MA2022-02, no. 40 (October 9, 2022): 1486. http://dx.doi.org/10.1149/ma2022-02401486mtgabs.
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Platinum group metal (PGM)-free catalysts for oxygen reduction reaction (ORR) have attracted significant attention in the last two decades. These catalysts typically perform better in alkaline aqueous electrolytes than in their acidic counterparts.1, 2 However, the performance of PGM-free ORR catalysts in anion exchange membrane fuels cells (AEMFCs) have been consistently lower than in the acidic polymer electrolyte fuel cells (PEFCs). The most likely reasons for the sub-par behavior of PGM-free catalysts in AEMFCs has been often linked to difficulties in preparing electrodes with anion exchange ionomers and assuring efficient water management. These challenges have been amplified by the high-loading requirement for PGM-free ORR catalysts, resulting in electrodes by as much as an order of magnitude thicker than the PGM-based ones. In this presentation, we will demonstrate AEMFCs with much improved performance of the PGM-free cathode (Fe-N-C catalyst-based). The performance improvement has been achieved by optimizing the electrode fabrication process, including changes to the electrode configuration and catalyst ink preparation. These changes have allowed us to elevate the AEMFC performance, including the peak power density of > 0.8 W cm-2 in H2-O2 cells, to the level comparable to that of the corresponding PEFC, operating with a PGM-free cathode under the same operating conditions. References: 1. Li, X.; Liu, G.; Popov, B. N., Activity and stability of non-precious metal catalysts for oxygen reduction in acid and alkaline electrolytes. Journal of Power Sources 2010, 195 (19), 6373-6378. 2. Choi, C. H.; Lim, H.-K.; Chung, M. W.; Chon, G.; Ranjbar Sahraie, N.; Altin, A.; Sougrati, M.-T.; Stievano, L.; Oh, H. S.; Park, E. S.; Luo, F.; Strasser, P.; Dražić, G.; Mayrhofer, K. J. J.; Kim, H.; Jaouen, F., The Achilles' heel of iron-based catalysts during oxygen reduction in an acidic medium. Energy & Environmental Science 2018, 11 (11), 3176-3182.
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Eguchi, Takuya, Ryoichi Sugawara, Yusuke Abe, Masahiro Tomioka, and Seiji Kumagai. "Impact of Full Prelithiation of Si-Based Anodes on the Rate and Cycle Performance of Li-Ion Capacitors." Batteries 8, no. 6 (May 27, 2022): 49. http://dx.doi.org/10.3390/batteries8060049.
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The impact of full prelithiation on the rate and cycle performance of a Si-based Li-ion capacitor (LIC) was investigated. Full prelithiation of the anode was achieved by assembling a half cell with a 2 µm-sized Si anode (0 V vs. Li/Li+) and Li metal. A three-electrode full cell (100% prelithiation) was assembled using an activated carbon (AC) cathode with a high specific surface area (3041 m2/g), fully prelithiated Si anode, and Li metal reference electrode. A three-electrode full cell (87% prelithiation) using a Si anode prelithiated with 87% Li ions was also assembled. Both cells displayed similar energy density levels at a lower power density (200 Wh/kg at ≤100 W/kg; based on the total mass of AC and Si). However, at a higher power density (1 kW/kg), the 100% prelithiation cell maintained a high energy density (180 Wh/kg), whereas that of the 87% prelithiation cell was significantly reduced (80 Wh/kg). During charge/discharge cycling at ~1 kW/kg, the energy density retention of the 100% prelithiation cell was higher than that of the 87% prelithiation cell. The larger irreversibility of the Si anode during the initial Li-ion uptake/release cycles confirmed that the simple full prelithiation process is essential for Si-based LIC cells.
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Pfeiffer, Lukas, Peter Axmann, and Margret Wohlfahrt-Mehrens. "NaxMnyNi1-YO2 Cathode Materials for Sodium-Ion Batteries: Structure, Synthesis, Electrochemistry and Influence of Ambient Storage." ECS Meeting Abstracts MA2022-02, no. 4 (October 9, 2022): 448. http://dx.doi.org/10.1149/ma2022-024448mtgabs.
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Expanding energy generation from renewables is inevitable to reduce the impact of man-made climate change. With that, the need for intermediate energy storage is gaining in significance. Today, lithium-ion batteries (LIBs) are dominating mobile drive-trains and also play a key role in stationary energy storage. LIBs are incorporating critical raw materials in view of availability and economic importance, such as cobalt, lithium, copper and graphite. Sodium-based batteries, in which sodium replaces lithium as ionic charge-carrier, utilize the same working principles but substitute critical raw materials for abundant and cost-effective alternatives. Hard carbon replaces graphite as anode active material, copper foils are substituted by aluminum current collectors and manganese-based cobalt-free layered host lattices offer promising performance as cathode active material 1,2. By applying established production processes, investment costs are reduced and a rapid scale-up is enabled (Drop-In technology) 3, making SIBs a sustainable, efficient and cost-effective complementary technology to LIBs 4. Among various known cathode active materials for SIBs, the family of layered sodium transition metal oxides (NaxMO2, 1>x>0) offers promising electrochemical performance 2,5–7. These compounds show a wide structural variety (O3, P3, P2) due to the ionic radius of sodium and the tendency for Na+/vacancy ordering 8. The scope of our presentation will be low-cost manganese-based, cobalt-free layered NaxMnyNi1-yO2 cathode active materials for SIBs. We will discuss the influence of the transition metal stoichiometry y on the structure based on Neutron and X-ray diffraction experiments. Using advanced electrochemical methods and diffraction experiments, these structural models are then correlated with physical and electrochemical properties such as Na+/vacancy orderings, solid diffusion coefficients and potential profiles. For y = 3/4, a synthesis phase diagram will be presented covering a broad range of sodium content x and calcination temperature. For phase-pure P2-NaxMn3/4Ni1/4O2, we will present the influence of the calcination process on the structure and discuss the electrochemical properties in half-cells in-depth. For optimized materials, attractive initial specific discharge capacities beyond 220 mAh g-1 are obtained in sodium half-cells between 1.5 – 4.3 V. A capacity decay occurs during electrochemical cycling within this full voltage window. The origin of the capacity decay will be discussed based on electrochemical studies and ex-situ investigations of the morphology with SEM and local structure with HRTEM. Finally, we will present the influence of storage in ambient air to gain insights on the large-scale processability of the materials. The chosen synthesis route adapts industrially established processes for NCM production for SIB cathode materials, enables to tune powder properties to technical specifications and is highly scalable. The broad scope of this work addresses raw material questions, fundamental investigations and industrially relevant production processes. ACKNOWLEDMENTS: The German Federal Ministry of Education and Research (BMBF) supported this work within the project TRANSITION (03XP0186C) and ExcellBattMat (03XP0257A and 03XP0257C). REFERENCES Larcher, D. & Tarascon, J.-M. Towards greener and more sustainable batteries for electrical energy storage. Nature Chem 7, 19–29; 10.1038/nchem.2085 (2015). Hasa, I. et al. Challenges of today for Na-based batteries of the future: From materials to cell metrics. Journal of Power Sources 482, 228872; 10.1016/j.jpowsour.2020.228872 (2021). Tarascon, J.-M. Na-ion versus Li-ion Batteries: Complementarity Rather than Competitiveness. Joule 4, 1616–1620; 10.1016/j.joule.2020.06.003 (2020). Vaalma, C., Buchholz, D., Weil, M. & Passerini, S. A cost and resource analysis of sodium-ion batteries. Nat Rev Mater 3, 1–11; 10.1038/natrevmats.2018.13 (2018). Nagore Ortiz-Vitoriano, Nicholas E. Drewett, Elena Gonzalo & Teófilo Rojo. High performance manganese-based layered oxide cathodes: overcoming the challenges of sodium ion batteries. Energy Environ. Sci. 10, 1051–1074; 10.1039/C7EE00566K (2017). Nuria Tapia-Ruiz et al. 2021 roadmap for sodium-ion batteries. J. Phys. Energy 3, 31503; 10.1088/2515-7655/ac01ef (2021). Gonzalo, E., Zarrabeitia, M., Drewett, N. E., López del Amo, Juan Miguel & Rojo, T. Sodium manganese-rich layered oxides: Potential candidates as positive electrode for Sodium-ion batteries. Energy Storage Materials 34, 682–707; 10.1016/j.ensm.2020.10.010 (2021). Kubota, K., Kumakura, S., Yoda, Y., Kuroki, K. & Komaba, S. Electrochemistry and Solid‐State Chemistry of NaMeO 2 (Me = 3d Transition Metals). Adv. Energy Mater. 8, 1703415; 10.1002/aenm.201703415 (2018).
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Ku, YuPing, Konrad Ehelebe, Markus Bierling, Florian Dominik Speck, Dominik Seeberger, Karl J. J. Mayrhofer, Simon Thiele, and Serhiy Cherevko. "The Interplay of Oxygen Reduction Reaction and Iron Dissolution from Fe-N-C Electrocatalysts." ECS Meeting Abstracts MA2022-01, no. 35 (July 7, 2022): 1486. http://dx.doi.org/10.1149/ma2022-01351486mtgabs.
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Fe-N-C catalysts are regularly proposed as promising earth-abundant and cheap catalysts replacing platinum group metal catalysts for fuel cells (FCs). Besides the activity, especially the stability of those materials remains challenging. It was found that the electrochemical activity and durability of Fe-N-C catalysts are superior in alkaline compared to acidic media, [1-3] yet most of their degradation studies are done in acidic media. [4-9] Moreover, although these are systematic works, discrepancies in these results from aqueous model systems (AMS) [5,6] and FC testing [7-9] remain puzzling. For example, the origin of the dissolved Fe species was found to be from poorly active sites in AMS [5] yet from highly active sites in operating FCs. [7,8] Additionally, the harmful effects of reactive oxygen species (ROS) on Fe-N-C catalysts are proven in AMS [6] but not directly correlated to the durability in FCs. [9] To bridge this gap, a gas diffusion electrode (GDE) half-cell coupled with inductively coupled plasma mass spectrometry (ICP-MS) has been developed to study on-line dissolution in realistic catalyst layers. [10] In this work, using a GDE-ICP-MS, we investigate the impacts of oxygen reduction reaction (ORR) on Fe leaching from realistic Fe-N-C alkaline catalyst layers. [11] For the first time, Fe dissolution is measured online at current densities above -100 mA·cm-2. The novel results show that compared to the model Ar-saturated environment, the Fe dissolution is dramatically higher during ORR. Furthermore, between 0.6 and 1.0 VRHE, we unveil an interesting correlation between Fe dissolution and charge transfer events. This subsequently leads to our hypothesis that the instability of the coordinated Fe during Fe3+/Fe2+ redox transitions is responsible for Fe leaching from Fe-N-C catalysts in alkaline media in this potential region. The novel insights into Fe-N-C catalyst degradation in realistic conditions can lead to rational design of this promising platinum group metal free catalyst for efficient, durable, and affordable FCs. References: [1] Santori, P. G. et al. Effect of pyrolysis atmosphere and electrolyte pH on the oxygen reduction activity, stability and spectroscopic signature of FeNx moieties in Fe-N-C catalysts. J. Electrochem. Soc. 2019, 166: F3311. [2] Holby, E. F. et al. Acid stability and demetalation of PGM-Free ORR electrocatalyst structures from density functional theory: a model for “single-atom catalyst” dissolution. ACS Catal. 2020, 10: 14527-14539. [3] Bae, G. et al. PH effect on the H2O2-induced deactivation of Fe-N-C catalysts. ACS Catal. 2020, 10: 8485-8495. [4] Kumar, K. et al. On the influence of oxygen on the degradation of Fe‐N‐C catalysts. Angew. Chem. 2020, 132: 3261-3269. [5] Choi, C. H. et al. Stability of Fe‐N‐C catalysts in acidic medium studied by operando spectroscopy. Angew. Chem. Int. Ed. 2015, 54: 12753-12757. [6] Choi, C. H. et al. The Achilles' heel of iron-based catalysts during oxygen reduction in an acidic medium. Energy Environ. Sci. 2018, 11: 3176-3182. [7] Li, J. et al. Identification of durable and non-durable FeNx sites in Fe–N–C materials for proton exchange membrane fuel cells. Nat. Catal. 2021, 4: 10-19. [8] Chenitz, R. et al. A specific demetalation of Fe–N4 catalytic sites in the micropores of NC_Ar + NH3 is at the origin of the initial activity loss of the highly active Fe/N/C catalyst used for the reduction of oxygen in PEM fuel cells. Energy Environ. Sci. 2018, 11: 365-382. [9] Zhang, Gaixia, et al. Is iron involved in the lack of stability of Fe/N/C electrocatalysts used to reduce oxygen at the cathode of PEM fuel cells? Nano Energy, 2016, 29: 111-125. [10] Ehelebe, K. et al. Platinum dissolution in realistic fuel cell catalyst layers. Angew. Chem. Int. Ed. 2021, 60: 8882-8888. [11] Ku, Y.-P. et al. Oxygen reduction reaction causes iron leaching from Fe-N-C electrocatalysts. 2021 Submitted, DOI: 10.21203/rs.3.rs-1171081/v1.
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Jeon, In-Yup, Changmin Kim, Guntae Kim, and Jong-Beom Baek. "Mechanochemically driven iodination of activated charcoal for metal-free electrocatalyst for fuel cells and hybrid Li-air cells." Carbon 93 (November 2015): 465–72. http://dx.doi.org/10.1016/j.carbon.2015.05.075.
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Wang, Hansen, Yayuan Liu, Yuzhang Li, and Yi Cui. "Lithium Metal Anode Materials Design: Interphase and Host." Electrochemical Energy Reviews 2, no. 4 (October 12, 2019): 509–17. http://dx.doi.org/10.1007/s41918-019-00054-2.
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Abstract Li metal is the ultimate anode choice due to its highest theoretical capacity and lowest electrode potential, but it is far from practical applications with its poor cycle lifetime. Recent research progresses show that materials designs of interphase and host structures for Li metal are two effective ways addressing the key issues of Li metal anodes. Despite the exciting improvement on Li metal cycling capability, problems still exist with these methodologies, such as the deficient long-time cycling stability of interphase materials and the accelerated Li corrosion for high surface area three-dimensional composite Li anodes. As a result, Coulombic efficiency of Li metal is still not sufficient for full-cell cycling. In the near future, an interphase protected three-dimensional composite Li metal anode, combined with high performance novel electrolytes might be the ultimate solution. Besides, nanoscale characterization technologies are also vital for guiding future Li metal anode designs. Graphic Abstract
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Sun, Yongjiang, Genfu Zhao, Yao Fu, Yongxin Yang, Conghui Zhang, Qi An, and Hong Guo. "Understanding a Single-Li-Ion COF Conductor for Being Dendrite Free in a Li-Organic Battery." Research 2022 (October 6, 2022): 1–10. http://dx.doi.org/10.34133/2022/9798582.
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In addition to improving ion conductivity and the transference number, single-Li-ion conductors (SLCs) also enable the elimination of interfacial side reactions and concentration difference polarization. Therefore, the SLCs can achieve high performance in solid-state batteries with Li metal as anode and organic molecule as cathode. Covalent organic frameworks (COFs) are leading candidates for constructing SLCs because of the excellent 1D channels and accurate chemical-modification skeleton. Herein, various contents of lithium-sulfonated covalently anchored COFs (denoted as LiO3S-COF1 and LiO3S-COF2) are controllably synthesized as SLCs. Due to the directional ion channels, high Li contents, and single-ion frameworks, LiO3S-COF2 shows exceptional Li-ion conductivity of 5.47×10−5 S·cm−1, high transference number of 0.93, and low activation energy of 0.15 eV at room temperature. Such preeminent Li-ion-transported properties of LiO3S-COF2 permit stable Li+ plating/stripping in a symmetric lithium metal battery, effectively impeding the Li dendrite growth in a liquid cell. Moreover, the designed quasi-solid-state cell (organic anthraquinone (AQ) as cathode, Li metal as anode, and LiO3S-COF2 as electrolyte) shows high-capacity retention and rate behavior. Consequently, LiO3S-COF2 implies a potential value restraining the dissolution of small organic molecules and Li dendrite growth.
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Li, Hongyan, Zheng Cheng, Avi Natan, Ahmed M. Hafez, Daxian Cao, Yang Yang, and Hongli Zhu. "Dual‐Function, Tunable, Nitrogen‐Doped Carbon for High‐Performance Li Metal–Sulfur Full Cell." Small 15, no. 5 (January 11, 2019): 1804609. http://dx.doi.org/10.1002/smll.201804609.
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Jia, Junyao, Zhuoqun Tang, Zixing Guo, Haiyao Xu, Huijie Hu, and Sa Li. "A 3D composite lithium metal anode with pre-fabricated LiZn via reactive wetting." Chemical Communications 56, no. 30 (2020): 4248–51. http://dx.doi.org/10.1039/d0cc00514b.
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Li@NFZO, a 3D composite anode, obtained by heat-treatment and reactive wetting reinforces the electrode/electrolyte interface stability and prolongs the full-cell cycling life under lean electrolyte conditions.
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Zhao, Yue, Ziqiang Liu, Zhendong Li, Zhe Peng, and Xiayin Yao. "Constructing stable lithium metal anodes using a lithium adsorbent with a high Mn3+/Mn4+ ratio." Energy Materials 2, no. 5 (2022): 34. http://dx.doi.org/10.20517/energymater.2022.44.
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Lithium (Li) metal batteries (LMBs) have emerged as the most prospective candidates for post-Li-ion batteries. However, the practical deployment of LMBs is frustrated by the notorious Li dendrite growth on hostless Li metal anodes. Herein, a protonated Li manganese (Mn) oxide with a high Mn3+/Mn4+ ratio is used as a Li adsorbent for constructing highly stable Li metal anodes. In addition to the Mn3+ sites with high Li affinity that afford an ultralow Li nucleation overpotential, the decrease in the average Mnn+ oxidation state also induces a disordered adsorbent structure via the Jahn-Teller effect, resulting in improved Li transfer kinetics with a significantly reduced Li electroplating overpotential. Based on the mutually improved Li diffusion and adsorption kinetics, the Li adsorbent is used as a versatile host to enable dendrite-free and stable Li metal anodes in LMBs. Consequently, a modified Li||LiNi0.8Mn0.1Co0.1O2 (NMC811) coin cell with a high NMC811 loading of 4.3 mAh cm-2 delivers a high Coulombic efficiency of 99.85% over 200 cycles and the modified Li||NMC811 pouch cell also achieves a remarkable improvement in electrochemical performance. This work demonstrates a novel approach for the preparation of highly efficient Li protection structures for safe LMBs with long lifespans.
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Yuan, Huadong, Jianwei Nai, He Tian, Zhijin Ju, Wenkui Zhang, Yujing Liu, Xinyong Tao, and Xiong Wen (David) Lou. "An ultrastable lithium metal anode enabled by designed metal fluoride spansules." Science Advances 6, no. 10 (March 2020): eaaz3112. http://dx.doi.org/10.1126/sciadv.aaz3112.
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The lithium metal anode (LMA) is considered as a promising star for next-generation high-energy density batteries but is still hampered by the severe growth of uncontrollable lithium dendrites. Here, we design “spansules” made of NaMg(Mn)F3@C core@shell microstructures as the matrix for the LMA, which can offer a long-lasting release of functional ions into the electrolyte. By the assistance of cryogenic transmission electron microscopy, we reveal that an in situ–formed metal layer and a unique LiF-involved bilayer structure on the Li/electrolyte interface would be beneficial for effectively suppressing the growth of lithium dendrites. As a result, the spansule-modified anode affords a high Coulombic efficiency of 98% for over 1000 cycles at a current density of 2 mA cm−2, which is the most stable LMA reported so far. When coupling this anode with the Li[Ni0.8Co0.1Mn0.1]O2 cathode, the practical full cell further exhibits highly improved capacity retention after 500 cycles.
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Kazyak, Eric, Srinivas Yadavalli, Kiwoong Lee, Michael Wang, Adrian J. Sanchez, M. D. Thouless, Jeff Sakamoto, and Neil P. Dasgupta. "Understanding Coupled Electro-Chemo-Mechanics during I n Situ Li Metal Anode Formation in Anode-Free Solid-State Batteries." ECS Meeting Abstracts MA2022-01, no. 37 (July 7, 2022): 1630. http://dx.doi.org/10.1149/ma2022-01371630mtgabs.
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Solid-state batteries (SSBs) are potentially disruptive for a range of applications owing to their promise of high energy density, improved safety, and long cycle life. Their ability to enable Li metal anodes is a major advantage for energy density, but Li presents challenges for manufacturing due to its reactivity and the difficulty of fabricating thin Li films and high-quality Li/Electrolyte interfaces. Recently, in situ anode formation has shown significant promise for overcoming these challenges. In this approach, the cells are assembled without an anode (“Anode-free”), and Li metal is plated out from the cathode after fabrication. This reduces the need for inert atmospheres and reduces cell complexity, potentially lowering cost. As Li is plated out for the first time, mechanical stresses evolve at the Li/Electrolyte interface due to the volumetric changes in the electrodes. These stresses and the coupling between mechanics and electrochemistry play an important role in the resulting uniformity and quality of the in situ formed Li electrode. This work leverages 3D operandooptical video microscopy to observe morphology changes during in situ anode formation on one of the most promising solid electrolytes, Li7La3Zr2O12 (LLZO). These morphology changes are linked to the electrochemical signatures and the dynamic evolution of mechanical stresses at the Li/LLZO interface. A mechanistic framework is built to understand these factors, which is then used to provide guidance on what parameters control uniformity, and how systems can be designed to improve the resulting electrode properties. The role of stack pressure and the importance of stack pressure uniformity is highlighted. The impact of interfacial toughness, current collector properties, and cell geometry are discussed. Based on this understanding, the areal Li coverage is improved by more than 50%, providing insight for future works to enable in situ anode formation in a range of material systems and cell architectures.
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Xie, Huanyu, Chaonan Wang, En Zhou, Hongchang Jin, and Hengxing Ji. "A black phosphorus-graphite hybrid as a Li-ion regulator enabling stable lithium deposition." JUSTC 52, no. 12 (2022): 3. http://dx.doi.org/10.52396/justc-2022-0105.
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Lithium (Li) metal anodes have been regarded as the most promising candidates for high energy density secondary lithium batteries due to their high specific capacity and low redox potential. However, the issues of Li dendrites caused by nonuniform lithium deposition during battery cycling severely hinder the practical applications of Li metal anodes. Herein, a hybrid of black phosphorus-graphite (BP-G) is introduced to serve as an artificial protective layer for the Li metal anode. The two-dimensional few-layer BP, which is lithophilic, combined with the high electronic conductive graphite can act as a regulator to adjust the migration of Li ions, delivering a uniform and stable lithium deposition. As the growth of lithium dendrites is inhibited, the utilization of Li metal achieves > 98.5% for over 500 cycles in Li||Cu half cells, and the life span is maintained over 2000 h in Li||Li symmetric cells with a low voltage hysteresis of 50 mV. Moreover, the LiFePO<sub>4</sub>||Li full cell with a BP-G Li-ion regulator presents significantly better specific capacity and cycling stability than that with the bare Li metal anode. Therefore, the introduction of the BP-G Li-ion regulator is demonstrated to be an effective approach to enable stable lithium deposition for rechargeable Li metal batteries.
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Li, Yao Yao, Yin Hu, and Cheng Tao Yang. "Regulating Li<sup>+</sup> Transfer and Solvation Structure via Metal-Organic Framework for Stable Li Anode." Key Engineering Materials 939 (January 25, 2023): 123–27. http://dx.doi.org/10.4028/p-in7u78.
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Lithium metal batteries (LMBs) possess large application potential for advanced rechargeable batteries due to the high energy density (> 500 Wh kg−1) and alternative cathode materials. Random Li dendrite growth caused by uneven Li+ distribution and local ion depletion near surface of Li anode induces battery failure with inferior long-term stability. Therefore, regulation of ion distribution near anode surface is essential to realize dendrite-free and uniform Li deposition. Herein, a metal-organic framework (MOF), i.e., ZIF-8, is applied to regulate Li+ solvation structure via unsaturated metal-ion sites to achieve uniform Li+ distribution and Li deposition. A stable cycling performance over 800 h for Li symmetrical cell at 3 mA cm−2 and 3 mAh cm−2 without short circuit is realized. The facilitated Li+ solvation via the adsorption effect of metal-ion sites on anions is demonstrated, which further enhances the uniform Li+ distribution near Li anode surface. This work demonstrates an effective strategy for regulating ion coordination and Li+ distribution to stabilize Li anode via MOF-based materials.
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Yuan, Guanghui, Rui Cao, Ye Chen, Xinyu Ge, Qiong Xu, and Zhaozhe Wang. "Half and full cell researches of ternary MoS2/graphene/CNT aerogel compostie for enhanced lithium storage performances." Journal of Physics: Conference Series 2085, no. 1 (November 1, 2021): 012027. http://dx.doi.org/10.1088/1742-6596/2085/1/012027.
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Abstract Without using any templates, a ternary MoS2/graphene/carbon nanotubes (MoS2/GN/CNT) aerogel compostie is prepared by convenient hydrothermal synthesis method. The free-standing MoS2/GN/CNT aerogel can be cut directly as binder free electrodes in lithium-ion batteries. The MoS2/GN/CNT electrodes can hold as high as 695 and 579 mAh g−1 discharge capacities after 200 cycles at 200 mA g−1 in MoS2/GN/CNT//Li half cells and MoS2/GN/CNT//LiCoO2 full-cells, respectively. The strengthened electrochemical properities are owed by the thin GN/CNT layers and their jagged and wrinkled surfaces, which can enhance the composite conductivity and shorten the Li+ diffusion distance, as well as buffer the volume change of electrodes druing the charge-discharge cycles.
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Zhang, Ji-Guang, Xia Cao, Wu Xu, and Ju-Myung Kim. "Development of Li Metal Batteries with Improved Safety." ECS Meeting Abstracts MA2022-02, no. 4 (October 9, 2022): 362. http://dx.doi.org/10.1149/ma2022-024362mtgabs.
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Development of Li metal batteries (LMBs) has attracted worldwide attention in recent years due to their much higher theoretical energy densities than those of conventional Li ion batteries. LMBs with high energy density and long cycle life have been demonstrated by several institutions and companies recently.1,2 LMBs may be safe in their early stage of cycling due to the small geometric surface area of Li metal anode. However, after long term cycling, mossy/dendritic/“dead Li” will form eventually. They will not only lead to the increase of cell thickness, but also lead to powdered Li which pose a safety concern when exposed to air in the extreme case of mechanical damage, especially for their large scale applications.3 Thus, a paradigm change in the electrolyte design is required to minimize the formation of “dead Li” and improve the thermal stability of the batteries. In this work, several approaches have been used to improve the thermal stability of LMBs. (1) Use of electrolyte with high coulombic efficiency to minimize the formation of “dead Li” or mossy Li; (2) use of non-flammable solvent in electrolyte; (3) use of solvent with high boiling point and high flash point. (4) use of electrolyte enabling formation of large size of Li deposition with minimal surface area. This will enable the formation of a lithiophobic SEI layer which can accommodate stress/strain during large volume changes. (5) Screening additives to improve Li CE and safety. The electrolytes with improved safety/stability at extreme conditions will also be reported in this work. 1 Niu, C. et al. Balancing interfacial reactions to achieve long cycle life in high-energy lithium metal batteries. Nature Energy, (2021). 2 Hu, Q. Li-metal batteries, https://s29.q4cdn.com/695431818/files/doc_presentation/2022/03/March-2022-Investor-Presentation.pdf (2022). 3 Louli, A. J. et al. Diagnosing and correcting anode-free cell failure via electrolyte and morphological analysis. Nature Energy 5, 693-702, (2020).
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Zaidi, Syed Danish Ali, Chong Wang, Qinjun Shao, Jing Gao, Shengdong Zhu, Haifeng Yuan, and Jian Chen. "Polymer-free electrospun separator film comprising silica nanofibers and alumina nanoparticles for Li-ion full cell." Journal of Energy Chemistry 42 (March 2020): 217–26. http://dx.doi.org/10.1016/j.jechem.2019.06.018.
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Sacci, Robert L., Andrew S. Westover, Zhiao Yu, and Zhenan Bao. "Dynamic Impedance Spectroscopy of Lithium Plating from Next Generation Electrolytes." ECS Meeting Abstracts MA2022-02, no. 2 (October 9, 2022): 149. http://dx.doi.org/10.1149/ma2022-022149mtgabs.
Full textAbstract:
The anode-free cells have emerged due to the need to maximize Li metal batteries' energy density. However, anode-free Li batteries suffer from short cycle life because of the lack of Li inventory at the anode. Freshly deposited Li metal anodes usually take hundreds of cycles to reach initial SEI stabilization optimum coulombic efficiency (CE) due to initial SEI stabilization and electrode activation. The anode-free cell design requires high Li metal CE over the whole cycling life, particularly during the initial activation cycles. A holistic approach to electrolyte design, mechanism understanding, and battery engineering is needed to fulfill these requirements. Here, we present a mechanistic study on lithium plating and stripping from next generation electrolytes. We conducted dynamic impedance spectroscopy (dEIS) to probe the formation and evolution of the SEI during Li plating and stripping on copper current collectors. dEIS superimposes a multisine waveform atop the dc stimulus signal, as shown by the lightly shaded curves in Fig 1 (top left). We applied a sliding window FFT protocol that takes the complex ratio of the measured potential and current signals obtained from Fig 1 (top right) and transforms it into complex impedance. We will discuss two Li platting systems, Lipon (an amorphous ceramic) and a liquid electrolyte with stabilizing additives. We observed drastic changes in the cells' impedance during plating and stripping, Figure 1 (bottom plots). We will show how the passivation layer's impedance continues to evolve during Li cycling and accounts for a significant amount of the overall cell resistance. The US Department of Energy’s Energy Efficiency and Renewable Energy Vehicles Technologies Office provided funding for this work under the US-German Cooperation on Energy Storage: Lithium-Solid-Electrolyte Interfaces program. Figure 1
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Kato, M., and M. Suzuki. "Effect of Li+ substitution for extracellular Na+ on GRF-induced GH secretion from rat pituitary cells." American Journal of Physiology-Cell Physiology 256, no. 4 (April 1, 1989): C712—C718. http://dx.doi.org/10.1152/ajpcell.1989.256.4.c712.
Full textAbstract:
Several observations have been made on the mechanism of human growth hormone-releasing factor (hGRF)-induced growth hormone (GH) secretion. 1) hGRF activates adenylate cyclase and the production of adenosine 3',5'-cyclic monophosphate (cAMP). 2) Extracellular Ca2+ is indispensable in both hGRF- and excess K+-induced GH secretion. 3) Extracellular Na+ is also essential in hGRF-induced but not in excess K+-induced GH secretion. 4) Both Ca2+ and Na+ are required in dibutyryl adenosine 3',5'-cyclic monophosphate (DBcAMP)-induced GH secretion. Thus hGRF may increase Na+ conductance via cAMP, which in turn depolarizes the somatotrophs and activates voltage-sensitive Ca2+ channels, thereby promoting Ca2+ entry and GH secretion. To further examine this possibility, replacement of Na+ with Li+ (an alkali metal ion permeant to Na+ channel) was studied in perifused dispersed rat anterior pituitary cells. Li+ substitution for extracellular Na+ did not suppress but augmented hGRF-and DBcAMP-induced GH secretion, whereas the rise in cellular cAMP content produced by hGRF was greatly attenuated in Na+-free, Li+ medium. This hGRF-induced GH secretion in Na+-free, Li+ medium was almost completely nullified by removing extracellular Ca2+. Thus Li+ was able to replace Na+, which further suggests the involvement of Na+ channels in hGRF-induced GH secretion. The possible mechanism of the augmented response in Na+-free, Li+ medium is discussed.
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Li, Dongdong, Yuan Gao, Chuan Xie, and Zijian Zheng. "Au-coated carbon fabric as Janus current collector for dendrite-free flexible lithium metal anode and battery." Applied Physics Reviews 9, no. 1 (March 2022): 011424. http://dx.doi.org/10.1063/5.0083830.
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Composite lithium metal anodes with three-dimensional (3D) conductive fabric present great potential to be used in high-energy-density flexible batteries for next-generation wearable electronics. However, lithium dendrites at the top of the fabric anode increase the risk of separator piercing and, therefore, cause a high possibility of short circuits, especially when undergoing large mechanical deformation. To ensure the safe application of the flexible lithium metal batteries, we herein propose a 3D Janus current collector by a simple modification of the bottom side of carbon fabric (CF) with a lithiophilic Au layer to construct highly flexible, stable, and safe Li metal anodes. The Janus Au layer can guide an orientated deposition of Li to the bottom of the CF. The lithium dendrite problem can be largely alleviated due to the lithium-free interface between the anode and separator, and meanwhile, the porous upper skeleton of the CF also provides large space to buffer the volume expansion of lithium metal. The resulting composite lithium metal anode exhibits a significant improvement in the life cycle (∼two fold) compared to the traditional top deposition of lithium metal. More importantly, assembled full batteries using the Janus anode structure exhibit high stability and safety during severe mechanical deformation, indicating the opportunity of the orientated deposition strategy to be used in future flexible and wearable electronics.