Anindityo Arifiadi, Feleke Demelash, Tobias Brake, Christian Lechtenfeld, Sven Klein, Lennart Alsheimer, Simon Wiemers-Meyer, Martin Winter, Johannes Kasnatscheew
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引用次数: 0
摘要
富含Li/ mn的层状氧化物(LMR)阴极活性材料在阳离子和阴离子氧化还原中都具有非常高的比放电容量(>250 mAh g - 1)。后者需要苛刻的充电条件以获得高阴极电位(>4.5 V vs Li|Li+),并伴随着晶格氧释放、相变、电压衰减和过渡金属(TM)溶解。在石墨阳极的电池中,TM溶解是特别有害的,因为它会引发电极串扰。二氟磷酸锂(LiDFP)以其通过清除TM抑制电极串扰的关键作用而闻名。在充电至4.5 V的高截止电压(UCV)的LMR ||石墨电池中,观察到LiDFP有效清除TM的效果。相比之下,对于4.7 V的UCV,清除效果有限,因为与4.5 V的UCV相比,TM溶解更严重。考虑到TM清除剂(LiDFP分解产物,如PO43 -和PO3F2 -)的溶解度饱和,高浓度的LiDFP作为“前体”不能增加清除物质的数量,而是开始沉淀并破坏阳极。
Elucidating the Limit of Lithium Difluorophosphate Electrolyte Additive for High-Voltage Li/Mn-Rich Layered Oxide || Graphite Li Ion Batteries
Li/Mn-rich layered oxide (LMR) cathode active materials offer remarkably high specific discharge capacity (>250 mAh g−1) from both cationic and anionic redox. The latter necessitates harsh charging conditions to high cathode potentials (>4.5 V vs Li|Li+), which is accompanied by lattice oxygen release, phase transformation, voltage fade, and transition metal (TM) dissolution. In cells with graphite anode, TM dissolution is particularly detrimental as it initiates electrode crosstalk. Lithium difluorophosphate (LiDFP) is known for its pivotal role in suppressing electrode crosstalk through TM scavenging. In LMR || graphite cells charged to an upper cutoff voltage (UCV) of 4.5 V, effective TM scavenging effects of LiDFP are observed. In contrast, for an UCV of 4.7 V, the scavenging effects are limited due to more severe TM dissolution compared an UCV of 4.5 V. Given the saturation in solubility of the TM scavenging agents, which are LiDFP decomposition products, e.g., PO43− and PO3F2−, higher concentrations of the LiDFP as “precursor” cannot enhance the amount of scavenging species, they rather start to precipitate and damage the anode.
期刊介绍:
Energy & Environmental Materials (EEM) is an international journal published by Zhengzhou University in collaboration with John Wiley & Sons, Inc. The journal aims to publish high quality research related to materials for energy harvesting, conversion, storage, and transport, as well as for creating a cleaner environment. EEM welcomes research work of significant general interest that has a high impact on society-relevant technological advances. The scope of the journal is intentionally broad, recognizing the complexity of issues and challenges related to energy and environmental materials. Therefore, interdisciplinary work across basic science and engineering disciplines is particularly encouraged. The areas covered by the journal include, but are not limited to, materials and composites for photovoltaics and photoelectrochemistry, bioprocessing, batteries, fuel cells, supercapacitors, clean air, and devices with multifunctionality. The readership of the journal includes chemical, physical, biological, materials, and environmental scientists and engineers from academia, industry, and policy-making.