The interplay between solid electrolyte interface (SEI) and dendritic lithium growth
TL;DR: In this article, a straightforward approach is proposed to induce the growth of detrimental dendritic Li so the cells are “shorted” frequently and consistently, based on this new protocol, various electrolytes are revisited and the SEI derived are compared and quantified, providing new insights for addressing the challenges in rechargeable Li metal battery technologies.
About: This article is published in Nano Energy.The article was published on 2017-10-01. It has received 177 citations till now.
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TL;DR: Liu et al. as mentioned in this paper discuss crucial conditions needed to achieve a specific energy higher than 350 Wh kg−1, up to 500 Wh kg −1, for rechargeable Li metal batteries using high-nickel-content lithium nickel manganese cobalt oxides as cathode materials.
Abstract: State-of-the-art lithium (Li)-ion batteries are approaching their specific energy limits yet are challenged by the ever-increasing demand of today’s energy storage and power applications, especially for electric vehicles. Li metal is considered an ultimate anode material for future high-energy rechargeable batteries when combined with existing or emerging high-capacity cathode materials. However, much current research focuses on the battery materials level, and there have been very few accounts of cell design principles. Here we discuss crucial conditions needed to achieve a specific energy higher than 350 Wh kg−1, up to 500 Wh kg−1, for rechargeable Li metal batteries using high-nickel-content lithium nickel manganese cobalt oxides as cathode materials. We also provide an analysis of key factors such as cathode loading, electrolyte amount and Li foil thickness that impact the cell-level cycle life. Furthermore, we identify several important strategies to reduce electrolyte-Li reaction, protect Li surfaces and stabilize anode architectures for long-cycling high-specific-energy cells. Jun Liu and Battery500 Consortium colleagues contemplate the way forward towards high-energy and long-cycling practical batteries.
1,747 citations
TL;DR: Liu et al. as discussed by the authors developed a prototype Li metal pouch cell by integrating a Li metal anode, a LiNi0.6Mn0.2Co 0.2O2 cathode and a compatible electrolyte.
Abstract: Lithium metal anodes have attracted much attention as candidates for high-energy batteries, but there have been few reports of long cycling behaviour, and the degradation mechanism of realistic high-energy Li metal cells remains unclear. Here, we develop a prototypical 300 Wh kg−1 (1.0 Ah) pouch cell by integrating a Li metal anode, a LiNi0.6Mn0.2Co0.2O2 cathode and a compatible electrolyte. Under small uniform external pressure, the cell undergoes 200 cycles with 86% capacity retention and 83% energy retention. In the initial 50 cycles, flat Li foil converts into large Li particles that are entangled in the solid-electrolyte interphase, which leads to rapid volume expansion of the anode (cell thickening of 48%). As cycling continues, the external pressure helps the Li anode maintain good contact between the Li particles, which ensures a conducting percolation pathway for both ions and electrons, and thus the electrochemical reactions continue to occur. Accordingly, the solid Li particles evolve into a porous structure, which manifests in substantially reduced cell swelling by 19% in the subsequent 150 cycles. Much has been said about the high-energy, long-lasting potential of Li metal batteries, and yet little has been demonstrated at the cell scale. Here, Jun Liu and colleagues demonstrate a Li metal pouch cell with a 300 Wh kg−1 energy density and a 200-cycle lifetime.
415 citations
TL;DR: In this article, the authors discuss the fundamental definition of Coulombic efficiency (CE) and unravel its true meaning in lithium-ion batteries and a few representative configurations of lithium metal batteries.
Abstract: Coulombic efficiency (CE) has been widely used in battery research as a quantifiable indicator for the reversibility of batteries While CE helps to predict the lifespan of a lithium-ion battery, the prediction is not necessarily accurate in a rechargeable lithium metal battery Here, we discuss the fundamental definition of CE and unravel its true meaning in lithium-ion batteries and a few representative configurations of lithium metal batteries Through examining the similarities and differences of CE in lithium-ion batteries and lithium metal batteries, we establish a CE measuring protocol with the aim of developing high-energy long-lasting practical lithium metal batteries The understanding of CE and the CE protocol are broadly applicable in other rechargeable metal batteries including Zn, Mg and Na batteries Coulombic efficiency (CE) has been frequently used to assess the cyclability of newly developed materials for lithium metal batteries The authors argue that caution must be exercised during the assessment of CE, and propose a CE testing protocol for the development of lithium metal batteries
409 citations
TL;DR: A self-smoothing lithium–carbon anode structure based on mesoporous carbon nanofibres, coupled with a lithium nickel–manganese–cobalt oxide cathode with a high nickel content, can lead to a cell-level energy density of 350–380 Wh kg−1 and a stable cycling life up to 200 cycles.
Abstract: Despite considerable efforts to stabilize lithium metal anode structures and prevent dendrite formation, achieving long cycling life in high-energy batteries under realistic conditions remains extremely difficult due to a combination of complex failure modes that involve accelerated anode degradation and the depletion of electrolyte and lithium metal. Here we report a self-smoothing lithium–carbon anode structure based on mesoporous carbon nanofibres, which, coupled with a lithium nickel–manganese–cobalt oxide cathode with a high nickel content, can lead to a cell-level energy density of 350–380 Wh kg−1 (counting all the active and inactive components) and a stable cycling life up to 200 cycles. These performances are achieved under the realistic conditions required for practical high-energy rechargeable lithium metal batteries: cathode loading ≥4.0 mAh cm−2, negative to positive electrode capacity ratio ≤2 and electrolyte weight to cathode capacity ratio ≤3 g Ah−1. The high stability of our anode is due to the amine functionalization and the mesoporous carbon structures that favour smooth lithium deposition. Metallic lithium wets a functionalized mesoporous carbon film to create a self-smoothing anode that, in conjunction with a standard lithium nickel–manganese–cobalt cathode, delivers long cycling life, 350 Wh kg−1 high-energy cells under realistic conditions.
399 citations
TL;DR: An overview of the fundamental understandings of solid electrolyte interphase (SEI) formation, conceptual models, and advanced real-time characterizations of LMI are presented and practical challenges in competing with graphite and silicon anodes are outlined.
Abstract: Lithium metal anodes are potentially key for next-generation energy-dense batteries because of the extremely high capacity and the ultralow redox potential. However, notorious safety concerns of Li metal in liquid electrolytes have significantly retarded its commercialization: on one hand, lithium metal morphological instabilities (LMI) can cause cell shorting and even explosion; on the other hand, breaking of the grown Li arms induces the so-called "dead Li"; furthermore, the continuous consumption of the liquid electrolyte and cycleable lithium also shortens cell life. The research community has been seeking new strategies to protect Li metal anodes and significant progress has been made in the last decade. Here, an overview of the fundamental understandings of solid electrolyte interphase (SEI) formation, conceptual models, and advanced real-time characterizations of LMI are presented. Instructed by the conceptual models, strategies including increasing the donatable fluorine concentration (DFC) in liquid to enrich LiF component in SEI, increasing salt concentration (ionic strength) and sacrificial electrolyte additives, building artificial SEI to boost self-healing of natural SEI, and 3D electrode frameworks to reduce current density and delay Sand's extinction are summarized. Practical challenges in competing with graphite and silicon anodes are outlined.
328 citations
References
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TL;DR: The phytochemical properties of Lithium Hexafluoroarsenate and its Derivatives are as follows: 2.2.1.
Abstract: 2.1. Solvents 4307 2.1.1. Propylene Carbonate (PC) 4308 2.1.2. Ethers 4308 2.1.3. Ethylene Carbonate (EC) 4309 2.1.4. Linear Dialkyl Carbonates 4310 2.2. Lithium Salts 4310 2.2.1. Lithium Perchlorate (LiClO4) 4311 2.2.2. Lithium Hexafluoroarsenate (LiAsF6) 4312 2.2.3. Lithium Tetrafluoroborate (LiBF4) 4312 2.2.4. Lithium Trifluoromethanesulfonate (LiTf) 4312 2.2.5. Lithium Bis(trifluoromethanesulfonyl)imide (LiIm) and Its Derivatives 4313
5,710 citations
TL;DR: The current understanding on Li anodes is summarized, the recent key progress in materials design and advanced characterization techniques are highlighted, and the opportunities and possible directions for future development ofLi anodes in applications are discussed.
Abstract: Lithium-ion batteries have had a profound impact on our daily life, but inherent limitations make it difficult for Li-ion chemistries to meet the growing demands for portable electronics, electric vehicles and grid-scale energy storage. Therefore, chemistries beyond Li-ion are currently being investigated and need to be made viable for commercial applications. The use of metallic Li is one of the most favoured choices for next-generation Li batteries, especially Li-S and Li-air systems. After falling into oblivion for several decades because of safety concerns, metallic Li is now ready for a revival, thanks to the development of investigative tools and nanotechnology-based solutions. In this Review, we first summarize the current understanding on Li anodes, then highlight the recent key progress in materials design and advanced characterization techniques, and finally discuss the opportunities and possible directions for future development of Li anodes in applications.
4,302 citations
TL;DR: A highly concentrated aqueous electrolyte whose window was expanded to ~3.0 volts with the formation of an electrode-electrolyte interphase, which could potentially be replaced with a safer aQueous alternative to lithium-ion batteries.
Abstract: Lithium-ion batteries raise safety, environmental, and cost concerns, which mostly arise from their nonaqueous electrolytes. The use of aqueous alternatives is limited by their narrow electrochemical stability window (1.23 volts), which sets an intrinsic limit on the practical voltage and energy output. We report a highly concentrated aqueous electrolyte whose window was expanded to ~3.0 volts with the formation of an electrode-electrolyte interphase. A full lithium-ion battery of 2.3 volts using such an aqueous electrolyte was demonstrated to cycle up to 1000 times, with nearly 100% coulombic efficiency at both low (0.15 C) and high (4.5 C) discharge and charge rates.
2,229 citations
TL;DR: In this article, the performance of Li, Li-C anodes and Li x MO y cathodes depends on their surface chemistry in solutions, which either contribute to electrode stabilization or to capacity fading due to an increase in the electrodes' impedance.
1,848 citations
TL;DR: It is reported that the use of highly concentrated electrolytes composed of ether solvents and the lithium bis(fluorosulfonyl)imide salt enables the high-rate cycling of a lithium metal anode at high Coulombic efficiency (up to 99.1%) without dendrite growth.
Abstract: Lithium metal is an ideal battery anode. However, dendrite growth and limited Coulombic efficiency during cycling have prevented its practical application in rechargeable batteries. Herein, we report that the use of highly concentrated electrolytes composed of ether solvents and the lithium bis(fluorosulfonyl)imide salt enables the high-rate cycling of a lithium metal anode at high Coulombic efficiency (up to 99.1%) without dendrite growth. With 4 M lithium bis(fluorosulfonyl)imide in 1,2-dimethoxyethane as the electrolyte, a lithium|lithium cell can be cycled at 10 mA cm(-2) for more than 6,000 cycles, and a copper|lithium cell can be cycled at 4 mA cm(-2) for more than 1,000 cycles with an average Coulombic efficiency of 98.4%. These excellent performances can be attributed to the increased solvent coordination and increased availability of lithium ion concentration in the electrolyte. Further development of this electrolyte may enable practical applications for lithium metal anode in rechargeable batteries.
1,824 citations