High Voltage, Transition Metal Complex Enables Efficient Electrochemical Energy Storage in a Li‐Ion Battery Full Cell

Zheng, Qi; Niu, Zhihui; Ye, Jing; Zhang, Shun; Zhang, Luwei; Zhao, Yu

doi:10.1002/adfm.201604299

Cited by 20 publications

(11 citation statements)

References 39 publications

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“…Fichtner and co‐workers have reported the use of a Cu‐porphyrin complex as both positive and negative electrode material, combining high storage capacity and rate capability with extended cycling stability . By synergizing the concept of both Li‐ion and redox flow batteries, a [Fe(bipyridine) 3 ](BF 4 ) 2 complex showed promising electrochemical performance as high‐voltage catholyte material for lithium storage . Along the same lines, 10‐phenanthroline‐5,6‐dione (phendione, hereafter denoted as phendi) was used to form stable MOCs by chelating with a large variety of transition metals (TMs) through N atoms .…”

Section: Methodsmentioning

confidence: 99%

Phendione–Transition‐Metal Complexes with Bipolar Redox Activity for Lithium Batteries

et al. 2020

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1,10-Phenanthroline-5,6-dione (phendione)-based transitionmetal complexes are known for their use in pharmacological and catalysis applications. However, their application in electrochemicale nergy storageh as not been investigated thus far. Herein, the feasibility of employing phendione-transitionmetal complexes was investigated for electrochemical charge storageb yt aking advantage of the reversible redox activity of both carbonyl groups and transition metal center, contributing to augmented charges torage. Interestingly,t he chemistry of the counter ion in the studied complexes effectively tuned the solubility and improved the cycling stability. Although further studies are required to limit the solubility and active-species shuttle,t his study explores the bottlenecks of phendione-transition-metal complexes as electrode materials for solid-electrode-format batteries.Quinone derivatives constitute an importantc lass of naturally occurring compounds found in plants, fungi, and bacteria, with an important role as charge-transfer mediators in photosynthesis and the respiratory chain of chloroplasts and mitochondria (plastoquinones and ubiquinones). [1] The redox activity of quinones is also well-established in molecular electrochemistry, [2] with interesting characteristics manifestedb y multi-electron redox reactions and fast kinetics. Owing to these properties, quinone derivatives have attracted significant interesti nt he electrochemical charge-storage research community.T he first mention of the use of quinones as active material in batteriesc an be traced back to 1972, when Alt et al. [3] reported the use of simple benzoquinone as electrode material for lithium storage.T he cell provided an output voltage of 2.50 Vv s. Li + /Li for at heoretical capacity of 496 mAh g À1 with an energy density as high as 1kWh g À1 .S ince then, many different molecular designs have been proposed, [4] with the use of quinone derivatives in many forms to fit with the desired energy-storage device requirements. So far,q uinones have been used as dissolved or bulky solid active material, but also in different molecular architectures such as smallm olecules (mainly in oxidized but also in reduced state:m etal-reservoir cathode), polymers, or hybrid frameworks.Quinone-based smallm olecules are usually privileged owing to their highere nergy density and easier structuralf lexibility. Indeed, their redox potential can be effectively modified by incorporating electron-withdrawing or -donating groups. [5] Along the same principles, fusing with heteroaromatic rings [6] or switching the isomerism to foster electrostatic interaction [7] was also shown to cause ap ositives hift of the redox potential. Althougha ni ncreaseo ft he redox potential achieves higher energy-density metrics,c ycling stability is still am ajor concern when integratingq uinoned erivatives in lithium cells. Indeed, solubility remains at opic of concern when dealingw ith small molecules, requiring various approaches to be applied. For example,i ntegration of ionic g...

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Section: Methodsmentioning

confidence: 99%

Phendione–Transition‐Metal Complexes with Bipolar Redox Activity for Lithium Batteries

et al. 2020

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“…Both BuPh/BuPh À and DMFc/DMFc + redox couples were electrochemically reversible and the ratio of peak cathodic and anodic current was close to 1.0 at different scan rates.T he calculated diffusion coefficients (D)o fB uPh and DMFc molecules were 8.2-9.9 10 À6 cm 2 s À1 and 3.0-3.2 10 À6 cm 2 s À1 ,r espectively,a ccording to the anodic and cathodic peak currents at different scan rates (see Figures S7 and S8), which are on the same order of magnitude with other redox couples used in nonaqueous RFBs. [22] BuPh and DMFc exhibited stable redox activity over 500 CV cycles without obvious decay,suggesting high chemical and electrochemical stabilities under CV conditions (see Figure S9). …”

Section: Angewandte Chemiementioning

confidence: 99%

Biredox Eutectic Electrolytes Derived from Organic Redox‐Active Molecules: High‐Energy Storage Systems

et al. 2019

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One promising candidate for high-energy storage systems is the nonaqueous redox flow battery (NARFB). However,their application is limited by lowsolubility of redoxactive materials and poor performance at high current density. Reported here is an ew strategy,abiredoxeutectic,a sthe sole electrolyte for NARFB to achieve as ignificantly higher concentration of redox-active materials and enhance the cell performance.W ithout other auxiliary solvents,t he biredox eutectic electrolyte is formed directly by the molecular interactions between two different redox-active molecules. Such au nique electrolyte possesses high concentration with low viscosity (3.5 m,for N-butylphthalimide and 1,1-dimethylferrocene system) and ar elatively high working voltage of 1.8 V, enabling high capacity and energy density of NARFB. The resulting high-performance NARFB demonstrates that the biredox eutectic based strategy is potentially promising for lowcost and high-energy storage systems.

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“…Wide‐scale integration of renewable energy into the electric grid requires the development of high energy density, low‐cost energy storage systems . Among the various energy storage systems, state‐of‐art lithium‐ion batteries (LIBs) are the most promising candidates for this application . However, the ever‐increasing demand for LIBs and geographic‐restriction of Li precursors impose limitations on the large‐scale applications of LIBs .…”

Section: Introductionmentioning

confidence: 99%

Long Cycle Life, Low Self‐Discharge Sodium–Selenium Batteries with High Selenium Loading and Suppressed Polyselenide Shuttling

Wang

Jiang

Manthiram

2017

Advanced Energy Materials

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of sodium. [9,13] In addition, the electrode dynamics and thermodynamic knowledge accrued recently for LIBs could be employed to ensure rapid advances in SIBs. [14][15][16][17][18] Thus, development of viable room-temperature sodium-ion batteries is attracting increasing attention. [19][20][21][22][23][24] Recently, room-temperature (RT) sodium-sulfur (NaS) batteries, based on the conversion reaction chemistry, have triggered extensive research interest due to the high charge-storage capacity and the abundance of both sodium and sulfur. [25][26][27][28][29][30] However, the practical applications of RT NaS batteries are facing two major challenges: (i) sulfur has a low electronic conductivity (5 × 10 −30 S cm −1 at 25 °C), thus leading to sluggish electrochemical reaction processes and low utilization of the active sulfur in the electrode; (ii) severe "polysulfide shuttle effect," i.e., migration of dissolved polysulfide intermediate products through the porous separator between the cathode and the anode, which leads to rapid capacity fade during cycling. [31] Many approaches have been pursued to mitigate these issues, including employing modified separators, [30] porous carbon matrix, [26] etc. However, the intrinsic challenges of RT NaS batteries have been far from completely solved. Selenium is a chemical analogue of S [32,33] and is considered to be an alternative electrode materials for SIBs due to its much higher electronic conductivity (1 × 10 −3 S m −1 ) as indicated in Figure S1 in the Supporting Information, volumetric capacity (3253 A h L −1 ) comparable to that of S (3467 A h L −1 ), and stable function in the relatively low-cost carbonate-based electrolytes. [34][35][36] However, bulk Se particles still suffer from low active material utilization and Coulombic efficiency due to its electronically insulating properties and shuttling of high-order polyselenides. To circumvent these problems, the current efforts are mainly concentrated on improving the electrical conductivity and entrapping the active material within the cathode region, which include microporous/mesoporous carbon-selenium, [37][38][39] slit microporous carbon-selenium, [34] and flexible porous carbon nanofiberselenium. [40,41] With these approaches, the introduction of additional components (such as carbon black and binders) often lowers the energy density of NaSe batteries. Also, fabrication of these electrodes often involves complex multistep processes.In light of these pros and cons, we present herein a facile and scalable strategy to design carbon nanofiber (CNF)/selenium The use of selenium as a cathode in rechargeable sodium-selenium batteries is hampered by low Se loading, inferior electrode kinetics, and polyselenide shuttling between the cathode and anode. Here a high-performance sodiumselenium cell is presented by coupling a binder-free, self-interwoven carbon nanofiber-selenium cathode with a light-weight carbon-coated bifunctional separator. With this strategy, electrodes with a high Se mass loading (4.4 mg cm −2 ) rende...

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High Voltage, Transition Metal Complex Enables Efficient Electrochemical Energy Storage in a Li‐Ion Battery Full Cell

Cited by 20 publications

References 39 publications

Phendione–Transition‐Metal Complexes with Bipolar Redox Activity for Lithium Batteries

Phendione–Transition‐Metal Complexes with Bipolar Redox Activity for Lithium Batteries

Biredox Eutectic Electrolytes Derived from Organic Redox‐Active Molecules: High‐Energy Storage Systems

Long Cycle Life, Low Self‐Discharge Sodium–Selenium Batteries with High Selenium Loading and Suppressed Polyselenide Shuttling

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