A functionalized membrane for lithium–oxygen batteries to suppress the shuttle effect of redox mediators

Chen, Zifang; Lin, Xiaodong; Xia, Hui; Hong, Yu‐Hao; Liu, Xiaoyu; Cai, Sanjun; Duan, Jia Ning; Yang, Junjie; Zhou, Zhi‐You; Chang, Jeng‐Kuei; Zheng, Mingsen; Dong, Quanfeng

doi:10.1039/c9ta03133b

Cited by 47 publications

(33 citation statements)

References 74 publications

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“…With the same cathode, the SBCG-and GF-based batteries yielded similar discharge capacities, while the BCG-based battery delivered a higher discharge capacity, which may be attributed to the presence of more protons (from the −OH groups of the BC), which have been reported to promote the formation of solution-growth discharge product. 42 It is worth noticing that the cells show very different charge behaviors. With the presence of LiI as the RM, it is widely agreed that the charge process first go with the electrochemical oxidation of I − to I 3 − at the surface of cathode.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…First, the initial full discharge–charge tests were carried out with a galvanostatic current of 100 mA g –1 , and the cutoff voltage range is between 2.2 and 4.4 V. The results are presented in Figure a. With the same cathode, the SBCG- and GF-based batteries yielded similar discharge capacities, while the BCG-based battery delivered a higher discharge capacity, which may be attributed to the presence of more protons (from the −OH groups of the BC), which have been reported to promote the formation of solution-growth discharge product . It is worth noticing that the cells show very different charge behaviors.…”

Section: Resultsmentioning

confidence: 99%

“…However, the combination of positively charged RM ox and negatively charged Nafion/PEDOT:PSS may not be the best choice since the RM ox would accumulate on the separator side due to the attractive force, while most discharge products were deposited on the oxygen-rich side of the cathode. 41 Dong's group 42 reported a strategy of mixing Nafion, PEO, and RGO into a composite membrane to prohibit I 3 − from shuttling, while the ionic conductivity may be sacrificed due to the use of ionic insulating materials. In addition, the high cost of Nafion and PEDOT:PSS restricts their practical uses as well.…”

Section: ■ Introductionmentioning

confidence: 99%

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Sulfonated Bacterial Cellulose-Based Functional Gel Polymer Electrolyte for Li–O₂ Batteries with LiI as a Redox Mediator

Shi

Wang

et al. 2021

ACS Sustainable Chem. Eng.

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The practical applications of Li–O2 batteries are hindered by the large charge polarization. Recently, the development of redox mediators (RMs) brings new hope for constructing low overpotential Li–O2 batteries. However, the “shuttle effect” of RMs causes new problems. Here, based on a low-cost and environmentally friendly biomaterial–bacterial cellulose, a sulfonation strategy was adopted to produce a functional gel polymer electrolyte for LiI-involved Li–O2 batteries. Benefiting from the high-density negatively charged sulfonate groups on the sulfonated bacterial cellulose, the functionalized gel electrolyte can produce strong electrostatic repulsion force to the negatively charged I3 – ions to suppress the shuttle effect. As a result, the Li–O2 battery shows a good cycling performance with eliminated self-discharge, and the Li anode is successfully protected by the inhibition of I3 – shuttling. This novel approach may provide new insights into the development of functionalized gel polymer electrolytes for Li–O2 batteries with redox mediators.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Sulfonated Bacterial Cellulose-Based Functional Gel Polymer Electrolyte for Li–O₂ Batteries with LiI as a Redox Mediator

Shi

Wang

et al. 2021

ACS Sustainable Chem. Eng.

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“…Alternatively, functionally modifying the separator gained considerable attention. The modification principle is to block the diffusion pathway of RMs through a physical barrier or coulombic interactions [ 70 , 71 ]. As shown in Fig.…”

Section: Challengesmentioning

confidence: 99%

Redox mediators for high-performance lithium–oxygen batteries

Dou

Xie

Wei

et al. 2022

National Science Review

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The aprotic lithium-oxygen (Li-O2) batteries are receiving intense research interest in virtue of their ultra-high theoretical specific energy. However, current Li-O2 batteries are sufferring from severe barriers, such as sluggish reaction kinetics and undesired parasitic reactions. Recently, molecular catlysts, i.e., redox mediators (RMs), have been explored to catalyze the oxygen electrochemistry in Li-O2 batteries and are regarded as an advanced solution. To fully unlock the capability of Li-O2 batteries, an in-depth understanding of the catalytic mechanisms of RMs is necessary. In this review, we summarize the working principles of RMs and their selection criteria, highlight the recent significant progress of RMs, and discuss the critical scientific and technical challenges on the design of efficient RMs for next-generation Li-O2 batteries.

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“…However, unstable RMs migrate to the anode and trigger severe anode corrosion due to the self‐discharge reaction between the oxidized RM and the Li metal, leading to poor cycle performance. [ 24 ] Besides this, RM + would react with the electrolyte as well, further causing serious side‐reactions between the oxidized electrolyte and Li 2 O 2 . Given all this, fabrication of a functional separator would be beneficial for blocking the migration of RMs.…”

Section: Theoretical Perspectives Of Porous Materials Applied In Li–omentioning

confidence: 99%

Porous Materials Applied in Nonaqueous Li–O₂ Batteries: Status and Perspectives

Wang

et al. 2020

Advanced Materials

143

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Li-O 2) batteries with high theoretical energy densities offer considerable potential for a new generation of energy storage technology. [1] In 1996, the first nonaqueous Li-O 2 battery was introduced with a polymer organic electrolyte and a carbon-cobalt composite cathode by Abraham and Jiang. [2] This was followed by the verification of the rechargeability of Li-O 2 batteries with manganese dioxide-super S cathodes for over 50 cycles by Bruce and co-workers, [3] after which nonaqueous Li-O 2 batteries received substantial research attention worldwide. A typical nonaqueous Li-O 2 battery includes a Li metal anode, an aprotic electrolyte and an O 2 cathode. It operates according to the reaction 2Li + O 2 ↔ Li 2 O 2 (2.96 V vs Li/Li +), in which O 2 is reduced to form Li 2 O 2 on the cathode during discharging and Li 2 O 2 is decomposed to O 2 and Li + through a reversible charging process. In this way, the battery delivers exceptional theoretical energy density of ≈3600 Wh kg −1. [4] This report is centered on nonaqueous Li-O 2 batteries, and the use of the term "Li-O 2 batteries" mentioned below represents "nonaqueous Li-O 2 batteries." To date, enormous progress has been achieved in the understanding and application of high-performance Li-O 2 batteries, however, their low practical discharge capacity, poor rate capability, low round-trip efficiency, and inferior cycling stability have greatly blocked their practical applications. The current major scientific and technical challenges of Li-O 2 batteries can be summarized as follows. 1) The slow kinetics of formation and decomposition of the discharge products lead to poor rate capability and low round-trip efficiency. 2) Cathode corrosion and electrolyte decomposition due to the attack by the discharge intermediates such as superoxide species, giving rise to poor cycling stability. 3) Pore clogging on the cathode arising from the stacking of insulated, insoluble discharge products blocks the mass transfer and oxygen/Li + diffusion, limiting the capacity and degrading the cycling performance. 4) The inevitable side reactions between the highly reactive Li anode and the organic electrolyte, crossover O 2 , CO 2 , etc., and the redox mediators (RMs), give rise to premature battery death. [1a,5] 5) The unavoidable Li dendrites caused by uncontrollable deposition of lithium, as well as the risk of collapse of the lithium anode due to the volume change during iterative plating/stripping processes, increase the probability of safety problems. [6] Consequently, the slow kinetics of Li 2 O 2 Porous materials possessing high surface area, large pore volume, tunable pore structure, superior tailorability, and dimensional effect have been widely applied as components of lithium-oxygen (Li-O 2) batteries. Herein, the theoretical foundation of the porous materials applied in Li-O 2 batteries is provided, based on the present understanding of the battery mechanism and the challenges and advantageous qualities of porous materials. Furthermore, recent progress in porous material...

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A functionalized membrane for lithium–oxygen batteries to suppress the shuttle effect of redox mediators

Abstract: By combining steric hindrance and electrostatic repulsion, a functionalized Nafion–PEO–graphene (NPG) composite membrane was constructed and used to suppress the shuttle effect of the I−/I3− redox couple.

Cited by 47 publications

References 74 publications

Sulfonated Bacterial Cellulose-Based Functional Gel Polymer Electrolyte for Li–O₂ Batteries with LiI as a Redox Mediator

Sulfonated Bacterial Cellulose-Based Functional Gel Polymer Electrolyte for Li–O₂ Batteries with LiI as a Redox Mediator

Redox mediators for high-performance lithium–oxygen batteries

Porous Materials Applied in Nonaqueous Li–O₂ Batteries: Status and Perspectives

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A functionalized membrane for lithium–oxygen batteries to suppress the shuttle effect of redox mediators

Abstract: By combining steric hindrance and electrostatic repulsion, a functionalized Nafion–PEO–graphene (NPG) composite membrane was constructed and used to suppress the shuttle effect of the I−/I3− redox couple.

Cited by 47 publications

References 74 publications

Sulfonated Bacterial Cellulose-Based Functional Gel Polymer Electrolyte for Li–O2 Batteries with LiI as a Redox Mediator

Sulfonated Bacterial Cellulose-Based Functional Gel Polymer Electrolyte for Li–O2 Batteries with LiI as a Redox Mediator

Redox mediators for high-performance lithium–oxygen batteries

Porous Materials Applied in Nonaqueous Li–O2 Batteries: Status and Perspectives

Contact Info

Product

Resources

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Sulfonated Bacterial Cellulose-Based Functional Gel Polymer Electrolyte for Li–O₂ Batteries with LiI as a Redox Mediator

Sulfonated Bacterial Cellulose-Based Functional Gel Polymer Electrolyte for Li–O₂ Batteries with LiI as a Redox Mediator

Porous Materials Applied in Nonaqueous Li–O₂ Batteries: Status and Perspectives