Reclaiming Inactive Lithium with a Triiodide/Iodide Redox Couple for Practical Lithium Metal Batteries

Jin, Chengbin; Zhang, Xueqiang; Sheng, Ouwei; Sun, Shu‐Yu; Hou, Li‐Peng; Shi, Peng; Li, Bo‐Quan; Huang, Jia‐Qi; Tao, Xinyong; Zhang, Qiang

doi:10.1002/anie.202110589

Cited by 62 publications

(38 citation statements)

References 71 publications

(11 reference statements)

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“…[25b] In addition, the amount of I 2 should be strictly controlled to prevent the further pitting corrosion on active Li according to the previous literature. [23,26] To explore the effect of additives on solvation structure, nuclear magnetic resonance (NMR) was employed. A series of LPFN-i 2 type electrolytes with 5 vt% varied G4 n were prepared (denoted as G n m 4 , n,m represents the concentration of LiNO 3 in G4 and in bulk electrolyte respectively.…”

Section: Resultsmentioning

confidence: 99%

High‐Concentration Additive and Triiodide/Iodide Redox Couple Stabilize Lithium Metal Anode and Rejuvenate the Inactive Lithium in Carbonate‐Based Electrolyte

Wen

Fang

et al. 2022

Adv Funct Materials

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Carbonate-based electrolytes are incompatible with lithium (Li) metal anode because the generated solid electrolyte interphase (SEI) undergoes repeated breakage-repair, resulting in the accumulation of inactive Li including Li + compounds and electrically isolated dead Li 0 in the SEI. Therefore, exploiting a suitable strategy to construct a stable SEI while efficiently rejuvenating the inactive Li capacity is urgent and more thoughtful than just building a stereotyped SEI layer. Herein, an innovative strategy is proposed of high-concentration additive (HCA) of LiNO 3 inspired by (localized) high-concentration electrolyte and inactive Li restoration methodology via triiodide/iodide (I 3 − / I − ) redox couple to improve the compatibility of carbonate-based electrolytes. The HCA of LiNO 3 can maintain the cation-anion aggregates solvation structures in the carbonate-based bulk electrolyte and induce the in situ formation of superior-ionic-conductivity NO 3 − -derived SEI. Moreover, the reversible I 3 − / I − redox couple can further optimize the SEI and constantly rejuvenate the inactive Li including solvent/LiNO 3 -derived Li 2 O, a derivative has almost been acquiescent in LiNO 3 -additive electrolytes, and dead Li 0 into delithiated cathode. Consequently, epitaxy-like planar Li deposition, better reversibility, and higher capacity retention can be realized and are systematically verified by Li||Cu half cells, full cells with excess/limited Li (N/P ratio = 1.5) and anode-free lithium metal batteries.

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Section: Resultsmentioning

confidence: 99%

High‐Concentration Additive and Triiodide/Iodide Redox Couple Stabilize Lithium Metal Anode and Rejuvenate the Inactive Lithium in Carbonate‐Based Electrolyte

Wen

Fang

et al. 2022

Adv Funct Materials

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“…[ 33 ] In the previous work, we have demonstrated that the LiI formation is based on a spontaneous reaction between iodine (I 2 ) species and Li metal, which enables the elimination of dead Li and SEI delicately driven by slight cell energy. [ 34,35 ] As such, it is highly desired that I 2 species be beneficial to the formation of a stable interphase between PEO electrolyte and Li metal. In this work, we propose a PEO‐LiTFSI‐I 2 electrolyte for stable solid‐state LMBs (SSLMBs).…”

Section: Introductionmentioning

confidence: 99%

Interfacial and Ionic Modulation of Poly (Ethylene Oxide) Electrolyte Via Localized Iodization to Enable Dendrite‐Free Lithium Metal Batteries

Sheng

Liu

et al. 2021

Adv Funct Materials

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Solid polymer electrolytes (SPEs) make contact with highly reductive lithium (Li) metal anodes, forming the interphase that largely determines the battery performance. In this work, trace iodine doping in a poly(ethylene oxide) (PEO) electrolyte to achieve a stable interphase on Li metal surface for long battery cycling, is proposed. The triiodide ion (I3−) stemming from iodine additives can coordinate with the COC bond of PEO to enable the increased ionic conductivity of the SPE. The I‐doped interphase contains I3− and IO3−, which spontaneously react with the dead Li and Li2O at the initial interphase to smooth the Li metal surface, eventually leading to significant improvements in interfacial resistance and dendrite suppression. When matching with the LiFePO4 cathode, the full cell exhibits higher capacity (150 mAh g−1) and excellent cycling stability after 300 cycles (capacity retention of 96.5%) at 0.5 C and 50 °C. This work opens up a promising avenue for using halogen to design solid‐state Li metal batteries.

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“…However, irreversible reactions inevitably occur between highly reactive anodes and electrolytes, which severely plagues the life span of batteries (8)(9)(10). Despite the formation of solid electrolyte interphase (SEI), yet the irreversible reactions occur continuously because of the fragility of SEI (11)(12)(13). Therefore, inhibiting the reactions occurring at anode/ electrolyte interface is necessary for long-cycling rechargeable batteries (14)(15)(16)(17).…”

Section: Introductionmentioning

confidence: 99%

Inhibiting intercrystalline reactions of anode with electrolytes for long-cycling lithium batteries

Shi

Zhou

et al. 2022

Sci. Adv.

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The life span of lithium batteries as energy storage devices is plagued by irreversible interfacial reactions between reactive anodes and electrolytes. Occurring on polycrystal surface, the reaction process is inevitably affected by the surface microstructure of anodes, of which the understanding is imperative but rarely touched. Here, the effect of grain boundary of lithium metal anodes on the reactions was investigated. The reactions preferentially occur at the grain boundary, resulting in intercrystalline reactions. An aluminum (Al)–based heteroatom-concentrated grain boundary (Al-HCGB), where Al atoms concentrate at grain boundary, was designed to inhibit the intercrystalline reactions. In particular, the scalable preparation of Al-HCGB was demonstrated, with which the cycling performance of a pouch cell (355 Wh kg −1 ) was significantly improved. This work opens a new avenue to explore the effect of the surface microstructure of anodes on the interfacial reaction process and provides an effective strategy to inhibit reactions between anodes and electrolytes for long–life-span practical lithium batteries.

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Reclaiming Inactive Lithium with a Triiodide/Iodide Redox Couple for Practical Lithium Metal Batteries

Cited by 62 publications

References 71 publications

High‐Concentration Additive and Triiodide/Iodide Redox Couple Stabilize Lithium Metal Anode and Rejuvenate the Inactive Lithium in Carbonate‐Based Electrolyte

High‐Concentration Additive and Triiodide/Iodide Redox Couple Stabilize Lithium Metal Anode and Rejuvenate the Inactive Lithium in Carbonate‐Based Electrolyte

Interfacial and Ionic Modulation of Poly (Ethylene Oxide) Electrolyte Via Localized Iodization to Enable Dendrite‐Free Lithium Metal Batteries

Inhibiting intercrystalline reactions of anode with electrolytes for long-cycling lithium batteries

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