Plating a Dendrite-Free Lithium Anode with a Polymer/Ceramic/Polymer Sandwich Electrolyte

Zhou, Weidong; Wang, Shaofei; Li, Yutao; Xin, Sen; Manthiram, Arumugam; Goodenough, John B

doi:10.1021/jacs.6b05341

Cited by 889 publications

(641 citation statements)

References 36 publications

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“…S10 showed that the black thin layer was (Fig. 4B), which is smaller than those of previously reported allsolid-state batteries (20). Fig.…”

Section: Significancementioning

confidence: 54%

“…The Li/LiZr 2 (PO 4 ) 3 /Li symmetric cell was prepared by putting lithium foil on both sides of the LiZr 2 (PO 4 ) 3 pellet, and the cell was cycled with different current densities in a Land instrument. The LiFePO 4 preparation process was the same as in our previous report (20). To prepare the cathode of an all-solid-state LiFePO 4 /Li cell, the active material LiFePO 4 was mixed with carbon black, cross-linked polyethylene oxide, and LiTFSI (60:12:20:8 by weight) and ground in a mortar.…”

Section: Methodsmentioning

confidence: 99%

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Mastering the interface for advanced all-solid-state lithium rechargeable batteries

Zhou

Chen

et al. 2016

Proc. Natl. Acad. Sci. U.S.A.

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A solid electrolyte with a high Li-ion conductivity and a small interfacial resistance against a Li metal anode is a key component in all-solid-state Li metal batteries, but there is no ceramic oxide electrolyte available for this application except the thin-film Li-P oxynitride electrolyte; ceramic electrolytes are either easily reduced by Li metal or penetrated by Li dendrites in a short time.Here, we introduce a solid electrolyte LiZr 2 (PO4) 3 with rhombohedral structure at room temperature that has a bulk Li-ion conductivity σ Li = 2 × 10 −4 S·cm −1 at 25°C, a high electrochemical stability up to 5. electrolyte has enabled the wireless revolution, but it is not able to power safely an electric road vehicle at a cost that is competitive with the gasoline-powered internal combustion engine (1-4). Safety concerns as well as cost, volumetric energy density, and cycle life have prevented realization of a commercially viable electric road vehicle. To address this problem, considerable effort is being given to the development of a solid Li + or Na + electrolyte that is wet by a metallic lithium or sodium anode and has an alkali ion conductivity σ i > 10 −4 S·cm −1 at the cell operating temperature T op , where a T op ≤ 25°C is desired (5-10). Such a development would allow new as well as traditional strategies for the cathode. Wetting of the solid electrolyte surface is desired not only because it prevents dendrite formation and growth during plating of an alkali metal anode, but also because wetting constrains the anode volume change in a charge/ discharge cycle to be perpendicular to the anode/electrolyte interface, thereby allowing a long cycle life. Therefore, the shear modulus of the electrolyte may not be critical where lithium wets the electrolyte surface.Ceramic oxide electrolytes offer a large energy gap between their conduction and valence bands, which can allow realization of a battery cell with a large energy separation between the anode and cathode chemical potentials without either reduction or oxidation of the electrolyte by an electrode (2). However, if an alkali-metal anode reduces the solid electrolyte, formation of a stable solid-electrolyte interphase (SEI) that conducts the working Li + or Na + ion is acceptable if the Li + or Na + transfer across the SEI has a low resistance. Although many ceramic solid Li + electrolytes have been investigated, they are easily reduced by Li metal and/or they have failed to block dendrite formation and growth into their grain boundaries (SI Appendix, Fig. S1). However, the rhombohedral structure of the Na electrolyte Na 1+3x Zr 2 (Si x P 1-x O 4 ) 3 (11), NASICON, which was developed over 45 y ago, has recently been used in a cell design in which a seawater cathode provides the sodium of the anode (12).The stability of the solid electrolyte on contact with a lithium anode is a critical issue. If a lithium anode reduces the electrolyte, (i) the electrolyte may become an electronic conductor, (ii) an interface layer may form that blocks Li + transfer, or (iii) a...

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“…S10 showed that the black thin layer was (Fig. 4B), which is smaller than those of previously reported allsolid-state batteries (20). Fig.…”

Section: Significancementioning

confidence: 54%

Section: Methodsmentioning

confidence: 99%

Mastering the interface for advanced all-solid-state lithium rechargeable batteries

Zhou

Chen

et al. 2016

Proc. Natl. Acad. Sci. U.S.A.

Self Cite

259

221

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“…The LiFePO 4 cathode was mixed with the CPEO-LITFSI polymer to reduce the interfacial resistance between garnet electrolyte and LiFePO 4 . [9] The XRD patterns of the as-prepared Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 (LLZT) with different amounts of LiF are shown in Figure 1 a and Figure S2; all the pellets crystallize in a cubic garnet structure with high purity and the lattice parameters of all the LLZT pellets calculated by the refinement with the Fullprof software were a = 12.9340 . LiF does not enter into the LLZT grains.…”

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confidence: 99%

Hybrid Polymer/Garnet Electrolyte with a Small Interfacial Resistance for Lithium‐Ion Batteries

et al. 2016

Angew Chem Int Ed

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Li La Zr O -based Li-rich garnets react with water and carbon dioxide in air to form a Li-ion insulating Li CO layer on the surface of the garnet particles, which results in a large interfacial resistance for Li-ion transfer. Here, we introduce LiF to garnet Li La Zr Ta O (LLZT) to increase the stability of the garnet electrolyte against moist air; the garnet LLZT-2 wt % LiF (LLZT-2LiF) has less Li CO on the surface and shows a small interfacial resistance with Li metal, a solid polymer electrolyte, and organic-liquid electrolytes. An all-solid-state Li/polymer/LLZT-2LiF/LiFePO battery has a high Coulombic efficiency and long cycle life; a Li-S cell with the LLZT-2LiF electrolyte as a separator, which blocks the polysulfide transport towards the Li-metal, also has high Coulombic efficiency and kept 93 % of its capacity after 100 cycles.

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“…However, brittleness results in high fracture energy, and interphase contacting problems between electrolyte and lithium metal restrict practical application severely 15, 16, 17, 18, 19, 20. In comparison, polymer electrolyte improves the contact matters because of its flexibility, but the low ion conductivity under room temperature and narrow electrochemical window greatly impose restrictions on its further applications.…”

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confidence: 99%

A Dual‐Salt Gel Polymer Electrolyte with 3D Cross‐Linked Polymer Network for Dendrite‐Free Lithium Metal Batteries

et al. 2018

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Lithium metal batteries show great potential in energy storage because of their high energy density. Nevertheless, building a stable solid electrolyte interphase (SEI) and restraining the dendrite growth are difficult to realize with traditional liquid electrolytes. Solid and gel electrolytes are considered promising candidates to restrain the dendrites growth, while they are still limited by low ionic conductivity and incompatible interphases. Herein, a dual‐salt (LiTFSI‐LiPF6) gel polymer electrolyte (GPE) with 3D cross‐linked polymer network is designed to address these issues. By introducing a dual salt in 3D structure fabricated using an in situ polymerization method, the 3D‐GPE exhibits a high ionic conductivity (0.56 mS cm−1 at room temperature) and builds a robust and conductive SEI on the lithium metal surface. Consequently, the Li metal batteries using 3D‐GPE can markedly reduce the dendrite growth and achieve 87.93% capacity retention after cycling for 300 cycles. This work demonstrates a promising method to design electrolytes for lithium metal batteries.

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Plating a Dendrite-Free Lithium Anode with a Polymer/Ceramic/Polymer Sandwich Electrolyte

Cited by 889 publications

References 36 publications

Mastering the interface for advanced all-solid-state lithium rechargeable batteries

Mastering the interface for advanced all-solid-state lithium rechargeable batteries

Hybrid Polymer/Garnet Electrolyte with a Small Interfacial Resistance for Lithium‐Ion Batteries

A Dual‐Salt Gel Polymer Electrolyte with 3D Cross‐Linked Polymer Network for Dendrite‐Free Lithium Metal Batteries

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