Search

Solid polymer electrolytes (SPEs) hold great application potential for solid-state lithium metal battery because of the excellent interfacial contact and processibility, but being hampered by the poor room-temperature conductivity (∼ 10−7 S·cm−1) and low lithium-ion transference number (t Li + ) . Here, a lamellar composite solid electrolyte (Vr-NH2@polyvinylidene fluoride (PVDF) LCSE) with β-conformation PVDF is fabricated by confining PVDF in the interlayer channel of -NH2 modified vermiculite lamellar framework. We demonstrate that the conformation of PVDF can be manipulated by the nanoconfinement effect and the interaction from channel wall. The presence of -NH2 groups could induce the formation of β-conformation PVDF through electrostatic interaction, which serves as continuous and rapid lithium-ion transfer pathway. As a result, a high room-temperature ionic conductivity of 1.77 × 10−4 S·cm−1 is achieved, 1–2 orders of magnitude higher than most SPEs. Furthermore, Vr-NH2@PVDF LCSE shows a high t Li + of 0.68 because of the high dielectric constant, ∼ 3 times of that of PVDF SPE, and surpassing most of reported SPEs. The LiNi0.8Co0.1Mn0.1O2∥Li cell assembled by Vr-NH2@PVDF LCSE obtains a discharge specific capacity of 137.1 mA·hg−1 after 150 cycles with a capacity retention rate of 93% at 1 C and 25 °C. This study may pave a new avenue for high-performance SPEs. [ABSTRACT FROM AUTHOR]

Electrolytes that can work over a wide temperature range are crucial forsustainable advanced energy systems. Here, a kind of lamellar ionic liquid composite electrolyte (L‐ILCE) is explored through confining ionic liquids (ILs) in ordered interlayer nanochannels of 2D vermiculite framework. It is demonstrated that, within nanochannels, the finely tuned microstructure can induce the rearrangement and crystallinity of ILs, affording L‐ILCE the combined superiorities of liquid electrolyte and solid‐state electrolyte. L‐ILCE exhibits high ionic conductivities (0.09–1.35 × 10−3 S cm−1 at −40 to 100 °C), whereas polymer and inorganic electrolytes usually lose ionic conduction ability below 0 °C. Additionally, L‐ILCE exhibits high transference number (0.89, comparable with single‐ion conductors) and wide electrochemical window (0–5.3 V). LiFePO4||Li and high‐voltage LiNi0.8Mn0.1Co0.1O2||Li cells assembled from L‐ILCEs exhibit highly stable electrochemical performance in −20 to 60 °C. Furthermore, pouch cells (0.1 Ah) exhibit high capacity of 93.8 and 45.0 mAh after 50 cycles along with capacity retention of 97% and 98% at 60 and −20 °C, respectively, as well as excellent flexibility and safety. This study offers promise in the rational design of advanced ion conductors for lithium‐based batteries with wider operating temperatures. [ABSTRACT FROM AUTHOR]

Developing laminar composite solid electrolyte with ultrathin thickness and continuous conduction channels in vertical direction holds great promise for all‐solid‐state lithium batteries. Herein, a thin, laminar solid electrolyte is synthesized by filtrating –NH2 functionalized metal‐organic framework nanosheets and then being threaded with poly(ethylene oxide) chains induced by the hydrogen‐bonding interaction from –NH2 groups. It is demonstrated that the threaded poly(ethylene oxide) chains lock the adjacent metal‐organic framework nanosheets, giving highly enhanced structural stability (Young's modulus, 1.3 GPa) to 7.5‐μm‐thick laminar composite solid electrolyte. Importantly, these poly(ethylene oxide) chains with stretching structure serve as continuous conduction pathways along the chains in pores. It makes the non‐conduction laminar metal‐organic framework electrolyte highly conductive: 3.97 × 10−5 S cm−1 at 25 °C, which is even over 25 times higher than that of pure poly(ethylene oxide) electrolyte. The assembled lithium cell, thus, acquires superior cycling stability, initial discharge capacity (148 mAh g−1 at 0.5 C and 60 °C), and retention (94% after 150 cycles). Besides, the pore size of nanosheet is tailored (24.5–40.9 Å) to evaluate the mechanisms of chain conformation and ion transport in confined space. It shows that the confined pore only with proper size could facilitate the stretching of poly(ethylene oxide) chains, and meanwhile inhibit their disorder degree. Specifically, the pore size of 33.8 Å shows optimized confinement effect with trans‐poly(ethylene oxide) and cis‐poly(ethylene oxide) conformation, which offers great significance in ion conduction. Our design of poly(ethylene oxide)‐threaded architecture provides a platform and paves a way to the rational design of next‐generation high‐performance porous electrolytes. [ABSTRACT FROM AUTHOR]

Inorganic superionic conductor holds great promise for high‐performance all‐solid‐state lithium batteries. However, the ionic conductivity of traditional inorganic solid electrolytes (ISEs) is always unsatisfactory owing to the grain boundary resistance and large thickness. Here, a 13 μm‐thick laminar framework with ≈1.3 nm interlayer channels is fabricated by self‐assembling rigid, hydrophilic vermiculite (Vr) nanosheets. Then, Li0.33La0.557TiO3 (LLTO) precursors are impregnated in interlayer channels and afterwards in situ sintered to large‐size, oriented, and defect‐free LLTO crystal. We demonstrate that the confinement effect permits ordered arrangement of LLTO crystal along the c‐axis (the fastest Li+ transfer direction), permitting the resultant 15 μm‐thick Vr‐LLTO electrolyte an ionic conductivity of 8.22×10−5 S cm−1 and conductance of 87.2 mS at 30 °C. These values are several times' higher than that of traditional LLTO‐based electrolytes. Moreover, Vr‐LLTO electrolyte has a compressive modulus of 1.24 GPa. Excellent cycling performance is demonstrated with all‐solid‐state Li/LiFePO4 battery. [ABSTRACT FROM AUTHOR]

[Display omitted] • LLZO nanosheets with lateral size of 3–5 μm and thickness of ~4.5 nm are synthesized. • LLZO laminar inorganic solid electrolyte with thickness of 12 μm is fabricated. • Ultrahigh ionic conductance of 0.17 S and energy density of 340 Wh kg−1 are achieved. • The compressive strength of LLZO laminar electrolyte reaches 3.2 GPa. • A superior cell performance of 143.2 mAh g−1 after 200 cycles is obtained. The development of thin solid-state electrolytes with high ionic conductivity and mechanical strength is essential for high-performance all-solid-state lithium batteries. Although Inorganic solid electrolytes (ISEs) possess high ionic conductivity, fabricating thin and mechanically stable ISEs is still challenging. Herein, Li 7 La 3 Zr 2 O 12 (LLZO) nanosheets with lateral size of 3–5 μm and thickness of ~4.5 nm were prepared, and then self-assembled into thin, defect-free, and freestanding LLZO laminar ISE (LLISE). Compared to LLZO pellet (>200 μm) obtained by cold-pressing method, LLISE with a thickness of 12 μm attains an almost 10-times higher ionic conductivity of 1.30 × 10−4 S cm−1 at 30 °C because of the short Li-ion diffusion distance. Importantly, this thin thickness gives high ionic conductance (0.17 S at 30 °C) and energy density of 340 Wh kg−1, ranking one of the highest values among reported solid-state electrolytes. Meanwhile, the compressive strength of LLISE with a thickness of 20 μm (LLISE-20) reaches 3.2 Gpa. The Li symmetrical cell assembled with LLISE-20 can work over 1500 h without obvious polarization under a current density of 0.2 mA cm−2 at 60 °C. The LFP/Li cell exhibits superior cycling stability of 143.2 mAh g−1 at 0.5C and 60 °C after 200 cycles with low capacity decay of 0.05% per cycle. [ABSTRACT FROM AUTHOR]

Garnet-type oxide Li 7 La 3 Zr 2 O 12 (LLZO) has attracted considerable attention as promising solid-state electrolyte (SSE) owing to the exceptional bulk ion conduction. However, the Li+ transfer capacity of most LLZO-based solid electrolytes remains inadequate, primarily due to the presence of extensive grain boundaries and excessive thickness. Herein, we report the fabrication of a LLZO-based lamellar composite inorganic solid electrolyte (LLZO/LIC LISE) by in-situ sintering Li 3 InCl 6 (LIC) in LLZO lamellar framework. LIC can act as an effective Li+-conductive grain boundary modifier within the electrolyte, leading to a remarkable reduction in grain boundary resistance of LLZO/LIC LISE (<9.2 Ω cm2), which is much lower than that of LLZO lamellar framework (827.2 Ω cm2). Together with the reduced internal grain boundary of LLZO nanosheet, a high ionic conductivity of 3.22 × 10−4 S cm−1 at 25 °C is obtained for LLZO/LIC LISE. In addition, combining with the thin thickness of 29 μm, LLZO/LIC LISE obtains high ionic conductance of 223 mS and exceptional energy density of 246 Wh kg−1, surpassing most developed SSEs. As a result, the cell assembled with LLZO/LIC LISE achieves superior cycling performance of 144.2 mAh g−1 after 200 cycles at 0.5C with a capacity decay of only 0.055% per cycle. This study may present a facile approach to effectively eliminate the grain boundary resistance of inorganic solid electrolytes toward high-performance all-solid-state lithium batteries. [Display omitted] • A 29 μm-thick LLZO/LIC lamellar composite solid electrolyte is fabricated. • The presence of LIC imparts ultralow grain boundary resistance (<9.2 Ω cm2). • The interfacial interaction between LLZO and LIC improves electrolyte stability. • The thin thickness affords high ionic conductance and energy density. • Superior performance with capacity of 144.2 mA h g−1 after 200 cycles is attained. [ABSTRACT FROM AUTHOR]

Inorganic superionic conductors hold great promise for all-solid-state lithium battery. However, the ionic conductivity of developed inorganic solid electrolytes (ISEs) is often insufficient owing to the enormous grain boundary resistance and large thickness. Herein, a 30 μm-thick Li 7 La 3 Zr 2 O 12 (LLZO) lamellar inorganic solid electrolyte (LLZO/CN LISE) is fabricated by assembling LLZO nanosheets into lamellar framework, followed by in-situ growing g-C 3 N 4 in the interlayer spacing. Based on the regular and unambiguous lamellar structure, g-C 3 N 4 is found to be an ideal grain boundary modifier, and the Li-ion transfer process at grain boundary is thus investigated in detail. We demonstrate that this LLZO/CN LISE achieves an ultralow grain boundary resistance (<12.3 Ω cm2 vs. 1608 Ω cm2 for LLZO pellet) and hence high ionic conduction properties (the ionic conductivity is 2.50 × 10−4 S cm−1 and the ionic conductance is 167 mS at 25 °C). The assembled Li symmetrical cell can stably cycle over 1500 h at 0.2 mA cm−2 and 60 °C. The assembled LiFePO 4 |Li cell also exhibits excellent cycling performances with a discharge capacity of 147.7 mAh g−1 at 0.5C and 60 °C after 150 cycles. This insight should present new opportunities in designing and developing high-performance ISEs. [Display omitted] • A 30 μm-thick Li 7 La 3 Zr 2 O 12 /g-C 3 N 4 lamellar inorganic solid electrolyte is prepared. • High ionic conductivity of 0.25 mS cm−1 and ionic conductance of 167 mS are gained. • The lamellar inorganic solid electrolyte exhibits an elastic modulus of 3.06 GPa. • With LiFePO 4 cathode, the energy densities reach 236 Wh kg−1. • A superior cell performance of 147.7 mAh g−1 after 150 cycles is obtained. [ABSTRACT FROM AUTHOR]

Succinonitrile (SN) plastic crystal electrolyte holds great promise for high-performance solid-state lithium metal batteries due to its high ionic conduction. However, the serious side reaction between SN and lithium anode always causes large interfacial resistance, deteriorating the battery capacity. Herein, we penetrated LiTFSI-SN (LSN) electrolyte into the interlayer channels of laminar metal-organic framework (MOF), then an ultra-thin and stable laminar LiTFSI–SN–MOF composite solid-state electrolyte (LSN-MOF CSE) was obtained. We demonstrate that the interlayer nanochannels for LSN electrolyte storage without sacrificing the mobility of SN molecules. Meanwhile, the unsaturated coordination of MOF, induced by Co/Ni metal sites, causes a horizontal arrangement of SN. Therefore, this electrolyte offers a remarkable ionic conductivity of 7.41 × 10−4 S cm−1 at 25 °C. Moreover, the interlayer nanochannels and covalent interaction of MOF synergistically suppress the migration of SN to lithium anode, thus improving the interface stability of lithium anode. Importantly, the assembled Li symmetrical cell performs stable operation over 800 h under 0.2 mA cm−2, and the LiFePO 4 /Li cell delivers excellent cycling stability of 148.2 mAh g−1 with a low capacity decay of 0.048% per cycle after 200 cycles under 0.2C and 25 °C. [Display omitted] • Ultrathin laminar MOF framework with 5.3-μm thick is prepared. • Nanochannels and metal sites confinement inhibit SN shuttling to lithium anode. • Horizontal arrangement of SN in MOF nanopores permits high ionic conductivity. • A high Li + transference number (0.59) is obtained. • Superior performance with capacity of 148.2 mAh g−1 at 25 °C is achieved. [ABSTRACT FROM AUTHOR]

[Display omitted] • Well-ordered vertical Li 7 La 3 Zr 2 O 12 sheet arrays are prepared. • An 8 μm-thick trilayer composite solid electrolyte with sheet arrays is fabricated. • Ultrahigh ionic conductance of 0.5 S and Young's modulus of 1.43 GPa are achieved. • Superior cycling behavior at low N/P ratio (80% retention at 158 cycles) is obtained. • The energy density of NCM/Li cell reaches 458.4 Wh kg−1. To achieve high energy density of all-solid-state lithium batteries, solid-state electrolytes (SSEs) are required to be thin and highly conductive. Although constructing efficient inorganic Li-ion transfer network can provide excellent conductivity for SSEs, it is still challenging for these SSEs to simultaneously realize thin thickness and mechanical stability. Herein, well-ordered vertical Li 7 La 3 Zr 2 O 12 sheet arrays (VLSA) were prepared, followed by introducing triple-layer ion-conducting polymers to fabricate 8 μm-thick VLSA composite solid electrolyte (CSE). We demonstrate that vertical and short VLSA (major path, accounting for 71.4% of Li-ion transfer) and VLSA/polymer interface (minor path, 27.8%) contribute to the high ionic conductivity of 2.60 × 10−4 S cm−1 and ionic conductance of 0.5 S at 30 °C, ranking one of the highest values among reported SSEs. The stiff VLSA enhances the mechanical strength of CSE, while the polymer existing in VLSA channels serves as a deformable buffer, endowing CSE with bendable property. Besides, the trilayer polymer structure permits this electrolyte to be compatible with lithium anode and high-voltage cathode. Therefore, the high-loading LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NCM523) cell can be cycled with limited lithium anode (N/P ratio = 1.18) over 158 cycles with capacity retention upon 80%, realizing a high energy density of 458.4 Wh kg−1. [ABSTRACT FROM AUTHOR]

Inorganic superionic conductor has been widely studied for potential application in all-solid-state lithium battery due to its high bulk ionic conductivity. However, the large grain boundary resistance and large thickness resulted from the poor film-forming ability, restricting its actual ionic conductivity. Inspired by the excellent film-forming ability and ultrathin thickness of 2D lamellar membrane, we reported an 11 μm-thick MOF lamellar membrane derived LLTO electrolyte (MLLTO). The electrolyte is prepared by impregnating LLTO precursors into the pores and interlayer channels of MOF lamellar membrane, followed by in situ sintering. It is demonstrated that the confined effect of interlayer channel in MOF lamellar membrane regulates the growth and arrangement of LLTO crystal, affording reduced grain boundary resistance. The porous structure of MOF nanosheet permits the construction of vertical Li+ transfer pathways between adjacent layers. Finally, MLLTO achieves a high ionic conductivity of 1.19 × 10−4 S cm−1 and ionic conductance of 0.215 S at room temperature, much higher than those of conventional LLTO electrolytes. The Li/MLLTO/Li symmetrical cell can stably cycle for 1000 h from 0.1 to 0.4 mA cm−2 at 60 °C without obvious polarization. The LFP/Li battery displays discharge capacity of 149.6 mAh g−1 at 0.5C after 200 cycles with low capacity decay of 0.04% per cycle. [Display omitted] • A thin MOF lamellar membrane derived LLTO electrolyte (MLLTO, 11 μm) is prepared. • Grain boundary resistance is reduced by controlling crystal growth and arrangement. • The porous structure of MOF permits the construction of vertical transfer pathways. • The ionic conductivity of MLLTO reaches 1.19 × 10−4 S cm−1 at room temperature. • Ultrahigh ionic conductance of 0.215 S is obtained due to the thin thickness. [ABSTRACT FROM AUTHOR]

• Thin solid electrolyte based on Vr-LLTO framework and permeated PEO is prepared. • LLTO crystals act as low-barrier Li+ conduction highways along Vr nanosheet surface. • High Li+ conduction property (1.04 × 10−4 s cm−1 at 25 °C and 67.45 mS) is achieved. • The covalently-bonded structure permits electrolyte superior structure stability. • Expected cell performances (e.g. low capacity decay after 200 cycles) are achieved. Inorganic superionic conductors hold great promise for all-solid-state lithium batteries because of their superior ionic conductivity. However, their application as electrolytes is limited by the trade-off between ion conduction and stability. Here, a thin composite solid electrolyte, vermiculite-Li 0.33 La 0.557 TiO 3 /poly(ethylene oxide) (Vr-LLTO/PEO), is prepared by in-situ co-sintering an interconnected Vr-LLTO framework and then impregnating PEO. Within this electrolyte, the continuous LLTO on Vr nanosheet surface acts as efficient pathways for vertical Li+ transfer with reduced grain boundary resistance. Together with the thin thickness (35 μm), Vr-LLTO/PEO electrolyte attains the ionic conductivity as high as 1.04 × 10−4 S cm−1 at 25 °C, over three times that of LLTO pellet and surpassing that of most reported ceramic electrolytes. Furthermore, the disordered stacked Vr nanosheets in framework are covalently linked by LLTO, together with the flexible PEO matrix, achieving highly enhanced structural stability with compressive strength of 319 MPa. In this manner, the trade-off between ion conduction and stability is overcome, which allows the assembled LiFePO 4 /Li cell achieving satisfactory cycling performances: an initial discharge capacity of 150.3 mAh g −1 at 1 C and capacity decay of only 0.08% per cycle after 200 cycles. This study may inspire insights into the subtle design of conductive and stable electrolytes for high-performance devices. [Display omitted] [ABSTRACT FROM AUTHOR]

Solid-state polymer electrolytes, featuring excellent processability and flexibility, have received considerable attentions. However, the inherent low ionic conductivity, especially at subzero temperatures, limits their widespread application. Herein, quasi-solid polymer electrolyte (QSPE) with high low-temperature ionic conduction ability is prepared by in-situ ring-opening polymerization of 1,3-Dioxlane with fluoroethylene carbonate (FEC) as plasticizer. The in-situ polymerization imparts good interface contact between QSPE and electrode. The addition of FEC improves the chain mobility and facilitates the dissociation of LiTFSI, giving QSPE a remarkable ionic conductivity and Li+ transference number (2.4 × 10−5 S cm−1 at −60 °C and 0.55 at −20 ° C), two orders of magnitude and 2.3 times higher than those of liquid electrolyte, respectively. As a result, the Li/QSPE/Li cell without significant polarization is obtained, which can operate at 0.2 mA cm−2 and 0 °C for 850 h. Moreover, the LiFePO 4 /Li cell exhibits excellent cycling stability at 0.2 C and 0 °C: its capacity remains 125.2 mAh g−1 at 400th cycle, exceeding most polymer electrolytes. Even at −20 °C, a discharge capacity of 73.3 mAh g−1 is obtained at 100th cycle under 0.2 C. [Display omitted] • QSPE is prepared by in-situ polymerization of DOL with FEC as plasticizer. • In-situ polymerization imparts good interface contact between QSPE and electrode. • The presence of FEC improves chain mobility and promotes lithium salt dissociation. • High ionic conductivity of 1.69 × 10−4 S cm−1 at −40 °C is achieved. • A high cell performance of 73.3 mAh g−1 after 100 cycles at −20 °C is obtained. [ABSTRACT FROM AUTHOR]

All-solid-state lithium–sulfur (Li–S) battery, with solid state electrolyte (SSE) replacing liquid electrolyte, is considered as promising candidate for next-generation energy storage devices due to the high capacity and safety. However, the fabrication of SSE with high ion conduction and efficient dendrite suppression remains a daunting challenge. Herein, an asymmetric Li 0.33 La 0.557 TiO 3 (LLTO) framework with porous layer and dense layer is designed and fabricated, followed by impregnating poly (ethylene oxide) (PEO) to prepare SSE. The continuous LLTO framework serves as rapid lithium ion (Li+) transfer pathway, imparting an excellent ionic conductivity of 1.49 × 10−4 S cm−1 at 30 °C, over 40 times higher than that of blank PEO. The presence of dense layer remarkably improves the compression strength of composite electrolyte and facilitates the Li+ uniform deposition, thus effectively suppressing the lithium dendrite growth. As a result, the assembled Li–S battery exhibits extraordinary cycling stability, which preserves a capacity of 907.6 mAh g−1 after 100 cycles with a Coulombic efficiency of ~ 99%. Meanwhile, the continuous PEO phase that rooted in the porous layer of framework also imparts composite electrolyte favorable flexibility and processability. [Display omitted] • Asymmetry-structure LLTO framework with porous and dense layers is fabricated. • Continuous LLTO framework acts as Li + transfer highway in composite electrolyte. • The dense layer promotes uniform Li + deposition and improves compression strength. • Continuous PEO phase rooted in porous layer affords electrolyte flexibility. • Superior Li–S battery performance (~ 907.6 mAh g−1 after 100 cycles) is achieved. [ABSTRACT FROM AUTHOR]

• A flexible, ion-conducting PEO-LLTO framework solid electrolyte is prepared. • The vertically bicontinuous transfer channels act as Li+ conduction highways. • Ultrahigh ionic conductivity (2.04 × 10−4 S cm−1 at 25 °C) is achieved. • The interconnected network offers PLLF electrolyte excellent structural stability. • Superior cell performances (~97.2% retention after 150 cycles) are achieved. All-solid-state lithium batteries, featuring high security and volume energy density, hold great potential as next-generation energy storage device. However, their development needs the fabrication of ionic conductive and structural stable solid electrolyte. Herein, Li 0.33 La 0.557 TiO 3 (LLTO) framework with interlocked porous structure is synthesized by sintering the gel permeated nylon. Then, poly(ethylene oxide) (PEO) is incorporated in the pores to produce PEO-LLTO framework solid electrolyte (PLLF electrolyte) with vertically bicontinuous phase. We demonstrate that LLTO framework fast transports Li+ through the intrinsic vacancy; meanwhile the confined PEO with low crystallization displays fast Li+ transfer ability, thus synergistically realizing efficient Li+ conduction. This novel PLLF electrolyte exhibits a remarkable ionic conductivity of 2.04 × 10−4 S cm−1, which is ~72 times higher than that of traditional PEO-based electrolytes and superior to most reported solid electrolytes. Moreover, the interconnected networks endow PLLF electrolyte with excellent structural stability. Thus, the LiFePO 4 (LFP)/Li cell exhibits extraordinary cycling stability: the discharge capacity of 154.7 mAh g−1 at 1 C after 150 cycles with capacity decay of only 0.03% per cycle. Briefly, such a vertically bicontinuous phase structure maximizes the cooperation between the conduction function of ceramic framework and the stability of polymer, offering a promising approach for all-solid-state batteries. [ABSTRACT FROM AUTHOR]