Polymer nanocomposites: a new strategy for synthesizing solid electrolytes for rechargeable lithium batteries

Krawiec, Włodzimierz; Scanlon, L. G.; Fellner, Joseph P.; Vaia, Richard A.; Vasudevan, Subramanyan; Giannelis, Emmanuel P.

doi:10.1016/0378-7753(94)02090-p

Cited by 254 publications

(151 citation statements)

References 7 publications

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“…1d). More importantly, PEO solid electrolyte has a high lithium ionic conductivity at this temperature 20,23 and can easily form a 3D continuous ionic conductive network among the active material particles, thus promoting Li + transportation between the LCO particles as shown in Fig. 1c.…”

Section: Resultsmentioning

confidence: 99%

High Capacity All-Solid-State Lithium Battery Using Cathodes with Three-Dimensional Li⁺Conductive Network

Zhang

Chen

Yang

et al. 2017

J. Electrochem. Soc.

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All-solid-state lithium batteries (ASLBs) have been dramatically attracted recently for its ability of solving the safety issues in traditional lithium ion batteries using liquid electrolyte. However the poor Li + transportation between the active material particles in the cathode greatly deteriorate the specific capacity of ASLBs. Herein, we design a composite cathode composed of polyethylene oxide (PEO) and LiCoO 2 (LCO) in which a three-dimensional (3D) continuous Li + conductive network forms. With the decrease of the LCO: PEO ratio, the 3D Li + conductive network gradually becomes continuous, and the corresponding discharge capacity increase from 50 to 136 mAh g −1 . At LCO: PEO = 6:1 and 4:1, the corresponding ASLBs has a very high discharge capacity of 136 and 124 mAh g −1 , respectively, representing approximately 98% and 90% of the theoretical discharge capacity. The capacity retention after 5 cycles is 97%∼98% of the 2 nd cycle, which confirms stable cycle performance of the battery. The FTIR results show that, in the composite cathode, the LCO particles transport Li + cations by coordinating CO functional group in PEO chains. Compared with other optimized ASLBs based on LLZO solid elctrolyte, our battery has higher specific capacity while being tested under the highest current rate. Recently, the all-solid-state lithium batteries (ASLBs) based on solid electrolyte are receiving significant attention for its safety by the displacement of the volatile and flammable liquid electrolyte.1-4 To develop high performance ASLBs, three critical issues must be considered: (1) get a high lithium ionic conductivity solid electrolyte of 10 −2 ∼10 −3 S cm −1 at room temperature and stability against chemical reaction with lithium anode, (2) lower the interfacial resistance between the electrodes and solid electrolyte, (3) solve the problem of poor Li ionic transportation among active material particles in the cathode. However, the third issue is often overlooked.The garnet-type inorganic oxide lithium ion conductor, nominal Li 7 La 3 Zr 2 O 12 (LLZO), is highly expected to be used as the solid electrolyte to accelerate the development of ASLBs.5-8 Recent reports reveal that doping with elements such as Ga 3+ and Ta 5+ can improve its room temperature conductivity to 0.4∼1.0 × 10 −3 S cm −1 . 9,10The LLZO system is reported to be stable with Li metal anode as well as possessing high electrochemical window (vs Li > 5 v). 11 The wide electrochemical window allows the use of high voltage cathode materials which may result in a potential high specific capacity for ASLBs.So far, the interfacial resistance between the electrodes and solid electrolyte has become the main contributor to the internal resistance of ASLBs, especially the resistance between cathode and solid electrolyte. Electrochemical performance of ASLBs based on LLZO solid electrolyte has been constructed by some groups using various methods aimed at reducing the interfacial resistance.12-15 Tan et al.12 reported a proto-type Li/LLZO/LiCoO 2 (LCO) cell whic...

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Section: Resultsmentioning

confidence: 99%

High Capacity All-Solid-State Lithium Battery Using Cathodes with Three-Dimensional Li⁺Conductive Network

Zhang

Chen

Yang

et al. 2017

J. Electrochem. Soc.

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“…2b). In the case of mica-type layered silicates it has been recently demonstrated that nanocomposites (both intercalated and delaminated) can be synthesized by direct melt intercalation even with high molecular weight polymers [7][8][9][10][11][12][13][14][15][16][17][18]. This synthetic method is quite general and is broadly applicable to a range of commodity polymers from essentially non-polar polystyrene, to weakly polar poly(ethylene terephthalate), to strongly polar nylon.…”

Section: Introductionmentioning

confidence: 99%

Polymer-Silicate Nanocomposites: Model Systems for Confined Polymers and Polymer Brushes

Giannelis

Krishnamoorti

Manias

1999

Advances in Polymer Science

1,122

789

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The static and dynamic properties of polymer-layered silicate nanocomposites are discussed, in the context of polymers in confined spaces and polymer brushes. A wide range of experimental techniques as applied to these systems are reviewed, and the salient results from these are compared with a mean field thermodynamic model and non-equilibrium molecular dynamics simulations. Despite the topological constraints imposed by the host lattice, mass transport of the polymer, when entering the galleries defined by adjacent silicate layers, is quite rapid and the polymer chains exhibit mobilities similar to or faster than polymer self-diffusion. However, both the local and global dynamics of the polymer in these nanoscopically confined galleries are dramatically different from those in the bulk. On a local scale, intercalated polymers exhibit simultaneously a fast and a slow mode of relaxation for a wide range of temperatures, with a marked suppression (or even absence) of cooperative dynamics typically associated with the glass transition. On a global scale, relaxation of polymer chains either tethered to or in close proximity (<1nm as in intercalated hybrids) to the host surface are also dramatically altered. In the case of the tethered polymer nanocomposites, similarities are drawn to the dynamics of other intrinsically anisotropic fluids such as ordered block copolymers and smectic liquid crystals. Further, new non-linear viscoelastic phenomena associated with melt-brushes are reported and provide complementary information to those obtained for solution-brushes studied using the Surface Forces Apparatus.

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“…While short chain polyethylene glycol (PEG) oligomers exhibit good ionic conductivity at room temperature as well as chemical and thermal stability, amorphous low molecular weight electrolytes lack mechanical strength. The addition of free inorganic particles [3][4][5][6][7] as well as inorganic networks [8] and inorganic-organic constituents [9][10][11] to polymer electrolytes has been shown to improve both mechanical properties and conductivity.In this communication, we report on a new class of solvent-free, nanoscale organic hybrid materials (NOHMs), which simultaneously manifest superionic conductivities, large electrochemical stability windows (-0.5V to > 5 V, vs Li), good lithium ion transference numbers (~0.45), no volatility and thermal stabilities up to 400 o C, and which offer multiple handles through which near molecular control can be exerted on mechanical properties. All of these features provide unusual opportunities for engineering new families of high-performance, nanoscale hybrid…”

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confidence: 99%

mentioning

confidence: 99%

Nanoscale Organic Hybrid Electrolytes

2010

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Significant effort has been devoted by research groups world-wide to the development of polymer and composite polymer electrolytes for use in lithium batteries [1,2] . The best known polymer ionic conductor, polyethylene oxide (PEO), is crystalline and has low conductivity at room temperature. While short chain polyethylene glycol (PEG) oligomers exhibit good ionic conductivity at room temperature as well as chemical and thermal stability, amorphous low molecular weight electrolytes lack mechanical strength. The addition of free inorganic particles [3][4][5][6][7] as well as inorganic networks [8] and inorganic-organic constituents [9][10][11] to polymer electrolytes has been shown to improve both mechanical properties and conductivity.In this communication, we report on a new class of solvent-free, nanoscale organic hybrid materials (NOHMs), which simultaneously manifest superionic conductivities, large electrochemical stability windows (-0.5V to > 5 V, vs Li), good lithium ion transference numbers (~0.45), no volatility and thermal stabilities up to 400 o C, and which offer multiple handles through which near molecular control can be exerted on mechanical properties. All of these features provide unusual opportunities for engineering new families of high-performance, nanoscale hybrid

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Polymer nanocomposites: a new strategy for synthesizing solid electrolytes for rechargeable lithium batteries

Cited by 254 publications

References 7 publications

High Capacity All-Solid-State Lithium Battery Using Cathodes with Three-Dimensional Li⁺Conductive Network

High Capacity All-Solid-State Lithium Battery Using Cathodes with Three-Dimensional Li⁺Conductive Network

Polymer-Silicate Nanocomposites: Model Systems for Confined Polymers and Polymer Brushes

Nanoscale Organic Hybrid Electrolytes

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Polymer nanocomposites: a new strategy for synthesizing solid electrolytes for rechargeable lithium batteries

Cited by 254 publications

References 7 publications

High Capacity All-Solid-State Lithium Battery Using Cathodes with Three-Dimensional Li+Conductive Network

High Capacity All-Solid-State Lithium Battery Using Cathodes with Three-Dimensional Li+Conductive Network

Polymer-Silicate Nanocomposites: Model Systems for Confined Polymers and Polymer Brushes

Nanoscale Organic Hybrid Electrolytes

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Product

Resources

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High Capacity All-Solid-State Lithium Battery Using Cathodes with Three-Dimensional Li⁺Conductive Network

High Capacity All-Solid-State Lithium Battery Using Cathodes with Three-Dimensional Li⁺Conductive Network