Determination of lithium-ion distributions in nanostructured block polymer electrolyte thin films by X-ray photoelectron spectroscopy depth profiling (original) (raw)
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The first characterization studies of the interface layer formed between a Li-ion battery electrode and a solid polymer electrolyte (SPE) are presented here. SPEs are well known for their electrochemical stability and excellent safety, and thus considered good alternatives to conventional liquid/gel electrolytes in highenergy density battery devices. This work comprises studies of solid electrolyte interphase (SEI) formation in SPE-based graphite|Li cells using X-ray photoelectron spectroscopy (XPS). SPEs based on high molecular weight poly(ethylene oxide) (PEO) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt are studied. Large amounts of LiOH are observed, and the XPS results indicate a correlation with moisture contamination in the SPEs. The water contents are quantitatively determined to be in the range of hundreds of ppm in the pure PEO as well as in the polymer electrolytes, which are prepared by a conventional SPE preparation method using different batches of PEO and at different drying temperatures. Moreover, severe salt degradation is observed at the graphite-SPE interface after the 1 st discharge, while the salt is found to be more stable at the Li-SPE interface or when using LiTFSI-based liquid electrolyte equivalents.
XPS study of lithium surface after contact with lithium-salt doped polymer electrolytes
Electrochimica Acta, 2001
X-ray photoelectron spectroscopy (XPS) is used to probe the surface layer and element composition of Li-metal electrodes before and after contact with polymer electrolytes containing LiN(SO 2 CF 3) 2 (LiTFSI) or LiBF 4. Native film on as-received metallic lithium was composed of Li 2 CO 3 /LiOH in the outer layer and Li 2 O in the inner layer. LiF was formed during lithium contact with electrolyte due to reaction between the native film and impurities in the electrolyte. The polymer electrolyte containing LiTFSI yielded a very thin film with limited porosity in the inner layers, which was reflected in the limited amplitude dependence of complex impedance spectra. LiBF 4 mixed with polymer resulted in a thicker film with high porosity, as was postulated from the greater influence of the amplitude of the oscillation level.
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Macromolecular rapid communications, 2015
Well-defined single-ion diblock copolymers consisting of a Li-ion conductive poly(styrenesulfonyllithium(trifluoromethylsulfonyl)imide) (PSLiTFSI) block associated with a glassy polystyrene (PS) block have been synthesized via reversible addition fragmentation chain transfer polymerization. Conductivity anisotropy ratio up to 1000 has been achieved from PS-b-PSLiTFSI thin films by comparing Li-ion conductivities of out-of-plane (aligned) and in-plane (antialigned) cylinder morphologies at 40 °C. Blending of PS-b-PSLiTFSI thin films with poly(ethylene oxide) homopolymer (hPEO) enables a substantial improvement of Li-ion transport within aligned cylindrical domains, since hPEO, preferentially located in PSLiTFSI domains, is an excellent lithium-solvating material. Results are also compared with unblended and blended PSLiTFSI homopolymer (hPSLiTFSI) homologues, which reveals that ionic conductivity is improved when thin films are nanostructured.
Asian Journal of Nanoscience and Materials, 2019
Batteries are a major technological challenge in this new century as they are a vital method to make use of energy efficiently. Nowadays Lithium-ion batteries (LIBs) appeared to be one of the most crucial energy storage technologies. Today's Li-ion technology has conquered the portable electronic markets and still on the track of fast development. The success of lithium-ion technology will depend mainly on the cost, safety, cycle life, energy, and power, which are in turn determined by the component materials used for its fabrication. Accordingly, this review focuses on the challenges of organic based materials and prospects associated with the electrode materials. Specifically, the issues related to organic based batteries, advances and opportunities are presented. This review aims to summarize the fundamentals of the polymer-based material for lithium-ion batteries (LIBs) and specifically highlight its recent significant advancement in material design, challenges, performance and finally its prospects. We anticipate that this Review will inspire further improvement in organic electrolyte materials and the electrode for the battery as energy device storages. Some of these concepts, relying on new ways to prepare electrode materials by the use of eco-efficient processes, on the use of organic rather than inorganic materials to overcome environmental issues associated with their use. Organic electrodes are essential for solid electrode batteries because they can make device cost-effective, allow flexibility, and can also enable the use of multivalent ions without the problems typically associated with inorganic compounds.
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The significant market for electric vehicles and portable electronic devices is driving the development of highenergy-density solid-state lithium batteries. However, the solid electrolyte is still the main obstacle to the development of solid-state lithium batteries, mainly due to the lack of a single solid electrolyte that is compatible with both high-voltage cathodes and lithium metal anodes. These problems can potentially be solved with multilayer electrolytes. The property of each layer of the electrolyte can be tuned separately, which not only meets the different needs of the cathode and anode but also makes up for the shortcomings of each layer of the electrolyte, thereby achieving good mechanical properties and chemical and electrochemical stability. This review first presents a brief introduction to homogeneous single-layer electrolytes. The design principles of multilayer polymer electrolytes and the application of these principles using examples from recent work are then introduced. Finally, several suggestions as guides for future work are given.
High lithium conductivities in weakly-ionophilic low-dimensional block copolymer electrolytes
Electrochimica Acta, 2005
The structure of amphiphilic low-dimensional copolymer electrolytes I of similar overall composition but prepared by different synthetic procedures X and Y are described. I are copolymers of poly[2,5,8,11,14-pentaoxapentadecamethylene(5-alkyloxy-1,3-phenylene)] (CmO5) and poly[2,-oxatrimethylene(5-alkyloxy-1,3-phenylene)] (CmO1) where the alkyl side chains having m carbons are hexadecyl or mixed dodecyl/octadecyl (50/50). 1 H NMR shows that the copolymers have 50% (m = 16) or only 18 and 13% of CmO5 units and DSC indicates that the copolymers have 'block' sequencing of CmO1 and CmO5 segments. Molecular dynamics modelling indicates that in CmO5 Li + and BF 4 − ions are separated by Li + encapsulation in tetraethoxy segments but in ionophobic CmO1 units the salt is mostly present as neutral aggregates decoupled from the polymer. Conductivities of these microphase-separated mixtures with salt-bridge amphiphilic polyethers II and III of each system are similar. They have low temperature dependence over the range 20 • C to 110 • C at ∼10 −3 S cm −1. 7 Li NMR linewidth measurements confirm high lithium mobilities at −20 • C. A conduction mechanism is proposed whereby Li + hopping takes place along rows of decoupled aggregates (dimers/quadrupoles) within an essentially block copolymer structure. Subambient measurements to −10 • C gave a conductivity of 4 × 10 −5 S cm −1 .
2019
Batteries are a major technological challenge in this new century as they are a key method to make use of energy efficiently. Nowadays Lithium-ion batteries (LIBs) appeared to be one of the most important energy storage technologies. Today’s Li-ion technology has conquered the portable electronic markets and still on the track of fast development. The success of lithium-ion technology will depend largely on the cost, safety, cycle life, energy, and power, which are in turn determined by the component materials used for its fabrication. Accordingly, this review focuses on the challenges of organic based materials and prospects associated with the electrode materials. Specifically, the issues associated with organic based batteries, advances and prospects are presented. This review aims to summarize the fundamentals of the polymer-based material for lithium-ion batteries (LIBs) and specifically highlight its recent major advancement in material design, challenges, performance and fina...
Electrochemical and Solid-State Letters, 2002
Block copolymer electrolytes of poly͓(oxyethylene) 9 methacrylate͔-b-poly͑butyl methacrylate͒ ͑POEM-b-PBMA͒ ͑60:40 by mass͒ synthesized for the first time by atom transfer radical polymerization ͑ATRP͒ exhibited mechanical and electrical properties indistinguishable from those of materials made by the more difficult anionic polymerization method. ATRP offers distinct processing advantages as it is easily scalable and almost solvent-free. Solid-state, thin-film batteries comprised of a metallic lithium anode, a binder-free, additive-free, fully dense vanadium oxide cathode, and an electrolyte of ATRP-synthesized POEM-b-PBMA ͑60:40͒ doped with LiCF 3 SO 3 demonstrate resistance to capacity fade during extended cycling at a discharge rate of C/2, and perform comparably to otherwise identical batteries operated with the liquid electrolyte 1 M LiPF 6 in ethylene carbonate:dimethyl carbonate ͑1:1 by mass͒.
Asian Journal of Nanoscience and Materials, 2018
Batteries are a major technological challenge in this new century as they are a vital method to make use of energy efficiently. Nowadays Lithium-ion batteries (LIBs) appeared to be one of the most crucial energy storage technologies. Today's Li-ion technology has conquered the portable electronic markets and still on the track of fast development. The success of lithium-ion technology will depend mainly on the cost, safety, cycle life, energy, and power, which are in turn determined by the component materials used for its fabrication. Accordingly, this review focuses on the challenges of organic based materials and prospects associated with the electrode materials. Specifically, the issues related to organic based batteries, advances and opportunities are presented. This review aims to summarize the fundamentals of the polymer-based material for lithium-ion batteries (LIBs) and specifically highlight its recent significant advancement in material design, challenges, performance and finally its prospects. We anticipate that this Review will inspire further improvement in organic electrolyte materials and the electrode for the battery as energy device storages. Some of these concepts, relying on new ways to prepare electrode materials by the use of eco-efficient processes, on the use of organic rather than inorganic materials to overcome environmental issues associated with their use. Organic electrodes are essential for solid electrode batteries because they can make device cost-effective, allow flexibility, and can also enable the use of multivalent ions without the problems typically associated with inorganic compounds.