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The growing demand for energy storage devices worldwide combined with limited resources for lithium attracts interest in other alkali or alkaline earth metals. In addition to conductivity, the cation transference number T+ is a decisive parameter to rank the electrolyte performance. However, the existing experimental methods for its determination suffer from various intrinsic problems. We demonstrate here a novel approach for T+ determination based on determining the total conductivity with impedance spectroscopy (IS) and the partial conductivity of the anion species, with the latter being obtained from the anion mobility by electrophoretic NMR. First, this eNMR/IS approach is validated by comparing T+ values from different methods in a Li-based solvate ionic liquid electrolyte. Then, it is applied to obtain T+ of cations with nuclei not detectable in NMR transport measurements, employing bis(trifluoromethanesulfonyl)imide (TFSI)-based metal salts. Solvate ionic liquids consisting of triethylene glycol dimethyl ether (G3) and Mg(TFSI)2 or NaTFSI yield values of TNa and TMg on the order of 0.4, similar to TLi. Furthermore, we apply the method to polymer electrolytes, again testing the concept with LiTFSI, and finally investigating NaTFSI, KTFSI, and Mg(TFSI)2 in poly(ethylene oxide). Values of TNa and TK are in the range of 0.14-0.2, similar to those of TLi, while Mg2+ shows a higher transference number (TMg = 0.3). The method is very versatile as it allows quantification of T+ for any type of cation, and moreover, it is applicable to highly concentrated electrolytes without suffering from assumptions about dissociation or from unknown interfacial resistances which impede electrochemical methods.
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Correction for 'Quantifying the ion coordination strength in polymer electrolytes' by Rassmus Andersson et al., Phys. Chem. Chem. Phys., 2022, 24, 16343-16352, https://doi.org/10.1039/D2CP01904C.
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By employing a variation of the polyamidation method using in situ silylated diamines and acid chlorides, it was possible to obtain a rod-type polyamide: poly(p-phenylene terephthalamide) (PPTA, a polymer used in the high-value-added material Kevlar), with a molecular weight much higher than that obtained with the classical and industrial polyamidation method. The optimization of the method has consisted of using, together with the silylating agent, a mixture of pyridine and a high-pKa tertiary amine. The research was complemented by a combination of nuclear magnetic resonance and molecular simulation studies, which determined that the improvements in molecular weight derive mainly from the formation of silylamide groups in the growing polymer.
Assuntos
Nylons , Polímeros , Peso Molecular , Espectroscopia de Ressonância Magnética , DiaminasRESUMO
Correction for 'Quantifying the ion coordination strength in polymer electrolytes' by Rassmus Andersson et al., Phys. Chem. Chem. Phys., 2022, https://doi.org/10.1039/d2cp01904c.
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In the progress of implementing solid polymer electrolytes (SPEs) into batteries, fundamental understanding of the processes occurring within and in the vicinity of the SPE are required. An important but so far relatively unexplored parameter influencing the ion transport properties is the ion coordination strength. Our understanding of the coordination chemistry and its role for the ion transport is partly hampered by the scarcity of suitable methods to measure this phenomenon. Herein, two qualitative methods and one quantitative method to assess the ion coordination strength are presented, contrasted and discussed for TFSI-based salts of Li+, Na+ and Mg2+ in polyethylene oxide (PEO), poly(ε-caprolactone) (PCL) and poly(trimethylene carbonate) (PTMC). For the qualitative methods, the coordination strength is probed by studying the equilibrium between cation coordination to polymer ligands or solvent molecules, whereas the quantitative method studies the ion dissociation equilibrium of salts in solvent-free polymers. All methods are in agreement that regardless of cation, the strongest coordination strength is observed for PEO, while PTMC exhibits the weakest coordination strength. Considering the cations, the weakest coordination is observed for Mg2+ in all polymers, indicative of the strong ion-ion interactions in Mg(TFSI)2, whilst the coordination strength for Li+ and Na+ seems to be more influenced by the interplay between the cation charge/radius and the polymer structure. The trends observed are in excellent agreement with previously observed transference numbers, confirming the importance and its connection to the ion transport in SPEs.
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In the search for novel solid polymer electrolytes (SPEs), primarily targeting battery applications, a range of different polymers is currently being explored. In this context, the non-coordinating poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) polymer is a frequently utilized system. Considering that PVdF-HFP should be a poor solvent for cation salts, it is counterintuitive that this is a functional host material for SPEs. Here, we do an in-depth study of the salt dissolution properties and ionic conductivity of PVdF-HFP-based electrolytes, using two different fabrication methods and also employing a low-molecular-weight solvent analogue. It is seen that PVdF-HFP is remarkably poor as an SPE host, despite its comparatively high dielectric constant, and that the salt dissolution properties instead are controlled by fluorophilic interactions of the anion with the polymer.
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The unusual physical and chemical properties of electrolytes with excessive salt contents have resulted in rising interest in highly concentrated electrolytes, especially for their application in batteries. Here, we report strikingly good electrochemical performance in terms of conductivity and stability for a binary electrolyte system, consisting of lithium bis(fluorosulfonyl)imide (LiFSI) salt and ethylene carbonate (EC) solvent. The electrolyte is explored for different cell configurations spanning both high-capacity and high-voltage electrodes, which are well known for incompatibilities with conventional electrolyte systems: Li metal, Si/graphite composites, LiNi0.33Mn0.33Co0.33O2 (NMC111), and LiNi0.5Mn1.5O4 (LNMO). As compared to a LiTFSI counterpart as well as a common LP40 electrolyte, it is seen that the LiFSI:EC electrolyte system is superior in Li-metal-Si/graphite cells. Moreover, in the absence of Li metal, it is possible to use highly concentrated electrolytes (e.g., 1:2 salt:solvent molar ratio), and a considerable improvement on the electrochemical performance of NMC111-Si/graphite cells was achieved with the LiFSI:EC 1:2 electrolyte both at the room temperature and elevated temperature (55 °C). Surface characterization with scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) showed the presence of thicker surface film formation with the LiFSI-based electrolyte as compared to the reference electrolyte (LP40) for both positive and negative electrodes, indicating better passivation ability of such surface films during extended cycling. Despite displaying good stability with the NMC111 positive electrode, the LiFSI-based electrolyte showed less compatibility with the high-voltage spinel LNMO electrode (â¼4.7 V vs Li+/Li).
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Proper understanding of solid polymer electrolyte-electrode interfacial layer formation and its implications on cell performance is a vital step toward realizing practical solid-state lithium-ion batteries. At the same time, probing these solid-solid interfaces is extremely challenging as they are buried within the electrochemical system, thereby efficiently evading exposure to surface-sensitive spectroscopic methods. Still, the probing of interfacial degradation layers is essential to render an accurate picture of the behavior of these materials in the vicinity of their electrochemical stability limits and to complement the incomplete picture gained from electrochemical assessments. In this work, we address this issue in conjunction with presenting a thorough evaluation of the electrochemical stability window of the solid polymer electrolyte poly(ε-caprolactone):lithium bis(trifluoromethanesulfonyl)imide (PCL:LiTFSI). According to staircase voltammetry, the electrochemical stability window of the polyester-based electrolyte was found to span from 1.5 to 4 V vs Li+/Li. Subsequent decomposition of PCL:LiTFSI outside of the stability window led to a buildup of carbonaceous, lithium oxide and salt-derived species at the electrode-electrolyte interface, identified using postmortem spectroscopic analysis. These species formed highly resistive interphase layers, acting as major bottlenecks in the SPE system. Resistance and thickness values of these layers at different potentials were then estimated based on the impedance response between a lithium iron phosphate reference electrode and carbon-coated working electrodes. Importantly, it is only through the combination of electrochemistry and photoelectron spectroscopy that the full extent of the electrochemical performance at the limits of electrochemical stability can be reliably and accurately determined.
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Two water-soluble binders of carboxymethyl cellulose (CMC) and sodium alginate (SA) have been studied in comparison with N-methylpyrrolidone-soluble poly(vinylidene difluoride-co-hexafluoropropylene) (PVdF-HFP) to understand their effect on the electrochemical performance of a high-voltage lithium nickel manganese oxide (LNMO) cathode. The electrochemical performance has been investigated in full cells using a Li4 Ti5 O12 (LTO) anode. At room temperature, LNMO cathodes prepared with aqueous binders provided a similar electrochemical performance as those prepared with PVdF-HFP. However, at 55 °C, the full cells containing LNMO with the aqueous binders showed higher cycling stability. The results are supported by intermittent current interruption resistance measurements, wherein the electrodes with SA showed lower resistance. The surface layer formed on the electrodes after cycling has been characterized by X-ray photoelectron spectroscopy. The amount of transition metal dissolutions was comparable for all three cells. However, the amount of hydrogen fluoride (HF) content in the electrolyte cycled at 55 °C is lower in the cell with the SA binder. These results suggest that use of water-soluble binders could provide a practical and more sustainable alternative to PVdF-based binders for the fabrication of LNMO electrodes.
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Fontes de Energia Elétrica , Água , Eletrodos , Eletrólitos , Níquel/química , Água/químicaRESUMO
In the quest for environmentally friendly and safe batteries, moving from fluorinated electrolytes that are toxic and release corrosive compounds, such as HF, is a necessary step. Here, the effects of electrolyte fluorination are investigated for full cells combining silicon-graphite composite electrodes with LiNi1/3Mn1/3Co1/3O2 (NMC111) cathodes, a viable cell chemistry for a range of potential battery applications, by means of electrochemical testing and postmortem surface analysis. A fluorine-free electrolyte based on lithium bis(oxalato)borate (LiBOB) and vinylene carbonate (VC) is able to provide higher discharge capacity (147 mAh gNMC -1) and longer cycle life at C/10 (84.4% capacity retention after 200 cycles) than a cell with a highly fluorinated electrolyte containing LiPF6, fluoroethylene carbonate (FEC) and VC. The cell with the fluorine-free electrolyte is able to form a stable solid electrolyte interphase (SEI) layer, has low overpotential, and shows a slow increase in cell resistance that leads to improved electrochemical performance. Although the power capability is limiting the performance of the fluorine-free electrolyte due to higher interfacial resistance, it is still able to provide long cycle life at C/2 and outperforms the highly fluorinated electrolyte at 40 °C. X-ray photoelectron spectroscopy (XPS) results showed a F-rich SEI with the highly fluorinated electrolyte, while the fluorine-free electrolyte formed an O-rich SEI. Although their composition is different, the electrochemical results show that both the highly fluorinated and fluorine-free electrolytes are able to stabilize the silicon-based anode and support stable cycling in full cells. While these results demonstrate the possibility to use a nonfluorinated electrolyte in high-energy-density full cells, they also address new challenges toward environmentally friendly and nontoxic electrolytes.
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To increase the energy storage density of lithium-ion batteries, silicon anodes have been explored due to their high capacity. One of the main challenges for silicon anodes are large volume variations during the lithiation processes. Recently, several high-performance schemes have been demonstrated with increased life cycles utilizing nanomaterials such as nanoparticles, nanowires, and thin films. However, a method that allows the large-scale production of silicon anodes remains to be demonstrated. Herein, we address this question by suggesting new scalable nanomaterial-based anodes. Si nanoparticles were grown on nanographite flakes by aerogel fabrication route from Si powder and nanographite mixture using polyvinyl alcohol (PVA). This silicon-nanographite aerogel electrode has stable specific capacity even at high current rates and exhibit good cyclic stability. The specific capacity is 455 mAh g-1 for 200th cycles with a coulombic efficiency of 97% at a current density 100 mA g-1.
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The development of new redox polymers is being boosted by the increasing interest in the area of energy and health. The development of new polymers is needed to further advance new applications or improve the performance of actual devices such as batteries, supercapacitors, or drug delivery systems. Here we show the synthesis and characterization of a new polymer which combines the present most successful conjugated polymer backbone and the most successful redox active side group, i.e., poly(3,4-ethylenedioxythiophene) (PEDOT), and a nitroxide stable radical. First, a derivative of the 3,4-ethylenedioxythiophene (EDOT) molecule with side nitroxide stable radical group (TEMPO) was synthesized. The electrochemical polymerization of the PEDOT-TEMPO monomer was investigated in detail using cyclic voltammetry, potential step, and constant current methods. Monomer and polymer were characterized by NMR, FTIR, matrix-assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF MS), electron spin resonance (ESR) spectroscopy, elemental analysis, cyclic voltammetry, and four-point probe conductivity. The new PEDOT-TEMPO radical polymer combines the electronic conductivity of the conjugated polythiophene backbone and redox properties of the nitroxide group. As an example of application, this redox active polymer was used as a conductive binder in lithium ion batteries. Good cycling stability with high Coulombic efficiency and increased cyclability at different rates were obtained using this polymer as a replacement of two ingredients: conductive carbon additive and polymeric binders.