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Register a new userSurface Reconstruction Limited Conductivity in Block-Copolymer Li Battery Electrolytes
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Solid polymer electrolytes for lithium batteries promise improvements in safety and energy density if their conductivity can be increased. Nanostructured block copolymer electrolytes specifically have the potential to provide both good ionic conductivity and good mechanical properties. This study shows that the previously neglected nanoscale composition of the polymer electrolyte close to the electrode surface has an important effect on impedance measurements, despite its negligible extent compared to the bulk electrolyte. Using standard stainless steel blocking electrodes, the impedance of lithium salt-doped poly(isoprene-b-styrene-b-ethylene oxide) (ISO) exhibited a marked decrease upon thermal processing of the electrolyte. In contrast, covering the electrode surface with a low molecular weight poly(ethylene oxide) (PEO) brush resulted in higher and more reproducible conductivity values, which were insensitive to the thermal history of the device. A qualitative model of this effect is based on the hypothesis that ISO surface reconstruction at the different electrode surfaces leads to a change in the electrostatic double layer, affecting electrochemical impedance spectroscopy measurements. As a main result, PEO-brush modification of electrode surfaces is beneficial for the robust electrolyte performance of PEO-containing block-copolymers and may be crucial for their accurate characterization and use in Li-ion batteries.
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Using a new class of (BH4)- substituted argyrodite Li6PS5Z0.83(BH4)0.17, (Z = Cl, I) solid electrolyte, Li-metal solid-state batteries operating at room temperature have been developed. The cells were made by combining the modified argyrodite with an In-Li anode and two types of cathode: an oxide, LixMO2 (M = 1/3Ni, 1/3Mn, 1/3Co; so called NMC) and a titanium disulfide, TiS2. The performance of the cells was evaluated through galvanostatic cycling and Alternating Current AC electrochemical impedance measurements. Reversible capacities were observed for both cathodes for at least tens of cycles. However, the high-voltage oxide cathode cell shows lower reversible capacity and larger fading upon cycling than the sulfide one. The AC impedance measurements revealed an increasing interfacial resistance at the cathode side for the oxide cathode inducing the capacity fading. This resistance was attributed to the intrinsic poor conductivity of NMC and interfacial reactions between the oxide material and the argyrodite electrolyte. On the contrary, the low interfacial resistance of the TiS2 cell during cycling evidences a better chemical compatibility between this active material and substituted argyrodites, allowing full cycling of the cathode material, 240 mAhg-1, for at least 35 cycles with a coulombic efficiency above 97%.
The reversible heat in lithium-ion batteries (LIBs) due to entropy change is fundamentally important for understanding the chemical reactions in LIBs and developing proper thermal management strategies. However, the direct measurements of reversible heat are challenging due to the limited temperature resolution of applied thermometry. In this work, by developing an ultra-sensitive thermometry with a differential AC bridge using two thermistors, the noise-equivalent temperature resolution we achieve (10 uK) is several orders of magnitude higher than previous thermometry applied on LIBs. We directly observe reversible heat absorption of a LIR2032 coin cell during charging with negligible irreversible heat generation and a linear relation between heat generations and discharging currents. The cell entropy changes determined from the reversible heat agree excellently with those measured from temperature dependent open circuit voltage. Moreover, it is found that the large reversible entropy change can cancel out the irreversible entropy generation at a charging rate as large as C/3.7 and produce a zero-heat-dissipation LIB during charging. Our work significantly contributes to fundamental understanding of the entropy changes and heat generations of the chemical reactions in LIBs, and reveals that reversible heat absorption can be an effective way to cool LIBs during charging.
An extensive study of single block copolymer knots containing two kinds of monomers $A$ and $B$ is presented. The knots are in a solution and their monomers are subjected to short range interactions that can be attractive or repulsive. In view of possible applications in medicine and the construction of intelligent materials, it is shown that several features of copolymer knots can be tuned by changing the monomer configuration. A very fast and abrupt swelling with increasing temperature is obtained in certain multiblock copolymers, while the size and the swelling behavior at high temperatures may be controlled in diblock copolymers. Interesting new effects appear in the thermal diagrams of copolymer knots when their length is increased.
Upon insertion and extraction of lithium, materials important for electrochemical energy storage can undergo changes in thermal conductivity (${Lambda}$) and elastic modulus ($it M$). These changes are attributed to evolution of the intrinsic thermal carrier lifetime and interatomic bonding strength associated with structural transitions of electrode materials with varying degrees of reversibility. Using in situ time-domain thermoreflectance (TDTR) and picosecond acoustics, we systemically study $Lambda$ and $it M$ of conversion, intercalation and alloying electrode materials during cycling. The intercalation V$_{2}$O$_{5}$ and TiO$_{2}$ exhibit non-monotonic reversible ${Lambda}$ and $it M$ switching up to a factor of 1.8 (${Lambda}$) and 1.5 ($it M$) as a function of lithium content. The conversion Fe$_{2}$O$_{3}$ and NiO undergo irreversible decays in ${Lambda}$ and $it M$ upon the first lithiation. The alloying Sb shows the largest and partially reversible order of the magnitude switching in ${Lambda}$ between the delithiated (18 W m$^{-1}$ K$^{-1}$) and lithiated states (<1 W m$^{-1}$ K$^{-1}$). The irreversible ${Lambda}$ is attributed to structural degradation and pulverization resulting from substantial volume changes during cycling. These findings provide new understandings of the thermal and mechanical property evolution of electrode materials during cycling of importance for battery design, and also point to pathways for forming materials with thermally switchable properties.
Lithium--sulfur (Li/S) batteries are regarded as one of the most promising energy storage devices beyond lithium-ion batteries because of their high energy density of 2600 Wh/kg and an affordable cost of sulfur. Meanwhile, some challenges inherent to Li/S batteries remain to be tackled, for instance, the polysulfide (PS) shuttle effect, the irreversible solidification of Li$_2$S, and the volume expansion of the cathode material during discharge. On the molecular level, these issues originate from the structural and solubility behavior of the PS species in bulk and in the electrode confinement. In this study, we use classical molecular dynamics (MD) simulations to develop a working model for PS of different chain lengths in applied electrolyte solutions of lithium bistriflimide (LiTFSI) in 1,2-dimethoxyethane (DME) and 1,3-dioxolane (DOL) mixtures. We investigate conductivities, diffusion coefficients, solvation structures, and clustering behavior and verify our simulation model with experimental measurements available in literature and newly performed by us. Our results show that diffusion coefficients and conductivities are significantly influenced by the chain length of PS. The conductivity contribution of the short chains, like Li$_2$S$_4$, is lower than of longer PS chains, such as Li$_2$S$_6$ or Li$_2$S$_8$, despite the fact that the diffusion coefficient of Li$_2$S$_4$ is higher than for longer PS chains. The low conductivity of Li$_2$S$_4$ can be attributed to its low degree of dissociation and even to a formation of large clusters in the solution. It is also found that an addition of 1 M LiTFSI into PS solutions considerably reduces the clustering behavior. Our simulation model enables future systematic studies in various solvating and confining systems for the rational design of Li/S electrolytes.
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