The Versatile Establishment of Charge Storage in Polymer Solid Electrolyte with Enhanced Charge Transfer for LiF-Rich SEI Generation in Lithium Metal Batteries.

The solid-state electrolyte interface (SEI) between the solid-state polymer electrolyte and the lithium metal anode dramatically affects the overall battery performance. Increasing the content of lithium fluoride (LiF) in SEI can help the uniform deposition of lithium and inhibit the growth of lithium dendrites, thus improving the cycle stability performance of lithium batteries. Currently, most methods of constructing LiF SEI involve decomposing the lithium salt by the polar groups of the filler. However, there is a lack of research reports on how to affect the SEI layer of Li-ion batteries by increasing the charge transfer number. In this study, a porous organic polymer with "charge storage" properties was prepared and doped into a polymer composite solid electrolyte to study the effect of sufficient charge transfer on the decomposition of lithium salts. The results show in contrast to porphyrins, the unique structure of POF allows for charge transfer between each individual porphyrin. Therefore, during TFSI- decomposition to the formation of LiF, TFSI- can obtain sufficient charge, thereby promoting the break of C-F and forming the LiF-rich SEI. Compared with single porphyrin (0.423 e-), POF provides 2.7 times more charge transfer to LiTFSI (1.147 e-). The experimental results show that Li//Li symmetric batteries equipped with PEO-POF can be operated stably for more than 2700 h at 60 °C. Even the Li//Li (45 µm) symmetric cells are stable for more than 1100 h at 0.1 mA cm-1. In addition, LiFePO4//PEO-POF//Li batteries have excellent cycling performance at 2 C (80 % capacity retention after 750 cycles). Even LiFePO4//PEO-POF//Li (45 µm) cells have excellent cycling performance at 1 C (96 % capacity retention after 300 cycles). Even when the PEO-base is replaced with a PEG-base and a PVDF-base, the performance of the cell is still significantly improved. Therefore, we believe that the concept of charge transfer offers a novel perspective for the preparation of high-performance assemblies.

Interface-Targeting Carrier-Catalytic Integrated Design Contributing to Lithium Dihalide-Rich SEI toward High Interface Stability for Long-Life Solid-State Lithium-Metal Batteries.

The generation of solid electrolyte interphase (SEI) largely determines the comprehensive performance of all-solid-state batteries. Herein, a novel "carrier-catalytic" integrated design is strategically exploited to in situ construct a stable LiF-LiBr rich SEI by improving the electron transfer kinetics to accelerate the bond-breaking dynamics. Specifically, the high electron transport capacity of Br-TPOM skeleton increases the polarity of C-Br, thus promoting the generation of LiBr. Then, the enhancement of electron transfer kinetics further promotes the fracture of C-F from TFSI- to form LiF. Finally, the stable and homogeneous artificial-SEI with enriched lithium dihalide is constructed through the in situ co-growth mechanism of LiF and LiBr, which facilitatse the Li-ion transport kinetics and regulates the lithium deposition behavior. Impressively, the PEO-Br-TPOM paired with LiFePO4 delivers ultra-long cycling stability over 1000 cycles with 81 % capacity retention at 1 C while the pouch cells possess 88 % superior capacity retention after 550 cycles with initial discharge capacity of 145 mAh g-1at 0.2 C in the absence of external pressure. Even under stringent conditions, the practical pouch cells possess the practical capacity with stable electric quantities plateau in 30 cycles demonstrates its application potential in energy storage field.

Regulating Steric Hindrance of Porous Organic Polymers in Composite Solid-State Electrolytes to Induce the Formation of LiF-Rich SEI in Li-Ion Batteries.

Lithium fluoride (LiF) at the solid electrolyte interface (SEI) contributes to the stable operation of polymer-based solid-state lithium metal batteries. Currently, most of the methods for constructing lithium fluoride SEI are based on the design of polar groups of fillers. However, the mechanism behind how steric hindrance of fillers impacts LiF formation remains unclear. This study synthesizes three kinds of porous polyacetal amides (PAN-X, X=NH2 , NH-CH3 , N-(CH3 )2 ) with varying steric hindrances by regulating the number of methyl substitutions of nitrogen atoms on the reaction monomer, which are incorporated into polymer composite solid electrolytes, to investigate the regulation mechanism of steric hindrance on the content of lithium fluoride in SEI. The results show that bis(trifluoromethanesulfonyl)imide (TFSI- ) will compete for the charge without steric effect, while excessive steric hindrance hinders the interaction between TFSI- and polar groups, reducing charge acquisition. Only when one hydrogen atom on the amino group is replaced by a methyl group, steric hindrance from the methyl group prevents TFSI- from capturing charge in that direction, thereby facilitating the transfer of charge from the polar group to a separate TFSI- and promoting maximum LiF formation. This work provides a novel perspective on constructing LiF-rich SEI.

State of Charge Estimation and Evaluation of Lithium Battery Using Kalman Filter Algorithms.

The accurate and rapid estimation of the state of charge (SOC) is important and difficult in lithium battery management systems. In this paper, an adaptive infinite Kalman filter (AUKF) was used to estimate the state of charge for a 18650 LiNiMnCoO2/graphite lithium-ion battery, and its performance was systematically evaluated under large initial errors, wide temperature ranges, and different drive cycles. In addition, three other Kalman filter algorithms on the predicted SOC of LIB were compared under different work conditions, and the accuracy and convergence time of different models were compared. The results showed that the convergence time of the AUKF algorithms was one order of magnitude smaller than that of the other three methods, and the mean absolute error was only less than 50% of the other methods. The present work can be used to help other researchers select an appropriate strategy for the SOC online estimation of lithium-ion cells under different applicable conditions.

Ultrafast Li/Fluorinated Graphene Primary Batteries with High Energy Density and Power Density.

Lithium/fluorinated carbon (Li/CFx) primary batteries have essential applications in consumer electronics and medical and high-power military devices. However, their application is limited due to the difficulty in achieving simultaneous high power density and high energy density in the CFx cathode. The tradeoff between conductivity and fluorine content is the decisive factor. Herein, by rational design, 3D porous fluorinated graphene microspheres (FGS-x) with both high conductivity and a high F/C ratio are successfully synthesized for the first time. FGS-x possesses an F/C ratio as high as 1.03, a nanosheet structure with hierarchical pores, abundant C═C bonds, few inactive C-F2 bonds, and electrochemically active C-F bonds. The beneficial features that can increase discharge capacity, shorten the diffusion length for both ions and electrons, enhance the Li+ intercalation kinetics, and accommodate the volume change are demonstrated. The Li/FGS-1.03 coin cell delivers an unprecedented power density of 71,180.9 W/kg at an ultrahigh rate of 50 C (43.25 A/g), coupled with a high energy density of 830.7 Wh/kg. Remarkably, the Li/FGS-1.03 pouch cell exhibits a record cell-level power density of 12,451.2 W/kg at 20 C. The in-depth investigation by the ex situ method on structural evolution at different discharge depths reveals that the excellent performance benefits from the structural stability and the uniform formation of LiF. The FGS-1.03 cathode also has excellent performance in extreme operating temperatures (0 to 100 °C) and high active material mass loading (4.3 mg/cm2). These results indicate that the engineered fluorinated graphene developed here has great potential in applications requiring both high power density and high energy density.

Large Scale Synthesis of Three-dimensional Hierarchical Porous Framework with High Conductivity and its Application in Lithium Sulfur Battery.

Quick capacity loss due to the polysulfide shuttle effects and poor rate performance caused by low conductivity of sulfur have always been obstacles to the commercial application of lithium sulfur batteries. Herein, an in-situ doped hierarchical porous biochar materials with high electron-ion conductivity and adjustable three-dimensional (3D) macro-meso-micropore is prepared successfully. Due to its unique physical structure, the resulting material has a specific surface area of 2124.9 m2 g-1 and a cumulative pore volume of 1.19 cm3 g-1 . The presence of micropores can effectively physically adsorb polysulfides and mesopores ensure the accessibility of lithium ions and active sites and give the porous carbon material a high specific surface area. The large pores provide channels for the storage of electrolyte and the transmission of ions on the surface of the substrate. The combined effect of these three kinds of pores and the N doping formed in-situ can effectively promote the cycle and rate performance of the battery. Therefore, prepared cathode can still reach a reversible discharge capacity of 616 mAh g-1 at a rate of 5 C. After 400 charge-discharge cycles at 1 C, the reversible capacity is maintained at 510.0 mAh g-1 . This new strategy has provided a new approach to the research and industrial-scale production of adjustable hierarchical porous biochar materials.

High Temperature Resistant Separator of PVDF-HFP/DBP/C-TiO2 for Lithium-Ion Batteries.

To improve the thermal shrinkage and ionic conductivity of the separator for lithium-ion batteries, adding carboxylic titanium dioxide nanofiber materials into the matrix is proposed as an effective strategy. In this regard, a poly(vinylidene fluoride-hexafluoro propylene)/dibutyl phthalate/carboxylic titanium dioxide (PVDF-HFP/DBP/C-TiO2) composite separator is prepared with the phase inversion method. When the content of TiO2 nanofibers reaches 5%, the electrochemical performance of the battery and ion conductivity of the separator are optimal. The PVDF-HFP/DBP/C-TiO2 (5%) composite separator shows about 55.5% of porosity and 277.9% of electrolyte uptake. The PVDF-HFP/DBP/C-TiO2 (5%) composite separator has a superior ionic conductivity of 1.26 × 10 -3 S cm-1 and lower interface impedance at room temperature, which brings about better cycle and rate performance. In addition, the cell assembled with a PVDF-HFP/DBP/C-TiO2 separator can be charged or discharged normally and has an outstanding discharge capacity of about 150 mAh g-1 at 110 °C. The battery assembled with the PVDF-HFP/DBP/C-TiO2 composite separator exhibits excellent electrochemical performance under high and room temperature environments.

Enhancement Effects of Co Doping on Interfacial Properties of Sn Electrode-Collector: A First-Principles Study.

The Co doping effects on the interfacial strength of Sn electrode-collector interface for lithium-ion batteries are investigated by using first-principles calculations. The results demonstrate that by forming strong chemical bonds with interfacial Sn, Li, and Cu atoms, Co doping in the interface region can enhance interfacial strengths and stabilities during lithiation. With doping, the highest strengths of Sn/Cu (1.74 J m-2) and LiSn/Cu (1.73 J m-2) interfaces are 9.4 and 17.7% higher than those of the corresponding interface systems before doping. Besides, Co doping can reduce interface charge accumulation and offset the decreasing interfacial strength during lithiation. Furthermore, the interfacial strength and electronic stability increase with rising Co content, whereas the increasing formation heat may result in thermodynamic instability. On the basis of the change of formation heat with Co content, an optimal Co doping content has been provided.

SnO2/Reduced Graphene Oxide Nanocomposite as Anode Material for Lithium-Ion Batteries with Enhanced Cyclability.

SnO2 is considered as one of the most promising anode materials for next generation lithium-ion batteries, however, how to build energetic SnO2-based electrode architectures has still remained a big challenge. In this article, we developed a facile method to prepare SnO2/reduced graphene oxide (RGO) nanocomposite for an anode material of lithium-ion batteries. It is shown that, at the current density of 0.25 A.g-1, SnO2/RGO has a high initial capacity of 1705 mAh.g-1 and a capacity retention of 500 mAh . g-1 after 50 cycles. The total specific capacity of SnO2/RGO is higher than the sum of their pure counterparts, indicating a positive synergistic effect on the electrochemical performance.

Ice Regelation: Hydrogen-bond extraordinary recoverability and water quasisolid-phase-boundary dispersivity.

Regelation, i.e., ice melts under compression and freezes again when the pressure is relieved, remains puzzling since its discovery in 1850's by Faraday. Here we show that hydrogen bond (O:H-O) cooperativity and its extraordinary recoverability resolve this anomaly. The H-O bond and the O:H nonbond possesses each a specific heat ηx(T/ΘDx) whose Debye temperature ΘDx is proportional to its characteristic phonon frequency ωx according to Einstein's relationship. A superposition of the ηx(T/ΘDx) curves for the H-O bond (x=H, ωH~3200 cm(-1)) and the O:H nonbond (x=L, ωL~200 cm(-1), ΘDL=198 K) yields two intersecting temperatures that define the liquid/quasisolid/solid phase boundaries. Compression shortens the O:H nonbond and stiffens its phonon but does the opposite to the H-O bond through O-O Coulomb repulsion, which closes up the intersection temperatures and hence depress the melting temperature of quasisolid ice. Reproduction of the Tm(P) profile clarifies that the H-O bond energy EH determines the Tm with derivative of EH=3.97 eV for bulk water and ice. Oxygen atom always finds bonding partners to retain its sp3-orbital hybridization once the O:H breaks, which ensures O:H-O bond recoverability to its original state once the pressure is relieved.

Potential Paths for the Hydrogen-Bond Relaxing With (H2O)N Cluster Size.

Relaxation of the inter- and intra-molecular interactions for the hydrogen bond (O:H-O) between undercoordinated molecules determines the unusual behavior of water nanodroplets and nanobubbles. However, probing such potentials remains unreality. Here we show that the Lagrangian solution [Huang et al., J. Phys. Chem. B, 2013. 117: 13639] transforms the observed H-O bond (x = H) and O:H nonbond (x = L) lengths and phonon frequencies (dx, x) [Sun et al., J. Phys. Chem. Lett., 2013. 4: 2565] into the respective force constants and bond energies (kx, Ex) and hence enables the mapping of the potential paths for the O:H-O bond relaxing with water cluster size. Results show that molecular undercoordination not only reduces the molecular size (dH) with enhanced H-O energy from the bulk value of 3.97 to 5.10 eV for a H2O monomer, but also enlarges the molecular separation (dL) with reduced O:H energy from 95 to 35 meV for a dimer. The H-O energy gain raises the melting point from bulk value 273 to 310 K for the skin and the O:H energy loss lowers the freezing temperature from bulk value 258 to 202 K for 1.4 nm sized droplet, by dispersing the quasisolid phase boundaries.

Water nanodroplet thermodynamics: quasi-solid phase-boundary dispersivity.

It has long been puzzling that water nanodroplets undergo simultaneously "supercooling" at freezing and "superheating" at melting. Recent progress (Sun et al. J. Phys. Chem. Lett. 2013, 4, 2565, 3238) enables us to resolve this anomaly from the perspective of hydrogen bond (O:H-O) specific heat disparity. A superposition of the specific heat ηx(T) curves for the H-O bond (x = H) and the O:H nonbond (x = L) defines two intersecting temperatures that form the ice/quasi-solid/liquid phase boundaries. Molecular undercoordination (with fewer than four nearest neighbors in the bulk) stretches the ηH(T) curve by raising the Debye temperature ΘDH through H-O bond shortening and phonon stiffening. The ηH(T) stretching is coupled with the ηL(T) depressing because of the Coulomb repulsion between electron pairs on oxygen ions. The extent of dispersion varies with the size of a droplet that prefers a core-shell structure configuration-the bulk interior and the skin. Understandings may open an effective way of dealing with the thermodynamic behavior of water droplets and bubbles from the perspective of O:H-O bond cooperativity.

Mediating relaxation and polarization of hydrogen-bonds in water by NaCl salting and heating.

Infrared spectroscopy and contact-angle measurements revealed that NaCl salting has the same effect as heating on O:H phonon softening and H-O phonon stiffening, but has the opposite effect on skin polarization of liquid water. The mechanics of thermal modulation of O-O Coulomb repulsion [Sun, et al., J. Phys. Chem. Lett., 2013, 4, 3238] may suggest a possible mechanism for this NaCl involved Hofmeister effect, aqueous solution modulated surface tension and its abilities in protein dissolution, from the perspective of Coulomb mediation of interaction within the O:H-O bond.

Hydrogen-bond memory and water-skin supersolidity resolving the Mpemba paradox.

The Mpemba paradox, that is, hotter water freezes faster than colder water, has baffled thinkers like Francis Bacon, René Descartes, and Aristotle since B.C. 350. However, a commonly accepted understanding or theoretical reproduction of this effect remains challenging. Numerical reproduction of observations, shown herewith, confirms that water skin supersolidity [Zhang et al., Phys. Chem. Chem. Phys., DOI: ] enhances the local thermal diffusivity favoring heat flowing outwardly in the liquid path. Analysis of experimental database reveals that the hydrogen bond (O:H-O) possesses memory to emit energy at a rate depending on its initial storage. Unlike other usual materials that lengthen and soften all bonds when they absorb thermal energy, water performs abnormally under heating to lengthen the O:H nonbond and shorten the H-O covalent bond through inter-oxygen Coulomb coupling [Sun et al., J. Phys. Chem. Lett., 2013, 4, 3238]. Cooling does the opposite to release energy, like releasing a coupled pair of bungees, at a rate of history dependence. Being sensitive to the source volume, skin radiation, and the drain temperature, the Mpemba effect proceeds only in the strictly non-adiabatic 'source-path-drain' cycling system for the heat "emission-conduction-dissipation" dynamics with a relaxation time that drops exponentially with the rise of the initial temperature of the liquid source.

A common supersolid skin covering both water and ice.

Consistency in experimental observations, numerical calculations, and theoretical predictions have revealed that the skins of water and ice share the same attribute of supersolidity characterized by an identical H-O vibration frequency of 3450 cm(-1). Molecular undercoordination and inter-electron-pair repulsion shortens the H-O bond and lengthens the O:H nonbond, leading to a dual process of nonbonding electron polarization. This relaxation-polarization process enhances the dipole moment, elasticity, viscosity, and thermal stability of these skins with a 25% density loss, which is responsible for the hydrophobicity and toughness of the water skin and results in the slippery behavior of ice.

Size, separation, structural order, and mass density of molecules packing in water and ice.

The structural symmetry and molecular separation in water and ice remain uncertain. We present herewith a solution to unifying the density, the structure order and symmetry, the size (H-O length dH), and the separation (d(OO) = d(L) + d(H) or the O:H length d(L)) of molecules packing in water and ice in terms of statistic mean. This solution reconciles: i) the d(L) and the d(H) symmetrization of the O:H-O bond in compressed ice, ii) the d(OO) relaxation of cooling water and ice and, iii) the d(OO) expansion of a dimer and between molecules at water surface. With any one of the d(OO), the density ρ(g·cm⁻³), the d(L), and the d(H), as a known input, one can resolve the rest quantities using this solution that is probing conditions or methods independent. We clarified that: i) liquid water prefers statistically the mono-phase of tetrahedrally-coordinated structure with fluctuation, ii) the low-density phase (supersolid phase as it is strongly polarized with even lower density) exists only in regions consisting molecules with fewer than four neighbors and, iii) repulsion between electron pairs on adjacent oxygen atoms dictates the cooperative relaxation of the segmented O:H-O bond, which is responsible for the performance of water and ice.

Hydrogen bond asymmetric local potentials in compressed ice.

A combination of the Lagrangian mechanics of oscillators vibration, molecular dynamics decomposition of volume evolution, and Raman spectroscopy of phonon relaxation has enabled us to resolve the asymmetric, local, and short-range potentials pertaining to the hydrogen bond (O:H-O) in compressed ice. Results show that both oxygen atoms in the O:H-O bond shift initially outwardly with respect to the coordination origin (H), lengthening the O-O distance by 0.0136 nm from 0.2597 to 0.2733 nm by Coulomb repulsion between electron pairs on adjacent oxygen atoms. Both oxygen atoms then move toward right along the O:H-O bond by different amounts upon being compressed, approaching identical length of 0.11 nm. The van der Waals potential VL(r) for the O:H noncovalent bond reaches a valley at -0.25 eV, and the lowest exchange VH(r) for the H-O polar-covalent bond is valued at -3.97 eV.

From chemistry to mechanics: bulk modulus evolution of Li-Si and Li-Sn alloys via the metallic electronegativity scale.

Toward engineering high performance anode alloys for Li-ion batteries, we proposed a useful method to quantitatively estimate the bulk modulus of binary alloys in terms of metallic electronegativity (EN), alloy composition and formula volume. On the basis of our proposed potential viewpoint, EN as a fundamental chemistry concept can be extended to be an important physical parameter to characterize the mechanical performance of Li-Si and Li-Sn alloys as anode materials for Li-ion batteries. The bulk modulus of binary alloys is linearly proportional to the combination of average metallic EN and atomic density of alloys. We calculated the bulk moduli of Li-Si and Li-Sn alloys with different Li concentrations, which can agree well with the reported data. The bulk modulus of Li-Si and Li-Sn alloys decreases with increasing Li concentration, leading to the elastic softening of the alloys, which is essentially caused by the decreased strength of constituent chemical bonds in alloys from the viewpoint of EN. This work provides a deep understanding of mechanical failure of Si and Sn anodes for Li-ion batteries, and permits the prediction of the composition dependent bulk modulus of various lithiated alloys on the basis of chemical formula, metallic EN and cell volume (or alloy density), with no structural details required.

A critical appraisal of the nanoindentation creep 'nose' effect in Ni thin films.

The creep behaviour of polycrystal Ni thin films under the same maximum load (Pmax = 8000 microN) and different unloading periods (ranging from 1 to 250 s) has been investigated at room temperature using nanoindentation tests. A 'nose' has been observed in the unloading segment of the load-penetration depth curve when the holding time at peak load is short and/or the unloading rate is small, and when the peak load is sufficient high. When a 'nose' presents, the apparent unloading stiffness Su, defined as dP/dh, is negative, and the reduced modulus can no longer be calculated from the Oliver-Pharr method. Taking such uncertainties into account, a critical appraisal is proposed for ranking creep propensities exhibited during nanoindentation under specified conditions.