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Cobalt-free LiNiO2 cathode materials offer a higher energy density at a lower cost than high Co-containing cathode materials. However, Ni(OH)2 precursors for LiNiO2 cathodes are traditionally prepared by the coprecipitation method, which is expensive, complex, and time-consuming. Herein, we report a fast, facile, and inexpensive electrolysis process to prepare a Ni(OH)2 precursor, which was mixed with LiOH/LiNO3 salts to obtain a LiNiO2 cathode material. A combination of advanced characterization techniques revealed that the LiNiO2 cathode material prepared in this way exhibited an excellent layered structure with negligible Li/Ni site mixing and surface structural distortion. Electrochemical cycling of the LiNiO2 cathode material showed an initial discharge capacity of 235.2 mA h/g and a capacity retention of 80.2% after 100 cycles (at 1 C) between 2.75 and 4.3 V. The degradation of the cycling performance of the LiNiO2 cathode material was mainly attributed to the formation of a surface solid-electrolyte interface and a ∼5 nm rock salt-like structure, while the bulk structure of the cathode after cycling was generally stable.

Rechargeable lithium-based batteries built with high-energy anode materials (e.g., silicon-based and silicon-derivative materials) are considered a feasible solution to satisfy the stringent requirements imposed by emerging markets, including electric vehicles and grid storage, due to their higher energy density compared to contemporary lithium-ion batteries. The robustness of the solid electrolyte interphase (SEI) layer on high-energy anodes is critical to achieve long-term and stable cycling performances of the batteries. Herein, we propose a new type of designer cathode additive (DCA), i.e., an ultrathin coating layer of elemental sulfur on the cathode, for the in situ formation of a thin and robust SEI layer on various types of high-energy anodes. The DCA elemental sulfur undergoes simultaneous oxidation and reduction paths, forming lithium alkyl sulfate (R-OSO

Sn anode materials with high specific capacity are an appealing alternative to graphite for next-generation advanced lithium-ion batteries. However, poor electrochemical performance originating from fracture and pulverization due to the enormous volume changes during lithium alloying/dealloying hinders their commercial applications. Here, we propose the synthesis of a novel 3D structured Sn anode material by a facile method: heat treatment of nanosized SnO2 spheres in a tube furnace with a flowing mixed atmosphere of C2H2/Ar at 400 °C. After the heat treatment, the nanosized SnO2 spheres convert into pure Sn bulk material (~20 μm), which consists of Sn nanowires (~50 nm in diameter and several microns in length). This unique 3D structure with sufficient voids between the nanowires effectively mitigates the volume expansion of Sn bulk material and ensures good electrical contact between the anode material and conducting additives. As a consequence, the 3D structured Sn anode material exhibits a specific reversible capacity of ~600 mA h/g and no significant capacity degradation (compared with that of the 20th cycle) over 500 cycles at 0.2 C.

The carbon-conducting additive-induced degradation of the cycling performance of lithium-ion batteries needs to be carefully controlled, particularly at a high operating voltage and elevated temperature. Herein, we report the investigation of surface coating with 2–3 nm of Al2O3, TiO2 and Ta2O5 oxides on Super P carbon black via atomic layer deposition. Detailed step potential tests revealed that after storage in EC/DMC electrolyte for 14 days at 55 °C, the stability of Ta2O5-coated Super P was the highest compared with those of Al2O3- and TiO2-coated counterparts. This result is attributed to Ta2O5 acting as a HF barrier, which mitigates the oxidation of electrolyte on the surface of Super P, as observed by XPS, thus showing less deposition of carbonate species. Further experiments showed that the surface of the Ta2O5 coating layer was stable, while the Al2O3 and TiO2 coating layers were completely dissolved in dilute HF after storage for 12 h Ta2O5-coated Super P was verified in a LiNi0.5Mn1.5O4 half-cell charged to 4.9 V at 55 °C. The results showed that with Ta2O5-coated Super P as the conducting additive, the half-cell exhibited an improved coulombic efficiency of 99.5%, compared with 98.3% for the pristine Super P.

Cobalt-free LiNiO

In this paper, we report a facile method for the in situ deposition of a thin solid electrolyte layer on the surface of anode materials, which can significantly improve the rate capability and reduce the time for reaching capacity maximum. The thin solid electrolyte layer (∼8 nm) is formed by adding a small amount of LiNO3 into the anode materials; the added LiNO3 decomposes irreversibly into Li3N and LiNxOy on the surface of the anode materials during the first cycle, facilitating fast diffusion of lithium ions and limiting the formation of the surface electrolyte interface films. This is verified by adding LiNO3 into graphite half-cells which shows a fast activation process at high current density: in particular, the charge capacity reaches its maximum after only ∼30 and ∼40 cycles at 170 and 340 mA g−1, respectively, compared to ∼50 and ∼80 cycles for the graphite half-cell. Furthermore, the LiNO3 additive results in high capacity retention at high C-rates, with a value of 82.4% at 680 mA g−1, compared with 22.4% for the graphite half-cell. The facile and low-cost method reported here is expected to be readily applicable to other electrode materials for high-performance lithium-ion batteries.

Spinel cathode materials (e.g., LiMn2O4 and LiNi0.5Mn1.5O4) with strongly bonded surface coatings are desirable for delivering improved electrochemical performance in long-term cycling. Here, we report that the introduction of bridging ions such as Fe and Co, which can diffuse into both the spinel cathode materials and Li3PO4, the latter is found to cover the spinel surface in the form of dense and uniform particles (∼2-3 nm). Detailed structural analysis of the surface reveals that the bridging ions diffuse into the 16c site of the spinel structure to form ion-doped spinel cathode materials, which contribute to the formation of strong bonds between the surface and Li3PO4, possibly via spinel-(surface bridging ions)-Li3PO4 bonds. The critical role of the surface bridging ions is further investigated by heating the as-formed Li3PO4-coated spinel cathode materials (with bridging ions) to high temperatures, resulting in further diffusion of bringing ions from the surface to the interior of the spinel materials and consequently depletion of the surface spinel-(surface bridging ions)-Li3PO4 bonds. This leads to the gradual growth of surface Li3PO4 particles (∼20 nm) and the exposure of the spinel surface.

High-voltage spinel LiNi0.5Mn1.5O4 cathode materials typically exhibit a perfect octahedral morphology; i.e., only the {111} planes are observed. However, a truncated octahedral morphology is sometimes observed with the appearance of both the {100} planes and the {111} planes. The underlying mechanism of this morphological transformation is unclear. CS corrected scanning transmission electron microscopy (STEM) techniques were used to study LiNi0.5Mn1.5O4 samples lifted by a focused ion beam (FIB) to determine the atomic-level crystal and electronic structures of the octahedral and truncated octahedral morphologies. STEM images directly show that the appearance of the {100} planes in the truncated octahedral particles of LiNi0.5Mn1.5O4 is closely associated with the atomic-level migration of Ni and Mn ions in the surface region. The STEM electron energy loss spectroscopy (EELS) confirms the presence of oxygen-deficient and Ni-rich areas, particularly in the region close to the newly formed {100} planes. Th...

Stabilization of the atomic-level surface structure of LiMn2O4 with Al3+ ions is shown to be significant in the improvement of cycling performance, particularly at a high temperature (55 °C) and high voltage (5.1 V). Detailed analysis by X-ray photoelectron spectroscopy, secondary ion mass spectrometry, scanning transmission electron microscopy-energy-dispersive X-ray spectroscopy, etc. reveals that Al3+ ions diffuse into the spinel to form a layered Li(Alx,Mny)O2 structure in the outmost surface where Al3+ concentration is the highest. Other Al3+ ions diffuse into the 8a sites of spinel to form a (Mn3-xAlx)O4 structure and the 16d sites of spinel to form Li(Mn2-xAlx)O4. These complicated surface structures, in particular the layered Li(Alx,Mny)O2, are present at the surface throughout cycling and effectively stabilize the surface structure by preventing dissolution of Mn ions and mitigating cathode-electrolyte reactions. With the Al3+ ions surface modification, a stable cycle performance (∼78% capacity retention after 150 cycles) and high Coulombic efficiency (∼99%) are achieved at 55 °C. More surprisingly, the surface-stabilized LiMn2O4 can be cycled up to 5.1 V without significant degradation, in contrast to the fast capacity degradation found in the unmodified case. Our findings demonstrate the critical role of ions coated on the surface in modifying the structural evolution of the surface of spinel electrode particles and thus will stimulate future efforts to optimize the surface properties of battery electrodes.

Mixed silicon and carbon (Si–C) materials with high capacity are ideal candidates for the substitution of graphite or other carbon anodes in lithium-ion batteries. However, the low coulombic efficiency of the Si–C anode in the first cycle due to the formation of a solid electrolyte interphase and the consumption of active lithium have hindered its commercial applications. Here, we report using Li2S as a prelithiation material to compensate for the loss of active lithium in the first cycle and, consequently, to enhance the specific energy of lithium-ion batteries. The Si–C anode has an initial discharge specific capacity of ∼738 mA h g−1 and a charge specific capacity of ∼638 mA h g−1. The prelithiation material with a core–shell structure is prepared by mixing Li2S, Ketjenblack (KB) and poly(vinylpyrrolidone) (PVP) in anhydrous ethanol, which shows a high irreversible capacity of ∼1084 mA h g−1. The effect of the compensation of lost active lithium is verified via a LiFePO4 (Li2S)/Si–C full cell, which exhibits not only a high specific capacity but also a stable cycling performance. The specific energy of the LiFePO4 (Li2S)/Si–C full cell shows a remarkable increase compared to the LiFePO4/Si–C full cell, exhibiting ∼13.4%, ∼26.7%, ∼65.0% and ∼110.2% more specific energy after the 1st, 10th, 100th and 200th cycle, respectively.

The formation of Li dendrites is effectively inhibited by utilizing a small amount of polysulfide (1 to 2 mM Li2Sx, 2 ≤ x ≤ 8) in a conventional carbonate electrolyte to introduce a significant amount of polyethylene oxide (PEO)-like polymers into solid-electrolyte interphase (SEI) films. The polysulfide added likely acts as a catalyst rather than an additive, which is not consumed during repeated charging/discharging cycles. Thus the stability of Li-metal batteries during prolonged cycling is remarkably improved.

High-capacity and high-rate anode materials are desperately desired for applications in the next generation lithium-ion batteries. Here, we report preparation of an anode showing a structure of Si nanoparticles wrapped inside Sn nanowires. This anode inherits the advantages of both Si and Sn, endowing lithiation/delithiation of Si nanoparticles inside the conducting networks of Sn nanowires. It demonstrates a high and reversible capacity of ∼1500 mAh g−1 over 300 cycles at 0.2 °C and a good rate capability (0.2 °C–5 °C) equivalent to Sn. The excellent cycling performance is attributed to the novel structure of the anode as well as the strong mechanical strength of the nanowires which is directly confirmed by in-situ lithiation and bending experiments.

Lithium-ion batteries with graphite as the anode consume ∼10% of the active lithium from the cathode to form a solid electrolyte interphase layer during the first cycle, resulting in a reduced reversible capacity. Here, we report using Li2S as a cathode pre-lithiation material to compensate for the loss of active lithium and, consequently, enhance the specific energy of lithium-ion batteries. A Li2S material with a core-shell structure is prepared by mixing Li2S, Ketjenblack (KB) and poly(vinylpyrrolidone) (PVP) in anhydrous ethanol, and the material shows a specific charge capacity of ∼1053 mAh g−1 (631 mAh g−1 based on the total weight of cathode pre-lithiation materials, binders and conductive additives). The ability of this material to compensate for active lithium is investigated by coating a typical cathode LiFePO4 as an example, with the core-shell Li2S/KB/PVP via a simple and non-toxic coating method. Our results show that the LiFePO4 (Li2S)/graphite full cell exhibits a specific discharge capacity of 146.7 mAh g−1 in the first cycle, which is the same as the specific discharge capacity of the LiFePO4 half cell. XPS analysis reveals Li2S decomposes into lithium ions and sulfur with release of electrons in the first charge. Such a successful extraction of the active lithium from Li2S results in excellent cycling performance with increased specific energy.

Distorted surface regions (5–6 nm) with an unusual layered-like structure on LiMn2O4 cathode material were directly observed after it was cycled (3–4.9 V), indicating a possible spinel-to-layered structural transformation. Formation of these distorted regions severely degrades LiMn2O4 cathode capacity. As we attempt to get a better understanding of the exact crystal structure of the distorted regions, the structural transformation pathways and the origins of the distortion are made difficult by the regions’ nanoscopic size. Inspired by the reduction of Mn4+ to Mn3+ in surface electronic structures that might be associated with oxygen loss during cycling, we further investigated the atomic-level surface structure of LiMn2O4 by heat-treatments between 600 and 900 °C in various atmospheres, finding similar surface spinel-to-layered structural transformation only for LiMn2O4 heat-treated in argon atmosphere for a few minutes (or more). Controllable and measurable oxygen loss during heat-treatments result in M...

Batteries with lithium metal anodes are promising because of lithium’s high energy density. However, the growth of Li dendrites on the surface of the Li electrode in a liquid electrolyte during cycling reduces the safety and cycle performance of batteries, hindering their commercial application. In this work, we observe for the first time a smooth and dendrite-free Li deposition with a vertically grown, self-aligned, and highly compact columnar structure formed during cycling in a mixed carbonate–ether electrolyte. The stable microsized (∼10 μm in diameter and ∼20 μm in length) Li deposits are aligned in arrays on the surface of the Li electrode. The columnar Li deposits still exhibit a dendrite-free morphology and a compact structure after 200 cycles at a current density of 1 mA/cm2 and a 1.5 mAh/cm2 cycling capacity in a mixed carbonate–ether electrolyte. This work shows an optimiztic outlook for Li batteries with liquid electrolytes.

Detailed investigation of the influence of surface modification using a typical oxide (TiO2) on the electrochemical cycling performance of LiNi0.5Mn1.5O4 at room temperature (25 °C) and elevated temperature (55 °C) is reported. This spinel cathode material is commonly surface-modified with various metal oxides to improve its electrochemical cycling performance in lithium ion batteries. However, the underlying mechanisms of such a treatment, with respect to the surface crystal structure and chemistry evolution, have remained unclear. Bare-LiNi0.5Mn1.5O4 and TiO2-modified LiNi0.5Mn1.5O4 both show excellent cycling performance, i.e. almost no capacity retention and ∼99% coulombic efficiency for 150 cycles, at room temperature. However, at 55 °C the latter shows significantly better electrochemical cycling performance, with 93% capacity retention and ∼96% coulombic efficiency for 100 cycles, than the former with 70% capacity retention and ∼93% coulombic efficiency. Via advanced electron microscopy techniques, we observed that titanium ions migrated into the surface region of LiNi0.5Mn1.5O4 during the surface modification process at high temperature and reconstructed the (1–3 nm) surface spinel structure into a rocksalt-like structure and the subsurface (several nanometers) into a pseudo-rocksalt-like structure. The reconstruction of the surface and subsurface of the LiNi0.5Mn1.5O4 spinel cathode material mitigates not only the migration of Mn ions from the bulk into the electrolyte but also the formation of a solid state electrolyte interface, which plays a critical role in the improvement of electrochemical cycling performance at elevated temperatures.

Spinel cathode materials (e.g., LiMn

Nickel-rich layered LiNi0.8Co0.1Mn0.1O2 is a promising cathode material due to its high specific capacity. However, commercial application of this material is impeded by its rapid capacity degradation associated with structural instability. In this work, 0.5–2 mol% Nb5+ doped LiNi0.8Co0.1Mn0.1O2 cathode material is prepared by heat treatment of a mixture of stoichiometric amounts of nano-sized Nb2O5 powders, co-precipitated NixMn1-x(OH)2 precursors, and LiOH·H2O. The results show that Nb5+ doping significantly improves the cycling properties of LiNi0.8Co0.1Mn0.1O2 cathode material and that the optimal Nb5+ content in the structure is 1 mol%. Under a voltage range of 2.75–4.3 V, 1 mol% Nb5+ doped LiNi0.8Co0.1Mn0.1O2 cathode material shows an initial discharge capacity of 180.2 mAh/g at 0.1C, with a capacity retention of 96.9% for subsequent 300 cycles at 1C at room temperature. In contrast, bare LiNi0.8Co0.1Mn0.1O2 shows a capacity retention of only ~79.8% under the same conditions, with an initial specific discharge capacity of 184.9 mAh/g. The improvement in cycling performance is attributed to stabilization of the layered structure by Nb5+, mitigated migration of Ni2+ to the Li layer, improved lithium diffusion kinetics and reduced lattice expansion/shrinkage during cycling. Stabilization of the layered structure by Nb5+ doping is further reflected by the observation of fewer cracks in cathode electrodes after prolonged cycling.

Lithium-rich manganese-based layer-structured oxides (xLi 2 MnO 3 ⋅(1-x)LiNi 1/3 Co 1/3 Mn 1/3 O 2 ) have attracted great attention for their potential applications as cathode materials of high energy-density lithium ion batteries. However, these oxides suffer from inferior cycling and poor rate capability due to presence of the Li 2 MnO 3 phase. Herein, the Li + ions in the Li-layer of the Li 1.2 Mn 0.54 Co 0.13 Ni 0.13 O 2 (or 0.5Li 2 MnO 3 ⋅0.5LiNi 1/3 Co 1/3 Mn 1/3 O 2 ) are partially substituted with aliovalent Ti 4+ ions to improve its long-term cycling stability and rate performance. The obtained oxide (Li 1.2-x Ti x Mn 0.54 Co 0.13 Ni 0.13 O 2 , x = 2.5%) exhibits an initial capacity of 320 mAh g −1 and a capacity retention of 71% after 300 cycles as well as good rate performance. In addition, although Ti doping cannot prevent the transformation from the layered to the spinel-like phase, it stabilizes the structure of the spinel-like phase below 3.0 V. Based on first-principles calculations and performance evaluation, these improvements are attributed to the Ti-doping induced enhancement in conductivity, diffusion, activation energy of Mn migration and Ti O bonding. This novel design may furthermore open a door for the synthesis of lithium-rich materials with high rate performance.

The submicron single crystals of LiCoPO4 with 500 nm diameter are prepared by solvothermal method. The carbon coated sample is obtained using sucrose as carbon source under 650 °C subsequently. It is investigated that the solvent composition has an effect on the morphology and the electrochemical performance of the cathode material. The as-prepared samples are characterized with X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopic, dynamic light scattering, and Fourier transform infrared spectra. The electrochemical performance is evaluated by cyclic voltammetry, galvanostatic charge–discharge, and electrochemical impedance spectroscopy. The LiCoPO4/C cathode can reach an initial discharge capacity of 123.8 mA h g−1 at 0.1C, with a retention of 83% after 100 cycles. A discharge capacity of 84.9 mA h g−1 is still attainable when the rate is up to 2C. The good cycling performance and rate capability are contributed to the decrease of particle size along with the lower antisite defect concentration in the LCP crystals, and uniform carbon coating.

Metallic tin (Sn) used as anode material for lithium ion batteries has long been proposed, but its low temperature electrochemical performance has been rarely concerned. Here, a Sn/C composite with nano-Sn embedded in expanded graphite (Sn/EG) is synthesized. The nano-Sn particles (∼30 nm) are uniformly distributed in the interlayers of expanded graphite forming a tightly stacked layered structure. The electrochemical performance of the Sn/EG, particularly at low temperature, is carefully investigated compared with graphite. At -20 °C, the Sn/EG shows capacities of 200 mAh g −1 at 0.1C and 130 mAh g −1 at 0.2C, which is much superior to graphite ( −1 ). EIS measurements suggest that the charge transfer impedance of the Sn/EG increases less rapidly than graphite with decreasing temperatures, which is responsible for the improved low temperature electrochemical performance. The Li-ion chemical diffusion coefficients of the Sn/EG obtained by GITT are an order of magnitude higher at room temperature than that at -20 °C. Furthermore, the Sn/EG exhibits faster Li-ion intercalation kinetics than graphite in the asymmetric charge/discharge measurements, which shows great promise for the application in electric vehicles charged at low temperature.

Due to the abundance of sodium in nature, sodium-ion batteries (SIBs) have attracted widespread attention. Numerous intercalated cathode materials have already been reported, but fewer intercalated anode materials are known. Among these materials, most anodes suffer from low coulombic efficiency and the dendritic growth of sodium due to the lower sodiated voltages (below 1.0 V). To improve the safety performance of batteries, exploring new anode materials which have higher sodiated voltage above 1.0 V is very important. Herein, a series of novel intercalated anode materials, ATiOPO4 (A = NH4, K, Na), is introduced for SIBs at the first time. Preparation of NaTiOPO4 by a traditional solid-state reaction is difficult. So we first synthesized NH4TiOPO4 (NTP) by a simple hydrothermal reaction, KTiOPO4 (KTP) and NaTiOPO4 (NaTP) were each prepared by ion exchange with the respective nitrate. These samples were investigated by electrochemical discharge/charge which showed average sodiated voltages of 1.45 V (NTP), 1.4 V (KTP) and 1.5 V (NaTP); respectively. In situ XRD results indicated that a two-phase reaction mechanism accompanies electrochemical Na insertion/extraction in NaTP. These anode materials are potential candidates for developing SEI-free and high safety SIBs.

Silicon is an important high capacity anode material for the next generation Li-ion batteries. The electrochemical performances of the Si anode are influenced strongly by the properties of the solid electrolyte interphase (SEI). It is well known that the addition of flouroethylene carbonate (FEC) in the carbonate electrolyte is helpful to improve the cyclic performance of the Si anode. The possible origin is suggested to relate to the modification of the SEI. However, detailed information is still absent. In this work, the structural and mechanical properties of the SEI on Si thin film anode in the ethylene-carbonate-based (EC-based) and FEC-based electrolytes at different discharging and charging states have been investigated using a scanning atomic force microscopy force spectroscopy (AFMFS) method. Single-layered, double-layered, and multi-layered SEI structures with various Young’s moduli have been visualized three dimensionally at nanoscale based on the hundreds of force curves in certain scanned area. The coverage of the SEI can be obtained quantitatively from the two-dimensional (2D) project plots. The related analysis indicates that more soft SEI layers are covered on the Si anode, and this could explain the benefits of the FEC additive.

The high-voltage spinel LiNi0.5Mn1.5O4 cathode material suffers from the rapid degradation of electrochemical cycling performance at elevated temperatures, which prevents its successful commercialization. Herein, we show that coating the surface of this material with Ta2O5, which has high resistance against hydrofluoric acid (HF) attack, is an effective way to improve its electrochemical cycling performance. A Ta2O5-coated LiNi0.5Mn1.5O4 half-cell shows a capacity retention of ∼93% and a Coulombic efficiency of ∼98% after 100 cycles at 55 °C, compared to the corresponding values of ∼76% and ∼95% measured for the bare LiNi0.5Mn1.5O4 half-cell. The detailed structural analysis of the Ta2O5-coated LiNi0.5Mn1.5O4 shows that a small amount of Ta5+ ions diffuse into the 16c site on the cathode surface during the coating process, as directly observed by Cs corrected scanning transmission electron microscopy. The modification of the LiNi0.5Mn1.5O4 surface with Ta5+, together with the residual Ta2O5 coating, stabi...

Stabilization of the atomic-level surface structure of LiMn

Silicon is the most promising anode material for the next generation high-performance lithium ion batteries. However, its commercial application is hindered by its poor performance due to the huge volume change during cycling. Although two-dimensional silicon-based materials show significantly improved performance, flexible synthesis of such materials is still a challenge. In this work, silicon-based nanosheets with a multilayer structure are synthesized for the first time by a topochemical reaction. The morphology and oxidation state of these nanosheets can be controlled by appropriate choice of reaction media and oxidants. Benefiting from the hierarchical structure and ultrathin size, when the silicon-based nanosheets are employed as anodes they exhibit a charge (delithiation) capacity of 800 mAh/g after 50 cycles with a maximum coulombic efficiency of 99.4% and good rate performance (647 mAh/g at 1 A/g). This work demonstrates a novel method for preparing nanosheets not only for lithium ion batteries but also having various potential applications in other fields, such as catalysts, electronics and photonics.

Si–Cu–Ti thin films with Cu 3 Si nanowires on the surface and voids in the Cu layer are fabricated for the first time by magnetron sputtering combined with atomic layer deposition (ALD) of alumina. The formation of the surface Cu 3 Si nanowires is strongly dependent on the thickness of the coated alumina and cooling rate of the thin films during annealing. The maximum coverage of the surface Cu 3 Si nanowires is obtained with an alumina thickness of 2 nm and a cooling rate of 1 °C min −1 . The electrode based on this thin film shows an excellent capacity retention of more than 900 mAh g −1 and a high columbic efficiency of more than 99% after 100 cycles. The improvement of the electrochemical performance of Si–Cu–Ti thin film electrode is attributed to the surface Cu 3 Si nanowires which reduce the polarization and inhomogeneous lithiation by formation of a surface conductive network, in addition to the alleviation of volume expansion of Si by voids in the Cu layer during cycling.

Cr-based cathode materials for Li-ion batteries have attracted significant attentions due to the feature of multiple electron transfer. The origin of the poor electrochemical inactivity of LiCrO2 has not been clarified for decades. Here an irreversible phase transformation from the layered to the rock-salt structure is observed at atomic scale in partially electrochemical delithiated LiCrO2: Cr ions migrate from Cr layers into Li layers in the surface regions. The Cr ions at Li layers in the surface regions could block extraction of lithium from the interior regions. Density functional theory (DFT) calculations confirm that Cr ions in Li layers can stabilize the structure in the Li-poor area, but the diffusion energy barrier of Li ions will be greatly increased. It is proposed accordingly that the surface phase transformation and the blocking of diffusion channel are the main origin for the poor electrochemical reactivity of LiCrO2. Such a surface blocking phenomenon may be a common origin for inactivity of some cathode materials, in which cation mixing become significant after initial delithiation. In addition, Cr ions in LiCrO2 are oxidized only from Cr3+ to Cr4+ during electrochemical delithiation, instead of Cr6+ as usually expected, based on synchrotron X-ray absorption spectra (XAS) studies.

Application of high-voltage spinel LiNi0.5Mn1.5O4 cathode material is the closest and the most realistic approach to meeting the midterm goal of lithium-ion batteries for electric vehicles (EVs) and plug-in hybrid electric vehicles (HEVs). However, this application has been hampered by long-standing issues, such as capacity degradation and poor first-cycle Coulombic efficiency of LiNi0.5Mn1.5O4 cathode material. Although it is well-known that the structure of LiNi0.5Mn1.5O4 into which Li ions are reversibly intercalated plays a critical role in the above issues, performance degradation related to structural changes, particularly in the first cycle, are not fully understood. Here, we report detailed investigations of local atomic-level and average structure of LiNi0.5Mn1.5O4 during first cycle (3.5–4.9 V) at room temperature. We observed two types of local atomic-level migration of transition metals (TM) ions in the cathode of a well-prepared LiNi0.5Mn1.5O4//Li half-cell during first charge via an aberrati...

A series of Li1+xAlxTi2-x(PO4)(3) samples (x = 0-0.4) were prepared by solid state reaction and were characterized. Lattice parameters a and c decrease continuously with increase of Al content. The relative density of the Al-doped samples is about 97%, which is much higher than 75% of the undoped LiTi2(PO4)(3) sample. Detailed ac impedance measurements from - 150 degrees C to 60 degrees C reveal clearly that three electrical response regions with different relaxation time constants coexist in the undoped LiTi2(PO4)(3) sample but only two in all Al-doped samples. The bulk ionic conductivities for the Al-doped samples show no significant variation from x = 0.1 to x = 0.4. Their ionic conductivities are slightly higher than those of the undoped sample. However, this increase is not caused by increasing bulk ionic conductivity through introducing more lithium ions via doping, but it is mainly attributed to a densification effect. (C) 2014 Elsevier B.V. All rights reserved.

Distorted surface regions (5-6 nm) with an unusual layered-like structure on LiMn

Surface dissolution of manganese is a long-standing issue hindering the practical application of spinel LiMn2O4 cathode material, while few studies concerning the crystal structure evolution at the surface area have been reported. Combining X-ray photoelectron spectroscopy, electron energy loss spectroscopy, scanning transmission electron microscopy, and density functional theory calculations, we investigate the chemical and structural evolutions on the surface of a LiMn2O4 electrode upon cycling. We found that an unexpected Mn3O4 phase was present on the surface of LiMn2O4 via the application of an advanced electron microscopy. Since the Mn3O4 phase contains 1/3 soluble Mn2+ ions, formation of this phase contributes significantly to the Mn2+ dissolution in a LiMn2O4 electrode upon cycling. It is further found that the Mn3O4 appears upon charge and disappears upon discharge, coincident with the valence change of Mn. Our results shed light on the importance of stabilizing the surface structure of cathode m...

High-voltage spinel LiNi0.5Mn1.5O4 (LNMO) athode material is subject to capacity degradation, particularly at elevated temperatures, which limits its practical applications. In this study, MgO and Ta2O5 co-coatings of LiNi0.5Mn1.5O4 are prepared, and their electrochemical performances at 25 °C and 55 °C are investigated using a combination of analytical techniques. The results reveal that the bare and co-coated LNMO half-cells exhibit a relative stable capacity retention and coulombic efficiency at 25 °C. However, at 55 °C, the bare LNMO half-cell only exhibits a capacity retention of 62.9% after 100 cycles, when compared with 88.2% of the co-coated LNMO half-cell. Detailed structural examinations suggested that the MgO and Ta2O5 co-coatings may stabilize the surface structure of LNMO while retaining a bulk structure similar to that of the bare LNMO. The improvement of the electrochemical cycling performance is attributed to the combined effects of the MgO and Ta2O5 co-coatings, i.e., MgO acted as an HF scavenger and Ta2O5 acted as an HF barrier, and they mitigate the Mn dissolution and side reactions caused by HF. These combined effects lead to a better cycling performance for co-coated LNMO than that of MgO-coated or Ta2O5-coated LNMO at 55 °C.

The energetics of La-doping in BaTiO3 are reported for both (electronic) donor-doping with the creation of Ti3+ cations and ionic doping with the creation of Ti vacancies. The experiments (for samples prepared in air) and simulations demonstrate that ionic doping is the preferred mechanism for all concentrations of La-doping. The apparent disagreement with electrical conduction of these ionic doped samples is explained by subsequent oxygen-loss, which leads to the creation of Ti3+ cations. Simulations show that oxygen-loss is much more favorable in the ionic-doped system than undoped BaTiO3 due to the unique local structure created around the defect site. These findings resolve the so-called “donor-doping” anomaly in BaTiO3 and explain the source of semiconductivity in positive temperature coefficient of resistance (PTCR) BaTiO3 thermistors. Postprint

The defect structures for Gd- and La-doping on the A-site of BaTiO3 with the creation of Ti vacancies are reported. The rare-earth cations cluster together around the vacancy. The local relaxations caused by the defect cluster lead to distortion and tilting of nearby TiO6 octahedra and this is responsible for the lowering of the Curie temperature with increasing dopant concentration. Larger distortions to the octahedra are observed for La-doping and this is the proposed origin of the greater decrease in Tc as observed by experimental results associated with La- compared to Gd-doped samples.

BaTi0.98Ca0.02O2.98 (BTC) ceramics where Ca2+ acts as an acceptor dopant show ferroelectric aging, reversible domain switching, and a nonlinear recoverable electrostrain of ∼0.04% at ∼11 kV/cm. This behavior is attributed to the mobility of oxide-ion vacancies created by the acceptor doping mechanism and a tendency for the defect symmetry to align with the crystal symmetry. The recoverable strain in unpoled ceramics is of comparable magnitude to that obtained from the linear piezoelectric effect in poled hard-PZT ceramics at a similar applied field. These preliminary results demonstrate the potential of BTC as a ‘Pb-free’ ceramic to achieve significant recoverable electrostrain.

The microstructure and mechanical properties of the solid electrolyte interphase (SEI) in non-aqueous lithium ion batteries are key issues for understanding and optimizing the electrochemical performance of lithium batteries. In this report, the three-dimensional (3D) multi-layered structures and the mechanical properties of the SEI formed on a silicon anode material for next generation lithium ion batteries have been visualized directly for the first time, through a scanning force spectroscopy method. The coverage of the SEI on silicon anodes is also obtained through 2D projection plots. The effects of temperature and the function of additives in the electrolyte on the SEI can be understood accordingly. A modified model about dynamic evolution of the SEI on the silicon anode material is also proposed, which aims to explain why the SEI is very thick and how the multi-layered structure is formed and decomposed dynamically.

Sodium-ion batteries are promising for grid-scale storage applications due to the natural abundance and low cost of sodium. However, few electrodes that can meet the requirements for practical applications are available today due to the limited routes to exploring new materials. Here, a new strategy is proposed through partially/fully substituting the redox couple of existing negative electrodes in their reduced forms to design the corresponding new positive electrode materials. The power of this strategy is demonstrated through the successful design of new tunnel-type positive electrode materials of Na0.61[Mn0.61-xFexTi0.39]O2, composed of non-toxic and abundant elements: Na, Mn, Fe, Ti. In particular, the designed air-stable Na0.61[Mn0.27Fe0.34Ti0.39]O2 shows a usable capacity of ≈90 mAh g−1, registering the highest value among the tunnel-type oxides, and a high storage voltage of 3.56 V, corresponding to the Fe3+/Fe4+ redox couple realized for the first time in non-layered oxides, which was confirmed by X-ray absorption spectroscopy and Mossbauer spectroscopy. This new strategy would open an exciting route to explore electrode materials for rechargeable batteries.

The influence of A-site Gd3+ doping on the c/a ratio, cell volume and Curie temperature (Tc) of ferroelectric BaTiO3 according to the titanium vacancy mechanism, viz., Ba1−xGdxTi1−x/4O3 has been investigated and compared to that of La3+-doping. The c/a ratio and cell volume of Gd-doped samples are larger than the equivalent La-doped samples and Tc decreases at a rate of only ∼8 °C/at. % for Gd3+ substitution compared to ∼24 °C/at. % for La3+ substitution. These trends are opposite to that expected based on ionic-radii and tolerance factor arguments. This anomalous behavior is attributed to an ion-size mismatch (cation variance) effect on the A-site between the Ba2+ and Gd3+ ions that induces local strain in the lattice that suppresses the reduction in the c/a ratio and cell volume, and as a consequence in the rate of decrease in Tc.

We present a new set of interatomic potentials for modelling the BaTiO3 perovskite system. The potential model is fitted using multiple parameters to a range of experimental and ab initio data including the cohesive energy and lattice parameters of BaTiO3, BaO and rutile TiO2. This procedure provides internal consistency to the potential model for studying the energetics of the defect chemistry of BaTiO3. This is tested by examining rare-earth cation doping in BaTiO3 and considering all five possible compensation schemes. Our simulations are in agreement with experiment and predict small rare-earth cations to dope exclusively on the Ti site; medium sized rare-earth cations to dope on both the Ti and Ba sites and large rare-earth cation doping exclusively on the Ba-site. For Ba-site substitution the simulations predict electron compensation to be energetically unfavourable compared to the formation of Ti vacancies.