Sustainable Fabrication of Graphene Oxide Cathodes from Graphite of Failed Commercial Li-Ion Batteries for High-Performance Aqueous Zn-Ion Batteries.

The need for revamping spent graphite (SG) from battery waste of commercial lithium-ion batteries and employing it as a source for the synthesis of graphene oxide (GO) is focused. Thus, this work emphasizes the study of GO sheets, synthesized via modified Hummer's method from spent graphite (SG-GO) as cathodes for an aqueous zinc ion battery (AZIB) system, for the first time in literature. For comparison, graphene oxide is also synthesized using commercial graphite powder, its structural and morphological properties are analyzed with SG-GO. The coin cell AZIB device is fabricated for both the GOs and the electrochemical performances revealed that SG-GO portrayed an enhanced charge capacity of 270 mAh g-1 at 0.1 A g-1 in 3 m ZnSO4 in comparison to GO which delivered ≈198 mAh g-1 at the same current density of 0.1 A g-1. The long-run cycling analysis of SG-GO elucidated the capacity retention of 77.3% at 1 A g-1 even after 1000 cycles. Moreover, the performance of SG-GO is inspected in different electrolyte systems and the suitable electrolyte underwent concentration variation studies to figure out the capability of the system in storing Zn2+ ions which is found to be more in 3 M ZnSO4 electrolyte.

Recent progress on the low and high temperature performance of nanoscale engineered Li-ion battery cathode materials.

Lithium ion batteries (LIB) are the domain power house that gratifies the growing energy needs of the modern society. Statistical records highlight the future demand of LIB for transportation and other high energy applications. Cathodes play a significant role in enhancement of electrochemical performance of a battery, especially in terms of energy density. Therefore, numerous innovative studies have been reported for the development of new cathode materials as well as improving the performance of existing ones. Literature designate stable cathode-electrolyte interface (CEI) is vital for safe and prolonged high performance of LIBs at different cycling conditions. Considering the context, many groups shed light on stabilizing the CEI with different strategies like surface coating, surface doping and electrolyte modulation. Local temperature variation across the globe is another major factor that influences the application and deployment of LIB chemistries. In this review, we discuss the importance of nano-scale engineering strategies on different class of cathode materials for their improved CEI and hence their low and high temperature performances. Based on the literature reviewed, the best nano-scale engineering strategies investigated for each cathode material have been identified and described. Finally, we discuss the advantages, limitations and future directions for enabling high performance cathode materials for a wide range of applications.

Nanoscale-engineered LiCoO2as a high energy cathode for wide temperature lithium-ion battery applications-role of coating chemistry and thickness.

Extending the charge cutoff voltage of LiCoO2(LCO) beyond 4.2 V is considered as a key parameter to obtain higher energy densities. Following gaps have been identified based on a thorough literature survey especially for higher cutoff voltage of nanoscale engineered LCO cathodes, (i) different metal oxides and metal fluoride surface coatings have been mostly done independently by different groups, (ii) room temperature performance was the focus with limited investigations at high temperature, (iii) nonexistence of low temperature cycling studies and (iv) no reports on high rate capability of LCO beyond 4.5 V (especially at 4.8 V) needs to be investigated. Herein, we report the effect of nanoscale engineering of LCO along with the role of coating chemistry and thickness to study its electrochemical performance at higher voltages and at wide operating temperatures. Surface coating was implemented with different metal oxides and a metal fluoride with tunable thickness. At 4.5 V, 5 wt% Al2O3coated LiCoO2(LCO@Al2O3-5) delivered a reversible capacity of 169 mAh g-1at 100 mA g-1and 151 mAh g-1at high rate of 10 C (2 A g-1) and 72% retention at the end of 500 cycles. At 55 °C, it exhibited better stability over 500 cycles at 5 C and even at -12.5 °C it maintained 72% of its initial capacity after 100 cycles at 200 mA g-1. At 4.8 V cut-off, LCO@Al2O3-5 rendered reversible capacity of 213 mAh g-1at 100 mA g-1, a high value compared to literatures reported for LCO. Also noted that it delivered a capacity of 126 mAh g-1at a current density of 1 A g-1, whereas bare could only exhibit 66 mAh g-1under same testing conditions. Enhanced performance of LCO@Al2O3-5 can be ascribed to the lower charge transfer resistance derived from the stable solid solution formation on the interface.Ex situXRD andex situRaman analysis at different stages of charge/discharge cycles correlates the enhanced performance of LCO@Al2O3-5 with its structural stability and minimal structural degradation.

Surface-Engineered Li4Ti5O12 Nanostructures for High-Power Li-Ion Batteries.

Materials with high-power charge-discharge capabilities are of interest to overcome the power limitations of conventional Li-ion batteries. In this study, a unique solvothermal synthesis of Li4Ti5O12 nanoparticles is proposed by using an off-stoichiometric precursor ratio. A Li-deficient off-stoichiometry leads to the coexistence of phase-separated crystalline nanoparticles of Li4Ti5O12 and TiO2 exhibiting reasonable high-rate performances. However, after the solvothermal process, an extended aging of the hydrolyzed solution leads to the formation of a Li4Ti5O12 nanoplate-like structure with a self-assembled disordered surface layer without crystalline TiO2. The Li4Ti5O12 nanoplates with the disordered surface layer deliver ultrahigh-rate performances for both charging and discharging in the range of 50-300C and reversible capacities of 156 and 113 mAh g-1 at these two rates, respectively. Furthermore, the electrode exhibits an ultrahigh-charging-rate capability up to 1200C (60 mAh g-1; discharge limited to 100C). Unlike previously reported high-rate half cells, we demonstrate a high-power Li-ion battery by coupling Li4Ti5O12 with a high-rate LiMn2O4 cathode. The full cell exhibits ultrafast charging/discharging for 140 and 12 s while retaining 97 and 66% of the anode theoretical capacity, respectively. Room- (25 °C), low- (- 10 °C), and high- (55 °C) temperature cycling data show the wide temperature operation range of the cell at a high rate of 100C.

Focused Ion Beam Fabrication of LiPON-based Solid-state Lithium-ion Nanobatteries for In Situ Testing.

Solid-state electrolytes are a promising replacement for current organic liquid electrolytes, enabling higher energy densities and improved safety of lithium-ion (Li-ion) batteries. However, a number of setbacks prevent their integration into commercial devices. The main limiting factor is due to nanoscale phenomena occurring at the electrode/electrolyte interfaces, ultimately leading to degradation of battery operation. These key problems are highly challenging to observe and characterize as these batteries contain multiple buried interfaces. One approach for direct observation of interfacial phenomena in thin film batteries is through the fabrication of electrochemically active nanobatteries by a focused ion beam (FIB). As such, a reliable technique to fabricate nanobatteries was developed and demonstrated in recent work. Herein, a detailed protocol with a step-by-step process is presented to enable the reproduction of this nanobattery fabrication process. In particular, this technique was applied to a thin film battery consisting of LiCoO2/LiPON/a-Si, and has further been previously demonstrated by in situ cycling within a transmission electron microscope.

Interface-engineered Li4Ti5O12-TiO2 dual-phase nanoparticles and CNT additive for supercapacitor-like high-power Li-ion battery applications.

The single-pot synthesis of dual-phase spinel-Li4Ti5O12 and anatase-TiO2 (LTO-TiO2) nanoparticles over all the phase fractions ranging from pure LTO to pure TiO2 is conducted. Carrying out the process over the complete range enabled the identification of a unique weight ratio of 85:15 (LTO:TiO2), providing the best combination of capacity, rate capability and cycling stability. We show that for this composition dual-phase nanoparticles have a predominant interfacial orientation of (111)LTO∣∣(004)TiO2 , while it is (111)LTO∣∣(101)TiO2 for other compositions. This study therefore shows that the dual-phase interface with these specific orientations gives the best performance. The synergistic combination of dual-phase nanoparticles with multi-wall carbon nanotubes improves the performance further. This results in an electrode with supercapacitor-like rate capability delivering high discharge capacities of 174, 127, 119, 110, 101 and 91 mAh g-1 at specific currents of 2000, 6000, 12 000, 18 000, 24 000 and 30 000 mA g-1, respectively. A discharge capacity of 174 mAh g-1 at a specific current of 2000 mA g-1 with only 0.005% capacity loss per cycle over 3000 cycles is demonstrated. At current densities of 6000, 12 000 and 24 000 mA g-1, stable cycling is obtained for 1500 cycles. The present work enables nano-engineered interfaces in LTO-TiO2 dual-phase nanoparticles with an electrochemical performance that is better than its individual components, opening up the potential for high-power Li-ion battery applications.

In Situ STEM-EELS Observation of Nanoscale Interfacial Phenomena in All-Solid-State Batteries.

Behaviors of functional interfaces are crucial factors in the performance and safety of energy storage and conversion devices. Indeed, solid electrode-solid electrolyte interfacial impedance is now considered the main limiting factor in all-solid-state batteries rather than low ionic conductivity of the solid electrolyte. Here, we present a new approach to conducting in situ scanning transmission electron microscopy (STEM) coupled with electron energy loss spectroscopy (EELS) in order to uncover the unique interfacial phenomena related to lithium ion transport and its corresponding charge transfer. Our approach allowed quantitative spectroscopic characterization of a galvanostatically biased electrochemical system under in situ conditions. Using a LiCoO2/LiPON/Si thin film battery, an unexpected structurally disordered interfacial layer between LiCoO2 cathode and LiPON electrolyte was discovered to be inherent to this interface without cycling. During in situ charging, spectroscopic characterization revealed that this interfacial layer evolved to form highly oxidized Co ions species along with lithium oxide and lithium peroxide species. These findings suggest that the mechanism of interfacial impedance at the LiCoO2/LiPON interface is caused by chemical changes rather than space charge effects. Insights gained from this technique will shed light on important challenges of interfaces in all-solid-state energy storage and conversion systems and facilitate improved engineering of devices operated far from equilibrium.

Effects of laser energy and wavelength on the analysis of LiFePO4 using laser assisted atom probe tomography.

The effects of laser wavelength (355 nm and 532 nm) and laser pulse energy on the quantitative analysis of LiFePO4 by atom probe tomography are considered. A systematic investigation of ultraviolet (UV, 355 nm) and green (532 nm) laser assisted field evaporation has revealed distinctly different behaviors. With the use of a UV laser, the major issue was identified as the preferential loss of oxygen (up to 10 at%) while other elements (Li, Fe and P) were observed to be close to nominal ratios. Lowering the laser energy per pulse to 1 pJ/pulse from 50 pJ/pulse increased the observed oxygen concentration to nearer its correct stoichiometry, which was also well correlated with systematically higher concentrations of (16)O2(+) ions. Green laser assisted field evaporation led to the selective loss of Li (~33% deficiency) and a relatively minor O deficiency. The loss of Li is likely a result of selective dc evaporation of Li between or after laser pulses. Comparison of the UV and green laser data suggests that the green wavelength energy was absorbed less efficiently than the UV wavelength because of differences in absorption at 355 and 532 nm for LiFePO4. Plotting of multihit events on Saxey plots also revealed a strong neutral O2 loss from molecular dissociation, but quantification of this loss was insufficient to account for the observed oxygen deficiency.

Interface Limited Lithium Transport in Solid-State Batteries.

Understanding the role of interfaces is important for improving the performance of all-solid-state lithium ion batteries. To study these interfaces, we present a novel approach for fabrication of electrochemically active nanobatteries using focused ion beams and their characterization by analytical electron microscopy. Morphological changes by scanning transmission electron microscopy imaging and correlated elemental concentration changes by electron energy loss spectroscopy mapping are presented. We provide first evidence of lithium accumulation at the anode/current collector (Si/Cu) and cathode/electrolyte (LixCoO2/LiPON) interfaces, which can be accounted for the irreversible capacity losses. Interdiffusion of elements at the Si/LiPON interface was also witnessed with a distinct contrast layer. These results highlight that the interfaces may limit the lithium transport significantly in solid-state batteries. Fabrication of electrochemically active nanobatteries also enables in situ electron microscopy observation of electrochemical phenomena in a variety of solid-state battery chemistries.