Piezoelectrochemical Energy Harvesting in Commercial Lithium Ion Batteries
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As technology becomes smaller and smaller, the need for micro-energy sources becomes increasingly imperative. One promising technology to address this need is piezoelectrochemical harvesting, a recently identified mechanism to directly convert mechanical energy to electrochemical potential [1-4] . In piezoelectrochemical (PEC) materials, the chemical potential of ions is affected by an applied stress, and under such circumstances these materials can be used in a thermodynamic cycle to harvest energy, at a relatively slow rate commensurate with the kinetic transport in electrochemical systems. Previous work [1] has demonstrated that commercial lithium cobalt oxide (LCO) batteries exhibit the PEC effect, as both the lithium cobalt oxide cathode and lithium-intercalated graphite anode are PEC materials. The coupling factor between the change in equilibrium potential and applied mechanical stress has been found to be linear. In this presentation, we will discuss our research to use piezoelectrochemical energy harvesting to increase the voltage generated from commercial lithium ion batteries. We measured the differential expansion and differential voltage of a lithium ion battery, and used this data to estimate the coupling factor as a function of state-of-charge (SOC). We analyzed the coupling factor for commercial LCO batteries, and found the SOC where the coupling factor was maximized. At this SOC, batteries were placed under a mechanical load to harvest energy. The voltage generated was quantified by measuring the voltage drop across a resistor. To understand how the PEC effect operates in multiple batteries, we wired cells in series and parallel, and performed similar mechanical load experiments. As expected, the PEC voltage can be increased by compressing batteries in series. Increasing the PEC voltage generated would allow the effect to be used in practical applications such as micro-energy devices. References: [1] J. Cannarella and C. B. Arnold, “Toward Low-Frequency Mechanical Energy Harvesting Using Energy-Dense Piezoelectrochemical Materials," Advanced Materials , 27 , 7440 (2015). [2] S. Kim, S. J. Choi, K. Zhao, H. Yang, G. Gobbi, S. Zhang, and J. Li, “Electrochemically driven mechanical energy harvesting," Nature Communications , 7 , 10146 (2016). [3] N. Muralidharan, M. Li, R. E. Carter, N. Galioto, and C. L. Pint, “Ultralow Frequency Electrochemical−Mechanical Strain Energy Harvester Using 2D Black Phosphorus Nanosheets,” ACS Energy Lett ., 2 , 1797 (2017). [4] E. Jacques, G. Lindbergh, D. Zenkert, S. Leijonmarck, and M. H. Kjell, “Piezo-Electrochemical Energy Harvesting with Lithium-Intercalating Carbon Fibers,” ACS Appl. Mater. Interfaces, 7 , 13898 (2015).Keywords:
Lithium cobalt oxide
Voltage drop
Cobalt oxide
Lithium cobalt oxide is synthesized by a novel solution combustion procedure. In this synthesis, a solution mixture of lithium nitrate, cobalt nitrate and glycine fuel is heated to 500, 600 and 700 °C for 3 hours to obtain an ordered crystalline-layered compound. Physical properties of the synthesized cathode materials were evaluated using a XRD, SEM and particle size analyzer. The charge-discharge cycling characteristics of the synthesized lithium cobalt oxide heated at 700 °C exhibited better performance than other materials.
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Nano-SiO2 modified lithium cobalt oxide thin film has been successfully synthesized by pulsed laser ablation of a mixture of SiO2,cobalt acetate and lithium carbonate. EDX revealed that the SiO2 content of the film is about 10wt%. By employing charge/discharge and cyclic voltammetry (CV) measurements,the electrochemical properties of as-deposited film with lithium has been investigated. Our results demonstrated that the addition of SiO2 into LiCoO2 should play an important role in the reversibility of the crystalline structure and morphological changes by using ex situ HRTEM,SAED and SEM. The nano-SiO2 modified lithium cobalt oxide film could be a promising candidate of cathode material for lithium ion battery due to its good reversibility.
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In this experiment, lithium cobalt oxide from a waste lithium ion battery (LIB) is recovered by flotation technique. At first, the waste LIB was classified by vertical cutting mill, air table and vibration screen. Referring to the result of a crushing, wasted LIB represented light materials (separator of anode and cathode of battery), metallic materials (aluminum, copper, etc) and electrode materials (a mixture of lithium cobalt oxide and graphite).Electrode materials were thermally treated in a muffle furnace at 773 K, followed by flotation to separate lithium cobalt oxide and graphite. This is due to the fact that the surface of the lithium cobalt oxide particles were changed from hydrophobic to hydrophilic as for the binder removed from the surface at 773 K.Referring to results that more than 97 % lithium cobalt oxide can be recovered from the mixture of 70 wt% lithium cobalt oxide and 30 wt% graphite, prior to the flotation test.Considering the results, 92 % lithium cobalt oxide can be recovered from electrode materials, whereas the purity is higher than 93 % while the optimum conditions where : 0.2 kg / t kerosene, 0.14 kg / t MIBC and 10 % pulp density.
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Lithium cobalt oxide (LiCoO{sub 2}) is known to be a good cathode material for high voltage (4V) rechargeable Li-ion batteries. New chemical routes based on aqueous solution chemistry have been developed to synthesize molecularly mixed precursors that transform to form LiCoO{sub 2} at temperatures as low as 400{degrees}C. The resultant oxide powders are nanocrystalline ({approx} 20-40 nm) and exhibit unique morphologies and microstructures depending on the molecular environment of the ions in solution. Cathodes fabricated from the oxide powders and tested in {open_quote}hockey-puck{close_quote} test cells exhibited specific capacities of about 135 mAh/g with a reversible range close to 0.5 Li ions. Results of the phase evolution and microstructural analysis are discussed in relation to the electrochemical performance of the cathodes.
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Lithium cobalt oxide
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Lithium cobalt oxide, as a popular cathode in portable devices, delivers only half of its theoretical capacity in commercial lithium-ion batteries. When increasing the cut-off voltage to release more capacity, solubilization of cobalt in the electrolyte and structural disorders of lithium cobalt oxide particles are severe, leading to rapid capacity fading and limited cycle life. Here, we show a class of ternary lithium, aluminum, fluorine-modified lithium cobalt oxide with a stable and conductive layer using a facile and scalable hydrothermal-assisted, hybrid surface treatment. Such surface treatment hinders direct contact between liquid electrolytes and lithium cobalt oxide particles, which reduces the loss of active cobalt. It also forms a thin doping layer that consists of a lithium-aluminum-cobalt-oxide-fluorine solid solution, which suppresses the phase transition of lithium cobalt oxide when operated at voltages >4.55 V.
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The combination of high voltage cathode and metal or graphite anodes provides a feasible way for future high-energy batteries. Among various battery cathodes, lithium cobalt oxide is outstanding for its excellent cycling performance, high specific capacity, and high working voltage and has achieved great success in the field of consumer electronics in the past decades. Recently, demands for smarter, lighter, and longer standby-time electronic devices have pushed lithium cobalt oxide-based batteries to their limits. To obtain high voltage batteries, various methods have been adopted to lift the cutoff voltage of the batteries above 4.45 V (vs Li/Li+). This review summarizes the mechanism of capacity decay of lithium cobalt oxide during cycling. Various modifications to achieve high voltage lithium cobalt oxide, including coating and doping, are also presented. We also extend the discussion of popular modification methods for electrolytes including electrolyte additives, quasi-solid electrolytes, and electrode/electrolyte interfaces.
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Lithium cobalt oxide (LiCoO2) is one of the most relevant components in lithium-ion batteries. The array of sought-after features of LiCoO2 depends on its synthesis method. In this work we synthesized and characterized a nanocrystalline LiCoO2 oxide obtained with a wet chemistry synthesis method. The oxide obtained was a homogeneous powder in the nanometric range (5-8 nm) and exhibited a series of improved properties. Characterization by FTIR and UV-Vis techniques led to identifying citrate species as main products in the first step of the synthesis process. X-ray diffraction (XRD), Raman, and transmission electron microscopy (TEM) characterizations led to identifying a pure crystalline phase of the synthesized LiCoO2 oxide. Steady state electrical characterization and solid-state impedance spectroscopy determined the high conductance of the synthesized oxide. All these features are desirable in the design of cathodes for lithium ion batteries.
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Lithium cobalt oxide (LiCoO2) was synthesized using two different sol−gel processes. The first method used stoichiometric molar ratios of cobalt 2-methoxyethoxide and lithium nitrate in alcoholic solutions; the second method used aqueous equimolar ratios of precursors of lithium nitrate and cobalt acetate with poly(ethylene glycol) (PEG) 200 as the chelating agent. Lithium cobalt oxide films were deposited on Si wafers and silica−soda−lime glass using a dipping technique. Based on differential thermal analysis/thermogravimetric analysis results, densification of the films was achieved by thermal treatment at both 500 and 800 °C in the case of silicon wafer substrates and at 500 °C for the silica−soda−lime glass. X-ray diffraction, spectroellipsometry, and atomic force microscopy were used to characterize the films. The correlation between the preparation procedure and the type of support on the structure and morphology of LiCoO2 compound films is discussed. Uniform ultrathin films were obtained on the glass (heat treated at 500 °C) and Si wafer (heat treated at 800 °C). The alcoholic synthetic procedure was also used to coat particles of LiMn2O4 with films of LiCoO2. The sol−gel method resulted in partial coverage of LiMn2O4 by LiCoO2 as determined by elemental mapping with scanning electron microscopy.
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