With the increasing importance of wireless microelectronic devices the need for on-board power supplies is evidently also increasing. Possible candidates for microenergy storage devices are planar all-solid-state Li-ion microbatteries, which are currently under development by several start-up companies. However, to increase the energy density of these microbatteries further and to ensure a high power delivery, three-dimensional (3D) designs are essential. Therefore, several concepts have been proposed for the design of 3D microbatteries and these are reviewed. In addition, an overview is given of the various electrode and electrolyte materials that are suitable for 3D all-solidstate microbatteries. Furthermore, methods are presented to produce fi lms of these materials on a nano-and microscale.www.MaterialsViews.com REVIEW www.advenergymat.de
Kelvin probe monitoring of metal-organic framework coated electrodes is demonstrated as a route for ppb-level detection of alkyl phosphonates.
Like all rechargeable battery systems, conventional Li-ion batteries (LIB) inevitably suffer from capacity losses during operation. This also holds for all-solid-state LIB. In this contribution an in operando Neutron Depth Profiling (NDP) method is developed to investigate the degradation mechanism of all-solid-state, thin film Si-Li 3 PO 4 -LiCoO 2 batteries. Important aspects of the long-term degradation mechanisms are elucidated. It is found that the capacity losses in these thin film batteries are mainly related to lithium immobilization in the solid-state electrolyte, starting to grow at the anode/electrolyte interface during initial charging. The Li-immobilization layer in the electrolyte is induced by silicon penetration from the anode into the solid-state electrolyte and continues to grow at a lower rate during subsequent cycling. X-ray Photoelectron Spectroscopy (XPS) depth profiling and Transmission Electron Microscopy (TEM) analyses confirm the formation of such immobilization layer, which favorably functions as an ionic conductor for lithium ions. As a result of the immobilization process, the amount of free moveable lithium ions is reduced, leading to the pronounced storage capacity decay. Insights gained from this research shed interesting light on the degradation mechanisms of thin film, all-solid-state LIB and facilitate potential interfacial modifications which finally will lead to substantially improved battery performance.
In situ neutron depth profiling (NDP) offers the possibility to observe lithium transport inside micro‐batteries during battery operation. It is demonstrated that NDP results are consistent with the results of electrochemical measurements, and that the use of an enriched 6LiCoO2 cathode offers more insight in transport processes occurring inside all‐solid‐state thin‐film batteries.
SUMMARY Wireless sensor nodes (WSNs) are expected to play an increasing role in multiple application areas. These application areas vary from networks around the human body, sensors in smart tires, sensor networks that can control the safety and comfort levels throughout smart buildings, sensors that monitor the necessity for maintenance and sensors that track the conditions of food throughout the distribution chain. These wireless sensors need energy, which can be supplied by a battery or an energy harvester. However, even when an energy harvester is applied, energy storage is required to serve as energy buffer. In this review, the requirements that different types of wireless sensor networks impose on these batteries are explored, and several suitable types of batteries are reviewed. Moreover, the trends in battery development are described, and the future improvements are predicted. Finally, the possibilities are discussed to select a battery with properties that are matched to the requirements of the sensor nodes. Copyright © 2012 John Wiley & Sons, Ltd.
High quality Lithium phosphate (Li 3 PO 4 ) thin films have been deposited by metal-organic chemical vapor deposition (MOCVD), using tert-butyllithium and trimethyl phosphate as precursors. The Li 3 PO 4 films deposited at 300 • C yielded the highest ionic conductivity (3.9 × 10 −8 S · cm −1 ). Increasing the deposition temperature led to crystallization of the deposited films and, consequently, to lower ionic conductivities. Kinetic studies on planar substrates showed that Li 3 PO 4 deposition is a diffusion-controlled process in the temperature range of 300 to 500 • C. Li 3 PO 4 films have also been deposited on highly structured substrates to investigate, for the first time, the feasibility of 3D deposition of Li 3 PO 4 by MOCVD. Furthermore, very thin films of Li 3 PO 4 have been deposited onto thin film Si anodes and it was found that these layers effectively suppress the SEI formation and dramatically improve the cycle performance of Si film anodes. Driven by the fast development of autonomous devices, all-solidstate micro-batteries currently attract a lot of attention. The three dimensional (3D) all-solid-state Li-ion battery is a challenging concept, which will significantly improve the volumetric capacity and rate capability of micro-batteries.1-3 A stable thin film electrolyte is one of the important components for micro-batteries. Due to the relatively high Li-ion conductivity and (electro)chemical stability upon contact with Li anodes, 4 lithium phosphate thin films are among the most popularly used electrolytes for micro-batteries.Lithium phosphate based thin film electrolytes are generally deposited by sputtering, 4-7 pulsed laser deposition 8 and E-beam evaporation.9 Because of shadow effects, these methods are hardly suitable for 3D deposition. In addition, during the deposition process using these methods, there is a temperature difference between the substrate and the deposited films. The resulting thermal tensile stress may disadvantageously cause film cracking. 10Atomic layer deposition (ALD) and metal-organic chemical vapor deposition (MOCVD) are two methods that can deposit very homogeneous and conformal films on highly structured substrates. Unfortunately, the ALD method is relatively slow 11 and therefore rather unpractical for the deposition of battery materials. Several papers reported the chemical vapor deposition of nitrogen doped lithium phosphate 10,12 but none of these papers explored the feasibility of deposition in 3D. In this study, MOCVD is investigated to deposit Li 3 PO 4 thin films, using tert-butyllithium (t-BuLi) and trimethyl phosphate (TMPO) as precursors. The MOCVD process for Li 3 PO 4 thin film deposition has been developed and the influence of the substrate temperature on the morphology, crystal structure and ionic conductivity has been systematically studied. In order to investigate the feasibility of three dimensional deposition of Li 3 PO 4 by MOCVD, thin films were also deposited onto highly-structured substrates. The thickness development of the deposited thin f...
The feasibility of volatile precursor low-pressure chemical vapor deposition (LPCVD) for the production of LiConormalO2 cathodes for all solid-state microbatteries was examined. To test this feasibility, and gain insight into the deposition behavior, the influence of the deposition parameters on the properties of LPCVD grown thin-film LiConormalO2 cathodes was systematically investigated. The deposition temperature, concentration of the various reactants, and duration of thin-film growth were varied. The resulting LiConormalO2 layers were subjected to X-ray diffraction, inductively coupled plasma–atomic emission spectrometry, Rutherford backscattering spectroscopy, and electrochemical analyses. Stoichiometry of the films could be controlled by varying the precursor flows. Samples deposited at high temperatures with the optimum stoichiometry showed a high crystallinity and a high electrochemical activity; a storage capacity corresponding to a reversible Li-content around the theoretical value of 0.55 per Co was reached, and a good cycling stability was obtained when using this electrode in combination with a solid-state electrolyte.
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