Optimization of 10-μm, sputtered, LiCoO 2 cathodes to enable higher energy density solid state batteries

Trask, J.; Anapolsky, Abraham; Cardozo, Ben; Januar, Eric; Kumar, K.M. Anil; Miller, Michael; Brown, R.; Bhardwaj, R. C.

doi:10.1016/j.jpowsour.2017.03.017

Cited by 36 publications

(39 citation statements)

References 25 publications

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“…Most likely an oxidation of the target surface occurs, suppressing the formation of Co 2 O 4 and thus favoring the formation of LiCoO 2 . [ 14 ] Also it has to be considered that increasing the oxygen partial pressure can lead to an increase in the Li/Co ratio in LiCoO 2 , as it was already observed by Liao et al [ 15 ]…”

Section: Resultsmentioning

confidence: 97%

“…Assuming these reflexes originate from Co 2 O 4 might be meaningful especially for the thin films produced with less oxygen or even pure Ar, as a reducing environment can lead to the formation of Co 2 O 4 . [ 14 ] Nevertheless with increasing the O 2 /Ar ratio, an increase in the (104) orientation, favorable for LIBs, can be observed. Figure 3b,c shows the influence of the substrate temperature on the (003) and (104) peak intensities when sputtering occurred under an O 2 /Ar ratio of 1/1.…”

Section: Resultsmentioning

confidence: 99%

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Structural and Electrochemical Characterization of Radio Frequency Magnetron‐Sputtered LiCoO₂ Thin Films

Michel

Couturier

Becker

et al. 2020

Physica Status Solidi (a)

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As known, the rechargeable lithium-ion battery (LIB) is the most representative candidate when it comes to powering portable, electrical devices such as cell phones or laptops. LiCoO 2 proposed by Goodenough et al., was the first commercially used cathode material in such a LIB. Even today, LiCoO 2 is one of the most important cathode materials due to its high energy density (125 Wh kg À1 , 440 Wh l À1), the high reversible capacity (140 mAh g À1), and an achievable battery voltage of over 4 V. [1] However, due to the ever increasing energy needs of humanity, it is important to further increase the energy density and to continue to ensure or even improve the safety of the batteries. These ideas should be satisfied by the so-called all-solid-state-battery (solid-state battery), a battery made entirely of solid-state materials. Easy miniaturization, no leakage of electrolyte or ignition, and prolonged lifetime are the major advantages that result from the use of a solid electrolyte. In recent years, there has been a severe interest in the application of thin-film cathodes in microelectromechanical systems (MEMS), smart cards, or implantable medical devices. For example, a miniaturized solid-state battery should serve as a so-called "on-chip power supply element" and enable a direct emergency power supply. [2] LiCoO 2 is an extremely promising cathode material due to its excellent electrochemical properties. To date, many studies have focused on LiCoO 2 thin-film cathodes fabricated using common techniques such as radio frequency (RF) magnetron sputtering, [3-5] pulsed laser deposition, [6,7] spray methods, [8] sol-gel coating, [9] and chemical vapor deposition. [10,11] LiCoO 2 crystallizes in the rhombohedral high temperature (HT) or cubic low temperature (LT) phase, depending on the manufacturing conditions. In battery applications, the HT phase is preferred because of its suitable electrochemical properties such as increased capacity and better cycle stability compared with the LT phase. Furthermore, there is a desire to obtain the HT-LiCoO 2 film in a suitable orientation in growth direction, as the efficiency of the Li þ diffusion can be further enhanced. An overview of the properties of RF-sputtered LiCoO 2 is given by Julien et al. [12] In this article, we will investigate the deposition of LiCoO 2 thin films via RF magnetron sputtering on heated platinum-coated c-sapphire substrates. Compared with the parameters given by Julien et al., we gain additional information about the thin film using a different substrate and deposition temperature. Structural characterization of the films was carried out as a function of the substrate temperature and the oxygen-to-argon ratio during the deposition. Elemental distribution of atomic compounds near the surface of optimized films was analyzed. Also the electrochemical performance of a LiCoO 2 film was evaluated.

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Section: Resultsmentioning

confidence: 97%

Section: Resultsmentioning

confidence: 99%

Structural and Electrochemical Characterization of Radio Frequency Magnetron‐Sputtered LiCoO₂ Thin Films

Michel

Couturier

Becker

et al. 2020

Physica Status Solidi (a)

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“…To demonstrate the advantages of the Li x MnO 2 cathode for practical applications, the Li x MnO 2 thin film cathode was further compared with the high temperature prepared LiCoO 2 and LiMn 2 O 4 thin film cathodes in different aspects (Figure 5f; Table S6, Supporting Information). First, the preparation temperature (180 °C) of Li x MnO 2 thin film cathode is obviously lower than those for LiCoO 2 and LiMn 2 O 4 thin film cathodes (≥500 °C), [ 7,42–44 ] which significantly broadens the choice of substrate materials and makes it easy for on‐chip integration. Second, the gravimetric specific capacity and energy density of Li x MnO 2 cathode are relatively higher than those of the LiCoO 2 and LiMn 2 O 4 cathodes, thus bringing in new opportunity to fabricate TFBs with large areal capacity and energy density in limited footprint.…”

Section: Figurementioning

confidence: 99%

Tunnel Intergrowth Li_xMnO₂ Nanosheet Arrays as 3D Cathode for High‐Performance All‐Solid‐State Thin Film Lithium Microbatteries

et al. 2020

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All‐solid‐state thin film lithium batteries (TFBs) are proposed as the ideal power sources for microelectronic devices. However, the high‐temperature (>500 °C) annealing process of cathode films, such as LiCoO2 and LiMn2O4, restricts the on‐chip integration and potential applications of TFBs. Herein, tunnel structured LixMnO2 nanosheet arrays are fabricated as 3D cathode for TFBs by a facile electrolyte Li+ ion infusion method at very low temperature of 180 °C. Featuring an interesting tunnel intergrowth structure consisting of alternating 1 × 3 and 1 × 2 tunnels, the LixMnO2 cathode shows high specific capacity with good structural stability between 2.0 and 4.3 V (vs. Li+/Li). By utilizing the 3D LixMnO2 cathode, all‐solid‐state LixMnO2/LiPON/Li TFB (3DLMO‐TFB) has been successfully constructed with prominent advantages of greatly enriched cathode/electrolyte interface and shortened Li+ diffusion length in the 3D structure. Consequently, the 3DLMO‐TFB device exhibits large specific capacity (185 mAh g−1 at 50 mA g−1), good rate performance, and excellent cycle performance (81.3% capacity retention after 1000 cycles), outperforming the TFBs using spinel LiMn2O4 thin film cathodes fabricated at high temperature. Importantly, the low‐temperature preparation of high‐performance cathode film enables the fabrication of TFBs on various rigid and flexible substrates, which could greatly expand their potential applications in microelectronics.

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“…On the other hand, the growth of LCO films under mixed-gas atmosphere requires less stringent annealing process, i.e., lower annealing temperature of ~300 °C. Trask et al [47] demonstrated that crystallographic texture of LCO films thicker than 5 µm deposited with an oxygen concentration of 4% in Ar, with a total flow rate controlled to 50 sccm and an operating pressure of 0.5 Pa, shows no detectable (003) peak after annealing at 800 °C for 1 h. Using such conditions, all solid-state microcells (Figure 3) fabricated with a ~15-µm thick cathodes exhibited discharge capacities of 60 µAh cm −2 µm −1 (600 µAh cm −2 as per cathode) at C/10 rate and a capacity retention greater than 95% after 100 cycles at a C/5 discharge rate. Yoon et al [48] made LCO thin film electrodes on Li 2 O/Al/Si substrates.…”

Section: Growth Of Lco Thin Filmsmentioning

confidence: 99%

Sputtered LiCoO2 Cathode Materials for All-Solid-State Thin-Film Lithium Microbatteries

2019

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This review article presents the literature survey on radio frequency (RF)-magnetron sputtered LiCoO2 thin films used as cathode materials in all-solid-state rechargeable lithium microbatteries. As the process parameters lead to a variety of texture and preferential orientation, the influence of the sputtering conditions on the deposition of LiCoO2 thin films are considered. The electrochemical performance is examined as a function of composition of the sputter Ar/O2 gas mixture, gas flow rate, pressure, nature of substrate, substrate temperature, deposition rate, and annealing temperature. The state-of-the-art of lithium microbatteries fabricated by the rf-sputtering method is also reported.

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Optimization of 10-μm, sputtered, LiCoO 2 cathodes to enable higher energy density solid state batteries

Cited by 36 publications

References 25 publications

Structural and Electrochemical Characterization of Radio Frequency Magnetron‐Sputtered LiCoO₂ Thin Films

Structural and Electrochemical Characterization of Radio Frequency Magnetron‐Sputtered LiCoO₂ Thin Films

Tunnel Intergrowth Li_xMnO₂ Nanosheet Arrays as 3D Cathode for High‐Performance All‐Solid‐State Thin Film Lithium Microbatteries

Sputtered LiCoO2 Cathode Materials for All-Solid-State Thin-Film Lithium Microbatteries

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Optimization of 10-μm, sputtered, LiCoO 2 cathodes to enable higher energy density solid state batteries

Cited by 36 publications

References 25 publications

Structural and Electrochemical Characterization of Radio Frequency Magnetron‐Sputtered LiCoO2 Thin Films

Structural and Electrochemical Characterization of Radio Frequency Magnetron‐Sputtered LiCoO2 Thin Films

Tunnel Intergrowth LixMnO2 Nanosheet Arrays as 3D Cathode for High‐Performance All‐Solid‐State Thin Film Lithium Microbatteries

Sputtered LiCoO2 Cathode Materials for All-Solid-State Thin-Film Lithium Microbatteries

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Structural and Electrochemical Characterization of Radio Frequency Magnetron‐Sputtered LiCoO₂ Thin Films

Structural and Electrochemical Characterization of Radio Frequency Magnetron‐Sputtered LiCoO₂ Thin Films

Tunnel Intergrowth Li_xMnO₂ Nanosheet Arrays as 3D Cathode for High‐Performance All‐Solid‐State Thin Film Lithium Microbatteries