Structural, morphological and electrochemical properties of nanocrystalline V2O5 thin films deposited by means of radiofrequency magnetron sputtering

Due to easiness of preparation and high energy density, V₂O₅ nanocrystalline thin films are particularly attractive as cathode materials for all-solid-state rechargeable lithium microbatteries. However, their electrochemical performances are strictly related to the film microstructure, which, in turn, is related to the nature and parameters of the deposition technique. For this reason, the preparation of thin films with reproducible electrochemical properties is still an open problem.Here, we report on the deposition of V₂O₅ crystalline thin films by means of reactive radiofrequency (r.f.) magnetron sputtering, using vanadium metal as the target. Different deposition times and substrate temperatures were adopted. X-ray powder diffraction (XRD) and atomic force microscopy were used to investigate the structural and morphological features of the films. In particular, XRD analysis revealed that the deposition parameters affect the crystallographic orientation of the films. A h 0 0 orientation is observed in case of thin samples (about 100 nm) prepared at 300 °C, whereas a 1 1 0 preferential growth is obtained for thicker films. Films deposited at 500 °C display a 0 0 1 orientation irrespective on the deposition time.Reversible Li intercalation/deintercalation processes and high specific capacity are observed for the h 0 0-oriented V₂O₅ thinner films, with the ab plane arranged perpendicular to the substrate. In this case, the cycling behaviour is very promising, and a stable capacity higher than 300 mAh g⁻¹ was delivered in the potential range 3.8-1.5 V at 1C rate over at least 70 cycles.     

Influence of deposition temperature on ionic conductivity of perovskite (Li0.5 La0.5) TiO3 solid state electrolyte thin film

Thin film microbattery is a promising micropower source for its high energy density and good cell performances, and the application of fast lithium ion conducting solids as electrolytes is thus very important. (Li0.5 La0.5 )TiO3 (LLTO) thin film electrolytes for thin film microbattery were prepared onto Pt/Si substrates using magnetron sputtering. As-deposited LLTO thin films showed amorphous-like phases and when deposition temperature increases the ionic conductivity raises accordingly. The ionic conductivity of LLTO thin film reaches 8. 7 × 10-6 S/cm when the deposition temperature is 400℃, which shows that the LLTO thin films deposited by magnetron sputtering are suitable for application as an electrolyte for thin film microbattery.     

Laser-printed thick-film electrodes for solid-state rechargeable Li-ion microbatteries

Laser-printed thick-film electrodes (LiCoO₂ cathode and carbon anode) are deposited onto metallic current collectors for fabricating Li-ion microbatteries. These microbatteries demonstrate a significantly higher discharge capacity, power and energy densities than those made by sputter-deposited thin-film techniques. This increased performance is attributed to the porous structure of the laser-printed electrodes, which allows improved ionic and electronic transport through the thick electrodes (∼100 μm) without a significant increase in internal resistance. These laser-printed electrodes are separated by a laser-cut porous membrane impregnated with a gel polymer electrolyte (GPE) in order to build mm-size scale solid-state rechargeable Li-ion microbatteries (LiCoO₂/GPE/carbon). The resulting packaged microbatteries exhibit a power density of ∼38 mW cm⁻² with a discharge capacity of ∼102 μAh cm⁻² at a high discharge rate of 10 mA cm⁻². The laser-printed microbatteries also exhibit discharge capacities in excess of 2500 μAh cm⁻² at a current density of 100 μA cm⁻². This is over an order of magnitude higher than that observed for sputter-deposited thin-film microbatteries (∼160 μAh cm⁻²).     

Electrochemical properties of tungsten oxysulphide thin films as positive electrodes for lithium microbatteries

Several WO_yS_z tungsten oxysulphide thin films were tested as positive electrodes for lithium microbatteries. The amorphous WO_1.05S₂ thin film was found very promising. A capacity decrease occurred during the first few cycles, after which the films were able to intercalate reversibly up to 11 lithium ion per formula unit under high regime (75 μA/cm²). They were tested for 250 charge-discharge cycles, between 30 V and 1.2 V. X-ray photoelectron spectroscopy measurements were performed on different compounds in both intercalated (Li₁WO_1.05S₂, Li_2.7WO_1.05S₂ and Li_3.8WO_1.05S₂) and partially deintercalated (Li₁WO_1.05S₂) states in order to understand the redox processes occurring during the first dischargecharge cycle. The analysis of both the W4f and the S2p peaks has shown that the redox processes involve not only the tungsten atoms but also sulphur atoms. At the beginning of the intercalation, W⁶⁺ was first partially reduced into W⁵⁺, and then into W⁴⁺, but the important stage was the reduction of W⁴⁺ into W⁰. In W⁰, the electron binding energy was very close to that of metallic tungsten. At the same time, S ₂ ^2- ions were partially reduced into S^2- ions. But only the reduction process of tungsten atoms appeared to be totally reversible.     

半导体器件在辐射作用下的电学输出性能研究

半导体结型器件是决定辐射伏特效应同位素电池能量转换效率的核心部件。采用加速器产生的不同能量电子束和63Ni源的β射线对硅基PIN结型器件进行辐照,在线测量了其电学输出性能。当电子束能量为18 keV,可得到大于4%的能量转换效率;电子束能量为6 keV,能量转换效率在0.16%～0.33%之间; 活度2.96×108 Bq的63Ni源片辐照的能量转换效率为0.1%左右。     

4H-SiC肖特基微型同位素电池(英文)

半导体同位素电池由于其寿命长、集成性优良、环境适应性强等特点成为解决MEMS能源问题的理想手段。利用4H-SiC材料的宽禁带特性,制造了4H-SiC肖特基同位素电池。对电池的耗尽层厚度以及掺杂浓度进行了优化设计,对肖特基金属进行了选择。使用4mCi/cm2的63Ni作为同位素电池的放射源对制造的同位素电池进行了测试。测试结果表明,该同位素电池可以获得31.3nW/cm2的功率密度、0.5V的开路电压、3.13×10-8A/cm2的短路电流密度和1.3%的转换效率。将电池的输出特性和硅基的平板型、3D结构电池输出特性进行了比较,证明4H-SiC肖特基同位素电池能够获得较高的功率密度。电池的性能可通过提升势垒高度、提高工艺质量、更换同位素等方式得到提高。     

Application of Magnetron Sputtering in Fabricating MEMS Microbatteries

With the development of MEMS and the electronic devices's miniaturization and integration, a new kind of power sources that can satisfy the need for high energy density is required. Microbatteries are being researched abroad for their advantages of extreme thinness and long-term power supply. The development of MEMS microbatteries are reviewed and suggestedmagnetron sputtering in fabricating a high-performance microbattery. The technics as annealing are analyzed. The microbattery with a LiNi1-x Cox O2 cathode exhibited stable cycle ability and a high specific discharge capacity, which was attributed to the alloying effect of the LiNiO2and LiCoO2.     

A betavoltaic microbattery based on PIN diodes

A betavoltaic Microbattery was studied.The diode was composed of a PIN structure with an active area of 10 mm×10 mm to collect the charge from a 10mCi Ni-63 source.An open circuit voltage of 0.16 V and a short circuit current density of 67.6 nA/cm2 were measured.An efficiency (η) of 1.44% was obtained.The performance of device was limited by high series resistance,edge recombination and attenuation of electron in PIN diodes.It is expected to be improved by optimizing the design and using more suitable radioisotope.     

Characterization of Al-doped spinel LiMn2O4 thin film cathode electrodes prepared by Liquid Source Misted Chemical Deposition (LSMCD) technique

A novel process called Liquid Source Misted Chemical Deposition (LSMCD) was used to synthesize Al-doped LiMn₂O₄ cathode films for Lithium microbatteries. The cathode films were characterized by XRD, SEM, cyclic volatmmetry, and charge/discharge test. LiMn_1.8Al_0.2O₄ film crystallized at 800 °C in rapid thermal annealing (RTA) for 5 min under oxygen atmosphere exhibited more improved electrochemical rechargeability than spinel LiMn₂O₄ film because the substitution of Al³⁺ for Mn³⁺ increased Mn---O bonding strength in the spinel framework and suppressed the two-phase behavior of the unsubstituted spinel during the intercalation/deintercalation that is the origin of the failure mechanism in the 4 V region. As a result, LiMn_1.8Al_0.2O₄ film showed an initial discharge capacity of 52 μAh/cm² μm and no capacity fade over 100 cycles.     

Dual‐Graphene Rechargeable Sodium Battery

Sodium (Na) ion batteries are attracting increasing attention for use in various electrical applications. However, the electrochemical behaviors, particularly the working voltages, of Na ion batteries are substantially lower than those of lithium (Li) ion batteries. Worse, the state‐of‐the‐art Na ion battery cannot meet the demand of miniaturized in modern electronics. Here, we demonstrate that electrochemically exfoliated graphene (EG) nanosheets can reversibly store (PF₆⁻) anions, yielding high charging and discharging voltages of 4.7 and 4.3 V vs. Na⁺/Na, respectively. The dual‐graphene rechargeable Na battery fabricated using EG as both the positive and negative electrodes provided the highest operating voltage among all Na ion full cells reported to date, together with a maximum energy density of 250 Wh kg⁻¹. Notably, the dual‐graphene rechargeable Na microbattery exhibited an areal capacity of 35 μAh cm⁻² with stable cycling behavior. This study offers an efficient option for the development of novel rechargeable microbatteries with ultra‐high operating voltage and high energy density.