新型固态薄膜电池及性能研究
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摘要
随着集成电路(IC)和微机电系统(MEMS)产业的不断发展,电子器件的小型化对电源的尺寸和兼容性提出了新的要求,迫切要求开发与此相匹配的微型电源。而薄膜电池以其超薄,可集成,可弯曲等特性,成为了目前最优的选择。
与粉体电极不同,薄膜电极由于不含导电剂和粘合剂,可以被视为一种仅含有被研究材料的“纯物质”体系,因此特别适用于研究电极材料的本征性质和反应机理。本文利用脉冲激光沉积技术制备了异质纳米复合物薄膜和双阴离子化合物薄膜材料作为锂离子电池的电极材料,测试了其电化学性能,利用各种材料表征手段探索了其反应机理,对理解复杂物质作为锂离子电池电极材料的反应特性有一定帮助,并对探索性能更好的电极材料提供了指导。
此外,无论是薄膜电池还是常规大小的电池,其离子传导机理几乎都是基于阳离子的移动,本文以金属-卤素电池体系为对象,研究了主要由阴离子负责电池内部离子传导的电池体系的电化学特征,设计并组装了全固态薄膜铝-碘电池和用液体作为电解液的常规金属-卤素电池,并加以比较,澄清了其离子传导的机理在不同条件下的变化。这项研究证明了阴离子传导的电池体系无论是作为薄膜电池还是常规大小的电池,均可以拥有较好的电化学性能,为寻找性能更好的储能体系提供了一个新的方向。
目前技术最为成熟的薄膜电池就是全固态薄膜锂离子电池,有可能作为下一代微电子和信息产业的能源,因此它的发展受到特别地关注。本文成功制备了大面积的全固态薄膜锂离子电池,并将其与RFID集成,提升了其识别性能,而且与射频充电设备进行集成,实现了非接触式充电,对于拓展薄膜电池的应用范围有一定的意义。
论文的第一部分是对于脉冲激光沉积技术制备的纳米薄膜材料的研究。用真空脉冲激光沉积制备的薄膜电极与金属锂片组装成电池,通过恒电流充放电和循环伏安法测量这些薄膜电极的充放电性能和电化学反应特性。利用X射线衍射(XRD),高分辨电子显微镜(HRTEM),选区电子衍射(SAED)以及X射线光电子能谱(XPS)等多种手段对其电化学过程中物质的组成和结构进行了测试和表征,从而探讨其电化学反应机理。主要包括以下体系：
一.异质纳米混合物Li2Se-MSex (M=Cu、Sb)薄膜的制备及其电化学性能研究(正文第三章,第四章)。我们首次采用脉冲激光沉积技术,通过调节靶的组成与脉冲激光沉积的参数,制备颗粒在纳米尺度的Li2Se-MSex (M=Cu、Sb)储锂薄膜电极。通过对其电化学过程的表征和充放电过程中薄膜组分和结构的变化,发现该类纳米薄膜在充放电循环过程中都包含了含锂惰性基质Li2Se可逆的分解和生成的过程。充放电反应机理有别于传统的锂离子脱嵌过程,而是一种可逆转换反应,主要包含了金属硒化物MSex和Li2Se的可逆转换反应。在研究Li2Se-Sb2Se3体系的过程中还意外的发现了在充电之后的产物中有Sb2Se5的生成,这是首次合成出这个物质,说明电化学合成是一种可行的合成手段,可用于合成一些常规手段不易合成的高价金属化合物。
二.双阴离子型化合物FeOF薄膜电极的的制备及其电化学性能研究(正文第五章)。首次采用脉冲激光沉积法制备了FeOF纳米复合薄膜电极。电化学表征结果显示其首次放电可得到884mAh/g的比容量,随后的可逆容量为约为629mAh/g,平均每次循环容量衰减小于0.1%。研究发现其在充放电过程中发生的电化学反应,既包括FeOF放电生成Fe、Fe2O3、LiF的不可逆转化反应,也包括Fe和Fe2O3的可逆转化反应。
本论文对异质纳米混合物Li2Se-MSex (M=Cu、Sb)薄膜的研究为在电势驱动下含锂惰性基质被金属化合物可逆的分解和生成提供了直接的证据,将转化机理引入了正极材料的设计,并通过电化学合成法首次成功制备了Sb2Se5,提供了一条合成高价金属化合物的途径。对FeOF薄膜电极的研究首次将双阴离子化合物作为薄膜锂离子电池负极材料,证明了在转化机理中,两种含锂惰性基质之间存在电化学反应选择性,这对制备和研究新型的高性能储锂材料具有一定的指导意义。
论文的第二部分是对于M/Xn(M=Al、Mg,X=Br、I)型电池体系的研究(正文第六章)。将铝片作为负极,将碘和乙炔黑混合压片作为正极,直接组装成薄膜电池,测试结果发现此种电池体系有着较高的能量密度,且有着价格低廉,无环境污染等优秀的特性。将铝片或镁片作为工作电极,石墨作为对电极,以碘或溴的乙腈溶液作为电解液,组装成常规液相电池,发现同样有着较好的放电特性,说明M/Xn(M=Al、Mg, X=Br、I)型电池体系适用于薄膜电池及常规电池。在薄膜电池的正负极间加入一层碘离子传导物质LiI(HPN)4-20 wt% 15nm SiO2,电化学测试的结果说明显示其性能和未加碘离子传导电解质之前相差不大,说明M/I2(M=Al、Mg)电池内部的导电机理是以阴离子传导为主。又将电解液中的乙腈换成水,组装成电池进行在线的交流阻抗以及放电性能测试的对比,结果显示不同类型的电解液的离子传导机理是不同的。又对放电结束后的铝电极作了SEM、TEM、XPS、XRD等测试,结果说明水溶液体系中放点结束后的铝没有任何物质在表面生成,而在非离子极性溶剂体系中生成了一层无定型的AlI3,说明在非离子极性溶剂体系中是阴离子传导为主的导电机理,而水体系中是阴阳离子共同传导的,这与电化学的特性是吻合的。
本论文对于M/Xn(M=Al、Mg, X=Br、I)类电池的研究拓展了薄膜电池的种类,证明了基于阴离子传导的电池体系应用于薄膜电池也能获得较好的电化学性能,澄清了阴离子传导型电池体系的电化学反应机理及离子传导机理,对选择合适的正负极材料、电解液体系及其改性方法都有一定的参考价值。
论文的第三部分是大面积的全固态薄膜锂离子电池的制备并应用(正文第七章)。用直流溅射在洁净的玻璃或硅片表面沉积一层金属作为集电极,用射频溅射在其上沉积一层LiMn2O4或LiFe(WO4)2作为正极材料,用磁控溅射的方式在其上制备一层LiPON作为电解质,用热蒸发的方式在其上蒸镀一层金属锂作为负极,通过调节各步靶材成分和成膜条件,成功制备了有效正对面积超过4cm2的全固态薄膜锂离子电池。在应用方面,通过设计全固态薄膜锂离子电池的形状,与RFID标签集成,制备了有源远程可识别标签,测试结果表明,相对于未集成内置电池的无源标签而言,其识别性能有所提升。另一方面,将射频充电设备与全固态薄膜锂离子电池集成,实验结果显示,在距离4.2cm的距离处,可以产生5微安的充电电流,充电后的薄膜电池可正常放电使用,成功实现了非接触式充电。本文这部分的研究改善了全固态薄膜电池的性能,研究了薄膜电池与其他用电及充电设备的集成,拓展了其应用范围。
With the development of IC and MEMS industry, it is urgent to develop the compatible power source. Thin film batteries proved to be the best choice because the quality of ultrathin, compatible and flexible.
It is well known that thin film electrodes are free of additives and binders used in powder-based electrodes and can be employed as an "ideal" system for the fundamental studies because they could yield greater insight into the intrinsic properties of the electrode materials. In this thesis, pulsed laser deposition (PLD) was utilized to prepare the heterogeneous mixture of nano-material thin-film and double-anion material thin-film, used as electrode material for Li-ion battery.The structure, composition, surface morphology, electrochemical properties and lithium reaction mechanism of the materials were examined.
Besides, either thin-film batteries or normal sized batteries, the electric charge transfer within batteries are based on the movement of cations. Here, we studied on the Metal-Halides battery system, which is proved to be based on anion transport mechanism. Both all-solid-state and liquid electrolyte batteries are designed and constructed, and its electrochemistry performance is tested. By comparing with each other, we found the ion-transfer mechanism altered within different condition. This proved anion transparent battery system possesses good electrochemical performance, either as all-solid-state or normal sized batteries provide a novel case of design energy storage devices.
Today the preferred thin-film battery is the all-solid-state thin film Li-ion battery. It is the most developed candidate of the power source for the next generation microchips and industry of information. Here, we successfully prepared the large sized all-solid-state thin film Li-ion batteries, and integrated with RFID devices to raised its performance of recognition. Besides, we also realized "non-contactable"charging of thin film batteries by integrating with radio-frequency charging device. It is meaningful to expand the application of thin-film batteries.
The first part of the thesis is studying on thin-film electrode material prepared by PLD technique. Use PLD instrument to deposit electrode material on stainless steel substrate, assemble a battery with Li metal as counter electrode and reference electrode. Characterizecharging-discharging performance and electrochemical feature. Using physical characterization method to identify the change of composition and status of the electrode material during electrochemical reaction, such as X-Ray diffraction (XRD), high-resolution transparent electroscope (HRTEM), selected area electronic diffraction (SAED) and X-Ray spectroscopy, to explore the electrochemical reaction mechanism. Following materials have been studied:
1. Heterogeneous mixture nanocomposite. Altering the composition of the target and other parameter of PLD to prepare the Li2Se-MSex (M= Cu, Sb) thin-film electrode. By characterize the electrochemical performance and the composition and structure during charging-discharging process, we found Li2Se has been decomposed and produced reversely when cycling. The electrochemical reaction mechanism is not insertion/deinsertion, but the conversion mechanism, mainly concluding reversible conversion reaction of MSex and Li2Se.
2. Double anion material. This is first time to use double anion material as thin-film electrode material. The electrochemical performance suggest the capacity of initial discharging can reach 884mAh/g, and in the following cycle drop down to 629 mAh/g. The average capacity fading except the first cycle is less than 0.1%. It is found that the electrochemical reaction during charging-discharging process including the decomposition of FeOF to produce Fe, Fe2O3 and LiF, also the conversion reaction between Fe and Fe2O3.
The research on heterogeneousmixture of Li2Se-MSex (M= Cu, Sb) nanocomposite provide the direct prove that the inertia containing lithium can be decomposed and reproduced reversibly, showed possibility of cathode based on conversion mechanism. Sb2Se5 is successfully synthesized by electrochemical oxidation for the first time, providing a strategy to prepare high oxidation-state metal compound.Study on FeOF thin-film electrode material employed double anion compound as anode material for thin-film lithium-ion batteries for the first time, which proved that there is electrochemical selectivity between different matrixes containing lithium in conversion reaction mechanism. It will guild us in the exploration of new high capacity lithium-storage material.
The second part of this paper is the study on M/Xn(M=Al、Mg, X=Br、I) battery.The metal/iodine thin-film battery can operate with solid electrolyte showing high voltage and moderate rate performances. The regular cell based on organic liquid electrolyte also showed similar electrochemical performance, in which Al or Mg sheet was used as a work electrode and a carbon sheet was used as a counter electrode.
As a comparison, the aqueous electrolyte based battery is assembled. Ac impedance spectra indicated that the resistance of the Al/I2 cell in water solution reduced during discharging process gradually, while the resistance of the Al/I2 cell in the acetonitrile solution increased during discharging process. This could be due to the formation of a layer of amorphous AlI3 on the surface of aluminum anode, which was confirmed by the scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy and selected area electron diffraction measurements.
An I- conductor, LiI(HPN)4 with 20 wt% 15nm SiO2 was employed as solid electrolyte between Al and 12 electrode to assemble the solid-state Al-I2 cell for further clarifying the transport mechanism. Our results demonstrated that the transport mechanism of Al-I2 cell in the water may be involved in both cation and anion transport mechanism, but in non-aqueous solution, it may be involved in cation transport mechanism. So the anion-conducting electrochemical batteries can be also promising for energy storage compared to cation-conducting systems in current batteries.
The last part of this paper is preparing and application of large-sized all-solid-state thin-film lithium ion batteries. Deposited a layer of metal on clean surface of glass or Si-sheet as electric charge collector employing DC-sputtering, a layer of LiMn2O4 or LiFe(WO4)2 as cathode material by RF-sputtering, a layer of LiPON as electrolyte by RF-sputtering, and a layer of lithium metal as anode by thermal vaporization to assembling an all-solid-state thin-film lithium ion batteries. By adjusting and controlling the target composition and preparing condition, the battery, effective area of which is larger than 4 cm2, is successfully prepared. For application, we've integrated the large area thin-film battery with RFID tag to assemble an active RFID tag by designing the shape of the battery and the antenna. The result showed the improvement of performance on recognition comparing with passive RFID tag. On the other hand, the experiment result of integrating RF-charging devices with thin-film battery shows the charging current larger than 5μA is produced when distance between the charging device and the battery is 4.2cm, and the battery after charging shows regular discharging performance, realized the "none-contactable" charging. This technique is useful for expanding the applicant of all-solid-state thin-film batteries.
与粉体电极不同,薄膜电极由于不含导电剂和粘合剂,可以被视为一种仅含有被研究材料的“纯物质”体系,因此特别适用于研究电极材料的本征性质和反应机理。本文利用脉冲激光沉积技术制备了异质纳米复合物薄膜和双阴离子化合物薄膜材料作为锂离子电池的电极材料,测试了其电化学性能,利用各种材料表征手段探索了其反应机理,对理解复杂物质作为锂离子电池电极材料的反应特性有一定帮助,并对探索性能更好的电极材料提供了指导。
此外,无论是薄膜电池还是常规大小的电池,其离子传导机理几乎都是基于阳离子的移动,本文以金属-卤素电池体系为对象,研究了主要由阴离子负责电池内部离子传导的电池体系的电化学特征,设计并组装了全固态薄膜铝-碘电池和用液体作为电解液的常规金属-卤素电池,并加以比较,澄清了其离子传导的机理在不同条件下的变化。这项研究证明了阴离子传导的电池体系无论是作为薄膜电池还是常规大小的电池,均可以拥有较好的电化学性能,为寻找性能更好的储能体系提供了一个新的方向。
目前技术最为成熟的薄膜电池就是全固态薄膜锂离子电池,有可能作为下一代微电子和信息产业的能源,因此它的发展受到特别地关注。本文成功制备了大面积的全固态薄膜锂离子电池,并将其与RFID集成,提升了其识别性能,而且与射频充电设备进行集成,实现了非接触式充电,对于拓展薄膜电池的应用范围有一定的意义。
论文的第一部分是对于脉冲激光沉积技术制备的纳米薄膜材料的研究。用真空脉冲激光沉积制备的薄膜电极与金属锂片组装成电池,通过恒电流充放电和循环伏安法测量这些薄膜电极的充放电性能和电化学反应特性。利用X射线衍射(XRD),高分辨电子显微镜(HRTEM),选区电子衍射(SAED)以及X射线光电子能谱(XPS)等多种手段对其电化学过程中物质的组成和结构进行了测试和表征,从而探讨其电化学反应机理。主要包括以下体系：
一.异质纳米混合物Li2Se-MSex (M=Cu、Sb)薄膜的制备及其电化学性能研究(正文第三章,第四章)。我们首次采用脉冲激光沉积技术,通过调节靶的组成与脉冲激光沉积的参数,制备颗粒在纳米尺度的Li2Se-MSex (M=Cu、Sb)储锂薄膜电极。通过对其电化学过程的表征和充放电过程中薄膜组分和结构的变化,发现该类纳米薄膜在充放电循环过程中都包含了含锂惰性基质Li2Se可逆的分解和生成的过程。充放电反应机理有别于传统的锂离子脱嵌过程,而是一种可逆转换反应,主要包含了金属硒化物MSex和Li2Se的可逆转换反应。在研究Li2Se-Sb2Se3体系的过程中还意外的发现了在充电之后的产物中有Sb2Se5的生成,这是首次合成出这个物质,说明电化学合成是一种可行的合成手段,可用于合成一些常规手段不易合成的高价金属化合物。
二.双阴离子型化合物FeOF薄膜电极的的制备及其电化学性能研究(正文第五章)。首次采用脉冲激光沉积法制备了FeOF纳米复合薄膜电极。电化学表征结果显示其首次放电可得到884mAh/g的比容量,随后的可逆容量为约为629mAh/g,平均每次循环容量衰减小于0.1%。研究发现其在充放电过程中发生的电化学反应,既包括FeOF放电生成Fe、Fe2O3、LiF的不可逆转化反应,也包括Fe和Fe2O3的可逆转化反应。
本论文对异质纳米混合物Li2Se-MSex (M=Cu、Sb)薄膜的研究为在电势驱动下含锂惰性基质被金属化合物可逆的分解和生成提供了直接的证据,将转化机理引入了正极材料的设计,并通过电化学合成法首次成功制备了Sb2Se5,提供了一条合成高价金属化合物的途径。对FeOF薄膜电极的研究首次将双阴离子化合物作为薄膜锂离子电池负极材料,证明了在转化机理中,两种含锂惰性基质之间存在电化学反应选择性,这对制备和研究新型的高性能储锂材料具有一定的指导意义。
论文的第二部分是对于M/Xn(M=Al、Mg,X=Br、I)型电池体系的研究(正文第六章)。将铝片作为负极,将碘和乙炔黑混合压片作为正极,直接组装成薄膜电池,测试结果发现此种电池体系有着较高的能量密度,且有着价格低廉,无环境污染等优秀的特性。将铝片或镁片作为工作电极,石墨作为对电极,以碘或溴的乙腈溶液作为电解液,组装成常规液相电池,发现同样有着较好的放电特性,说明M/Xn(M=Al、Mg, X=Br、I)型电池体系适用于薄膜电池及常规电池。在薄膜电池的正负极间加入一层碘离子传导物质LiI(HPN)4-20 wt% 15nm SiO2,电化学测试的结果说明显示其性能和未加碘离子传导电解质之前相差不大,说明M/I2(M=Al、Mg)电池内部的导电机理是以阴离子传导为主。又将电解液中的乙腈换成水,组装成电池进行在线的交流阻抗以及放电性能测试的对比,结果显示不同类型的电解液的离子传导机理是不同的。又对放电结束后的铝电极作了SEM、TEM、XPS、XRD等测试,结果说明水溶液体系中放点结束后的铝没有任何物质在表面生成,而在非离子极性溶剂体系中生成了一层无定型的AlI3,说明在非离子极性溶剂体系中是阴离子传导为主的导电机理,而水体系中是阴阳离子共同传导的,这与电化学的特性是吻合的。
本论文对于M/Xn(M=Al、Mg, X=Br、I)类电池的研究拓展了薄膜电池的种类,证明了基于阴离子传导的电池体系应用于薄膜电池也能获得较好的电化学性能,澄清了阴离子传导型电池体系的电化学反应机理及离子传导机理,对选择合适的正负极材料、电解液体系及其改性方法都有一定的参考价值。
论文的第三部分是大面积的全固态薄膜锂离子电池的制备并应用(正文第七章)。用直流溅射在洁净的玻璃或硅片表面沉积一层金属作为集电极,用射频溅射在其上沉积一层LiMn2O4或LiFe(WO4)2作为正极材料,用磁控溅射的方式在其上制备一层LiPON作为电解质,用热蒸发的方式在其上蒸镀一层金属锂作为负极,通过调节各步靶材成分和成膜条件,成功制备了有效正对面积超过4cm2的全固态薄膜锂离子电池。在应用方面,通过设计全固态薄膜锂离子电池的形状,与RFID标签集成,制备了有源远程可识别标签,测试结果表明,相对于未集成内置电池的无源标签而言,其识别性能有所提升。另一方面,将射频充电设备与全固态薄膜锂离子电池集成,实验结果显示,在距离4.2cm的距离处,可以产生5微安的充电电流,充电后的薄膜电池可正常放电使用,成功实现了非接触式充电。本文这部分的研究改善了全固态薄膜电池的性能,研究了薄膜电池与其他用电及充电设备的集成,拓展了其应用范围。
With the development of IC and MEMS industry, it is urgent to develop the compatible power source. Thin film batteries proved to be the best choice because the quality of ultrathin, compatible and flexible.
It is well known that thin film electrodes are free of additives and binders used in powder-based electrodes and can be employed as an "ideal" system for the fundamental studies because they could yield greater insight into the intrinsic properties of the electrode materials. In this thesis, pulsed laser deposition (PLD) was utilized to prepare the heterogeneous mixture of nano-material thin-film and double-anion material thin-film, used as electrode material for Li-ion battery.The structure, composition, surface morphology, electrochemical properties and lithium reaction mechanism of the materials were examined.
Besides, either thin-film batteries or normal sized batteries, the electric charge transfer within batteries are based on the movement of cations. Here, we studied on the Metal-Halides battery system, which is proved to be based on anion transport mechanism. Both all-solid-state and liquid electrolyte batteries are designed and constructed, and its electrochemistry performance is tested. By comparing with each other, we found the ion-transfer mechanism altered within different condition. This proved anion transparent battery system possesses good electrochemical performance, either as all-solid-state or normal sized batteries provide a novel case of design energy storage devices.
Today the preferred thin-film battery is the all-solid-state thin film Li-ion battery. It is the most developed candidate of the power source for the next generation microchips and industry of information. Here, we successfully prepared the large sized all-solid-state thin film Li-ion batteries, and integrated with RFID devices to raised its performance of recognition. Besides, we also realized "non-contactable"charging of thin film batteries by integrating with radio-frequency charging device. It is meaningful to expand the application of thin-film batteries.
The first part of the thesis is studying on thin-film electrode material prepared by PLD technique. Use PLD instrument to deposit electrode material on stainless steel substrate, assemble a battery with Li metal as counter electrode and reference electrode. Characterizecharging-discharging performance and electrochemical feature. Using physical characterization method to identify the change of composition and status of the electrode material during electrochemical reaction, such as X-Ray diffraction (XRD), high-resolution transparent electroscope (HRTEM), selected area electronic diffraction (SAED) and X-Ray spectroscopy, to explore the electrochemical reaction mechanism. Following materials have been studied:
1. Heterogeneous mixture nanocomposite. Altering the composition of the target and other parameter of PLD to prepare the Li2Se-MSex (M= Cu, Sb) thin-film electrode. By characterize the electrochemical performance and the composition and structure during charging-discharging process, we found Li2Se has been decomposed and produced reversely when cycling. The electrochemical reaction mechanism is not insertion/deinsertion, but the conversion mechanism, mainly concluding reversible conversion reaction of MSex and Li2Se.
2. Double anion material. This is first time to use double anion material as thin-film electrode material. The electrochemical performance suggest the capacity of initial discharging can reach 884mAh/g, and in the following cycle drop down to 629 mAh/g. The average capacity fading except the first cycle is less than 0.1%. It is found that the electrochemical reaction during charging-discharging process including the decomposition of FeOF to produce Fe, Fe2O3 and LiF, also the conversion reaction between Fe and Fe2O3.
The research on heterogeneousmixture of Li2Se-MSex (M= Cu, Sb) nanocomposite provide the direct prove that the inertia containing lithium can be decomposed and reproduced reversibly, showed possibility of cathode based on conversion mechanism. Sb2Se5 is successfully synthesized by electrochemical oxidation for the first time, providing a strategy to prepare high oxidation-state metal compound.Study on FeOF thin-film electrode material employed double anion compound as anode material for thin-film lithium-ion batteries for the first time, which proved that there is electrochemical selectivity between different matrixes containing lithium in conversion reaction mechanism. It will guild us in the exploration of new high capacity lithium-storage material.
The second part of this paper is the study on M/Xn(M=Al、Mg, X=Br、I) battery.The metal/iodine thin-film battery can operate with solid electrolyte showing high voltage and moderate rate performances. The regular cell based on organic liquid electrolyte also showed similar electrochemical performance, in which Al or Mg sheet was used as a work electrode and a carbon sheet was used as a counter electrode.
As a comparison, the aqueous electrolyte based battery is assembled. Ac impedance spectra indicated that the resistance of the Al/I2 cell in water solution reduced during discharging process gradually, while the resistance of the Al/I2 cell in the acetonitrile solution increased during discharging process. This could be due to the formation of a layer of amorphous AlI3 on the surface of aluminum anode, which was confirmed by the scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy and selected area electron diffraction measurements.
An I- conductor, LiI(HPN)4 with 20 wt% 15nm SiO2 was employed as solid electrolyte between Al and 12 electrode to assemble the solid-state Al-I2 cell for further clarifying the transport mechanism. Our results demonstrated that the transport mechanism of Al-I2 cell in the water may be involved in both cation and anion transport mechanism, but in non-aqueous solution, it may be involved in cation transport mechanism. So the anion-conducting electrochemical batteries can be also promising for energy storage compared to cation-conducting systems in current batteries.
The last part of this paper is preparing and application of large-sized all-solid-state thin-film lithium ion batteries. Deposited a layer of metal on clean surface of glass or Si-sheet as electric charge collector employing DC-sputtering, a layer of LiMn2O4 or LiFe(WO4)2 as cathode material by RF-sputtering, a layer of LiPON as electrolyte by RF-sputtering, and a layer of lithium metal as anode by thermal vaporization to assembling an all-solid-state thin-film lithium ion batteries. By adjusting and controlling the target composition and preparing condition, the battery, effective area of which is larger than 4 cm2, is successfully prepared. For application, we've integrated the large area thin-film battery with RFID tag to assemble an active RFID tag by designing the shape of the battery and the antenna. The result showed the improvement of performance on recognition comparing with passive RFID tag. On the other hand, the experiment result of integrating RF-charging devices with thin-film battery shows the charging current larger than 5μA is produced when distance between the charging device and the battery is 4.2cm, and the battery after charging shows regular discharging performance, realized the "none-contactable" charging. This technique is useful for expanding the applicant of all-solid-state thin-film batteries.
引文
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