工程科学学报，第39卷，第6期：896-902.2017年6月 Chinese Journal of Engineering,Vol.39,No.6:896-902,June 2017 D0L:10.13374/j.issn2095-9389.2017.06.012;htp:/journals.ustb.edu.cn 超细晶钛酸钡基储能陶瓷的性能与微观结构 刘佰博，王晓慧区，李龙土 清华大学新型陶瓷与精细工艺国家重点实验室，北京100084 ☒通信作者，E-mail:wxh@tsinghua.cdu.cn 摘要利用水基化学包覆法在纳米钛酸钡粉体包覆氧化铝、二氧化硅和氧化锌等物质，并通过两段式烧结法制备了平均晶 粒尺寸120m的超细晶钛酸钡基储能陶瓷.包覆层的存在抑制了晶粒生长和异常晶粒长大，同时将陶瓷的交流击穿场强大 幅提高至150kV·cm1以上，储能密度达到0.829J·cm3.电子能量损失谱显示，包覆掺杂的元素明显偏聚于陶瓷晶界，形成 具有芯-壳结构的品粒.而高温阻抗谱的测试和拟合结果则进一步解释了陶瓷性能改善的原因.虽然此超细品晶陶瓷的储能密 度并不十分突出，但其晶粒细小均匀、烧结温度低，因而可用于制备多层陶瓷电容器，从而大幅提高储能密度，这是常见的储 能陶瓷无法实现的. 关键词储能陶瓷：钛酸钡；晶粒尺寸；电滞回线；芯-壳结构 分类号TB321 Properties and microstructure of ultrafine-crystalline BaTiO,-based energy storage ceramics LIU Bai-bo,WANG Xiao-hui,LI Long-tu State Key Laboratory of New Ceramics and Fine Processing,Tsinghua University,Beijing 100084,China Corresponding author,E-mail:wxh@tsinghua.edu.cn ABSTRACT AL,O.,SiO,and ZnO were coated around nano-sized BaTiO,particles by means of aqueous chemical coating.Then, BaTiO,-based energy storage ceramic material with average grain size of 120 nm was fabricated by the two-step sintering method.The coating layer can restrain grain growth and abnormal grain growth,and can enhance significantly the AC breakdown strength of the ma- terial to over 150kV.cm,while providing energy density of 0.829 J.cm3.Energy-dispersive spectroscopy proves the gathering of doping elements near grain boundaries,thus indicating the existence of a core-shell structure.High-temperature impedance spectrosco- py and fitting results further explain that the energy storage properties were improved.Although the energy density of this ultrafine- crystalline ceramic material is moderate,the advantages of fine grains and low sintering temperature make it possible for the material to be used in multilayer ceramic capacitors,which can increase energy storage by orders of magnitude.This improvement is impossible to achieve with conventional energy storage ceramics. KEY WORDS energy storage ceramics;barium titanate;grain size;hysteresis loop;core-shell structure 随着人们对环境的日益重视，新能源的开发与利 超级电容器、以及电介质电容器等，根据其不同的能量 用日益受到重视，其中电能已经开始广泛地运用于交 密度和功率密度，可以应用于不同的领域].相比电 通运输行业.除了获取方式，能源的储存与传输也十 池和超级电容器，电介质电容器的能量密度很低，但是 分重要.常见的电能的储存器件主要有二次电池、 功率密度很高，因此在电脉冲领域有广泛应用).常 收稿日期：2016-10-19 基金项目：国家重点基础研究发展计划资助项目(2015CB654604):国家自然科学基金创新研究群体项目(51221291)：国家自然科学基金资助 项目(51272123)工程科学学报,第 39 卷,第 6 期:896鄄鄄902,2017 年 6 月 Chinese Journal of Engineering, Vol. 39, No. 6: 896鄄鄄902, June 2017 DOI: 10. 13374 / j. issn2095鄄鄄9389. 2017. 06. 012; http: / / journals. ustb. edu. cn 超细晶钛酸钡基储能陶瓷的性能与微观结构 刘佰博, 王晓慧苣 , 李龙土 清华大学新型陶瓷与精细工艺国家重点实验室, 北京 100084 苣通信作者, E鄄mail: wxh@ tsinghua. edu. cn 摘 要 利用水基化学包覆法在纳米钛酸钡粉体包覆氧化铝、二氧化硅和氧化锌等物质,并通过两段式烧结法制备了平均晶 粒尺寸 120 nm 的超细晶钛酸钡基储能陶瓷. 包覆层的存在抑制了晶粒生长和异常晶粒长大,同时将陶瓷的交流击穿场强大 幅提高至 150 kV·cm - 1以上,储能密度达到 0郾 829 J·cm - 3 . 电子能量损失谱显示,包覆掺杂的元素明显偏聚于陶瓷晶界,形成 具有芯鄄鄄壳结构的晶粒. 而高温阻抗谱的测试和拟合结果则进一步解释了陶瓷性能改善的原因. 虽然此超细晶陶瓷的储能密 度并不十分突出,但其晶粒细小均匀、烧结温度低,因而可用于制备多层陶瓷电容器,从而大幅提高储能密度,这是常见的储 能陶瓷无法实现的. 关键词 储能陶瓷; 钛酸钡; 晶粒尺寸; 电滞回线; 芯鄄鄄壳结构 分类号 TB321 Properties and microstructure of ultrafine鄄crystalline BaTiO3 鄄based energy storage ceramics LIU Bai鄄bo, WANG Xiao鄄hui 苣 , LI Long鄄tu State Key Laboratory of New Ceramics and Fine Processing, Tsinghua University, Beijing 100084, China 苣 Corresponding author, E鄄mail: wxh@ tsinghua. edu. cn ABSTRACT Al 2O3 , SiO2 and ZnO were coated around nano鄄sized BaTiO3 particles by means of aqueous chemical coating. Then, BaTiO3 鄄based energy storage ceramic material with average grain size of 120 nm was fabricated by the two鄄step sintering method. The coating layer can restrain grain growth and abnormal grain growth, and can enhance significantly the AC breakdown strength of the ma鄄 terial to over 150 kV·cm - 1 , while providing energy density of 0郾 829 J·cm - 3 . Energy鄄dispersive spectroscopy proves the gathering of doping elements near grain boundaries, thus indicating the existence of a core鄄shell structure. High鄄temperature impedance spectrosco鄄 py and fitting results further explain that the energy storage properties were improved. Although the energy density of this ultrafine鄄 crystalline ceramic material is moderate, the advantages of fine grains and low sintering temperature make it possible for the material to be used in multilayer ceramic capacitors, which can increase energy storage by orders of magnitude. This improvement is impossible to achieve with conventional energy storage ceramics. KEY WORDS energy storage ceramics; barium titanate; grain size; hysteresis loop; core鄄shell structure 收稿日期: 2016鄄鄄10鄄鄄19 基金项目: 国家重点基础研究发展计划资助项目(2015CB654604);国家自然科学基金创新研究群体项目(51221291);国家自然科学基金资助 项目(51272123) 随着人们对环境的日益重视,新能源的开发与利 用日益受到重视,其中电能已经开始广泛地运用于交 通运输行业. 除了获取方式,能源的储存与传输也十 分重要[1] . 常见的电能的储存器件主要有二次电池、 超级电容器、以及电介质电容器等,根据其不同的能量 密度和功率密度,可以应用于不同的领域[2] . 相比电 池和超级电容器,电介质电容器的能量密度很低,但是 功率密度很高,因此在电脉冲领域有广泛应用[3] . 常