技术领域technical field
本发明属于电能储存材料领域，更具体地，涉及一种介电储能反铁电陶瓷材料及其制备方法。The invention belongs to the field of electric energy storage materials, and more specifically relates to a dielectric energy storage antiferroelectric ceramic material and a preparation method thereof.
背景技术Background technique
按工作机制分类，电储存器件可分为蓄电池、电化学电容器和介电电容器三大类。介质电容器通过介质极化、电畴转向或相变行为来进行能量存储，比容量较小(低于30W·h/kg)，但比功率非常高(可达108W/kg)，适于高脉冲电压或者电流供应，且在抗循环老化和快速放电方面明显优于蓄电池和电化学电容器。目前，介电电容器已成为太阳能、风能等新能源发电系统以及混合动力交通工具逆变设备储能系统中不可或缺的组成部分；电磁炮、定向能武器、综合全电力推动舰艇等负载所需要的高驱动电流也只有该类电容器可以提供。然而，介电电容器实际应用中朝小型化、轻型化、恶劣环境下工作及多功能方向发展对电容器储能密度及温度稳定性提出了更高的要求。提高电容器储能特性的关键在于开发出具有高储能密度及高温度稳定性的电介质材料。According to the working mechanism, electrical storage devices can be divided into three categories: batteries, electrochemical capacitors and dielectric capacitors. Dielectric capacitors store energy through dielectric polarization, domain steering or phase change behavior, with small specific capacity (less than 30W h/kg), but very high specific power (up to 108W/kg), suitable for high pulse Voltage or current supply, and is significantly better than batteries and electrochemical capacitors in terms of resistance to cyclic aging and rapid discharge. At present, dielectric capacitors have become an indispensable part of solar energy, wind energy and other new energy power generation systems and hybrid vehicle inverter equipment energy storage systems; electromagnetic guns, directed energy weapons, integrated all-electric propulsion ships and other loads are required The high drive current can only be provided by this type of capacitor. However, the development of dielectric capacitors in the direction of miniaturization, light weight, working in harsh environments and multi-functions in practical applications has put forward higher requirements for capacitor energy storage density and temperature stability. The key to improving the energy storage characteristics of capacitors is to develop dielectric materials with high energy storage density and high temperature stability.
国内外在高储能密度反铁电材料上的研制水平基本一致，主要研究对象为铅镧锆锡钛(PLZST)材料。已有结果表明，结合四方相PLZST饱和极化强度高、铁电→反铁电相变场(EA)小和正交相PLZST陶瓷饱和极化强度偏低，铁电-反铁电相变电场通常高于普通陶瓷的击穿场强的特点，设计四方相/正交相复合反铁电陶瓷，可实现提高反铁电陶瓷储能密度的目的。如专利号为CN201310659224.9的中国发明专利《一种反铁电储能陶瓷材料及其制备方法》(授权公告号为CN103641477A)，又如题为《PLZST基反铁电陶瓷的相变行为及储能性能研究》的博士学位论文。上述文献均提到采用结合两相优势的方法达到提升反铁电陶瓷储能密度的目的，对电子产品朝小型化、轻型化发展具有重要的应用价值。The development level of antiferroelectric materials with high energy storage density is basically the same at home and abroad, and the main research object is lead lanthanum zirconium tin titanium (PLZST) material. The existing results show that the combination of high saturation polarization of tetragonal PLZST, small ferroelectric→antiferroelectric phase transition field (EA ) and low saturation polarization of orthorhombic PLZST ceramics, ferroelectric-antiferroelectric phase transition The electric field is usually higher than the breakdown field strength of ordinary ceramics. Designing tetragonal phase/orthogonal phase composite antiferroelectric ceramics can achieve the purpose of increasing the energy storage density of antiferroelectric ceramics. For example, the Chinese invention patent "An Antiferroelectric Energy Storage Ceramic Material and Its Preparation Method" with the patent number CN201310659224.9 (authorized announcement number is CN103641477A), and another example entitled "Phase Change Behavior and Energy Storage of PLZST-Based Antiferroelectric Ceramics" Ph.D. dissertation in "Performance Research". The above-mentioned documents all mentioned that the method of combining the advantages of two phases to achieve the purpose of increasing the energy storage density of antiferroelectric ceramics has important application value for the development of electronic products towards miniaturization and light weight.
然而，除了高储能密度外，目前的电力电子设备和系统面临着亟待解决问题：良好的温度稳定性，尤其是当材料在高温下使用，如＞100℃时。恶劣的温度稳定性使材料不能满足在极端条件下的应用，如航空航天电力电子、地下天然气和石油勘探等。薄膜方面，Biaolin Peng等对PBZ进行研究，得到温度从25℃到275℃温区范围内储能密度降低5％的弛豫薄膜。厚膜方面，内蒙古科技大学获得在25℃到200℃温区范围内储能密度由6.80J/cm3下降到6.40J/cm3的PBLZST反铁电厚膜材料。陶瓷方面，Zhen Liu等制备出了储能密度W＝1.37J/cm3且温度由20℃升至100℃时储能密度降幅≤15％的反铁电陶瓷材料。Ran Xu等研究的PLZST反铁电陶瓷材料的储能密度由0.74J/cm3(20℃)下降到0.29J/cm3(140℃)。可知，现有陶瓷材料的储能密度温度稳定性远不能满足应用需求。However, in addition to high energy storage density, current power electronic devices and systems face an urgent problem: good temperature stability, especially when the materials are used at high temperatures, such as >100 °C. Poor temperature stability makes the material unsuitable for applications under extreme conditions, such as aerospace power electronics, underground gas and oil exploration, etc. In terms of thin films, Biaolin Peng et al. conducted research on PBZ and obtained a relaxed thin film with a 5% reduction in energy storage density in the temperature range from 25°C to 275°C. In terms of thick film, Inner Mongolia University of Science and Technology has obtained PBLZST antiferroelectric thick film material whose energy storage density drops from 6.80J/cm3 to 6.40J/cm3 in the temperature range of 25°C to 200°C. In terms of ceramics, Zhen Liu et al. prepared an antiferroelectric ceramic material with an energy storage density of W=1.37J/cm3 and a drop in energy storage density of ≤15% when the temperature increased from 20°C to 100°C. The energy storage density of the PLZST antiferroelectric ceramic material studied by Ran Xu et al. decreased from 0.74J/cm3 (20°C) to 0.29J/cm3 (140°C). It can be seen that the temperature stability of the energy storage density of existing ceramic materials is far from meeting the application requirements.
由此可见，现有的反铁电陶瓷材料存在温度稳定性差的技术问题。It can be seen that the existing antiferroelectric ceramic materials have the technical problem of poor temperature stability.
发明内容Contents of the invention
针对现有技术的以上缺陷或改进需求，本发明提供了一种介电储能反铁电陶瓷材料及其制备方法，由此解决现有的反铁电陶瓷材料存在温度稳定性差的技术问题。In view of the above defects or improvement needs of the prior art, the present invention provides a dielectric energy storage antiferroelectric ceramic material and a preparation method thereof, thereby solving the technical problem of poor temperature stability of the existing antiferroelectric ceramic material.
为实现上述目的，按照本发明的一个方面，提供了一种介电储能反铁电陶瓷材料的制备方法，包括：In order to achieve the above object, according to one aspect of the present invention, a method for preparing a dielectric energy storage antiferroelectric ceramic material is provided, including:
(1)将储能密度负温度系数反铁电陶瓷粉体材料和储能密度正温度系数反铁电陶瓷粉体材料按照质量比(30-80)∶(20-70)混合得到混合粉末；(1) mixing the antiferroelectric ceramic powder material with a negative temperature coefficient of energy storage density and the antiferroelectric ceramic powder material with a positive temperature coefficient of energy storage density according to the mass ratio (30-80):(20-70) to obtain a mixed powder;
(2)向混合粉末中添加聚乙烯醇溶液，然后烧结得到介电储能反铁电陶瓷材料。(2) Add polyvinyl alcohol solution to the mixed powder, and then sinter to obtain the dielectric energy storage antiferroelectric ceramic material.
进一步的，储能密度负温度系数反铁电陶瓷粉体材料和储能密度正温度系数反铁电陶瓷粉体材料的质量比优选为：80∶20、60∶40、50∶50、45∶55或者30∶70。Further, the mass ratio of the antiferroelectric ceramic powder material with a negative temperature coefficient of energy storage density and the antiferroelectric ceramic powder material with a positive temperature coefficient of energy storage density is preferably: 80:20, 60:40, 50:50, 45: 55 or 30:70.
进一步的，储能密度负温度系数反铁电陶瓷粉体材料的化学式为(Pb0.97-xBaxLa0.02)(Zr0.65Sn0.3Ti0.05)O3，x＝0～0.08。Further, the chemical formula of the antiferroelectric ceramic powder material with negative temperature coefficient of energy storage density is (Pb0.97-x Bax La0.02 )(Zr0.65 Sn0.3 Ti0.05 )O3 , x=0-0.08.
进一步的，储能密度负温度系数反铁电陶瓷粉体材料的制备方法为：Further, the preparation method of the antiferroelectric ceramic powder material with negative temperature coefficient of energy storage density is as follows:
依照摩尔比(0.97-x)∶x∶0.01∶0.65∶0.3∶0.05，x＝0～0.08，称取原料PbO、BaCO3、La2O3、ZrO2、SnO2和TiO2，将原料混合后依次进行球磨、烘干，在800℃～850℃中保温2小时～3小时得到粉料，将粉料依次进行球磨、烘干、过筛、并以20MPa的压力进行预压，预压后的粉料进行二次过筛，得到储能密度负温度系数反铁电陶瓷粉体材料。According to the molar ratio (0.97-x): x: 0.01: 0.65: 0.3: 0.05, x = 0 ~ 0.08, weigh the raw materials PbO, BaCO3 , La2 O3 , ZrO2 , SnO2 and TiO2 , mix the raw materials Afterwards, ball milling and drying are carried out in sequence, and the powder is obtained by heat preservation at 800°C to 850°C for 2 hours to 3 hours. The powder is sieved twice to obtain the antiferroelectric ceramic powder material with negative temperature coefficient of energy storage density.
进一步的，储能密度正温度系数反铁电陶瓷粉体材料的化学式为Pb0.97La0.02(Zr0.93Sn0.05Ti0.02)O3。Further, the chemical formula of the antiferroelectric ceramic powder material with positive temperature coefficient of energy storage density is Pb0.97 La0.02 (Zr0.93 Sn0.05 Ti0.02 )O3 .
进一步的，储能密度正温度系数反铁电陶瓷粉体材料的制备方法为：Further, the preparation method of the antiferroelectric ceramic powder material with positive temperature coefficient of energy storage density is as follows:
依照摩尔比0.97∶0.01∶0.93∶0.05∶0.02，称取原料PbO、La2O3、ZrO2、SnO2和TiO2，将原料混合后依次进行球磨、烘干，在800℃～850℃中保温2小时～3小时得到粉料，将粉料依次进行球磨、烘干、过筛，得到储能密度正温度系数反铁电陶瓷粉体材料。According to the molar ratio of 0.97:0.01:0.93:0.05:0.02, weigh the raw materials PbO, La2 O3 , ZrO2 , SnO2 and TiO2 , mix the raw materials and perform ball milling and drying in sequence. Heat preservation for 2 hours to 3 hours to obtain the powder material, and the powder material is sequentially ball milled, dried, and sieved to obtain an energy storage density positive temperature coefficient antiferroelectric ceramic powder material.
进一步的，步骤(2)的具体实现方式为：Further, the specific implementation of step (2) is:
将混合粉末依次经过球磨、烘干和粉碎后，加入浓度3％～5％的聚乙烯醇溶液，聚乙烯醇溶液占混合粉末的质量百分比为6～10％，再经造粒、干压成型后，在1220℃～1250℃温度下烧结2～3小时，得到介电储能反铁电陶瓷材料。After the mixed powder is ball milled, dried and pulverized in sequence, a polyvinyl alcohol solution with a concentration of 3% to 5% is added, and the polyvinyl alcohol solution accounts for 6 to 10% by mass of the mixed powder, and then granulated and dry-pressed Afterwards, sintering at a temperature of 1220° C. to 1250° C. for 2 to 3 hours to obtain a dielectric energy storage antiferroelectric ceramic material.
按照本发明的另一方面，提供了一种介电储能反铁电陶瓷材料，所述介电储能反铁电陶瓷材料由本发明的制备方法制备得到。According to another aspect of the present invention, a dielectric energy storage antiferroelectric ceramic material is provided, and the dielectric energy storage antiferroelectric ceramic material is prepared by the preparation method of the present invention.
总体而言，通过本发明所构思的以上技术方案与现有技术相比，能够取得下列有益效果：Generally speaking, compared with the prior art, the above technical solutions conceived by the present invention can achieve the following beneficial effects:
本发明通过将储能密度负温度系数反铁电陶瓷粉体材料和储能密度正温度系数反铁电陶瓷粉体材料固溶，获得了在宽温区范围内(20℃-150℃)，储能密度稳定性＞85％、储能效率为85％(150℃)且最低储能密度为2.77J/cm3的储能材料。本发明解决了现有的反铁电陶瓷材料存在温度稳定性差的技术问题，这对反铁电储能陶瓷材料的实际应用具有重要价值。In the present invention, the antiferroelectric ceramic powder material with negative temperature coefficient of energy storage density and antiferroelectric ceramic powder material with positive temperature coefficient of energy storage density are solid-dissolved to obtain a wide temperature range (20°C-150°C), An energy storage material with an energy storage density stability >85%, an energy storage efficiency of 85% (150°C) and a minimum energy storage density of 2.77J/cm3 . The invention solves the technical problem of poor temperature stability of the existing antiferroelectric ceramic materials, which is of great value to the practical application of the antiferroelectric energy storage ceramic materials.
附图说明Description of drawings
图1是本发明对比例1提供的储能密度负温度系数反铁电陶瓷材料的电滞回线示意图；Fig. 1 is the hysteresis loop schematic diagram of the energy storage density negative temperature coefficient antiferroelectric ceramic material provided by comparative example 1 of the present invention;
图2是本发明对比例1提供的储能密度负温度系数反铁电陶瓷材料的储能效率及储能密度温度稳定性示意图；2 is a schematic diagram of energy storage efficiency and energy storage density temperature stability of the energy storage density negative temperature coefficient antiferroelectric ceramic material provided by Comparative Example 1 of the present invention;
图3是本发明对比例2提供的储能密度正温度系数反铁电陶瓷材料的电滞回线示意图；Fig. 3 is the hysteresis loop schematic diagram of the energy storage density positive temperature coefficient antiferroelectric ceramic material provided by comparative example 2 of the present invention;
图4是本发明对比例2提供的储能密度正温度系数反铁电陶瓷材料的储能效率及储能密度温度稳定性示意图；Fig. 4 is a schematic diagram of the energy storage efficiency and the temperature stability of the energy storage density of the energy storage positive temperature coefficient antiferroelectric ceramic material provided by Comparative Example 2 of the present invention;
图5是本发明实施例1-5和对比例1-2提供的反铁电陶瓷样品XRD示意图；Fig. 5 is the XRD schematic diagram of the antiferroelectric ceramic sample provided by Example 1-5 of the present invention and Comparative Example 1-2;
图6(a)是本发明对比例1提供的储能密度负温度系数反铁电陶瓷材料的SEM图谱；Fig. 6 (a) is the SEM spectrum of the energy storage density negative temperature coefficient antiferroelectric ceramic material provided by comparative example 1 of the present invention;
图6(b)是本发明对比例2提供的储能密度正温度系数反铁电陶瓷材料的SEM图谱；Fig. 6 (b) is the SEM spectrum of the energy storage density positive temperature coefficient antiferroelectric ceramic material provided by comparative example 2 of the present invention;
图6(c)为本发明实施例3提供的介电储能反铁电陶瓷材料的SEM图谱；Figure 6 (c) is the SEM spectrum of the dielectric energy storage antiferroelectric ceramic material provided by Embodiment 3 of the present invention;
图7是本发明实施例3提供的介电储能反铁电陶瓷材料在不同温度下的电滞回线示意图。Fig. 7 is a schematic diagram of hysteresis loops of the dielectric energy storage antiferroelectric ceramic material provided by Example 3 of the present invention at different temperatures.
具体实施方式detailed description
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。In order to make the object, technical solution and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not constitute a conflict with each other.
本发明提供了一种介电储能反铁电陶瓷材料的制备方法，包括：The invention provides a method for preparing a dielectric energy storage antiferroelectric ceramic material, comprising:
(1)将储能密度负温度系数反铁电陶瓷粉体材料和储能密度正温度系数反铁电陶瓷粉体材料按照质量比(30-80)∶(20-70)混合得到混合粉末；(1) mixing the antiferroelectric ceramic powder material with a negative temperature coefficient of energy storage density and the antiferroelectric ceramic powder material with a positive temperature coefficient of energy storage density according to the mass ratio (30-80):(20-70) to obtain a mixed powder;
(2)向混合粉末中添加聚乙烯醇溶液，然后烧结得到介电储能反铁电陶瓷材料。(2) Add polyvinyl alcohol solution to the mixed powder, and then sinter to obtain the dielectric energy storage antiferroelectric ceramic material.
实施例1Example 1
(1)储能密度负温度系数反铁电陶瓷粉体材料的制备：(1) Preparation of antiferroelectric ceramic powder material with negative temperature coefficient of energy storage density:
依照摩尔比0.93∶0.04∶0.01∶0.65∶0.3∶0.05称取原料PbO(99.9％)、BaCO3(99.8％)、La2O3(99.9％)、ZrO2(99.5％)、SnO2(99.6％)和TiO2(99.6％)，采用湿式球磨法，按照原料∶酒精＝1∶0.6的质量比球磨6个小时，烘干后以5℃每分钟升至850℃，于空气中保温3小时。将所得粉料进行球磨、烘干、过筛，以20MPa的压力进行预压，预压后的粉料进行二次过筛，得到储能密度负温度系数反铁电陶瓷材料的预烧粉体。Weigh raw materials PbO (99.9%), BaCO3 (99.8%), La2 O3 (99.9%), ZrO2 (99.5%), SnO2 (99.6% %) and TiO2 (99.6%), using wet ball milling, ball milling for 6 hours according to the mass ratio of raw materials: alcohol = 1: 0.6, after drying, it was raised to 850°C at 5°C per minute, and kept in air for 3 hours . The obtained powder is ball milled, dried, and sieved, pre-pressed with a pressure of 20 MPa, and the pre-pressed powder is subjected to secondary sieving to obtain a pre-fired powder of an antiferroelectric ceramic material with a negative temperature coefficient of energy storage density .
(2)储能密度正温度系数反铁电陶瓷粉体材料的制备：(2) Preparation of antiferroelectric ceramic powder material with positive temperature coefficient of energy storage density:
依照摩尔比0.97∶0.01∶0.93∶0.05∶0.02，称取原料PbO(99.9％)、La2O3(99.9％)、ZrO2(99.5％)、SnO2(99.6％)和TiO2(99.6％)，采用湿式球磨法，按照原料∶酒精＝1∶0.6的质量比球磨6个小时，烘干后以5℃每分钟升至850℃，于空气中保温3小时。将所得粉料进行球磨、烘干、过筛，即得储能密度正温度系数反铁电陶瓷材料的预烧粉体。According to the molar ratio of 0.97:0.01:0.93:0.05:0.02, weigh raw materials PbO (99.9%), La2 O3 (99.9%), ZrO2 (99.5%), SnO2 (99.6%) and TiO2 (99.6%) ), using the wet ball milling method, according to the mass ratio of raw materials: alcohol=1:0.6 ball milling for 6 hours, after drying, rise to 850°C at 5°C per minute, and keep warm in the air for 3 hours. The obtained powder is subjected to ball milling, drying, and sieving to obtain a pre-fired powder body of an antiferroelectric ceramic material with a positive temperature coefficient of energy storage density.
(3)储能密度负温度系数反铁电陶瓷粉体材料与储能密度正温度系数反铁电陶瓷粉体材料固溶：(3) Solid solution of antiferroelectric ceramic powder material with negative temperature coefficient of energy storage density and antiferroelectric ceramic powder material with positive temperature coefficient of energy storage density:
将储能密度负温度系数反铁电陶瓷粉体材料与储能密度正温度系数反铁电陶瓷粉体材料按照30∶70的质量比进行混合，球磨混合4小时，烘干和粉碎后，加入浓度5％的PVA(聚乙烯醇)溶液，溶液占粉末的质量百分比为8％，再经造粒、干压成型后，在1230℃温度下烧结3小时，并在1000℃下退火1个小时，制成介电储能反铁电陶瓷材料。Mix the antiferroelectric ceramic powder material with negative temperature coefficient of energy storage density and antiferroelectric ceramic powder material with positive temperature coefficient of energy storage density according to the mass ratio of 30:70, ball mill and mix for 4 hours, after drying and crushing, add Concentration of 5% PVA (polyvinyl alcohol) solution, the solution accounts for 8% by mass of the powder, after granulation and dry pressing, sintering at 1230°C for 3 hours, and annealing at 1000°C for 1 hour , made of dielectric energy storage antiferroelectric ceramic materials.
实施例2Example 2
(1)用实施例1中(1)相同的方法制得储能密度负温度系数反铁电陶瓷材料的预烧粉体；(1) make the calcined powder body of energy storage density negative temperature coefficient antiferroelectric ceramic material with (1) identical method in embodiment 1;
(2)用实施例1中(2)相同的方法制得储能密度正温度系数反铁电陶瓷材料的预烧粉体；(2) make the calcined powder body of energy storage density positive temperature coefficient antiferroelectric ceramic material with (2) identical method in embodiment 1;
(3)将储能密度负温度系数反铁电陶瓷材料与储能密度正温度系数反铁电陶瓷材料按照50∶50的质量比进行混合，球磨混合4小时，烘干和粉碎后，加入浓度5％的PVA溶液，溶液占粉末的质量百分比为8％，再经造粒、干压成型后，在1230℃温度下烧结3小时，并在1000℃下退火1个小时，制成介电储能反铁电陶瓷材料。(3) Mix the antiferroelectric ceramic material with negative temperature coefficient of energy storage density and antiferroelectric ceramic material with positive temperature coefficient of energy storage density according to the mass ratio of 50:50, ball mill and mix for 4 hours, after drying and pulverizing, add concentration 5% PVA solution, the solution accounted for 8% by mass of the powder, after granulation and dry pressing, sintering at 1230°C for 3 hours, and annealing at 1000°C for 1 hour to make a dielectric storage Antiferroelectric ceramic materials.
实施例3Example 3
(1)用实施例1中(1)相同的方法制得储能密度负温度系数反铁电陶瓷材料的预烧粉体；(1) make the calcined powder body of energy storage density negative temperature coefficient antiferroelectric ceramic material with (1) identical method in embodiment 1;
(2)用实施例1中(2)相同的方法制得储能密度正温度系数反铁电陶瓷材料的预烧粉体；(2) make the calcined powder body of energy storage density positive temperature coefficient antiferroelectric ceramic material with (2) identical method in embodiment 1;
(3)将储能密度负温度系数反铁电陶瓷材料与储能密度正温度系数反铁电陶瓷材料按照55∶45的质量比进行混合，球磨混合4小时，烘干和粉碎后，加入浓度5％的PVA溶液，溶液占粉末的质量百分比为8％，再经造粒、干压成型后，在1230℃温度下烧结3小时，并在1000℃下退火1个小时，制成介电储能反铁电陶瓷材料。(3) Mix the antiferroelectric ceramic material with negative temperature coefficient of energy storage density and antiferroelectric ceramic material with positive temperature coefficient of energy storage density according to the mass ratio of 55:45, ball mill and mix for 4 hours, after drying and crushing, add concentration 5% PVA solution, the solution accounted for 8% by mass of the powder, after granulation and dry pressing, sintering at 1230°C for 3 hours, and annealing at 1000°C for 1 hour to make a dielectric storage Antiferroelectric ceramic materials.
实施例4Example 4
(1)用实施例1中(1)相同的方法制得储能密度负温度系数反铁电陶瓷材料的预烧粉体；(1) make the calcined powder body of energy storage density negative temperature coefficient antiferroelectric ceramic material with (1) identical method in embodiment 1;
(2)用实施例1中(2)相同的方法制得储能密度正温度系数反铁电陶瓷材料的预烧粉体；(2) make the calcined powder body of energy storage density positive temperature coefficient antiferroelectric ceramic material with (2) identical method in embodiment 1;
(3)将储能密度负温度系数反铁电陶瓷材料与储能密度正温度系数反铁电陶瓷材料按照60∶40的质量比进行混合，球磨混合4小时，烘干和粉碎后，加入浓度5％的PVA溶液，溶液占粉末的质量百分比为8％，再经造粒、干压成型后，在1230℃温度下烧结3小时，并在1000℃下退火1个小时，制成介电储能反铁电陶瓷材料。(3) Mix the antiferroelectric ceramic material with negative temperature coefficient of energy storage density and antiferroelectric ceramic material with positive temperature coefficient of energy storage density according to the mass ratio of 60:40, ball mill and mix for 4 hours, after drying and pulverizing, add concentration 5% PVA solution, the solution accounted for 8% by mass of the powder, after granulation and dry pressing, sintering at 1230°C for 3 hours, and annealing at 1000°C for 1 hour to make a dielectric storage Antiferroelectric ceramic materials.
实施例5Example 5
(1)用实施例1中(1)相同的方法制得储能密度负温度系数反铁电陶瓷材料的预烧粉体；(1) make the calcined powder body of energy storage density negative temperature coefficient antiferroelectric ceramic material with (1) identical method in embodiment 1;
(2)用实施例1中(2)相同的方法制得储能密度正温度系数反铁电陶瓷材料的预烧粉体；(2) make the calcined powder body of energy storage density positive temperature coefficient antiferroelectric ceramic material with (2) identical method in embodiment 1;
(3)将储能密度负温度系数反铁电陶瓷材料与储能密度正温度系数反铁电陶瓷材料按照80∶20的质量比进行混合，球磨混合4小时，烘干和粉碎后，加入浓度5％的PVA溶液，溶液占粉末的质量百分比为8％，再经造粒、干压成型后，在1230℃温度下烧结3小时，并在1000℃下退火1个小时，制成介电储能反铁电陶瓷材料。(3) Mix the antiferroelectric ceramic material with negative temperature coefficient of energy storage density and antiferroelectric ceramic material with positive temperature coefficient of energy storage density according to the mass ratio of 80:20, ball mill and mix for 4 hours, after drying and pulverizing, add concentration 5% PVA solution, the solution accounted for 8% by mass of the powder, after granulation and dry pressing, sintering at 1230°C for 3 hours, and annealing at 1000°C for 1 hour to make a dielectric storage Antiferroelectric ceramic materials.
对比例1Comparative example 1
依照摩尔比0.93∶0.04∶0.01∶0.65∶0.3∶0.05称取原料PbO(99.9％)、BaCO3(99.8％)、La2O3(99.9％)、ZrO2(99.5％)、SnO2(99.6％)和TiO2(99.6％)，采用湿式球磨法，按照原料∶酒精＝1∶0.6的质量比球磨6个小时，烘干后以5℃每分钟升至850℃，于空气中保温3小时。加入浓度5％的PVA溶液，溶液占粉末的质量百分比为8％，再经造粒、干压成型后，在1230℃温度下烧结3小时，并在1000℃下退火1个小时，制成反铁电储能陶瓷材料。Weigh raw materials PbO (99.9%), BaCO3 (99.8%), La2 O3 (99.9%), ZrO2 (99.5%), SnO2 (99.6% %) and TiO2 (99.6%), using wet ball milling, ball milling for 6 hours according to the mass ratio of raw materials: alcohol = 1: 0.6, after drying, it was raised to 850°C at 5°C per minute, and kept in air for 3 hours . Add a PVA solution with a concentration of 5%, and the solution accounts for 8% by mass of the powder. After granulation and dry pressing, it is sintered at 1230°C for 3 hours and annealed at 1000°C for 1 hour. Ceramic materials for ferroelectric energy storage.
对比例2Comparative example 2
依照摩尔比0.97∶0.01∶0.93∶0.05∶0.02，称取原料PbO(99.9％)、La2O3(99.9％)、ZrO2(99.5％)、SnO2(99.6％)和TiO2(99.6％)，采用湿式球磨法，按照原料∶酒精＝1∶0.6的质量比球磨6个小时，烘干后以5℃每分钟升至850℃，于空气中保温3小时。加入浓度5％的PVA溶液，溶液占粉末的质量百分比为8％，再经造粒、干压成型后，在1230℃温度下烧结3小时，并在1000℃下退火1个小时，制成反铁电储能陶瓷材料。According to the molar ratio of 0.97:0.01:0.93:0.05:0.02, weigh raw materials PbO (99.9%), La2 O3 (99.9%), ZrO2 (99.5%), SnO2 (99.6%) and TiO2 (99.6%) ), using the wet ball milling method, according to the mass ratio of raw materials: alcohol=1:0.6 ball milling for 6 hours, after drying, rise to 850°C at 5°C per minute, and keep warm in the air for 3 hours. Add a PVA solution with a concentration of 5%, and the solution accounts for 8% by mass of the powder. After granulation and dry pressing, it is sintered at 1230°C for 3 hours and annealed at 1000°C for 1 hour. Ceramic materials for ferroelectric energy storage.
将实施例1-5及对比例1-2所得的陶瓷试样磨片、清洗、烧制电极后进行电学性能测试，结果如表1所示。其中，储能密度稳定性以20℃下的有效储能密度为基准。After the ceramic samples obtained in Examples 1-5 and Comparative Examples 1-2 were ground, cleaned, and fired, the electrical properties were tested, and the results are shown in Table 1. Among them, the energy storage density stability is based on the effective energy storage density at 20°C.
表1样品主要性能参数Table 1 main performance parameters of samples
根据主要性能参数及图1-7可知，本发明的反铁电储能材料主要具有以下特点：According to the main performance parameters and Figures 1-7, the antiferroelectric energy storage material of the present invention mainly has the following characteristics:
(1)图1所示本发明对比例1提供的储能密度负温度系数反铁电陶瓷材料的电滞回线示意图，图2是本发明对比例1提供的储能密度负温度系数反铁电陶瓷材料的储能效率及储能密度温度稳定性示意图；综合分析图1和图2得知储能密度负温度系数反铁电陶瓷材料的储能密度随温度的升高明显降低，当温度达到150℃时，材料的储能密度温度稳定性＜50％。储能效率随温度变化较小。(1) The hysteresis loop schematic diagram of the energy storage density negative temperature coefficient antiferroelectric ceramic material provided by comparative example 1 of the present invention shown in Fig. 1, Fig. 2 is the energy storage density negative temperature coefficient antiferroelectric ceramic material that comparative example 1 of the present invention provides Schematic diagram of energy storage efficiency and temperature stability of energy storage density of electric ceramic materials; comprehensive analysis of Figure 1 and Figure 2 shows that the energy storage density of antiferroelectric ceramic materials with negative temperature coefficient of energy storage density decreases significantly with the increase of temperature, when the temperature When reaching 150°C, the temperature stability of the energy storage density of the material is less than 50%. Energy storage efficiency changes little with temperature.
(2)图3是本发明对比例2提供的储能密度正温度系数反铁电陶瓷材料的电滞回线示意图；图4是本发明对比例2提供的储能密度正温度系数反铁电陶瓷材料的储能效率及储能密度温度稳定性示意图；综合分析图3和图4得知储能密度正温度系数反铁电陶瓷材料的储能密度随温度的升高呈现先增加后减小的趋势，当温度低于100℃时，储能密度＜1J/cm3在150℃时获得最大值。储能效率随温度增加明显下降。(2) Fig. 3 is the hysteresis loop schematic diagram of the energy storage density positive temperature coefficient antiferroelectric ceramic material provided by comparative example 2 of the present invention; Fig. 4 is the energy storage density positive temperature coefficient antiferroelectric ceramic material provided by comparative example 2 of the present invention Schematic diagram of energy storage efficiency and temperature stability of energy storage density of ceramic materials; comprehensive analysis of Figure 3 and Figure 4 shows that the energy storage density of antiferroelectric ceramic materials with positive temperature coefficient of energy storage density increases first and then decreases with the increase of temperature The trend is that when the temperature is lower than 100°C, the energy storage density <1J/cm3 reaches the maximum value at 150°C. The energy storage efficiency decreases significantly with the increase of temperature.
(3)图5是本发明实施例1-5和对比例1-2提供的反铁电陶瓷样品XRD示意图；实施例1-5和对比例1-2反铁电陶瓷样品的XRD表明，所有陶瓷主晶相均为钙钛矿结构，负温度系数及正温度系数固溶样品在44℃左右展现四个衍射峰。左右两边分别在(002)和(200)方向出现劈裂峰。该结果说明负温度系数及正温度系数反铁电材料得到了良好的固溶，这与固溶材料储能密度温度稳定性得到调整的结果相一致。(3) Fig. 5 is the XRD schematic diagram of the antiferroelectric ceramic sample that embodiment 1-5 of the present invention and comparative example 1-2 provide; The XRD of embodiment 1-5 and comparative example 1-2 antiferroelectric ceramic sample shows that all The main crystal phase of ceramics is perovskite structure, and the negative temperature coefficient and positive temperature coefficient solid solution samples show four diffraction peaks at around 44 °C. Splitting peaks appear in the (002) and (200) directions on the left and right sides, respectively. The results indicate that the antiferroelectric materials with negative temperature coefficient and positive temperature coefficient have been well solid-soluted, which is consistent with the result that the temperature stability of the energy storage density of solid-solution materials has been adjusted.
(4)图6(a)是本发明对比例1提供的储能密度负温度系数反铁电陶瓷材料的SEM图谱；图6(b)是本发明对比例2提供的储能密度正温度系数反铁电陶瓷材料的SEM图谱；图6(c)为本发明实施例3提供的介电储能反铁电陶瓷材料的SEM图谱；图6(a)、图6(b)、图6(c)所示的反铁电陶瓷样品的SEM图谱均呈现良好的致密度。其中图6(a)、图6(b)所示图谱中均呈现单一的晶粒形态；由于相同条件下晶粒生长的相异性图6(c)图中明显可见两种不同的晶粒形态。该结果同样说明负温度系数及正温度系数反铁电材料得到了良好的固溶，这与固溶材料储能密度温度稳定性得到调整的结果相一致。(4) Fig. 6 (a) is the SEM spectrum of the energy storage density negative temperature coefficient antiferroelectric ceramic material provided by Comparative Example 1 of the present invention; Fig. 6 (b) is the positive temperature coefficient of energy storage density provided by Comparative Example 2 of the present invention The SEM spectrum of antiferroelectric ceramic material; Fig. 6 (c) is the SEM spectrum of the dielectric energy storage antiferroelectric ceramic material that the embodiment of the present invention 3 provides; Fig. 6 (a), Fig. 6 (b), Fig. 6 ( The SEM spectra of the antiferroelectric ceramic samples shown in c) all show good density. Among them, the spectra shown in Figure 6(a) and Figure 6(b) all present a single grain shape; due to the dissimilarity of grain growth under the same conditions, two different grain shapes can be clearly seen in Figure 6(c) . The results also indicate that the antiferroelectric materials with negative temperature coefficient and positive temperature coefficient have been solid-soluted, which is consistent with the result that the temperature stability of the energy storage density of solid-solution materials has been adjusted.
(5)图7是本发明实施例3提供的介电储能反铁电陶瓷材料在不同温度下的电滞回线示意图。将图7与对比例1-2的电滞回线图谱对比可知，实施例3样品在20-150℃温区范围内均具有较典型的双电滞回线，样品的极化强度维持在较高的水平，并没有随温度发生突变。结合表1可知，实施例3样品在150℃时具有2.77J/cm3的有效储能密度，85％的储能效率以及86.67％的储能密度温度稳定性。(5) FIG. 7 is a schematic diagram of hysteresis loops of the dielectric energy storage antiferroelectric ceramic material provided by Embodiment 3 of the present invention at different temperatures. Comparing Figure 7 with the electric hysteresis loop spectrum of Comparative Example 1-2, it can be seen that the sample of Example 3 has a more typical double electric hysteresis loop in the temperature range of 20-150 ° C, and the polarization intensity of the sample is maintained at a relatively high temperature. High level, and did not change with temperature. It can be seen from Table 1 that the sample of Example 3 has an effective energy storage density of 2.77J/cm3 at 150°C, an energy storage efficiency of 85%, and a temperature stability of energy storage density of 86.67%.
实施例6Example 6
(1)储能密度负温度系数反铁电陶瓷材料的制备：(1) Preparation of antiferroelectric ceramic materials with negative temperature coefficient of energy storage density:
依照摩尔比0.97∶0∶0.01∶0.65∶0.3∶0.05称取原料PbO(99.9％)、BaCO3(99.8％)、La2O3(99.9％)、ZrO2(99.5％)、SnO2(99.6％)和TiO2(99.6％)，采用湿式球磨法，按照原料∶酒精＝1∶0.6的质量比球磨6个小时，烘干后以5℃每分钟升至800℃，于空气中保温2小时。将所得粉料进行球磨、烘干、过筛，以20MPa的压力进行预压，预压后的粉料进行二次过筛，得到储能密度负温度系数反铁电陶瓷材料的预烧粉体。Weigh raw materials PbO (99.9%), BaCO3 (99.8%), La2 O3 (99.9%), ZrO2 (99.5%), SnO2 (99.6 %) and TiO2 (99.6%), using wet ball milling method, ball milled for 6 hours according to the mass ratio of raw materials: alcohol = 1:0.6, after drying, it was raised to 800°C at 5°C per minute, and kept in air for 2 hours . The obtained powder is ball milled, dried, and sieved, pre-pressed with a pressure of 20 MPa, and the pre-pressed powder is subjected to secondary sieving to obtain a pre-fired powder of an antiferroelectric ceramic material with a negative temperature coefficient of energy storage density .
(2)储能密度正温度系数反铁电陶瓷材料的制备：(2) Preparation of antiferroelectric ceramic materials with positive temperature coefficient of energy storage density:
依照摩尔比0.97∶0.01∶0.93∶0.05∶0.02，称取原料PbO(99.9％)、La2O3(99.9％)、ZrO2(99.5％)、SnO2(99.6％)和TiO2(99.6％)，采用湿式球磨法，按照原料∶酒精＝1∶0.6的质量比球磨6个小时，烘干后以5℃每分钟升至800℃，于空气中保温2小时。将所得粉料进行球磨、烘干、过筛，即得储能密度正温度系数反铁电陶瓷材料的预烧粉体。According to the molar ratio of 0.97:0.01:0.93:0.05:0.02, weigh raw materials PbO (99.9%), La2 O3 (99.9%), ZrO2 (99.5%), SnO2 (99.6%) and TiO2 (99.6%) ), using wet ball milling, according to the mass ratio of raw materials: alcohol=1:0.6 ball milling for 6 hours, after drying, it was raised to 800°C at 5°C per minute, and kept in air for 2 hours. The obtained powder is subjected to ball milling, drying, and sieving to obtain a pre-fired powder body of an antiferroelectric ceramic material with a positive temperature coefficient of energy storage density.
(3)储能密度负温度系数反铁电陶瓷材料与储能密度正温度系数反铁电陶瓷材料固溶：(3) Solid solution of antiferroelectric ceramic material with negative temperature coefficient of energy storage density and antiferroelectric ceramic material with positive temperature coefficient of energy storage density:
将储能密度负温度系数反铁电陶瓷材料与储能密度正温度系数反铁电陶瓷材料按照30∶70的质量比进行混合，球磨混合4小时，烘干和粉碎后，加入浓度3％的PVA(聚乙烯醇)溶液，溶液占粉末的质量百分比为10％，再经造粒、干压成型后，在1220℃温度下烧结2.5小时，并在1000℃下退火1个小时，制成介电储能反铁电陶瓷材料。Mix the antiferroelectric ceramic material with a negative temperature coefficient of energy storage density and the antiferroelectric ceramic material with a positive temperature coefficient of energy storage density according to the mass ratio of 30:70, ball mill and mix for 4 hours, after drying and pulverizing, add a concentration of 3% PVA (polyvinyl alcohol) solution, the solution accounts for 10% by mass of the powder, and after granulation and dry pressing, it is sintered at 1220°C for 2.5 hours and annealed at 1000°C for 1 hour to make a medium Antiferroelectric ceramic materials for electrical energy storage.
实施例7Example 7
(1)储能密度负温度系数反铁电陶瓷材料的制备：(1) Preparation of antiferroelectric ceramic materials with negative temperature coefficient of energy storage density:
依照摩尔比0.89∶0.08∶0.01∶0.65∶0.3∶0.05称取原料PbO(99.9％)、BaCO3(99.8％)、La2O3(99.9％)、ZrO2(99.5％)、SnO2(99.6％)和TiO2(99.6％)，采用湿式球磨法，按照原料∶酒精＝1∶0.6的质量比球磨6个小时，烘干后以5℃每分钟升至820℃，于空气中保温2.5小时。将所得粉料进行球磨、烘干、过筛，以20MPa的压力进行预压，预压后的粉料进行二次过筛，得到储能密度负温度系数反铁电陶瓷材料的预烧粉体。Weigh raw materials PbO (99.9%), BaCO3 (99.8%), La2 O3 (99.9%), ZrO2 (99.5%), SnO2 (99.6% %) and TiO2 (99.6%), using wet ball milling method, ball milled for 6 hours according to the mass ratio of raw materials: alcohol = 1:0.6, after drying, it was raised to 820°C at 5°C per minute, and kept in air for 2.5 hours . The obtained powder is ball milled, dried, and sieved, pre-pressed with a pressure of 20 MPa, and the pre-pressed powder is subjected to secondary sieving to obtain a pre-fired powder of an antiferroelectric ceramic material with a negative temperature coefficient of energy storage density .
(2)储能密度正温度系数反铁电陶瓷材料的制备：(2) Preparation of antiferroelectric ceramic materials with positive temperature coefficient of energy storage density:
依照摩尔比0.97∶0.01∶0.93∶0.05∶0.02，称取原料PbO(99.9％)、La2O3(99.9％)、ZrO2(99.5％)、SnO2(99.6％)和TiO2(99.6％)，采用湿式球磨法，按照原料∶酒精＝1∶0.6的质量比球磨6个小时，烘干后以5℃每分钟升至820℃，于空气中保温2.5小时。将所得粉料进行球磨、烘干、过筛，即得储能密度正温度系数反铁电陶瓷材料的预烧粉体。According to the molar ratio of 0.97:0.01:0.93:0.05:0.02, weigh raw materials PbO (99.9%), La2 O3 (99.9%), ZrO2 (99.5%), SnO2 (99.6%) and TiO2 (99.6%) ), using wet ball milling, according to the mass ratio of raw materials: alcohol = 1: 0.6 ball milling for 6 hours, after drying, the temperature was raised to 820°C at 5°C per minute, and kept in air for 2.5 hours. The obtained powder is subjected to ball milling, drying, and sieving to obtain a pre-fired powder body of an antiferroelectric ceramic material with a positive temperature coefficient of energy storage density.
(3)储能密度负温度系数反铁电陶瓷材料与储能密度正温度系数反铁电陶瓷材料固溶：(3) Solid solution of antiferroelectric ceramic material with negative temperature coefficient of energy storage density and antiferroelectric ceramic material with positive temperature coefficient of energy storage density:
将储能密度负温度系数反铁电陶瓷材料与储能密度正温度系数反铁电陶瓷材料按照30∶70的质量比进行混合，球磨混合4小时，烘干和粉碎后，加入浓度4％的PVA(聚乙烯醇)溶液，溶液占粉末的质量百分比为6％，再经造粒、干压成型后，在1250℃温度下烧结2小时，并在1000℃下退火1个小时，制成介电储能反铁电陶瓷材料。Mix the antiferroelectric ceramic material with a negative temperature coefficient of energy storage density and the antiferroelectric ceramic material with a positive temperature coefficient of energy storage density according to a mass ratio of 30:70, mix them by ball milling for 4 hours, dry and pulverize them, and add a concentration of 4% PVA (polyvinyl alcohol) solution, the solution accounts for 6% by mass of the powder, and after granulation and dry pressing, it is sintered at 1250°C for 2 hours and annealed at 1000°C for 1 hour to make a medium Antiferroelectric ceramic materials for electrical energy storage.
本领域的技术人员容易理解，以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。It is easy for those skilled in the art to understand that the above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention, All should be included within the protection scope of the present invention.
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