CN116082034B - 一种高储能特性的钛酸铋钠基高熵陶瓷材料及其制备方法和应用 - Google Patents
一种高储能特性的钛酸铋钠基高熵陶瓷材料及其制备方法和应用 Download PDFInfo
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- FSAJRXGMUISOIW-UHFFFAOYSA-N bismuth sodium Chemical compound [Na].[Bi] FSAJRXGMUISOIW-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 39
- 238000004146 energy storage Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229910002115 bismuth titanate Inorganic materials 0.000 claims abstract description 22
- 239000011734 sodium Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 37
- 239000000919 ceramic Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 14
- 238000000498 ball milling Methods 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 230000015556 catabolic process Effects 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000000748 compression moulding Methods 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 239000003985 ceramic capacitor Substances 0.000 claims description 3
- 230000005684 electric field Effects 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000010287 polarization Effects 0.000 description 5
- 239000004677 Nylon Substances 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000012856 weighed raw material Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
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Abstract
本发明涉及一种高储能特性的钛酸铋钠基高熵陶瓷材料及其制备方法和应用。所述钛酸铋钠基高熵陶瓷材料的化学组成为(1‑x)(Bi0.5Na0.5)TiO3‑x(Sr0.2Ca0.2Ba0.2Ag0.2K0.2)(Ti0.6Nb0.4)O3，其中x＝0.1～0.5，优选为x＝0.15～0.45，更优选为x＝0.35～0.45。
Description
技术领域
本发明涉及一种高储能特性的钛酸铋钠基高熵陶瓷材料及其制备方法和应用，属于功能材料领域。
背景技术
随着电子信息行业的飞速发展，储能装置也日益成为研究热点目标。陶瓷介质材料由于高的功率密度、快的充放电速率而受到广泛关注。目前，无铅材料替代铅基材料已成为必然趋势，但无铅介电陶瓷由于其储能密度低，稳定性差，难以达到器件小型化、集成化的要求。钛酸铋钠基陶瓷有着大的极化强度，在储能领域有着较大应用潜力，但其较高的剩余极化强度、较低的击穿场强以及较差的稳定性，限制了其在介质电容器中的应用。如何提高钛酸铋钠基陶瓷的储能特性和温度、频率、抗疲劳等稳定性，使其满足实际应用需求是亟待解决的研究难题。
发明内容
针对以上不足，本发明提供了一种高储能特性的钛酸铋钠基高熵陶瓷材料及其制备方法和应用。
第一方面，本发明提供了一种钛酸铋钠基高熵陶瓷材料，所述钛酸铋钠基高熵陶瓷材料的化学组成为(1-x)(Bi0.5Na0.5)TiO3-x(Sr0.2Ca0.2Ba0.2Ag0.2K0.2)(Ti0.6Nb0.4)O3，其中x＝0.1～0.5，优选x＝0.15～0.45，更优选为x＝0.35～0.45。
本发明中，引入了高熵组分，通过等摩尔地增加钙钛矿A位上的元素数量以及B位引入Nb元素的方法，构筑钛酸铋钠基高熵结构。特别地，引入大离子半径的Ag+、K+离子加剧晶格畸变进一步增大位点无序度，减小剩余极化强度，诱导弛豫特性的产生和增强，并使晶粒减小，增大击穿场强，进而获得优异储能特性的新型弛豫铁电材料。特别地，所述钛酸铋钠基高熵陶瓷材料为单一钙钛矿结构。
较佳的，所述钛酸铋钠基高熵陶瓷材料的击穿电场为344.86～405.49kV/cm。
较佳的，所述钛酸铋钠基高熵陶瓷材料的可回收储能密度为5.531～6.252J/cm3。
较佳的，所述钛酸铋钠基高熵陶瓷材料的储能效率为79.71～83.94％。
第二方面，本发明提供了一种钛酸铋钠基高熵陶瓷材料的制备方法，包括：
(1)按照化学式计量比(1-x)(Bi0.5Na0.5)TiO3-x(Sr0.2Ca0.2Ba0.2Ag0.2K0.2)(Ti0.6Nb0.4)O3，称取Bi2O3粉体、TiO2粉体、Na2CO3粉体、SrCO3粉体、CaCO3粉体、BaCO3粉体、Ag2O粉体、K2CO3粉体、Nb2O5粉体作为原料粉体并混料，经煅烧和球磨，得到陶瓷粉体；
(2)将陶瓷粉体置于搅拌磨中再次细磨，经造粒、陈化和模压成型得到陶瓷生坯；
(3)将陶瓷生坯经排塑和烧结，得到所述钛酸铋钠基高熵陶瓷材料。
较佳的，步骤(1)中，所述原料粉体的纯度＞99％；所述球磨的参数包括：所用球磨介质为无水乙醇和直径为6mm的氧化锆球，球磨转速为300～360转/分钟，时间为4～8h；
所述密闭煅烧的气氛为氧气气氛，温度为950～1050℃，时间为2～4小时。
较佳的，步骤(2)中，所述搅拌磨的转速为400～500转/分钟，所用锆球直径为1mm，时间为4～6h；
所述造粒所用粘结剂为聚乙烯醇水溶液，所述粘结剂的加入量为陶瓷粉体质量的5～7％；
所述陈化时间为18～24小时。
较佳的，步骤(3)中，所述排塑的温度为650～800℃，时间为1～3小时；
所述烧结的氛围为氧气气氛，烧结温度为1100～1200℃，保温时间为2～3小时；优选地，所述烧结的升温速率为2～4℃/min。
第三方面，本发明提供了一种储能陶瓷元件，包括：上述钛酸铋钠基高熵陶瓷材料、以及分布在钛酸铋钠基高熵陶瓷材料表面的电极。
第四方面，本发明提供了一种钛酸铋钠基高熵陶瓷材料在多层陶瓷电容器(MLCC)中的应用。
有益效果：
本发明方法制备的(1-x)(Bi0.5Na0.5)TiO3-x(Sr0.2Ca0.2Ba0.2Ag0.2K0.2)(Ti0.6Nb0.4)O3(x＝0.15-0.45)陶瓷材料，通过引入高熵组分，调控钙钛矿A位无序度，进一步增大钙钛矿晶格畸变。不仅诱导了弛豫特性的产生，获得了优异的储能性能，而且该制备工艺稳定，绿色环保，是储能电容器的有力候选材料。
附图说明
图1为(1-x)(Bi0.5Na0.5)TiO3-x(Sr0.2Ca0.2Ba0.2Ag0.2K0.2)(Ti0.6Nb0.4)O3陶瓷的XRD图谱；
图2为(1-x)(Bi0.5Na0.5)TiO3-x(Sr0.2Ca0.2Ba0.2Ag0.2K0.2)(Ti0.6Nb0.4)O3陶瓷的P-E曲线；
图3为(1-x)(Bi0.5Na0.5)TiO3-x(Sr0.2Ca0.2Ba0.2Ag0.2K0.2)(Ti0.6Nb0.4)O3陶瓷的储能特性参数随x的变化曲线。
具体实施方式
以下通过下述实施方式进一步说明本发明，应理解，下述实施方式仅用于说明本发明，而非限制本发明。
本公开中，钛酸铋钠基高熵陶瓷材料的化学组成为(1-x)(Bi0.5Na0.5)TiO3-x(Sr0.2Ca0.2Ba0.2Ag0.2K0.2)(Ti0.6Nb0.4)O3，x＝0.15～0.45。本发明的高熵组分是自主选择设计的，并形成单相的完全固溶体。特别地，Ag+、K+有着大的离子半径，会导致晶格畸变加剧，从而带来弛豫特性和储能特性的提升。本发明除在A位形成局部高熵外，也在B位引入了Nb元素，进一步增大了格点的无序度。
本发明中，钛酸铋钠基高熵陶瓷材料使用固相反应法在氧气氛围下制备得到。其工艺包括配料、球磨和煅烧后得到预合成的粉体，再经过细磨、造粒、陈化、模压成型和烧结等步骤得到钛酸铋钠基陶瓷样品。其不仅性能优异，而且工艺稳定，绿色环保，是储能电容器的有力候选材料。其所用原料包括纯度都大于99％的Bi2O3、TiO2、Na2CO3、SrCO3、CaCO3、BaCO3、Ag2O、K2CO3、Nb2O5粉体。
本发明中，采用铁电分析仪测试高储能特性的钛酸铋钠基高熵陶瓷材料的击穿电场为344.86～405.49kV/cm。
本发明中，采用铁电分析仪测试高储能特性的钛酸铋钠基高熵陶瓷材料的储能密度5.531～6.252J/cm3。
本发明中，采用铁电分析仪测试高储能特性的钛酸铋钠基高熵陶瓷材料的储能效率为79.71～83.94％。
下面进一步例举实施例以详细说明本发明。同样应理解，以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。下述示例具体的工艺参数等也仅是合适范围中的一个示例，即本领域技术人员可以通过本文的说明做合适的范围内选择，而并非要限定于下文示例的具体数值。下述实施例和对比例中若无特殊说明，都由纯度都大于99％的Bi2O3、TiO2、Na2CO3、SrCO3、CaCO3、BaCO3、Ag2O、K2CO3、Nb2O5粉体按化学式配料。
实施例1：(1-x)(Bi0.5Na0.5)TiO3-x(Sr0.2Ca0.2Ba0.2Ag0.2K0.2)(Ti0.6Nb0.4)O3，x＝0.35
(1)将称取的原料称取放入尼龙罐中，以氧化锆球和无水乙醇为介质，将尼龙罐置于行星球磨机上混合4小时；烘干后再用40目尼龙筛进行过筛，将过筛后的混合粉体在压力机上压成尺寸为直径10cm×高6cm的圆柱体；在通氧条件下于1000℃合成2小时，然后砸碎过40目筛网得到陶瓷预合成粉体；
(2)将所得粉体放入尼龙罐中，以(1)中所述的氧化锆球和无水乙醇为介质二次球磨6小时，在烘烤箱中烘干，得陶瓷粉体；将所得粉体置于搅拌磨中，使用直径为1mm的锆球磨细。
(3)在磨细陶瓷粉体中加入浓度为6wt％的聚乙烯醇水溶液，聚乙烯醇水溶液的加入量为陶瓷粉体质量的5％，然后均匀造粒，过40目筛，模压成型，得到尺寸为直径13mm×高1mm的小圆柱体，并进行排塑；
(4)将排塑后的坯体置于氧气气氛的马弗炉腔体中，以2℃/min的升温速率升温至1160℃，并保温2小时，随炉自然冷却。
(5)加工并超声清洗后，采用丝网印刷方法镀上银电极，并在650℃下烧制30分钟。采用磁控溅射方法镀上金电极。
图1展示了实施例1的X射线衍射图。将陶瓷两面磨平、抛光、镀电极，测试电学性能，图2和图3展示了实施例1的P-E曲线和储能参数。
实施例2：(1-x)(Bi0.5Na0.5)TiO3-x(Sr0.2Ca0.2Ba0.2Ag0.2K0.2)(Ti0.6Nb0.4)O3，x＝0.40
除x取值为0.40之外，其他步骤与实施例1相同。
图1展示了实施例2的X射线衍射图。将陶瓷两面磨平、抛光、镀电极，测试电学性能，图2和图3展示了实施例2的P-E曲线和储能参数。
实施例3：(1-x)(Bi0.5Na0.5)TiO3-x(Sr0.2Ca0.2Ba0.2Ag0.2K0.2)(Ti0.6Nb0.4)O3，x＝0.45
除x取值为0.45之外，其他步骤与实施例1相同。
图1展示了实施例3的X射线衍射图。将陶瓷两面磨平、抛光、镀电极，测试电学性能，图2和图3展示了实施例3的P-E曲线和储能参数。
实施例4：(1-x)(Bi0.5Na0.5)TiO3-x(Sr0.2Ca0.2Ba0.2Ag0.2K0.2)(Ti0.6Nb0.4)O3，x＝0.15。
除x取值为0.15之外，其他步骤与实施例1相同。
图1展示了实施例4的X射线衍射图。将陶瓷两面磨平、抛光、镀电极，测试电学性能，图2和图3展示了实施例4的P-E曲线和储能参数。
实施例5：(1-x)(Bi0.5Na0.5)TiO3-x(Sr0.2Ca0.2Ba0.2Ag0.2K0.2)(Ti0.6Nb0.4)O3，x＝0.25。
除x取值为0.25之外，其他步骤与实施例4相同。
图1展示了实施例5的X射线衍射图。将陶瓷两面磨平、抛光、镀电极，测试电学性能，图2和图3展示了实施例5的P-E曲线和储能参数。
图1是实施例1-5制备的钛酸铋钠基高熵陶瓷材料的XRD曲线。可以看出，(1-x)(Bi0.5Na0.5)TiO3-x(Sr0.2Ca0.2Ba0.2Ag0.2K0.2)(Ti0.6Nb0.4)O3呈单相钙钛矿结构，表明各元素全部进入晶格位点，A位局域高熵形成。
图2是实施例1-5制备的钛酸铋钠基高熵陶瓷材料的P-E曲线。随着高熵组分(Sr0.2Ca0.2Ba0.2Ag0.2K0.2)(Ti0.6Nb0.4)O3的增加，陶瓷的P-E曲线呈现规律性变化，电滞回线变细，剩余极化强度渐小，极化响应明显延迟，弛豫特性明显生成和增强。
图3是实施例1-5制备的钛酸铋钠基高熵陶瓷材料的储能特性随组分的变化曲线。可见，可回收储能密度Wrec、击穿场强Eb和效率η随着高熵组分固溶量的增多而增大，并在实施例2(x＝0.40)处达到最优值，Wrec、Eb和η分别为6.252J/cm3、405.49kV/cm、80.95％。各样品关键储能参数如表1所示，显示了其在多层陶瓷电容器领域有着巨大的应用潜力。
表1为钛酸铋钠基高熵陶瓷材料的储能特性参数：
| x | Wrec(J/cm3) | Eb(kV/cm) | η(％) | |
| 实施例1 | 0.35 | 5.621 | 344.86 | 79.70 |
| 实施例2 | 0.40 | 6.252 | 405.49 | 80.95 |
| 实施例3 | 0.45 | 5.531 | 397.06 | 83.94 |
| 实施例4 | 0.15 | 2.175 | 142.5 | 55.51 |
| 实施例5 | 0.25 | 3.65 | 214.73 | 74.39 |
。
Claims (9)
1.一种钛酸铋钠基高熵陶瓷材料，其特征在于，所述钛酸铋钠基高熵陶瓷材料的化学组成为(1-x)(Bi0.5Na0.5)TiO3-x(Sr0.2Ca0.2Ba0.2Ag0.2K0.2)(Ti0.6Nb0.4)O3，其中x=0.35～0.45。
2.根据权利要求1所述的钛酸铋钠基高熵陶瓷材料，其特征在于，所述钛酸铋钠基高熵陶瓷材料为单一钙钛矿结构。
3. 根据权利要求1或2所述的钛酸铋钠基高熵陶瓷材料，其特征在于，所述钛酸铋钠基高熵陶瓷材料的击穿电场为344.86～405.49 kV/cm；
所述钛酸铋钠基高熵陶瓷材料的可回收储能密度为5.531～6.252J/cm3；
所述钛酸铋钠基高熵陶瓷材料的储能效率为79.71～83.94%。
4.一种如权利要求1-3中任一项所述的钛酸铋钠基高熵陶瓷材料的制备方法，其特征在于，包括：
（1）按照化学式计量比(1-x)(Bi0.5Na0.5)TiO3-x(Sr0.2Ca0.2Ba0.2Ag0.2K0.2)(Ti0.6Nb0.4)O3，称取Bi2O3粉体、TiO2粉体、Na2CO3粉体、SrCO3粉体、CaCO3粉体、BaCO3粉体、Ag2O粉体、K2CO3粉体、Nb2O5粉体作为原料粉体并混料，经煅烧和球磨，得到陶瓷粉体；
（2）将陶瓷粉体置于搅拌磨中再次细磨，经造粒、陈化和模压成型得到陶瓷生坯；
（3）将陶瓷生坯经排塑和烧结，得到所述钛酸铋钠基高熵陶瓷材料。
5.根据权利要求4所述的制备方法，其特征在于，步骤（1）中，所述原料粉体的纯度＞99%；所述球磨的参数包括：所用球磨介质为无水乙醇和直径为6mm的氧化锆球，球磨转速为300～360转/分钟，时间为4～8h；
所述煅烧的气氛为氧气气氛，温度为950～1050℃，时间为2～4小时。
6.根据权利要求4所述的制备方法，其特征在于，步骤（2）中，所述搅拌磨的转速为400～500转/分钟，所用锆球直径为1mm，时间为4～6h；
所述造粒所用粘结剂为聚乙烯醇水溶液，所述粘结剂的加入量为陶瓷粉体质量的5～7%；
所述陈化时间为18～24小时。
7.根据权利要求4-6中任一项所述的制备方法，其特征在于，步骤（3）中，所述排塑的温度为650～800℃，时间为1～3小时；
所述烧结的氛围为氧气气氛，烧结温度为1100～1200℃，保温时间为2～3小时；所述烧结的升温速率为2～4℃/min。
8.一种储能陶瓷元件，其特征在于，包括：权利要求1-3中任一项所述的钛酸铋钠基高熵陶瓷材料以及分布在钛酸铋钠基高熵陶瓷材料表面的电极。
9.一种权利要求1-3中任一项所述的钛酸铋钠基高熵陶瓷材料在多层陶瓷电容器中的应用。
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