CN116751051A - 一种钛酸铋钠基高储能性能陶瓷电容器及制备方法 - Google Patents
一种钛酸铋钠基高储能性能陶瓷电容器及制备方法 Download PDFInfo
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- 238000000034 method Methods 0.000 claims abstract description 14
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Abstract
本发明公开了一种钛酸铋钠基高储能性能陶瓷电容器及制备方法，该陶瓷电容器的陶瓷材料化学组成式为[(Bi0.5Na0.5)1‑xSrx]1‑3y/2MyTiO3，属ABO3型钙钛矿结构；x＝0‑0.5，y＝0.02‑0.2；M为掺杂元素且占据钙钛矿结构的A位，M为La及La系稀土元素。本发明通过在钛酸铋钠基陶瓷体系中引入掺杂离子来提高储能性能的同时，并采用两步烧结法优化了击穿场强，最终获得综合储能性能优异的陶瓷电容器；大幅提高了储能性能及温度稳定性，且制备过程简单，成本低廉，适合工业化大批量生产，可广泛应用于脉冲电子功率器件中。
Description
技术领域
本发明属于功能陶瓷材料技术领域，涉及不含铅等有害元素的钛酸铋钠基高储能性能陶瓷电容器及制备方法。
背景技术
为解决人类社会面临的能源危机，人们开发了各种可再生能源，包括太阳能、风能和潮汐能，以逐渐取代化石能源。但是，可再生能源的间歇性特性严重影响了能源的利用。为了解决上述问题，有必要将能源收集技术与储能装置相结合。现有的储能装置包括电池、电化学电容器和介电电容器。其中，介电电容器因具有高功率密度、快速的充放电效率以及良好的抗疲劳特性而广泛应用于电子脉冲功率领域，如电磁弹射器和混合动力汽车。
电介质可分为线性电介质、铁电体、反铁电体和弛豫铁电体。其中，弛豫铁电体因为具有较高的极化强度和击穿场强，在储能方面有很大潜力。目前钛酸铋钠基弛豫铁电材料备受研究人员的青睐，比如：专利CN114315350A制备的钐掺杂的钛酸铋钠-锆钛酸钡陶瓷，在60-200℃温度范围内，击穿场强为200-209kV/cm，放电能量密度为1.12-1.32J/cm3，储能效率为86.9-89.6％。专利CN110540423A制备的钛酸铋钠-铌铝酸锶储能陶瓷，击穿场强达到280kV/cm，其放电能量密度为3.01J/cm3，储能效率为85％。尽管如此，钛酸铋钠基陶瓷的储能密度依旧需要进一步提高，以满足器件集成化的发展。
因此，通过对钛酸铋钠基陶瓷进行掺杂改性，提高其室温下的储能密度和温度稳定性具有重要的实际应用意义。
发明内容
针对现有技术中存在的不足，本发明的目的在于，提供一种钛酸铋钠基高储能性能陶瓷电容器及制备方法，通过在钛酸铋钠基陶瓷体系中引入掺杂离子来提高储能性能的同时，并采用两步烧结法优化了击穿场强，最终获得综合储能性能优异的陶瓷电容器。
为了解决上述技术问题，本发明采用如下技术方案予以实现：
一种钛酸铋钠基高储能性能陶瓷电容器，该陶瓷电容器的陶瓷材料化学组成式为[(Bi0.5Na0.5)1-xSrx]1-3y/2MyTiO3，属ABO3型钙钛矿结构；x＝0-0.5，y＝0.02-0.2；M为掺杂元素且占据钙钛矿结构的A位，M为La及La系稀土元素。
本发明还包括如下技术特征：
具体的，该陶瓷电容器的陶瓷材料包括以下原料：Bi2O3、Na2CO3、SrCO3、TiO2以及M的氧化物，各原料纯度均高于99％。
具体的，当M为La时，其原料中M的氧化物为La2O3。
具体的，陶瓷材料化学组成式为[(Bi0.5Na0.5)0.85Sr0.15]1-3y/2LayTiO3，y＝0.02-0.2。
一种所述的钛酸铋钠基高储能性能陶瓷电容器的制备方法，包括以下步骤：
步骤1，根据化学组成式中的配比称取上述各原料，通过一次球磨将原料混合均匀，得到初始粉体；
步骤2，将初始粉体置入马弗炉，在800～900℃预烧2～4h，得到预合成的陶瓷粉体；
步骤3，将预合成的陶瓷粉体通过二次球磨、造粒、预压成型以及冷等静压过程得到陶瓷生坯；
步骤4，将陶瓷生坯置于马弗炉，在500～700℃排胶5～10h，然后开始高温烧结，烧结温度为1150-1180℃保温5min，快速降至1070-1100℃保温2h，接着随炉自然冷却至室温取出；
步骤5，将烧结成瓷的样品分别在300目、800目和1500目的砂纸上磨薄抛光；在样品上下表面被银，并置于马弗炉700℃保温30min得到陶瓷电容器，或在样品表面溅射Pt电极得到陶瓷电容器。
具体的，所述步骤1中，一次球磨转速为400～500r/min，球磨时间为6～12h。
具体的，所述步骤3中，二次球磨转速为400～500r/min，球磨时间为6～12h。
具体的，所述步骤3中，造粒采用6wt％的聚乙烯醇作为粘结剂。
具体的，所述步骤3中，预压成型的压力控制在2MPa.。
具体的，所述步骤3中，冷等静压的条件是200MPa保压60s。
本发明与现有技术相比，具有如下技术效果：
(1)本发明大幅提高了储能性能及温度稳定性，且制备过程简单，成本低廉，适合工业化大批量生产，可广泛应用于脉冲电子功率器件中。
(2)本发明提供的钛酸铋钠基储能陶瓷电容器，具有优异的储能性能，最大电场强度可以达到510kV/cm，与之相对应的放电能量密度为9.65J/cm3，储能效率为91.12％。
(3)本发明在钛酸铋钠-钛酸锶基的A位引入掺杂离子，提高体系的弛豫行为，使铁电畴被破坏，从而降低极化强度在电场下的滞后；制备的陶瓷其介电常数在宽温域内保持稳定，同时获得了细长的电滞回线，大幅提高了陶瓷的放电能量密度和储能效率，并且可以在很宽的温度范围内(-50-200℃)保持优异的储能性能稳定性。
(4)本发明中未使用Hf、Nb和Ta等高成本的原料，因此制备成本低廉。
(5)本发明采用两步烧结工艺，降低晶粒尺寸，大幅提高了击穿电场。
(6)本发明能应用于电磁弹射器和混合动力汽车等脉冲功率体系中。
附图说明
图1为本发明各实施例和对比例的X射线衍射(XRD)图谱；
图2为实施例2制得的y＝0.12陶瓷组分的扫描电子显微镜(SEM)照片；
图3为实施例2制得的y＝0.12陶瓷组分的介电常数(εr)和介电损耗(tanδ)随温度变化曲线；
图4为实施例2制得的y＝0.12陶瓷组分在室温下的极化强度-电场关系曲线(Polarization-Electric field，简称P-E电滞回线)；
图5为实施例2制得的y＝0.12陶瓷组分随温度变化的电滞回线。
具体实施方式
本发明提供一种钛酸铋钠基高储能性能陶瓷电容器及制备方法，该陶瓷电容器的陶瓷材料的化学组成式为[(Bi0.5Na0.5)1-xSrx]1-3y/2MyTiO3，属于ABO3型钙钛矿结构。其中，x＝0-0.5，y＝0.02-0.2，M为掺杂元素，占据钙钛矿结构的A位；M可以是La及La系稀土元素。
本发明制备方法包括以下原料：Bi2O3，Na2CO3，SrCO3，TiO2以及M的氧化物(纯度均高于99％)。
具体的，当M为La时，其原料中M的氧化物为La2O3，制得的陶瓷材料化学组成式为[(Bi0.5Na0.5)0.85Sr0.15]1-3y/2LayTiO3。
本发明制备方法包括以下步骤：
步骤1，根据化学组成式中的配比称取上述各原料，通过一次球磨将原料混合均匀，得到初始粉体；球磨转速为400～500r/min，球磨时间为6～12h；
步骤2，将初始粉体置入马弗炉，在800～900℃预烧2～4h，得到预合成的陶瓷粉体；
步骤3，将预合成的陶瓷粉体通过二次球磨、造粒、预压成型以及冷等静压过程得到陶瓷生坯；球磨转速为400～500r/min，球磨时间为6～12h；造粒采用6wt％的聚乙烯醇(PVA)作为粘结剂；预压成型的压力控制在2MPa；冷等静压的条件是200MPa保压60s；
步骤4，将陶瓷生坯置于马弗炉，在500～700℃排胶5～10h，然后开始高温烧结，烧结温度为1150-1180℃保温5min，快速降至1070-1100℃保温2h，接着随炉自然冷却至室温取出；
步骤5，将烧结成瓷的样品分别在300目、800目和1500目的砂纸上磨薄抛光；在样品上下表面被银，并置于马弗炉700℃保温30min得到陶瓷电容器，或在样品表面溅射Pt电极得到陶瓷电容器。
本发明制备的储能陶瓷能用于混合动力汽车、分布式功率系统以及电磁弹射领域。
以下给出本发明的具体实施例，需要说明的是本发明并不局限于以下具体实施例，凡在本申请技术方案基础上做的等同变换均落入本发明的保护范围。
实施例1：
本实施例提供本实施例提供一种钛酸铋钠基高储能性能陶瓷电容器及制备方法，本实施例中的陶瓷材料化学组成为[(Bi0.5Na0.5)0.85Sr0.15]0.88La0.08TiO3，制备步骤如下：
步骤1，选取纯度高于99％的Bi2O3，Na2CO3，SrCO3，La2O3和TiO2作为原料；根据化学组成计算需称取的原料质量，然后用电子天平称量各原料(比计算的质量多0.5g)，分别放入洗干净的烧杯中，用锡纸封口并用牙签扎10个孔，置于烘箱中150℃烘干10h备用；根据化学组成比称取上述烘干的各粉体，置于50mL聚四氟乙烯球磨罐内，采用玛瑙圆珠和无水乙醇作为球磨介质，其总量不超过球磨罐容积的三分之二，球磨转速为400r/min，球磨时间为12h，得到初始粉体；
步骤2，将上述初始粉体倒入蒸发皿中，并加盖以防止杂质进入，置于烘箱中80℃烘干8h备用；将烘干的初始粉体用玛瑙研钵研磨之后装入氧化铝坩埚中，用药匙将粉体压实，加盖放入马弗炉中预烧以获得预合成粉体，设置升温速率为3℃/min，预烧温度为850℃，保温时间为3h，之后随炉自然冷却至室温取出，得到预合成的陶瓷粉体；
步骤3，将预合成的陶瓷粉体用玛瑙研钵研磨之后再次装入球磨罐中进行二次球磨，该过程依然采用玛瑙圆珠和无水乙醇作为球磨介质，其总量不超过球磨罐容积的三分之二，球磨转速为400r/min，球磨时间为12h；上述球磨之后的浆料倒入蒸发皿中，并加盖以防止杂质进入，置于烘箱中80℃烘干8h备用；取出烘干的粉体，置于研钵中充分研磨，然后逐滴加入6wt％的聚乙烯醇(PVA)造粒直至均匀，接着过100目筛，装袋备用；称取0.25g上述粉料，装入直径为10mm的圆柱形模具中，在粉末压片机上预压成型；将预压成型的生坯装入实验室用手套，抽真空，接着放入冷等静压机，条件为200MPa保压60s，获得密实的陶瓷生坯；
步骤4，将上述陶瓷生坯置于马弗炉排胶，500℃保温10h，然后开始高温烧结，烧结条件为1150-1180℃保温5min，快速降至1070-1100℃保温2h，接着随炉自然冷却至室温取出；需要注意的是，由于Bi和Na属于易挥发性元素，因此烧结时需要将陶瓷生坯用其粉体覆盖以减少挥发。
步骤5，将烧结成瓷的样品分别在300目、800目和1500目的砂纸上磨薄抛光；在样品上下表面被银，并置于马弗炉700℃保温30min，用于测试介电性能；在样品表面溅射Pt电极，用于测试P-E电滞回线；其他性能直接使用烧结成瓷的样品即可。
实施例2：
本实施例提供一种钛酸铋钠基高储能性能陶瓷电容器及制备方法，本实施例中的陶瓷材料化学组成为[(Bi0.5Na0.5)0.85Sr0.15]0.82La0.12TiO3，制备步骤与实施例1相同。
实施例3：
本实施例提供一种钛酸铋钠基高储能性能陶瓷电容器及制备方法，本实施例中的陶瓷材料化学组成为[(Bi0.5Na0.5)0.85Sr0.15]0.79La0.14TiO3，制备步骤与实施例1相同。
对比例1：
本对比例提供一种陶瓷电容器及制备方法，该陶瓷电容器的陶瓷材料化学组成为[(Bi0.5Na0.5)0.85Sr0.15]TiO3，制备步骤与实施例1相比，除了步骤1中无La2O3原料，其他步骤均相同。
与实施例相比，该对比例的击穿电场强度仅有280kV/cm，与之相对应的放电能量密度仅为2.18J/cm3，储能效率只有70.55％，该产品性能不利于作为储能电容器。
图1为本发明各实施例和对比例陶瓷组分的XRD图谱；从图中可以看出，本发明制备的陶瓷呈现典型的钙钛矿结构。图2为实施例2制得的y＝0.12陶瓷组分的SEM照片，从图中可以看出，该陶瓷呈现致密的微观结构，平均晶粒尺寸为0.51μm。图3为实施例2制得的y＝0.12陶瓷组分的εr和tanδ随温度变化曲线，测试温度范围是室温-500℃，测试频率分别为1kHz，10kHz，100kHz，1000kHz和2000kHz；从图中可以看出，该陶瓷组分具有两个特征介电峰，一个在室温附近，呈现出明显的频率弥散特性，另一个位于300℃附近，在两个介电峰之间，介电常数随温度变化不大，呈现出优异的温度稳定性。此外，该陶瓷组分的介电损耗在室温至400℃温度区间内均小于0.05。图4为实施例2制得的y＝0.12陶瓷组分在室温下的P-E电滞回线，从图中可以看出，该陶瓷组分的电滞回线呈现细长型，并且击穿电场强度可以达到510kV/cm，与之相对应的放电能量密度为9.65J/cm3，储能效率为91.12％。图5为实施例2制得的y＝0.12陶瓷组分随温度变化的P-E电滞回线，从图中可以看出，该陶瓷组分的储能性能呈现出优异的温度稳定性，在-50-200℃测试范围内，当电场强度为400kV/cm时，与之相对应的放电能量密度为6.3-6.82J/cm3，储能效率为87.36-94.97％。
Claims (10)
1.一种钛酸铋钠基高储能性能陶瓷电容器，其特征在于，该陶瓷电容器的陶瓷材料化学组成式为[(Bi0.5Na0.5)1-xSrx]1-3y/2MyTiO3，属ABO3型钙钛矿结构；x＝0-0.5，y＝0.02-0.2；M为掺杂元素且占据钙钛矿结构的A位，M为La及La系稀土元素。
2.如权利要求1所述的钛酸铋钠基高储能性能陶瓷电容器，其特征在于，该陶瓷电容器的陶瓷材料包括以下原料：Bi2O3、Na2CO3、SrCO3、TiO2以及M的氧化物，各原料纯度均高于99％。
3.如权利要求1所述的钛酸铋钠基高储能性能陶瓷电容器，其特征在于，当M为La时，其原料中M的氧化物为La2O3。
4.如权利要求3所述的钛酸铋钠基高储能性能陶瓷电容器，其特征在于，陶瓷材料化学组成式为[(Bi0.5Na0.5)0.85Sr0.15]1-3y/2LayTiO3，y＝0.02-0.2。
5.一种如权利要求2所述的钛酸铋钠基高储能性能陶瓷电容器的制备方法，其特征在于，包括以下步骤：
步骤1，根据化学组成式中的配比称取上述各原料，通过一次球磨将原料混合均匀，得到初始粉体；
步骤2，将初始粉体置入马弗炉，在800～900℃预烧2～4h，得到预合成的陶瓷粉体；
步骤3，将预合成的陶瓷粉体通过二次球磨、造粒、预压成型以及冷等静压过程得到陶瓷生坯；
步骤4，将陶瓷生坯置于马弗炉，在500～700℃排胶5～10h，然后开始高温烧结，烧结温度为1150-1180℃保温5min，快速降至1070-1100℃保温2h，接着随炉自然冷却至室温取出；
步骤5，将烧结成瓷的样品分别在300目、800目和1500目的砂纸上磨薄抛光；在样品上下表面被银，并置于马弗炉700℃保温30min得到陶瓷电容器，或在样品表面溅射Pt电极得到陶瓷电容器。
6.如权利要求5所述的钛酸铋钠基高储能性能陶瓷电容器的制备方法，其特征在于，所述步骤1中，一次球磨转速为400～500r/min，球磨时间为6～12h。
7.如权利要求5所述的钛酸铋钠基高储能性能陶瓷电容器的制备方法，其特征在于，所述步骤3中，二次球磨转速为400～500r/min，球磨时间为6～12h。
8.如权利要求5所述的钛酸铋钠基高储能性能陶瓷电容器的制备方法，其特征在于，所述步骤3中，造粒采用6wt％的聚乙烯醇作为粘结剂。
9.如权利要求5所述的钛酸铋钠基高储能性能陶瓷电容器的制备方法，其特征在于，所述步骤3中，预压成型的压力控制在2MPa.。
10.如权利要求5所述的钛酸铋钠基高储能性能陶瓷电容器的制备方法，其特征在于，所述步骤3中，冷等静压的条件是200MPa保压60s。
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