CN116854464B - 一种铁电复合储能陶瓷材料及其制备方法 - Google Patents
一种铁电复合储能陶瓷材料及其制备方法 Download PDFInfo
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- 239000000463 material Substances 0.000 claims abstract description 14
- 229910010252 TiO3 Inorganic materials 0.000 claims abstract description 10
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 3
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- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 210000001161 mammalian embryo Anatomy 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
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- 238000001035 drying Methods 0.000 claims 1
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- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000004044 response Effects 0.000 description 1
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Abstract
本发明公开了一种铁电复合储能陶瓷材料及其制备方法，相比现有技术，本发明陶瓷材料储能密度更高且频率稳定性更强。本发明中陶瓷材料通式为(1‑x)(Bi0.46Sr0.06Na0.5)TiO3‑xCa1‑ ySryTiO3，式中0.4≤x≤0.8，0.1≤y≤0.9，下标数字代表元素的摩尔比。本发明材料在25℃环境温度下，当测试频率变化范围为10Hz‑150Hz时，饱和极化强度变化范围为27.58μC/cm2≤Ps≤41.76μC/cm2，抗击穿场强变化范围为300kV/cm≤Eb≤440kV/cm，有效储能密度变化范围为3.34J/cm3≤Wrec≤4.91J/cm3，储能效率变化范围为67.8％≤η≤88％。
Description
技术领域
本发明属于储能陶瓷材料技术领域，具体涉及一种无铅弛豫铁电储能陶瓷材料及其制备方法。
背景技术
无铅弛豫铁电储能陶瓷以其优秀的环保特性和出色的弛豫铁电性，在储能技术领域受到广泛关注。该类陶瓷在外加电场激励下，极化响应较平缓，其电滞回线呈狭长状态，表现出剩余极化强度低的特点，因此通常具有较高的储能效率，但也存在明显的缺点。当其在低外加电场作用下，饱和极化强度普遍较低，所得储能密度相应偏低。因此，要提高弛豫铁电陶瓷的储能密度，需要提高其抗击穿场强以及强外加电场作用下的饱和极化强度。
为优化无铅弛豫铁电储能陶瓷的综合性能，研究人员在工艺调整和配方改进方面开展了大量工作。工艺调整是通过调整制备流程参数，从而优化陶瓷晶粒形状、尺寸和分布，但技术相对成熟，提升空间有限；配方设计是通过调整陶瓷材料的元素配比，达到优化陶瓷的相组成和晶粒形态的目的，主要围绕离子掺杂改性和多元组分复合两方面展开。其中，离子掺杂可以调节材料的缺陷结构和电学性质，使其具备更好的能量储存和释放能力，但因离子种类较少，可调性明显受限；而多元组分复合则是通过引入其他功能材料来形成复合结构，其结构的多元化以及复合材料的多样性极大地丰富了配方设计方案，因此广受研究人员青睐。
发明内容
为了克服无铅弛豫铁电陶瓷剩余极化强度大以及抗击穿场强低的缺点，提升其储能应用空间，本发明提供一种高储能密度无铅弛豫铁电复合陶瓷材料及其制备方法。本发明以(Bi0.5Na0.5)TiO3为基体材料，引入CaTiO3相复合，并采用Sr2+离子掺杂改性，降低了其剩余极化强度的同时提高了抗击穿场强低，进而达到优化陶瓷储能性能的目的。
为实现上述目的，本发明采用的技术方案如下：
一种铁电复合储能陶瓷材料，其特征在于，该陶瓷材料的通式为(1-x)(Bi0.46Sr0.06Na0.5)TiO3-xCa1-ySryTiO3，式中0.4≤x≤0.8，0.1≤y≤0.9，下标数字代表元素的摩尔比。制备方法采用传统固相烧结法，包括以下步骤：
(1)以Bi2O3(99.9％)、SrCO3(99.95％)、Na2CO3(99.5％)、CaCO3(99％)和TiO2(99％)为原料，按照材料化学通式计算并称料，然后依次进行一次球磨、一次烧结、二次球磨、造粒、成型、排胶和烧结等工艺流程，即得铁电复合储能陶瓷材料。
(2)步骤1中所述一次球磨是指将称取的原料装罐球磨，球磨介质采用无水乙醇，球磨转速为350r/min-450r/min，球磨时间为6h-8h。
(3)步骤1中所述一次烧结是指将一次球磨浆料干燥过筛后装钵，在750℃-850℃保温2h-4h。
(4)步骤1中所述二次球磨是指将一次烧结所得粉体按通式的摩尔比计算称取，装罐球磨，球磨介质采用无水乙醇，球磨转速为350r/min-450r/min，球磨时间为6h-8h。
(5)步骤1中所述造粒是指将为二次球磨浆料烘干过筛，添加5wt％-7wt％的聚乙烯醇水溶液(PVA)，然后混合均匀，其中PVA浓度为5wt％。
(6)步骤1中所述成型是指将造粒料在200MPa-250MPa下干压，制备厚度1.2mm、直径10mm的圆柱胚体。
(7)步骤1中所述排胶是指将成型胚体装钵，在450℃-550℃保温30min-60min，升温速率为2℃/min-8℃/min。
(8)步骤1中所述烧结是指将已排胶胚体在980℃-1050℃保温3h-5h，升温速率为2℃/min-4℃/min；随炉冷却至室温，即得复合储能陶瓷样片。
(9)烧结完成后，对所得样片进行打磨、抛光、清洗、烘干、涂覆电极并进行一系列性能测试。
与已有报道相比，本发明采取的上述技术方案具有以下优势：
(1)本发明复合储能陶瓷材料是环境友好型材料，对人体无毒性且对环境无重金属污染。
(2)本发明陶瓷材料在制备过程中，未采用贵金属元素和稀土元素，生产成本较低，有利于推广应用。
(3)本发明铁电复合陶瓷综合储能性能优异且频率稳定性强，例如当材料化学式为0.3(Bi0.46Sr0.06Na0.5)TiO3-0.7Ca0.25Sr0.75TiO3时，在50Hz测试频率和25℃环境温度下，抗击穿场强为420KV/cm，储能密度高达4.91J/cm3，相应储能效率达到88.0％；当测试频率变化范围为10Hz-150Hz时，该陶瓷材料储能效率波动限定在6％以内，与同类无铅储能陶瓷材料相比，表现更为突出。
附图说明
图1为实施例1-5储能陶瓷材料的XRD图。
图2为实施例1-5储能陶瓷材料在50Hz测试频率和25℃环境温度下的电滞回线图。
图3为实施例4储能陶瓷材料在不同测试频率下的电滞回线图。
具体实施方式
下面结合五个实施例对本发明进行详细阐述，所述实施例仅用于解释本发明的具体实施方式，本发明的保护范围不限于所列举实施例。
实施例1
按照化学式0.6(Bi0.46Sr0.06Na0.5)TiO3-0.4Ca0.25Sr0.75TiO3计算并称料；将称取的原料装罐球磨，球磨介质为无水乙醇，球磨速度为400r/min，球磨时间为8h；将球磨所得浆料烘干装钵，进行一次烧结，烧结温度为800℃，保温时间为4h；将一次烧结后的粉体再次装罐球磨，球磨介质为无水乙醇，球磨速度为400r/min，球磨时间为8h；将二次球磨浆料烘干造粒，粘结剂采用5wt％的聚乙烯醇水溶液，添加量为5wt％；将造粒料在250MPa压力下干压成型，制备厚度1.2mm、直径10mm的圆柱胚体；将成型胚体在500℃保温30min进行排胶，升温速率为5℃/min；排胶后进行烧结，烧结温度为980℃，保温时间为3h，保温完成后随炉膛冷却至室温，即得储能陶瓷样片。
实施例2
按照化学式0.5(Bi0.46Sr0.06Na0.5)TiO3-0.5Ca0.25Sr0.75TiO3计算后称料；将称取的原料装罐球磨，球磨介质为无水乙醇，球磨速度为400r/min，球磨时间为8h；将球磨后的浆料烘干装钵，进行一次烧结，烧结温度为800℃，保温时间为4h；将一次烧结后的粉体再次装罐球磨，球磨介质为无水乙醇，球磨速度为400r/min，球磨时间为8h；将二次球磨浆料烘干造粒，粘结剂采用5wt％的聚乙烯醇水溶液，添加量为5wt％；将造粒料在250MPa压力下干压成型，制备厚度1.2mm、直径10mm的圆柱胚体；将成型胚体在500℃保温30min进行排胶，升温速率为5℃/min；排胶后进行烧结，烧结温度为1000℃，保温时间为3h，保温完成后随炉膛冷却至室温，即得储能陶瓷样片。
实施例3
按照化学式0.4(Bi0.46Sr0.06Na0.5)TiO3-0.6Ca0.25Sr0.75TiO3计算后称料；将称取的原料装罐球磨，球磨介质为无水乙醇，球磨速度为400r/min，球磨时间为8h；将球磨后的浆料烘干装钵，进行一次烧结，烧结温度为800℃，保温时间为4h；将一次烧结后的粉体再次装罐球磨，球磨介质为无水乙醇，球磨速度为400r/min，球磨时间为8h；将二次球磨浆料烘干造粒，粘结剂采用5wt％的聚乙烯醇水溶液，添加量为5wt％；将造粒料在250MPa压力下干压成型，制备厚度1.2mm、直径10mm的圆柱胚体；将成型胚体在500℃保温30min进行排胶，升温速率为5℃/min；排胶后进行烧结，烧结温度为1010℃，保温时间为3h，保温完成后随炉膛冷却至室温，即得储能陶瓷样片。
实施例4
按照化学式0.3(Bi0.46Sr0.06Na0.5)TiO3-0.7Ca0.25Sr0.75TiO3计算后称料；将称取的原料装罐球磨，球磨介质为无水乙醇，球磨速度为400r/min，球磨时间为8h；将球磨后的浆料烘干装钵，进行一次烧结，烧结温度为800℃，保温时间为4h；将一次烧结后的粉体再次装罐球磨，球磨介质为无水乙醇，球磨速度为400r/min，球磨时间为8h；将二次球磨浆料烘干造粒，粘结剂采用5wt％的聚乙烯醇水溶液，添加量为5wt％；将造粒料在250MPa压力下干压成型，制备厚度1.2mm、直径10mm的圆柱胚体；将成型胚体在500℃保温30min进行排胶，升温速率为5℃/min；排胶后进行烧结，烧结温度为1020℃，保温时间为3h，保温完成后随炉膛冷却至室温，即得储能陶瓷样片。
实施例5
按照化学式0.2(Bi0.46Sr0.06Na0.5)TiO3-0.8Ca0.25Sr0.75TiO3计算后称料；将称取的原料装罐球磨，球磨介质为无水乙醇，球磨速度为400r/min，球磨时间为8h；将球磨后的浆料烘干装钵，进行一次烧结，烧结温度为800℃，保温时间为4h；将一次烧结后的粉体再次装罐球磨，球磨介质为无水乙醇，球磨速度为400r/min，球磨时间为8h；将二次球磨浆料烘干造粒，粘结剂采用5wt％的聚乙烯醇水溶液，添加量为5wt％；将造粒料在250MPa压力下干压成型，制备厚度1.2mm、直径10mm的圆柱胚体；将成型胚体在500℃保温30min进行排胶，升温速率为5℃/min；排胶后进行烧结，烧结温度为1050℃，保温时间为3h，保温完成后随炉膛冷却至室温，即得储能陶瓷样片。
将上述实施例1-5制备的陶瓷样片，经超声波清洗后烘干。利用X射线衍射仪(XRD-6100，Shimadzu，日本)对各实施例样片进行物相分析，结果见图1。由图可知，各样品均呈现单纯钙钛矿结构，表明各组分间固溶完全，整体结晶度较好。
将上述实施例1-5制备的陶瓷样片均采用1500目金刚砂打磨至0.1mm，经超声波清洗后烘干，两面涂覆高温导电银浆，烘干后在500℃下固化银电极，保温30min后即可自然冷却待测，使用铁电测试仪(LCII-100V，Radiant，美国)在50Hz测试频率和25℃环境温度下测得各样品的电滞回线，结果见图2。经整理和分析可得，各例复合陶瓷材料储能性能如下：
实施例1：抗击穿场强Eb为300kV/cm，饱和极化强度Ps为41.76μC/cm2，由此计算得其有效储能密度Wrec为3.465J/cm3，储能效率η为67.8％。
实施例2：抗击穿场强Eb为320kV/cm，饱和极化强度Ps为340.6μC/cm2，由此计算得其有效储能密度Wrec为3.34J/cm3，储能效率η为73.2％。
实施例3：抗击穿场强Eb为360kV/cm，饱和极化强度Ps为32.65μC/cm2，由此计算得其有效储能密度Wrec为3.96J/cm3，储能效率η为83.5％。
实施例4：抗击穿场强Eb为420kV/cm，饱和极化强度Ps为34μC/cm2，由此计算得其储能有效密度Wrec为4.91J/cm3，储能效率η为88％。
实施例5：抗击穿场强Eb为440kV/cm，饱和极化强度Ps为27.58μC/cm2，由此计算得其有效储能密度Wrec为4.21J/cm3，储能效率η为72.2％。
提高无铅弛豫铁电陶瓷的稳定性也是本发明的一个重要目的，图3为实施例3无铅储能陶瓷材料在320kV/cm外加电场和25℃环境温度下，在10Hz-150Hz频率范围内的电滞回线，储能效率η波动小于6％，稳定性表现出色。
Claims (2)
1.一种铁电复合储能陶瓷材料，其特征在于，材料化学通式为(1-x)(Bi0.46Sr0.06Na0.5)TiO3-xCa1-ySryTiO3，式中0.4≤x≤0.8，0.1≤y≤0.9，下标数字代表元素的摩尔比。
2.一种铁电复合储能陶瓷材料的制备方法，其特征在于，包括以下步骤：
(1)以Bi2O3、SrCO3、Na2CO3、CaCO3和TiO2为原料，按照权利要求1所述通式计算并称料，然后依次进行一次球磨、一次烧结、二次球磨、造粒、成型、排胶和烧结工艺流程，即得铁电复合储能陶瓷材料；
(2)根据步骤1所述工艺流程，一次球磨是指将称取的原料装罐球磨，球磨介质采用无水乙醇，球磨转速为350r/min-450r/min，球磨时间为6h-8h；
(3)根据步骤1所述工艺流程，一次烧结是指将球磨浆料干燥过筛后装钵，在750℃-850℃保温2h-4h；
(4)根据步骤1所述工艺流程，二次球磨是指将一次烧结所得粉体按通式的摩尔比计算称取，装罐球磨，球磨介质采用无水乙醇，球磨转速为350r/min-450r/min，球磨时间为6h-8h；
(5)根据步骤1所述工艺流程，造粒是指将二次球磨浆料烘干过筛，添加5wt％-7wt％的聚乙烯醇水溶液(PVA)，然后混合均匀，其中PVA浓度为5wt％；
(6)根据步骤1所述工艺流程，成型是指将造粒料在200MPa-250 MPa下干压，制备厚度1.2mm、直径10mm的圆柱胚体；
(7)根据步骤1所述工艺流程，排胶是指将成型胚体装钵，在450℃-550℃保温30min-60min，升温速率为2℃/min-8℃/min；
(8)根据步骤1所述工艺流程，烧结是指将已排胶胚体在980℃-1050℃保温3h-5h，升温速率为2℃/min-4℃/min。
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