CN113526950A - 一种高储能高效率的NaNbO3掺杂BaTiO3基氧化物陶瓷材料、制备方法及应用 - Google Patents
一种高储能高效率的NaNbO3掺杂BaTiO3基氧化物陶瓷材料、制备方法及应用 Download PDFInfo
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- 238000004146 energy storage Methods 0.000 title claims abstract description 29
- 229910052574 oxide ceramic Inorganic materials 0.000 title claims abstract description 7
- 229910010252 TiO3 Inorganic materials 0.000 claims abstract description 63
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 54
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
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Abstract
一种高储能高效率的NaNbO3掺杂BaTiO3基氧化物陶瓷材料、制备方法及应用,其化学式为(1‑x)(0.6BaTiO3‑0.4Bi0.5Na0.5TiO3)‑xNaNbO3,其中0≤x≤0.2,x为摩尔百分比。该陶瓷材料根据化学式配料并进行预烧球磨制备。制备所得的陶瓷材料可制作陶瓷产品。本发明所制备的陶瓷材料,具有明显的弥散相变特征,制备工艺简单,制作成本低,通过选择适当的x值,可使放电储能密度达到2.2J/cm3,同时储能效率达到91.7%,提供了一种新的无铅储能材料基体。
Description
技术领域
本发明涉及弛豫铁电体的技术领域,具体涉及一种(1-x)(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-xNaNbO3高功率密度高熵钙钛矿氧化物陶瓷材料、制备方法及其应用。
背景技术
为了满足电动汽车和脉冲武器发展的需要,先进储能装置的研究受到了世界各国的广泛关注。与电池等储能系统相比,铁电电容器具有充放电速度快、功率密度高、寿命长等优点。铁电电容器储能特性的改善离不开材料的介电特性。虽然已经有许多重要的工作报告,但具有温度稳定性的高效储能铁电材料仍然缺乏。弛豫铁电体由于在理想状态下具有零剩余极化(Pr)和高饱和极化(Ps),在储能中的应用越来越受到重视。但大多数弛豫铁电体都含有铅,在制备和使用过程中对环境造成了极大的破坏,因此需要开发无铅的弛豫铁电体体系。
发明内容
本发明的目的在于是提供一种高储能高效率的NaNbO3掺杂BaTiO3基氧化物陶瓷材料及其制备方法,通过本方法制得的陶瓷电容器材料,不但制备工艺简单,材料成本低,而且具有较高的介电常数、低的介电损耗、良好温度稳定性,有可能成为替代铅基陶瓷材料成为多层陶瓷电容器在技术和经济上兼优的重要候选材料。
本发明所要解决的技术问题是通过NaNbO3(简称NN)的掺杂对0.6BaTiO3-0.4Bi0.5Na0.5TiO3(简称BT-NBT)基体材料进行改性,得到的(1-x)(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-xNaNbO3作为弛豫铁电材料,具有相较于一般铁电材料较低的剩余极化。NaNbO3的加入能够有效地增强试样的弛豫特性,提高试样的储能效率,这是由于NN的掺杂可以削弱BT-NBT陶瓷的极性菱形相,减少剩余极化,从而获得良好的储能性能。此外,NN本身具有较高的居里温度(370℃)和非常复杂的相变序列。考虑到NN的这些固有特性,NN的加入可能会干扰PNRs的耦合,从而影响PNRs的响应时间,最终提高0.6BaTiO3-0.4Bi0.5Na0.5TiO3陶瓷的高温稳定性。因此,NaNbO3掺杂改性能够增强击穿场强和储能效率。
为解决上述技术问题,本发明提供的技术方案是:
一种高储能高效率的NaNbO3掺杂BaTiO3基氧化物陶瓷材料,化学式为(1-x)(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-xNaNbO3,其中0≤x≤0.2,x为摩尔百分比。
优选地,所述各组分由Na2CO3、Bi2O3、BaCO3、TiO2和Nb2O5引入。
本发明还提供了陶瓷材料粉体的制备方法,其特征在于,包括如下步骤:
按照化学式(1-x)(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-xNaNbO3,其中0≤x≤0.2,x为摩尔百分比;取Na2CO3、Bi2O3、BaCO3、TiO2和Nb2O5配料,预烧后球磨,烘干得到陶瓷材料粉体。
优选地,所述预烧温度850℃。
优选地,预烧制度为:以5℃/min升温至850℃,保温2小时,之后,以5℃/min降温至500℃,随炉冷却到室温。
优选地,对配料进行球磨后再预烧。一种高储能高效率的NaNbO3掺杂BaTiO3基氧化物陶瓷材料,其化学式为(1-x)(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-xNaNbO3,其中x为NaNbO3的掺杂量,0≤x≤0.2,其中x表示摩尔百分比。
本发明还提供了一种上述陶瓷材料在制作陶瓷产品中的应用。利用本发明的陶瓷材料粉体通过成型烧结被电极等工艺制作陶瓷产品,该陶瓷产品烧结温度为1150℃。
与现有的技术相比,本发明具有的有益结果:本发明将NaNbO3掺杂进0.6BaTiO3-0.4Bi0.5Na0.5TiO3基体材料中,通过配方设计,验证了五价Nb离子在0.6BaTiO3-0.4Bi0.5Na0.5TiO3的B位取代四价Ti离子。NaNbO3的加入能够有效地增强试样的弛豫特性,提高试样的储能效率,这是由于NN的掺杂可以削弱BT-NBT陶瓷的极性菱形相,减少剩余极化,从而获得良好的储能性能。此外,NN本身具有较高的居里温度(370℃)和非常复杂的相变序列。考虑到NN的这些固有特性,NN的加入可能会干扰PNRs的耦合,从而影响PNRs的响应时间,最终提高0.6BaTiO3-0.4Bi0.5Na0.5TiO3陶瓷的高温稳定性。因此,NN掺杂改性能够增强击穿强度和储能密度。此外,通过B位Nb5+掺杂可以进一步加大弛豫程度,使电滞回线细化,陶瓷材料的储能效率得到提高。通过与之前的类似方法进行改性的材料进行对比,发现本发明所制备的材料储能性能更加优异。
在本发明的试样的制备过程当中,采用了更加先进的冷等静压成型技术,避免了试样的浪费和粘结剂的加入,节省了制作的成本,加快了生产周期并且避免了粘结剂对试样污染的可能性,在后续步骤之中,减少了排除粘结剂的步骤,减少了资源的浪费和制作时间的浪费,除此之外,由于冷等静压成型技术是利用液体进行压力的传递,与传统单项加压的压制相比,冷等静压成型会让试样从各个方向受到压力,并且压力相比较更大,制备的生坯更加的致密,为下一步优异实验结果奠定了基础。
另外,随着人们的环保意识的加强,材料的生产要规避对环境的影响,本发明所采用的原材料中由于不含铅等重金属元素,对环境友好,所以制备过程中不会对环境破坏。本发明所制备的材料致密性良好,无明显的气孔存在,晶粒尺寸均匀,所以本发明能够保证NaNbO3掺杂的0.6BaTiO3-0.4Bi0.5Na0.5TiO3具有优异的储能及充放电性能。
附图说明
图1为(1-x)(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-xNaNbO3陶瓷材料组分中当x=0、0.03、0.06、0.10、0.15和0.20时,陶瓷材料粉体的XRD图谱;
图2为(1-x)(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-xNaNbO3(x=0,0.03,0.06,0.10,0.15,0.20)陶瓷材料的极化强度随电场变化图谱;
图3为(1-x)(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-xNaNbO3陶瓷的储能密度,击穿场强,储能效率随掺杂量的变化曲线;
图4为(1-x)(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-xNaNbO3陶瓷电容器温度系数随温度的变化曲线。
具体实施方式
下面结合附图及实施例对本发明进行详细说明,但是本发明不局限于以下实施例。
本发明中,制备了NaNbO3掺杂的0.6BaTiO3-0.4Bi0.5Na0.5TiO3陶瓷材料。其化学式(1-x)(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-xNaNbO3,其中0≤x≤0.2,x为摩尔百分比。为各元素分别由分析纯的Na2CO3、Bi2O3、BaCO3、TiO2和Nb2O5引入。
实施例一
1、陶瓷材料制备
该陶瓷材料的化学式为:(1-x)(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-xNaNbO3,其中x表示摩尔百分比,且x=0。
上述NaNbO3掺杂的0.6BaTiO3-0.4Bi0.5Na0.5TiO3陶瓷材料的制备方法,包括以下步骤:
(1)x=0时,化学式为0.6BaTiO3-0.4Bi0.5Na0.5TiO3,按照该化学式取Na2CO3、Bi2O3、BaCO3、TiO2配制后与锆球石及去离子水,按照质量比为1:5:1混合后球磨8h。在80℃下将混合料干燥36个小时,经过研磨后将混合料置于马弗炉中于1000℃预烧2小时,预烧制度:以5℃/min升温至1000℃,保温2小时,之后,以5℃/min降温至500℃,随炉冷却到室温,得到块状固体;
(2)将块状固体粉碎后,再次与锆球石及去离子水,按照质量比为1:5:1混合后球磨8h。产品过120目筛得到尺寸均匀的0.6BaTiO3-0.4Bi0.5Na0.5TiO3粉体;
2、测试用陶瓷试样制备
(3)将得到的0.6BaTiO3-0.4Bi0.5Na0.5TiO3粉体,以每份质量0.35g进行称量,然后倒入模具当中,施加600N的力,将成型好的圆片进行脱模,得到形状完好的试样;
(4)将圆片放置于胶套当中,利用抽真空设备将胶套的空气排出,密封胶套口,放入冷等静压成型,在200Mpa的压力下保压300s;
(5)将得到的试样从胶套中取出后于箱式炉中1150℃烧结2小时成瓷,得到0.6BaTiO3-0.4Bi0.5Na0.5TiO3电介质陶瓷材料试样;
(6)打磨、清洗步骤(5)中一次烧结好的陶瓷试样后,在陶瓷试样的正反两面均匀涂覆银电极浆料,在550℃进行热处理25min,得到0.6BaTiO3-0.4Bi0.5Na0.5TiO3陶瓷材料。
实施例二
1、陶瓷材料制备
该陶瓷材料的化学式为:(1-x)(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-xNaNbO3,其中x表示摩尔百分比,且x=0.03。
上述NaNbO3掺杂的0.6BaTiO3-0.4Bi0.5Na0.5TiO3陶瓷材料的制备方法,包括以下步骤:
(1)按照化学式(1-x)(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-xNaNbO3(x=0.03)将分析纯的Na2CO3、Bi2O3、BaCO3、TiO2和Nb2O5配制后与锆球石及去离子水,按照质量比为1:5:1混合后球磨8h。在80℃下将混合料干燥36个小时,经过研磨后将混合料置于马弗炉中于850℃预烧2小时,预烧制度:以5℃/min升温至850℃,保温2小时,之后,以5℃/min降温至500℃,随炉冷却到室温。得到块状固体;
(2)将块状固体粉碎后,再次与锆球石及去离子水,按照质量比为1:5:1混合后球磨8h。产品过120目筛得到尺寸均匀的0.97(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-0.03NaNbO3粉体;
2、测试用陶瓷试样制备
(3)将得到的0.97(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-0.03NaNbO3粉体,以每份质量0.38g进行称量,然后倒入模具当中,施加600N的力,将成型好的圆片进行脱模,得到形状完好的试样;
(4)将圆片放置于胶套当中,利用抽真空设备将胶套的空气排出,密封胶套口,放入冷等静压成型,在200Mpa的压力下保压300s;
(5)将得到的试样从胶套中取出后于箱式炉中1150℃烧结2小时成瓷,得到0.97(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-0.03NaNbO3电介质陶瓷材料试样;
(6)打磨、清洗步骤(5)中一次烧结好的陶瓷试样后,在陶瓷试样的正反两面均匀涂覆银电极浆料,在550℃进行热处理25min,得到0.97(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-0.03NaNbO3陶瓷材料。
实施例三
1、陶瓷材料制备
该陶瓷材料的化学式为:(1-x)(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-xNaNbO3,其中x表示摩尔百分比,且x=0.06。
上述NaNbO3掺杂的0.6BaTiO3-0.4Bi0.5Na0.5TiO3陶瓷材料的制备方法,包括以下步骤:
(1)按照化学式(1-x)(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-xNaNbO3(x=0.06)将分析纯的Na2CO3、Bi2O3、BaCO3、TiO2和Nb2O5配制后与锆球石及去离子水,按照质量比为1:5:1混合后球磨8h。在80℃下将混合料干燥36个小时,经过研磨后将混合料置于马弗炉中于850℃预烧2小时,预烧制度:以5℃/min升温至850℃,保温2小时,之后,以5℃/min降温至500℃,随炉冷却到室温。得到块状固体;
(2)将块状固体粉碎后,再次与锆球石及去离子水,按照质量比为1:5:1混合后球磨8h。产品过120目筛得到尺寸均匀的0.94(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-0.06NaNbO3粉体;
2、测试用陶瓷试样制备
(3)将得到的0.94(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-0.06NaNbO3粉体,以每份质量0.36g进行称量,然后倒入模具当中,施加600N的力,将成型好的圆片进行脱模,得到形状完好的试样;
(4)将圆片放置于胶套当中,利用抽真空设备将胶套的空气排出,密封胶套口,放入冷等静压成型,在200Mpa的压力下保压300s;
(5)将得到的试样从胶套中取出后于箱式炉中1150℃烧结2小时成瓷,得到0.94(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-0.06NaNbO3电介质陶瓷材料试样;
(6)打磨、清洗步骤(5)中一次烧结好的陶瓷试样后,在陶瓷试样的正反两面均匀涂覆银电极浆料,在550℃进行热处理25min,得到0.94(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-0.06NaNbO3陶瓷材料。
实施例四
1、陶瓷材料制备
该陶瓷材料的化学式为:(1-x)(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-xNaNbO3,其中x表示摩尔百分比,且x=0.1。
上述NaNbO3掺杂的0.6BaTiO3-0.4Bi0.5Na0.5TiO3陶瓷材料的制备方法,包括以下步骤:
(1)按照化学式(1-x)(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-xNaNbO3(x=0.1)将分析纯的Na2CO3、Bi2O3、BaCO3、TiO2和Nb2O5配制后与锆球石及去离子水,按照质量比为1:5:1混合后球磨8h。在80℃下将混合料干燥36个小时,经过研磨后将混合料置于马弗炉中于850℃预烧2小时,预烧制度:以5℃/min升温至850℃,保温2小时,之后,以5℃/min降温至500℃,随炉冷却到室温。得到块状固体;
(2)将块状固体粉碎后,再次与锆球石及去离子水,按照质量比为1:5:1混合后球磨8h。产品过120目筛得到尺寸均匀的0.9(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-0.1NaNbO3粉体;
2、测试用陶瓷试样制备
(3)将得到的0.9(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-0.1NaNbO3粉体,以每份质量0.38g进行称量,然后倒入模具当中,施加600N的力,将成型好的圆片进行脱模,得到形状完好的试样;
(4)将圆片放置于胶套当中,利用抽真空设备将胶套的空气排出,密封胶套口,放入冷等静压成型,在200Mpa的压力下保压300s;
(5)将得到的试样从胶套中取出后于箱式炉中1150℃烧结2小时成瓷,得到0.9(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-0.1NaNbO3电介质陶瓷材料试样;
(6)打磨、清洗步骤(5)中一次烧结好的陶瓷试样后,在陶瓷试样的正反两面均匀涂覆银电极浆料,在550℃进行热处理25min,得到0.9(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-0.1NaNbO3陶瓷材料。
实施例五
1、陶瓷材料制备
该陶瓷材料的化学式为:(1-x)(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-xNaNbO3,其中x表示摩尔百分比,且x=0.15。
上述NaNbO3掺杂的0.6BaTiO3-0.4Bi0.5Na0.5TiO3陶瓷材料的制备方法,包括以下步骤:
(1)按照化学式(1-x)(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-xNaNbO3(x=0.15)将分析纯的Na2CO3、Bi2O3、BaCO3、TiO2和Nb2O5配制后与锆球石及去离子水,按照质量比为1:5:1混合后球磨8h。在80℃下将混合料干燥36个小时,经过研磨后将混合料置于马弗炉中于850℃预烧2小时,预烧制度:以5℃/min升温至850℃,保温2小时,之后,以5℃/min降温至500℃,随炉冷却到室温,得到块状固体;
(2)将块状固体粉碎后,再次与锆球石及去离子水,按照质量比为1:5:1混合后球磨8h。产品过120目筛得到尺寸均匀的0.85(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-0.15NaNbO3粉体;
2、测试用陶瓷试样制备
(3)将得到的0.85(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-0.15NaNbO3粉体,以每份质量0.35g进行称量,然后倒入模具当中,施加600N的力,将成型好的圆片进行脱模,得到形状完好的试样;
(4)将圆片放置于胶套当中,利用抽真空设备将胶套的空气排出,密封胶套口,放入冷等静压成型,在200Mpa的压力下保压300s;
(5)将得到的试样从胶套中取出后于箱式炉中1150℃烧结2小时成瓷,得到0.85(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-0.15NaNbO3电介质陶瓷材料试样;
(6)打磨、清洗步骤(5)中一次烧结好的陶瓷试样后,在陶瓷试样的正反两面均匀涂覆银电极浆料,在550℃进行热处理25min,得到0.85(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-0.15NaNbO3陶瓷材料。
实施例六
1、陶瓷材料制备
该陶瓷材料的化学式为:(1-x)(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-xNaNbO3,其中x表示摩尔百分比,且x=0.2。
上述NaNbO3掺杂的0.6BaTiO3-0.4Bi0.5Na0.5TiO3陶瓷材料的制备方法,包括以下步骤:
(1)按照化学式(1-x)(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-xNaNbO3(x=0.2)将分析纯的Na2CO3、Bi2O3、BaCO3、TiO2和Nb2O5配制后与锆球石及去离子水,按照质量比为1:5:1混合后球磨8h。在80℃下将混合料干燥36个小时,经过研磨后将混合料置于马弗炉中于850℃预烧2小时,预烧制度:以5℃/min升温至850℃,保温2小时,之后,以5℃/min降温至500℃,随炉冷却到室温,得到块状固体;
(2)将块状固体粉碎后,再次与锆球石及去离子水,按照质量比为1:5:1混合后球磨8h。产品过120目筛得到尺寸均匀的0.8(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-0.2NaNbO3粉体;
2、测试用陶瓷试样制备
(3)将得到的0.8(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-0.2NaNbO3粉体,以每份质量0.36g进行称量,然后倒入模具当中,施加600N的力,将成型好的圆片进行脱模,得到形状完好的试样;
(4)将圆片放置于胶套当中,利用抽真空设备将胶套的空气排出,密封胶套口,放入冷等静压成型,在200Mpa的压力下保压300s;
(5)将得到的试样从胶套中取出后于箱式炉中1150℃烧结2小时成瓷,得到0.8(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-0.2NaNbO3电介质陶瓷材料试样;
(6)打磨、清洗步骤(5)中一次烧结好的陶瓷试样后,在陶瓷试样的正反两面均匀涂覆银电极浆料,在550℃进行热处理25min,得到0.8(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-0.2NaNbO3陶瓷材料。
对实施例1至实施例6的测试试样进行测试。
参照图1,图1为以上六个实施例制备试样的XRD曲线,由图1可以看出陶瓷材料(1-x)(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-xNaNbO3(x=0,0.03,0.06,0.10,0.15,0.20)在不同的掺杂量下,均合成了纯相的陶瓷材料。
参照图2及图3,图2中为以上六个实施例制备试样的电滞回线,图3为图2中计算所得参数值。从图2中可以看出,随着NN掺杂量的增加,电滞回线逐渐“细化”,剩余极化显著降低。从图3中可以看出,相比于x=0组分,掺入NN后,击穿场强Eb得到提高,电滞回线细化,陶瓷材料的储能效率明显增加。当x=0.15时,储能密度Wrec为2.2J/cm3,储能效率η为91.7%。
参照图4,图4为以上六个实施例制备试样的温度系数随温度的变化曲线。由图4可以看出x=0.15组分的曲线在-55℃至125℃的温度范围内表现出良好的稳定性,非常接近X7R标准。
Claims (8)
1.一种高储能高效率的NaNbO3掺杂BaTiO3基氧化物陶瓷材料,其特征在于,化学式为(1-x)(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-xNaNbO3,其中0≤x≤0.2,x为摩尔百分比。
2.根据权利要求1所述的陶瓷材料,其特征在于所述各组分由Na2CO3、Bi2O3、BaCO3、TiO2和Nb2O5引入。
3.根据权利要求1至2任一所述的陶瓷材料的制备方法,其特征在于,包括如下步骤:
按照化学式(1-x)(0.6BaTiO3-0.4Bi0.5Na0.5TiO3)-xNaNbO3,其中0≤x≤0.2,x为摩尔百分比;取Na2CO3、Bi2O3、BaCO3、TiO2和Nb2O5配料,预烧后球磨,烘干得到陶瓷材料粉体。
4.根据权利要求3所述的陶瓷材料的制备方法,其特征在于,所述预烧温度850℃~1000℃。
5.根据权利要求4所述的陶瓷材料的制备方法,其特征在于,预烧制度为:以5℃/min升温至预烧温度,保温2小时,之后,以5℃/min降温至500℃,随炉冷却到室温。
6.根据权利要求3所述的陶瓷材料的制备方法,其特征在于,对配料进行球磨后再预烧。
7.根据权利要求1至2任一所述的陶瓷材料在制作陶瓷产品中的应用。
8.根据权利要求7所述的陶瓷材料在制作陶瓷产品中的应用,其特征在于,制作所述陶瓷产品时,烧结温度1150℃。
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CN114163231A (zh) * | 2021-11-29 | 2022-03-11 | 华中科技大学 | 无铅脉冲电介质储能复合陶瓷材料及其制备方法和应用 |
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