CN112341192B - 一种高储能密度钛酸铋钠基无铅介质材料及其制备方法 - Google Patents
一种高储能密度钛酸铋钠基无铅介质材料及其制备方法 Download PDFInfo
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- 238000004146 energy storage Methods 0.000 title claims abstract description 57
- 229910002115 bismuth titanate Inorganic materials 0.000 title claims abstract description 38
- FSAJRXGMUISOIW-UHFFFAOYSA-N bismuth sodium Chemical compound [Na].[Bi] FSAJRXGMUISOIW-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000003989 dielectric material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000919 ceramic Substances 0.000 claims abstract description 64
- 229910010252 TiO3 Inorganic materials 0.000 claims abstract description 25
- 239000011734 sodium Substances 0.000 claims abstract description 25
- 238000000498 ball milling Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000007873 sieving Methods 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 14
- 238000005498 polishing Methods 0.000 claims abstract description 13
- 238000005245 sintering Methods 0.000 claims abstract description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000009694 cold isostatic pressing Methods 0.000 claims abstract description 7
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000007747 plating Methods 0.000 claims abstract description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 7
- 229910052709 silver Inorganic materials 0.000 claims abstract description 7
- 239000004332 silver Substances 0.000 claims abstract description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 7
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910000018 strontium carbonate Inorganic materials 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 39
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 5
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract description 4
- 150000008040 ionic compounds Chemical class 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000010304 firing Methods 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 16
- 230000015556 catabolic process Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 235000012431 wafers Nutrition 0.000 description 6
- 238000003825 pressing Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 239000003985 ceramic capacitor Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
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Abstract
本发明公开了一种高储能密度钛酸铋钠基无铅介质材料,化学式为(0.8‑x)Bi0.5Na0.5TiO3‑xSrTi0.9(Cu1/3Nb2/3)0.1O3‑0.2Bi0.5K0.5TiO3,其中x为xSrTi0.9(Cu1/3Nb2/3)0.1O3离子化合物掺杂量的摩尔百分比,值在0.1~0.3之间。上述材料的制备方法,具体为:以Bi2O3、Na2CO3、TiO2、K2CO3、SrCO3、CuO、Nb2O5为原料,根据化学计量式配料,经球磨、烘干、过筛、冷等静压压制成陶瓷生坯,在马弗炉中烧结成型,得到陶瓷样品,再进行抛光、镀银、烧电极即得。其过程简单、重复性好、成本低廉且对环境友好。
Description
技术领域
本发明属于应用于电子元器件陶瓷材料技术领域,涉及一种高储能密度钛酸铋钠基无铅介质材料,本发明还涉及上述高储能密度钛酸铋钠基无铅介质材料的制备方法。
背景技术
随着电子设备的高度集成化、高性能化及多元化的应用领域,微电子行业毫无疑问已成为当今世界最大的产业之一,因此其对电子器件的小型化、各项性能稳定性的要求越来越高。陶瓷电容器是电子设备使用量最大的电子元器件之一,其因功率密度高、充放电速度快、循环次数多、抗老化能力强且能够适应高温高压等极端环境而符合新时期电子设备的要求,因此其无论是在手机、电脑、汽车,还是在医疗、军工、航空航天等领域,都扮演着越来越重要的角色。
传统钛酸铋钠(BNT)基无铅介质材料无法同时拥有高的介电常数、储能密度和击穿场强,并且介电损耗相对较大,从而限制了其在脉冲、滤波等电子产品中的广泛应用。
发明内容
本发明的目的是提供一种高储能密度钛酸铋钠基无铅介质材料,解决了现有技术中存在的无法同时具备高的介电常数、储能密度和击穿场强,并且介电损耗相对较大的问题。
本发明的另一目的是提供上述高储能密度钛酸铋钠基无铅介质材料的制备方法。
本发明所采用的技术方案是,一种高储能密度钛酸铋钠基无铅介质材料,化学式为:
(0.8-x)Bi0.5Na0.5TiO3-xSrTi0.9(Cu1/3Nb2/3)0.1O3-0.2Bi0.5K0.5TiO3,其中x=0.1~0.3。
本发明所采用的另一种技术方案是,一种高储能密度钛酸铋钠基无铅介质材料的制备方法,具体按照以下步骤实施:
步骤1、计算化学式中金属元素的化学计量比,根据计算结果将分析纯的Bi2O3、Na2CO3、TiO2、K2CO3、SrCO3、CuO、Nb2O5配制成粉体,化学式为(0.8-x)Bi0.5Na0.5TiO3-xSrTi0.9(Cu1/3Nb2/3)0.1O3-0.2Bi0.5K0.5TiO3,其中x=0.1~0.3;
步骤2、将步骤1得到的粉体进行混料球磨、烘干、过筛、预烧得到陶瓷粉体;
步骤3、将步骤2得到的陶瓷粉体经模具初成型后进行冷等静压成型得到陶瓷生坯;
步骤4、将步骤3得到的陶瓷生坯在高温下进行烧结,得到高储能密度的(0.8-x)Bi0.5Na0.5TiO3-xSrTi0.9(Cu1/3Nb2/3)0.1O3-0.2Bi0.5K0.5TiO3陶瓷样品;
步骤5、将步骤4得到的陶瓷样品进行抛光、镀银、烧电极得到高储能密度钛酸铋钠基无铅介质材料。
本发明另一技术方案的特点还在于:
步骤2中预烧以2~4℃/min的升温速率升温至800~880℃,保温2~4h。
步骤2中混料球磨是以氧化锆球和无水乙醇为介质,置于球磨罐中球磨10~15h。
步骤2中烘干温度为80~100℃,时间为24~30h。
步骤2中过筛采用60目筛网。
步骤3中冷等静压的压力为220~280MPa,时间为130~170s。
步骤3得到的陶瓷生坯直径为7mm,厚度为1mm。
步骤4中烧结温度为1170~1200℃,时间为1~3h。
步骤5中,抛光具体为,将步骤4得到的陶瓷样品经自动精密研磨机抛光至0.1mm;烧电极的温度为800~850℃,时间为10~15min。
本发明的有益效果是:
1、本发明所制备的高储能密度钛酸铋钠基无铅介质材料具有良好的储能性能。向Bi0.5Na0.5TiO3-Bi0.5K0.5TiO3中加入SrTi0.9(Cu1/3Nb2/3)0.1O3,形成(0.8-x)Bi0.5Na0.5TiO3-xSrTi0.9(Cu1/3Nb2/3)0.1O3-0.2Bi0.5K0.5TiO3的固溶体,利用[Cu1/3Nb2/3]4+离子替换了BNT-ST-BKT中部分Ti4+离子,使得所制陶瓷材料在100Hz下,具有较高的介电常数3335~3584和极低的介电损耗(≤0.037),在160~220kV/cm击穿场强下,还具有高的储能密度1.76~2.04J/cm3;
2、本发明所用原料中不含重金属等污染性元素,对环境友好,且制备工艺简单,重复性与可操作性高,成本低廉;所有的烧结温度均在1200度以下,有利于节能减排。
附图说明
图1是本发明实施例1得到的高储能密度钛酸铋钠基无铅介质材料的介电温谱曲线;
图2是本发明实施例1得到的高储能密度钛酸铋钠基无铅介质材料的单轴极化强度随电场强度变化曲线;
图3是本发明实施例2得到的高储能密度钛酸铋钠基无铅介质材料的介电温谱曲线;
图4是本发明实施例2得到的高储能密度钛酸铋钠基无铅介质材料的单轴极化强度随电场强度变化曲线;
图5是本发明实施例3得到的高储能密度钛酸铋钠基无铅介质材料的介电温谱曲线;
图6是本发明实施例3得到的高储能密度钛酸铋钠基无铅介质材料的单轴极化强度随电场强度变化曲线。
具体实施方式
下面结合附图和具体实施方式对本发明进行详细说明。
本发明一种高储能密度钛酸铋钠(BNT)基无铅介质材料,化学式为(0.8-x)Bi0.5Na0.5TiO3-xSrTi0.9(Cu1/3Nb2/3)0.1O3-0.2Bi0.5K0.5TiO3,其中x为xSrTi0.9(Cu1/3Nb2/3)0.1O3离子化合物掺杂量的摩尔百分比,值为0.1~0.3。
一种高储能密度钛酸铋钠基无铅介质材料的制备方法,具体按照以下步骤实施:
步骤1、计算化学式中金属元素的化学计量比,根据计算结果将分析纯的Bi2O3、Na2CO3、TiO2、K2CO3、SrCO3、CuO、Nb2O5配制成粉体,化学式为(0.8-x)Bi0.5Na0.5TiO3-xSrTi0.9(Cu1/3Nb2/3)0.1O3-0.2Bi0.5K0.5TiO3,其中x=0.1~0.3;
步骤2、将步骤1得到的粉体进行混料球磨、烘干、过筛、预烧得到陶瓷粉体;
步骤3、将步骤2得到的陶瓷粉体经模具初成型后进行冷等静压成型得到陶瓷生坯;
步骤4、将步骤3得到的陶瓷生坯在高温下进行烧结,得到高储能密度的(0.8-x)Bi0.5Na0.5TiO3-xSrTi0.9(Cu1/3Nb2/3)0.1O3-0.2Bi0.5K0.5TiO3陶瓷样品;
步骤5、将步骤4得到的陶瓷样品进行抛光、镀银、烧电极得到高储能密度钛酸铋钠基无铅介质材料;
步骤2中预烧以2~4℃/min的升温速率升温至800~880℃,保温2~4h;
步骤2中混料球磨是以氧化锆球和无水乙醇为介质,置于球磨罐中球磨10~15h;
步骤2中烘干温度为80~100℃,时间为24~30h;
步骤2中过筛采用60目筛网;
步骤3中冷等静压的压力为220~280MPa,时间为130~170s;
步骤3得到的陶瓷生坯直径为7mm,厚度为1mm;
步骤4中烧结温度为1170~1200℃,时间为1~3h;
步骤5中,抛光具体为,将步骤4得到的陶瓷样品经自动精密研磨机抛光至0.1mm;烧电极的温度为800~850℃,时间为10~15min。
通过上述方法制备的高储能密度钛酸铋钠基无铅介质材料在160~220kV/cm击穿场强下,储能密度在1.76~2.04J/cm3范围内,在100Hz下,介电常数在3335~3584之间,介电损耗均≤0.037。
实施例1
一种高储能密度钛酸铋钠基无铅介质材料,其化学组成表达式为(0.8-x)Bi0.5Na0.5TiO3-xSrTi0.9(Cu1/3Nb2/3)0.1O3-0.2Bi0.5K0.5TiO3,其中x表示摩尔百分比,且x=0.1,其具体制备步骤如下:
(1)根据0.7Bi0.5Na0.5TiO3-0.1SrTi0.9(Cu1/3Nb2/3)0.1O3-0.2Bi0.5K0.5TiO3的化学组成表达进行计算,再将分析纯的Bi2O3、Na2CO3、TiO2、K2CO3、SrCO3、CuO、Nb2O5按照计算结果配制成粉体;
(2)将配制的粉体放入球磨罐中,以氧化锆球和无水乙醇为介质,在行星球磨机上球磨,时间为15h;随后在90℃下烘干24h后过60目筛,过完筛后将粉体放入氧化铝坩埚中在空气气氛中预烧,预烧是以3°/min的升温速率从室温升温至800℃,保温2h,后随炉冷却,即得到0.7Bi0.5Na0.5TiO3-0.1SrTi0.9(Cu1/3Nb2/3)0.1O3-0.2Bi0.5K0.5TiO3粉体;
(3)然后对得到的粉体进行二次球磨,时间为9h,随后在90℃下烘干24h后过60目筛,取过筛后均匀的粉体颗粒于模具中干压,压制成直径7mm、厚度1mm的陶瓷圆片,再将陶瓷圆片置于冷等静压机中以250MPa的压力,保压150s,得到初成型的陶瓷生坯;
(4)将所得陶瓷生坯在空气气氛的马弗炉中以4℃/min的升温速率升温至1190℃,并保温3h,后随炉自然冷却,最终得到高储能密度的0.7Bi0.5Na0.5TiO3-0.1SrTi0.9(Cu1/ 3Nb2/3)0.1O3-0.2Bi0.5K0.5TiO3陶瓷样品;
(5)将所得陶瓷样品打磨厚度至0.1mm,清洗烘干后在其两面均匀镀银导电层,随后在马弗炉中以4℃/min的升温速率升温至850℃,保温15min,得到测试样品。
结合图1,图1所示为本实施例制备样品当x=0.1时的介电温谱和介电损耗曲线。由图1可以看出该陶瓷样品在1Hz、100Hz、1000Hz、10kHz和1MHz频率下,温度范围80~380℃时,均具有较高的介电常数(3344≤εr≤4651)和极低的介电损耗(≤0.037)。
结合图2,图2所示为本实施例制备样品当x=0.1时的单轴电滞回线。由图2可以看出该陶瓷样品在室温25℃和1Hz频率下,场强在160kV/cm(击穿场强)时,具有较为纤细的饱和电滞回线(虚线部分表示储能密度)。经计算可得储能密度为1.76J/cm3,储能效率为70%。
实施例2
一种高储能密度钛酸铋钠基无铅介质材料,其化学组成表达式为(0.8-x)Bi0.5Na0.5TiO3-xSrTi0.9(Cu1/3Nb2/3)0.1O3-0.2Bi0.5K0.5TiO3,其中x表示摩尔百分比,且x=0.2。其具体制备步骤如下:
(1)根据0.6Bi0.5Na0.5TiO3-0.2SrTi0.9(Cu1/3Nb2/3)0.1O3-0.2Bi0.5K0.5TiO3的化学组成表达进行计算,再将分析纯的Bi2O3、Na2CO3、TiO2、K2CO3、SrCO3、CuO、Nb2O5按照计算结果配制成粉体;
(2)将配制的粉体放入球磨罐中,以氧化锆球和无水乙醇为介质,在行星球磨机上球磨,时间为15h;随后在90℃下烘干24h后过60目筛,过完筛后将粉体放入氧化铝坩埚中在空气气氛中预烧,预烧是以3°/min的升温速率从室温升温至800℃,保温2h,后随炉冷却,即得到0.6Bi0.5Na0.5TiO3-0.2SrTi0.9(Cu1/3Nb2/3)0.1O3-0.2Bi0.5K0.5TiO3粉体;
(3)然后对得到的粉体进行二次球磨,时间为9h,随后在90℃下烘干24h后过60目筛。取过筛后均匀的粉体颗粒于模具中干压,压制成直径7mm、厚度1mm的陶瓷圆片,再将陶瓷圆片置于冷等静压机中以250MPa的压力,保压150s,得到初成型的陶瓷生坯;
(4)将所得陶瓷生坯在空气气氛的马弗炉中以4℃/min的升温速率升温至1190℃,并保温3h,后随炉自然冷却,最终得到高储能密度的0.6Bi0.5Na0.5TiO3-0.2SrTi0.9(Cu1/ 3Nb2/3)0.1O3-0.2Bi0.5K0.5TiO3陶瓷样品;
(5)将所得陶瓷样品打磨厚度至0.1mm,清洗烘干后在其两面均匀镀银导电层,随后在马弗炉中以4℃/min的升温速率升温至850℃,保温15min,得到测试样品。
结合图3,图3所示为本实施例制备样品当x=0.2时的介电温谱和介电损耗曲线。由图3可以看出该陶瓷样品在1Hz、100Hz、1000Hz、10kHz和1MHz频率下,温度范围68~243℃时,均具有较高的介电常数(3584≤εr≤3840)和极低的介电损耗(≤0.012)。
结合图4,图4所示为本实施例制备样品当x=0.2时的单轴电滞回线。由图4可以看出该陶瓷样品在室温25℃和1Hz频率下,场强在220kV/cm(击穿场强)时,具有较为纤细的饱和电滞回线(虚线部分表示储能密度)。经计算可得储能密度为2.04J/cm3,储能效率为76%。
实施例3
一种高储能密度钛酸铋钠基无铅介质材料,其化学组成表达式为(0.8-x)Bi0.5Na0.5TiO3-xSrTi0.9(Cu1/3Nb2/3)0.1O3-0.2Bi0.5K0.5TiO3,其中x表示摩尔百分比,且x=0.3。其具体制备步骤如下:
(1)根据0.5Bi0.5Na0.5TiO3-0.3SrTi0.9(Cu1/3Nb2/3)0.1O3-0.2Bi0.5K0.5TiO3的化学组成表达进行计算,再将分析纯的Bi2O3、Na2CO3、TiO2、K2CO3、SrCO3、CuO、Nb2O5按照计算结果配制成粉体;
(2)将配制的粉体放入球磨罐中,以氧化锆球和无水乙醇为介质,在行星球磨机上球磨,时间为15h;随后在90℃下烘干24h后过60目筛,过完筛后将粉体放入氧化铝坩埚中在空气气氛中预烧,预烧是以3℃/min的升温速率从室温升温至800℃,保温2h,后随炉冷却,即得到0.5Bi0.5Na0.5TiO3-0.3SrTi0.9(Cu1/3Nb2/3)0.1O3-0.2Bi0.5K0.5TiO3粉体;
(3)然后对得到的粉体进行二次球磨,时间为9h,随后在90℃下烘干24h后过60目筛,取过筛后均匀的粉体颗粒于模具中干压,压制成直径7mm、厚度1mm的陶瓷圆片,再将陶瓷圆片置于冷等静压机中以250MPa的压力,保压150s,得到初成型的陶瓷生坯;
(4)将所得陶瓷生坯在空气气氛的马弗炉中以4℃/min的升温速率升温至1190℃,并保温3h,后随炉自然冷却,最终得到高储能密度的0.5Bi0.5Na0.5TiO3-0.3SrTi0.9(Cu1/ 3Nb2/3)0.1O3-0.2Bi0.5K0.5TiO3陶瓷样品;
(5)将所得陶瓷样品打磨厚度至0.1mm,清洗烘干后在其两面均匀镀银导电层,随后在马弗炉中以4℃/min的升温速率升温至850℃,保温15min,得到测试样品。
结合图5,图5所示为本实施例制备样品当x=0.3时的介电温谱和介电损耗曲线。由图5可以看出该陶瓷样品在1Hz、100Hz、1000Hz、10kHz和1MHz频率下,温度范围77~320℃时,均具有较高的介电常数(3335≤εr≤3780)和极低的介电损耗(≤0.027)。
结合图6,图6所示为本实施例制备样品当x=0.3时的单轴电滞回线。由图6可以看出该陶瓷样品在室温25℃和1Hz频率下,场强在210kV/cm(击穿场强)时,具有较为纤细的饱和电滞回线(虚线部分表示储能密度)。经计算可得储能密度为1.82J/cm3,储能效率为72%。
表1中所示为各实施例所制备的高储能密度钛酸铋钠基无铅陶瓷介质材料在频率为100Hz下的介电性能和频率为1Hz,室温25℃下的储能性能一览表。
表1
综合以上实施例所述可知,本发明一种高储能密度钛酸铋钠基无铅介质材料(0.8-x)Bi0.5Na0.5TiO3-xSrTi0.9(Cu1/3Nb2/3)0.1O3-0.2Bi0.5K0.5TiO3(x=0.1~0.3),很好的解决了目前复合钛酸铋钠基无铅陶瓷介质材料高介电常数与高储能密度无法共存的问题,使得在拥有较高介电常数和储能密度的同时,还具有极低的介电损耗。并且制备工艺简单,操作性强、成本低廉,有利于大规模生产。
Claims (7)
1.一种高储能密度钛酸铋钠基无铅介质材料,其特征在于,化学式为(0.8-x)Bi0.5Na0.5TiO3-xSrTi0.9(Cu1/3Nb2/3)0.1O3-0.2Bi0.5K0.5TiO3,其中x=0.1~0.3。
2.一种高储能密度钛酸铋钠基无铅介质材料的制备方法,其特征在于,具体按照以下步骤实施:
步骤1、计算化学式中金属元素的化学计量比,根据计算结果将分析纯的Bi2O3、Na2CO3、TiO2、K2CO3、SrCO3、CuO、Nb2O5配制成粉体,化学式为(0.8-x)Bi0.5Na0.5TiO3-xSrTi0.9(Cu1/ 3Nb2/3)0.1O3-0.2Bi0.5K0.5TiO3,其中x=0.1~0.3;
步骤2、将步骤1得到的粉体进行混料球磨、烘干、过筛、预烧得到陶瓷粉体;
步骤3、将步骤2得到的陶瓷粉体经模具初成型后进行冷等静压成型得到陶瓷生坯;
冷等静压的压力为220~280MPa,时间为130~170s;
步骤4、将步骤3得到的陶瓷生坯在高温下进行烧结,得到高储能密度的(0.8-x)Bi0.5Na0.5TiO3-xSrTi0.9(Cu1/3Nb2/3)0.1O3-0.2Bi0.5K0.5TiO3陶瓷样品;
烧结温度为1170~1200℃,时间为1~3h;
步骤5、将步骤4得到的陶瓷样品进行抛光、镀银、烧电极得到高储能密度钛酸铋钠基无铅介质材料;
抛光具体为,将步骤4得到的陶瓷样品经自动精密研磨机抛光至0.1mm;烧电极的温度为800~850℃,时间为10~15min。
3.根据权利要求2所述的一种高储能密度钛酸铋钠基无铅介质材料的制备方法,其特征在于,所述步骤2中预烧以2~4℃/min的升温速率升温至800~880℃,保温2~4h。
4.根据权利要求2所述的一种高储能密度钛酸铋钠基无铅介质材料的制备方法,其特征在于,所述步骤2中混料球磨是以氧化锆球和无水乙醇为介质,置于球磨罐中球磨10~15h。
5.根据权利要求2所述的一种高储能密度钛酸铋钠基无铅介质材料的制备方法,其特征在于,所述步骤2中烘干温度为80~100℃,时间为24~30h。
6.根据权利要求2所述的一种高储能密度钛酸铋钠基无铅介质材料的制备方法,其特征在于,所述步骤2中过筛采用60目筛网。
7.根据权利要求2所述的一种高储能密度钛酸铋钠基无铅介质材料的制备方法,其特征在于,所述步骤3得到的陶瓷生坯直径为7mm,厚度为1mm。
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1419246A (zh) * | 2001-11-12 | 2003-05-21 | 日本特殊陶业株式会社 | 介电陶瓷组合物 |
KR20090088991A (ko) * | 2008-02-18 | 2009-08-21 | 창원대학교 산학협력단 | 비스무스(Bi)계통의 무연 세라믹스의 조성물 및 그제조방법 |
CN103896587A (zh) * | 2012-12-26 | 2014-07-02 | 三星电机株式会社 | 介电组合物、及包括其作为介电层的多层陶瓷电容器 |
CN104628379A (zh) * | 2013-11-06 | 2015-05-20 | 同济大学 | 高度取向的无铅压电织构陶瓷材料及其制备方法和应用 |
CN107056281A (zh) * | 2016-12-19 | 2017-08-18 | 西安科技大学 | 一种高应变钛酸铋钠基陶瓷及其制备方法 |
CN108191428A (zh) * | 2018-02-02 | 2018-06-22 | 天津大学 | 一种制备SrTiO3基巨介电常数介质陶瓷材料的方法 |
CN110312692A (zh) * | 2017-02-03 | 2019-10-08 | 赛尔科技有限公司 | 包含赝立方相的陶瓷材料、其制备方法和用途 |
CN111792931A (zh) * | 2020-07-14 | 2020-10-20 | 广东华中科技大学工业技术研究院 | 一种复合陶瓷材料及其制备方法 |
-
2020
- 2020-11-20 CN CN202011308873.0A patent/CN112341192B/zh active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1419246A (zh) * | 2001-11-12 | 2003-05-21 | 日本特殊陶业株式会社 | 介电陶瓷组合物 |
KR20090088991A (ko) * | 2008-02-18 | 2009-08-21 | 창원대학교 산학협력단 | 비스무스(Bi)계통의 무연 세라믹스의 조성물 및 그제조방법 |
CN103896587A (zh) * | 2012-12-26 | 2014-07-02 | 三星电机株式会社 | 介电组合物、及包括其作为介电层的多层陶瓷电容器 |
CN104628379A (zh) * | 2013-11-06 | 2015-05-20 | 同济大学 | 高度取向的无铅压电织构陶瓷材料及其制备方法和应用 |
CN107056281A (zh) * | 2016-12-19 | 2017-08-18 | 西安科技大学 | 一种高应变钛酸铋钠基陶瓷及其制备方法 |
CN110312692A (zh) * | 2017-02-03 | 2019-10-08 | 赛尔科技有限公司 | 包含赝立方相的陶瓷材料、其制备方法和用途 |
CN108191428A (zh) * | 2018-02-02 | 2018-06-22 | 天津大学 | 一种制备SrTiO3基巨介电常数介质陶瓷材料的方法 |
CN111792931A (zh) * | 2020-07-14 | 2020-10-20 | 广东华中科技大学工业技术研究院 | 一种复合陶瓷材料及其制备方法 |
Non-Patent Citations (2)
Title |
---|
Dielectric relaxations in fine-grained SrTiO3 ceramics with Cu and Nb codoping;Junwei Liu et al.;《Ceramics International》;20190214;第45卷(第8期);10334-10341页 * |
Effect of SrTiO3 template on electric properties of textured BNT–BKT ceramics prepared by templated grain growth process;Wangfeng Bai et al.;《Journal of Alloys and Compounds》;20140320;第603卷;149-157页 * |
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