CN110436920A - 一种钛酸铋钠-钽酸钠固溶陶瓷材料及其制备方法和应用 - Google Patents
一种钛酸铋钠-钽酸钠固溶陶瓷材料及其制备方法和应用 Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 54
- 239000011734 sodium Substances 0.000 title claims abstract description 41
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 32
- FSAJRXGMUISOIW-UHFFFAOYSA-N bismuth sodium Chemical compound [Na].[Bi] FSAJRXGMUISOIW-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000004146 energy storage Methods 0.000 claims abstract description 58
- 239000000919 ceramic Substances 0.000 claims abstract description 47
- 239000003990 capacitor Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000000498 ball milling Methods 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 25
- 238000005245 sintering Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000000748 compression moulding Methods 0.000 claims description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 3
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- -1 special Sign is Inorganic materials 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims 1
- 239000004615 ingredient Substances 0.000 claims 1
- 238000007670 refining Methods 0.000 claims 1
- 230000005684 electric field Effects 0.000 abstract description 14
- 238000012360 testing method Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 238000001228 spectrum Methods 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 230000007547 defect Effects 0.000 description 7
- 230000010287 polarization Effects 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229910010252 TiO3 Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005621 ferroelectricity Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910003256 NaTaO3 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- HKMBRYJOLZAEJV-UHFFFAOYSA-N [Na].[Bi].[Na] Chemical compound [Na].[Bi].[Na] HKMBRYJOLZAEJV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
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- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
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Abstract
本发明公开了一种宽温度稳定性的钛酸铋钠‑钽酸钠固溶陶瓷材料,其化学通式为(1‑x)Bi0.5Na0.5TiO3‑xNaTaO3,x=0.10~0.30。本发明还公开了所述的陶瓷材料的制备和在介电电容器中的应用。研究发现,该陶瓷材料在38kV/mm的外加电场下可以实现放电能量密度高达4.21J/cm3,储能密度高达5.41J/cm3,储能效率高达77.8%;此外,其介电和储能性能的温度稳定性也十分优异:在‑50℃~350℃的温度范围内,介电常数浮动低于10%;在‑50℃~300℃的温度范围内,放电能量密度浮动低于10%。本发明所述陶瓷十分适于高电场和高低温介电储能电容器应用。
Description
技术领域
本发明涉及一种宽温度稳定性的钛酸铋钠-钽酸钠固溶陶瓷材料及其制备方 法和应用,属于无铅铁电陶瓷技术领域。
背景技术
为满足电力系统和电子设备日益增长的需求,近年来高功率储能材料受到了 广泛关注。在众多能量存储装置中,与电池和超级电容器相比,介电电容器具有 高功率密度,快速充放电速率和优异耐久性的明显优点,特别适用于武器,混合 动力电动车辆和电力电子设备等。然而其较低的储能密度,远远不能满足人们对 储能器件小型化、集成化的要求。近年来,介电陶瓷储能电容器的研究受到广泛 关注,主要工作方向包括提升其储能密度和增强性能稳定性。特别的,储能性能 的高低温稳定性对保证介电陶瓷储能电容器在各种复杂环境下稳定工作至关重 要,典型的应用领域如汽车发动机、飞行记录器、火箭喷射器和行星探测器等。 因此亟需开发出具有高储能密度以及优异高低温稳定性的介电陶瓷材料。介电陶 瓷的储能密度可通过其电滞回线计算得出:其中E为施加电场 强度,Pmax为饱和极化强度,Pr为剩余极化强度。高E,高Pmax和低Pr有利于实 现高储能密度,同时电滞回线的温度稳定性则决定了介电陶瓷储能密度的温度稳 定性。钛酸铋钠(Bi0.5Na0.5TiO3,BNT)是一类A位复合取代的无铅钙钛矿结构弛 豫铁电体。BNT基陶瓷具有较高的Pmax和居里温度,在获得高储能密度和优异 温度稳定性方面具有很大潜力,然而纯BNT的Pr高,储能密度低,且电滞回线 的温度稳定性差导致储能密度的温度稳定性也较差。为解决该不足,目前通常通 过掺杂或固溶改性等手段调控BNT基陶瓷相结构,在室温下获得各态历经弛豫 相,降低Pr以提升其储能密度,同时,实现随温度变化的弥散相变,提升介电 和储能密度温度稳定性。然而目前大多数BNT基陶瓷的储能密度仍低于4J/cm3, 且温度稳定范围局限于室温-200℃区间,因此亟需进一步提高BNT基陶瓷的储 能密度,拓宽温度稳定范围。
发明内容
针对现有技术的不足,本发明的第一个目的在于提供一种具有高储能密度与 效率、优异介电和储能性能温度稳定性的钛酸铋钠-钽酸钠固溶陶瓷材料(本发 明也简称为陶瓷材料)。
本发明的第二个目的在于提供上述钛酸铋钠-钽酸钠固溶陶瓷材料的制备方 法。
本发明的第三个目的在于提供上述钛酸铋钠-钽酸钠固溶陶瓷材料的应用。
本发明的技术方案为:
本发明一种钛酸铋钠-钽酸钠固溶陶瓷材料,其化学通式为 (1-x)Bi0.5Na0.5TiO3-xNaTaO3,x=0.10~0.30。
本发明提供了一种具有高的储能密度和效率,优异介电和储能性能、以及超 宽温度范围稳定性的陶瓷材料。
本发明所述的陶瓷材料,为Bi0.5Na0.5TiO3与NaTaO3固溶的陶瓷材料。本发 明人通过研究意外发现,所述的x对该陶瓷材料的储能密度以及介电和储能性能 温度稳定性具有重要影响。控制在本发明所要求的范围下,能够出人意料地表现 出优异的性能。研究发现,低于所述的下限,会导致Pr偏大,而含量过高会导 致Pmax过于降低;未控制在所要求的x范围下,均会影响陶瓷材料的储能密度以 及介电和储能性能的温度稳定性。
作为优选,x=0.20。优选的酸铋钠-钽酸钠固溶陶瓷材料,化学式为0.80Bi0.5Na0.5TiO3-0.20NaTaO3。研究发现,控制在该比例下,储能密度最高,且 介电和储能性能的温度稳定性更优。
作为优选,所述钛酸铋钠-钽酸钠固溶陶瓷材料为伪立方相结构。不存在三 方或四方的晶格畸变,呈现伪立方相结构,晶粒为2~4μm。陶瓷中存在纳米畴和 极化纳米微区结构,为各态历经弛豫态,所得电滞回线瘦长,实现了高储能密度 与效率;同时陶瓷表现出随温度变化的弥散相变,介电常数和储能密度的温度稳 定性十分优异。
本发明还提供了一种钛酸铋钠基陶瓷材料的制备方法,包括下述步骤:
根据(1-x)Bi0.5Na0.5TiO3-xNaTaO3的化学计量比配取钠源、铋源、钽源、钛源, 获得混合物,将混合物进行第一次球磨获得混匀料A,混匀料A进行预烧获得 预烧粉;
预烧粉进行第二次球磨,获得混匀料B,将混匀料B造粒,压制成型获得生 坯,生坯经排胶、烧结后即获得所述的钛酸铋钠-钽酸钠固溶陶瓷材料;所述的 烧结温度为1150~1180℃。
本发明制备方法的关键在于控制制得的材料的晶态、形貌、晶粒纯度以及致 密性。通过研究发现,根据所述的化学式配比、配合所述的烧结温度的精准控制, 可以获得晶态形貌好、晶粒纯度高的材料。研究发现,该制备方法制得的材料具 有高的储能密度以及优异的介电和储能性能温度稳定性。
在本发明方案中,烧结温度对材料的形态以及介电性能有重要影响,烧结温 度过低会导致陶瓷烧结不完全,不能形成致密的陶瓷块体;烧结温度过高会导致 陶瓷晶粒异常长大,陶瓷过烧。欠烧和过烧都会使陶瓷中出现大量缺陷,易击穿。 当然烧结温度与材料的成份也是直接相关的,成份含量变化,必然带来烧结温度 的变化,共同都会影响最终的烧成材料的晶粒与形貌,从而影响到性能。
作为优选,所述的钠源为钠的碳酸盐、碳酸氢盐、硝酸盐中的至少一种;优 选为碳酸钠。
作为优选,所述的铋源为铋的氧化物;进一步优选为Bi2O3。
作为优选,所述的钽源为钽的氧化物;进一步优选为Ta2O5。
作为优选,所述的钛源为钛的氧化物;进一步优选为TiO2。
第一次球磨方式优选为湿法球磨,球磨设备采用现有技术常规设备即可,球 磨介质优选为无水乙醇,磨球优选为氧化锆球,在尼龙罐中球磨。
优选的方案,第一次球磨的转速为200-300rpm,球磨时间为6-10h。
优选的方案,第一次球磨后所得浆料,于75-85℃烘干,然后过200目筛, 取筛下物,获得混匀料A。
优选的方案,将混匀料A在空气气氛下进行预烧。
优选的方案,所述预烧温度为750-850℃,预烧时间为2-4h。
本发明中,对预烧粉进行第二次球磨,所述的第二次球磨方式优选为湿法球 磨,球磨设备采用现有技术常规设备即可,球磨介质优选为无水乙醇,磨球优选 为氧化锆球,在尼龙罐中球磨。
第二次球磨转速会一定程度影响后续的造粒工艺。优选的方案,第二次球磨 的转速为200-300rpm,球磨时间为18-24h。
优选的方案,第二次球磨后所得浆料,于75-85℃烘干,然后过200目筛, 取筛下物,获得混匀料B。
优选的方案,将混匀料B造粒工艺为:在混匀料B中加入粘结剂后通过研 磨混匀料呈粒状。
所述的粘结剂可以采用造粒行业内所熟知的具有粘结性的物质;优选为聚乙 烯醇缩丁醛。
优选的方案,所述粘结剂的加入量为总混合物质量的0.8-1.2%。
优选的方案,所述压制成型的所用压强为20-30Mpa,保压时间为3-8min, 所得生坯的尺寸为8-12mm,厚度为1.0-1.4mm。
将压制的生坯进行排胶、烧结处理,处理过程的气氛为空气气氛。
作为优选,排胶过程的温度为550-650℃,时间为2-4h。
本发明研究发现,精准控制所述的烧结温度,能够获得纯度高、致密度高、 缺陷少的陶瓷材料。
作为优选,烧结的温度为1155-1165℃;进一步优选为1160℃。
作为优选,烧结的时间为2-4h。
作为优选,所述生坯排胶烧结的程序为,先以1-3℃/min的速率升温至 550-650℃保温2-4h排胶,然后以4-6℃/min的速率升温至1150-1180℃保温2-4h 烧结。
本发明还提供了一种钛酸铋钠-钽酸钠固溶陶瓷材料应用,将所述钛酸铋钠- 钽酸钠固溶陶瓷材料用于制备介电储能电容器。
可采用现有方法将本发明所述的钛酸铋钠-钽酸钠固溶陶瓷材料制备成介电 储能电容器。
本发明的有益效果:
1、本发明提供了一种具有高储能密度,优异介电和储能性能温度稳定性的 的陶瓷材料。
2、本发明研究发现,控制所述的陶瓷材料的x的含量,可以获得各项性能 优异的陶瓷材料,例如,本发明得到的0.80BNT-0.20NT陶瓷材料缺陷少、致密 度高、结晶性好、晶粒尺寸均匀且平均晶粒尺寸约为2~4μm;且该陶瓷材料具有 高的介电弛豫性和抗击穿电场,可以获得瘦长的电滞回线;此外,该陶瓷材料还 具有优异的储能特性,在38kV/mm的外加电场下,放电能量密度达到4.21J/cm3, 储能密度为5.41J/cm3,储能效率达到77.8%。不仅如此,该陶瓷材料还具有具有 优异的温度稳定性,其在-50℃~350℃的超宽温度范围内,介电常数浮动低于 10%。本发明得到的0.80BNT-0.20NT陶瓷材料储能性能具有优异的温度稳定性, 在-50℃~300℃的温度范围内,放电能量密度浮动低于10%。
3、本发明提供了一种通过化学式控制和烧结温度协同控制制得所述陶瓷材 料的方法。研究发现,该制备方法可以制得缺陷少、致密度高、结晶性好、晶粒 尺寸均匀,具有高储能密度,优异介电和储能性能温度稳定性的陶瓷材料。
4、本发明还创新地提供了一种所述的陶瓷材料在介电电容器中的应用。研 究发现,本发明所述的陶瓷材料具有高的储能密度,优异的介电和储能性能温度 稳定性,其在高电场和高低温介电储能电容器中具有较大的应用前景。
附图说明
图1为实施例1中制备的0.80BNT-0.20NT陶瓷的X-射线衍射图谱和扫描电 子显微镜图。
图2为实施例1中制备的0.80BNT-0.20NT陶瓷的低倍透射电子显微镜图。
图3为实施例1中制备的0.80BNT-0.20NT陶瓷的介电性能测试图,其中图 3(a)为介电温谱,图3(b)为利用介电温谱所做Δεr/εr25℃vs.T图谱。
图4为实施例1中制备的0.80BNT-0.20NT陶瓷的室温铁电电滞回线,和计 算得出的放电能量密度、储能密度和效率。
图5为实施例1中制备的0.80BNT-0.20NT陶瓷的变温铁电电滞回线,以及 放电能量密度和效率随温度变化曲线。
具体实施方式
实施例1
0.80BNT-0.20NT陶瓷材料的制备
按照0.80Bi0.5Na0.5TiO3-0.20NaTaO3(0.80BNT-0.20NT)的摩尔化学计量比 称取原料Bi2O3,Na2CO3,Ta2O5和TiO2混合均匀,将配好的料放入以无水乙醇 为介质、氧化锆球为磨球的尼龙罐中球磨,在250r/min的转速下球磨8h。再将 球磨后的浆料于80℃烘干。烘干后的粉料过200目筛后置于氧化铝坩埚中,在 800℃下预烧3h,得到预烧粉。将预烧粉放入以无水乙醇为介质、氧化锆球为磨 球的尼龙罐中球磨,在250r/min的转速下球磨24h,再于80℃烘干。将上述粉 末过筛后,加入质量分数为1%的聚乙烯醇缩丁醛(PVA),充分研磨至粉料呈粒 状,得到颗粒均匀的粉料,并在20Mpa的压强下保压5min压制成直径为10mm, 厚度为1.2mm左右的圆柱生坯。将上述生坯置于氧化铝坩埚中,利用同等组分 的预烧粉埋烧,首先以2℃/min的升温速率至600℃保温2h排胶,然后以5℃/min 的升温速率至1160℃保温2h烧结,随炉自然冷却,制得0.80BNT-0.20NT陶瓷 材料。
对0.80BNT-0.20NT陶瓷材料进行晶相检测,检测手段为X-射线衍射分析 (XRD)。如图1(a)所示,可以看出制备的陶瓷材料为纯钙钛矿结构,没有杂质相 存在,且XRD结果中不存在三方或四方的晶格畸变,呈现伪立方相结构。利用 阿基米德排水法测试陶瓷致密度,发现其相对密度高达98%。
将所得0.80BNT-0.20NT陶瓷材料进行扫描电子显微镜(SEM)检测,测试之 前陶瓷被研磨至厚度为0.3mm,且经过抛光和热腐蚀处理。从图1(b)中可以看出, 制备的陶瓷没有明显的缺陷、结晶性好、晶粒尺寸均匀且平均晶粒尺寸约为 2~4μm。
将所得0.80BNT-0.20NT陶瓷材料进行透射电子显微镜(TEM)检测,测试之 前陶瓷被研磨至厚度~70μm,再经过离子减薄得到供TEM测试所用薄区。从图 2可以看出,陶瓷中存在纳米畴和极化纳米微区。
0.80BNT-0.20NT陶瓷的电性能测试和储能特性表征
将烧结好的陶瓷片打磨至厚度为0.3mm,在两面涂覆中温银浆,在550℃下 保温30min烧成银电极。上述被银后的陶瓷片被用于介电温谱和铁电电滞回线测 试。介电温谱测试采用高温阻抗分析仪,测试陶瓷片介电常数εr和介电损耗tanδ 随着温度T和频率f的变化曲线,本测试中测试温度区间为-100~500℃,测试频 率包括1kHz、10kHz、100kHz和1MHz。然后利用测得的介电温谱计算出各个 频率下Δεr/εr25℃((某一温度点的介电常数-25℃时的介电常数)/25℃时的介电常数) 随温度的变化,评估陶瓷介电常数的温度稳定性。
电滞回线测试采用铁电分析仪,测试陶瓷片饱和极化强度Pmax,剩余极化强 度Pr和抗击穿电场等性能参数,然后利用公式:
计算出储能密度WS、放电能量密度WD和储能效率η(η=WD/WS),本测试中 测试频率为10Hz,测试电场从1kV/mm逐渐增加直至样品被击穿。对陶瓷片电 滞回线的变温测试,表征其储能特性的温度稳定性,测试温度范围是-50~300℃。 获得其WD和η随测试次数的变化关系。
图3(a)为获得的0.80BNT-0.20NT陶瓷的介电温谱,表现出明显的介电峰宽 化和频率色散现象,证明了陶瓷中存在随温度的弥散相变;(b)为利用介电温谱 所作Δεr/εr25℃vs.T图谱,从介电温谱分析结果可以看出此陶瓷具有显著的弛豫特 性和温度稳定性,在-50℃~350℃的温度范围内,介电常数浮动低于10%。
图4为获得的0.80BNT-0.20NT陶瓷的室温铁电电滞回线,可以看出电滞回 线瘦长,外加电场达38kV/mm,计算得出的储能密度Ws达5.41J/cm3,放电能量 密度WD为4.21J/cm3,储能效率η为77.8%;
图5(a)为获得的0.80BNT-0.20NT陶瓷的变温铁电电滞回线,可以看出在 -50~300℃的温度区间内,铁电电致回线都保持瘦长和较低的Pr值;(b)为计算得 出的WD和η随温度的变化关系,可以看出此陶瓷具有优异的储能性能温度稳定 性,在-50℃~300℃的温度范围内,WD浮动低于10%。
实施例2:
和实施例1相比,区别仅在于x为0.10。所制备陶瓷仍为纯钙钛矿结构,没 有杂质相存在,呈现伪立方相结构,且陶瓷没有明显的缺陷、结晶性好、晶粒尺 寸均匀且平均晶粒尺寸约为2~4μm。然而陶瓷介电温谱显示其介电常数浮动 (Δεr/εr25℃)低于10%的温度区间范围仅为-15~80℃;同时其电滞回线迟滞性较大, 虽然Pmax值较大,但同时Pr值也较大,且抗击穿电场仅为18kV/mm,导致其 WD为2.15J/cm3,η为56.5%。
实施例3:
和实施例1相比,区别仅在于x为0.30。所制备陶瓷仍为纯钙钛矿结构,没 有杂质相存在,呈现伪立方相结构,且陶瓷没有明显的缺陷、结晶性好、晶粒尺 寸均匀且平均晶粒尺寸约为2~4μm。其介电常数的温度稳定性良好,介电常数浮 动(Δεr/εr25℃)低于10%的温度区间范围为-60~308℃,抗击穿电场高达38kV/mm, 电滞回线瘦长,Pr值低,但是其Pmax值过低,导致WD有所下降,为3.16J/cm3, η较高,为82.5%。
对比例1
其他条件均与实施例1相同,仅是烧结温度为1120℃。结果发现此烧结温 度下制得的陶瓷致密度较低,为92%,陶瓷中存在大量微孔,导致其抗击穿电场 较低,为25kV/mm,且陶瓷漏导较大,导致其电滞回线迟滞性较大,WD仅为 1.65J/cm3,η仅为62.5%。
对比例2
其他条件均与实施例1相同,仅是烧结温度为1200℃。结果发现此烧结温 度下,陶瓷出现过烧现象,晶粒长大明显,且致密度较低,为86%,陶瓷中存在 大量微孔,导致其抗击穿电场低,仅为16kV/mm,且陶瓷漏导较大,导致其电 滞回线迟滞性较大,WD仅为0.65J/cm3,η仅为54.8%。
对比例3
其他条件与实施例1相同,只是陶瓷材料的设计分子式为:Bi0.5Na0.5TiO3, 其介电常数随温度显著变化,介电常数浮动(Δεr/εr25℃)低于10%的温度区间范围 仅为-15~50℃;同时其电滞回线饱满,虽然Pmax值较大,但同时Pr值过大,且 抗击穿电场仅为10kV/mm,导致其WD仅为0.15J/cm3,η仅为4.87%。
对比例4
和实施例1相比,区别仅在于,x为0.05,其介电常数随温度显著变化,介 电常数浮动(Δεr/εr25℃)低于10%的温度区间范围仅为-15~50℃;同时其电滞回线 饱满,虽然Pmax值较大,但同时Pr值过大,且抗击穿电场仅为12kV/mm,导致 其WD仅为0.45J/cm3,η仅为10.27%。
Claims (10)
1.一种钛酸铋钠-钽酸钠固溶陶瓷材料,其特征在于,其化学通式为(1-x)Bi0.5Na0.5TiO3-xNaTaO3,x=0.10~0.30。
2.如权利要求1所述的钛酸铋钠-钽酸钠固溶陶瓷材料,其特征在于,所述的x为0.20。
3.如权利要求1或2所述的钛酸铋钠-钽酸钠固溶陶瓷材料,其特征在于,呈现伪立方相结构,晶粒为2~4μm。
4.一种权利要求1~3任一项所述的钛酸铋钠-钽酸钠固溶陶瓷材料的制备方法,其特征在于,将钠源、铋源、钽源、钛源按所述的化学通式元素计量比配料、混合得混合物,将混合物进行第一次球磨获得混匀料A,混匀料A进行预烧获得预烧粉;
预烧粉进行第二次球磨,获得混匀料B,将混匀料B造粒,压制成型获得生坯,生坯经排胶、烧结后即获得所述的钛酸铋钠-钽酸钠固溶陶瓷材料;所述的烧结温度为1150~1180℃。
5.如权利要求4所述的钛酸铋钠-钽酸钠固溶陶瓷材料的制备方法,其特征在于,所述的钠源为钠的碳酸盐、碳酸氢盐、硝酸盐中的至少一种;
优选地,所述的铋源为铋的氧化物;优选为Bi2O3;
优选地,所述的钽源为钽的氧化物;优选为Ta2O5;
优选地,所述的钛源为钛的氧化物;优选为TiO2。
6.如权利要求4所述的钛酸铋钠-钽酸钠固溶陶瓷材料的制备方法,其特征在于,第一次球磨、第二次球磨均为湿法球磨,球磨转速为200-300rpm;其中,第一次球磨的时间为6-10h;第二次球磨的时间为18-24h。
7.如权利要求4所述的钛酸铋钠-钽酸钠固溶陶瓷材料的制备方法,其特征在于,所述预烧温度为750-850℃,预烧时间为2-4h。
8.如权利要求4所述的钛酸铋钠-钽酸钠固溶陶瓷材料的制备方法,其特征在于,将混匀料B造粒工艺为:在混匀料B中加入粘结剂后通过研磨混匀料呈粒状;其中,所述粘结剂的加入量为总混合物质量的0.8-1.2%;
所述的粘结剂为聚乙烯醇缩丁醛。
9.如权利要求4所述的钛酸铋钠-钽酸钠固溶陶瓷材料的制备方法,其特征在于,排胶过程的温度为550-650℃,时间为2-4h;
烧结的时间为2-4h。
10.一种权利要求1~3任一项所述的钛酸铋钠-钽酸钠固溶陶瓷材料,或者权利要求4~9任一项所述的制备方法制得的钛酸铋钠-钽酸钠固溶陶瓷材料的应用,其特征在于,用于制备介电储能电容器。
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