CN105198410B - A kind of preparation method of core shell structure high energy storage density dielectric ceramics - Google Patents
A kind of preparation method of core shell structure high energy storage density dielectric ceramics Download PDFInfo
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- 238000004146 energy storage Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000011258 core-shell material Substances 0.000 title claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 91
- 238000000034 method Methods 0.000 claims abstract description 18
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 41
- 238000010438 heat treatment Methods 0.000 claims description 25
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 15
- 238000010306 acid treatment Methods 0.000 claims description 13
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- 229910021641 deionized water Inorganic materials 0.000 claims description 13
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
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- 229910010252 TiO3 Inorganic materials 0.000 claims 14
- 229910052681 coesite Inorganic materials 0.000 claims 5
- 229910052906 cristobalite Inorganic materials 0.000 claims 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 5
- 229910052682 stishovite Inorganic materials 0.000 claims 5
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- 239000000377 silicon dioxide Substances 0.000 claims 4
- 239000012895 dilution Substances 0.000 claims 2
- 238000010790 dilution Methods 0.000 claims 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Inorganic materials [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 229910000018 strontium carbonate Inorganic materials 0.000 claims 1
- 238000002490 spark plasma sintering Methods 0.000 abstract description 13
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- 229910004298 SiO 2 Inorganic materials 0.000 description 43
- 229910052788 barium Inorganic materials 0.000 description 17
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Abstract
本发明公开了一种核壳结构高储能密度电介质陶瓷的制备方法，该方法首先通过溶胶凝胶法制备Ba0.4Sr0.6TiO3粉末；其次利用正硅酸乙酯水解制备SiO2包覆Ba0.4Sr0.6TiO3粉末；然后将制得的粉料装入模具，利用放电等离子烧结***在真空环境中1000℃～1050℃进行烧结，制得陶瓷烧结体；最后在空气气氛下，将陶瓷烧结体1100℃～1150℃处理1～5小时，制得核壳结构高储能密度电介质陶瓷。利用本发明的制备方法制备的核壳结构高储能密度电介质陶瓷在室温下储能密度可达1.60J/cm3以上，比同样条件制备的未包覆SiO2的Ba0.4Sr0.6TiO3电介质陶瓷的储能密度提高了0.40J/cm3。The invention discloses a method for preparing a core-shell structure dielectric ceramic with high energy storage density. The method firstly prepares Ba 0.4 Sr 0.6 TiO 3 powder by a sol-gel method; 0.4 Sr 0.6 TiO 3 powder; then put the prepared powder into the mold, and use the spark plasma sintering system to sinter in a vacuum environment at 1000°C to 1050°C to obtain a ceramic sintered body; finally, the ceramic is sintered in an air atmosphere The body is treated at 1100°C to 1150°C for 1 to 5 hours to prepare a core-shell structure high energy storage density dielectric ceramic. The core-shell structure high energy storage density dielectric ceramic prepared by the preparation method of the present invention has an energy storage density of more than 1.60 J/cm 3 at room temperature, which is higher than that of the uncoated Ba 0.4 Sr 0.6 TiO 3 dielectric prepared under the same conditions. The energy storage density of ceramics is increased by 0.40J/cm 3 .
Description
技术领域technical field
本发明涉及储能电容器用介质材料技术领域，尤其涉及一种核壳结构高储能密度电介质陶瓷的制备方法。The invention relates to the technical field of dielectric materials for energy storage capacitors, in particular to a method for preparing dielectric ceramics with a core-shell structure and high energy storage density.
背景技术Background technique
电介质电容器储能方式是将电能以电容器对极板间的富集电荷电势场的形式储存。与传统的燃料电池、锂电池相比，电介质储能电容器的特点是响应速度快、功率密度高、使用寿命长、全固态安全结构、使用温度范围广等，在大功率和脉冲功率器件中有着非常广泛的应用。对于线性电介质，其储能密度与介电常数成正比、与介电击穿场强的平方成正比，因此探索具有高介电常数、高介电击穿场强和低介电损耗的介电材料，是提高储能密度、实现器件小型化的关键。钛酸锶钡陶瓷因具有良好的铁电性、压电性、非线性光学性能等被广泛应用于微电子、光电子、集成光学和微电子机械***等领域。在储能方面，较低的介电损耗、较高的介电常数和击穿场强，也使得钛酸锶钡陶瓷获得了重点关注。The dielectric capacitor energy storage method is to store electrical energy in the form of a charge-enriched electric potential field between the capacitor pair of plates. Compared with traditional fuel cells and lithium batteries, dielectric energy storage capacitors are characterized by fast response speed, high power density, long service life, all-solid-state safety structure, and wide operating temperature range. Very wide range of applications. For linear dielectrics, the energy storage density is proportional to the dielectric constant and the square of the dielectric breakdown field strength, so explore dielectrics with high dielectric constant, high dielectric breakdown field strength and low dielectric loss Materials are the key to improving energy storage density and realizing device miniaturization. Barium strontium titanate ceramics are widely used in the fields of microelectronics, optoelectronics, integrated optics, and microelectromechanical systems because of their good ferroelectricity, piezoelectricity, and nonlinear optical properties. In terms of energy storage, low dielectric loss, high dielectric constant and breakdown field strength have also made barium strontium titanate ceramics gain focus.
申请号为201110046717.6的中国专利公开了一种钛酸锶钡基储能介质陶瓷的制备方法，其步骤如下：(1)BST陶瓷细粉的制备；(2)玻璃料的制备；(3)按各原料所占体积百分数为：BST陶瓷细粉80～99％、玻璃料1～20％，选取上述BST陶瓷细粉和玻璃料；BST陶瓷细粉中加入玻璃料，用氧化锆和无水乙醇球磨24～36h，烘干制得陶瓷-玻璃混合粉末，加入粘结剂造粒，粘结剂的加入量为陶瓷-玻璃混合粉末质量的3～5％，压片得到生坯片；生坯片在600℃下保温2h排胶，冷却至室温，最后在升温速率为2～4℃/min，1050～1280℃下保温2～4h，得到钛酸锶钡基储能介质陶瓷。该方法制备的储能介质陶瓷，测得介电常数为380，击穿强度28.0kV/mm，有效储能密度为1.50J/cm3。The Chinese patent application number 201110046717.6 discloses a method for preparing strontium barium titanate-based energy storage medium ceramics, the steps are as follows: (1) preparation of BST ceramic fine powder; (2) preparation of glass frit; (3) according to The volume percentage of each raw material is: BST ceramic fine powder 80-99%, glass frit 1-20%, select the above-mentioned BST ceramic fine powder and glass frit; add glass frit to BST ceramic fine powder, use zirconia and dehydrated alcohol Ball milling for 24-36 hours, drying to obtain ceramic-glass mixed powder, adding binder to granulate, the amount of binder added is 3-5% of the mass of ceramic-glass mixed powder, and pressing to obtain green sheet; The sheet was kept at 600°C for 2 hours to remove the glue, cooled to room temperature, and finally kept at 1050-1280°C for 2-4 hours at a heating rate of 2-4°C/min to obtain strontium barium titanate-based energy storage medium ceramics. The energy storage dielectric ceramic prepared by the method has a measured dielectric constant of 380, a breakdown strength of 28.0kV/mm, and an effective energy storage density of 1.50J/cm 3 .
上述专利通过在钛酸锶钡陶瓷中添加玻璃相，使陶瓷的介电击穿强度提高，从而获得了较高的储能密度。但添加了玻璃相的钛酸锶钡复相陶瓷的介电常数下降明显，因此如何通过配方调整和工艺改进，在大幅度提高陶瓷的介电击穿强度的同时，仍旧保持适中的介电常数，是制备高储能密度电容器的关键。The above-mentioned patents increase the dielectric breakdown strength of the ceramics by adding a glass phase to the barium strontium titanate ceramics, thereby obtaining a higher energy storage density. However, the dielectric constant of strontium barium titanate composite ceramics with the addition of a glass phase drops significantly. Therefore, how to maintain a moderate dielectric constant while greatly improving the dielectric breakdown strength of the ceramic through formula adjustment and process improvement , is the key to the preparation of capacitors with high energy storage density.
发明内容Contents of the invention
本发明的目的在于针对现有技术的不足，提供一种核壳结构高储能密度电 介质陶瓷的制备方法，通过SiO2包覆Ba0.4Sr0.6TiO3纳米粉末及放电等离子烧结方法，提高电介质陶瓷的介电击穿强度，从而提高电介质陶瓷的储能密度。The object of the present invention is to aim at the deficiencies in the prior art, provide a kind of preparation method of core-shell structure high energy storage density dielectric ceramics, through SiO 2 coating Ba 0.4 Sr 0.6 TiO 3 nanopowder and discharge plasma sintering method, improve the dielectric ceramics The dielectric breakdown strength, thereby improving the energy storage density of dielectric ceramics.
本发明的目的是通过以下技术方案来实现的：一种核壳结构高储能密度电介质陶瓷的制备方法，该方法包括以下步骤：The object of the present invention is achieved through the following technical solutions: a method for preparing a core-shell structure high energy storage density dielectric ceramic, the method comprising the following steps:
(1)溶胶凝胶法制备Ba0.4Sr0.6TiO3粉末：将Ti(C4H9O)4溶于乙二醇，搅拌至澄清；加入柠檬酸，继续搅拌至澄清；再加入BaCO3和SrCO3粉末，滴加质量浓度为65％的HNO3数滴，得到混合溶液；将混合溶液置于水浴中搅拌至黄棕色透明溶胶随后烘箱中烘干，直至溶胶颜色变为深棕色；最后煅烧获得Ba0.4Sr0.6TiO3纳米粉末；(1) Prepare Ba 0.4 Sr 0.6 TiO 3 powder by sol-gel method: dissolve Ti(C 4 H 9 O) 4 in ethylene glycol and stir until clear; add citric acid and continue stirring until clear; then add BaCO 3 and SrCO 3 powder, add a few drops of HNO 3 with a mass concentration of 65% to obtain a mixed solution; place the mixed solution in a water bath and stir until the yellow-brown transparent sol is then dried in an oven until the color of the sol turns dark brown; finally calcined Obtain Ba 0.4 Sr 0.6 TiO 3 nanometer powder;
(2)利用正硅酸乙酯(TEOS)水解制备SiO2包覆Ba0.4Sr0.6TiO3粉末：将Ba0.4Sr0.6TiO3粉末进行表面处理，具体为：将Ba0.4Sr0.6TiO3粉末加入到稀释的HNO3溶液中，超声振荡后静置，去除上层清液，去离子水洗涤数次；硝酸处理过的Ba0.4Sr0.6TiO3粉末加入到柠檬酸溶液中，超声振荡后静置，去除上层清液；柠檬酸处理后的Ba0.4Sr0.6TiO3粉末分散在乙醇/去离子水/氨水的混合液中，超声振荡后，一边搅拌一边缓慢滴加正硅酸乙酯(TEOS)，加入正硅酸乙酯的量使得柠檬酸处理后的Ba0.4Sr0.6TiO3粉末与SiO2的摩尔比为(100-x):x；接着加热搅拌至溶剂全部蒸发，剩余粉末烘干后煅烧，获得具有核壳结构的Ba0.4Sr0.6TiO3@SiO2粉末；(2) Preparation of SiO 2 coated Ba 0.4 Sr 0.6 TiO 3 powder by hydrolysis of tetraethyl orthosilicate (TEOS): surface treatment of Ba 0.4 Sr 0.6 TiO 3 powder, specifically: adding Ba 0.4 Sr 0.6 TiO 3 powder into the diluted HNO 3 solution, put it aside after ultrasonic oscillation, remove the supernatant, and wash it several times with deionized water; add the Ba 0.4 Sr 0.6 TiO 3 powder treated with nitric acid into the citric acid solution, leave it still after ultrasonic oscillation, Remove the supernatant; the Ba 0.4 Sr 0.6 TiO 3 powder treated with citric acid is dispersed in the mixed solution of ethanol/deionized water/ammonia water, and after ultrasonic oscillation, slowly add orthoethyl silicate (TEOS) dropwise while stirring, Add the amount of ethyl orthosilicate so that the molar ratio of Ba 0.4 Sr 0.6 TiO 3 powder after citric acid treatment to SiO 2 is (100-x):x; then heat and stir until the solvent is completely evaporated, and the remaining powder is dried and then calcined , to obtain Ba 0.4 Sr 0.6 TiO 3 @SiO 2 powder with core-shell structure;
(3)将步骤(2)制得的粉料装入模具，利用放电等离子烧结***在真空环境中1000℃～1050℃进行烧结，制得陶瓷烧结体；(3) Load the powder obtained in step (2) into a mold, and sinter in a vacuum environment at 1000°C to 1050°C using a spark plasma sintering system to obtain a ceramic sintered body;
(4)空气气氛下，将步骤(3)制得的陶瓷烧结体1100℃～1150℃处理1～5小时，制得所述核壳结构高储能密度电介质陶瓷。(4) Under an air atmosphere, the ceramic sintered body obtained in step (3) is treated at 1100° C. to 1150° C. for 1 to 5 hours to obtain the core-shell structure high energy storage density dielectric ceramic.
进一步地，步骤(2)中，柠檬酸处理后的Ba0.4Sr0.6TiO3粉末与SiO2的摩尔比为(100-x):x，其中x＝5～12.5。Further, in step (2), the molar ratio of Ba 0.4 Sr 0.6 TiO 3 powder after citric acid treatment to SiO 2 is (100-x):x, wherein x=5˜12.5.
进一步地，柠檬酸处理后的Ba0.4Sr0.6TiO3粉末与SiO2的摩尔比为(100-x):x，其中，x＝5，8或12.5。Further, the molar ratio of Ba 0.4 Sr 0.6 TiO 3 powder to SiO 2 after citric acid treatment is (100-x):x, where x=5, 8 or 12.5.
进一步地，步骤(1)中，溶胶凝胶法制备Ba0.4Sr0.6TiO3粉末时，Ti(C4H9O)4与乙二醇的摩尔分数比为1:15～1:25，Ti(C4H9O)4与柠檬酸的摩尔分数比为1:1～1:4；水浴加热温度为50～80℃；烘干温度为100℃～150℃；粉末煅烧温度为850℃～1150℃，煅烧时间为2～5小时。Further, in step (1), when Ba 0.4 Sr 0.6 TiO 3 powder is prepared by sol-gel method, the mole fraction ratio of Ti(C 4 H 9 O) 4 to ethylene glycol is 1:15-1:25, and Ti The mole fraction ratio of (C 4 H 9 O) 4 to citric acid is 1:1~1:4; the heating temperature of water bath is 50~80℃; the drying temperature is 100℃~150℃; the powder calcining temperature is 850℃~ 1150°C, the calcination time is 2 to 5 hours.
进一步地，步骤(1)中，溶胶凝胶法制备Ba0.4Sr0.6TiO3粉末时，Ti(C4H9O)4与乙二醇的摩尔分数比为1:20，Ti(C4H9O)4与柠檬酸的摩尔分数比为1:2；水浴 加热温度为70℃；烘干温度为120℃；粉末煅烧温度为1050℃，时间为3小时。Further, in step (1), when Ba 0.4 Sr 0.6 TiO 3 powder is prepared by sol-gel method, the mole fraction ratio of Ti(C 4 H 9 O) 4 to ethylene glycol is 1:20, and Ti(C 4 H The molar ratio of 9 O) 4 to citric acid is 1:2; the heating temperature of the water bath is 70°C; the drying temperature is 120°C; the powder calcining temperature is 1050°C for 3 hours.
进一步地，步骤(2)中，制备SiO2包覆Ba0.4Sr0.6TiO3粉末时，Ba0.4Sr0.6TiO3粉末表面处理中使用的稀释的硝酸浓度为0.5～2mol/L；使用的柠檬酸溶液的浓度为0.005mol/L～0.02mol/L；分散使用的乙醇/去离子水/氨水的混合液中，乙醇、去离子水、氨水按体积分数比50:10:1混合；SiO2包覆Ba0.4Sr0.6TiO3粉末的煅烧温度为800℃～900℃，时间为1～4小时。Further, in step (2), when preparing SiO 2 coated Ba 0.4 Sr 0.6 TiO 3 powder, the concentration of diluted nitric acid used in the surface treatment of Ba 0.4 Sr 0.6 TiO 3 powder is 0.5-2 mol/L; the citric acid used The concentration of the solution is 0.005mol/L～0.02mol/L; in the mixture of ethanol/deionized water/ammonia water used for dispersion, ethanol, deionized water, and ammonia water are mixed in a volume fraction ratio of 50:10:1; SiO 2 packs The calcining temperature of the Ba 0.4 Sr 0.6 TiO 3 -coated powder is 800°C-900°C, and the time is 1-4 hours.
进一步地，步骤(2)中，制备SiO2包覆Ba0.4Sr0.6TiO3粉末时，Ba0.4Sr0.6TiO3粉末表面处理中使用的稀释硝酸浓度为1mol/L；使用的柠檬酸溶液的浓度为0.01mol/L mol/L；SiO2包覆Ba0.4Sr0.6TiO3粉末的煅烧温度为850℃，时间为3小时。Further, in step (2), when preparing SiO 2 coated Ba 0.4 Sr 0.6 TiO 3 powder, the concentration of dilute nitric acid used in the surface treatment of Ba 0.4 Sr 0.6 TiO 3 powder is 1mol/L; the concentration of the citric acid solution used is 0.01mol/L mol/L; the calcination temperature of SiO 2 coated Ba 0.4 Sr 0.6 TiO 3 powder is 850°C and the time is 3 hours.
进一步地，步骤(3)中，所述的烧结温度为1050℃，保温时间为0min。Further, in step (3), the sintering temperature is 1050° C., and the holding time is 0 min.
进一步地，步骤(4)中，所述的热处理温度为1125℃，时间为3小时。Further, in step (4), the heat treatment temperature is 1125° C. and the time is 3 hours.
与现有技术相比，本发明的有益效果在于：采用本发明的制备方法，放电等离子烧结制备的Ba0.4Sr0.6TiO3@SiO2陶瓷在室温下储能密度达可到1.60J/cm3以上，而同样条件制备的未包覆SiO2的Ba0.4Sr0.6TiO3电介质陶瓷的储能密度仅为1.20J/cm3左右，储能密度提高了0.40J/cm3。本发明制备的核壳结构高储能密度电介质陶瓷，可用于高密度储能电容器等元器件，在大功率和脉冲功率领域有着极大的应用价值。Compared with the prior art, the beneficial effect of the present invention is that: adopting the preparation method of the present invention, the energy storage density of Ba 0.4 Sr 0.6 TiO 3 @SiO 2 ceramics prepared by spark plasma sintering can reach 1.60J/cm 3 at room temperature However, the energy storage density of Ba 0.4 Sr 0.6 TiO 3 dielectric ceramics not coated with SiO 2 prepared under the same conditions is only about 1.20J/cm 3 , and the energy storage density has increased by 0.40J/cm 3 . The core-shell structure high energy storage density dielectric ceramic prepared by the invention can be used for components such as high density energy storage capacitors, and has great application value in the field of high power and pulse power.
附图说明Description of drawings
图1为SPS烧结原理图；Figure 1 is a schematic diagram of SPS sintering;
图2为液相法制备核壳结构(100-x)mol％Ba0.4Sr0.6TiO3+x mol％SiO2(x＝0,5,8,12.5)陶瓷粉末透射电镜照片：(a)Ba0.4Sr0.6TiO3(对比例1)；(b)95mol％Ba0.4Sr0.6TiO3+5mol％SiO2(实施例1)；(c)92mol％Ba0.4Sr0.6TiO3+8mol％SiO2(实施例2)；(d)87.5mol％Ba0.4Sr0.6TiO3+12.5mol％SiO2(实施例3)；Figure 2 is a transmission electron microscope photo of the core-shell structure (100-x) mol% Ba 0.4 Sr 0.6 TiO 3 +x mol% SiO 2 (x=0,5,8,12.5) ceramic powder prepared by the liquid phase method: (a) Ba 0.4 Sr 0.6 TiO 3 (comparative example 1); (b) 95mol% Ba 0.4 Sr 0.6 TiO 3 + 5mol% SiO 2 (Example 1); (c) 92mol% Ba 0.4 Sr 0.6 TiO 3 + 8mol% SiO 2 ( Example 2); (d) 87.5 mol% Ba 0.4 Sr 0.6 TiO 3 +12.5 mol% SiO 2 (Example 3);
图3为放点等离子烧结制备(100-x)mol％Ba0.4Sr0.6TiO3+x mol％SiO2(x＝0,5,8,12.5)陶瓷XRD衍射图谱：(a)Ba0.4Sr0.6TiO3(对比例1)；(b)95mol％Ba0.4Sr0.6TiO3+5mol％SiO2(实施例1)；(c)92mol％Ba0.4Sr0.6TiO3+8mol％SiO2(实施例2)；(d)87.5mol％Ba0.4Sr0.6TiO3+12.5mol％SiO2(实施例3)；Figure 3 is the XRD diffraction pattern of (100-x) mol% Ba 0.4 Sr 0.6 TiO 3 +x mol% SiO 2 (x=0,5,8,12.5) ceramics prepared by spot plasma sintering: (a) Ba 0.4 Sr 0.6 TiO 3 (Comparative Example 1); (b) 95mol% Ba 0.4 Sr 0.6 TiO 3 +5mol% SiO 2 (Example 1); (c) 92mol% Ba 0.4 Sr 0.6 TiO 3 +8mol% SiO 2 (Example 2 ); (d) 87.5 mol% Ba 0.4 Sr 0.6 TiO 3 +12.5 mol% SiO 2 (Example 3);
图4为放电等离子烧结制备(100-x)mol％Ba0.4Sr0.6TiO3+x mol％SiO2(x＝0,5,8,12.5)陶瓷样品的抛光热腐蚀表面扫描电镜照片：(a)Ba0.4Sr0.6TiO3(对比例1)；(b)95mol％Ba0.4Sr0.6TiO3+5mol％SiO2(实施例1)；(c)92mol％Ba0.4Sr0.6TiO3+8mol％SiO2(实施例2)；(d)87.5mol％Ba0.4Sr0.6TiO3+12.5mol％SiO2(实施例3)；Figure 4 is a scanning electron micrograph of the polished hot corrosion surface of a ceramic sample prepared by spark plasma sintering (100-x) mol% Ba 0.4 Sr 0.6 TiO 3 +x mol% SiO 2 (x=0,5,8,12.5): (a ) Ba 0.4 Sr 0.6 TiO 3 (comparative example 1); (b) 95mol% Ba 0.4 Sr 0.6 TiO 3 + 5mol% SiO 2 (Example 1); (c) 92mol% Ba 0.4 Sr 0.6 TiO 3 + 8mol% SiO 2 (Example 2); (d) 87.5 mol% Ba 0.4 Sr 0.6 TiO 3 + 12.5 mol% SiO 2 (Example 3);
图5为放电等离子烧结制备(100-x)mol％Ba0.4Sr0.6TiO3+x mol％SiO2(x＝0,5,8,12.5)陶瓷样品室温60Hz时最高电场强度下的电滞回线：(a)Ba0.4Sr0.6TiO3(对比例1)；(b)95mol％Ba0.4Sr0.6TiO3+5mol％SiO2(实施例1)；(c)92mol％Ba0.4Sr0.6TiO3+8mol％SiO2(实施例2)；(d)87.5mol％Ba0.4Sr0.6TiO3+12.5mol％SiO2(实施例3)；Figure 5 shows the electric hysteresis of (100-x) mol% Ba 0.4 Sr 0.6 TiO 3 +x mol% SiO 2 (x=0,5,8,12.5) ceramic samples prepared by spark plasma sintering under the highest electric field strength at room temperature of 60Hz Lines: (a) Ba 0.4 Sr 0.6 TiO 3 (Comparative Example 1); (b) 95mol% Ba 0.4 Sr 0.6 TiO 3 + 5mol% SiO 2 (Example 1); (c) 92mol% Ba 0.4 Sr 0.6 TiO 3 +8 mol% SiO 2 (Example 2); (d) 87.5 mol% Ba 0.4 Sr 0.6 TiO 3 +12.5 mol% SiO 2 (Example 3);
具体实施方式detailed description
下面结合具体实施例进一步阐释本发明。The present invention is further explained below in conjunction with specific examples.
实施例1Example 1
(1)溶胶凝胶法制备Ba0.4Sr0.6TiO3粉末：将Ti(C4H9O)4溶于乙二醇，搅拌至澄清，其中Ti(C4H9O)4与乙二醇的摩尔分数比为1:15；加入柠檬酸，继续搅拌至澄清，其中Ti(C4H9O)4与柠檬酸的摩尔分数比为1:1；再加入BaCO3和SrCO3粉末，滴加质量分数为65％的HNO3数滴，得到混合溶液；将混合溶液置于50℃水浴中搅拌至黄棕色透明溶胶随后烘箱中100℃烘干，直至溶胶颜色变为深棕色；最后850℃煅烧5小时获得Ba0.4Sr0.6TiO3纳米粉末；(1) Preparation of Ba 0.4 Sr 0.6 TiO 3 powder by sol-gel method: Dissolve Ti(C 4 H 9 O) 4 in ethylene glycol and stir until clear, wherein Ti(C 4 H 9 O) 4 and ethylene glycol The mole fraction ratio of Ti(C 4 H 9 O) 4 to citric acid is 1:15; add citric acid and continue to stir until clarification, wherein the mole fraction ratio of Ti(C 4 H 9 O) 4 to citric acid is 1:1; then add BaCO 3 and SrCO 3 powder, drop Add a few drops of HNO 3 with a mass fraction of 65% to obtain a mixed solution; place the mixed solution in a 50°C water bath and stir until the yellow-brown transparent sol is then dried in an oven at 100°C until the color of the sol turns dark brown; finally 850°C Calcined for 5 hours to obtain Ba 0.4 Sr 0.6 TiO 3 nanometer powder;
(2)利用正硅酸乙酯(TEOS)水解制备SiO2包覆Ba0.4Sr0.6TiO3粉末：将Ba0.4Sr0.6TiO3粉末进行表面处理，具体为：将Ba0.4Sr0.6TiO3粉末加入到稀释的HNO3溶液中(稀释硝酸浓度为0.5mol/L)，超声振荡后静置，去除上层清液，去离子水洗涤数次；硝酸处理过的Ba0.4Sr0.6TiO3粉末加入到柠檬酸溶液中(柠檬酸溶液的浓度为0.005mol/L)，超声振荡后静置，去除上层清液；柠檬酸处理后的Ba0.4Sr0.6TiO3粉末分散在乙醇/去离子水/氨水的混合液中，超声振荡后，一边搅拌一边缓慢滴加正硅酸乙酯(TEOS)，加入正硅酸乙酯的量使得柠檬酸处理后的Ba0.4Sr0.6TiO3粉末与SiO2的摩尔比为95:5；接着加热搅拌至溶剂全部蒸发，剩余粉末烘干后800℃煅烧4小时，获得具有核壳结构的Ba0.4Sr0.6TiO3@SiO2粉末；(2) Preparation of SiO 2 coated Ba 0.4 Sr 0.6 TiO 3 powder by hydrolysis of tetraethyl orthosilicate (TEOS): surface treatment of Ba 0.4 Sr 0.6 TiO 3 powder, specifically: adding Ba 0.4 Sr 0.6 TiO 3 powder into the diluted HNO 3 solution (diluted nitric acid concentration is 0.5mol/L), after ultrasonic vibration, let it stand, remove the supernatant, and wash with deionized water several times; the Ba 0.4 Sr 0.6 TiO 3 powder treated with nitric acid was added to the lemon In acid solution (the concentration of citric acid solution is 0.005mol/L), after ultrasonic vibration, let it stand still, and remove the supernatant; the Ba 0.4 Sr 0.6 TiO 3 powder after citric acid treatment is dispersed in the mixture of ethanol/deionized water/ammonia water In the solution, after ultrasonic oscillation, slowly add orthosilicate ethyl ester (TEOS) dropwise while stirring, the amount of adding orthosilicate ethyl ester makes the molar ratio of Ba 0.4 Sr 0.6 TiO 3 powder to SiO 2 after citric acid treatment be 95:5; then heat and stir until the solvent is completely evaporated, and the remaining powder is dried and calcined at 800°C for 4 hours to obtain Ba 0.4 Sr 0.6 TiO 3 @SiO 2 powder with a core-shell structure;
(3)将步骤(2)制得的粉末装入直径为10mm的石墨模具，放入放电等离子烧结***在1000℃、50MPa机械压力下烧结，保温时间为0min。从室温到900℃的升温速率为100℃/min，从900℃到980℃升温速率为40℃/min，980℃到1000℃升温速率为20℃/min，1000℃保温0min，烧结完成后，卸去压力并随炉冷。如图1所示，SPS烧结原理为：SPS利用直流脉冲电流直接进行通电加压烧结，通过调节直流脉冲电流的功率大小来控制升温速率。整个烧结过程在真空环境下进行；脉冲电流直接作用于样品及模具上，快速发热，快速传热，快速升温，大幅缩短样品烧结时间。(3) Put the powder prepared in step (2) into a graphite mold with a diameter of 10 mm, put it into a spark plasma sintering system and sinter at 1000° C. under a mechanical pressure of 50 MPa, and the holding time is 0 min. The heating rate from room temperature to 900°C is 100°C/min, the heating rate from 900°C to 980°C is 40°C/min, the heating rate from 980°C to 1000°C is 20°C/min, and the temperature is kept at 1000°C for 0 min. After sintering, Release the pressure and cool in the oven. As shown in Figure 1, the principle of SPS sintering is as follows: SPS uses DC pulse current to directly energize and pressurize sintering, and controls the heating rate by adjusting the power of DC pulse current. The whole sintering process is carried out in a vacuum environment; the pulse current acts directly on the sample and the mold, rapid heat generation, rapid heat transfer, rapid temperature rise, and greatly shorten the sample sintering time.
(4)将步骤(3)制得的陶瓷样品在磨去粘附的石墨纸后在空气中1100℃下热处理5小时。从室温到1100℃的升温速率为5℃/min，1100℃保温5h，1100℃到800℃的降温速率为2℃/min，之后随炉冷，得到核壳结构高储能密度电介质陶瓷。(4) Heat-treat the ceramic sample prepared in step (3) at 1100° C. for 5 hours in air after grinding off the adhered graphite paper. The heating rate from room temperature to 1100°C is 5°C/min, the temperature is kept at 1100°C for 5 hours, the cooling rate from 1100°C to 800°C is 2°C/min, and then cooled in the furnace to obtain a core-shell structure high energy storage density dielectric ceramic.
实施例2Example 2
(1)溶胶凝胶法制备Ba0.4Sr0.6TiO3粉末：将Ti(C4H9O)4溶于乙二醇，搅拌至澄清，其中Ti(C4H9O)4与乙二醇的摩尔分数比为1:20；加入柠檬酸，继续搅拌至澄清，其中Ti(C4H9O)4与柠檬酸的摩尔分数比为1:2；再加入BaCO3和SrCO3粉末，滴加质量分数为65％的HNO3数滴，得到混合溶液；将混合溶液置于70℃水浴中搅拌至黄棕色透明溶胶随后烘箱中120℃烘干，直至溶胶颜色变为深棕色；最后1050℃煅烧3小时获得Ba0.4Sr0.6TiO3纳米粉末；(1) Preparation of Ba 0.4 Sr 0.6 TiO 3 powder by sol-gel method: Dissolve Ti(C 4 H 9 O) 4 in ethylene glycol and stir until clear, wherein Ti(C 4 H 9 O) 4 and ethylene glycol The mole fraction ratio of Ti(C 4 H 9 O) 4 to citric acid is 1:20; add citric acid and continue to stir until clarification, wherein the mole fraction ratio of Ti(C 4 H 9 O) 4 to citric acid is 1:2; then add BaCO 3 and SrCO 3 powder, drop Add a few drops of HNO 3 with a mass fraction of 65% to obtain a mixed solution; place the mixed solution in a 70°C water bath and stir until the yellow-brown transparent sol is then dried in an oven at 120°C until the color of the sol turns dark brown; finally 1050°C Calcining for 3 hours to obtain Ba 0.4 Sr 0.6 TiO 3 nanometer powder;
(2)利用正硅酸乙酯(TEOS)水解制备SiO2包覆Ba0.4Sr0.6TiO3粉末：将Ba0.4Sr0.6TiO3粉末进行表面处理，具体为：将Ba0.4Sr0.6TiO3粉末加入到稀释的HNO3溶液中(稀释硝酸浓度为1mol/L)，超声振荡后静置，去除上层清液，去离子水洗涤数次；硝酸处理过的Ba0.4Sr0.6TiO3粉末加入到柠檬酸溶液中(柠檬酸溶液的浓度为0.01mol/L)，超声振荡后静置，去除上层清液；柠檬酸处理后的Ba0.4Sr0.6TiO3粉末分散在乙醇/去离子水/氨水的混合液中，超声振荡后，一边搅拌一边缓慢滴加正硅酸乙酯(TEOS)，加入正硅酸乙酯的量使得柠檬酸处理后的Ba0.4Sr0.6TiO3粉末与SiO2的摩尔比为92:8；接着加热搅拌至溶剂全部蒸发，剩余粉末烘干后850℃煅烧3小时，获得具有核壳结构的Ba0.4Sr0.6TiO3@SiO2粉末；(2) Preparation of SiO 2 coated Ba 0.4 Sr 0.6 TiO 3 powder by hydrolysis of tetraethyl orthosilicate (TEOS): surface treatment of Ba 0.4 Sr 0.6 TiO 3 powder, specifically: adding Ba 0.4 Sr 0.6 TiO 3 powder into the diluted HNO 3 solution (diluted nitric acid concentration is 1mol/L), put it aside after ultrasonic oscillation, remove the supernatant, and wash with deionized water several times; the Ba 0.4 Sr 0.6 TiO 3 powder treated with nitric acid was added to the citric acid solution (the concentration of citric acid solution is 0.01mol/L), put it aside after ultrasonic oscillation, and remove the supernatant; the Ba 0.4 Sr 0.6 TiO 3 powder after citric acid treatment is dispersed in the mixed solution of ethanol/deionized water/ammonia water In the process, after ultrasonic oscillation, slowly add tetraethyl orthosilicate (TEOS) dropwise while stirring, the amount of tetraethyl orthosilicate added makes the molar ratio of Ba 0.4 Sr 0.6 TiO 3 powder to SiO 2 after citric acid treatment be 92 :8; then heated and stirred until the solvent was completely evaporated, and the remaining powder was dried and calcined at 850°C for 3 hours to obtain Ba 0.4 Sr 0.6 TiO 3 @SiO 2 powder with a core-shell structure;
(3)将步骤(2)制得的粉末装入直径为10mm的石墨模具，放入放电等离子烧结***在1050℃、50MPa机械压力下烧结，保温时间为0min。从室温到950℃的升温速率为100℃/min，从950℃到1030℃升温速率为40℃/min，1030℃到1050℃升温速率为20℃/min，1050℃保温0min，烧结完成后，卸去压力并随炉冷。(3) Put the powder prepared in step (2) into a graphite mold with a diameter of 10 mm, put it into a spark plasma sintering system and sinter at 1050° C. under a mechanical pressure of 50 MPa, and the holding time is 0 min. The heating rate from room temperature to 950°C is 100°C/min, the heating rate from 950°C to 1030°C is 40°C/min, the heating rate from 1030°C to 1050°C is 20°C/min, and the temperature is kept at 1050°C for 0 min. After sintering, Release the pressure and cool in the oven.
(4)将步骤(3)制得的陶瓷样品在磨去粘附的石墨纸后在空气中1125℃下热处理3小时。从室温到1125℃的升温速率为5℃/min，1125℃保温3h，1125℃到800℃的降温速率为2℃/min，之后随炉冷，得到核壳结构高储能密度电介质陶瓷。(4) Heat-treat the ceramic sample prepared in step (3) at 1125° C. for 3 hours in air after grinding off the adhered graphite paper. The heating rate from room temperature to 1125°C is 5°C/min, the temperature is kept at 1125°C for 3 hours, the cooling rate from 1125°C to 800°C is 2°C/min, and then cooled in the furnace to obtain a core-shell structure high energy storage density dielectric ceramic.
实施例3Example 3
(1)溶胶凝胶法制备Ba0.4Sr0.6TiO3粉末：将Ti(C4H9O)4溶于乙二醇，搅拌 至澄清，其中Ti(C4H9O)4与乙二醇的摩尔分数比为1:25；加入柠檬酸，继续搅拌至澄清，其中Ti(C4H9O)4与柠檬酸的摩尔分数比为1:4；再加入BaCO3和SrCO3粉末，滴加质量分数为65％的HNO3数滴，得到混合溶液；将混合溶液置于80℃水浴中搅拌至黄棕色透明溶胶随后烘箱中150℃烘干，直至溶胶颜色变为深棕色；最后1150℃煅烧2小时获得Ba0.4Sr0.6TiO3纳米粉末；(1) Preparation of Ba 0.4 Sr 0.6 TiO 3 powder by sol-gel method: Dissolve Ti(C 4 H 9 O) 4 in ethylene glycol and stir until clear, wherein Ti(C 4 H 9 O) 4 and ethylene glycol The mole fraction ratio of Ti(C 4 H 9 O) 4 to citric acid is 1:25; add citric acid and continue to stir until clarification, wherein the mole fraction ratio of Ti(C 4 H 9 O) 4 to citric acid is 1:4; then add BaCO 3 and SrCO 3 powder, drop Add a few drops of HNO 3 with a mass fraction of 65% to obtain a mixed solution; place the mixed solution in a water bath at 80°C and stir until the yellow-brown transparent sol is then dried in an oven at 150°C until the color of the sol turns dark brown; finally 1150°C Calcined for 2 hours to obtain Ba 0.4 Sr 0.6 TiO 3 nanometer powder;
(2)利用正硅酸乙酯(TEOS)水解制备SiO2包覆Ba0.4Sr0.6TiO3粉末：将Ba0.4Sr0.6TiO3粉末进行表面处理，具体为：将Ba0.4Sr0.6TiO3粉末加入到稀释的HNO3溶液中(稀释硝酸浓度为2mol/L)，超声振荡后静置，去除上层清液，去离子水洗涤数次；硝酸处理过的Ba0.4Sr0.6TiO3粉末加入到柠檬酸溶液中(柠檬酸溶液的浓度为0.02mol/L)，超声振荡后静置，去除上层清液；柠檬酸处理后的Ba0.4Sr0.6TiO3粉末分散在乙醇/去离子水/氨水的混合液中，超声振荡后，一边搅拌一边缓慢滴加正硅酸乙酯(TEOS)，加入正硅酸乙酯的量使得柠檬酸处理后的Ba0.4Sr0.6TiO3粉末与SiO2的摩尔比为87.5:12.5；接着加热搅拌至溶剂全部蒸发，剩余粉末烘干后900℃煅烧1小时，获得具有核壳结构的Ba0.4Sr0.6TiO3@SiO2粉末；(2) Preparation of SiO 2 coated Ba 0.4 Sr 0.6 TiO 3 powder by hydrolysis of tetraethyl orthosilicate (TEOS): surface treatment of Ba 0.4 Sr 0.6 TiO 3 powder, specifically: adding Ba 0.4 Sr 0.6 TiO 3 powder into the diluted HNO 3 solution (diluted nitric acid concentration is 2mol/L), put it aside after ultrasonic oscillation, remove the supernatant, and wash with deionized water several times; the Ba 0.4 Sr 0.6 TiO 3 powder treated with nitric acid is added to the citric acid solution (the concentration of citric acid solution is 0.02mol/L), put it aside after ultrasonic oscillation, and remove the supernatant; the Ba 0.4 Sr 0.6 TiO 3 powder after citric acid treatment is dispersed in the mixed solution of ethanol/deionized water/ammonia water In the process, after ultrasonic oscillation, slowly add orthosilicate (TEOS) dropwise while stirring, the amount of added orthosilicate makes the molar ratio of Ba 0.4 Sr 0.6 TiO 3 powder to SiO 2 after citric acid treatment be 87.5 : 12.5; then heated and stirred until the solvent was completely evaporated, and the remaining powder was dried and calcined at 900°C for 1 hour to obtain Ba 0.4 Sr 0.6 TiO 3 @SiO 2 powder with a core-shell structure;
(3)将步骤(2)制得的粉末装入直径为10mm的石墨模具，放入放电等离子烧结***在1050℃、50MPa机械压力下烧结，保温时间为0min。从室温到950℃的升温速率为100℃/min，从950℃到1030℃升温速率为40℃/min，1030℃到1050℃升温速率为20℃/min，1050℃保温0min，烧结完成后，卸去压力并随炉冷。(3) Put the powder prepared in step (2) into a graphite mold with a diameter of 10 mm, put it into a spark plasma sintering system and sinter at 1050° C. under a mechanical pressure of 50 MPa, and the holding time is 0 min. The heating rate from room temperature to 950°C is 100°C/min, the heating rate from 950°C to 1030°C is 40°C/min, the heating rate from 1030°C to 1050°C is 20°C/min, and the temperature is kept at 1050°C for 0 min. After sintering, Release the pressure and cool in the oven.
(4)将步骤(3)制得的陶瓷样品在磨去粘附的石墨纸后在空气中1150℃下热处理1小时。从室温到1150℃的升温速率为5℃/min，1150℃保温5h，1150℃到800℃的降温速率为2℃/min，之后随炉冷，得到核壳结构高储能密度电介质陶瓷。(4) Heat-treat the ceramic sample prepared in step (3) at 1150° C. for 1 hour in air after grinding off the adhered graphite paper. The heating rate from room temperature to 1150°C is 5°C/min, the temperature is kept at 1150°C for 5 hours, the cooling rate from 1150°C to 800°C is 2°C/min, and then cooled in the furnace to obtain a core-shell structure high energy storage density dielectric ceramic.
对比例1Comparative example 1
(1)溶胶凝胶法制备Ba0.4Sr0.6TiO3粉末：将Ti(C4H9O)4溶于乙二醇，搅拌至澄清，其中Ti(C4H9O)4与乙二醇的摩尔分数比为1:20；加入柠檬酸，继续搅拌至澄清，其中Ti(C4H9O)4与柠檬酸的摩尔分数比为1:2；再加入BaCO3和SrCO3粉末，滴加质量分数为65％的HNO3数滴，得到混合溶液；将混合溶液置于70℃水浴中搅拌至黄棕色透明溶胶随后烘箱中120℃烘干，直至溶胶颜色变为深棕色；最后1050℃煅烧3小时获得Ba0.4Sr0.6TiO3纳米粉末；(1) Preparation of Ba 0.4 Sr 0.6 TiO 3 powder by sol-gel method: Dissolve Ti(C 4 H 9 O) 4 in ethylene glycol and stir until clear, wherein Ti(C 4 H 9 O) 4 and ethylene glycol The mole fraction ratio of Ti(C 4 H 9 O) 4 to citric acid is 1:20; add citric acid and continue to stir until clarification, wherein the mole fraction ratio of Ti(C 4 H 9 O) 4 to citric acid is 1:2; then add BaCO 3 and SrCO 3 powder, drop Add a few drops of HNO 3 with a mass fraction of 65% to obtain a mixed solution; place the mixed solution in a 70°C water bath and stir until the yellow-brown transparent sol is then dried in an oven at 120°C until the color of the sol turns dark brown; finally 1050°C Calcining for 3 hours to obtain Ba 0.4 Sr 0.6 TiO 3 nanometer powder;
(3)将步骤(1)制得的粉末装入直径为10mm的石墨模具，放入放电等 离子烧结***在1050℃、50MPa机械压力下烧结，保温时间为0min。从室温到950℃的升温速率为100℃/min，从950℃到1030℃升温速率为40℃/min，1030℃到1050℃升温速率为20℃/min，1050℃保温0min，烧结完成后，卸去压力并随炉冷。(3) Put the powder prepared in step (1) into a graphite mold with a diameter of 10mm, put it into a spark plasma sintering system and sinter at 1050°C and 50MPa mechanical pressure, and the holding time is 0min. The heating rate from room temperature to 950°C is 100°C/min, the heating rate from 950°C to 1030°C is 40°C/min, the heating rate from 1030°C to 1050°C is 20°C/min, and the temperature is kept at 1050°C for 0 min. After sintering, Release the pressure and cool in the oven.
(4)将步骤(3)制得的陶瓷样品在磨去粘附的石墨纸后在空气中1125℃下热处理3小时。从室温到1125℃的升温速率为5℃/min，1125℃保温3h，1125℃到800℃的降温速率为2℃/min，之后随炉冷。(4) Heat-treat the ceramic sample prepared in step (3) at 1125° C. for 3 hours in air after grinding off the adhered graphite paper. The heating rate from room temperature to 1125°C is 5°C/min, the temperature is kept at 1125°C for 3 hours, the cooling rate from 1125°C to 800°C is 2°C/min, and then cooled with the furnace.
将实施例1～3和对比例1制备得到的圆柱形电介质陶瓷样品用砂纸磨至0.18～0.22mm厚度，表面喷上金电极后，利用铁电分析仪测量其60Hz频率下的电滞回线，利用积分法计算其储能密度。Grind the cylindrical dielectric ceramic samples prepared in Examples 1-3 and Comparative Example 1 to a thickness of 0.18-0.22 mm with sandpaper, and after spraying gold electrodes on the surface, use a ferroelectric analyzer to measure its hysteresis loop at a frequency of 60 Hz , using the integral method to calculate its energy storage density.
表1Table 1
表1为利用本发明的制备方法制得的(100-x)mol％Ba0.4Sr0.6TiO3+x mol％SiO2(x＝5,8,12.5)陶瓷和无SiO2包覆的的Ba0.4Sr0.6TiO3陶瓷在室温、60Hz频率下的介电击穿强度和储能密度。图2，图3，图4，图5展示了样品微结构，相组成和铁电性能；由测试数据可知，本发明制得的高储能密度电介质陶瓷在室温下储能密度最高可达1.60J/cm3，而放电等离子烧结制备的未包覆SiO2的Ba0.4Sr0.6TiO3电介质陶瓷的储能密度仅为1.20J/cm3左右，储能密度提高了0.40J/cm3。Table 1 is the (100-x) mol% Ba 0.4 Sr 0.6 TiO 3 +x mol% SiO 2 (x=5,8,12.5) ceramics prepared by the preparation method of the present invention and Ba without SiO 2 coating Dielectric breakdown strength and energy storage density of 0.4 Sr 0.6 TiO 3 ceramics at room temperature and frequency of 60 Hz. Fig. 2, Fig. 3, Fig. 4, Fig. 5 show sample microstructure, phase composition and ferroelectric performance; As can be known from the test data, the high energy storage density dielectric ceramics prepared by the present invention can store energy density up to 1.60 at room temperature J/cm 3 , while the energy storage density of Ba 0.4 Sr 0.6 TiO 3 dielectric ceramics prepared by spark plasma sintering without SiO 2 is only about 1.20J/cm 3 , and the energy storage density has increased by 0.40J/cm 3 .
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