CN115403358A - 一种过渡金属离子与Eu3+共掺杂型固体电解质陶瓷材料及其制备方法 - Google Patents

一种过渡金属离子与Eu3+共掺杂型固体电解质陶瓷材料及其制备方法 Download PDF

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CN115403358A
CN115403358A CN202211112362.0A CN202211112362A CN115403358A CN 115403358 A CN115403358 A CN 115403358A CN 202211112362 A CN202211112362 A CN 202211112362A CN 115403358 A CN115403358 A CN 115403358A
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洪燕
李恺
王竹梅
左建林
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Jingdezhen Ceramic Institute
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Abstract

本发明公开了一种过渡金属离子与Eu3+共掺杂型Na‑β(β″)‑Al2O3固体电解质陶瓷材料，在化学式ⅠNa1.67Li0.33Al10.67O17的基础上，引入过渡金属离子M和Eu3+；M为Mn2+、Co2+、Ni2+、Zn2+、Cu2+离子中的一种，其引入量按照摩尔比为Al3+∶M＝50～150∶1；Eu3+的引入量按照摩尔比为Al3+∶Eu3+＝300～800∶1；M离子和Eu3+掺杂进入陶瓷晶格代替Al3+。此外，还公开了上述固体电解质陶瓷材料的制备方法。本发明在引入Li+稳定β″‑Al2O3相结构的基础上，过渡金属离子和Eu3+的掺杂均能降低烧结温度，减少Na+的挥发，同时抑制β"‑Al2O3晶相向β‑Al2O3晶相的转变而得到β″‑Al2O3纯相，从而增强了Na‑β"(β)‑Al2O3固体电解质的电学性能，进而有利于促进钠硫电池生产技术的进步和发展。

Description

一种过渡金属离子与Eu3+共掺杂型固体电解质陶瓷材料及其 制备方法
技术领域
本发明涉及固体电解质陶瓷材料技术领域，尤其涉及一种在1550℃以上高温烧结、具有高Na+电导率的固体电解质陶瓷材料及其制备方法。
背景技术
钠硫电池具有储能密度大、效率高、运行费用低、维护较容易、不污染环境、使用寿命长等优点，特别适合做削峰填谷的储能电池，1992年开始商用至今已30年。
Na-β"(β)-Al2O3不仅是钠硫电池的电解质材料，同时还是钠硫电池的选择性透过膜，是钠硫电池的重要组成部分，电池的性能很大程度上依赖其固体电解质Na-β"(β)-Al2O3的性能，因此，Na-β"(β)-Al2O3电解质的制备和性能研究也逐渐成为备受重视的研究领域。
传统合成Na-β"(β)-Al2O3的主要方法是将高纯α-Al2O3、Na2CO3以及少量掺杂剂如MgO或Li2O等混合，在1600℃以上的高温下烧结而成。在高温烧结过程中，往往存在以下问题：一是Na+容易挥发，使得Na-β"(β)-Al2O3固体电解质偏离目标成分，导致性能降低；二是在Na2O-Al2O3体系中往往同时存在β-Al2O3与β"-Al2O3两种晶相，β"-Al2O3相的电导率是β-Al2O3相的10倍左右，但在高温烧结过程中，β"-Al2O3相极易向β-Al2O3相转变，导致性能降低；三是在高温烧结过程中，电解质中晶粒容易长大，由此产生的“双重结构”不但会降低电解质离子电导率，而且会影响钠硫电池使用寿命。
发明内容
本发明的目的在于克服现有技术的不足，提供一种过渡金属离子与Eu3+共掺杂型Na-β(β″)-Al2O3固体电解质陶瓷材料，在引入Li+稳定β″-Al2O3相结构的基础上，过渡金属离子和Eu3+的掺杂均能降低烧结温度，减少Na+的挥发，同时抑制β"-Al2O3晶相向β-Al2O3晶相的转变而得到β″-Al2O3纯相，从而增强Na-β"(β)-Al2O3固体电解质的电学性能，进而促进钠硫电池生产技术的进步和发展。本发明的另一个目的在于提供上述过渡金属离子与Eu3+共掺杂型Na-β(β″)-Al2O3固体电解质陶瓷的制备方法及其制得的产品。
本发明的目的通过以下技术方案予以实现：
本发明提供的一种过渡金属离子与Eu3+共掺杂型Na-β(β″)-Al2O3固体电解质陶瓷材料，在化学式ⅠNa1.67Li0.33Al10.67O17的基础上，引入过渡金属离子M和Eu3+；M为Mn2+、Co2+、Ni2+、Zn2+、Cu2+离子中的一种，其引入量按照摩尔比为Al3+∶M＝50～150∶1；Eu3+的引入量按照摩尔比为Al3+∶Eu3+＝300～800∶1；M离子和Eu3+掺杂进入陶瓷晶格代替Al3+。
上述方案中，本发明所述固体电解质陶瓷材料的体积密度大于3.17g/cm3、300℃下的电导率＞0.070S·cm-1、电导活化能＜0.106eV。
本发明的另一目的通过以下技术方案予以实现：
本发明提供的上述过渡金属离子与Eu3+共掺杂型Na-β(β″)-Al2O3固体电解质陶瓷材料的制备方法，包括以下步骤：
(1)埋烧料的制备
将α-Al2O3和Na2CO3按照化学式Na2Al10.67O17进行配料，以无水乙醇为球磨介质进行球磨处理；球磨后得到的物料经烘干、过筛、压制成型后进行煅烧处理；煅烧处理后的物料经研磨、过筛，即制得埋烧料；
(2)预合成前驱体粉料的制备
以铝源、钠源、锂源、铕源、过渡金属离子M源为原料，其中铝源、锂源按照化学式ⅠNa1.67Li0.33Al10.67O17进行配料，钠源的用量比化学式Ⅰ中的计量数多加8～10wt％，过渡金属离子M源的用量按照摩尔比为Al3+∶M＝50～150∶1，铕源的用量按照摩尔比为Al3+∶Eu3+＝300～800∶1；然后以无水乙醇为球磨介质进行一次球磨处理；球磨后得到的物料经烘干、过筛、压制成型后进行煅烧处理；煅烧处理后的物料经研磨、过筛，即制得预合成前驱体粉料；
(3)固体电解质陶瓷的制备
将所述预合成前驱体粉料进行二次球磨处理，球磨后得到的物料经烘干、研磨、过筛、造粒、陈腐，得到处理料；将所述处理料放入模具中压制成型后，再用冷等静压压制，之后进行排胶热处理，得到预烧件；然后，将所述预烧件置于埋烧料内进行埋烧，即制得固体电解质陶瓷材料。
进一步地，本发明制备方法所述步骤(1)中α-Al2O3和Na2CO3的纯度不低于99.2％；所述步骤(2)中原料的纯度不低于99.9％，所述铝源为α-Al2O3或Al(OH)3、钠源为无水Na2CO3或Na2C2O4、锂源为Li2CO3或Li2C2O4、铕源为Eu2O3；过渡金属离子M源中，锰源为MnCO3、钴源为CoO或2CoCO3·3Co(OH)2·H2O、镍源为NiO或NiCO3·2Ni(OH)2·4H2O、锌源为ZnO或Zn2(OH)2CO3、铜源为CuO或CuCO3·Cu(OH)2。
进一步地，本发明制备方法所述步骤(1)中的球磨处理为按照球∶料∶无水乙醇＝4∶1∶1～1.5，球磨12h以上；所述步骤(2)中的一次球磨处理和二次球磨处理相同，为按照球∶料∶无水乙醇＝4∶1∶1～3，球磨12h以上。
进一步地，本发明制备方法所述步骤(1)和步骤(2)的压制成型压力均为4～6Mpa，煅烧处理均为以5℃/min升温至1100～1150℃。
进一步地，本发明制备方法所述步骤(3)中造粒所用粘结剂采用聚乙烯醇缩丁醛或聚乙烯醇，聚乙烯醇缩丁醛或聚乙烯醇的用量为物料的3～7wt％。
进一步地，本发明制备方法所述步骤(3)中在6～8Mpa下压制成型；冷等静压的压力为200～300MPa，保压时间至少为90s；排胶热处理的温度为以1℃/min升温至630～650℃。
进一步地，本发明制备方法所述步骤(3)中埋烧处理的温度为以5℃/min升温至1570～1610℃。
利用上述过渡金属离子与Eu3+共掺杂型Na-β(β″)-Al2O3固体电解质陶瓷材料的制备方法制得的产品。
本发明具有以下有益效果：
(1)本发明在制备固体电解质陶瓷材料的过程中，采取了以下三项措施：(a)在配料时引入过量的钠源，以补偿高温烧结过程中Na+的损失；(b)采用含钠的埋烧料进行埋烧，一定程度上减少了高温烧结过程中Na+的挥发损失；(c)在引入了Li+作为β″-Al2O3相晶型稳定剂的同时，掺杂的过渡金属离子M和Eu3+进入陶瓷晶格代替Al3+，进一步稳定β″-Al2O3相，抑制了β″-Al2O3相向β-Al2O3相的转化。以上三项措施使得所制备的固体电解质陶瓷材料为β″-Al2O3纯相。
(2)本发明在引入Li+稳定β″-Al2O3相结构的基础上，把稀土氧化物Eu2O3和过渡金属(如锰、钴、镍、锌、铜)的氧化物或盐添加到固体电解质中。一方面能降低固体电解质陶瓷的烧结温度，从而减少Na+的挥发、抑制β"-Al2O3晶相向β-Al2O3晶相的转变，制得了β"-Al2O3纯相结构的固体电解质；另一方面能使陶瓷晶粒更加细小均匀，陶瓷更为致密(平均体积密度大于3.17g/cm3)，从而增强了Na-β"(β)-Al2O3固体电解质的性能(300℃下陶瓷材料电导率＞0.070S·cm-1、电导活化能＜0.106eV)。
(3)本发明制备方法无需昂贵的设备，工艺简单易操作，影响因素易控制，所使用的埋烧料可重复使用，生产成本低，有助于推广和应用。
附图说明
下面将结合实施例和附图对本发明作进一步的详细描述：
图1是本发明实施例制得的固体电解质陶瓷材料的XRD图谱；
图2是本发明实施例制得的固体电解质陶瓷材料的扫描电镜SEM图片(a：1000倍；b：5000倍)；
图3是本发明实施例制得的固体电解质陶瓷材料的交流阻抗图谱。
具体实施方式
实施例一：
本实施例一种过渡金属离子与Eu3+共掺杂型Na-β(β″)-Al2O3固体电解质陶瓷材料的制备方法，其步骤如下：
(1)埋烧料的制备
将纯度为99.31％、细度为325目的α-Al2O3和纯度为99.28％的Na2CO3按照化学式Na2Al10.67O17进行配料，以无水乙醇为球磨介质，按照球∶料∶无水乙醇＝4∶1∶1.2，进行球磨处理12h；球磨后得到的物料经烘干、过60目筛、在4Mpa下压制成型后，以5℃/min升温至1100℃进行煅烧处理，保温2h；煅烧处理后的物料经研磨、过60目筛，即制得埋烧料；
(2)预合成前驱体粉料的制备
以纯度为99.9％的α-Al2O3(细度为325目)、无水Na2CO3、Li2CO3、Eu2O3和CoO为原料进行配料，其中α-Al2O3、Na2CO3、Li2CO3、Eu2O3、CoO的用量分别为：100g、17.58g、2.2410g、1.22g、0.7675g；然后以无水乙醇为球磨介质，按照球∶料∶无水乙醇＝4∶1∶2，进行一次球磨处理12h；球磨后得到的物料经烘干、过60目筛、在4Mpa下压制成型后，以5℃/min升温至1100℃进行煅烧处理，保温2h；煅烧处理后的物料经研磨、过60目筛，即制得预合成前驱体粉料；
(3)固体电解质陶瓷的制备
将上述预合成前驱体粉料进行二次球磨处理(与上述一次球磨处理相同)，球磨后得到的物料经烘干、研磨、过80目筛、造粒(加入浓度为2wt％的聚乙烯醇缩丁醛的无水乙醇溶液作为粘结剂，聚乙烯醇缩丁醛的用量为物料的5wt％)、陈腐24h，得到处理料；将该处理料4.5g放入模具中在6Mpa压力下压制成厚度为1.5mm、直径为13mm的圆片，再将圆片放入橡胶手套中，抽真空，置于冷等静压机内于200MPa下保压90s；之后以1℃/min升温至650℃进行排胶处理，保温4h，随炉冷却，得到预烧件；然后，将该预烧件置于埋烧料内，以5℃/min升温至1580℃进行埋烧处理，保温30min，随炉冷却，即制得固体电解质陶瓷材料。
实施例二：
本实施例一种过渡金属离子与Eu3+共掺杂型Na-β(β″)-Al2O3固体电解质陶瓷材料的制备方法，与实施例一不同之处在于：
本实施例步骤(2)中铝源和M源分别为纯度99.9％的Al(OH)3和ZnO；步骤(2)中Al(OH)3、Na2CO3、Li2CO3、Eu2O3、ZnO的用量分别为：76.5006g、17.90g、2.2410g、1.05g、0.8330g；步骤(3)中埋烧处理温度为1610℃。
实施例三：
本实施例一种过渡金属离子与Eu3+共掺杂型Na-β(β″)-Al2O3固体电解质陶瓷材料的制备方法，与实施例一不同之处在于：
本实施例步骤(2)中铝源为纯度99.9％的Al(OH)3；步骤(2)中Al(OH)3、Na2CO3、Li2CO3、Eu2O3、CoO的用量分别为：76.5006g、17.74g、2.2410g、1.55g、1.2200g；步骤(3)中埋烧处理温度为1590℃。
本发明实施例制得的过渡金属离子与Eu3+共掺杂型Na-β(β″)-Al2O3固体电解质陶瓷材料，其XRD晶相图谱如图1所示，制得的陶瓷材料为β″-Al2O3纯相，由于M离子和Eu3+进入晶格代替Al3+，主晶相峰向左偏移。其扫描电镜图如图2所示，陶瓷材料具有致密的结构，孔隙率小。
性能测试：
交流阻抗图谱和电导率测试：采用交流阻抗法、利用中国东华公司的DH7000型电化学工作站(交流电振幅范围为10-1Hz-106Hz，交流电电压为20mV)测试陶瓷样品在300℃温度下的交流阻抗图谱。通过计算得到材料的Na+电导率：σ＝h/(S·R)，其中，σ是电导率，S·cm-1；h是样品厚度，cm；S是样品被银面积，cm2；R是样品交流阻抗值，Ω。测得的交流阻抗图谱如图3所示。
电导活化能计算：利用样品的电导率σ，将Arrnhenius公式σT＝Ae-Ea/(R·T)方程两边取对数得到lnσT＝lnA-Ea·R-1T-1，通过软件拟合得到图线的斜率，斜率的大小即为活化能数值，式中，A为特征常数；R为摩尔气体常数；Ea为电导活化能，单位为eV；T是热力学温度，单位为K。
通过交流阻抗图谱，经过相关计算，本发明实施例陶瓷材料的电导率和电导活化能如表1所示。
表1本发明实施例陶瓷材料的电导率和电导活化能
Figure BDA0003844064860000061

Claims (10)

1.一种过渡金属离子与Eu3+共掺杂型Na-β(β″)-Al2O3固体电解质陶瓷材料，其特征在于：在化学式ⅠNa1.67Li0.33Al10.67O17的基础上，引入过渡金属离子M和Eu3+；M为Mn2+、Co2+、Ni2+、Zn2+、Cu2+离子中的一种，其引入量按照摩尔比为Al3+∶M＝50～150∶1；Eu3+的引入量按照摩尔比为Al3+∶Eu3+＝300～800∶1；M离子和Eu3+掺杂进入陶瓷晶格代替Al3+。
2.根据权利要求1所述的过渡金属离子与Eu3+共掺杂型Na-β(β″)-Al2O3固体电解质陶瓷材料，其特征在于：所述固体电解质陶瓷材料的体积密度大于3.17g/cm3、300℃下的电导率＞0.070S·cm-1、电导活化能＜0.106eV。
3.权利要求1或2所述过渡金属离子与Eu3+共掺杂型Na-β(β″)-Al2O3固体电解质陶瓷材料的制备方法，其特征在于包括以下步骤：
(1)埋烧料的制备
将α-Al2O3和Na2CO3按照化学式Na2Al10.67O17进行配料，以无水乙醇为球磨介质进行球磨处理；球磨后得到的物料经烘干、过筛、压制成型后进行煅烧处理；煅烧处理后的物料经研磨、过筛，即制得埋烧料；
(2)预合成前驱体粉料的制备
以铝源、钠源、锂源、铕源、过渡金属离子M源为原料，其中铝源、锂源按照化学式ⅠNa1.67Li0.33Al10.67O17进行配料，钠源的用量比化学式Ⅰ中的计量数多加8～10wt％，过渡金属离子M源的用量按照摩尔比为Al3+∶M＝50～150∶1，铕源的用量按照摩尔比为Al3+∶Eu3+＝300～800∶1；然后以无水乙醇为球磨介质进行一次球磨处理；球磨后得到的物料经烘干、过筛、压制成型后进行煅烧处理；煅烧处理后的物料经研磨、过筛，即制得预合成前驱体粉料；
(3)固体电解质陶瓷的制备
将所述预合成前驱体粉料进行二次球磨处理，球磨后得到的物料经烘干、研磨、过筛、造粒、陈腐，得到处理料；将所述处理料放入模具中压制成型后，再用冷等静压压制，之后进行排胶热处理，得到预烧件；然后，将所述预烧件置于埋烧料内进行埋烧，即制得固体电解质陶瓷材料。
4.根据权利要求3所述的过渡金属离子与Eu3+共掺杂型Na-β(β″)-Al2O3固体电解质陶瓷材料的制备方法，其特征在于：所述步骤(1)中α-Al2O3和Na2CO3的纯度不低于99.2％；所述步骤(2)中原料的纯度不低于99.9％，所述铝源为α-Al2O3或Al(OH)3、钠源为无水Na2CO3或Na2C2O4、锂源为Li2CO3或Li2C2O4、铕源为Eu2O3；过渡金属离子M源中，锰源为MnCO3、钴源为CoO或2CoCO3·3Co(OH)2·H2O、镍源为NiO或NiCO3·2Ni(OH)2·4H2O、锌源为ZnO或Zn2(OH)2CO3、铜源为CuO或CuCO3·Cu(OH)2。
5.根据权利要求3所述的过渡金属离子与Eu3+共掺杂型Na-β(β″)-Al2O3固体电解质陶瓷材料的制备方法，其特征在于：所述步骤(1)中的球磨处理为按照球∶料∶无水乙醇＝4∶1∶1～1.5，球磨12h以上；所述步骤(2)中的一次球磨处理和二次球磨处理相同，为按照球∶料∶无水乙醇＝4∶1∶1～3，球磨12h以上。
6.根据权利要求3所述的过渡金属离子与Eu3+共掺杂型Na-β(β″)-Al2O3固体电解质陶瓷材料的制备方法，其特征在于：所述步骤(1)和步骤(2)的压制成型压力均为4～6Mpa，煅烧处理均为以5℃/min升温至1100～1150℃。
7.根据权利要求3所述的过渡金属离子与Eu3+共掺杂型Na-β(β″)-Al2O3固体电解质陶瓷材料的制备方法，其特征在于所述步骤(3)中造粒所用粘结剂采用聚乙烯醇缩丁醛或聚乙烯醇，聚乙烯醇缩丁醛或聚乙烯醇的用量为物料的3～7wt％。
8.根据权利要求3所述的过渡金属离子与Eu3+共掺杂型Na-β(β″)-Al2O3固体电解质陶瓷材料的制备方法，其特征在于：所述步骤(3)中在6～8Mpa下压制成型；冷等静压的压力为200～300MPa，保压时间至少为90s；排胶热处理的温度为以1℃/min升温至630～650℃。
9.根据权利要求3所述的过渡金属离子与Eu3+共掺杂型Na-β(β″)-Al2O3固体电解质陶瓷材料的制备方法，其特征在于：所述步骤(3)中埋烧处理的温度为以5℃/min升温至1570～1610℃。
10.利用权利要求3-9之一所述过渡金属离子与Eu3+共掺杂型Na-β(β″)-Al2O3固体电解质陶瓷材料的制备方法制得的产品。
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