CN115504770B - 一种过渡金属离子与Nd3+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Nd3+共掺杂型固体电解质陶瓷材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种过渡金属离子与Nd3+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Nd3+;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;Nd3+的引入量按照摩尔比为Al3+∶Nd3+=150~350∶1;M离子和Nd3+掺杂进入陶瓷晶格代替Al3+,Nd3+还以NdAlO3晶相的形式存在。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,掺杂过渡金属离子M以利于降低烧结温度而减少Na+挥发,同时抑制β"‑Al2O3晶相向β‑Al2O3晶相的转变;通过Nd3+的掺杂使材料缺陷少、致密度高,从而增强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。
Description
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Nd3+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,把过渡金属离子掺杂到固体电解质中,在利于降低烧结温度以减少Na+挥发的同时,抑制β"-Al2O3晶相向β-Al2O3晶相的转变,提高β″-Al2O3相含量;通过Nd3+的掺杂使材料缺陷少、致密度高,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Nd3+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Nd3+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Nd3+;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;Nd3+的引入量按照摩尔比为Al3+∶Nd3+=150~350∶1;M离子和Nd3+掺杂进入陶瓷晶格代替Al3+,Nd3+还以NdAlO3晶相的形式存在。
上述方案中,本发明所述固体电解质陶瓷材料体积密度大于3.19g/cm3、300℃下的电导率>0.08S·cm-1、电导活化能≤0.1031eV。
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Nd3+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、钕源、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8~12%,过渡金属离子M源的用量按照摩尔比为Al3+∶M=50~150∶1,钕源的用量按照摩尔比为Al3+∶Nd3+=150~350∶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、钕源为Nd2O3;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1560~1640℃。
利用上述过渡金属离子与Nd3+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和部分Nd3+进入陶瓷晶格代替Al3+,部分Nd3+以NdAlO3晶相的形式存在,均具有稳定β″-Al2O3相的作用,减少了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的β″-Al2O3相含量高。
(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Nd2O3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。掺杂的部分Nd3+以NdAlO3晶相的形式存在,一方面能够抑制晶界的生长,阻碍晶粒的异常长大,使陶瓷晶粒更加细小均匀;另一方面能减少断裂缺陷,并加速致密化,使得材料缺陷少、致密度高(其平均体积密度大于3.19g/cm3)。过渡金属离子的掺杂能降低烧结温度,减少Na+挥发,提高高温下β″-Al2O3相的稳定性。在两者的协同作用下,最终增强了Na-β"(β)-Al2O3固体电解质的性能。
(3)本发明制得的固体电解质陶瓷材料,由于β″-Al2O3相含量高、晶粒细小均匀、致密性好,因而陶瓷材料的电学性能好,300℃下陶瓷材料电导率>0.08S·cm-1、电导活化能≤0.1031eV。
(4)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:5000倍;b:1000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Nd3+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、Nd2O3和CoO为原料进行配料,其中α-Al2O3、Na2CO3、Li2CO3、Nd2O3、CoO的用量分别为:100g、17.90g、2.2410g、1.2177g、0.7675;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1600℃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Nd3+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、Nd2O3、ZnO的用量分别为:76.5006g、19.53g、2.2410g、1.8g、0.8330g;步骤(3)中埋烧处理温度为1620℃。
实施例三:
本实施例一种过渡金属离子与Nd3+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、Nd2O3、CoO的用量分别为:76.5006g、19.53g、2.2410g、1.1g、1.2200g;步骤(3)中埋烧处理温度为1580℃。
本发明实施例制得的过渡金属离子与Nd3+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,制得的陶瓷材料主晶相为β″-Al2O3,含有少量β-Al2O3相和NdAlO3相;由于M离子和Nd3+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
Claims (9)
1.一种过渡金属离子与Nd3+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Nd3+;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;Nd3+的引入量按照摩尔比为Al3+∶Nd3+=150~350∶1;M离子和Nd3+掺杂进入陶瓷晶格代替Al3+,Nd3+还以NdAlO3晶相的形式存在;所述固体电解质陶瓷材料的体积密度大于3.19 g/cm3、300℃下的电导率>0.08 S·cm-1、电导活化能≤0.1031 eV。
2.权利要求1所述过渡金属离子与Nd3+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、钕源、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8~12%,过渡金属离子M源的用量按照摩尔比为Al3+∶M=50~150∶1,钕源的用量按照摩尔比为Al3+∶Nd3+=150~350∶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。
3.根据权利要求2所述的过渡金属离子与Nd3+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、钕源为Nd2O3;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。
4.根据权利要求2所述的过渡金属离子与Nd3+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12 h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12 h以上。
5.根据权利要求2所述的过渡金属离子与Nd3+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℃。
6.根据权利要求2所述的过渡金属离子与Nd3+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%。
7.根据权利要求2所述的过渡金属离子与Nd3+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℃。
8.根据权利要求2所述的过渡金属离子与Nd3+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1560~1640℃。
9.利用权利要求2-8之一所述过渡金属离子与Nd3+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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