CN116254608A - 一种笼状有机-无机杂化多聚碘晶体材料及其制备方法与应用 - Google Patents
一种笼状有机-无机杂化多聚碘晶体材料及其制备方法与应用 Download PDFInfo
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- VLYLVPWRADZEDL-UHFFFAOYSA-N methylsulfanylmethane;hydroiodide Chemical compound [I-].C[SH+]C VLYLVPWRADZEDL-UHFFFAOYSA-N 0.000 claims abstract description 3
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Abstract
Description
技术领域
本专利于涉及新材料及其制备技术,特别涉及一种笼状有机-无机杂化多聚碘晶体材料及其制备方法与用途。
背景技术
碘及其化合物在工业生产、太阳能电池、动物饲料、着色剂、医学、药学、光学器件、公共卫生、消毒剂和树脂稳定剂等各领域均有广泛的应用。近几年来,随着能源结构调整,可再生能源技术及新型储能技术得到快速发展,碘因其自身具有的较高的理论比热容量(211mAh g-1)、体积比热容(1040mAh g-1),较高的工作电压(2.9V),在太阳能电池尤其钙钛矿太阳能电池及新能源电池(锌碘电池、锂碘电池、钠碘电池)中有重要应用。但截至目前,基于碘离子的电池一直未实现商业化应用,一是因为碘热稳定性,易升华,在材料制备过程中产生的碘蒸气具有较强腐蚀性和毒性;二是碘导电性不高,反应动力学条件差,材料倍率性能较差;三是其在充电过程形成的三碘离子(I3–)极易穿梭至负极造成的自放电及库伦效率降低。
为了克服以上问题,现有技术中,一种常用做法是使用离子交换膜阻挡I3–穿梭,但这会增加电池成本和内阻;另一种有效策略是通过制备合适的碳材料来增强碘的负载量和导电性,例如将I2封装在微孔碳正极中,从而将I2/I–转化反应限制在微孔内并防止I3–的产生和穿梭,但受限于微孔碳中I2的载量,存在库伦效率低、能量密度低等问题。
发明内容
鉴于上述领域的需求,本发明通过选择小分子阳离子作为模板剂,在高温下与碘单质溶熔反应,形成的聚碘离子链通过卤素键及分子内相互作用形成笼型超分子框架,形成了一种高含量碘、高稳定性的有机无机杂化晶体材料,其具有稳定的热化学及电化学性质,应用在电池正极材料中更加稳定,克服碘含量不足、能量密度低及传统I3-离子的穿梭效应,在储能电池领域显示出潜在的应用前景。具体技术方案如下:
根据本发明的示例性技术方案,所述晶体材料具有以下晶胞参数:
根据本发明的笼状有机-无机杂化多聚碘晶体材料,其特征在于,所述多聚碘晶体材料的基本结构单元由小分子阳离子及多聚碘阴离子构成;
所述阳离子为质子化二甲基亚砜。
3个式(I)所示的质子化DMSO,
1个式(II)所示的I11 -,
0.5个式(III)所示的I12 -,
1个式(IV)所示的I9 -,
根据本发明所述的笼状有机-无机杂化多聚碘晶体材料,其特征在于,其晶胞结构示意图如图1所示;其堆积图示意图如图2所示;其笼型框架示意图如图3所示。
根据本发明所述的笼状有机-无机杂化多聚碘晶体材料,其特征在于,在6℃以上环境中所述晶体材料为流体状,在100℃条件下起蒸发量低于0.1g/小时。
根据本发明所述的笼状有机-无机杂化多聚碘晶体材料,其特征在于,所述晶体材料中碘的摩尔质量分数为93%。
本发明的另一方面提供上述晶体材料的制备方法,其步骤如下:
将碘单质溶于二甲基亚砜中,在60~80℃条件下保温溶解1~2小时,然后升温至100~120℃条件下保温反应20~40min,放出所产生气体后,升温至150~180℃条件下保温反应20~40min,所得产品冷却至室温后,至-2~2℃条件下低温结晶,除去上层液体,然后恢复至室温条件下液化,再用蒸馏水反复洗涤5-10次,再次低温结晶既得本晶体材料。
根据本发明的示例性技术方案:将碘单质溶于二甲基亚砜中,在60、70或80℃条件下保温溶解1~2小时,然后升温至100或110或120℃条件下保温反应20~40min,放出所产生气体后,升温至150、160、170或180℃条件下保温反应20~40min,所得产品冷却至室温后,至-2~2℃条件下低温结晶,除去上层液体,然后恢复至室温条件下液化,再用蒸馏水反复洗涤5-10次,再次低温结晶既得本晶体材料。
根据本发明的示例性技术方案,所述的晶体材料的制备方法,其特征在于,碘单质与二甲基亚砜的质量比为1:2~5。
本发明的再一方面,提供一种电池正极材料,其特征在于,包含本发明提供的上述笼状有机-无机杂化多聚碘晶体材料与多孔碳材料在真空密闭条件下加热复合而得。
优选地,所述正极材料中碘含量在30%-80%之间;
优选地,所述多孔碳材料选自石墨烯、碳纳米管、乙炔黑、活性炭布、CMK-3、多孔导电碳黑等中的一种或几种;
所述复合制备方法为:50-90℃条件下,将所述多聚碘晶体材料与多孔碳材料充分混合搅拌,反应1-4小时后除去未反应多聚碘晶体材料,用水洗涤,干燥既得正极复合材料。
本发明的再一方面,提供一种电池,其特征在于,其采用上述正极材料。
上述笼状有机-无机杂化多聚碘晶体材料在制备电池或电池正极材料中的应用。
本发明提供了一种新型的笼状有机-无机杂化晶体材料,具有以下有有益效果:
(1)本发明提供的晶体材料具有良好的导电性,电导率在25℃时为68.23ms/cm,且随着温度的升高逐渐升高;在6℃以上为流体状态,并且在100℃条件下蒸发率低于0.1克/小时,具有非常强的热稳定性;由于三维网络框架的存在,提供高比表面积,充分利用氧化还原活性位点,且更容易与碳材料杂化结合。
(2)本发明提供的晶体材料制备方法简单,通过一锅法制备所得,无需经过中间体分离即可直接获得终产物,工艺经济性高,环境友好,易于控制。
(3)本发明提供的晶体材料中碘的摩尔质量分数为93%,远超传统锌碘液流电池常用电解液碘化锌、碘化钾中碘摩尔质量分数(76%-79%),所以理论能量密度及比热容量均高于碘盐;由于小分子阳离子模板剂的引入,及卤键(类似于氢键)组成的I9 -、I11 -、I12 ﹣聚碘负离子链的形成,该晶体材料具有超强的抗溶解能力及抗穿梭效应,极大降低碘在有机电解液中的溶解性,可作为锌碘电池正极材料的电化学活性物质;与传统碘单质不同,其具有一定良好的导电性,可赋予电池材料良好的电化学性能。
附图说明
图1.本发明提供的晶体材料的晶胞结构示意图;
图2.本发明提供的晶体材料堆积结构示意图;
图3.本发明提供的晶体材料,其中聚碘阴离子形成的片层笼型框架示意图;
图4.本发明提供的晶体材料的电导率测定结果。
具体实施方式
以下通过实施例示范本发明提供的晶体材料的制备方法及应用效果,但是并不作为本发明保护范围的限定。
实施例1
取50克碘置于250毫升圆底烧瓶中,加入100毫升二甲基亚砜,搅拌溶解后,在70℃油浴条件下,保温2小时,再升温至120℃,保温反应60min;反应过程中注意及时放出反应过程溶解分解所产生的气体,再升温至180℃,保温反应30min,所得产品置于0℃条件下低温结晶,除去上层液体,然后恢复至室温条件下液化,再用蒸馏水反复洗涤10次,再次低温结晶,既得本发明晶体材料39g,得率78%。
实施例2
取50克碘置于250毫升底烧瓶中,加入150毫升二甲基亚砜,搅拌溶解后,在70℃油浴条件下,保温2小时,再升温至120℃,保温反应60min,反应过程中注意及时放出反应过程溶解分解所产生的气体,再升温至180℃,保温反应30min,所得产品置于0℃条件下低温结晶,除去上层液体,然后恢复至室温条件下液化,再用蒸馏水反复洗涤10次,再次低温结晶,既得本晶体材料41g,得率82%。
实施例3
取50克碘置于250毫升圆底烧瓶中,加入100毫升二甲基亚砜,搅拌溶解后,在80℃油浴条件下,保温1小时,再升温至120℃,保温反应40min,反应过程中注意及时放出反应过程溶解分解所产生的气体,再升温至150℃,保温反应40min,所得产品置于0℃条件下低温结晶,除去上层液体,然后恢复至室温条件下液化,再用蒸馏水反复洗涤5次,再次低温结晶,既得本晶体材料36.2g,得率72%。
实施例4
取50克碘置于250毫升圆底烧瓶中,加入100毫升二甲基亚砜,搅拌溶解后,在80℃油浴条件下,保温2小时,再升温至120℃,保温反应40min,反应过程中注意及时放出反应过程溶解分解所产生的气体,再升温至180℃,保温反应40min,所得产品置于0℃条件下低温结晶,除去上层液体,然后恢复至室温条件下液化,再用蒸馏水反复洗涤8次,再次低温结晶,既得本晶体材料43g,得率86%。
实施例5
取50克碘至于250毫升圆底烧瓶中,加入200毫升二甲基亚砜,搅拌溶解后,在80℃油浴条件下,保温1小时,再升温至120℃,保温反应20min,反应过程中注意及时放出反应过程溶解分解所产生的气体,再升温至150℃,保温反应20min,所得产品至0℃条件下低温结晶,除去上层液体,然后恢复至室温条件下液化,再用蒸馏水反复洗涤5次,再次低温结晶,既得本晶体材料33g,得率66%。
实施例6
取50克碘至于250毫升圆底烧瓶中,加入100毫升二甲基亚砜,搅拌溶解后,在70℃油浴条件下,保温1小时,再升温至120℃,保温反应40min,反应过程中注意及时放出反应过程溶解分解所产生的气体,再升温至180℃,保温反应20min,所得产品至0℃条件下低温结晶,除去上层液体,然后恢复至室温条件下液化,再用蒸馏水反复洗涤5次,再次低温结晶,既得本晶体材料23.5g,得率47%。
实验例1.
取实施例1~6所得晶体材料进行单晶X-衍射测定。
方法为:在单晶衍射仪上用经石墨单色器单色化的Mo Kα射线,温度为117.45K,收集衍射数据。
晶胞参数用最小二乘法确定:先用差值函数法和最小二乘法确定全部非氢原子坐标,并用理论加氢法得到主体骨架的氢原子位置,然后用最小二乘法对晶体结构进行精修。
本申请制备晶体材料的晶体学衍射点数据收集与结构精修的部分参数见下表1:
表1晶体学结构参数
实验例2.导电性测定
采用赛默飞台式电导率仪测定本发明所得晶体材料在20℃-90℃条件下的导电性。
以实施例4所得晶体材料为例,测定结果如图4所示,其电导率在25℃时为68.23ms/cm,且随着温度的升高逐渐升高。
实验例3.热稳定性测定
实施例4所得晶体材料为例进行热稳定性测定。
测定步骤:分别取0.5克晶体材料置于表面皿中,在100-200℃条件下蒸发,测定完全蒸发所需时间。
实施例4所得晶体材料的结果如表2所示,结果表明,流体碘在高温条件下,200℃时碘蒸发时间为29分钟;在100℃条件下每小时蒸发量低于0.1g,表现出极强的稳定性。
表2流体碘在高温条件下的稳定性
实验例4电化学性能测定
将本发明所提供晶体材料与活性炭布按质量比3:1充分混合,搅拌条件下加热至60℃,保温反应1小时后,取出活性炭布,在80℃条件下干燥既得正极复合材料;所得复合材料中碘含量为76.5%,
将复合材料制作为正极片,进行恒电流充放电测试和循环性能测定(测试流程参考:赵庆.金属二次电池正极材料(硫、碘、碳氧盐)的室温制备和电化学性能研究,南开大学,2017.)
结果显示:在1C的速率下充放电容量为359m Ah g-1,循环500次之后,比容量保持在271m Ah g-1;在5C的大电流密度下,依然表现出200m Ah g-1的电池容量;当电流密度重新回到1C时,电池容量可恢复到1C循环时96%以上的电池容量,较对比例1体现出了优异的循环稳定性和倍率性能。
对比例1
将实验例4中的本发明的晶体材料替换为单质碘材料,同样质量比例、反应温度、反应时间及干燥条件下将单质碘溶于水中,并将活性炭布放入活性炭布,采用溶解吸附法制备电极复合材料(方法参考赵庆.金属二次电池正极材料(硫、碘、碳氧盐)的室温制备和电化学性能研究,南开大学,2017.)所得复合材料中碘含量为49.5%。
将其制作为正极片进行恒电流充放电测试,在1C的速率下充放电容量为251m Ahg-1,循环500次之后,容量为159m Ah g-1;在5C的大电流密度下,为127m Ah g-1的电池容量,当电流密度重新回到1C时,电池容量仅恢复到1C循环时74%左右。
可以看出,与单质碘相比,本发明提供的晶体材料在电化学性能上极显著提高。
本领域的技术人员容易理解,以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内的所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (10)
2.根据权利要求1所述的笼状有机-无机杂化多聚碘晶体材料,其特征在于,所述多聚碘晶体材料的基本结构单元由小分子阳离子及多聚碘阴离子构成;所述阳离子为质子化二甲基亚砜。
4.根据权利要求1所述的笼状有机-无机杂化多聚碘晶体材料,其特征在于,其晶胞结构如图1所示;其堆积图如图2所示;其笼型框架如图3所示。
5.根据权利要求1所述的笼状有机-无机杂化多聚碘晶体材料,其特征在于,在6℃以上环境中所述晶体材料为流体状;在100℃条件下其蒸发量低于0.1g/小时。
6.根据权利要求1所述的笼状有机-无机杂化多聚碘晶体材料,其特征在于,所述晶体材料中碘的摩尔质量分数为93%。
7.权利要求1-6任一所述的晶体材料的制备方法,其步骤如下:
将碘单质溶于二甲基亚砜中,在60~80℃条件下保温溶解1~2小时,然后升温至100~120℃条件下保温反应20~60min,放出所产生气体后,升温至150~180℃条件下保温反应20~40min,所得产品冷却至室温后,置于-2~2℃条件下低温结晶,除去上层液体,然后恢复至室温条件下液化,再用蒸馏水反复洗涤5-10次,再次低温结晶既得本晶体材料。
8.权利要求7所述的晶体材料的制备方法,其特征在于,碘单质与二甲基亚砜的质量比为1:2~5。
9.一种电池正极材料,其特征在于,是权利要求1~6任一所述的笼状有机-无机杂化多聚碘晶体材料与多孔碳材料复合制备而得。
优选地,所述正极材料中碘含量在30%-80%之间;
优选地,所述多孔碳材料选自石墨烯、碳纳米管、活性炭布、CMK-3、多孔导电碳黑等中的一种或几种;
优选地,所述复合制备方法为:50-90℃条件下,将所述多聚碘晶体材料与多孔碳材料充分混合搅拌,反应1-4小时后除去未反应多聚碘晶体材料,用水洗涤,干燥既得正极复合材料。
10.权利要求1-6任一所述的晶体材料在电池正极材料中的应用。
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