CN113955786B - 一种明矾基水凝胶及其制备方法与其在能量存储中的应用 - Google Patents
一种明矾基水凝胶及其制备方法与其在能量存储中的应用 Download PDFInfo
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Abstract
本发明首次提出一种明矾基水凝胶，可作为水凝胶电解质，其具有由非晶态的明矾类化合物构成的三维网状结构;所述三维网状结构中填充硫酸盐水溶液；所述明矾类化合物包含金属M，所述硫酸盐水溶液为所述M的硫酸盐水溶液。这种水凝胶展现出高的离子电导率（110 mS cm‑1），水含量为71 wt%。本发明为低浓度电解质实现宽电化学稳定窗口提供了可行性方案，为水系高能量密度存储器件（如，固态超级电容器）的发展奠定基础，有望实现大规模应用。
Description
技术领域
本发明属于新能源领域，具体涉及水系高能量密度电化学能量存储领域，更具体涉及高能量密度固态超级电容器、宽电化学稳定窗口水凝胶电解质的制备方法。
背景技术
电动汽车储能单元的安全问题越来越受到广泛关注，如夏季自燃，其中液态电解质起负面作用。近年来，非液态电解质得到更多的发展，它们是陶瓷、聚合物和水凝胶电解质。然而，非液体电解质存在不可忽视的缺点。水凝胶电解质具有低的电化学稳定窗口，导致低的能量密度。目前的改善策略集中在选择合适的溶剂和溶质以获得宽电压窗口。此外，实现陶瓷电解质在电极上的良好界面接触和聚合物电解质的高离子电导率,也具有很大的挑战。因此，获得一种同时具有宽电压窗口和高离子电导的非液体电解质是一个巨大的挑战。
水凝胶电解质(例如，聚乙烯醇/Li2SO4)展现出低的电化学稳定窗口。通过提高盐浓度，降低水活性，可拓宽电化学稳定窗口。“盐包水”电解质是近年来首次报道的高浓度水系电解质。例如，21mol kg-1的LiTFSI“盐包水”电解质，由于溶剂水的活性降低，显示出高达3V的电化学稳定窗口，离子电导仅有10mS cm-1。但普通聚合物(例如，聚乙烯醇)只能容纳低浓度的电解质盐。此外，电解质盐的成本昂贵和氟化盐产生的毒性在很大程度上限制了它们更进一步的实际应用。基于此，最近报道了一种不含聚合物的CH3COOK凝胶电解质，其浓度高达48mol kg-1，展现出4V的宽电化学稳定窗口，室温下离子电导率只有10.9mS cm-1。因此，可将“盐包水”引入凝胶电解质拓宽其电化学稳定窗口，也有文献报道采用自由基聚合法，在聚电解质水凝胶中嵌入24mol kg-1CH3COOK，制备出了“盐包水”水凝胶，其电化学稳定窗口电压达到3.1V，离子电导率为35.8mS cm-1。为了提高离子电导，一种新型聚丙烯酰胺-壳聚糖基“盐包水”水凝胶电解质显示出51.3mS cm-1的高离子电导率，但电化学稳定窗口只有2.6V。由此可见，电压窗口越高，离子电导率越低，尽管二者之间没有直接关系。因此，同时获得具有宽电化学稳定窗口和高离子电导率的水凝胶电解质是一个巨大的挑战。
发明内容
一方面，本发明提供一种明矾基水凝胶，可作为电解质在应用于能量存储中。该水凝胶具有由非晶态的明矾类化合物构成的三维网状结构；所述三维网状结构中填充硫酸盐水溶液；所述明矾类化合物包含金属M，所述硫酸盐水溶液为所述M的硫酸盐水溶液。
本发明不依托于提高电解液浓度来拓宽电化学稳定窗口，因此不存在因电解液浓度高而带来的离子电导下降的问题，其水含量达到71wt％。本发明利用明矾的强水合作用，抑制水凝胶中水的活性，使得其电化学稳定窗口达到了～4.6V，获得高的能量密度，在水系储能领域和固态储能器件中具有广泛的应用。
具体的，上述金属M可以为第一主族金属，包括Na、K、Cs等，但不限于此。对应的明矾类化合物为NaAl(SO4)2·12H2O、KAl(SO4)2·12H2O和CsAl(SO4)2·12H2O；对应的硫酸盐水溶液为：Na2SO4水溶液、K2SO4水溶液、Cs2SO4水溶液。
另一方面，上述水凝胶通过溶胶凝胶法即可制备得到，具体为：将硫酸铝、MSO4、MOH混合，搅拌形成溶胶，室温下，静置15天以上得到水凝胶；所述MSO4表示金属M的硫酸盐，MOH表示金属M的氢氧化物。
上述硫酸铝、MSO4、MOH组合的混合体系中，OH-小于2mol/L。
本发明的有益效果在于:
本发明使用原料简单，制备条件简单，这对未来工业大规模应用十分有利。相比于在工业生产中，由硫酸钠和硫酸铝在80℃下混合制备NaAl(SO4)2·12H2O具有更低的成本。
本发明在保证高离子电导(110mS cm-1)的同时，使得水凝胶的电化学稳定窗口达到4.6V，水含量达到71wt％。水凝胶固态的特征，也可以使其兼做隔膜。可以提高水系储能器件的工作电压窗口，极大的提高储能器件的能量密度和安全性，如电化学超级电容器。
总之，本发明为低浓度电解质实现宽电化学稳定窗口提供了可行性方案，为水系高能量密度存储器件(如，固态超级电容器)的发展奠定基础，有望实现大规模应用。
附图说明
图1填充有硫酸钠水溶液的三维网状固态NaAl(SO4)2·12H2O固态水凝胶(SASSH)。
图2SASSH和1mol L-1硫酸钠水溶液分别作为电解质的线性扫描伏安曲线。
图3SASSH和1mol L-1硫酸钠水溶液分别作为电解质的离子电导(25℃)和水含量。
图4SASSH的X射线衍射图谱。
图5冷冻干燥的和惰性气氛退火的SASSH的X射线衍射图谱。
图6SASSH热重曲线。
图7基于SASSH固态电化学电容器光学图片。
图8长循环后的能量密度和功率密度图。
图9长循环后的循环伏安曲线。
图10KAl(SO4)2·12H2O固态水凝胶和CsAl(SO4)2·12H2O固态水凝胶的线性扫描伏安曲线。
图11KAl(SO4)2·12H2O固态水凝胶和CsAl(SO4)2·12H2O固态水凝胶的离子电导图(25℃)。
具体实施方式
为了使本发明的目的、技术方案等更加清楚，结合以下图例及实施例，对本发明作进一步的详述。此处所描述的具体实施例用于解释本发明，并不用于限定本发明。
实施例1：将8.6084g硫酸钠加入装有60mL去离子水的烧杯中(容积100mL)，磁力搅拌，使其完全溶解。在磁力搅拌的同时，加入14.40208g十八水合硫酸铝，待其完全溶解后，再加入4g NaOH，在磁力搅拌的同时，使用玻璃棒辅助搅拌，进而形成白色溶胶。将盛有溶胶的烧杯置于室温的水浴锅中，放置5分钟，取出，磁力搅拌5分钟。取出磁子，于实验室中静置15天，使其完成转变成凝胶。所得的凝胶SASSH位于烧杯底部，如图1所示。
将本实施例得到的白色凝胶为固态电解质，将两个铂片电极插入其中，在电化学工作站上测试交流阻抗谱，频率参数范围为0.01-1MHz，振幅为默认参数。计数其电导，得到25℃下的离子电导为110mS cm-1。用线性扫描伏安法测其电化学稳定窗口，具体方法是以钛片作为工作电极，以铂片为工作电极，饱和甘共电极为参比电极，扫速为10mV s-1，电位区间为-1.8-5V。如图2所示，该SASSH的稳定电化学窗口能达到4.6V。如图3所示，该SASSH的离子电导110mS cm-1，和1M Na2SO4水溶液电解质(1M Na2SO4 AE)的离子电导相当。
通过X射线衍射确定本实施例得到的凝胶电解质的物相。如图4所示，SASSH的X射线衍射展现出典型的水凝胶特征。通过冷冻干燥，得到SASSH白色粉末，其X射线衍射出现Na2SO4(PDF#37-1465，硫酸铝和氢氧化钠生成)和Na2SO4(PDF#24-1132，添加的硫酸钠)。对SASSH白色粉末在500℃和氩气氛围下，进行热处理后，发现其X射线衍射谱线出现了结晶的Na3Al(SO4)3和Na2SO4(PDF#24-1132)。由热处理前后的X射线衍射谱线，可确定失去水的SASSH白色粉末中含有NaAl(SO4)2。根据图6的SASSH热重曲线(TGA)，计算得到水合物中水的计量数为12，也就是一个NaAl(SO4)2分子，可以结合12份水，即NaAl(SO4)2·12H2O。因此，可得到SASSH水凝胶由非晶NaAl(SO4)2·12H2O和硫酸钠水溶液构成。
对于基于SASSH固态水凝胶电解质的电化学电容器，采用原位凝胶化制备，如图7所示，制备方法具体如下：
将夹有1平方厘米见方的碳布作为正负极，插入本实施例制备的溶胶中，待其凝胶化，便可制备获得固态电化学超级电容器。其电解质水含量达到71wt％，也即电解质是低浓度。因该凝胶是固态的，所以，既能做电解质，也能充隔膜。如图8所示，该固态超级电容器的能量密度可达到29Wh kg-1；如图9所示，稳定工作电压区间可从0至2.5V。其工作电压窗口明显高于目前水系超级电容器2V的工作电压窗口，且其能量密度高于目前的10Wh kg-1。
实施例2：本实施例采用硫酸钾(10.56g)和氢氧化钾(5.44g)分别替代实施例1中的硫酸钠和氢氧化钠,其余操作不变，制备出非晶KAl(SO4)2·12H2O凝胶(PASSH)。
如图10和11所示，该PASSH凝胶展现出宽的电化学稳定窗口(4.6V左右)和高的离子电导率(137mS cm-1以上)。
实施例3：本实施例采用硫酸铯(21.73g)和氢氧化铯(16.97g)分别替代实施例1中的硫酸钠和氢氧化钠,其余操作不变，制备出CsAl(SO4)2·12H2O凝胶(CASSH)。
如图10和11所示，该CASSH凝胶展现出宽的电化学稳定窗口(4.6V左右)和高的离子电导率(104mS cm-1以上)。
Claims (3)
1.一种明矾基水凝胶，其特征在于，具有由非晶态的明矾类化合物构成的三维网状结构；所述三维网状结构中填充硫酸盐水溶液；所述明矾类化合物包含金属M，所述硫酸盐水溶液为所述M的硫酸盐水溶液；
所述金属M为第一主族金属，包括Na、K和Cs，对应明矾类化合物为NaAl(SO4)2·12H2O、KAl(SO4)2·12H2O和CsAl(SO4)2·12H2O，对应的硫酸盐水溶液为Na2SO4水溶液、K2SO4水溶液和Cs2SO4水溶液。
2.如权利要求1所述水凝胶的制备方法，该方法为：将硫酸铝、MSO4、MOH混合形成溶胶，室温下静置15天以上得到水凝胶；所述MSO4表示金属M的硫酸盐，MOH表示金属M的氢氧化物。
3.如权利要求1所述水凝胶作为电解质在能量存储中的应用。
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