CN108385132B - 一种Co掺杂MoS2阵列原位电极的CVD制备方法 - Google Patents
一种Co掺杂MoS2阵列原位电极的CVD制备方法 Download PDFInfo
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Abstract
本发明提供一种Co掺杂MoS2阵列原位电极的CVD制备方法，具体制备方法为：钴盐和氯化钼溶于挥发非水溶剂中，获得Co‑Mo前躯液；上述前躯液涂布到基底上，干燥后在Ar+S气氛中或N2+S气氛中，CVD硫化。硫化反应温度为600~800℃，反应时间为10 min~2 h。本发明的技术方案可用于电解水制氢和染料敏化太阳能电池，对于原位电极的批量生产有重大意义。
Description
技术领域
本发明涉及原位电极及其制备方法，属于能量存储和转换新型材料领域。
背景技术
二硫化钼MoS2作为一种类石墨新型材料，被广泛用于加氢脱硫、锂离子电池、超级电容器、电解水制氢和染料敏化太阳能电池等诸多领域。MoS2层内 S-Mo-S以共价键结合，层间以分子键结合，因而层内的电导率是层间的上千倍。此外，二硫化钼层边缘Mo、S原子因配位不饱和而具有高的催化活性，而层内配位饱和的S原子基本是惰性的。因此，制备S-Mo-S层垂直于基底生长的硫化钼片层将极大地提高二硫化钼的电催化性能，、其一，经基底传输过来的电子将沿 MoS2的S-Mo-S层内方向传输，电荷传输加快；其二，定向生长MoS2能缩短电催化反应需要电子的传输路径；其三，绝大部分边缘Mo、S原子将直接暴露于反应体系，使得二硫化钼的活性位点能被充分高效地利用。斯坦福大学的崔毅课题组于2015年报道了垂直于基底生长的二硫化钼，所制备的二硫化钼几乎90°垂直于基底，结构非常完整致密。然而，这样二硫化钼电极的制备工艺较复杂，首先用物理方法沉积一层约20nm的Mo金属膜，再气氛硫化。
此外，这种垂直生长MoS2的催化性能较Pt仍有十分的差距，如何进一步提高二硫化钼的电催化活性仍是一个研究热难点。2017年，中科院包信和院士课题组发现单金属原子掺杂能将惰性的基面硫原子变得具有高的催化活性，例如：钴、金、铂等。其中钴掺杂相比于金和铂，更廉价，因而更具优势。然而，这种Co 掺杂MoS2是粉末，仍需制成浆料或墨水状再涂覆成膜，这在增加了工艺复杂性和成本的同时也无法实现二硫化钼片层的垂直生长。
发明内容
有鉴于此，本发明的目的是提供一种原位制备垂直生长Co掺杂MoS2阵列的方法，该方法具有设备要求低、所需原料成本低廉、反应条件易于控制、生产工艺简单、所形成的产品一致性好，环境污染小等优点，可用于电解水制氢和染料敏化太阳能电池，对于原位电极的批量生产有重大意义。
为此，本发明提供了一种Co-Mo前躯液成均匀膜后再气氛硫化，制备出垂直于基底生长的Co掺杂MoS2阵列的化学气相沉积方法，包括如下步骤：
第一步、在室温搅拌条件下，将钴盐和氯化钼溶于乙醇等极性易挥发溶剂，获得Co-Mo前躯液，其中Co、Mo原子的浓度之和为200～700mM。该步骤的意义在于：前驱液内几乎无水分子，防止氯化钼水解；反应试剂均匀分散，获得均匀无沉淀的Co元素与Mo元素在原子尺度均匀混合的前躯液为制备均匀Co掺杂 MoS2阵列打下良好基础。
第二步、将上述前躯液滴涂或旋涂到基底上，如导电玻璃、石墨纸、碳布、铜或镍箔，于干燥空气中干燥，或于热台上70～100℃快速干燥，该步骤的意义在于：乙醇快速挥发后留下由钴盐和氯化钼均匀混合的前驱膜层，且该前驱膜厚度均匀，保证后续化学气相沉积反应后仍获得均匀的Co掺杂MoS2膜。
第三步、将步骤二中前驱膜于Ar+S气氛中或N2+S气氛中，经600～800℃烧结10min～2h，随炉冷却取出即可得到垂直于基底生长的Co掺杂MoS2阵列原位电极。该步骤的意义在于：利用高温下Co源等较Mo源更易气化这一特点，它们被快速蒸发的蒸气流是垂直于基底的，这相当于模板或模具使得高温硫化新生长出的二硫化钼垂直于基底；利用Co-Mo-S之间强的原子相互作用，形成Co掺杂 MoS2。
附图说明
图1为实施例1所制备电极的SEM图。
图2为实施例2所制备电极的SEM图。
图3为实施例3所制备电极的SEM图，(a)2万放大倍率图，(b)5万放大高倍率图。
图4为实施例4所制备电极的(a)SEM图，(b)元素能谱EDS图，(c)元素分布 EDS-mapping图。
图5为实施例4所制备电极的XRD图。
图6为实施例5所制备电极的SEM图，(a)2万放大倍率图，(b)5万放大高倍率图
图7为实施例6所制备电极的SEM图，(a)2万放大倍率图，(b)5万放大高倍率图
图8为实施例7所制备电极的SEM图，(a)2万放大倍率图，(b)5万放大高倍率图
图9为实施例2所制备电极(Co-doped MoS2-1)、实施例4所制备电极(Co-dopedMoS2-2)、二硫化钼电极(MoS2)、硫化钴电极(CoSx)、负载在掺氟二氧化锡透明导电玻璃基底上的铂电极(Pt)所组成对称电池的EIS图。
图10为实施例2所制备电极(Co-doped MoS2-1)、实施例4所制备电极(Co-dopedMoS2-2)、二硫化钼电极(MoS2)、硫化钴电极(CoSx)、负载在掺氟二氧化锡透明导电玻璃基底上的铂电极(Pt)的CV图。
图11为实施例2所制备电极(Co-doped MoS2-1)、实施例4所制备电极(Co-dopedMoS2-2)、二硫化钼电极(MoS2)、硫化钴电极(CoSx)、负载在掺氟二氧化锡透明导电玻璃基底上的铂电极(Pt)所组成染料敏化太阳能电池的JV图。
图12实施例2所制备电极(Co-doped MoS2-1)、实施例4所制备电极(Co-dopedMoS2-2)、二硫化钼电极(MoS2)、硫化钴电极(CoSx)、负载在掺氟二氧化锡透明导电玻璃基底上的铂电极(Pt)的LSV图。
实施例1：
在室温下，将氯化钴、氯化钼溶于乙醇溶液，其中氯化钴的浓度为10mM，氯化钼的浓度为290mM，钴原子与钴原子加钼原子数目之和的比为5％，通Ar 气抽真空反复三次将管式炉内残余空气排出后，再通Ar，流量为5SCCM，管式炉上部放有0.2g硫粉，随着管式炉内温度升高，硫粉蒸发形成硫蒸气，。将该前躯液滴涂到平整的石墨纸基底表面，于热台上90℃干燥10min。将有涂层的基底放入管式炉，在Ar+S气氛下800℃反应30min，自然冷却后取出即可。图1示意了本实施例的SEM图，由图可知有少量的100nm左右的纳米片约垂直于基底生长。
实施例2：
在室温下，将氯化钴、氯化钼溶于乙醇溶液，其中氯化钼的浓度为290mM，钴原子与钴原子加钼原子数目之和的比为10％。将该前躯液滴涂到平整的石墨纸基底表面，于热台上90℃干燥10min。将有涂层的基底放入管式炉，通Ar气抽真空反复三次将管式炉内残余空气排出后，再通Ar，流量为2SCCM，管式炉上部放有1g硫粉，随着管式炉内温度升高，硫粉蒸发形成硫蒸气，在Ar+S气氛下800℃反应30min，自然冷却后取出即可。图2示意了本实施例的SEM图，由图可知许多的100nm宽、20nm厚的纳米片垂直于基底生长。图9示意了本实施例所制备样品(Co-doped MoS2-1)的交流阻抗EIS图，相对于同样制备工艺未添加钴源的纯的MoS2(MoS2)，本实施例所制备样品的性能大幅提高，串联电阻(Rs)由 5.22Ωcm-2下降为1.07Ωcm-2，界面电荷转移电阻(Rct)由4.09Ωcm-2下降为1.10 Ωcm-2，如表1所示。图10示意了本实施例所制备样品(Co-doped MoS2-1)的循环伏安CV图，相对于同样制备工艺未添加钴源的纯的MoS2(MoS2，其未出现明显的氧化还原峰)，本实施例所制备样品出现了与Pt类似的氧化还原峰，表明本实施例所制备样品已具备较好的电催化碘三负还原为碘负的能力，且可逆性较好。图11示意了本实施例所制备样品(Co-doped MoS2-1)的光电流-电压JV曲线图，如表1中所示，相对于同样制备工艺未添加钴源的纯的MoS2(MoS2)和Pt电极，本实施例所制备样品所组装的染料敏化太阳能电池的光电转化性能大幅提高，效率为8.06％，高于纯的MoS2(6.94％)和Pt(7.90％)。图12示意了本实施例所制备样品(Co-doped MoS2-1)的电催化产氢的线性伏安扫描LSV曲线图，如表1中所示，相对于同样制备工艺未添加钴源的纯的MoS2(MoS2)和同样制备工艺未添加钼源的纯的CoSx电极，本实施例所制备样品的催化产氢性能大幅提高，当电流密度为10mAcm-2，所需的过电位为245mV，低于MoS2(385mV)和CoSx(291 mV)。
实施例3：
在室温下，将氯化钴、氯化钼溶于乙醇溶液，其中氯化钼的浓度为290mM，钴原子与钴原子加钼原子数目之和的比为15％。将该前躯液滴涂到平整的石墨纸基底表面，于热台上90℃干燥10min。将有涂层的基底放入管式炉中部，通Ar 气抽真空反复三次将管式炉内残余空气排出后，再通Ar，流量为1SCCM，管式炉上部放有0.5g硫粉,随着管式炉内温度升高，硫粉蒸发形成硫蒸气，在Ar+S 气氛下800℃反应30min，自然冷却后取出即可。图3(a)示意了本实施例的SEM 图，由图可知许多的150～200nm宽、20～30nm厚的纳米片垂直于基底生长。
实施例4：
在室温下，将氯化钴、氯化钼溶于乙醇溶液，其中氯化钼的浓度为290mM，钴原子与钴原子加钼原子数目之和的比为20％。将该前躯液滴涂到平整的石墨纸基底表面，于热台上90℃干燥10min。将有涂层的基底放入管式炉，通Ar气抽真空反复三次将管式炉内残余空气排出后，再通Ar，流量为2SCCM，管式炉上部放有1g硫粉，随着管式炉内温度升高，硫粉蒸发形成硫蒸气，在Ar+S气氛下800℃反应30min，自然冷却后取出即可。图4(a)示意了本实施例的SEM图，由图可知大量的150nm宽、30nm厚的纳米片垂直于基底生长；图4(b)示意了本实施例的元素能谱EDS图，由图知本实施例所制备样品含有Co、Mo、S三种元素，其中C来自于石墨纸基底；图4(c)示意了本实施例的元素能谱EDS-mapping图，由图知本实施例所制备样品中Co、Mo、S三种元素均匀分布，说明Co均匀地掺入了MoS2，形成了Co掺杂MoS2阵列原位电极。图5示意了本实施例所制备电极的XRD图，说明该样品的物相为2H型的MoS2。图9示意了本实施例所制备样品 (Co-doped MoS2-2)的交流阻抗EIS图，相对于同样制备工艺未添加钴源的纯的 MoS2(MoS2)，本实施例所制备样品的性能大幅提高，串联电阻(Rs)由5.22Ω cm-2下降为0.78Ωcm-2，界面电荷转移电阻(Rct)由4.09Ωcm-2下降为0.16Ωcm-2，甚至低于同样制备工艺未添加钼源的纯的CoSx电极(0.38)，如表1所示。图10示意了本实施例所制备样品(Co-doped MoS2-2)的循环伏安CV图，相对于CoSx和 Pt电极，本实施例所制备样品出现了与Pt类似的氧化还原峰且峰电流最大，表明本实施例所制备样品具备较CoSx和Pt电极更优异的电催化碘三负还原为碘负的能力。图11示意了本实施例所制备样品(Co-doped MoS2-2)的光电流-电压JV曲线图，如表1中所示，效率提高至8.99％，高于纯的CoSx(8.49％)和Pt(7.90％)。图12示意了本实施例所制备样品(Co-doped MoS2-2)的电催化产氢的线性伏安扫描LSV曲线图，如表1中所示，当电流密度为10mAcm-2，所需的过电位为185 mV，与负载在掺氟二氧化锡透明导电玻璃基底上的铂电极(Pt)所需的过电位 172mV很接近，且本实施例所制备样品在大电流密度下性能优于Pt电极。
实施例5：
在室温下，将氯化钴、氯化钼溶于乙醇溶液，其中氯化钼的浓度为330mM，钴原子与钴原子加钼原子数目之和的比为50％。将该前躯液滴涂到平整的石墨纸基底表面，于热台上90℃干燥10min。将有涂层的基底放入管式炉，通Ar气抽真空反复三次将管式炉内残余空气排出后，再通Ar，流量为10SCCM，管式炉上部放有1g硫粉，随着管式炉内温度升高，硫粉蒸发形成硫蒸气，在Ar+S气氛下800℃反应30min，自然冷却后取出即可。图6示意了本实施例所制备电极的SEM图，由图可知许多的100nm宽、20nm厚的纳米片垂直于基底生长。
实施例6：
在室温下，将氯化钴、氯化钼溶于乙醇溶液，其中氯化钼的浓度为330mM，钴原子与钴原子加钼原子数目之和的比为10％。将该前躯液滴涂到平整的石墨纸基底表面，于热台上90℃干燥10min。将有涂层的基底放入管式炉，在Ar+S气氛下600℃反应2h，自然冷却后取出即可。图7示意了本实施例所制备电极的SEM 图，由图可知一些的70nm宽、15nm厚的纳米片垂直于基底生长。
实施例7：
在室温下，将氯化钴、氯化钼溶于乙醇溶液，其中氯化钼的浓度为330mM，钴原子与钴原子加钼原子数目之和的比为5％。将该前躯液滴涂到平整的石墨纸基底表面，于热台上90℃干燥10min。将有涂层的基底放入管式炉，通Ar气抽真空反复三次将管式炉内残余空气排出后，再通Ar，流量为2SCCM，管式炉上部放有1g硫粉，随着管式炉内温度升高，硫粉蒸发形成硫蒸气，在Ar+S气氛下700℃反应1h，自然冷却后取出即可。图8示意了本实施例所制备电极的SEM图，由图可知一些的100nm宽、15nm厚的纳米片垂直于基底生长。
表1为实施例2所制备电极(Co-doped MoS2-1)、实施例4所制备电极(Co-dopedMoS2-2)、二硫化钼电极(MoS2)、硫化钴电极(CoSx)、负载在掺氟二氧化锡透明导电玻璃基底上的铂电极(Pt)的染敏电池四大性能参数、电化学阻抗性能参数和催化产氢性能参数。*对应的电流密度为10mA cm-2。
其它说明：
发明实施例中EIS的测试方法为：将相同的两片电极和电解质组成“三明治”结构的对称电池，电解质的组成为：0.1M 1-propy-3-methylimidazolium iodide(1- 丙基-3-甲基咪唑碘)，0.05M LiI,0.1M GNCS,0.03M I2,0.5M 4-tert-butylpridine (4-叔丁基吡啶)，溶剂为碳酸丙烯脂与乙腈的混合溶液(体积比为1:1)，再测试该“伪电池”开路条件下的交流阻抗性能，扫描范围：0.1Hz-1MHz，电位扰动： 50mV。
发明实施例中CV的测试方法为：Co掺杂MoS2阵列原位电极为工作电极、以 Pt片为对电极、以饱和Ag/AgCl电极为参比电极，所用电解质为:0.1M LiClO4， 10mMLiI，1mM I2乙腈溶液，扫描速度为50mV s-1，扫描范围：-0.2V～0.57V。
发明实施例中J-V性能测试方法为：将从营口振越实验器材销售中心购买的 TiO2光阳极用N719染料敏化，并在Co掺杂MoS2阵列原位电极上滴加氧化还原电解质，电解质的组成与测EIS的相同，将滴加了氧化还原电解质的对电极与敏化后的光阳极贴合在一起组成染料敏化太阳能电池，在辐照强度为100W/cm2的模拟太阳光下进行J-V性能测试。
发明实施例中晰氢性能LSV测试方法为：Co掺杂MoS2阵列原位电极为工作电极、以碳棒为对电极、以饱和Hg/Hg2SO4电极为参比电极，所用电解质为:0.5M H2SO4水溶液，扫描速度为5mV s-1，扫描范围：-0.6V～-1.2V。校正的可逆氢电极的电位相对于饱和Hg/Hg2SO4电极为-0.690V。
Claims (2)
1.一种Co掺杂MoS2阵列原位电极的CVD制备方法，其特征在于，在室温下，将氯化钴、氯化钼溶于乙醇溶液，其中氯化钼的浓度为290 mM，钴原子与钴原子加钼原子数目之和的比为20%；将该前躯液滴涂到平整的石墨纸基底表面，于热台上90℃干燥10 min；将有涂层的基底放入管式炉，通Ar气抽真空反复三次将管式炉内残余空气排出后，再通Ar，流量为2SCCM，管式炉上部放有1g硫粉，随着管式炉内温度升高，硫粉蒸发形成硫蒸气，在Ar+S气氛下800℃反应30 min，自然冷却后取出，所制备样品含有Co、Mo、S三种元素，其中C来自于石墨纸基底，Co、Mo、S三种元素均匀分布，即Co均匀地掺入了MoS2，形成了Co掺杂MoS2阵列原位电极，该样品的物相为2H型的MoS2。
2.一种Co掺杂MoS2阵列原位电极的CVD制备方法，其特征在于，在室温下，将氯化钴、氯化钼溶于乙醇溶液，其中氯化钼的浓度为290 mM，钴原子与钴原子加钼原子数目之和的比为10%；将该前躯液滴涂到平整的石墨纸基底表面，于热台上90℃干燥10 min；将有涂层的基底放入管式炉，通Ar气抽真空反复三次将管式炉内残余空气排出后，再通Ar，流量为2SCCM，管式炉上部放有1 g硫粉，随着管式炉内温度升高，硫粉蒸发形成硫蒸气，在Ar+S气氛下800℃反应30 min，自然冷却后取出即可，该产品许多的100 nm宽、20 nm厚的纳米片垂直于基底生长。
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