CN109395752A - 一种自支撑双金属磷化物Ni2P-Cu3P复合材料及其制备方法 - Google Patents
一种自支撑双金属磷化物Ni2P-Cu3P复合材料及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种原位生长连续双相的二元活性过渡金属磷化物Ni2P‑Cu3P及其制备方法,该方法仅包含自支撑双金属合金前驱体的制备及低温磷化合成两个步骤。本方法为首次专利报道,大大简化了双金属磷化物体系的合成工艺,并实现了其在同质相容基底表面的原位生长,提高了结构稳定性,避免了粉体活性磷化物固定对粘合剂的依赖问题,且活性物质Ni2P、Cu3P物相成分及分布精确可控,适宜于大规模工业制备及应用。
Description
技术领域:
本发明属于金属磷化物功能复合材料制备领域,涉及一种原位生长连续双相的活性磷化物(Ni2P、Cu3P)、复合多维孔道、自支撑性能良好的复合双金属磷化物材料及其制备方法,所制备的具有多维孔道结构Ni2P-Cu3P材料适用于电解水,动力电池,气相催化还原等行业作功能应用的核心材料。
背景技术:
伴随工业技术的迅速发展,全世界煤炭、石油、天然气等有限的、不可再生的化石燃料的过度消耗,造成了一系列严重的诸如空气污染、水体污染及全球变暖等环境问题。因此,开发低成本、高活性和较长使用寿命的可再生能源技术,如燃料电池和金属-空气电池以及水分解技术,是科学界面临的一项紧迫而富有挑战性的任务。过渡族单金属磷化物由于其特殊的电催化、储能、化学催化等功能特性,在面向可再生能源技术核心材料的开发中引起了研究者们的广泛关注,如Ni2P、CoP、Cu3P等,在燃料电池、超级电容器、传感器、电催化等过程中都表现出潜在应用前景,是功能材料开发的热点之一。此外,应用于电催化体系,一些理论工作指出,物相可控的二元过渡金属复合结构更加有利于有效地调节体系的三维电子结构,改进催化功能反应动力学,大幅提高电催化综合性能。本专利首次提出一种具有自支撑结构的双金属磷化物及其可控简易合成方法,可望在一系列功能应用体系如电催化、超级电容、化学催化等领域发挥重要作用。
发明内容:
为了解决现有二元金属磷化物制备技术的不完善情况,本发明旨在克服单金属磷化物材料的缺陷,通过磷化物前驱体的改进,及对二元体系物相分布及电子结构的调控,提供以Ni2P-Cu3P为活性组分,以NiCuC为同质相容自支撑基底形成的结构稳定的复合功能材料。本发明采用如下技术方案实现:
1.Ni2P-Cu3P双金属磷化物前驱体的制备;
以不同比例高纯高比表面积羰基镍粉、电解铜粉混合聚乙烯醇缩丁醛液形成前驱体生膜浆料并覆膜;将生膜进行真空控温烧结得到Ni2P-Cu3P双金属磷化物前驱体;
2.低温磷化得到自支撑双金属磷化物Ni2P-Cu3P;
前驱体通过NaH2PO2分解产生的活性磷化氢还原得到自支撑双金属磷化物 Ni2P-Cu3P。
附图说明:
图1是自支撑双金属磷化物Ni2P-Cu3P复合材料XRD谱图(Ni2P(JCPDS card No.03-0953);Cu3P(JCPDS card No.71-2261)),强信号组峰为Ni;
图2是可见双连续磷化物相的双金属磷化物EDS扫描图谱。
实施例:本实施例给出一种自支撑双金属磷化物Ni2P-Cu3P复合材料的制备方法,包括以下具体步骤:将羰基镍粉(中位径6.4μm),电解铜粉(中位径5.8μm) 在氮气保护氛下混合8小时;取聚乙烯醇缩丁醛2.8g,以无水乙醇28.5mL超声溶解得到聚乙烯醇缩丁醛液;取镍铜混合粉6g,聚乙烯醇缩丁醛液12g,磁力搅拌至形成均匀浆料。平板上覆前驱体生膜,置入真空烧结炉进行烧结得前驱体基底。取基底(面积1.0×1.5cm),经0.5mol/L HF活化表面30min,去离子水清洗至pH呈中性,置于真空干燥箱干燥2h;将基底样品与NaH2PO2质量0.15mg 置于管式炉在Ar气氛下进行低温磷化,升温速率1.0℃/min,最高温度300℃保持50min,随炉冷却至室温即得到自支撑双金属磷化物Ni2P-Cu3P复合材料。自支撑双金属磷化物Ni2P-Cu3P复合材料物相及表面形貌见附图1,EDS扫描图谱见图2。
Claims (10)
1.一种自支撑双金属磷化物Ni2P-Cu3P复合材料,其特征在于,该复合材料同时以NiCuC合金膜为自支撑基底及低温磷化前驱体;双金属磷化物为双连续相,组成及分布可精确控制;该复合材料Ni2P相在基底表面横向覆盖,Cu3P以颗粒形式纵向嵌入(颗粒直径0.2~1.0 μm),形成多维复合磷化结构,有利于磷化活性物与反应气相或液相介质的充分接触和电子传递。
2.一种自支撑双金属磷化物Ni2P-Cu3P复合材料的制备方法,其特征在于,包括以下步骤:
(1)Ni2P-Cu3P双金属磷化物前驱体的制备;
(2)低温磷化得到自支撑双金属磷化物Ni2P-Cu3P。
3.根据权利要求2所述的一种自支撑双金属磷化物Ni2P-Cu3P复合材料的制备方法,其特征在于,所述步骤(1)Ni2P-Cu3P双金属磷化物前驱体的制备,其方法为以不同比例高纯高比表面积羰基镍粉、电解铜粉混合聚乙烯醇缩丁醛液形成前驱体生膜制备浆料;控制厚度将混合浆料覆膜;真空控温烧结得到Ni2P-Cu3P双金属磷化物前驱体。
4.根据权利要求2所述步骤(1)Ni2P-Cu3P双金属磷化物前驱体的制备,其特征在于,前驱体中碳元素以石墨形式存在,部分石墨固溶于镍铜合金中,另一总分以聚集体分散于合金表面。
5.根据权利要求4所述步骤(1)Ni2P-Cu3P双金属磷化物前驱体的制备,其特征在于,所述镍粉粒度在5~10 μm,镍粉形貌由羰基镍粉,电解镍粉中的一种;所述电解铜粉粒度在5~10 μm;镍铜混合粉中铜粉质量百分数为10.0 wt.%~45.0 wt.%,混合时间5~12小时。
6.根据权利要求4所述步骤(1)Ni2P-Cu3P双金属磷化物前驱体的制备,其特征在于,所述聚乙烯醇缩丁醛分子量范围为30000~60000;聚乙烯醇缩丁醛液质量浓度为8.0wt.%~30.0 wt.%;聚乙烯醇缩丁醛溶剂为乙醇、聚乙烯吡咯烷酮、乙二醇中的一种;混合粉浆料质量浓度为10 wt.%~45.0 wt.%。
7.根据权利要求4所述步骤(1)Ni2P-Cu3P双金属磷化物前驱体的制备,其特征在于,在隔离空气环境内制备前驱体生膜,控制生膜厚度为50~500 μm,干燥后从平板上移出。
8.根据权利要求2一种自支撑双金属磷化物Ni2P-Cu3P复合材料的制备方法,其特征在于,所述步骤(2)低温磷化得到自支撑双金属磷化物Ni2P-Cu3P,其方法为,前驱体通过NaH2PO2分解产生的活性磷化氢还原得到自支撑双金属磷化物Ni2P-Cu3P。
9.根据权利要求8所述步骤(2)低温磷化得到自支撑双金属磷化物Ni2P-Cu3P,其特征在于,前驱体经0.5~ 2.0mol/L HF 活化表面30 ~ 50 min;Ni2P-Cu3P双金属磷化物前驱体的面积为2.0~6.0 cm2,NaH2PO2的质量范围0.15~0.45 mg可在基底表面实现双相共存结构。
10.根据权利要求8所述步骤(2)低温磷化得到自支撑双金属磷化物Ni2P-Cu3P,其特征在于,在反应温度为250 oC ~ 350 oC下保持30至180min,升温速率0.5~2 oC/min,控制活性磷化物的分布面积。
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