CN109980210B - 一种五氧化二铌三维掺杂石墨烯复合材料及其制备方法和应用 - Google Patents
一种五氧化二铌三维掺杂石墨烯复合材料及其制备方法和应用 Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 118
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 title claims abstract description 66
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 title claims abstract description 64
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Abstract
本发明公开一种五氧化二铌三维掺杂石墨烯复合材料及其制备方法和应用,采用水热法以及后续的高温煅烧,制备出均匀的五氧化二铌三维掺杂石墨烯复合材料,石墨烯在水热反应可原位自组装成三维状石墨烯,为比表面积大提供了可能;五氧化二铌与三维石墨烯复合大幅度改善了五氧化二铌的导电性差问题;同时N、S掺杂在石墨烯表面提供了更多的活性位点,细化了五氧化二铌的粒径,利于导电性能的提升;合成方法简单,实验药品便宜易得,成本低廉;所制备的五氧化二铌三维掺杂石墨烯复合材料,可在锂离子电池,锂硫电池,超级电容器以及电催化等领域应用,具有广阔的应用前景。
Description
技术领域
本发明涉及电池电极材料领域,特别涉及一种五氧化二铌三维掺杂石墨烯复合材料及其制备方法和应用。
背景技术
Nb2O5作为一种嵌入式赝电容材料,其脱嵌锂过程发生在体相中,没有相变的发生,响应时间短,是一种可以实现快充快放的电极材料。Nb2O5由于其安全运行,高速率,稳定的循环性能,已被广泛研究应用。但五氧化二铌的电子导电性非常差,需要将纳米结构的五氧化二铌和碳材料复合,利用碳材料为电子传输提供良好的导电网络,提高其导电性。而石墨烯由于其高电子导电性,大的比表面积,良好的力学性能及化学稳定性,成为碳材料的不二之选。然而,实验和理论证明,纯石墨烯的活性位点不够,不具有选择性,在实际应用中不具备很好的匹配度。研究表明异原子掺杂能有效解决石墨烯的应用问题,引入缺陷以提供活性位点。所以采用N、S共掺杂的三维石墨烯与纳米五氧化二铌复合。
发明内容
本发明目的在于是提供一种五氧化二铌三维掺杂石墨烯复合材料及其制备方法和应用,制备方法安全无毒,成本低廉,操作简便;制备的五氧化二铌三维掺杂石墨烯复合材料,可在锂离子电池、锂硫电池、超级电容器以及电催化等领域应用。
为实现上述目的,本发明采用的技术方案是:
一种五氧化二铌三维掺杂石墨烯复合材料及其制备方法和应用,包括以下步骤:
第一步、三维掺杂石墨烯前驱体溶液的制备:
将氧化石墨烯分散于足量的去离子水中,超声震荡使氧化石墨烯均匀分散开,得到氧化石墨烯分散液,按照氧化石墨烯、三聚氰胺、三聚硫氰酸、氯化铌的质量比为1:(0.1~2):(0.15~2):(1~10)向氧化石墨烯分散液中加入三聚氰胺粉体,搅拌均匀,然后加入三聚硫氰酸的乙醇溶液,搅拌均匀后备用;
第二步、五氧化二铌三维掺杂石墨烯复合材料的制备:
将第一步制备的三维掺杂石墨烯前驱体溶液倒入烧杯中,加入氯化铌搅拌均匀,然后转到聚四氟乙烯衬底的反应釜中,置于均相反应仪中在120~200℃进行水热反应4~36h;将水热产物用水和乙醇反复洗涤抽滤,冷冻干燥,待处理;
第三步、五氧化二铌三维掺杂石墨烯复合材料的后处理:
将第二步所得的五氧化二铌三维掺杂石墨烯复合材料进行热处理,在惰性气体保护下置于管式炉中,以5~10℃/min升温至600~1000℃进行热处理2~6h,热处理后在保护气氛下自然冷却,即得五氧化二铌三维掺杂石墨烯复合材料。
进一步,用于配置氧化石墨烯分散液去离子水与用于配置三聚硫氰酸乙醇溶液的乙醇体积比为(1~4):1。
进一步,所述第一步中两次搅拌温度为70~120℃,每次搅拌时间均为10~60min。
进一步,所述第二步中水热反应时反应釜的的填充比为40~75%。
一种五氧化二铌三维掺杂石墨烯复合材料。
一种五氧化二铌三维掺杂石墨烯复合作为电极材料的应用。
发明的有益效果体现在:
本发明采用水热法以及后续的高温煅烧,绿色安全并且制备出均匀的五氧化二铌三维掺杂石墨烯复合材料,合成方法简单,实验药品便宜易得,成本低廉;石墨烯在水热反应可原位自组装成三维状石墨烯,为比表面积大提供了可能;五氧化二铌与三维石墨烯复合大幅度改善了五氧化二铌的导电性差问题;同时N、S掺杂在石墨烯表面提供了更多的活性位点,细化了五氧化二铌的粒径,利于导电性能的提升。所制备的五氧化二铌三维掺杂石墨烯复合材料,可在锂离子电池,锂硫电池,超级电容器以及电催化等领域应用,具有广阔的应用前景。
附图说明
图1a为实施例2所制备的五氧化二铌三维掺杂石墨烯复合材料的扫描电子显微(SEM)照片一
图1b为实施例2所制备的五氧化二铌三维掺杂石墨烯复合材料的扫描电子显微(SEM)照片二
图2为实施例2所制备的五氧化二铌三维掺杂石墨烯复合材料的X射线衍射(XRD)谱图
具体实施方式
下面结合具体实施例对本发明作进一步详细描述,但不作为对本发明的限定。
实施例1
第一步、三维掺杂石墨烯前驱体溶液的制备:
将0.1g氧化石墨烯分散于25ml去离子水中,超声震荡4h,离心取上层清液,使氧化石墨烯均匀分散开,得到氧化石墨烯分散液,加入0.1g三聚氰胺粉体,80℃搅拌至完全溶解,得到A液;另取0.15g三聚硫氰酸溶于25ml乙醇中,后得到B液;将B液缓慢加入A液中,70℃搅拌10min,搅拌均匀后备用。
第二步、五氧化二铌三维掺杂石墨烯复合材料的制备:
将第一步制备的三维掺杂石墨烯前驱体溶液倒入烧杯中,搅拌均匀,加入0.1g氯化铌,搅拌均匀,转到聚四氟乙烯衬底的反应釜中,填充比为45%,置于均相反应仪中进行水热反应120℃/12h;将水热产物用水和乙醇反复洗涤抽滤,冷冻干燥,待处理;
第三步、五氧化二铌三维掺杂石墨烯复合材料的后处理:
将第二步所得的五氧化二铌三维掺杂石墨烯复合材料进行热处理,在氩气保护下置于管式炉中,以5℃/min的升温速率升温到650℃保温2h。
实施例2
第一步、三维掺杂石墨烯前驱体溶液的制备:
将0.15g氧化石墨烯分散于50ml去离子水中,超声震荡4h,离心取上层清液,使氧化石墨烯均匀分散开,加入0.25g三聚氰胺粉体,80℃搅拌至完全溶解,得到A液;另取0.3g三聚硫氰酸溶于25ml乙醇中,后得到B液;将B液缓慢加入A液中,80℃搅拌20min,搅拌均匀后备用。
第二步、五氧化二铌三维掺杂石墨烯复合材料的制备:
将第一步制备的三维掺杂石墨烯前驱体溶液倒入烧杯中,搅拌均匀,加入0.2g氯化铌,搅拌均匀,转到聚四氟乙烯衬底的反应釜中,填充比为65%,置于均相反应仪中进行水热反应150℃/12h;将水热产物用水和乙醇反复洗涤抽滤,冷冻干燥,待处理;
第三步、五氧化二铌三维掺杂石墨烯复合材料的后处理:
将第二步所得的五氧化二铌三维掺杂石墨烯复合材料进行热处理,在氩气保护下置于管式炉中,以5℃/min的升温速率升温到650℃保温2h。
图1a和图1b为本实施例制备样品的SEM照片,用扫描电子显微镜(SEM)进行形貌观察,能明显的看到由纳米级厚度的石墨烯组装成的三维石墨烯,结构疏松,五氧化二铌颗粒细小均匀分布在三维石墨烯上。图2为本实施例制备样品的XRD图。
实施例3
第一步、三维掺杂石墨烯前驱体溶液的制备:
将0.2g氧化石墨烯分散于50ml去离子水中,超声震荡4h,离心取上层清液,使氧化石墨烯均匀分散开,加入0.2g三聚氰胺粉体,80℃搅拌至完全溶解,得到A液;另取0.35g三聚硫氰酸溶于25ml乙醇中,后得到B液;将B液缓慢加入A液中,80℃搅拌30min,搅拌均匀后备用。
第二步、五氧化二铌三维掺杂石墨烯复合材料的制备:
将第一步制备的三维掺杂石墨烯前驱体溶液倒入烧杯中,搅拌均匀,加入0.3g氯化铌,搅拌均匀,转到聚四氟乙烯衬底的反应釜中,填充比为75%,置于均相反应仪中进行水热反应180℃/12h;将水热产物用水和乙醇反复洗涤抽滤,冷冻干燥,待处理;
第三步、五氧化二铌三维掺杂石墨烯复合材料的后处理:
将第二步所得的五氧化二铌三维掺杂石墨烯复合材料进行热处理,在氩气保护下置于管式炉中,以10℃/min的升温速率升温到650℃保温2h。
实施例4
第一步、三维掺杂石墨烯前驱体溶液的制备:
将0.3g氧化石墨烯分散于100ml去离子水中,超声震荡4h,离心取上层清液,使氧化石墨烯均匀分散开,加入0.5g三聚氰胺粉体,80℃搅拌至完全溶解,得到A液;另取0.6g三聚硫氰酸溶于25ml乙醇中,后得到B液;将B液缓慢加入A液中,80℃搅拌30min,搅拌均匀后备用。
第二步、五氧化二铌三维掺杂石墨烯复合材料的制备:
将第一步制备的三维掺杂石墨烯前驱体溶液倒入烧杯中,搅拌均匀,加入0.4g氯化铌,搅拌均匀,转到聚四氟乙烯衬底的反应釜中,填充比为75%,置于均相反应仪中进行水热反应180℃/24h;将水热产物用水和乙醇反复洗涤抽滤,冷冻干燥,待处理;
第三步、五氧化二铌三维掺杂石墨烯复合材料的后处理:
将第二步所得的五氧化二铌三维掺杂石墨烯复合材料进行热处理,在氩气保护下置于管式炉中,以5℃/min的升温速率升温到800℃保温2h。
实施例5
第一步、三维掺杂石墨烯前驱体溶液的制备:
将0.4g氧化石墨烯分散于80ml去离子水中,超声震荡4h,离心取上层清液,使氧化石墨烯均匀分散开,加入0.6g三聚氰胺粉体,80℃搅拌至完全溶解,得到A液;另取0.8g三聚硫氰酸溶于40ml乙醇中,后得到B液;将B液缓慢加入A液中,80℃搅拌30min,搅拌均匀后备用。
第二步、五氧化二铌三维掺杂石墨烯复合材料的制备:
将第一步制备的三维掺杂石墨烯前驱体溶液倒入烧杯中,搅拌均匀,加入0.5g氯化铌,搅拌均匀,转到聚四氟乙烯衬底的反应釜中,填充比为65%,置于均相反应仪中进行水热反应180℃/24h;将水热产物用水和乙醇反复洗涤抽滤,冷冻干燥,待处理;
第三步、五氧化二铌三维掺杂石墨烯复合材料的后处理:
将第二步所得的五氧化二铌三维掺杂石墨烯复合材料进行热处理,在氩气保护下置于管式炉中,以10℃/min的升温速率升温到800℃保温2h。
实施例6
第一步、三维掺杂石墨烯前驱体溶液的制备:
将0.5g氧化石墨烯分散于100ml去离子水中,超声震荡4h,离心取上层清液,使氧化石墨烯均匀分散开,加入0.8g三聚氰胺粉体,80℃搅拌至完全溶解,得到A液;另取0.92g三聚硫氰酸溶于50ml乙醇中,后得到B液;将B液缓慢加入A液中,80℃搅拌30min,搅拌均匀后备用。
第二步、五氧化二铌三维掺杂石墨烯复合材料的制备:
将第一步制备的三维掺杂石墨烯前驱体溶液倒入烧杯中,搅拌均匀,加入0.6g氯化铌,搅拌均匀,转到聚四氟乙烯衬底的反应釜中,填充比为65%,置于均相反应仪中进行水热反应200℃/24h;将水热产物用水和乙醇反复洗涤抽滤,冷冻干燥,待处理;
第三步、五氧化二铌三维掺杂石墨烯复合材料的后处理:
将第二步所得的五氧化二铌三维掺杂石墨烯复合材料进行热处理,在氩气保护下置于管式炉中,以10℃/min的升温速率升温到1000℃保温2h。
实施例7
第一步、三维掺杂石墨烯前驱体溶液的制备:
将0.8g氧化石墨烯分散于100ml去离子水中,超声震荡4h,离心取上层清液,使氧化石墨烯均匀分散开,加入1.6g三聚氰胺粉体,80℃搅拌至完全溶解,得到A液;另取1.54g三聚硫氰酸溶于50ml乙醇中,后得到B液;将B液缓慢加入A液中,70℃搅拌60min,搅拌均匀后备用。
第二步、五氧化二铌三维掺杂石墨烯复合材料的制备:
将第一步制备的三维掺杂石墨烯前驱体溶液倒入烧杯中,搅拌均匀,加入8g氯化铌,搅拌均匀,转到聚四氟乙烯衬底的反应釜中,填充比为40%,置于均相反应仪中进行水热反应200℃/4h;将水热产物用水和乙醇反复洗涤抽滤,冷冻干燥,待处理;
第三步、五氧化二铌三维掺杂石墨烯复合材料的后处理:
将第二步所得的五氧化二铌三维掺杂石墨烯复合材料进行热处理,在氩气保护下置于管式炉中,以8℃/min的升温速率升温到600℃保温6h。
实施例8
第一步、三维掺杂石墨烯前驱体溶液的制备:
将1g氧化石墨烯分散于100ml去离子水中,超声震荡4h,离心取上层清液,使氧化石墨烯均匀分散开,加入0.1g三聚氰胺粉体,120℃搅拌至完全溶解,得到A液;另取0.15g三聚硫氰酸溶于65ml乙醇中,后得到B液;将B液缓慢加入A液中,70℃搅拌60min,搅拌均匀后备用。
第二步、五氧化二铌三维掺杂石墨烯复合材料的制备:
将第一步制备的三维掺杂石墨烯前驱体溶液倒入烧杯中,搅拌均匀,加入3g氯化铌,搅拌均匀,转到聚四氟乙烯衬底的反应釜中,填充比为60%,置于均相反应仪中进行水热反应120℃/36h;将水热产物用水和乙醇反复洗涤抽滤,冷冻干燥,待处理;
第三步、五氧化二铌三维掺杂石墨烯复合材料的后处理:
将第二步所得的五氧化二铌三维掺杂石墨烯复合材料进行热处理,在氩气保护下置于管式炉中,以7℃/min的升温速率升温到800℃保温5h。
最后应该说明的是:以上实施例仅用于说明本发明的技术方案而非对其限制,尽管参照上述实施例对本发明进行了详细说明,所属领域的普通技术人员应当理解:依然可以对本发明的具体实施方式进行修改或者等同替换,而未脱离本发明精神和范围的任何修改或者等同替换,其均应涵盖在本权利要求范围当中。
Claims (6)
1.一种五氧化二铌三维掺杂石墨烯复合材料及其制备方法和应用,其特征在于包括以下步骤:
第一步、三维掺杂石墨烯前驱体溶液的制备:
将氧化石墨烯分散于足量的去离子水中,超声震荡使氧化石墨烯均匀分散开,得到氧化石墨烯分散液,按照氧化石墨烯、三聚氰胺、三聚硫氰酸、氯化铌的质量比为1:(0.1~2):(0.15~2):(1~10)向氧化石墨烯分散液中加入三聚氰胺粉体,搅拌均匀,然后加入三聚硫氰酸的乙醇溶液,搅拌均匀后备用;
第二步、五氧化二铌三维掺杂石墨烯复合材料的制备:
将第一步制备的三维掺杂石墨烯前驱体溶液倒入烧杯中,加入氯化铌搅拌均匀,然后转到聚四氟乙烯衬底的反应釜中,置于均相反应仪中在120~200℃进行水热反应4~36h;将水热产物用水和乙醇反复洗涤抽滤,冷冻干燥,待处理;
第三步、五氧化二铌三维掺杂石墨烯复合材料的后处理:
将第二步所得的五氧化二铌三维掺杂石墨烯复合材料进行热处理,在惰性气体保护下置于管式炉中,以5~10℃/min升温至600~1000℃进行热处理2~6h,热处理后在保护气氛下自然冷却,即得五氧化二铌三维掺杂石墨烯复合材料。
2.根据权利要求1所述的方法,其特征在于:用于配置氧化石墨烯分散液去离子水与用于配置三聚硫氰酸乙醇溶液的乙醇体积比为(1~4):1。
3.根据权利要求1所述的方法,其特征在于:所述第一步中两次搅拌温度为70~120℃,每次搅拌时间均为10~60min。
4.根据权利要求1所述的方法,其特征在于:所述第二步中水热反应时反应釜的的填充比为40~75%。
5.一种根据权利要求1~4任一项方法制备的五氧化二铌三维掺杂石墨烯复合材料。
6.一种权利要求5所述五氧化二铌三维掺杂石墨烯复合材料作为电极材料的应用。
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Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103657698A (zh) * | 2013-11-27 | 2014-03-26 | 复旦大学 | 一种高氧还原性能的氮掺石墨烯-五氧化二铌插层复合催化剂的制备方法 |
CN103691420A (zh) * | 2013-12-21 | 2014-04-02 | 海安县吉程机械有限公司 | 一步自组装法制备介孔五氧化二铌/石墨烯复合光催化剂 |
CN105688965A (zh) * | 2016-01-12 | 2016-06-22 | 南通职业大学 | 介孔五氧化二铌/掺氮石墨烯高效复合光催化剂的制备方法 |
CN107626338A (zh) * | 2017-10-11 | 2018-01-26 | 南通科技职业学院 | 硫化钼纳米粒子修饰介孔五氧化二铌/氮掺杂石墨烯复合光催化剂的制备方法 |
CN108470890A (zh) * | 2018-03-15 | 2018-08-31 | 陕西科技大学 | 一种氮硫共掺杂三维石墨烯的制备方法、其制备的产品及该产品的应用 |
CN108493424A (zh) * | 2018-04-11 | 2018-09-04 | 中科锂电新能源有限公司 | 一种氮、磷、硫共掺杂复合碳材料、其制备方法和锂离子电池 |
CN108493427A (zh) * | 2018-04-20 | 2018-09-04 | 浙江大学 | 用于锂离子电池电极材料的微纳米Nb2O5粉体的制备方法 |
CN108607593A (zh) * | 2016-01-26 | 2018-10-02 | 苏州大学 | 硫化镉纳米粒子修饰的五氧化二铌纳米棒/氮掺杂石墨烯复合光催化剂与应用 |
CN108840318A (zh) * | 2018-06-15 | 2018-11-20 | 陕西科技大学 | 一种蜂窝状多级孔氮硫掺杂三维碳材料及其制备方法 |
CN109037678A (zh) * | 2018-06-15 | 2018-12-18 | 陕西科技大学 | 一种氮硫共掺杂三维石墨烯泡沫电极活性材料的制备方法 |
CN109019565A (zh) * | 2018-06-15 | 2018-12-18 | 陕西科技大学 | 一种三维多孔氮硫掺杂碳纳米片的制备方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10411264B2 (en) * | 2017-02-27 | 2019-09-10 | Global Graphene Group, Inc. | Cathode active material layer for lithium secondary battery and method of manufacturing |
-
2019
- 2019-04-19 CN CN201910317698.2A patent/CN109980210B/zh active Active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103657698A (zh) * | 2013-11-27 | 2014-03-26 | 复旦大学 | 一种高氧还原性能的氮掺石墨烯-五氧化二铌插层复合催化剂的制备方法 |
CN103691420A (zh) * | 2013-12-21 | 2014-04-02 | 海安县吉程机械有限公司 | 一步自组装法制备介孔五氧化二铌/石墨烯复合光催化剂 |
CN105688965A (zh) * | 2016-01-12 | 2016-06-22 | 南通职业大学 | 介孔五氧化二铌/掺氮石墨烯高效复合光催化剂的制备方法 |
CN108607593A (zh) * | 2016-01-26 | 2018-10-02 | 苏州大学 | 硫化镉纳米粒子修饰的五氧化二铌纳米棒/氮掺杂石墨烯复合光催化剂与应用 |
CN107626338A (zh) * | 2017-10-11 | 2018-01-26 | 南通科技职业学院 | 硫化钼纳米粒子修饰介孔五氧化二铌/氮掺杂石墨烯复合光催化剂的制备方法 |
CN108470890A (zh) * | 2018-03-15 | 2018-08-31 | 陕西科技大学 | 一种氮硫共掺杂三维石墨烯的制备方法、其制备的产品及该产品的应用 |
CN108493424A (zh) * | 2018-04-11 | 2018-09-04 | 中科锂电新能源有限公司 | 一种氮、磷、硫共掺杂复合碳材料、其制备方法和锂离子电池 |
CN108493427A (zh) * | 2018-04-20 | 2018-09-04 | 浙江大学 | 用于锂离子电池电极材料的微纳米Nb2O5粉体的制备方法 |
CN108840318A (zh) * | 2018-06-15 | 2018-11-20 | 陕西科技大学 | 一种蜂窝状多级孔氮硫掺杂三维碳材料及其制备方法 |
CN109037678A (zh) * | 2018-06-15 | 2018-12-18 | 陕西科技大学 | 一种氮硫共掺杂三维石墨烯泡沫电极活性材料的制备方法 |
CN109019565A (zh) * | 2018-06-15 | 2018-12-18 | 陕西科技大学 | 一种三维多孔氮硫掺杂碳纳米片的制备方法 |
Non-Patent Citations (1)
Title |
---|
Nb2O5/graphene nanocomposites for electrochemical energy storage;Paulraj Arunkumar;《RSC Advances》;20150729(第5期);59998页实验部分,附图3 * |
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