CN111232963B - 一种镀镍石墨烯空心球的制备方法 - Google Patents
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Abstract
本发明涉及一种镀镍石墨烯空心球的制备方法,属于吸波材料制备领域。本发明所述方法中,石墨烯在旋转外力和范德华力的作用下自组装形成空心球结构,在石墨烯自组装的同时利用水热法进行化学镀镍,镀液中电极电位低于镍的金属氧化腐蚀释放电子并传导到石墨烯上,镍离子在石墨烯表面得电子被还原形成自催化的活性中心,在还原剂的配合作用下,镀镍层以活性中心为基础逐渐沉积,形成具有空心结构的镀镍石墨烯球。本发明所述方法操作简单,成本低,成球率高,可重复性好;所制备的镀镍石墨烯空心球能够发挥镍和石墨烯优良的吸波性能,颗粒的整体密度低,在吸波材料领域具有很好的应用前景。
Description
技术领域
本发明涉及一种镀镍石墨烯空心球的制备方法,属于吸波材料制备领域。
背景技术
吸波材料的电磁吸波性能对于保障电子设备的正常工作、优化人们的生活环境,提高军事装备的战斗能力具有十分重要的意义。
石墨烯是近些年发现的一种新材料,由稳定的苯六元环紧密堆积而成的二维蜂巢状晶格构成,这种特殊的结构使其具有超轻的密度和大的比表面积。石墨烯的介电常数较高,而且它表面暴露的化学键在电磁场的作用下很容易因为外层电子的极化弛豫而衰减电磁波。另外,用化学方法制备出的石墨烯由于有大量缺陷和官能团的残留,会产生费米能级的局域化态,这有利于对电磁波的吸收和衰减。因此石墨烯可作为潜在的介电损耗基材,应用于吸波领域。
镍是一种银白色金属,具有良好的电磁吸波性能。目前新型磁性金属吸波材料要求具有“厚度薄、质量轻、频带宽、吸收强”等特性,然而镍的密度相对较高,这是限制其在吸波材料领域内广泛应用的重要原因。
磁性金属空心粒子能有效降低材料的密度,一定程度上可以满足电磁波吸收领域对磁性金属材料轻质化的应用要求。在这个基础上,将石墨烯和磁性金属设计成复合空心球结构,可以在保证吸波性能的前提下,进一步降低材料的密度,这对于吸波材料的发展具有重要意义。
发明内容
有鉴于此,本发明提供一种镀镍石墨烯空心球的制备方法,主要是基于具有特殊纳米结构的石墨烯在旋转外力和范德华力作用下进行自组装,并利用水热法对石墨烯进行化学镀镍,为吸波领域提供一种新型的低密度空心磁性微球,该方法工艺简单,成本低,可重复性好。
本发明的目的是通过以下技术方案实现的。
一种镀镍石墨烯空心球的制备方法,所述方法步骤如下,
(1)先用砂纸打磨除去电极电位低于镍的非粉体状的金属介质表面的氧化层,再浸入无机酸溶液中,待金属介质表面产生连续不断的气泡时开始计时,继续反应不少于3min,再进行清洗、干燥,得到酸处理的金属介质;
(2)将石墨烯按照0.08g/L~0.15g/L的浓度均匀分散到化学镀液中,并将酸处理的金属介质浸入化学镀液中,待化学镀液的温度达到60℃~80℃时,再加入还原剂,然后在120r/min~180r/min的搅拌速率下搅拌反应不少于90min,除去未反应完的金属介质并收集固体粉体,再对收集的固体粉体进行清洗、干燥,得到镀镍石墨烯空心球。
其中,化学镀液是由可溶性镍盐、柠檬酸盐、pH调节剂和水配制成的pH为10~13的溶液,Ni2+在化学镀液中的浓度为0.03mol/L~0.06mol/L,柠檬酸根在化学镀液中的浓度为0.02mol/L~0.04mol/L,pH调节剂为NaOH、KOH、氨水等;还原剂为水合肼、次亚磷酸钠或硼氢化钠。
进一步地,无机酸溶液优选盐酸溶液、硫酸溶液或硝酸溶液。
进一步地,金属介质的材质优选铁或者铝。
进一步地,金属介质的形状为片状、块状、条状或颗粒状。
进一步地,将金属介质加工成搅拌桨桨头,并按照步骤(1)的操作对桨头进行酸处理;在步骤(2)中,将搅拌桨的桨头浸入化学镀液中,化学镀过程中桨头的搅拌速度为120r/min~180r/min。
进一步地,桨头由连接杆和叶片组成,叶片为弧形扁片状,一层以上(包含一层)叶片沿轴向安装在连接杆上,每一层中两个以上(包含两片)叶片沿轴向对称安装在连接杆上。
进一步地,化学镀液是由六水合硫酸镍、柠檬酸钠、氢氧化钠和水配制成的pH为10~13的溶液,六水合硫酸镍在化学镀液中的浓度为8g/L~16g/L,柠檬酸钠在化学镀液中的浓度为6g/L~12g/L。
进一步地,石墨烯加入化学镀液中,在超声和机械搅拌的共同作用下分散处理20min~40min,使石墨烯均匀分散在化学镀液中;其中,超声功率为80W~120W,搅拌速率为150r/min~200r/min。
进一步地,水合肼在化学镀液中的质量分数为3%~6%;次亚磷酸钠在化学镀液中的浓度为15g/L~25g/L,硼氢化钠与化学镀液中镍离子的摩尔比为1:(10~1000);
有益效果:本发明所述方法中,石墨烯在旋转外力(即机械搅拌)和范德华力的作用下自组装形成空心球结构,在石墨烯自组装的同时利用水热法进行化学镀镍,镀液中电极电位低于镍的金属氧化腐蚀释放电子并传导到石墨烯上,镍离子在石墨烯表面得电子被还原形成自催化的活性中心,在还原剂的配合作用下,镀镍层以活性中心为基础逐渐沉积,形成具有空心结构的镀镍石墨烯球。本发明所述方法操作简单,成本低,成球率高,可重复性好;所制备的镀镍石墨烯空心球能够发挥镍和石墨烯优良的吸波性能,颗粒的整体密度低,在吸波材料领域具有很好的应用前景。
附图说明
图1为实施例1制备的镀镍石墨烯空心球放大100倍的扫描电子显微镜(SEM)图。
图2为实施例1制备的镀镍石墨烯空心球放大2000倍的扫描电子显微镜图。
图3为实施例1制备的镀镍石墨烯空心球放大5000倍的扫描电子显微镜图。
图4为实施例1制备的镀镍石墨烯空心球的能谱分析图。
图5为实施例中采用金属介质制备的搅拌桨桨头的结构示意图。
具体实施方式
下面结合具体实施方式对本发明作进一步阐述,其中,所述方法如无特别说明均为常规方法,所述原材料如无特别说明均能从公开商业途径而得。
以下实施例中:
稀盐酸:质量分数15%的盐酸水溶液;
稀硫酸:质量分数20%的硫酸水溶液;
石墨烯:纯度为99.7%,层数为6~11,苏州碳丰石墨烯有限公司;
水合肼:分析纯,质量分数80%;
扫描电子显微镜:Quanta-200F,美国FEI。
以下实施例中所涉及的搅拌桨桨头由连接杆和叶片组成,叶片为弧形扁片状,且叶片宽度由一端到另一端逐渐变小,连接杆沿其轴向(或长度方向)上安装有三层叶片,每一层包含两片叶片,两片叶片对称安装在连接杆上,叶片的宽头端与连接杆连接,如图5所示。
实施例1
制备镀镍石墨烯空心球的具体步骤如下:
(1)将铁片加工成搅拌桨桨头,先用砂纸打磨除去铁片表面的氧化层,再浸入稀盐酸或稀硫酸中,待铁片表面产生连续不断的气泡时开始计时,继续反应5min,然后用去离子水清洗并干燥,得到酸处理的桨头;
(2)将六水合硫酸镍、柠檬酸钠、氢氧化钠和去离子水配制成六水合硫酸镍浓度为8g/L、柠檬酸钠浓度为6g/L以及pH为10的化学镀液;将石墨烯按照0.08g/L的浓度加入到化学镀液中,在80W的超声功率和150r/min的搅拌速率下分散处理20min,使石墨烯均匀分散在化学镀液中,然后将搅拌桨中酸处理的桨头浸入化学镀液中,待化学镀液的温度到60℃时,将水合肼按照1:10的比例水解后缓慢滴入化学镀液中并使水合肼在化学镀液中的质量分数为3%,随后在120r/min的搅拌速率下搅拌反应90min,利用磁铁收集固体产物,并用去离子水、乙醇将收集的固体产物清洗干净,然后放入40℃的真空干燥箱中烘干,得到镀镍石墨烯空心球。
根据图1可知,石墨烯经过处理后呈现为球形颗粒,从整体上来看成球率很高且粒径比较均匀。根据图2可知,球形颗粒由超声分散后的石墨烯片组装而成,且石墨烯球表面被细小的镍颗粒包覆。根据图3和图4可知,镀镍石墨烯球是由片状石墨烯和镀镍层复合而成,且具有明显的空心结构,另外,能谱结果还表明镍镀层成分纯净,氧化程度很低。
实施例2
制备镀镍石墨烯空心球的具体步骤如下:
(1)将铁片加工成搅拌桨桨头,先用砂纸打磨除去铁片表面的氧化层,再浸入稀盐酸或稀硫酸中,待铁片表面产生连续不断的气泡时开始计时,继续反应3min,然后用去离子水清洗并干燥,得到酸处理的桨头;
(2)将六水合硫酸镍、柠檬酸钠、氢氧化钠和去离子水配制成六水合硫酸镍浓度为12g/L、柠檬酸钠浓度为9g/L以及pH为11的化学镀液;将石墨烯按照0.12g/L的浓度加入到化学镀液中,在100W的超声功率和180r/min的搅拌速率下分散处理30min,使石墨烯均匀分散在化学镀液中,然后将搅拌桨中酸处理的桨头浸入化学镀液中,待化学镀液的温度到70℃时,将水合肼按照1:10的比例水解后缓慢滴入化学镀液中并使水合肼在化学镀液中的质量分数为4%,随后在150r/min的搅拌速率下搅拌反应120min,利用磁铁收集固体产物,并用去离子水、乙醇将收集的固体产物清洗干净,然后放入40℃的真空干燥箱中烘干,得到镀镍石墨烯空心球。
由SEM的表征结果可知,所制备的镀镍石墨烯空心球是由石墨烯片组装而成的空心结构,且石墨烯球表面被细小的镍颗粒包覆;由能谱分析结果可知,镍镀层成分纯净,氧化程度很低。
实施例3
制备镀镍石墨烯空心球的具体步骤如下:
(1)将铁片加工成搅拌桨桨头,先用砂纸打磨除去铁片表面的氧化层,再浸入稀盐酸或稀硫酸中,待铁片表面产生连续不断的气泡时开始计时,继续反应5min,然后用去离子水清洗并干燥,得到酸处理的桨头;
(2)将六水合硫酸镍、柠檬酸钠、氢氧化钠和去离子水配制成六水合硫酸镍浓度为16g/L、柠檬酸钠浓度为12g/L以及pH为13的化学镀液;将石墨烯按照0.15g/L的浓度加入到化学镀液中,在120W的超声功率和200r/min的搅拌速率下分散处理40min,使石墨烯均匀分散在化学镀液中,然后将搅拌桨中酸处理的桨头浸入化学镀液中,待化学镀液的温度到80℃时,将水合肼按照1:10的比例水解后缓慢滴入化学镀液中并使水合肼在化学镀液中的质量分数为6%,随后在180r/min的搅拌速率下搅拌反应150min,利用磁铁收集固体产物,并用去离子水、乙醇将收集的固体产物清洗干净,然后放入40℃的真空干燥箱中烘干,得到镀镍石墨烯空心球。
由SEM的表征结果可知,所制备的镀镍石墨烯空心球是由石墨烯片组装而成的空心结构,且石墨烯球表面被细小的镍颗粒包覆;由能谱分析结果可知,镍镀层成分纯净,氧化程度很低。
实施例4
制备镀镍石墨烯空心球的具体步骤如下:
(1)将铁片加工成搅拌桨桨头,先用砂纸打磨除去铁片表面的氧化层,再浸入稀盐酸或稀硫酸中,待铁片表面产生连续不断的气泡时开始计时,继续反应5min,然后用去离子水清洗并干燥,得到酸处理的桨头;
(2)将六水合硫酸镍、柠檬酸钠、氢氧化钠和去离子水配制成六水合硫酸镍浓度为12g/L、柠檬酸钠浓度为9g/L以及pH为11的化学镀液;将石墨烯按照0.12g/L的浓度加入到化学镀液中,在100W的超声功率和180r/min的搅拌速率下分散处理30min,使石墨烯均匀分散在化学镀液中,然后将搅拌桨中酸处理的桨头浸入化学镀液中,待化学镀液的温度到70℃时,将次亚磷酸钠溶液缓慢滴入化学镀液中并使次亚磷酸钠在化学镀液中的浓度为20g/L,随后在150r/min的搅拌速率下搅拌反应120min,利用磁铁收集固体产物,并用去离子水、乙醇将收集的固体产物清洗干净,然后放入40℃的真空干燥箱中烘干,得到镀镍石墨烯空心球。
由SEM的表征结果可知,所制备的镀镍石墨烯空心球是由石墨烯片组装而成的空心结构,且石墨烯球表面被细小的镍颗粒包覆;由能谱分析结果可知,镍镀层成分纯净,氧化程度很低。
实施例5
制备镀镍石墨烯空心球的具体步骤如下:
(1)将铝片加工成搅拌桨桨头,先用砂纸打磨除去铝片表面的氧化层,再浸入稀盐酸或稀硫酸中,待铝片表面产生连续不断的气泡时开始计时,继续反应5min,然后用去离子水清洗并干燥,得到酸处理的桨头;
(2)将六水合硫酸镍、柠檬酸钠、氢氧化钠和去离子水配制成六水合硫酸镍浓度为12g/L、柠檬酸钠浓度为9g/L以及pH为11的化学镀液;将石墨烯按照0.12g/L的浓度加入到化学镀液中,在100W的超声功率和180r/min的搅拌速率下分散处理30min,使石墨烯均匀分散在化学镀液中,然后将搅拌桨中酸处理的桨头浸入化学镀液中,待化学镀液的温度到70℃时,将水合肼按照1:10的比例水解后缓慢滴入化学镀液中并使水合肼在化学镀液中的质量分数为4%,随后在150r/min的搅拌速率下搅拌反应120min,利用磁铁收集固体产物,并用去离子水、乙醇将收集的固体产物清洗干净,然后放入40℃的真空干燥箱中烘干,得到镀镍石墨烯空心球。
由SEM的表征结果可知,所制备的镀镍石墨烯空心球是由石墨烯片组装而成的空心结构,且石墨烯球表面被细小的镍颗粒包覆;由能谱分析结果可知,镍镀层成分纯净,氧化程度很低。
综上所述,以上仅为本发明的较佳实施例而已,并非用于限定本发明的保护范围。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (8)
1.一种镀镍石墨烯空心球的制备方法,其特征在于:所述方法步骤如下,
(1)先用砂纸打磨除去电极电位低于镍的非粉体状的金属介质表面的氧化层,再浸入无机酸溶液中,待金属介质表面产生连续不断的气泡时开始计时,继续反应不少于3min,再进行清洗、干燥,得到酸处理的金属介质;
(2)将石墨烯按照0.08g/L~0.15g/L的浓度均匀分散到化学镀液中,并将酸处理的金属介质浸入化学镀液中,待化学镀液的温度达到60℃~80℃时,再加入还原剂,然后在120r/min~180r/min的搅拌速率下搅拌反应不少于90min,除去未反应完的金属介质并收集固体粉体,再对收集的固体粉体进行清洗、干燥,得到镀镍石墨烯空心球;
其中,金属介质的材质为铁或者铝;
化学镀液是由可溶性镍盐、柠檬酸盐、pH调节剂和水配制成的pH为10~13的溶液,Ni2+在化学镀液中的浓度为0.03mol/L~0.06mol/L,柠檬酸根在化学镀液中的浓度为0.02mol/L~0.04mol/L,pH调节剂为NaOH、KOH或氨水;还原剂为水合肼、次亚磷酸钠或硼氢化钠。
2.根据权利要求1所述的一种镀镍石墨烯空心球的制备方法,其特征在于:无机酸溶液为盐酸溶液、硫酸溶液或硝酸溶液。
3.根据权利要求1所述的一种镀镍石墨烯空心球的制备方法,其特征在于:金属介质的形状为片状、块状、条状或颗粒状。
4.根据权利要求1所述的一种镀镍石墨烯空心球的制备方法,其特征在于:将金属介质加工成搅拌桨桨头,并按照步骤(1)的操作对桨头进行酸处理;在步骤(2)中,将搅拌桨的桨头浸入化学镀液中,化学镀过程中桨头的搅拌速度为120r/min~180r/min。
5.根据权利要求4所述的一种镀镍石墨烯空心球的制备方法,其特征在于:桨头由连接杆和叶片组成,叶片为弧形扁片状,一层以上叶片沿轴向安装在连接杆上,每一层中两个以上叶片沿轴向对称安装在连接杆上。
6.根据权利要求1所述的一种镀镍石墨烯空心球的制备方法,其特征在于:化学镀液是由六水合硫酸镍、柠檬酸钠、氢氧化钠和水配制成的pH为10~13的溶液,六水合硫酸镍在化学镀液中的浓度为8g/L~16g/L,柠檬酸钠在化学镀液中的浓度为6g/L~12g/L。
7.根据权利要求1所述的一种镀镍石墨烯空心球的制备方法,其特征在于:石墨烯加入化学镀液中,在超声和机械搅拌的共同作用下分散处理20min~40min,使石墨烯均匀分散在化学镀液中;其中,超声功率为80W~120W,搅拌速率为150r/min~200r/min。
8.根据权利要求1所述的一种镀镍石墨烯空心球的制备方法,其特征在于:还原剂为水合肼时,水合肼在化学镀液中的质量分数为3%~6%;还原剂为次亚磷酸钠时,次亚磷酸钠在化学镀液中的浓度为15g/L~25g/L;还原剂为硼氢化钠时,硼氢化钠与化学镀液中镍离子的摩尔比为1:(10~1000)。
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