CN109665513B - 一种电化学处理炭粒子的方法及装置 - Google Patents

一种电化学处理炭粒子的方法及装置 Download PDF

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CN109665513B
CN109665513B CN201910100153.6A CN201910100153A CN109665513B CN 109665513 B CN109665513 B CN 109665513B CN 201910100153 A CN201910100153 A CN 201910100153A CN 109665513 B CN109665513 B CN 109665513B
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吴刚平
刘玉婷
张巍松
李文君
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Shanxi Institute of Coal Chemistry of CAS
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Abstract

本发明提供一种电化学处理炭粒子的方法及装置，主要解决了现有酸氧化法处理炭粒子存在对设备强腐蚀性强和接枝法不符合环保标准的技术问题。本发明将炭粒子的悬浮液置于平行且有一定间隔的阳极和阴极之间，利用电化学方法在阴极和阳极之间施加恒定电压、通入恒定强度的电流或采用循环伏安法，使炭粒子与阳极表面接触并反应生成含氧、含氮官能团。本发明提供的炭粒子的表面处理方法，具有原料易得、成本低廉、操作简单、可规模化制备的优点，且官能团种类、数量和分布可调控。

Description

一种电化学处理炭粒子的方法及装置
技术领域
本发明属于电化学处理技术领域，也属于炭粒子材料的加工领域。
背景技术
炭粒子是指包括炭黑、碳纳米管、纳米碳纤维、短切碳纤维、石墨烯、碳量子点等在内的炭材料。通常炭粒子具有优异的力学、电学和热学特性，可作为涂料添加剂、复合材料的填充剂或增强材料使用。然而，一般来说，炭粒子表面呈惰性，比表面能高，与基体材料的亲和性差，严重影响了炭粒子在涂料、复合材料等领域的应用。如何对炭粒子进行适当表面处理，使炭粒子表面具有一定的活性官能团，对于充分发挥炭粒子的特性，扩大炭粒子的应用范围具有重要的意义。
为了改善炭粒子表面性能，赋予一定活性官能团，氧化法是一种常用方法。陈喆等对比了不同酸氧化体系对含氧官能团含量的影响(见文献陈喆，何华，谭树华.3种酸氧化法制备的功能化多壁碳纳米管中含氧官能团含量的比较.分析化学，2011，39(5)：718-722)。但这种方法要使用大量浓酸，不仅废液处理成本高、酸液对设备的腐蚀性高，而且环境污染大，不符合环保标准。接枝法和涂层法也常被用于改善炭粒子表面浸润性。吴凡等利用有机分子对石墨烯进行修饰,提高其在溶剂中的分散性(见文献吴凡，陈东梁，张东胜.石墨烯接枝9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)的功能化合成.解放军理工大学学报(自然科学版)，2013，14)，但是过程中使用氯化亚砜，所产生的酰氯均不利于人体与环境健康，不符合环保标准。而涂层后对炭粒子的导电导热性能会造成一定影响。
发明内容
本发明的目的是为了解决现有酸氧化法处理炭粒子存在对设备强腐蚀性强和接枝法不符合环保标准的技术问题，本发明提供了一种成本低廉、操作简单、适合工业化的电化学处理炭粒子方法及装置，可得到表面官能团丰富的炭粒子。
为实现上述目的，本发明采用的技术方案为：
一种电化学处理炭粒子的方法，包括以下步骤：
1)炭粒子预分散：配制电解质溶液，将炭粒子与电解质溶液混合均匀，得到炭粒子悬浮液；
2)炭粒子电化学处理：将炭粒子悬浮液置于电化学处理装置内，调节极板位置保证与电解质溶液接触，通电后对炭粒子进行电化学处理，同时对电解质溶液施以搅拌，电化学处理完成后，得到官能化的炭粒子；
3)炭粒子的后处理：洗涤过滤去除官能化的炭粒子表面的电解质，干燥即可。
本发明适用的炭粒子包括炭黑、碳纳米管、纳米碳纤维、短切碳纤维、石墨烯、氧化石墨烯、富勒烯、碳量子点等微米、纳米尺寸的炭材料。可对任何碳含量大于70％且通过分散可形成悬浮的炭粒子进行处理。
进一步，所述步骤1)中电解质溶液为无机或有机电解质溶液，无机电解质溶液是酸、碱或盐的水溶液，包括硫酸、磷酸、草酸、氢氧化钠、氢氧化钾、碳酸氢铵、硫酸钠等电解质的水溶液；有机电解质溶液是有机溶剂的电解质体系，包括四丁基四氟硼酸铵的乙腈溶液或四丁基四氟硼酸铵的四氢呋喃溶液等。在通电作用下可形成活性中间体，且与炭粒子主体结构发生反应，形成官能团。
更进一步，所述步骤1)中电解质溶液的浓度为0.01wt.％～50wt.％，此浓度区间足矣产生可与炭粒子主体结构发生反应的活性中间体，同时调节浓度改变官能团分布。
所述步骤1)中每1g炭粒子使用电解质溶液量为0.001L-1000L，此比例区间可保证炭粒子充分浸润分散。
再进一步，所述步骤1)中炭粒子与电解质溶液的混合采用具有分散效果的装置，包括搅拌装置、摇床、超声装置，可实现炭粒子充分分散形成悬浮液。
本发明提供的电化学处理装置为两电极及以上电极体系：具有阳极和阴极，也可额外增加参比电极。电解质溶液为炭粒子的悬浮液。图1为处理示意图，将炭粒子的悬浮液置于平行且有一定间隔的阳极和阴极之间，利用电化学方法在阳极和阴极之间施加固定电压，或通入恒定强度电流，对炭粒子进行改性处理，使炭粒子表面引入活性官能团。
再进一步，所述步骤2)中电化学处理装置为两电极及以上电极体系；所述两电极电化学处理装置的阳极材料为惰性电极材料，包括金、铂或石墨等惰性电极材料；所述两电极电化学处理装置的阴极材料为常用导电材料或惰性电极材料，包括铁、铜、铝、金、铂或石墨等电极材料；所述的两电极以上电极体系，是在两电极体系的基础上增加参比电极，所述参比电极为银-氯化银电极或饱和甘汞电极等参比电极。两电极体系可保证足够电流通过，在部分精密性要求较高的情况下可使用三电极体系。
本发明所使用的电化学处理方法，是利用电化学设备使阴极和阳极之间产生一定的电压，并使炭粒子与阳极接触并发生电化学反应，使炭粒子表面产生含氧官能团。所述的电化学处理方法无特定限制，包括恒压法、恒流法和循环伏安法等。所述的电化学设备，包括电化学工作站、直流电源、恒电压仪器、恒电流仪器。多种处理方法和电化学设备工艺条件不变的情况下处理效果相同，为实际工艺中提供了多重选择。
再进一步，所述步骤2)中对炭粒子进行电化学处理的电压为0.5～30V，或者施加1mA～5A电流处理，或者采用循环伏安法使电压在0.5～20V之间进行任意次数的扫描，扫描速度为50～500mV/s；处理时间为5～1200min。在以上处理条件范围内均可实现炭粒子的表面官能化，且可调节官能团的数量和分布。
再进一步，所述步骤2)中对电解质溶液施以搅拌的搅拌装置可连续运行，也可间歇运行。连续搅拌可保持反应体系的时刻均匀性，而间歇搅拌可控制被处理程度，
本发明的发明效果：
本发明通过电化学处理炭粒子，可以向表面引入活性官能团，通过改变电解质种类可以改变官能团种类：无机电解质溶液中电化学方法处理，是电解水过程中阳极生成活性氧原子，对吸附于阳极表面的炭粒子进行氧化，从而引入羟基、羧基、羰基等含氧基团；使用铵盐作为电解质，可引入含氮官能团。通过调节电解质浓度和电压、电流、处理时间等处理条件，可以调节炭粒子表面官能团种类、数量及分布。
本发明可通过调节电解质溶液粘度和性质，实现具有一定分散性炭粒子脱离阳极极板，稳定分散于电解质溶液中。
本发明处理方法可增加炭粒子的亲水性，改善炭粒子的分散性和稳定性。
本发明的优势：
本发明处理方法操作简单，原料易得、成本低廉、环境友好，适合工业生产处理炭粒子。
本发明可实现炭粒子的表面官能团种类、含量及分布可调控。
本发明可显著改善炭粒子的表面浸润性，改善分散性。
一种电化学处理炭粒子的装置，包括电源、阴极板、阳极板、至少2个隔板柱、反应器壳体、底座、搅拌棒、搅拌叶片、极板距离调节螺杆、密封圈和反应器盖板，所述反应器壳体与底座通过法兰盘连接，反应器盖板设置在反应器壳体的上端口，所述阳极板设置在反应器壳体与底座的连接处，并通过密封圈密封，极板距离调节螺杆与反应器盖板中间设置的螺孔螺纹连接，所述阴极板设置在极板距离调节螺杆的下端，在极板距离调节螺杆上设有贯通极板距离调节螺杆上下端的通孔，搅拌棒穿过极板距离调节螺杆的通孔并伸入至反应器壳体的内腔中，搅拌叶片设置在搅拌棒的下端，所述至少2个隔板柱纵向等间距的设置在反应器壳体的内壁，电源连接阴极板和阳极板。
进一步，所述隔板柱主要作用是防止搅拌过程中形成涡流，导致悬浮液体系发生纵向分层，其横截面为四边形，四边形前底角θ的角度范围为0.1-90°，可通过调节θ设计角度，改善悬浮液体系的循环方式，角度越大，对形成涡流的阻力越高。
更进一步，所述阳极板为惰性材料电极，包括金电极、铂电极或石墨电极；所述阴极板为常用电极或惰性材料电极，包括铁电极、铜电极、铝电极、金电极、铂电极或石墨电极。阳极采用惰性电极，防止在处理过程中失去电子损伤极板同时副反应影响处理效果。
附图说明
图1是本发明电化学处理炭粒子方法的示意图；
图2是本发明电化学处理炭粒子装置的结构示意图；
图3是图2的A-A剖视图；
图4是隔板柱的横截面图，为图3中B部2:1放大图；
图5是本发明实施例1处理前碳纳米管TEM图；
图6是本发明实施例1处理后碳纳米管TEM图；
图7是本发明实施例1处理前碳纳米管铺层接触角；
图8是本发明实施例1处理后碳纳米管铺层接触角。
其中，图2-3中，1.电源；2.阴极板；3.阳极板；4.隔板柱；5.反应器壳体；6.底座；7.搅拌棒；8.搅拌叶片；9.极板距离调节螺杆；10.密封圈；11.反应器盖板。
具体实施方式
为了能更好的说明本发明，下面实施例对本发明作进一步介绍，但是本发明所要求保护的范围并不限于实施例说明的范围。
(炭粒子的表面氧浓度(O/C)和氮浓度(N/C)的测定)
炭粒子表面氧浓度和氮浓度是采用X射线光电子能谱测定，测定装置和测试条件(英国Kratos公司的XSAM800多功能表面分析电子能谱仪，Al Kα靶(1486.6ev)光枪工作在12KV×15mA功率下，采用FAT方式，数据采用污染碳C1s(284.8ev)校正)，按以下顺序测定。
首先，取炭粒子粉末，用双面胶将其固定在样品架上，设定光电子的脱出角度为90°，装置的测定腔内保持2×10-6Pa的真空。
测定时，首先，将C1s(表面碳浓度)的主峰的结合能值校正到285.6eV；然后，在282～296eV范围内引直线的基线求出C1s(表面碳浓度)的峰面积。然后，在528～540eV范围内引直线作为基线求出O1s(表面氧浓度)的峰面积，在393～406eV范围内引直线作为基线求出N1s(表面氮浓度)的峰面积。
按下式算出炭粒子的表面氧浓度(O/C)和氮浓度(N/C)。
炭粒子的表面氧浓度(O/C)＝(O1s的峰面积/O的灵敏度因子)/(C1s的峰面积/C的灵敏度因子)。
炭粒子的表面氮浓度(N/C)＝(N1s的峰面积/N的灵敏度因子)/(C1s的峰面积/C的灵敏度因子)。
实施例1
如图2-4所示，本实施例中的一种电化学处理炭粒子的装置，包括电源1、铜阴极板2、石墨阳极板3、4个横截面为矩形(即θ为90°)的隔板柱4、反应器壳体5、底座6、搅拌棒7、搅拌叶片8、极板距离调节螺杆9、密封圈10和反应器盖板11，所述反应器壳体5与底座6通过法兰盘连接，反应器盖板11设置在反应器壳体5的上端口，所述阳极板3设置在反应器壳体5与底座6的连接处，并通过密封圈10密封，极板距离调节螺杆9与反应器盖板11中间设置的螺孔螺纹连接，所述阴极板2设置在极板距离调节螺杆9的下端，在极板距离调节螺杆9上设有贯通极板距离调节螺杆9上下端的通孔，搅拌棒7穿过极板距离调节螺杆9的通孔并伸入至反应器壳体5的内腔中，搅拌叶片8设置在搅拌棒7的下端，所述4个横截面为矩形(即θ为90°)的隔板柱4纵向等间距的设置在反应器壳体5的内壁，电源1连接阴极板2和阳极板3。
本实施例中的一种电化学处理炭粒子的方法，包括以下步骤：
1)炭粒子预分散：配制质量分数为0.05wt.％的氢氧化钾水溶液为电解质溶液，向其中加入多壁碳纳米管(由深圳碳纳米港有限公司提供，直径10-50nm，长度10-50μm，纯度﹥97wt％)，二者按mCNT：V电解质溶液＝1g：0.5L比例混合，通过搅拌充分分散浸润，得到炭粒子悬浮液；
2)炭粒子电化学处理：将悬浮液加入到用图2所示电化学处理装置(配置铂电极为阳极，铜电极为阴极，阴阳极板平行放置)，调节极板与电解质溶液接触，使用直流稳压电源采用恒压模式在阴阳两极间施加0.5V电压，同时通过机械搅拌使碳纳米管悬浮于电解质溶液中，连续搅拌处理20小时后，得到官能化的炭粒子；
3)炭粒子的后处理过滤、反复洗涤碳纳米管至滤液为中性，取滤饼80℃真空烘干，研磨为粉末。
取少量切断后的碳纳米管在乙醇溶液中分散，经超声形成均匀分散液，分散液以铜网为支撑制样采集透射电子显微镜照片(图6)，与未经处理碳纳米管透射电子显微镜照片(图5)比较，可看出碳纳米管缠绕现象较少，分散性更好且碳纳米管无无明显损伤；测试处理后碳纳米管表面的氧浓度(O/C比)和氮浓度(N/C比)，结果列于表1。对碳纳米管铺层使用接触角测量仪(Dataphysics，OCA-20)测量水滴在碳纳米管表面接触角，图片如图8，接触角结果为71°，与原始碳纳米管的120°相比较，明显降低，证明碳纳米管的表面浸润性得到明显改善，为碳纳米管的良好分散提供基础。通过激光粒度仪评价碳纳米管分散液粒度分布，结果为88nm，与原始相比，明显降低，说明团聚减少，更好分散。
实施例2～3
采用与实施例1相同结构的电化学处理炭粒子的装置，改变隔板柱设计和电极板：横截面为矩形(即θ为90°)的隔板柱(4)的横截面前底角θ角度在0.1-90°范围内调节；阳极板可为金电极、铂电极或石墨电极等惰性材料电极，阴极板可为铁电极、铜电极、铝电极、金电极、铂电极或石墨电极等任意电极；具体角度设计与极板材料列于表1。
使用与实施例1相同的电化学处理炭粒子的方法，改变电极材料炭粒子种类、电解质种类和浓度、处理电压、处理时间、搅拌方式、进行电化学处理，处理后经离心、真空过滤、反复洗涤炭粒子至滤液为中性，取滤饼80℃真空烘干，研磨为粉末。取样测试炭粒子表面的氧浓度(O/C比)和氮浓度(N/C比)，接触角，粒径结果如表1所示。
实施例4～6
采用与实施例1相同结构的电化学处理炭粒子的装置，改变隔板柱设计和电极板：横截面为矩形(即θ为90°)的隔板柱(4)的横截面前底角θ角度在0.1-90°范围内调节；阳极板可为金电极、铂电极或石墨电极等惰性材料电极，阴极板可为铁电极、铜电极、铝电极、金电极、铂电极或石墨电极等任意电极；具体角度设计与极板材料列于表1。
使用与实施例1相同的电化学处理炭粒子的方法，使用直流稳压电源采用恒流模式处理炭粒子，改变电极材料炭粒子种类、电解质种类和浓度、处理电流、处理时间、搅拌方式、进行电化学处理，处理后经离心、真空过滤、反复洗涤炭粒子至滤液为中性，取滤饼80℃真空烘干，研磨为粉末。取样测试炭粒子表面的氧浓度(O/C比)和氮浓度(N/C比)，接触角，粒径结果如表1所示。
实施例7～9
采用与实施例1相同结构的电化学处理炭粒子的装置，改变隔板柱设计和电极板：横截面为矩形(即θ为90°)的隔板柱(4)的横截面前底角θ角度在0.1-90°范围内调节；阳极板可为金电极、铂电极或石墨电极等惰性材料电极，阴极板可为铁电极、铜电极、铝电极、金电极、铂电极或石墨电极等任意电极；具体角度设计与极板材料列于表1。
使用与实施例1相同的电化学处理炭粒子的方法，使用CHI600E电化学工作站采用循环伏安法处理炭粒子，改变电极材料炭粒子种类、电解质种类和浓度、扫描速度、处理时间、搅拌方式、进行电化学处理，处理后经离心、真空过滤、反复洗涤炭粒子至滤液为中性，取滤饼80℃真空烘干，研磨为粉末。取样测试炭粒子表面的氧浓度(O/C比)和氮浓度(N/C比)，接触角，粒径结果如表1所示。
比较例1
取与实施例1相同碳纳米管，不经任何处理，取少量样品在乙醇溶液中分散，经超声形成均匀分散液，分散液以铜网为支撑制样采集透射电子显微镜照片(图5)，可看出碳纳米管缠绕严重，分散明显不佳。测试其表面氧浓度(O/C比为0.058)和氮浓度(N/C比为0.002)，表面接触角(图片如图7所示，接触角为120°)、分散液粒径测试结果为872nm。
比较例2
取与实施例2相同石墨烯，测试其表面氧浓度(O/C比为0.012)和氮浓度(N/C比为0.001)，表面接触角(接触角为125°)、分散液粒径测试结果为583nm。
Figure BDA0001965484490000111

Claims (10)

1.一种电化学处理炭粒子的方法，其特征在于：包括以下步骤：
1)炭粒子预分散：配制电解质溶液，将炭粒子与电解质溶液混合均匀，得到炭粒子悬浮液；
2)炭粒子电化学处理：将炭粒子悬浮液置于电化学处理装置内，调节极板位置保证与电解质溶液接触，通电后对炭粒子进行电化学处理，同时对电解质溶液施以搅拌，电化学处理完成后，得到官能化的炭粒子；
3)炭粒子的后处理：洗涤过滤去除官能化的炭粒子表面的电解质，干燥即可；
所述步骤2)中对电解质溶液施以搅拌的搅拌装置可连续运行，也可间歇运行。
2.根据权利要求1所述的电化学处理炭粒子的方法，其特征在于：所述步骤1)中电解质溶液为无机或有机电解质溶液，无机电解质溶液是酸、碱或盐的水溶液；有机电解质溶液是有机溶剂的电解质体系。
3.根据权利要求2所述的电化学处理炭粒子的方法，其特征在于：所述无机电解质溶液包括硫酸、磷酸、草酸、氢氧化钠、氢氧化钾、碳酸氢铵或硫酸钠的水溶液；所述有机电解质溶液包括四丁基四氟硼酸铵的乙腈溶液或四丁基四氟硼酸铵的四氢呋喃溶液。
4.根据权利要求2所述的电化学处理炭粒子的方法，其特征在于：所述步骤1)中电解质溶液的浓度为0.01wt.％～50wt.％；
所述步骤1)中每1g炭粒子使用电解质溶液量为0.001L-1000L。
5.根据权利要求4所述的电化学处理炭粒子的方法，其特征在于：所述步骤2)中电化学处理装置为两电极及以上电极体系；所述两电极电化学处理装置的阳极材料为惰性电极材料；所述两电极电化学处理装置的阴极材料为常用导电材料或惰性电极材料；所述的两电极以上电极体系，是在两电极体系的基础上增加参比电极，所述参比电极为银-氯化银电极或饱和甘汞电极。
6.根据权利要求5所述的电化学处理炭粒子的方法，其特征在于：所述惰性电极材料包括金、铂或石墨；所述常用导电材料或惰性电极材料包括铁、铜、铝、金、铂或石墨。
7.根据权利要求6所述的电化学处理炭粒子的方法，其特征在于：所述步骤2)中对炭粒子进行电化学处理的电压为0.5～30V，或者施加1mA～5A电流处理，或者采用循环伏安法使电压在0.5～20V之间进行任意次数的扫描，扫描速度为50～500mV/s；处理时间为5～1200min。
8.一种电化学处理炭粒子的装置，其特征在于：包括电源(1)、阴极板(2)、阳极板(3)、至少2个隔板柱(4)、反应器壳体(5)、底座(6)、搅拌棒(7)、搅拌叶片(8)、极板距离调节螺杆(9)、密封圈(10)和反应器盖板(11)，所述反应器壳体(5)与底座(6)通过法兰盘连接，反应器盖板(11)设置在反应器壳体(5)的上端口，所述阳极板(3)设置在反应器壳体(5)与底座(6)的连接处，并通过密封圈(10)密封，极板距离调节螺杆(9)与反应器盖板(11)中间设置的螺孔螺纹连接，所述阴极板(2)设置在极板距离调节螺杆(9)的下端，在极板距离调节螺杆(9)上设有贯通极板距离调节螺杆(9)上下端的通孔，搅拌棒(7)穿过极板距离调节螺杆(9)的通孔并伸入至反应器壳体(5)的内腔中，搅拌叶片(8)设置在搅拌棒(7)的下端，所述至少2个隔板柱(4)纵向等间距的设置在反应器壳体(5)的内壁，电源(1)连接阴极板(2)和阳极板(3)。
9.根据权利要求8所述的电化学处理炭粒子的装置，其特征在于：所述隔板柱(4)的横截面为四边形，四边形前底角θ的角度范围为0.1-90°。
10.根据权利要求8-9任一项所述的电化学处理炭粒子的装置，其特征在于：所述阳极包括金电极、铂电极或石墨电极；所述阴极包括铁电极、铜电极、铝电极、金电极、铂电极或石墨电极。
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