CN103840129A - 石墨烯电极、包含它的能量储存装置、及其制造方法 - Google Patents
石墨烯电极、包含它的能量储存装置、及其制造方法 Download PDFInfo
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Abstract
本发明提供一种石墨烯电极、包含它的能量储存装置、及其制造方法。其中,该石墨烯电极包含金属箔;未掺杂石墨烯层;以及杂原子掺杂石墨烯层,其中该杂原子掺杂石墨烯层与该金属箔被该未掺杂石墨烯层隔开。
Description
技术领域
本发明涉及一种石墨烯电极结构及其制造方法,且特别是涉及一种可应用于能量储存装置的石墨烯电极结构及其制造方法。
背景技术
随着绿色环保议题受到世界各国的重视,电动车的开发已成为目前最热门的研究课题之一。然而,传统锂离子电池无法满足电动车对于所使用之电池的高电容量、高功率以及快充等需求。为改善传统锂离子电池,业界目前亟需能够取代石墨的新世代负极材料。
石墨烯因具备优异的电子导电度和多孔性结构,使得电子的传导以及锂离子的扩散都相当快速。另外,由于石墨烯的不规则结构,使其具备比石墨更高的电容量。然而,由于石墨烯的不可逆电容太大及导电度较低,使得石墨烯负极在锂电池的应用迟迟无法商业化。
发明内容
本发明提供一种石墨烯电极及其制造方法,其利用干式表面改性处理,在低温下对石墨烯表面进行杂原子掺杂,可提升石墨烯电极的电容量、以及降低不可逆电容。此外,所得的石墨烯电极适合应用于能源储存系统中。
本发明所述的石墨烯电极,包含:金属箔;未掺杂石墨烯层;以及,杂原子掺杂石墨烯层,其中该杂原子掺杂石墨烯层与该金属箔被该未掺杂石墨烯层隔开。
本发明还提出一种石墨烯电极的制造方法,用以形成上述的石墨烯电极。该方法包含,提供金属箔;形成石墨烯层于该金属箔之上;以及,对该石墨烯层进行干式表面改性处理,从而将杂原子掺杂至该石墨烯层表面。
根据本发明一种实施方式,本发明还提供一种能量储存装置,其中该能量储存装置包含上述石墨烯电极作为第一电极、第二电极、以及配置于该第一电极与该第二电极之间的隔离膜。
为让本发明的上述和其它目的、特征、和优点能更明显易懂,下文特举出较佳实施例,并配合所附图式,作详细说明如下:
附图说明
图1为剖面示意图,说明本发明一种实施方式的石墨烯电极。
图2为本发明一种实施方式所述的石墨烯电极制造方法的步骤流程图。
图3为剖面示意图,说明本发明一种实施方式的能量储存装置。
图4说明石墨烯电极(II)、石墨烯电极(III)、及石墨烯电极(IV)其杂原子掺杂石墨烯层的氮元素含量。
图5为电池(I)及电池(II)的充放电曲线图。
图6说明电池(I)及电池(II)不同的充电率(C-rate)下的放电电容。
图7为电池(I)、电池(III)、以及电池(IV)的充放电次数及放电电容的关系图。
附图中的标号具有以下含义:
10~金属箔;
20~石墨烯层;
21~表面;
22~杂原子掺杂石墨烯层;
23~杂原子;
24~未掺杂石墨烯层;
100~石墨烯电极;
101、102、103~步骤;
200~能量储存装置;
202~第一电极;
204~隔离膜;以及
206~第二电极。
具体实施方式
请参照图1,本发明所述之石墨烯电极100,可具有金属箔(metal foil)10,其上具有石墨烯层20。其中,该石墨烯层20包含未掺杂石墨烯层24,以及杂原子掺杂石墨烯层22。值得注意的是,该杂原子掺杂石墨烯层22与该金属箔10被该未掺杂石墨烯层24所隔开。该金属箔10的材料可为导电金属,例如为铜箔。该金属箔10的厚度并无限制,可例如介于0.1至200μm之间。该杂原子掺杂石墨烯层22为该石墨烯层20的表面21经杂原子23掺杂后所得,而该石墨烯层20未被掺杂的部份则定义为该未掺杂石墨烯层24。该杂原子23可为氮原子、磷原子、硼原子、或其组合,例如为氮原子。该杂原子掺杂石墨烯层22的杂原子掺杂量可为0.1-3原子%(原子百分比),上述原子百分比的分母为该杂原子掺杂石墨烯层22的总原子数。该未掺杂石墨烯层24可为单层石墨烯(graphene)、多层石墨烯(graphene nanosheets、GNS)、或上述的组合;且该杂原子掺杂石墨烯层22可为杂原子掺杂单层石墨烯(graphene)、杂原子掺杂多层石墨烯(graphene nanosheets、GNS)、或上述的组合。
本发明还提供上述石墨烯电极的制造方法,请参照图2,其为本发明一种实施方式所述石墨烯电极的制造方法的步骤流程图。首先,提供金属箔(步骤101),该金属箔可例如为铜箔。接着,形成石墨烯层于该金属箔上(步骤102)。最后,对该石墨烯层进行干式表面改性处理,以将杂原子掺杂至该石墨烯层表面(步骤103)。该干式表面改性处理的目的在于将杂原子掺入该石墨烯层表面,以使该石墨烯层的一部份形成杂原子掺杂石墨烯层,而该石墨烯层其它未被杂原子所掺杂的部份则定义为未掺杂石墨烯层。该干式表面改性处理可例如等离子体改性过程,值得注意的是,由于本发明仅需将杂原子掺杂至该石墨烯层的表面,不需要使其扩散致整层石墨烯层,因此在进行该干式表面改性处理时,不需要额外对该石墨烯层或金属箔进行加热。此外,在该等离子体改性过程中通入反应气体,以使杂原子掺入石墨烯层中。举例来说,该反应气体包含所欲掺杂的杂原子的气体(例如氮气、氨气、空气、或其组合),或是含所欲掺杂的杂原子的气体(例如氮气、氨气、空气、或其组合)与其它气体(例如氢气、氩气、氧气、或其组合)的混合。根据本发明另一实施例,等离子体改性过程中可进一步通入承载气体以稳定该等离子体改性过程,该承载气体可包含氦气、氩气、氮气、氖气、或其组合。本发明所述的等离子体改性过程,所使用的反应器可为低压(low pressure)操作的等离子体反应器或是常压(atmospheric pressure)操作的等离子体反应器。在进行等离子体改性过程时,由于所使用的机台不同,过程参数会有所改变,因此本发明在进行该进行等离子体改性过程时,可依实际需要调整该反应气体的流量、该承载气体流量、反应压力、功率、反应时间、以及石墨烯层与等离子体反应器电极间的距离,以使杂原子掺杂石墨烯层的杂原子掺杂量可为0.1-3原子%(原子百分比)。
根据本发明一种实施方式,石墨烯层的形成方式可包含以下步骤。首先,在该金属箔上形成由含石墨烯的组合物所构成的涂层,其中形成该涂层的方法可例如为丝网印刷、旋转涂布法(spin coating)、棒状涂布法(bar coating)、刮刀涂布法(blade coating)、滚筒涂布法(roller coating)、或浸渍涂布法(dipcoating)。接着,对该涂层进行烘干过程,得到石墨烯层。该烘干过程的温度可为40-150℃,烘烤时间可为1分钟至10小时。在此,该含石墨烯的组合物可包含石墨烯、以及增粘剂。根据本发明其它实施例,该含石墨烯的组合物可更包含助导剂。该增粘剂可为水系复合增粘剂、有机增粘剂、或其组合,例如羧甲基纤维素钠盐(CMC)、苯乙烯-丁二烯橡胶(styrene butadiene rubber、SBR)、或是聚偏二氟乙烯(PVdF)。该助导剂可例如为石墨、碳黑、或其组合。
请参照图3,本发明还提供一种能量储存装置(例如:锂电池、或燃料电池)200,其包含上述的石墨烯电极100。该能量储存装置200可包含石墨烯电极作为第一电极202(例如负极)、第二电极206(例如正极)、以及隔离膜204,所述隔离膜204配置于该第一电极202与该第二电极206之间。值得注意的是,该石墨烯电极以该杂原子掺杂石墨烯层与该隔离膜接触。该第二电极206之材料为锂或含有锂的金属氧化物,例如为锂、LiCoO2、LiFePO4、LiCo1/3Ni1/3Mn1/3O2、LiMn2O4或其它正极材料及其组合。该隔离膜的材料为高分子,例如聚乙烯、聚丙烯、或其组合,且可具有多个孔洞。该隔离膜204内可具有电解质(未图示),例如碳酸亚乙基酯(ethylene carbonate,EC)、碳酸亚丙基酯(propylene carbonate,PC)、与γ-丁酸内酯(gamma-butyrolactone,GBL)、碳酸二乙酯(diethyl carbonate,DEC)、碳酸二甲酯(dimethyl carbonate,DMC)、碳酸甲基乙基酯(ethyl methyl carbonate,EMC)、与碳酸甲基丙基酯(methylpropyl carbonate、MPC)、碳酸亚乙烯基酯(vinylene carbonate、VC)、锂盐或其组合。
为了让本发明之上述和其它目的、特征、和优点能更明显易懂,下文特举数实施例及比较实施例,来说明本发明所述之石墨烯电极、及包含它的装置。
石墨烯电极的制备
实施例1
首先取5.3571g的去离子水、以及0.0337g羧甲基纤维素钠盐(CMC,作为增粘剂)置入反应瓶中,以均质机在2000rpm的转速下搅拌20分钟。然后,加入0.0056g乙炔黑(由Timcal制造及出售,商品号为Super P,作为助导剂)、以及0.5g石墨烯(graphene)于反应瓶中,并搅拌20分钟。接着,加入0.0562g苯乙烯-丁二烯橡胶(styrene butadiene rubber、SBR,作为增粘剂)于反应瓶中,并搅拌30分钟,得到含石墨烯的组合物。
接着,将上述含石墨烯的组合物以150μm的刮刀涂布于铜箔上形成涂层,并在120℃烘干,得到具有石墨烯层的石墨烯电极(I)。
值得注意的是,石墨烯电极(I)的石墨烯层并未掺杂有任何杂原子。
实施例2
将实施例所得的石墨烯电极(I)置于等离子体反应器内,其中该石墨烯电极(I)以该铜箔部份置于等离子体反应器内的支撑基板(石墨烯层与等离子体反应器电极间的距离为2.2mm)。接着,在通入氮气(流量为5sccm)及氦气(等离子体反应器内5.88L/min)于该等离子体反应器后,在操作压力为1atm、及射频(RF)功率65W下对石墨烯极板表面进行等离子体改性过程以将氮元素掺杂至该石墨烯层表面(此过程中不需要加温)。在反应6秒后,得到石墨烯电极(II)。
接着,以X光光电子光谱仪(X-ray Photoelectron Spectrometer、XPS)对所得的石墨烯电极(II)的表面进行分析,以统计石墨烯层表面的氮元素含量,结果请参照图4。
实施例3
如实施例2的相同方式进行,但将实施例2所述的氮气流量由5sccm增加至30sccm,得到石墨烯电极(III)。
接着,以X光光电子光谱仪(X-ray Photoelectron Spectrometer、XPS)对所得的石墨烯电极(III)的表面进行分析,以统计石墨烯层表面的氮元素含量,结果请参照图4。
实施例4
如实施例2的相同方式进行,但将实施例2所述的反应时间由6秒增加至18秒,得到石墨烯电极(IV)。
接着,以X光光电子光谱仪(X-ray Photoelectron Spectrometer、XPS)对所得的石墨烯电极(IV)的表面进行分析,以统计石墨烯层表面的氮元素含量,结果请参照图4。
由该图可知,在经等离子体处理后,本发明所述的石墨烯电极(II)-(IV)的石墨烯层表面含有氮原子,证实氮原子确实掺入该石墨烯层表面。
实施例5
如实施例2的相同方式进行,但将实施例2所述的氮气流量由5sccm增加至15sccm、且反应时间由6秒增加至18秒,得到石墨烯电极(V)。
实施例6
如实施例2的相同方式进行,但将实施例2所述的氮气流量由5sccm增加至30sccm、且反应时间由6秒增加至18秒,得到石墨烯电极(VI)。
请参照表1,其显示实施例2-6所述的等离子体改性过程的过程参数。
表1
具有石墨烯电极的电池制作
实施例7
将实施例1所述的石墨烯电极(I)经裁切成适当大小(直径13mm)作为负极,搭配聚乙烯/聚丙烯(PE/PP)复合膜(厚度为20μm)作为隔离膜(注入碳酸亚乙基酯(ethylene carbonate、EC)、碳酸甲基乙基酯(ethyl methyl carbonate、EMC)、碳酸亚乙烯基酯(vinylene carbonate、VC)以及1M的LiPF6作为电解液)、以及锂金属层作为正极,进行组装,得到钮扣型锂电池(I)。
实施例8
将实施例4所述的石墨烯电极(IV)经裁切成适当大小(直径13mm)作为负极,搭配聚乙烯/聚丙烯(PE/PP)复合膜(厚度为20μm)作为隔离膜(注入碳酸亚乙基酯(ethylene carbonate,EC)、碳酸甲基乙基酯(ethyl methylcarbonate,EMC)、碳酸亚乙烯基酯(vinylene carbonate、VC)以及1M的LiPF6作为电解液)、以及锂金属层作为正极,进行组装,得到钮扣型锂电池(II)。
实施例9
将实施例5所述的石墨烯电极(I)经裁切成适当大小(直径13mm)作为负极,搭配聚乙烯/聚丙烯(PE/PP)复合膜(厚度为20μm)作为隔离膜(注入碳酸亚乙基酯(ethylene carbonate,EC)、碳酸甲基乙基酯(ethyl methyl carbonate,EMC)、碳酸亚乙烯基酯(vinylene carbonate、VC)以及1M的LiPF6作为电解液)、以及锂金属层作为正极,进行组装,得到钮扣型锂电池(III)。
实施例10
将实施例6所述的石墨烯电极(I)经裁切成适当大小(直径13mm)作为负极,搭配聚乙烯/聚丙烯(PE/PP)复合膜(厚度为20μm)作为隔离膜(注入碳酸亚乙基酯(ethylene carbonate,EC)、碳酸甲基乙基酯(ethyl methyl carbonate,EMC)、碳酸亚乙烯基酯(vinylene carbonate、VC)以及1M的LiPF6作为电解液)、以及锂金属层作为正极,进行组装,得到钮扣型锂电池(IV)。
电性测试
将实施例7所得的电池(I)及实施例8所得的电池(II)进行充放电测试,得到充放电曲线图如图5所示。
接着,对实施例7所得的电池(I)及实施例8所得的电池(II)在不同的充电率(C-rate)下评估其放电电容,结果请参照图6。由图可知,电池(II)(具有经等离子体改性过程掺入氮原子的石墨烯电极)在不同的充电率(C-rate)下,其电容量皆大于电池(I)(石墨烯电极未掺杂氮原子)的电容量。
将实施例7所得的电池(I)、实施例9所得的电池(III)、以及实施例10所得的电池(IV)进行电池循环寿命测试,结果如图7所示。由该图可知,电池(III)及电池(IV)(具有经等离子体改性过程掺入氮原子的石墨烯电极)其电容量都比具有未进行等离子体改性过程的石墨烯电极的电池(I)来得高。尤其是电池(III),其电容量足足高出电池(I)1倍之多,效果相当优异。此外,由电池循环寿命测试的结果可知,电池(III)及电池(IV)在使用数次后其效能仍维持一定的水准。
将实施例7所得的电池(I)、实施例8所得的电池(II)、及实施例9所得的电池(III)进行充放电循环测试,并量测其不可逆电容与库仑效率,结果如表2所示。
表2
由表2可知,具有本发明所述石墨烯电极的电池,无论是在第1循环充放电测试或第2循环充放电测试,其库仑效率明显增加,且不可逆电容大幅下降,这表示经过等离子体改性过程的石墨烯电极在电性表现上更加稳定。
基于上述,本发明所述的石墨烯电极,由于其石墨烯层表面经过干式表面改性处理,提升了石墨烯的电化学特性(电容量与载子迁移率增加、不可逆电容下降),因此非常适合应用于能源储存装置中。
虽然本发明已以数个较佳实施例揭露如上,然其并非用以限定本发明,任何所属技术领域中具有通常知识者,在不脱离本发明之精神和范围内,当可作任意之更动与润饰,因此本发明之保护范围当视后附之申请专利范围所界定者为准。
Claims (21)
1.一种石墨烯电极,包含:
金属箔;
未掺杂石墨烯层;以及
杂原子掺杂石墨烯层,其中该杂原子掺杂石墨烯层与该金属箔被该未掺杂石墨烯层隔开。
2.权利要求1所述的石墨烯电极,其中该杂原子掺杂石墨烯层所掺杂的杂原子包含氮原子、磷原子、硼原子、或其组合。
3.权利要求1所述的石墨烯电极,其中该杂原子掺杂石墨烯层的杂原子掺杂量为0.1-3原子%,以该杂原子掺杂石墨烯层的总原子数为基准。
4.权利要求1所述的石墨烯电极,其中该未掺杂石墨烯层为单层石墨烯、多层石墨烯、或上述的组合。
5.权利要求1所述的石墨烯电极,其中该杂原子掺杂石墨烯层为杂原子掺杂单层石墨烯、杂原子掺杂多层石墨烯、或上述的组合。
6.一种石墨烯电极的制造方法,包含:
提供金属箔;
形成石墨烯层于该金属箔之上;以及
对该石墨烯层进行干式表面改性处理,从而将杂原子掺杂至该石墨烯层表面。
7.权利要求6所述的石墨烯电极的制造方法,其中该杂原子包含氮原子、磷原子、硼原子、或其组合。
8.权利要求6所述的石墨烯电极的制造方法,其中该杂原子掺杂至该石墨烯层表面,形成杂原子掺杂石墨烯层。
9.权利要求6所述的石墨烯电极的制造方法,其中该石墨烯层至少一部份未掺杂该杂原子。
10.权利要求9所述的石墨烯电极的制造方法,其中该石墨烯层未掺杂该杂原子的部份定义为未掺杂石墨烯层。
11.权利要求6所述的石墨烯电极的制造方法,其中该石墨烯层的形成方式包含:
在该金属箔上形成由含石墨烯的组合物所构成的涂层;以及
对该涂层进行烘干过程,得到石墨烯层。
12.权利要求11所述的石墨烯电极的制造方法,其中该含石墨烯之组合物包含:
石墨烯;以及
增粘剂。
13.权利要求12所述的石墨烯电极的制造方法,其中该增粘剂包含水系复合增粘剂、有机增粘剂、或其组合。
14.权利要求12所述的石墨烯电极的制造方法,其中该含石墨烯的组合物还包含助导剂。
15.权利要求14所述的石墨烯电极的制造方法,其中该助导剂包含石墨、碳黑、或其组合。
16.权利要求6所述的石墨烯电极的制造方法,其中该干式表面改性处理包含等离子体改性过程。
17.权利要求16所述的石墨烯电极的制造方法,其中在该等离子体改性过程中通入反应气体,且该反应气体包含氮气、氨气、空气、或其组合。
18.权利要求17所述的石墨烯电极的制造方法,其中该反应气体更包含氩气、氢气、氧气、或其组合。
19.权利要求17所述的石墨烯电极的制造方法,其中在该等离子体改性过程中进一步通入承载气体,且该承载气体包含氦气、氩气、氮气、氖气、或其组合。
20.一种能量储存装置,包含:
第一电极,其中该第一电极系为权利要求1所述的石墨烯电极;
第二电极;以及
隔离膜,配置于该第一电极与该第二电极之间。
21.权利要求20所述的能量储存装置,其中该能量储存装置系为锂电池、或燃料电池。
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