CN104071766B - 碳材料及其制造方法 - Google Patents
碳材料及其制造方法 Download PDFInfo
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- CN104071766B CN104071766B CN201410350726.8A CN201410350726A CN104071766B CN 104071766 B CN104071766 B CN 104071766B CN 201410350726 A CN201410350726 A CN 201410350726A CN 104071766 B CN104071766 B CN 104071766B
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- graphite
- carbon material
- carbon
- vapor phase
- phase growth
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/522—Graphite
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Abstract
本发明提供制造石墨晶体性优异、且含有具有良好的载流子迁移率的适度的空间的多孔质碳材料,碳六边形网面的端部位于粒子及结构体的外表面的多孔质碳材料、类似石墨烯的薄片状石墨。通过对在适当的范围设定了材料中的闭气孔率、残留氢量的碳材料进行热等静压加压处理,由此发生以从碳材料中产生的氢、烃形成的闭气孔为核的石墨的气相生长反应,从而廉价且大量地制造目标的多孔质碳材料。通过对得到的多孔质碳材料施加物理性冲击、或生成以多孔质碳材料为主体的石墨层间化合物后再进行急速加热,由此可制造类石墨烯的石墨薄片。
Description
本申请是申请人于2010年05月01日提交的国际申请号PCT/JP2010/057725、进入国家阶段的申请号201080019171.9、发明名称为“碳材料及其制造方法”的申请的分案申请。
技术领域
本发明涉及可以适合在锂离子电池、各种电容器、燃料电池电极等电池材料或各种催化剂材料中使用的碳材料。
背景技术
在锂离子电池负极或电双层电容器负极中由于适合与锂离子等发生插层反应,所以使用各种石墨材料。通过捅层(intercalation)在碳石墨六边形网面(图1)的层间插入锂、钾等碱金属、硫酸离子、硝酸离子等离子而成的化合物被称为石墨层间化合物。
在锂离子电池、高密度电容器等中,通过如上所述的石墨层间化合物的生成、在层间插入的插入物的插层、去插层(deintercalation),能获得电能,因此使用石墨材料作为电极材料。
在基于石墨材料与插入物(被插入的物质)的插层反应中,作为主体材料的石墨的石墨化度(结晶性)与反应性相关,对于通过向石墨给予电子而导致以电正性离子形式发生插层的供体型而言,石墨化度高的主体材料中的反应性良好。需要说明的是,作为供体型产生插层的插入物,有锂、钠、钾、铯等碱金属、钡、锶等碱土类金属。(非专利文献1)
这些供体型的石墨层间化合物通常在空气中不稳定,与氧气或水分反应,插入剂被从石墨层间排出(去插层)。使用通常的石墨材料时,其微晶尺寸为数微米大,而且不是完全的单晶,所以一部分的插入剂滞留在石墨层间形成所谓的残留化合物。
利用插层作为锂离子电池或电容器等的电池反应时,理想的是不形成残留化合物而高速、可逆性地发生插层、去插层。用这样理想的反应可以得到作为电池的高的充放电容量,因此需要作为主体材料的石墨材料具有高的石墨化度,需要其微晶尺寸为微细、且发生反应的面积大的多孔质的碳材料。(专利文献1)
另外,由于插层反应从碳六边形网面的端部发生,所以希望作为主体材料的石墨材料中碳六边形网面的端部位于其外表面上,在与碳六边形网面平行的表面中不发生反应。天然产出的天然石墨、在铁的制造工序中熔融后的铁冷却时析出的凝析石墨(Kishgraphite)等在高温、高压条件下由液相析出的石墨材料各向异性、取向性大,在粒子表面主要存在碳六边形网面本身,并且碳六边形网面的端部存在的情况限定于粒子的端部。(图7)
以聚丙烯腈(PAN)等树脂、或煤、石油系沥青为原料的碳纤维在高分子材料的阶段、通过拉丝成纤维状且进行后续的热处理而使其炭化、石墨化。因此碳纤维中形成碳六边形网面沿着该纤维方向以同心圆状平行地层叠而成的结构、或者碳六边形网面以放射状层叠而成的结构,特别是对于碳六边形网面平行地层叠而成的结构而言,在碳纤维表面上碳六边形网面成为主要的结构。即使在具有放射状组织的碳纤维中,也成为用于维持纤维结构的表皮组织(放射状的组织在表面部呈卧倒状的结构),并且碳六边形网面成为主要的结构。
有以烃、氢气作为原料在高温下使用金属等催化剂以气相生长制造碳、石墨材料的方法。作为以气相生长法制造的碳材料,有气相生长碳纤维、碳纳米管、碳纳米角、富勒烯等,但均是从作为反应的起点的金属催化剂起开始各向异性地生长。因此,即便在这些气相生长法中在材料的外表面上碳六边形网面也成为主要存在的结构。(专利文献2、3)
作为制造各向同性的石墨材料的方法,有以石油焦炭为骨架、以石油、煤沥青为粘合剂进行混炼,使用冷等静压(isostaticpress,日文原文:静水压)加压装置(CIP)使其预备成型、炭化、石墨化的方法。这些各向同性石墨材料虽然作为材料为各向同性,但需要以高密度填充填料的工序,所以材料的气孔率不足10%,用于维持强度的难以石墨化的成分多,而作为石墨的结晶性降低。(专利文献4)
日本专利公报2633638号(专利文献5)中公开的高取向性石墨晶体虽然是在玻璃状碳中使气相生长石墨生长的物质,但为高度地填充至体积密度达2.15的高密度石墨。因此,石墨六边形网面的端部在外表面显示的比率相对较低,从体积密度和真密度的差异算出的气孔率低到几%左右,反应的效率差。
现有技术文献
专利文献
专利文献1:日本专利第3850918号
专利文献2:日本特公昭62-49363
专利文献3:日本专利第2664819号
专利文献4:日本特公平7-91107
专利文献5:日本专利第2633638号
非专利文献
非专利文献1:稻垣道夫,村松一生、《含有机分子的三元石墨层间化合物》(有機分子を含む三元系黒鉛間化合物)、碳素No.127(1986)p196
发明内容
发明要解决的问题
以往的石墨材料基本上各向异性高、表面主要为碳六边形网面的平面构成、材料端部主要为碳六边形网面的端部构成、且存在越是提高热处理温度,石墨化度越高、各向异性越高的倾向。锂离子电池、电容器等中有效使用的插层反应在碳六边形网面的端部发生,且作为石墨晶体的石墨化度(结晶性)越高反应效率越高,但难以制造材料的整个外表面由碳六边形网面的端部构成的碳材料。
另外,在对碳的原料用冷轧等静压加压装置(CIP)预备成型的方法、对玻璃状碳进行热等静压加压处理而制造在材料内部高取向性的石墨材料的方法中,会变成高密度的材料,难以制造气孔率高的多孔性的材料。
用于解决问题的方法
对在热处理后变成碳的高分子材料成形为规定的形状,以规定的升温速度进行炭化烧成,由此制造内部具有适当的闭气孔的预备烧成体。炭化烧成的烧成温度以能够适度产生在接下来的工序中作为气相生长石墨的原料的烃、氢的方式进行设定。炭化烧成后含有氢的碳材料,必须含有适度的浓度的氢,且必须适度含有成为在接下来的气相生长石墨生成的起点的闭气孔。
通过对上述的碳材料进行热处理产生甲烷等烃气、氢气,且以这些产生气体高浓度存在于材料周围的方式,利用各向同性的气体压力进行高压加压。通过以热等静压加压处理并保持在高温高压,由此氢原子被激发,进行基于甲烷等CnHm系气体的CVD反应,以上述的闭气孔为核析出气相生长的石墨。
上述的制造方法的特征在于,通过将炭化烧成后的残留氢量、闭气孔率设定在适当的范围,且使炭化烧成后的热等静压加压处理时的最高到达温度设定为1400℃以上、加压压力设定为10MPa以上,由此制造结晶性高、且碳六边形网面生长为放射状的多孔质的碳材料。
图2及图3中示出了用上述的方法制造的碳材料的电子显微镜照片作为替代附图的照片。需要说明的是,图3是图2的放大照片。从图中明显可知,得到了碳六边形网面的端部位于外表面的多孔质的材料。从该电子显微镜照片算出的碳六边形网面的层叠方向的厚度为0.01微米~0.2微米的范围。
图4中示出了图2及图3所示的碳材料的拉曼光谱。由图中明显示出源于碳的SP2杂化轨道的1580cm-1的强峰,具有结晶性高的石墨结构。激光拉曼分光法测定中的光谱中表示碳六边形网面的层叠结构的1580cm-1附近的峰和表示乱层结构的1360cm-1附近的峰的强度比ID/IG(I1360/I1580)所示的R值显示0.085这样极低的值,是石墨晶体性极优异的结构。
为了进一步提高多孔质的气相生长石墨的气孔率,合成用以上述的方法制造的碳材料为主体材料的石墨层间化合物,接下来再进行急速加热,由此有效破坏碳六边形网面间连接。具体而言,可优选使用与碱金属、碱土类金属等供体型2元系、硫酸、硝酸等的受体型2元系、碱金属·四氢呋喃、碱土类金属·四氢呋喃等有机三元系、碱金属·醚类、碱金属土类·醚类等多元系等各种石墨层间化合物。
通过将上述的石墨层间化合物投入到保持在600℃以上的温度的电炉等,通过急速加热,由此破坏由以范德华力进行弱键合的石墨六边形网面形成的层堆叠,制造气孔率高的气相生长石墨。使急热温度提高到900℃左右进行更急速的加热时,多孔质结构被破坏,得到厚度0.001~0.01微米的类石墨烯的石墨薄片。
或者,对得到的多孔质的气相生长石墨结构在液氮温度下的施加冲击、在溶剂中进行的超音波等施加物理性冲击,多孔质结构也会被破坏,得到厚度0.01~0.1微米左右的类石墨烯的石墨薄片。
发明的效果
以往的石墨材料虽然是各向异性大,且石墨六边形网面的端部位于外表面的比例低的材料,但可以制造石墨六边形网面的端部在外表面所占的比例极高且为多孔质的碳材料。由此,可以大量且廉价地制造插层反应等中最佳的电极材料、催化剂材料用的碳材料。
以石墨六边形网面的端部位于外表面的多孔体的碳材料作为主体材料,通过对石墨层间化合物进行急速加热等可以制造气孔率大、石墨晶体性好的气相生长石墨,可以使碳材料在有效利用具有高的电子迁移率的石墨六边形网面的特性的电子器件等中实用化。
附图说明
图1为说明碳的石墨晶体的示意图。
图2为表示生成的气相生长石墨的电子显微镜照片的替代附图的照片。(实施例4)
图3为图2的放大照片,且为表示碳六边形网面的端部位于粒子的外表面且为多孔质的材料的替代附图的照片。(实施例4)
图4为生成的气相生长石墨的拉曼光谱图,且表示结晶性良好的石墨材料。(实施例4)
图5为表示破坏多孔质石墨结构得到的类石墨烯结构的石墨薄片的电子显微镜照片的替代附图的照片。(实施例15)
图6为非多孔质、致密的形态的石墨表面的扫描型电子显微镜(SEM)照片。(实施例16)
图7为非多孔质、致密的形态的石墨表面的高倍率SEM照片。(实施例16)
图8为比较以往的碳材料、石墨材料和本发明的碳材料的结构的示意图。
具体实施方式
将热处理后以高收率炭化的高分子材料成形为规定的形状。具体而言,作为该高分子材料,可优选使用石油系沥青、煤系沥青、沥青、PVC沥青、四苯并吩嗪沥青、萘沥青、蒽沥青、石油系中间相沥青、聚丙烯腈、人造纤维、酚醛系树脂、呋喃系树脂、纤维素系树脂等。
进而,在天然有机高分子中,可以使用淀粉、纤维素、蛋白质、胶原蛋白、褐藻酸、达玛树脂、科瓦铁镍钴合金(Kovar)、松香、古塔胶、天然橡胶等;在半合成高分子中,可以使用纤维素系树脂、纤维素乙酸酯,纤维素硝酸酯、纤维素乙酸酯丁酸酯、酪蛋白塑料、大豆蛋白塑料等;在合成高分子中,可使用作为热固化性树脂的酚醛树脂、尿素树脂、蜜胺树脂、苯并胍胺树脂、环氧树脂、邻苯二甲酸二烯丙酯树脂、不饱和聚酯树脂、双酚A型环氧树脂、酚醛清漆型环氧树脂、多官能团环氧树脂、脂环状环氧树脂、醇酸树脂、聚氨酯树脂等,及作为热塑性树脂的氯乙烯树脂、聚乙烯、聚丙烯、聚苯乙烯等,作为合成橡胶的聚异戊二烯、丁二烯等,作为合成纤维的尼龙、维尼纶、丙烯酸纤维、人造丝等,其他的聚乙酸乙烯酯、ABS树脂、AS树脂、丙烯酸树脂、聚缩醛、聚酰亚胺、聚碳酸酯、改性聚苯醚(PPE)、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、多芳基化合物、聚砜、聚苯硫醚、聚醚醚酮、氟树脂、聚酰胺亚胺、聚醚醚酮、硅树脂等。
对于成形的方法和形状没有特别限定,只要能够使上述高分子材料维持一定的形状,任何的方法和形状都可以适用于本发明中。例如,上述高分子材料利用热压制等形成想要的形状(例如,圆盘状)。
对成形后的高分子材料在氮气等惰性气体氛围中以规定的升温速度进行炭化烧成。炭化烧成时,通过设定该升温速度使得在材料内部生成多个数微米~数十微米的闭气孔。具体而言,通过在室温~500℃的温度区域以每小时3℃以上的升温速度,在500℃以上的温度区域以每小时5℃以上的升温速度进行炭化烧成,由此在材料内部生成数微米~数十微米的闭气孔并同时进行炭化。
从真比重和表观比重的差异算出的表观气孔率(闭气孔率)必须为2%以上。闭气孔率不足2%时,作为气相生长石墨生长的核的闭气孔相对少,作为反应气体的氢、烃向材料外部扩散、逸散,阻碍石墨的气相生长。作为优选的闭气孔率为约2%~约15%、更优选为约2.5%~约15%,进一步优选约2.5%~10%。
高分子材料的炭化烧成时,在300℃左右的温度区域主要生成水分,在400℃以上的温度区域生成水、一氧化碳、甲烷、氢、氨等,由此碳以外的元素脱离而进行炭化。在接下来的热等静压加压处理中,为了使多孔质的气相生长石墨生长,需要以适度残留氢的状态结束炭化烧成。具体而言,优选以残留的氢量为0.2~5重量%的方式设定炭化烧成温度。作为炭化烧成的温度通常约为400℃~约1100℃的范围。
为了生成气相生长石墨,需要同时满足上述的闭气孔率和残留氢量的范围,即便闭气孔率含有2%以上,在残留氢量少时石墨的气相生长也会停止。
将调整成适当的闭气孔率和残留氢量的炭化烧成后的材料装填在热等静压加压装置中,使用惰性气体进行各向同性的加压加热处理。为了得到多孔质的气相生长石墨,希望在约1400℃以上的温度、10MPa以上的压力下实施加压加热处理。可以认为在温度低于约1400℃时,由氢的激发导致氢载流子的生成,烃载流子的生成不充分,所以气相生长停止。可以认为在压力低于10MPa时,由于氢气、烃气的扩散、逸散加速,所以不能达到石墨的气相生长所需要的反应气体的浓度、压力。
本发明中,热等静压加压(HIP)处理时的最高到达温度的优选范围为约1400℃~约2200℃的范围,更优选约1500℃~约2100℃的范围。另外,作为HIP处理时的最高到达压力约为10MPa以上,优选约50MPa以上、更优选约100MPa以上、进一步优选约180MPa以上。另一方面,关于该最高到达压力的上限值没有特别限制,使用HIP装置时,通常根据装置的性能自然而然地设定上限值。所述上限值对于本领域技术人员来说,是显而易见的,通常约为200MPa,特别是高性能的装置的情况下,约为300MPa。优选的压力的范围可以从上述适当选择。
在各向同性的加压加热处理中,利用如下的压力优先的处理模式进行处理时,可以更有效地制造气相生长石墨,所述压力优先的处理模式为在达到处理的材料的预先的炭化烧成温度之前,保持在50MPa以上的压力,接下来加热到规定的最高到达温度。需要说明的是,当HIP处理时的最高到达压力低于50MPa时,则在达到处理的材料(高分子材料)的预先的炭化烧成温度之前,保持在该最高到达压力,接下来加热到规定的最高到达温度即可。
本发明的碳材料因为是多孔质而有用,特别是优选总气孔率为40%以上,更优选60%以上,进一步优选70%以上。另外,本发明的碳材料的石墨晶体性高,因此是有用的,特别优选利用激光拉曼分光法测定得到的上述R值(ID/IG(I1360/I1580))不足0.2。
本说明书中,氢量利用惰性气体熔解热传导法进行测定。在此,惰性气体熔解热传导法是指利用高频波加热试样,通过惰性气体输送产生的氢气,利用热导率检测器进行定量。需要说明的是,测定装置使用了堀场制作所EMGA621。
闭气孔率(表观气孔率)用
(真密度-表观密度)÷真密度×100(%)
进行计算,是用于表示试样中存在的闭气孔相对于试样体积的比率的指标。
总气孔率是指用(真密度-体积密度)÷真密度×100(%)进行计算,是用于表示该试样中所含的全部的气孔、即作为试样内部封闭的空间的闭气孔及作为试样表面的凸凹部的空间的开气孔两者之和相对于试样体积的比率的指标。
在此,真密度是指使试样中所含的空隙(包含开气孔和闭气孔)带来的影响尽量最小化,在将其粉碎成微粉末的状态下进行测定的密度(每单位体积的质量),本发明的实施例中,使用通过了74μm的筛子的粉末试样,用试样重量除以利用液相置换比重计法进行测定的体积来求出。微粉末化是用于除去原来的试样中所含的气泡等的闭气孔的操作。液相置换比重计法是指将粉末试样与丁醇等分散介质一起放入测定皿中,进行用于液体浸入试样中的空隙的脱气,并求出除去这些空隙的体积的方法。本发明的实施例中,使用SEISHINENTERPRISE公司制密度计AUTOTRUEDENSERMAT-500,测定了该体积。本说明书中,以上述操作求出的体积去除试样重量的值作为真密度。
表观密度是指用不除去试样所含的闭气孔的体积而除去开气孔的体积得到的体积去除试样重量的值。该体积除了使用不粉碎的状态的试样以外,与上述真密度的测定同样,利用液相置换比重计法进行测定。
体积密度是指以由试样的外形状算出的体积去除试样重量的值。体积密度使用由试样的外形状算出的体积,在此除了试样本身的体积外,不仅包含闭气孔也包含开气孔(通常为细孔)的体积。另一方面,算出表观密度时使用的体积虽然包含闭气孔,但由于是开气孔被除去后的体积,所以通常表观密度的数值高于体积密度的数值。
需要说明的是,体积密度与体积比重同义,真密度与真比重同义,表观密度与表观比重同义。
激光拉曼分光法测定中的R值是指在相同测定结果中,表示乱层结构的1360cm-1附近的峰的强度(表示为ID或I1360)相对于表示碳六边形网面的层叠结构的1580cm-1附近的峰的强度(表示为IG或I1580)之比。即用ID/IG(I1360/I1580)表示的值。
实施例1
对酚醛树脂用热压成形为外径100mm、厚度5mm的形状。在氮气氛围中加热至950℃的温度,对成形后的树脂成形体进行炭化烧成。对炭化烧成后的试样在110℃加热2小时,用惰性气体熔解热传导法测定残留氢量时,残留有0.8重量%的氢。另外,从通过液相置换法测定的表观密度、试样粉碎后用液相置换法测定的真比重算出的表观气孔率(闭气孔率)为7%。需要说明的是,在室温~200℃的温度区域以20℃/小时的升温速度、在200℃~500℃的温度区域以5℃/小时的升温速度、在500℃~700℃的温度区域以8℃/小时的升温速度、在700℃~最高到达温度的温度区域以10℃/小时的升温速度实施了上述炭化烧成。
实施例2
将实施例1中制作的试样填充到热等静压加压装置中,使用氩气,实施了最高到达温度1200℃、最高到达压力150MPa的各向同性的加压加热处理。切断处理后的材料并进行了剖面观察,但未生成气相生长石墨。
实施例3
将实施例1中制作的试样填充到热等静压加压装置中,使用氩气,实施了最高到达温度1500℃、最高到达压力150MPa的各向同性的加压加热处理。切断处理后的材料并进行了剖面观察,结果稍微生成了气相生长石墨。气相生长石墨的收率(气相生长石墨在材料中所照的容积比率)为3%。
实施例4
将实施例1中制作的试样填充到热等静压加压装置中,使用氩气,实施了最高到达温度2000℃、最高到达压力150MPa的各向同性的加压加热处理。切断处理后的材料,结果在材料内部生成了大量的气相生长石墨。气相生长石墨的收率(气相生长石墨在材料中所占的容积比率)为70%。另外,得到的气相生长石墨的体积密度为0.3、真密度为2.1,由体积密度、真密度的差异算出的总气孔率为86%。
实施例5
对酚醛树脂用热压成形为外径100mm、厚度5mm的形状。在氮气氛围中加热至1100℃的温度对成形后的树脂成形体进行炭化烧成。对炭化烧成后的试样在110℃加热2小时,利用惰性气体熔解热传导法测定残留氢量时,残留有0.2重量%的氢。另外,由通过液相置换法测定的表观密度、试样粉碎后用液相置换法测定的真比重算出的表观气孔率(闭气孔率)为4%。需要说明的是,在室温~200℃的温度区域以20℃/小时的升温速度、在200℃~500℃的温度区域以5℃/小时的升温速度、在500℃~700℃的温度区域以8℃/小时的升温速度、在700℃~最高到达温度的温度区域以10℃/小时的升温速度实施了上述炭化烧成。
实施例6
将实施例5制作的试样填充到热等静压加压装置中,使用氩气,实施了最高到达温度2000℃、最高到达压力190MPa的各向同性的加压加热处理。切断处理后的材料,结果在材料内部生成了气相生长石墨。气相生长石墨的收率(气相生长石墨在材料中所占的容积比率)为50%。另外,得到的气相生长石墨的体积密度为0.7、真密度为2.1,从体积密度、真密度的差异算出的总气孔率为67%。
实施例7
对酚醛树脂用热压成形为外径100mm、厚度5mm的形状。在氮气氛围中加热至1200℃的温度对成形后的树脂成形体进行炭化烧成。对炭化烧成后的试样在110℃加热2小时、利用惰性气体熔解热传导法测定残留氢量时,残留有0.05重量%的氢。另外,从用液相置换法测定的表观密度、试样粉碎后用液相置换法测定的真比重算出的表观气孔率(闭气孔率)为2%。需要说明的是,在室温~200℃的温度区域以20℃/小时的升温速度、在200℃~500℃的温度区域以5℃/小时的升温速度、在500℃~700℃的温度区域以8℃/小时的升温速度、在700℃~最高到达温度的温度区域以10℃/小时的升温速度实施了上述炭化烧成。
实施例8
将实施例7制作的试样填充到热等静压加压装置中,使用氩气,实施了最高到达温度2000℃、最高到达压力190MPa的各向同性的加压加热处理。切断处理后的材料,结果在材料内部未生成气相生长石墨。
实施例9
对酚醛树脂用热压成形为外径100mm、厚度5mm的形状。在氮气氛围中加热至450℃的温度对成形后的树脂成形体进行炭化烧成。对炭化烧成后的试样在110℃加热2小时,利用惰性气体熔解热传导法测定残留氢量时,残留有5重量%的氢。另外,从通过液相置换法测定的表观密度、试样粉碎后用液相置换法测定的真比重算出的表观气孔率(闭气孔率)为3%。需要说明的是,在室温~200℃的温度区域以20℃/小时的升温速度、在200℃~最高到达温度的温度区域以5℃/小时的升温速度实施了上述炭化烧成。
实施例10
将实施例9制作的试样填充到热等静压加压装置中,使用氩气,实施了最高到达温度2000℃、最高到达压力190MPa的各向同性的加压加热处理。对处理后的材料进行粉碎,材料周围生成了大量的气相生长石墨。气相生长石墨的收率(气相生长石墨在材料中所占的容积比率)为60%。
实施例11
将实施例1和实施例5制作的试样分别填充到热等静压加压装置中,使用氩气,进行了最高到达温度2000℃、最高到达压力10MPa的各向同性的加压加热处理。切断处理后的材料,进行了剖面观察,结果稍微生成了气相生长石墨。气相生长石墨的收率(气相生长石墨在材料中所占的容积比率)在任何情况下都为10%。
实施例12
将实施例1和实施例5制作的试样分别填充到热等静压加压装置中,使用氩气,实施了最高到达温度2000℃、最高到达压力1MPa的各向同性的加压加热处理。切断处理后的材料,进行了剖面观察,结果在任何一种中都未生成气相生长石墨。
实施例13
将实施例4制作的试样浸渍在硫酸、硝酸混合水溶液,制作第一阶段的石墨-硫酸层间化合物。水洗得到的石墨层间化合物后,投入到加热至600℃的加热坩埚中,进行了急速加热。通过急速加热试样膨胀约2倍的容积,得到了体积密度0.15的石墨材料。
实施例14
将实施例4制作的试样浸渍到硫酸、硝酸混合水溶液中,制作第一阶段的石墨-硫酸层间化合物。水洗得到的层间化合物后,投入到加热到900℃的加热坩埚中,进行了急速加热。通过急速加热石墨层间化合物破碎,得到了厚度0.001~0.01微米的类石墨烯的石墨薄片。
实施例15
将实施例4制作的试样用液氮冷却后,用金属制的锤子粉碎。通过粉碎多孔质结构被破坏,得到厚度0.01~0.1微米的类石墨烯的石墨薄片。
实施例16
将实施例1中制作的试样填充到热等静压加压装置中,使用氩气,实施了最高到达温度2500℃、最高到达压力150MPa的各向同性的加压加热处理。切断处理后的材料,结果在材料内部生成了大量石墨,但不是多孔质,另外,在其表面未观察到石墨晶体边缘的取向。气相生长石墨的收率(气相生长石墨在材料中所占的容积比率)为80%。另外,得到的气相生长石墨的体积密度为1.90、真密度为1.96,从体积密度、真密度的差异算出的总气孔率为3%。得到的石墨的表面的SEM照片示于图6、图7。
对以往的碳材料、石墨材料与本发明的多孔质碳材料的一例,比较其碳六边形网面的结构,示于图8。由于天然石墨、高取向性石墨、HOPG、凝析石墨等的石墨晶体性高,所以为各向异性大的结构,如图所示,仅在粒子、结构体的端部集中碳六边形网面的端部,在表面,主要是碳六边形网面的表面。这是由于通常的石墨化(结晶化)根据加压方向来进行并产生碳六边形网面的层叠。
另外,如图8所示,以往的碳纤维、石墨纤维、碳纳米管等也为各向异性大的结构,多数情况是碳六边形网面的端部仅位于纤维的两端部。如图8所示,各向同性石墨或通常的人造石墨的情况,在所有的方向碳六边形网面的表面与端部混合存在。
由本发明得到的多孔质的气相生长石墨构成的碳材料如图8所示,为具有与以往的碳材料、石墨材料不同的新型结构的碳材料。通过生成以该多孔质石墨结构为主体材料的石墨层间化合物,接下来再进行急速加热,或者破坏多孔质石墨结构,由此可以得到如图5所示的极薄的类石墨烯结构的石墨薄片。
本发明的实施例1~12及16中的处理条件及生成物的状況汇于表1。表1
产业上的可利用性
本发明的碳材料为石墨晶体性优异、碳六边形网面的端部位于外表面的多孔质的材料,可以适合使用于利用与石墨的插层反应的锂离子电池、电容器等的电极材料、燃料电池的铂担载电极、各种一次电池、二次电池电极等。另外,根据本发明,可以廉价且大量地制造上述的新型的材料。另外,通过对得到的多孔质碳材料进行膨胀化、破碎处理,可以制造类石墨烯的石墨薄片,实现在有效利用碳六边形网面的高的载流子迁移率的电子器件(高电传导性、高导热性膜、或使用了其的接触面板、面向平板显示的电极、面向太阳能电池的电极片等)等中的应用。
Claims (3)
1.一种气相生长多孔质碳材料,其外表面由生长为放射状的碳六边形网面的端部构成,且总气孔率为40%以上,
碳六边形网面的厚度为0.001微米~0.2微米。
2.如权利要求1所述的气相生长多孔质碳材料,其中,激光拉曼分光法测定中的R值不足0.2,所述R值为I1360/I1580所示的峰强度比。
3.如权利要求1或2所述的气相生长多孔质碳材料,其为球状、椭圆体状,或这些连续地结合而成的结构体。
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CN108947533B (zh) * | 2018-08-31 | 2022-02-15 | 万华化学集团股份有限公司 | 一种多孔炭材料的制备方法及得到的多孔炭材料的用途 |
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