CN114105660A - 储氢结构用材料组合物、储氢结构用材料及储氢单体管 - Google Patents
储氢结构用材料组合物、储氢结构用材料及储氢单体管 Download PDFInfo
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- CN114105660A CN114105660A CN202010884669.7A CN202010884669A CN114105660A CN 114105660 A CN114105660 A CN 114105660A CN 202010884669 A CN202010884669 A CN 202010884669A CN 114105660 A CN114105660 A CN 114105660A
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- hydrogen storage
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- D—TEXTILES; PAPER
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
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Abstract
本发明提供储氢结构用材料、储氢单体管和用于制备储氢结构用材料和储氢单体管的储氢结构用材料组合物。本发明的储氢单体管具有微米级孔径蜂巢高压储氢结构,质量比重轻,孔径为150μm、管壁厚度为35μm的储氢结构的极限压强>200MPa,洛氏硬度86~89,耐高温>1900℃,耐低温<‑260℃,热传导低,高温隔热,耐强酸碱。在高密度氢工作氛围与复杂的动态环境下,本发明的高压储氢结构均非常稳定。
Description
技术领域
本发明属于储氢技术领域,具体涉及储氢结构用材料及储氢单体管。
背景技术
2019年是我国全面启动氢能产业链的初始发展阶段。氢能作为洁净替代能源,关键的储氢技术直接影响到社会安全,以及氢储存、移动运输、移动应用的宏观社会效益与效率。因此,建立在高安全稳定性上的70MPa~110MPa高压储氢技术被日益重视。
我国35MPa与70MPa移动储氢容器在技术上大都沿用国际普遍采用的空心内胆结构并结合使用日本东丽M40或T1000型号的高质碳素纤维,在实现了轻量化优点的同时亦存在综合性安全问题。要真正实现高质量密度比的高压强、高安全性与稳定性,本发明需对实现难度极大的微米级孔径的高压储氢结构与耐高压轻质材料进行技术层面的突破。
储氢技术的高安全性与稳定性是考量氢能产业健康发展最重要的衡量指标。目前所依赖的容器碳纤厚包覆层所实现的外形压强,其应用层面决定了在使用期内存在不可预见的高危性,需要在使用期内经常的定期通过安全性能检测,但氢动态高压能与应力导致容器压强层破坏与老化,潜藏的高危隐患依然存在。
我国目前35MPa的储氢容量导致的续航能力不足,大多采用多容器并联,在狭小的安置空间内增大了几倍的高危隐患;即便是70MPa容器,也是千篇一律的硕大笨拙的圆桶外形,占据了非常可观的体积空间。
35MPa~70MPa的空心内胆结构无法避免在高温与动态环境下产生的极限高压,必须通过容器高压自动泄放达到安全值,在高压泄放的同时氢气损失也非常严重。
我国当前的容器储氢技术与未来的发展如继续依赖进口碳纤維,其高昂的应用成本不利于氢能的快速普及与发展,不利于经济效益和社会效益,众所担心的供应链紧张问题终将成为瓶颈。
因此,本领域亟需一种能够解决空心内胆移动高压储氢技术所存在的上述综合性问题的高压强高安全稳定性的新型高压储氢技术。
发明内容
具体而言,本发明提供一种储氢结构用材料组合物,所述储氢结构用材料组合物的原料包括以下组分:
20-24重量份的聚酰亚胺,12-13重量份的聚醋酸乙烯酯,15-17重量份的氯化铝,3-5重量份的氯化镁,3-5重量份的氯化钡,10-12重量份的三氧化二铝,15-17重量份的二氧化锆,0.5-0.7重量份的三氧化二镧、铈氧化物和/或镧铈氧化物,32-35重量份的二氧化硅、碳化硅和/或氧化铍,1.5-2.5重量份的氢氧化钠和/或氢氧化钾,1.5-3重量份的三氧化二钇,6-8重量份的二氧化钛和/或碳化钛,0.3-0.5重量份的二氧化铪和/或碳化铪,任选的0.3-0.5重量份的氯化钙,和任选的不超过10重量份的碳化锌。
在一个或多个实施方案中,所述储氢结构用材料组合物的原料还包括水和极性溶剂。
在一个或多个实施方案中,所述极性溶剂选自二甲基乙酰胺、二甲基甲酰胺和N-甲基吡咯烷酮。
在一个或多个实施方案中,所述储氢结构用材料组合物的粘度为90000±10000cP。
本发明还提供一种制备本文任一实施方案所述的储氢结构用材料组合物的方法,所述方法包括以下步骤:
(1)混合氯化铝和氯化镁,加水溶解,加入氢氧化钠和/或氢氧化钾,反应生产白色沉淀,取白色沉淀,加入氯化钡和任选的氯化钙,搅拌均匀后,烘干,经700-900℃高温处理,粉碎,得到组合物A;
(2)混合三氧化二铝、二氧化锆、三氧化二钇、二氧化钛和/或碳化钛、二氧化铪和/或碳化铪、和任选的碳化锌,得到组合物B;
(3)向聚酰亚胺溶液中加入二氧化硅、碳化硅和/或氧化铍,搅拌均匀后,加入组合物B,搅拌均匀后,加入氧化镧、铈氧化物和/或镧铈氧化物,搅拌均匀后,得到组合物C;
(4)向聚醋酸乙烯酯溶液中加入组合物A,搅拌均匀后,将得到的混合物与组合物C混合,搅拌均匀;
由此得到所述储氢结构用材料组合物。
在一个或多个实施方案中,所述方法具有以下一项或多项特征:
(1)步骤(1)中,加水溶解得到的氯化铝和氯化镁混合溶液的浓度为40-60wt%;
(2)步骤(1)中,高温处理的时间为80-100min;
(3)步骤(1)中,粉碎后组合物A的目数在8000目以上;
(4)步骤(3)中,所述聚酰亚胺溶液为聚酰亚胺溶解在极性溶剂中得到的溶液,所述极性溶剂选自二甲基乙酰胺、二甲基甲酰胺和N-甲基吡咯烷酮,所述聚酰亚胺溶液的粘度为90000cP±2000cP;
(5)步骤(3)在35-45℃和-94kPa至-101kPa的真空度下进行;
(6)步骤(4)中,所述聚醋酸乙烯酯溶液为聚醋酸乙烯酯的水溶液,其浓度为70-80wt%;
(7)步骤(4)中,在35-45℃和-94kPa至-101kPa的真空度下对聚醋酸乙烯酯溶液和组合物A的混合物与组合物C进行混合;
(8)步骤(4)中,混合聚醋酸乙烯酯溶液和组合物A的混合物与组合物C后,加入极性溶剂,将混合物的粘度调节到90000±10000cP,所述极性溶剂选自二甲基乙酰胺、二甲基甲酰胺和N-甲基吡咯烷酮。
本发明还提供一种储氢结构用材料,以所述储氢结构用材料的总质量计,所述储氢结构用材料包括以下成分:33-39wt%的二氧化硅和/或氧化铍,17-22wt%的三氧化二铝,20-28wt%的二氧化锆,6-10wt%的二氧化钛,0.25-0.5wt%的氧化铪,0.45-0.9wt%的氧化镧、铈氧化物和/或镧铈氧化物,1-2.7wt%的三氧化二钇,0.12-1wt%的氧化钾和/或氧化钠,0.18-0.4wt%的氧化镁,1-1.7wt%的氧化钡,0-10wt%的氧化锌,任选存在的0.07-0.7wt%氧化钙,和不可避免的杂质。
本发明还提供一种储氢结构用复合材料,所述储氢结构用复合材料包括本文任一实施方案所述的储氢结构用材料和增强填料。
本发明还提供一种制备本文所述的储氢结构用材料或储氢结构用复合材料的方法,所述方法包括对本文任一实施方案所述的储氢结构用材料组合物或储氢结构用材料组合物和增强填料的混合物在40-45℃下进行200-250min的固化处理,然后在50-60℃下进行50-70min的加热处理,然后在360-480℃下进行50-70min的加热处理,然后在850-900℃下进行80-100min的烧结处理,然后在1400-1450℃下进行250-350min的烧结处理或在3000℃±100℃下进行烧结处理。
本发明还提供一种储氢单体管,所述储氢单体管包括储氢单元,所述储氢单元的材质为文本任一实施方案所述的储氢结构用材料,所述储氢单元具有蜂巢微孔结构;优选地,微孔壁厚为35-40μm;优选地,微孔直径为140-150μm。
在一个或多个实施方案中,所述储氢单体管还包括外壳,所述外壳的材质为本文任一实施方案所述的储氢结构用材料或储氢结构用复合材料。
本发明还提供一种制备本文所述的储氢单体管的方法,所述方法包括:
(1)使用本文任一实施方案所述的储氢结构用材料组合物对聚合物纤维集束进行浸渍;
(2)对浸渍了储氢结构用材料组合物的聚合物纤维集束在40-45℃下进行200-250min的固化处理,然后在50-60℃下进行50-70min的加热处理,然后在360-480℃下进行50-70min的加热处理,然后在850-900℃下进行80-100min的烧结处理,然后在1400-1450℃下进行250-350min的烧结处理或在3000℃±100℃下进行烧结处理;或者将浸渍了储氢结构用材料组合物的聚合物纤维集束填入管状模具后再在40-45℃下进行200-250min的固化处理,然后在50-60℃下进行50-70min的加热处理,然后在360-480℃下进行50-70min的加热处理,然后在850-900℃下进行80-100min的烧结处理,然后在1400-1450℃下进行250-350min的烧结处理或在3000℃±100℃下进行烧结处理。
在一个或多个实施方案中,进行步骤(1)的浸渍前,先将储氢结构用材料组合物的粘度调节至200000±10000cP。
在一个或多个实施方案中,所述聚合物纤维的熔点在150℃-380℃之间。
在一个或多个实施方案中,所述聚合物纤维集束中单根纤维的直径为100-150μm。
在一个或多个实施方案中,步骤(1)中,所述浸渍使得聚合物纤维集束中各单根纤维表面包覆的储氢结构用材料组合物的平均厚度为25-30μm。
本发明还提供本文所述的储氢结构用材料组合物、储氢结构用材料、储氢结构用复合材料、储氢结构、储氢单体管在高压储氢和/或液氢保存中的应用。
附图说明
图1为本发明的单体管内部微米蜂巢储氢结构示意图。
图2为本发明的一种圆形单体管照片。
图3为实施例2的六角形储氢单体管组成的蜂巢结构模块力学示意图。
具体实施方式
为使本领域技术人员可了解本发明的特点及效果,以下谨就说明书及权利要求书中提及的术语及用语进行一般性的说明及定义。除非另有指明,否则文中使用的所有技术及科学上的字词,均为本领域技术人员对于本发明所了解的通常意义,当有冲突情形时,应以本说明书的定义为准。
本文描述和公开的理论或机制,无论是对或错,均不应以任何方式限制本发明的范围,即本发明内容可以在不为任何特定的理论或机制所限制的情况下实施。
本文中,所有以数值范围或百分比范围形式界定的特征如数量、含量与浓度仅是为了简洁及方便。据此,数值范围或百分比范围的描述应视为已涵盖且具体公开所有可能的次级范围及范围内的个别数值(包括整数与分数)。
本文中,若无特别说明,比例是指质量比,百分比是指质量百分比。
本文中,为使描述简洁,未对各个实施方案或实施例中的各个技术特征的所有可能的组合都进行描述。因此,只要这些技术特征的组合不存在矛盾,各个实施方案或实施例中的各个技术特征可以进行任意的组合,所有可能的组合都应当认为是本说明书记载的范围。
氢能源普及与发展最重要的环节是高安全性的高压储氢。国际上现行的高压储氢容器大都采用空心内胆外表包覆多层高质碳纤维/环氧树脂复合材料(CFRP),依赖表层压强载荷实现的高压强,具有质量与密度比的优势,当前我国也在沿用此技术。然而,在复杂的动态环境下,因氢的动态高压与温升、内应力而产生的崩裂泄漏高危隐患,并非通过加厚碳纤维铺层所能解决,我国已出现多起70MPa天然气移动工具应用泄漏爆炸伤亡事故。除此之外,大量使用进口碳纤维不仅成本高昂,且资源有限,亦存在可持续发展和经济实用性等诸多问题。针对当下空心内胆高压储氢容器安全性与稳定性的各种问题,本发明提出了一种新型高压储氢结构用复合材料及高压储氢结构。本发明的基本设计思路包括:1、研发质量比重轻的高性能材料,取代依赖进口碳纤;2、微米级微孔蜂巢结构取代空心内胆。本发明将大容量氢分隔为头发丝般细小的隔离储存空间,可以非常有效地限制高压氢的活跃能,集束的微孔蜂巢结构可以彻底消除空心内胆高压储氢存在的高危问题,安全压强达到70MPa~110MPa,并有几倍的安全系数,省去空心内胆外厚笨硕大的包覆层、提高储氢效率、将体积大幅减小,有效地提升储氢经济效益。
本发明提供一种可用于制备储氢结构的复合材料组合物(也称储氢结构用材料组合物),该复合材料组合物在常温下为具有一定粘度的固液混合物。本发明的储氢结构用材料由本发明的储氢结构用材料组合物经固化、烧结而得到。本发明的储氢结构由本发明的复合材料组合物浸渍聚合物纤维后经固化、烧结而得到。本发明的储氢结构适用于高压储氢,因此也称为高压储氢结构。
本发明的复合材料组合物的原料包含聚酰亚胺(PI)。本发明的复合材料具有无机物金相结构。因此,本文中,本发明的复合材料简称PMTS材料(有机高分子PI+无机物金相结构的简称),本发明的复合材料组合物简称PMTS材料组合物,本发明的高压储氢结构简称PMTS材料高压储氢结构。本发明的复合材料适用于作为储氢结构的材料,因此也称为储氢结构用材料。
本发明的PMTS材料组合物的原料包括:10-40重量份的聚酰亚胺,8-18重量份的聚醋酸乙烯酯,15-40重量份的金属氯化物,10-70重量份的金属氧化物和/或金属碳化物,10-40重量份的二氧化硅和/或碳化硅,0.5-5重量份的稀土金属氧化物,1-5重量份的碱金属氢氧化物。在一些实施方案中,PMTS材料组合物的原料还包括适量的水和极性溶剂。在一些实施方案中,作为PMTS材料组合物的原料,金属氯化物包括选自氯化铝、氯化镁、氯化钡和氯化钙中的一种或多种;优选地,金属氯化物包括氯化铝、氯化镁和氯化钡,任选地还包括氯化钙。当含有时,PMTS材料组合物的原料中,氯化铝的用量优选为10-20重量份,氯化镁的用量优选为1-10重量份,氯化钡的用量优选为1-10重量份,氯化钙的用量优选为0.1-1重量份。本文中,金属氧化物不包括稀土金属氧化物。在一些实施方案中,作为PMTS材料组合物的原料,金属氧化物包括选自氧化铝、氧化锆、氧化钛、氧化铪和氧化铍中的一种或多种。当含有时,PMTS材料组合物的原料中,氧化铝的用量优选为5-15重量份,氧化锆的用量优选为10-20重量份,氧化钛的用量优选为5-10重量份,氧化铪的用量优选为0.1-1重量份,氧化铍的用量优选为30-40重量份。在一些实施方案中,作为PMTS材料组合物的原料,金属碳化物包括选自碳化硅、碳化钛、碳化铪和碳化锌中的一种或多种。当含有时,PMTS材料组合物的原料中,碳化硅的用量优选为10-40重量份,碳化钛的用量优选为5-10重量份,碳化铪的用量优选为0.1-1重量份。在一些实施方案中,作为PMTS材料组合物的原料,稀土金属氧化物包括选自氧化镧、铈氧化物、镧铈氧化物和氧化钇中的一种或多种,优选包括选自氧化镧、铈氧化物、镧铈氧化物中的一种或多种和氧化钇。当含有时,PMTS材料组合物的原料中,氧化镧、铈氧化物、镧铈氧化物的总用量优选为0.2-1重量份,氧化钇的用量优选为1-5重量份。在一些实施方案中,作为PMTS材料组合物的原料,碱金属氢氧化物包括氢氧化钠和氢氧化钾中的一种或两种。
在优选的实施方案中,PMTS材料组合物的原料包含以下成分:20-24重量份的聚酰亚胺(PI),12-13重量份的聚醋酸乙烯酯(PVAc),15-17重量份的氯化铝(AlCl3),3-5重量份的氯化镁(MgCl2),3-5重量份的氯化钡(BaCl2),10-12重量份的三氧化二铝(Al2O3),15-17重量份的二氧化锆(ZrO2),0.5-0.7重量份的三氧化二镧(La2O3)、铈氧化物和/或镧铈氧化物,32-35重量份的二氧化硅(SiO2)、碳化硅和/或氧化铍,1.5-2.5重量份的氢氧化钠(NaOH)和/或氢氧化钾(KOH),1.5-3重量份的三氧化二钇(Y2O3),6-8重量份的二氧化钛(TiO2)和/或碳化钛,0.3-0.5重量份的二氧化铪(HfO2)和/或碳化铪,任选的0.3-0.5重量份的氯化钙(CaCl2),和任选的不超过10重量份的碳化锌;在一些实施方案中,所述32-35重量份的二氧化硅、碳化硅和/或氧化铍为:32-35重量份的二氧化硅和/或碳化硅;或32-35重量份的二氧化硅和/或碳化硅、和氧化铍,其中氧化铍的用量优选为5-15重量份。在一些实施方案中,PMTS材料组合物的原料包含以下成分:20-24重量份的PI,12-13重量份的聚醋酸乙烯酯,15-17重量份的氯化铝,3-5重量份的氯化镁,3-5重量份的氯化钡,10-12重量份的三氧化二铝,15-17重量份的二氧化锆,0.5-0.7重量份的三氧化二镧、铈氧化物和/或镧铈氧化物,32-35重量份的二氧化硅和/或氧化铍,1.5-2.5重量份的氢氧化钠和/或氢氧化钾,1.5-3重量份的三氧化二钇,6-8重量份的二氧化钛(TiO2),0.3-0.5重量份的二氧化铪(HfO2),和任选的0.3-0.5重量份的氯化钙(CaCl2);在一些实施方案中,所述32-35重量份的二氧化硅和/或氧化铍为:32-35重量份的二氧化硅;或32-35重量份的二氧化硅和氧化铍,其中氧化铍的用量优选为5-15重量份。本发明中,任选的5-15重量份的氧化铍,取代部分二氧化硅或碳化硅,以实现更优异的质量比重和硬度。
PMTS材料组合物的原料还包括适量的水和极性溶剂。相对于12-13重量份的PVAc,PMTS材料组合物的原料优选包括3-5.5重量份的水,更优选包括3.5-5重量份的水。在一些实施方案中,PMTS材料组合物的原料包括或由以下成分组成:上述重量份的PI,PVAc,氯化铝,氯化镁,氯化钡,三氧化二铝,二氧化锆,三氧化二镧、铈氧化物和/或镧铈氧化物,二氧化硅、碳化硅和/或氧化铍,氢氧化钠和/或氢氧化钾,三氧化二钇,二氧化钛和/或碳化钛,二氧化铪和/或碳化铪,水,任选的氯化钙,和任选的碳化锌,以及适量的极性溶剂。本发明中,作为PMTS材料组合物原料的极性溶剂的用量优选使得PMTS材料组合物的粘度达到90000±10000cP。
本发明中,水优选为蒸馏水或去离子水。本发明中,极性溶剂优选选自二甲基乙酰胺(DMAc)、二甲基甲酰胺(DMF)和N-甲基吡咯烷酮(NMP)中的一种或多种。
本文中,重量份表示的是各原料/材料之间的重量份配比,可以理解的是,各原料的重量份之和不要求为100重量份。
本发明中,除二氧化锆、氧化铪、碳化铪、氧化镧、铈氧化物和镧铈氧化物以外的金属氧化物和金属碳化物原料优选为纳米级超细粉末,细度优选为一万级以上,平均粒径优选为300nm~2μm。为了保证PMTS材料的高质量,避免有害杂质在高温烧结过程中的氧化与崩裂,本发明优选使用高纯度的原料,例如纯度为4N级、5N级或6N级的原料。本发明所使用的原料均市售可得,亦可自行采用高压气流粉碎悬浮细粉收集法等方法进行超细加工得到。
PMTS材料组合物可通过包含以下步骤的方法制备得到:
(1)混合氯化铝和氯化镁,加入适量水溶解,加入氢氧化钠和/或氢氧化钾,反应生产白色沉淀,取白色沉淀,加入氯化钡和任选的氯化钙,搅拌,烘干,经700-900℃高温处理,粉碎,得到组合物A;
(2)混合三氧化二铝、二氧化锆、三氧化二钇、二氧化钛和/或碳化钛、二氧化铪和/或碳化铪、和任选的碳化锌,得到组合物B;
(3)向PI溶液中加入二氧化硅、碳化硅和/或氧化铍,搅拌,加入组合物B,搅拌,加入氧化镧、铈氧化物和/或镧铈氧化物,搅拌,得到组合物C;
(4)向PVAc溶液中加入组合物A,搅拌,将得到的混合物与组合物C混合,搅拌;
由此得到PMTS材料组合物。
可以理解的是,上述步骤的序号只是为了区分各步骤,并不限制各步骤的操作顺序,只要在进行某一步骤前准备好所需的原料和/材料即可,例如可先进行步骤(2)和(3),再进行步骤(1),最后进行步骤(4)。
本发明中,氯化铝优选为分析纯无水氯化铝,氯化镁优选为分析纯氯化镁,氢氧化钠和氢氧化钾优选为分析纯。步骤(1)中,氯化铝的用量为15-17重量份;氯化镁的用量为3-5重量份。步骤(1)中,水的用量优选使得溶解氯化铝和氯化镁后得到的溶液的浓度为40wt%-60wt%,例如40wt%-50wt%。步骤(1)中,氢氧化钠和/或氢氧化钾的总用量为1.5-2.5重量份,氢氧化钠和氢氧化钾各自的用量通常不受特别限制,例如可以仅用氢氧化钠或仅用氢氧化钾。步骤(1)中,加入氢氧化钠和/或氢氧化钾时优选逐步加入。在优选的实施方案中,步骤(1)中,加入1.2-2重量份氢氧化钠和0.3-0.5重量份氢氧化钾。加入氢氧化钠和/或氢氧化钾后,反应放热。优选待反应至冷却,生成白色沉淀,取白色沉淀,加入氯化钡和任选的氯化钙。步骤(1)中,氯化钡的用量为3-5重量份。氯化钙可以添加或不添加,当添加时,氯化钙的用量为0.3-0.5重量份。在一些实施方案中,步骤(1)中,加入氯化钡和任选的氯化钙,搅拌后,先静置,再烘干;静置时间优选为30分钟或以上。步骤(1)中,烘干温度优选为90-110℃。步骤(1)中,高温处理的温度优选为700-900℃,时间优选为80-100分钟。在一些实施方案中,步骤(1)中,高温处理后,冷却,球磨粉碎至8000目以上,得到组合物A。
本发明中,三氧化二铝为纳米三氧化二铝;二氧化锆为超细二氧化锆、优选为微米级二氧化锆(例如粒径在1-5μm);三氧化二钇为纳米级三氧化二钇;二氧化钛为纳米级二氧化钛,二氧化钛优选为金红石型二氧化钛;二氧化铪为超细二氧化铪(例如粒径在800nm~2μm);碳化铪为超细碳化铪(例如粒径在800nm~2μm);碳化钛为纳米碳化钛;碳化锌为纳米碳化锌。步骤(2)中,三氧化二铝的用量为10-12重量份,二氧化锆的用量为15-17重量份,三氧化二钇的用量为1.5-3重量份,二氧化钛和碳化钛的总用量为6-8重量份,二氧化铪和碳化铪的总用量为0.3-0.5重量份;当添加时,碳化锌的用量不超过10重量份。
适用于本发明的PI优选为电工级或以上级别的PI,可以是热固性PI,例如美国杜邦的SP-1,也可以是热塑性PI,例如日本三井化学的JNF3020。适用于本发明的PI的特性黏度优选为0.52-0.81dL/g。本发明中,PI溶液为用极性溶剂稀释PI得到的溶液。步骤(3)中,PI的用量为20-24重量份,即使用的PI溶液所含的PI的重量份为20-24重量份。步骤(3)中,使用的PI溶液的粘度为90000cP±2000cP。本发明中,粘度为常温常压(25℃、一个大气压下)测得的粘度。步骤(3)所使用的PI溶液的制备方式不受特别限制,例如可以使用固体PI原料,将固体PI溶解在适量的极性溶剂中,得到粘度为90000cP±2000cP的PI溶液;也可以使用预先溶解在极性溶剂中的粘度较大的PI溶液(例如浓度为28-32wt%的PI溶液)作为原料,使用极性溶剂进行稀释,得到粘度为90000cP±2000cP的PI溶液。在一些实施方案中,在35-45℃和-94kPa至-101kPa的真空度下向固体PI或浓度为28-32wt%的PI溶液中加入极性溶剂,搅拌,得到粘度为90000cP±2000cP的PI溶液;搅拌的转速优选为8-12r/min,搅拌时间优选为15-25min。步骤(3)中,优选在35-45℃和-94kPa至-101kPa的真空度下混合PI溶液和二氧化硅、碳化硅和/或氧化铍,以及进一步与组合物B混合,以及进一步与氧化镧、铈氧化物和/或镧铈氧化物混合。步骤(3)中,搅拌的转速优选为8-12r/min。步骤(3)中,混合PI溶液和二氧化硅、碳化硅和/或氧化铍时,优选搅拌10-15min;加入组合物B后,优选搅拌15-20min;加入氧化镧、铈氧化物和/或镧铈氧化物后,优选搅拌15-20min。本发明中,二氧化硅为纳米级二氧化硅,粒径优选为100nm-500nm。碳化硅为纳米级碳化硅,粒径优选为100nm-500nm。氧化铍优选纯度99.95%以上,因该物剧毒,需加强生产安全管理。步骤(3)中,二氧化硅、碳化硅和氧化铍的总用量为32-35重量份,且当使用时,氧化铍的用量优选为5-15重量份。步骤(3)中,加入二氧化硅时优选逐步加入。步骤(3)中,组合物B的用量为步骤(2)制备得到的组合物B的总量。本发明中,氧化镧、铈氧化物、镧铈氧化物为超细氧化镧、超细铈氧化物、超细镧铈氧化物(粒径优选为1μm-5μm)。步骤(3)中,可以选择使用氧化镧、铈氧化物和镧铈氧化物中的一种或多种,氧化镧、铈氧化物和镧铈氧化物的总用量为0.5-0.7重量份。
PI具有理想的高绝缘、抗静电、耐高压强等精密的可塑性,不足之处是高分子聚合特性决定的高温局限。为了得到PI微米级精密加工的可塑性及无机物耐高低温的高强度,并在高温烧结不收缩变形,本发明通过配比中的离子螯合与金相结构,不断调整组分,在固化过程与温度相互牵连的关系中实现质量比重轻量化的高强度和耐高温特性。
适用于本发明的PVAc为工业级或以上级别的PVAc。PVAc的纯度优选为99.9%以上。适用于本发明的PVAc的特性黏度优选为0.7-0.9dL/g。本发明中,PVAc溶液为PVAc的水溶液。步骤(4)中,PVAc的用量为12-13重量份,即使用的PVAc溶液所含的PVAc的重量份为12-13重量份。步骤(4)中,使用的PVAc溶液的固含量为70-80wt%、例如73-77wt%左右。步骤(4)中,组合物A的用量为步骤(1)制备得到的组合物A的总量。步骤(4)中,加入组合物A后,优选搅拌15-25min。步骤(4)中,组合物C的用量为步骤(3)制备得到的组合物C的总量。步骤(4)中,优选在35-45℃和-94kPa至-101kPa的真空度下混合组合物A与PVAc溶液的混合物和组合物C。在一些实施方案中,在35-45℃和-94kPa至-101kPa的真空度下,将组合物A与PVAc溶液的混合物加入到步骤(3)得到的组合物C中。混合组合物A与PVAc溶液的混合物和组合物C时的搅拌转速优选为8-12r/min。在一些实施方案中,混合组合物A与PVAc溶液的混合物和组合物C时,加入极性溶剂,将PMTS材料组合物的粘度调节到90000±10000cP。在优选的实施方案中,混合组合物A与PVAc溶液的混合物和组合物C时,加入极性溶剂,加热至45-52℃,以8-12r/min的转速搅拌,将PMTS材料组合物的粘度调节到90000±10000cP。本发明的PMTS材料组合物为白色、无气泡的具有一定粘度的固液混合物,粘度优选为90000±10000cP。本发明的PMTS材料组合物在粘度为90000±10000cP的状态可稳定储存。
本发明根据有机-无机复合物的改良特性,通过调节有机相和无机相组分,在有机-无机离子之间的螯合亲和反应中得到PMTS材料组合物。PMTS材料组合物具有PI的水平延展性,可以得到十几微米厚度的薄膜。经过50℃~60℃的脱溶剂处理,可以得到三个不同特性的应用:1、液态至可塑固相,具PI可弯曲特性的应用;2、经排胶后,可加工精密的微米级结构,具PI可塑特性的应用;3、经排胶后至高温烧结,具有轻量化的高硬度精密应用。
PMTS材料组合物可以在常温常压下实现固化,可以根据需要制备得到下列产品/材料:1、加工成几十微米至几百微米厚度的性能薄膜;2、通过注塑得到各种精密零部件,亦可高温烧结;3、做成各种型材经高温烧结后精密加工;
4、通过精密加工与高温烧结成型制备得到本发明的高压储氢结构。
PMTS材料组合物经40-45℃固化、50-60℃加热处理和360-480℃高温处理后,可得到固态半成品。因此,本发明也包括一种固态半成品,由PMTS材料组合物经40-45℃、50-60℃和360-480℃三步处理后得到。本发明中,40-45℃固化的时间优选为200-250min,40-45℃固化时的环境湿度优选为8-12%。本发明中,50-60℃加热处理的时间优选为50-70min,360-480℃加热处理的时间优选为50-70min。在一些实施方案中,PMTS材料组合物经40-45℃固化200-250min,再经50-60℃处理50-70min,再经360-480℃排胶(排胶即高分子材料高温分解为气相的俗称)50-70min,得到固态半成品。
PMTS材料组合物经40-45℃固化、50-60℃加热处理、360-480℃高温处理和850-900℃高温烧结后,可得到具有金相结构的半成品。因此,本发明也包括一种具有金相结构半成品,由PMTS材料组合物经40-45℃、50-60℃、360-480℃和850-900℃四步处理后得到。本发明中,850-900℃加热处理的时间优选为80-100min。在一些实施方案中,PMTS材料组合物经40-45℃固化200-250min,再经50-60℃处理50-70min,再经360-480℃处理50-70min,再经850-900℃烧结80-100min,得到具有金相结构的半成品。
PMTS材料组合物经40-45℃固化、50-60℃加热处理、360-480℃高温处理、850-900℃高温烧结和1400-1450℃高温烧结后,可得到PMTS材料。因此,本发明的PMTS材料可由PMTS材料组合物经40-45℃、50-60℃、360-480℃、850-900℃和1400-1450℃五步处理后得到。本发明中,1400-1450℃加热处理的时间优选为250-350min。在一些实施方案中,PMTS材料组合物经40-45℃固化200-250min,再经50-60℃处理50-70min,再经360-480℃处理50-70min,再经850-900℃烧结80-100min,再经1400-1450℃烧结250-350min,得到PMTS材料。在采用第五步为1400-1450℃烧结的方法制备PMTS材料时,使用的PMTS材料组合物可以是本文所述的原料包括:聚酰亚胺,聚醋酸乙烯酯,氯化铝,氯化镁,氯化钡,三氧化二铝,二氧化锆,三氧化二镧、铈氧化物和/或镧铈氧化物,二氧化硅,氢氧化钠和/或氢氧化钾,三氧化二钇,二氧化钛,二氧化铪和任选的氯化钙的PMTS材料组合物,也可以是上述原料中部分或全部的二氧化硅被替换成碳化硅、部分或全部的二氧化钛被替换成碳化钛、部分或全部的二氧化铪被替换成碳化铪和/或进一步包括碳化锌后得到的PMTS材料组合物。当使用碳化硅部分或全部替换原料中的二氧化硅、使用碳化钛部分或全部替换原料中的二氧化钛、使用碳化铪部分或全部替换原料中的二氧化铪和/或进一步在原料中包括碳化锌时,碳化物的总用量优选不超过原料中的碳化物和氧化物总用量的45%,更优选不超过30%。
本文中,固化、固化处理、加热、加热处理、高温处理、高温烧结、烧结、烧结处理等类似用语均用于表达在一定温度下对材料进行热处理的含义,通常是在一定温度的环境中放置一段时间。本发明中,“经50-60℃处理50-70min,再经360-480℃处理50-70min”是指材料在50-60℃的环境中放置50-70min后,再转移至360-480℃的环境中放置50-70min,以此类推。本发明中,用于加热/高温/烧结处理的设备不受特别限制。在一些实施方案中,本发明的加热/高温/烧结处理在隧道窑中进行,隧道窑预先设定各段窑体温度,逐段烧结,例如在制备PMTS材料时,隧道窑可包括四段,温度分别设置为50-60℃、360-480℃、850-900℃和1400-1450℃。
PMTS材料组合物经40-45℃固化、50-60℃加热处理、360-480℃高温处理、850-900℃高温烧结和3000℃±100℃烧结后,也可得到PMTS材料。因此,本发明的PMTS材料可由PMTS材料组合物经40-45℃、50-60℃、360-480℃、850-900℃和3000℃±100℃五步处理后得到。本发明中,3000℃±100℃烧结的方式不受特别限制,只要温度能够达到3000℃±100℃即可,例如可以采用放电等离子烧结(Spark Plasma Sintering,简称SPS)工艺进行3000℃±100℃烧结。适用于本发明的SPS可以是已知的各种SPS技术,例如直流型放电等离子烧结(Direct Current Sintering,简称DCS)。本发明中,采用SPS进行3000℃±100℃烧结时,烧结时间通常为1-10s、优选为3-6s。采用其他烧结方式进行3000℃±100℃烧结时,烧结时间可以根据实际情况确定。在一些实施方案中,PMTS材料组合物经40-45℃固化200-250min,再经50-60℃处理50-70min,再经360-480℃处理50-70min,再经850-900℃烧结80-100min,再经3000℃±100℃烧结,得到PMTS材料。在采用第五步为3000℃±100℃烧结的方法制备PMTS材料时,使用的PMTS材料组合物可以是本文所述的原料包括:聚酰亚胺,聚醋酸乙烯酯,氯化铝,氯化镁,氯化钡,三氧化二铝,二氧化锆,三氧化二镧、铈氧化物和/或镧铈氧化物,二氧化硅,氢氧化钠和/或氢氧化钾,三氧化二钇,二氧化钛,二氧化铪和任选的氯化钙的PMTS材料组合物,优选是上述原料中部分或全部的二氧化硅被替换成碳化硅、部分或全部的二氧化钛被替换成碳化钛、部分或全部的二氧化铪被替换成碳化铪和/或进一步优选包括碳化锌后得到的PMTS材料组合物。本发明中,当使用相应的碳化物替代PMTS材料组合物原料中的氧化物(例如使用碳化硅替代二氧化硅、使用碳化钛替代二氧化钛、使用碳化铪替代二氧化铪)以及在PMTS材料组合物原料中引入碳化锌时,这些碳化物在烧结过程中能够作为微电极,从而有利于3000℃±100℃烧结的进行,特别是有利于3000℃±100℃下SPS烧结的进行。当使用碳化硅部分或全部替换原料中的二氧化硅、使用碳化钛部分或全部替换原料中的二氧化钛、使用碳化铪部分或全部替换原料中的二氧化铪和/或进一步在原料中包括碳化锌时,碳化物的总用量优选不超过原料中的碳化物和氧化物总用量的45%,更优选不超过30%。
可以理解的是,在使用PMTS材料组合物制备本文所述的固态半成品、具有金相结构的半成品和PMTS材料时,可以根据需要调节PMTS材料组合物的粘度后,再进行所述40-45℃固化和后续处理,例如,可以通过加热将PMTS材料组合物的粘度调整至200000cP±10000cP后,再进行所述40-45℃固化和后续处理。
PMTS材料组合物、本发明的固态半成品、本发明的具有金相结构的半成品和PMTS材料适用于光刻胶/精密模压/3D打印,制备耐高温、抗强酸碱、耐高压强、阻燃隔热、强拉伸张力、抗静电、高绝缘、高硬度和/或具有可塑精密微米级微孔的材料和特殊结构。本发明的PMTS材料的特点还在于其不与氢发生化学反应。
本发明的高压储氢结构的材质为PMTS材料,由PMTS材料组合物浸渍聚合物纤维后经固化、烧结得到,因此也称为PMTS材料储氢结构。具体而言,高压储氢结构可使用PMTS材料组合物浸渍聚合物纤维后,经40-45℃固化200-250min,再经50-60℃处理50-70min,再经360-480℃处理50-70min后,再经850-900℃烧结80-100min,再经1400-1450℃烧结250-350min或3000℃±100℃烧结后得到。
本发明的高压储氢结构具有蜂巢结构(如图1所示)。使用PMTS材料组合物浸渍聚合物纤维时,聚合物纤维以纤维集束的形式进行浸渍。浸渍后的纤维集束中的各单根纤维表面包覆有一定厚度的PMTS材料组合物,且相邻的各单根纤维相互粘接在一起,因此,各单根纤维在纤维集束的横截面上排列成蜂巢状;该浸渍了PMTS材料组合物的纤维集束经烧结后,聚合物纤维被分解为气相,留下蜂巢结构的微孔(又称为单孔管),纤维表面的PMTS材料组合物形成PMTS材料,形成蜂巢结构的孔壁。本文中,蜂巢结构具有通常的含义,从横截面上看,每个微孔周围紧密排布着6个邻近的微孔。可以理解,本文中,微孔为具有长径比的单孔管,微孔的直径(即单孔管的内径)通常为100-200μm。本发明的储氢结构所具备的上述蜂巢结构和微孔结构也称为蜂巢微孔结构。本文中,相邻的单孔管的管壁融合在一起,微孔的管壁厚度是指两个相邻的单孔管之间的融合在一起的管壁厚度。
本发明的PMTS材料储氢结构具有以下突出优势:质量比重轻,可塑精度误差±2μm,孔径为150μm、管壁厚度为35μm的微孔蜂巢结构的极限压强>200MPa,洛氏硬度86~89,耐高温>1900℃,耐低温<-260℃,热传导低,高温隔热,耐强酸碱,在高密度氢工作氛围与复杂的动态环境下,PMTS材料储氢结构均非常稳定。
当前在材料领域可实现集束蜂巢结构且具有一定压强的材料有:石英玻璃毛细管、四类纤维、与氢不发生反应的金属类材质、有机高分子类毛细管、无机陶瓷毫米级蜂巢结构等成品材料。本发明在对上述材料研究后发现:这些材质虽各具优点,但其材质和工艺决定了在氢氛围与高压强下的不适用,具体表现在易氢化老化、氢敏感的温升反应、质量密度比重大、成品瑕疵等诸多不确定因素、存在很高的瑕疵剔除成本、高昂的材料成本和高昂的再加工成本等几大问题。本发明根据所需要的理想化的材料特性与微米级微孔蜂巢结构的可控质量,形成了本发明的高压储氢结构。
本发明根据微小体积与质量密度比的压强关系,建立可靠的高氢密度高安全性高稳定性的存储结构,通过有机-无机优化实现的PMTS材料特性是关键的决定性因素。针对储氢容器高压工作的高危性,对所研发的PMTS材料结合微米级孔径可以实现的高安全稳定性的蜂巢结构进行了加工工艺的研究:如要实现对PMTS材料洛氏硬度在86~89、直径在约25mm的型材中加工由约14000个微孔组成的蜂窝网巢结构、孔径在约150μm、孔径壁厚在约35μm、深度在约600mm,以现有的各种微米级孔径的精密加工技术均难以实现。经过研发,本发明实现的解决方法如下:以PMTS材料组合物细密的液相粘附性与细密的金相结构在高温熔融烧结的高精密度和几十微米壁厚的高强度,利用微米级直径的高分子聚合纤维自身占有的空间体积为骨架,通过高温热分解形成微米空间,与此同时PMTS已固化的微米级涂覆层经高温烧结形成微米空间紧密互连的隔离管壁,从而实现了微米级孔径蜂巢结构。
本发明的PMTS材料储氢结构可通过包含以下步骤的方法制备得到:
(1)使用PMTS材料组合物对聚合物纤维集束进行浸渍;
(2)对浸渍了PMTS材料组合物的聚合物纤维集束在40-45℃固化,再在50-60℃处理,再在360-480℃处理,再在850-900℃烧结,再在1400-1450℃烧结或3000℃±100℃烧结;
由此得到PMTS材料储氢结构。
步骤(2)中,40-45℃固化、50-60℃处理、360-480℃处理、850-900℃烧结、1400-1450℃烧结和3000℃±100℃烧结的优选的工艺条件(例如时间)如前文任一实施方案所述。
在本发明面对的很多需要攻克的加工难题中,高温烧结收缩变形与高残次率是攻克的主要难点,需实现如下要求:高温烧结过程有比较高的承受稳定性,通过金相实现比较轻的质量比重,耐高温大于1900℃、抗低温小于-260℃,孔径100-150μm/管壁厚度35μm的储氢结构压强极限大于200MPa,所形成的蜂巢力学结构具有强拉伸张力,洛氏硬度需达到86左右,有比较高的隔热系数。本发明通过对步骤(2)的工艺参数的优选,实现了上述要求。
在一些实施方案中,为了提供适宜的粘结性和流动性,先通过加热将PMTS材料组合物的粘度调整至200000cP±10000cP后,再对聚合物纤维集束进行浸渍。优选地,在40-45℃下处理PMTS材料组合物,将其粘度调节至200000cP±10000cP。一些实施方案中,PMTS材料组合物的初始粘度为90000±10000cP。PMTS材料组合物的用量通常满足能够完全浸渍聚合物纤维即可。在一些实施方案中,聚合物纤维完全浸入PMTS材料组合物后,PMTS材料组合物的液面高于纤维约10mm。
适用于本发明的聚合物纤维的材质不受特别限制,只要熔点在150℃-380℃即可。聚合物纤维例如可以是包括但不限于聚氯乙烯(PVC)、聚苯乙烯(PS)、ABS塑料、聚乙烯(PE)、聚丙烯(PP)、聚碳酸脂(PC)、聚氨酯(PU)、聚酰胺(PA、尼龙、锦纶)等聚合物的连续纤维、细丝。聚合物纤维的直径可在微米级至毫米级,例如70μm至5000μm。可以根据所需要的微孔的大小选择合适直径的聚合物纤维。在一些实施方案中,聚合物纤维的直径为100-150μm,例如140-150μm。聚合物纤维的长度优选在10mm以上。聚合物纤维的长度上限不受特别限制,只要浸渍了PMTS材料组合物的聚合物纤维集束在高温烧结下不变形即可。优选地,本发明使用直径误差小、无杂质、柔韧性一致的聚合物纤维。
纤维集束中纤维的根数不受特别限制,例如可以是1万根至20万根。浸渍前集束体积与浸渍后集束体积的关系为:浸渍后集束体积=浸渍前集束体积+集束浸渍涂覆层体积。使用PMTS材料组合物对聚合物纤维集束进行浸渍的方式不受特别限制,只要使得浸渍后的纤维集束中的各单根纤维表面包覆有一定厚度的PMTS材料组合物,且相邻的各单根纤维相互粘接在一起即可。在一些实施方案中,将纤维集束的二头锁紧(例如用悬空工作吊夹锁紧),纤维集束二头各预留一定长度(例如50mm左右)的纤维集束不浸渍,将纤维集束浸没入PMTS材料组合物中,推动二头向中间移动使纤维集束松散开,反复几次,直至各单根纤维表面包覆一定厚度的PMTS材料组合物;取出集束纤维,二头绷紧,在长度二分之一处剪切,经一头垂直悬空,利用PMTS材料组合物的平衡张力与重力的流滴过程,自动粘合集束。本发明中,浸渍了PMTS材料组合物的纤维集束中,各单根纤维的包覆层的平均厚度优选为25-30μm。
在一些实施方案中,步骤(2)中,浸渍了PMTS材料组合物的纤维集束先填入管状模具中,再进行40-45℃固化后、50-60℃处理、360-480℃处理、850-900℃烧结、以及1400-1450℃烧结或3000℃±100℃烧结,这样就可以制备得到具有储氢结构的单体管(简称储氢单体管)。可以理解的是,由于PMTS材料在常温常压下会发生固化,因此需要在基本没有固化时将浸渍了PMTS材料组合物的纤维集束填入管状模具中。本发明中,管状模具的材质优选为本发明的PMTS材料或PMTS复合材料。本发明的PMTS复合材料含有本发明的PMTS材料和增强填料或由本发明的PMTS材料和增强填料组成,可通过在本发明的PMTS材料组合物中加入增强填料,再经过本文所述的40-45℃、50-60℃、360-480℃、850-900℃和1400-1450℃五步处理后得到。适用于本发明的PMTS复合材料的增强填料可以是已知的各种质轻、强度高的增强填料,用于减轻PMTS材料的比重和/或提高其强度。增强填料例如可以是碳纤维。增强填料的添加量可以根据需要确定。适用于本发明的管状模具的形式不受特别限制,只要能够装载并固定浸渍了PMTS材料组合物的纤维集束的形状即可,例如管状模具可以包括内管和套管。管状模具的剖面形状不受特别限制,例如可以是六角形、圆形、矩形、方形、三角形、凹凸楔合形、平行多边形等。为了方便装填,内管可以分为两半;在两半内管中分别铺满集束纤维,平整后,将两半内管粘合在一起,从而完成装填。内管的壁厚可在150μm-300μm。内管内部空间的横截面面积优选为69mm2-1940mm2,内管的外径以圆形截面为例优选为10mm-50mm。可以理解的是,管状模具的长度与聚合物纤维的长度相匹配,通常略小于填入的聚合物纤维的长度。套管两端开口。可以理解的是,套管的剖面形状和大小、长度与内管的剖面形状和大小、长度相匹配,例如套管的剖面形状通常与内管的剖面形状相同,套管的内径通常略大于内管的外径,套管的长度可以与内管的长度相同。套管的壁厚优选为1.0mm-2.5mm、例如1.5mm左右。在一些实施方案中,将内管装入套管中后,用PMTS材料组合物(例如粘度为1000000±20000cP的PMTS封端液,由PMTS材料组合物除溶剂调节粘度而得到)密封,再套上塑料封口膜,再进行40-45℃固化及后续处理。可以理解的是,步骤(2)中,在50-60℃处理之前,可以根据需要修除集束纤维未浸渍部分。
浸渍了PMTS材料组合物的聚合物纤维集束经过步骤(2)后,即得到本发明的高压储氢结构,或者在填入管状模具的情况下,经过步骤(2)后,即得到本发明的具有蜂巢储氢结构的单体管(简称单体管)。因此,本发明的单体管包括本发明的高压储氢结构和单体管管壁(又称为外壳,来自于制备单体管时使用的管状模具)。烧结后,高压储氢结构与管状模具(例如内管和套管)融为一个整体。
本发明的高压储氢结构的微孔壁厚优选为35-40μm,微孔直径优选为140-150μm。本发明的单体管可被制成多种管型并可应用于特殊设计及装备,单体管的剖面形状包括但不限于六角形、圆形、矩形、方形、三角形、凹凸楔合形、平行多边形等。单体管的管体长度在800mm内为宜。单体管的高压储氢结构的横截面面积不受特别限制,以剖面为圆形的单体管为例,如应用于移动储氢交通工具,单体管的高压储氢结构的直径可在10mm-50mm之间优化选择;如应用在储氢移动运输及移动加氢站,包括大型储氢站及舰船、高铁等大型移动工具,其直径可扩展至200mm。根据单体管内高压储氢结构的大小,单体管的管壁厚度可以为1-15mm,例如1-5mm。在一些实施方案中,如图2所示,本发明的单体管为圆形管,其外径为25mm、内径(高压储氢结构的直径)为22mm、长度为600mm,微孔孔径为150μm、壁厚为35μm,单个微孔(又称为单孔管)的容积为10.5975mm3,单孔管数量约为14,000个,单体管储氢总容积为148365mm3。
本发明的PMTS材料储氢结构可满足70MPa的储氢需要,特别适用于高压气态氢的储存。此外,本发明的PMTS材料具有优异的耐低温性能,将PMTS材料制备成类似保温热水瓶胆的双层真空结构、辅以高隔热材料,可用于液氢超低温保存。因此,本发明也包括本发明的PMTS材料在高压储氢和液氢保存中的应用。
在上述单体管制作完成后,根据设定的单体管集束的形状和直径,把N个单体管置入PMTS匹配型管中成为一个集束管;通过N个集束管安置在蜂窝网巢结构的模块箱中,就得到了综合性能优异的模块;N多模块可以非常灵活地组合成所需要的容量和各种形状;当把众多N个模块并联在一起时就形成了所需要的超大规模容量。用小容量高压强、具高安全稳定性的微米级微孔蜂巢结构的单体储氢管,通过N管集束组合成模块(以下称模块),组合成需要的任意容量。这是通过材料和结构性能实现高安全高稳定性的高压储氢方法。任何储氢容量都可以通过N单体管组合成集束管、N集束管组合成模块加以实现。模块安全储氢压强在70MPa~110MPa,压强极限大于200MPa,在100MPa的储氢安全系数为2.3倍。
以PMTS材料的总质量计,本发明的PMTS材料通常包含以下成分:15-50wt%的二氧化硅、0.5-5wt%的过渡金属氧化物、45-85wt%的金属氧化物和不可避免的杂质。过渡金属氧化物可包括氧化镧、铈氧化物、镧铈氧化物和氧化钇中的一种或多种,优选包括氧化镧、铈氧化物和镧铈氧化物中的一种或多种和氧化钇。当含有时,PMTS材料中,氧化镧、铈氧化物和镧铈氧化物的总含量优选为0.2-1wt%,氧化钇的含量优选为0.5-5wt%。金属氧化物可包括三氧化二铝、二氧化锆、二氧化钛、氧化铪、氧化钾、氧化钠、氧化镁、氧化钙、氧化锌和氧化铍中的一种或多种,优选包含以下成分:三氧化二铝,二氧化锆,二氧化钛,氧化铪,氧化钾和/或氧化钠,氧化镁,任选的氧化锌,任选的氧化钙,和任选的氧化铍。当含有时,PMTS材料中,三氧化二铝的含量优选为15-30wt%,二氧化锆的含量优选为15-35wt%,二氧化钛的含量优选为5-15wt%,氧化铪的含量优选为0.1-10wt%,氧化钾和氧化钠的总含量优选为0.1-1wt%,氧化镁的含量优选为0.1-0.5wt%,氧化钡的含量优选为1-2wt%,氧化钙的含量优选为0.05-1wt%,氧化锌的含量优选为0-10wt%,氧化铍的含量优选为1-20wt%。
优选地,以PMTS材料的总质量计,PMTS材料包含以下成分,或由以下成分组成:33-39wt%的二氧化硅和/或氧化铍,17-22wt%的三氧化二铝,20-28wt%的二氧化锆,6-10wt%的二氧化钛,0.25-0.5wt%的氧化铪,0.45-0.9wt%的氧化镧、铈氧化物和/或镧铈氧化物,1-2.7wt%的三氧化二钇,0.12-1wt%的氧化钾和/或氧化钠(例如0.1-0.2wt%的氧化钾和0.5-0.9wt%的氧化钠),0.18-0.4wt%的氧化镁,1-1.7wt%的氧化钡,0-10wt%的氧化锌,任选存在的0.07-0.7wt%氧化钙,和不可避免的杂质。本发明中,不可避免的杂质通常包括碳、氧化铬和三氧化二铁中的一种或多种,还可能包括汞、砷、磷、锰、铜、锌等元素。当含有时,以PMTS材料的总重量计,碳的含量通常为0.013-0.015wt%。当含有时,以PMTS材料的总重量计,氧化铬的含量通常为0.01-0.02wt%。当含有时,以PMTS材料的总重量计,三氧化二铁的含量通常0.01-0.015wt%。可以理解的是,三氧化二铁和氧化铬是原料中包含的微量成分所带来的,碳是聚合物或碳化物烧结后所残留的。在一些实施方案中,以PMTS材料的总质量计,PMTS材料包含0.013-0.015wt%的碳、0.01-0.015wt%的三氧化二铁和0.01-0.02wt%的氧化铬。本发明中,不可避免的杂质中除碳、氧化铬和三氧化二铁以外的杂质的总含量通常不超过PMTS材料总质量的0.01wt%,这类杂质例如可以包括汞、砷、磷、锰、铜、锌等元素。在一些实施方案中,PMTS材料所含的33-39wt%的二氧化硅和/或氧化铍为:33-39wt%的二氧化硅;或33-39wt%的二氧化硅和氧化铍,其中,氧化铍的含量优选为PMTS材料总质量的3-15wt%,例如3-13wt%、5-15wt%。
在一些实施方案中,PMTS材料由不含碳化锌的PMTS材料组合物制备得到,则以PMTS材料的总质量计,此类PMTS材料优选包含以下成分,或由以下成分组成:37-39wt%的二氧化硅和/或氧化铍,19-22wt%的三氧化二铝,23-28wt%的二氧化锆,7-10wt%的二氧化钛、0.3-0.5wt%的氧化铪,0.5-0.9wt%的氧化镧、铈氧化物和/或镧铈氧化物,1.2-2.7wt%的三氧化二钇,0.12-1wt%的氧化钾和/或氧化钠(例如0.1-0.2wt%的氧化钾和0.5-0.9wt%的氧化钠),0.2-0.4wt%的氧化镁,1.2-1.7wt%氧化钡,任选存在的0.08-0.7wt%氧化钙,和不可避免的杂质。在这些实施方案中,PMTS材料所含的37-39wt%的二氧化硅和/或氧化铍可以为:37-39wt%的二氧化硅;或37-39wt%的二氧化硅和氧化铍,其中,氧化铍的含量优选为PMTS材料总质量的5-18wt%,例如7-18wt%、5-15wt%。
与本发明近似的实现方案:微米级玻璃毛细管一般应用在非压力用途,在高压储氢方面,也可以作为一定压强的集束储氢材料。其优点:可满足70MPa的储氢需要,压强极限140MPa,安全系数2。缺点在于:1、材质决定的压强上限,没有发展潜力;2、难以解决原料和工艺决定的杂质/气泡/裂缝瑕疵,肉眼难以查觉的瑕疵率非常高。一个毛细管上的瑕疵在高压下发生的崩裂会连带整个公共储氢系统泄漏,数量几十万个毛细管所集束成的储氢容器,质量难以把控,存在高危隐患;3、微米级孔径的玻璃毛细管应用于储氢容器产生的高成本=(1)一个毛细管的应用成本×几十万个毛细管+(2)毛细管瑕疵挑出成本+(3)每根毛细管的高温封口成本与封口瑕疵挑出成本+(4)N个毛细管粘结集束成本+(5)时间成本。
本发明与微米级玻璃毛细管方案相比具有以下突出的优势:
1、为新型高压储氢结构定向设计的PMTS材料和特殊工艺制成的微米孔径一体化的蜂巢储氢结构单体管由智能化高温烧结,具有比重轻、高光洁度、高精密度与高硬度的广谱应用,工艺质量有比较好的一致性;
2、PMTS微米孔径蜂巢结构各方面性能超越石英毛细管的极限指标2倍以上,其蜂巢结构在150μm孔径、35μm壁厚的微米管压强>200MPa;
3、生产成本比较:一个直径为25mm的微孔蜂巢结构单体管孔径150μm的微孔数量为14000个,长度600mm,在量产流水线的生产成本与孔径150μm/长度1000mm的一根石英毛细管成本比较,是石英毛细管成本的三分之一;
4、PMTS材质金相结构分析与老化实验:PMTS微孔蜂巢结构储氢容器的连续使用寿命大于20000小时,比石英毛细管的连续使用寿命8000小时高出2倍以上。
本发明具有以下优点:
1、本发明提供了一种PMTS轻质耐高压耐高温耐强酸碱的高安全稳定性的储氢容器材料(以下简称PMTS,是有机高分子PI+无机物金相结构的简称),替代进口高质碳纤实现更高的储氢质量密度。
2、在PMTS基础上发明了微米级微孔一体化的蜂巢高压储氢结构,通过微米孔径的微小储氢空间限制氢的动态活泼互撞产生的连锁恶化反应,实现在复杂的动态工作环境下具有高安全性及高稳定性的70MPa~110MPa的高压储氢能力,并具有2倍以上的安全系数,与同等压强同等容量碳纤容器相比体积减小50%,颠覆了容器包覆层CFRP形体硕大笨拙的现状。本发明的微米级微孔蜂巢高压储氢结构可以非常方便地形成各种形状,具有非常强的使用便利性与灵活性,可以作为更适合我国国情具有广阔发展前景的参考技术。
3、PMTS材料与微米孔径蜂巢结构的突出优势:
(1)质量比重:可以达到5.2g/cm3左右;
(2)充气快:相同容量充气只需几秒,大大小于5kg/3min充气标准;
(3)体积小可至微小型化:微米级微孔蜂巢结构具有超强的高压储氢能力,省却了厚而笨拙的碳纤铺层,储氢模块比同样压强容量的碳纤容器体积要小一半;储氢单体管具有放置灵活性,通过科学设计合理安置在机翼、车厢板、车底板、任何板壁中,几乎看不到储氢容器。微米微孔蜂巢高压储氢结构可微小型化,与微型氢燃料电池结合(结合体积如烟盒大小),可作为佩戴式微型移动供电装备;
(4)硬度:洛氏86~89;
(5)高压强:PMTS材质的优异性及微米微孔蜂窝网巢的力学结构,可以很容易的实现70MPa~110MPa的储氢压强,安全系数达2.3倍;与质量比重较大的石英集束毛细管进行高压储氢对比试验,石英集束毛细管在140MPa破裂,而PMTS微孔蜂巢结构单体管在达到200MPa仍有承受余量;
(6)储氢容量大:微小体积耐高压强的高密度储氢,由单体管并联集束形成的模块,与任何数量的模块并联,可以实现任意容量的氢移动工具、高密度氢气运输、移动加氢站和大规模储氢站;
(7)稳定性强:模块拉伸张力3200MPa,耐高温>1900℃,耐酸碱pH3~14,在不可预见的不可抗力中有良好的安全稳定性;
(8)安全性高:PMTS微孔蜂巢结构其密布的微孔在高压注氢气流冲击下分解了流体湍流,因此不会产生高压温升。其微孔蜂巢结构在任何动态下有效地限制了氢的动态活化能,即使不可预见的超高压强所产生的内应力在蜂巢结构中即瞬时分解,可以有效地避免高压高流速温升导致的内应力危害,从而保证了容器的质量稳定性和高安全性;
(9)使用寿命:大于20000小时以上的连续使用寿命,是石英毛细管连续使用寿命的近三倍;
(10)经济性强:结构牢固,瑕疵率极小,使用寿命长,成本仅为碳素纤维容器的30-40%。
4、本发明的PMTS与微孔蜂巢结构所形成的集束储氢模块在轻量化小体积下实现了大于100MPa的高安全高稳定性的高压储氢技术,颠覆了空心储氢质量密度依赖CFRP的技术路线。相对于CFRP技术在70MPa高压储氢的应用极限而言,PMTS与微孔蜂巢结构在高压储氢能力上还有很大的质量提升潜力及更多的氢能应用领域。本发明的微孔单体管集束模块不拘于任何容量与外形局限。本发明的高安全/高稳定性的储氢方法,其应用效益和经济性可极大地促进氢能普及应用。本发明在特种领域可以胜任各种复杂的工作环境,在微小型化氢燃料电池移动发电领域还有更广阔的应用潜力。
下文将以具体实施例的方式描述本发明,其目的在于更好地理解本发明的内容。应理解,这些实施例仅仅是阐述性的,而非限制性的。实施例中所使用的原料和试剂,除非另有说明,否则都是从市场上常规购得。实施例中所使用的实验方法、制备方法和检测方法,若无特殊说明,均为常规方法,或按照厂商推荐的方法。实施例中使用的仪器设备,若无特殊说明,均为本领域常规的仪器设备。实施例中,若无特别说明,百分比是指质量百分比。
下列实施例中,除高纯度超细氧化铪、超细氧化镧外,其它高纯度氧化物(纯度4N、5N、6N级)均为用高压气流粉碎悬浮细粉收集法得到的一万级以上超细粉末;所用金属氧化物颗粒全部采用纳米级高纯度原料。
本文采用如下的材料/产品的性质/性能检测设备/方法和实验设备/条件:
1、原料质量检测:赛默飞世尔尼通(Niton)XL5手持式合金分析仪。
2、过程产品及终端产品元素检测:赛默飞ARL Perform’X 4200XRF波长色散顺序扫描式X射线荧光光谱仪;X射线发生器最大输出功率:≥4.2kW,额定电压:≥70kV,额定电流:≥140mA;X射线光管:Rh靶,陶瓷端窗X光管,不低于4.2kW;铍窗厚度:≤50μm;样品激发距离:≤16mm;照射方式:下照射方式,即样品在X射线光管上方;固态高频发生器:外电压波动1%,输出电压的稳定性为±0.00005%,保证测试高精度;扫描方式:连续扫描;探测器:流气正比计数器、闪烁计数器,两个计数器平行放置,全部在光谱室内;检测形式:顺序检测,自动记录;样品要求无任何污染。
3、粘度测试:NDJ-8S旋转数显粘度计。
4、金相分析:卡尔·蔡司研究级正立金相显微镜Axio Lab A1 Pol。
5、耐酸碱性测试:pH3测试:从PMTS样板上激光切割尺寸为30mm3的立方体若干枚,不需精密打磨,经显微备存;实验室25℃环境,置入装有纯乙醇的玻璃烧杯中浸没密闭30min,用竹夹取出置于干燥滤纸盘中放置20min,取3枚置入操作箱中的装有pH=3的盐酸溶液的玻璃烧杯中密闭静置24小时取出,清水漂洗,干燥纸吸干;pH14测试:操作箱中的pH=3的盐酸溶液的玻璃烧杯替换为装有pH=14的氢氧化钠溶液的玻璃烧杯,余下步骤pH3测试;pH显微组织检验与评级标准:微蚀金属和合金规程ASTM E407-07(Reapproved2015)el7.1-7.15检测标准。
6、耐高温性能测试:热传导系数测试仪,测试模拟夏季酷暑暴晒车内温度60℃。
7、高低温夏比冲击测试:将负载70MPa气压的单体管置于50℃高温环境中保持15min,然后经20s转移到-15℃低温环境中保持15min,转换17次(高温9次、低温8次),各次高低温的保持时间均为15min,高温、低温之间转换时间均为20s,观察单体管是否发生破裂。
8、拉伸强度测试:万能材料性能试验机,力值精度±0.5%;试样厚度30mm、长1000mm、宽500mm,送检PMTS成型样板3个。
9、密度测试:电子比重计。
10、烧结分析、温度监控:远红外温度自动检测仪。
11、电液伺服疲劳测试:MTS电液伺服疲劳试验机;检测标准:发动机叶片及材料振动疲劳试验方法HB 5287-96 7;持续耐久性与连续使用寿命模拟。
12、极限压强测试:计算机型200MPa试验台,思明特,型号:SUPC_XT_200。
13、充气速度测试:思明特SUPC XT 200试验台0.1Pa-70MPa水压速度测试:根据试样压力,由增压泵输出设定高压;试验压力:0-200MPa;增压流量:1.2L/min;控压精度:上限+2%、下限-1%;试验介质:液体水;压力控制:计算机/手动;操作方式:计算机/手动;结构:循环系统、压力控制系统;工件:安装装置,手动控制;注:本测试内容与方法,没有相应的检测机构与检测标准,故由发明人自行设计的测试方法;设施安装测试步骤:
(1)将试验用70MPa 5Kg容量的气压罐(A罐)充气阀安装连接至试验台增压泵高压输出接头,增压泵进水口连接至试验专用的过滤型净化水源;
(2)将PMTS储氢容量在2Kg的储氢模块(B罐)供气阀打开,充气阀用铬钼连接管连接至高压流量计→压力表→电脑控制压力电磁阀连接至A罐供气电磁阀接口,打开A罐供气阀与充气阀,然后在B罐供气阀连接真空泵,经检查后启动真空泵,将连接的A、B罐抽真空后关闭A、B罐供气阀;
(3)在试验台计算机设定输出压力值:70MPa;
(4)打开A罐充气阀门;
(5)试验台计算机启动或人工启动;
(6)试验台增压输出至A罐达到设定压力值70MPa时,保持承受压力时间2min,打开A罐供气电磁阀供压给B罐,数秒间B罐压力达到70MPa,B充气电磁阀关闭,测试完成。
14、间歇与恒温温度控制:智能高温调节控制台。
15、真空反应釜/真空泵/温度/智能控制:真空反应釜预工作状态35℃、工作状态40℃~42℃,真空度需时常保持在-96KPa至-101KPa范围。
16、工作状态/工作稳定性测试:Tenney(TJR-T2)环境试验箱/压力表,PMTS材料及储氢管在70MPa压强时在-18℃至65℃温度下的工作状态/工作稳定性。
17、洛氏硬度测试:测试精度标准符合标准GB/T230、ISO6508;120度角金刚石圆锥压头分两个步骤压入试样表面,卸除主试验力后,在初试验力下测量压痕残余深度,以压痕残余深度代表硬度的高低。
18、液氮超低温试验:PMTS精密结构件置入液氮10min后取出。
实施例1
本实施例通过以下工艺制备本发明的PMTS材料组合物:
(1)制备组合物A:透明反应釜中加入17重量份分析纯无水氯化铝和5重量份分析纯氯化镁,混合,加入22重量份蒸馏水,搅拌,得到浓度为50wt%的氯化铝、氯化镁混合溶液,逐步加入1.2重量份分析纯氢氧化钠与0.5重量份分析纯氢氧化钾,反应至冷却,生成白色沉淀,抽出透明液体,向白色沉淀中加入3重量份分析纯氯化钡,搅拌后静置30min,100℃烘干,经高温870℃处理90min后,冷却,球磨粉碎至8000目以上,得到组合物A,备用;
(2)制备组合物B:混合12重量份纳米三氧化二铝(型号:MG-AI032,纯度99.99%)、16重量份二氧化锆(型号:VK-R60,粒径1-5μm,纯度99.9%)、2.5重量份纳米三氧化二钇(纯度99.99%)、8重量份纳米二氧化钛(型号:DT-O-007-2,金红石型,纯度>99.9%)和0.5重量份超细氧化铪(型号:H301462,纯度99.99%),搅拌,得到组合物B;
(3)制备组合物C:将24重量份PI(美国杜邦SP-1)溶解于二甲基甲酰胺中,得到浓度为30wt%的PI溶液,加入到真空反应釜中,保持釜内温度为40℃,维持真空度-94KPa,逐步加入二甲基甲酰胺调节粘度至90000cP,以10r/min的转速搅拌25min,然后逐步加入33重量份纳米级二氧化硅(纯度99.999%,5N级),搅拌15min,加入步骤(2)制备得到的全部组合物B,混合20min,再加入0.5重量份超细氧化镧(纯度99.99%),搅拌15min,得到组合物C;
(4)制备PMTS材料组合物:将12重量份PVAc(山东济南普莱华化工有限公司,工业级,纯度为99.9%,特性黏度为0.80dL/g)用蒸馏水稀释至浓度为75wt%,搅拌10min,加入步骤(1)制备得到的全部组合物A搅拌20min,将得到的混合物加入到盛有步骤(3)制备得到的全部组合物C的真空反应釜中,注入适量的二甲基甲酰胺,加温至45℃,以10r/min的转速搅拌,将粘度调节到90000cP,得到呈白色无气泡的产物,即为PMTS材料组合物。
本实施例制得的PMTS材料组合物可稳定储存,可用于制备PMTS材料高压储氢结构单体管,详见实施例2。
实施例2
本实施例采用实施例1制备得到的PMTS材料组合物通过以下工艺制备本发明的PMTS材料高压储氢结构单体管:
第一步:将实施例1制备得到的粘度为90000cP的PMTS材料组合物放料至不锈钢U型平底槽(长度1500mm,宽度500mm,高度200mm),加温至42℃,将粘度调节至200000cP,得到PMTS浓缩液,最终PMTS浓缩液在平底槽的添加量使得聚合物纤维放入后、PMTS浓缩液的液面高于被完全浸渍纤维10mm;
第二步:预先准备好由16800根左右的直径为150μm、长度为1340mm的聚丙烯连续纤维组成的纤维集束,将纤维集束的二头用悬空工作吊夹锁紧,纤维集束二头各预留50mm不浸渍,将纤维集束浸没入第一步得到的PMTS浓缩液中,推动二头向中间移动使纤维集束松散开,反复几次,直至各单根纤维表面包覆厚度约25μm~30μm的PMTS浓缩液;从液槽中取出集束纤维,二头绷紧,在长度二分之一处剪切,经一头垂直悬空,利用PMTS浓缩液的平衡张力与重力的流滴过程,自动粘合集束;在粘合完成的集束纤维没有固化前,置入剖面为正六边形、平行对边外径(包括壁厚在内平行对边之间的距离)为24.5mm、壁厚为150μm、长度为620mm的内管中,内管分为两半,在两半内管中铺满集束纤维,平整后粘合上另一半内管;将内管插入剖面为正六边形、平行对边内径(不包括壁厚在内平行对边之间的距离)为25mm、管壁厚度为1.5mm、长度为620mm的套管中,一端用粘度为1000000cP的PMTS封端液(由实施例1的PMTS材料组合物经45℃去除溶剂调节粘度而得到)密封后套上塑料封口膜,继续悬空固化,在保持室内恒温42℃、空气湿度保持在10%的密闭环境中固化240min;
本实施例中使用的管状模具(包括内管和套管)的材质为PMTS材料,由实施例1制备得到的PMTS材料组合物在42℃、湿度10%的密闭环境中固化240min,然后在50℃下固化60min,然后在480℃烧结60min,得到固化半成品,再在880℃下烧结90min,得到金相结构半成品,再在1430℃下烧结300min得到;
第三步:修除集束纤维未浸渍部分,置入隧道窑,隧道窑预先设定各段窑体温度,在50℃下固化60min,然后在480℃烧结60min,得到固化半成品,再在880℃下烧结90min,得到金相结构半成品,再在1430℃下烧结300min,烧结完成,得到PMTS材料高压储氢结构单体管。
利用X射线荧光光谱仪(赛默飞ARL Perform’X 4200XRF)测得,以PMTS材料的总质量计,本实施例制备得到的PMTS材料由以下成分组成:38.74wt%二氧化硅、19.71wt%三氧化二铝、26.32wt%二氧化锆、8.65wt%二氧化钛、0.46wt%氧化铪、0.71wt%氧化镧、2.43wt%三氧化二钇、0.12wt%氧化钾、0.84wt%氧化钠、0.36wt%氧化镁、0.015wt%碳、1.61wt%氧化钡、0.013wt%三氧化二铁、0.014wt%氧化铬和0.008wt%的杂质。
本实施例制备得到的PMTS材料高压储氢结构单体管具有微米微孔蜂巢结构,单体管长度为620mm、剖面为正六边形,套管平行对边外径为28mm、平行对边内径为25mm,每个微孔壁厚显微尺寸在35μm~40μm之间,每个微孔显微直径在140μm~150μm之间。一个单体管大约有16800个微米单孔管,每一个微米单孔管的储氢容积约10.6mm3左右。因此,一个具有微孔蜂巢结构的单体管的储氢容积大约为178080mm3,即0.000178m3。该PMTS材料高压储氢结构单体管可应用于复杂动态环境,实现高安全高稳定性储氢。该PMTS材料高压储氢结构单体管的体积相比70MPa同容量的空心内胆碳纤容器减少了50%。通过N个单体管并联得到集束管、N个集束管结合成模块和/或N个模块可以实现需要的储氢容量或规模。由本实施例的单体管组成的蜂巢结构模块力学示意图如图3所示。
测试例1:PMTS材料高压储氢结构单体管性能测试
对实施例2制备得到的单体管进行高低温夏比冲击测试,结果显示单体管无爆裂泄露,表明本发明的单体管可满足70MPa的储氢需要。
对实施例2制备得到的单体管进行电液伺服疲劳测试,结果显示单体管连续使用寿命模拟测定>20000小时,表明本发明的单体管具有很长的使用寿命。
使用200MPa试验台测定实施例2制备得到的单体管的极限压强,结果显示单体管可以承受的压强超过检测极限(检测极限为200MPa),表明本发明的单体管具有很高的极限压强。安全储氢压强根据极限压强设定,安全储氢压强=储氢极限压强÷安全系数(通常为2);特殊用途须以更大的安全系数设定比较小的安全储氢压强。本发明的微米级微孔蜂巢储氢结构有效地抑制了高压氢活化能在任何环境下的压力上升,故本发明的微米级微孔蜂巢储氢结构以2倍的安全系数可以在任何复杂的环境下具有特别的高安全性和高稳定性。
对实施例2制备得到的单体管进行充气速度测试,结果显示70MPa模拟充气速率为2kg/3s,表明本发明的储氢结构具有很快的充气速度,说明PMTS材质与微孔蜂巢储氢结构消除了空心内胆储氢结构在高速充气流所产生的湍流对充气速率的影响,目前国内外70MPa空心内胆储氢容器的充气速率达标标准为5kg/3min。
对实施例2制备得到的单体管进行液氮超低温试验,结果显示单体管置入液氮10min后取出,无破裂变形,表明本发明的单体管具有优异的耐低温性能。
对实施例2制备得到的单体管进行工作状态/工作稳定性测试,结果显示单体管在低温(-18℃)和高温(65℃)各15min,在70MPa时,有±5%范围内的压强变化,表明本发明的单体管具有较佳的工作稳定性。
测试例2:PMTS材料性能测试
将实施例1的PMTS材料组合物浇注成薄板,在42℃、湿度10%的密闭环境中固化240min,然后在50℃下固化60min,然后在480℃烧结60min,得到固化半成品,再在880℃下烧结90min,得到金相结构半成品,再在1430℃下烧结300min,得到厚度为5mm和30mm的PMTS样板。
由实施例1的PMTS材料组合物制备得到的厚度为5mm的PMTS样板的比重为5.2g/cm3,洛氏硬度为87,表明本发明的PMTS材料具有很高的硬度。
对厚度为5mm的PMTS样板进行耐酸碱性测试,结果显示在pH=3和pH=14下,PMTS样板均无腐蚀损伤(依据ASTM E407-07(Reapproved2015)el7.1-7.15检测标准);对经过耐酸碱性pH3测试和pH14测试的PMTS样板进行洛氏硬度检测,结果显示硬度均为87,表明本发明的PMTS材料具有优异的耐酸碱性。
对厚度为5mm的PMTS样板模拟夏季酷暑暴晒车内温度60℃进行耐高温性能测试,结果显示由实施例1的PMTS材料组合物制备得到的PMTS样板导热系数为2.67W/(m·K),表明本发明的PMTS材料具有优异的耐高温性能。
对厚度为30mm的PMTS样板进行拉伸强度测试,结果显示由实施例1的PMTS材料组合物制备得到的PMTS样板的拉伸强度>3000MPa,表明本发明的PMTS材料具有很高的拉伸强度。
Claims (10)
1.一种储氢结构用材料组合物,其特征在于,所述储氢结构用材料组合物的原料包括以下组分:
20-24重量份的聚酰亚胺,12-13重量份的聚醋酸乙烯酯,15-17重量份的氯化铝,3-5重量份的氯化镁,3-5重量份的氯化钡,10-12重量份的三氧化二铝,15-17重量份的二氧化锆,0.5-0.7重量份的三氧化二镧、铈氧化物和/或镧铈氧化物,32-35重量份的二氧化硅、碳化硅和/或氧化铍,1.5-2.5重量份的氢氧化钠和/或氢氧化钾,1.5-3重量份的三氧化二钇,6-8重量份的二氧化钛和/或碳化钛,0.3-0.5重量份的二氧化铪和/或碳化铪、任选的0.3-0.5重量份的氯化钙和任选的不超过10重量份的碳化锌;
优选地,所述储氢结构用材料组合物的原料还包括水和极性溶剂,所述极性溶剂选自二甲基乙酰胺、二甲基甲酰胺和N-甲基吡咯烷酮;
优选地,所述储氢结构用材料组合物的粘度为90000±10000cP。
2.一种制备权利要求1所述的储氢结构用材料组合物的方法,其特征在于,所述方法包括以下步骤:
(1)混合氯化铝和氯化镁,加水溶解,加入氢氧化钠和/或氢氧化钾,反应生成白色沉淀,取白色沉淀,加入氯化钡和任选的氯化钙,搅拌均匀后,烘干,经700-900℃高温处理,粉碎,得到组合物A;
(2)混合三氧化二铝、二氧化锆、三氧化二钇、二氧化钛和/或碳化钛、二氧化铪和/或碳化铪、和任选的碳化锌,得到组合物B;
(3)向聚酰亚胺溶液中加入二氧化硅、碳化硅和/或氧化铍,搅拌均匀后,加入组合物B,搅拌均匀后,加入氧化镧、铈氧化物和/或镧铈氧化物,搅拌均匀后,得到组合物C;
(4)向聚醋酸乙烯酯溶液中加入组合物A,搅拌均匀后,将得到的混合物与组合物C混合,搅拌均匀;
由此得到所述储氢结构用材料组合物。
3.如权利要求2所述的方法,其特征在于,所述方法具有以下一项或多项特征:
(1)步骤(1)中,加水溶解得到的氯化铝和氯化镁混合溶液的浓度为40-60wt%;
(2)步骤(1)中,高温处理的时间为80-100min;
(3)步骤(1)中,粉碎后组合物A的目数在8000目以上;
(4)步骤(3)中,所述聚酰亚胺溶液为聚酰亚胺溶解在极性溶剂中得到的溶液,所述极性溶剂选自二甲基乙酰胺、二甲基甲酰胺和N-甲基吡咯烷酮,所述聚酰亚胺溶液的粘度为90000cP±2000cP;
(5)步骤(3)在35-45℃和-94kPa至-101kPa的真空度下进行;
(6)步骤(4)中,所述聚醋酸乙烯酯溶液为聚醋酸乙烯酯的水溶液,其浓度为70-80wt%;
(7)步骤(4)中,在35-45℃和-94kPa至-101kPa的真空度下对聚醋酸乙烯酯溶液和组合物A的混合物与组合物C进行混合;
(8)步骤(4)中,混合聚醋酸乙烯酯溶液和组合物A的混合物与组合物C后,加入极性溶剂,将混合物的粘度调节到90000±10000cP,所述极性溶剂选自二甲基乙酰胺、二甲基甲酰胺和N-甲基吡咯烷酮。
4.一种储氢结构用材料,其特征在于,以所述储氢结构用材料的总质量计,所述储氢结构用材料包括以下成分:33-39wt%的二氧化硅和/或氧化铍,17-22wt%的三氧化二铝,20-28wt%的二氧化锆,6-10wt%的二氧化钛,0.25-0.5wt%的氧化铪,0.45-0.9wt%的氧化镧、铈氧化物和/或镧铈氧化物,1-2.7wt%的三氧化二钇,0.12-1wt%的氧化钾和/或氧化钠,0.18-0.4wt%的氧化镁,1-1.7wt%的氧化钡,0-10wt%的氧化锌,任选存在的0.07-0.7wt%氧化钙,和不可避免的杂质。
5.一种储氢结构用复合材料,其特征在于,所述储氢结构用复合材料包括权利要求4所述的储氢结构用材料和增强填料。
6.一种制备权利要求4所述的储氢结构用材料或权利要求5所述的储氢结构用复合材料的方法,其特征在于,所述方法包括对权利要求1所述的储氢结构用材料组合物或权利要求1所述的储氢结构用材料组合物和增强填料的混合物在40-45℃下进行200-250min的固化处理,然后在50-60℃下进行50-70min的加热处理,然后在360-480℃下进行50-70min的加热处理,然后在850-900℃下进行80-100min的烧结处理,然后在1400-1450℃下进行250-350min的烧结处理或在3000℃±100℃下进行烧结处理。
7.一种储氢单体管,其特征在于,所述储氢单体管包括储氢单元,所述储氢单元的材质为权利要求4所述的储氢结构用材料,所述储氢单元具有蜂巢微孔结构;优选地,微孔壁厚为35-40μm;优选地,微孔直径为140-150μm。
8.如权利要求7所述的储氢单体管,其特征在于,所述储氢单体管还包括外壳,所述外壳的材质为权利要求4所述的储氢结构用材料或权利要求5所述的储氢结构用复合材料。
9.一种制备权利要求7或8所述的储氢单体管的方法,其特征在于,所述方法包括:
(1)使用权利要求1所述的储氢结构用材料组合物对聚合物纤维集束进行浸渍;
(2)对浸渍了储氢结构用材料组合物的聚合物纤维集束在40-45℃下进行200-250min的固化处理,然后在50-60℃下进行50-70min的加热处理,然后在360-480℃下进行50-70min的加热处理,然后在850-900℃下进行80-100min的烧结处理,然后在1400-1450℃下进行250-350min的烧结处理或在3000℃±100℃下进行烧结处理;或者将浸渍了储氢结构用材料组合物的聚合物纤维集束填入管状模具后再在40-45℃下进行200-250min的固化处理,然后在50-60℃下进行50-70min的加热处理,然后在360-480℃下进行50-70min的加热处理,然后在850-900℃下进行80-100min的烧结处理,然后在1400-1450℃下进行250-350min的烧结处理或在3000℃±100℃下进行烧结处理,所述管状模具的材质为权利要求4所述的储氢结构用材料或权利要求5所述的储氢结构用复合材料;
优选地,进行步骤(1)的浸渍前,先将储氢结构用材料组合物的粘度调节至200000±10000cP;
优选地,所述聚合物纤维的熔点在150℃-380℃之间;
优选地,所述聚合物纤维集束中单根纤维的直径为100-150μm;
优选地,步骤(1)中,所述浸渍使得聚合物纤维集束中各单根纤维表面包覆的储氢结构用材料组合物的平均厚度为25-30μm。
10.权利要求1所述的储氢结构用材料组合物、权利要求4所述的储氢结构用材料、权利要求5所述的储氢结构用复合材料、权利要求7或8所述的储氢单体管在高压储氢和/或液氢保存中的应用。
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