CN106714946A - 氢气排出膜 - Google Patents
氢气排出膜 Download PDFInfo
- Publication number
- CN106714946A CN106714946A CN201580032639.0A CN201580032639A CN106714946A CN 106714946 A CN106714946 A CN 106714946A CN 201580032639 A CN201580032639 A CN 201580032639A CN 106714946 A CN106714946 A CN 106714946A
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- Prior art keywords
- hydrogen
- film
- hydrogen discharge
- discharges
- electrochemical element
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 200
- 239000001257 hydrogen Substances 0.000 title claims abstract description 200
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 18
- 239000000956 alloy Substances 0.000 claims abstract description 18
- 238000003860 storage Methods 0.000 claims abstract description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 118
- 239000010931 gold Substances 0.000 claims description 28
- 239000003990 capacitor Substances 0.000 claims description 14
- 239000012528 membrane Substances 0.000 claims description 11
- 230000035699 permeability Effects 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 7
- 229920002492 poly(sulfone) Polymers 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 239000004760 aramid Substances 0.000 claims description 4
- 229920003235 aromatic polyamide Polymers 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 2
- 229910052729 chemical element Inorganic materials 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- 229920002620 polyvinyl fluoride Polymers 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 239000005001 laminate film Substances 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 18
- 238000005096 rolling process Methods 0.000 description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 15
- 238000004544 sputter deposition Methods 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 229910052763 palladium Inorganic materials 0.000 description 10
- 239000010949 copper Substances 0.000 description 9
- 238000005266 casting Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910001316 Ag alloy Inorganic materials 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 229910001020 Au alloy Inorganic materials 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000007767 bonding agent Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000005097 cold rolling Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229910002668 Pd-Cu Inorganic materials 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- 108700031620 S-acetylthiorphan Proteins 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910001093 Zr alloy Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000000254 damaging effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- HJUFTIJOISQSKQ-UHFFFAOYSA-N fenoxycarb Chemical compound C1=CC(OCCNC(=O)OCC)=CC=C1OC1=CC=CC=C1 HJUFTIJOISQSKQ-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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Abstract
本发明提供即使在电化学元件内大量产生氢气而使氢气排出量变多、或者长时间使用电化学元件时也不会发生不良状况的氢气排出膜和氢气排出层叠膜。本发明的氢气排出膜含有将Pd作为必要金属的合金,在50℃、氢分压0.01MPa的条件下进行测定时的贮氢量为0.4(H/M)以下。
Description
技术领域
本发明涉及设置在电池、电容器(condenser)、电容器(capacitor)和传感器等电化学元件等中的氢气排出膜。具体而言,涉及一种氢气排出膜,其在使用中产生氢气而使内部压力上升的电化学元件等中,具有在150℃左右以下的使用环境下将产生的氢气排出到外部的功能。
背景技术
近些年,铝电解电容器被用于风力发电和太阳光发电等的逆变器、蓄电池等大型电源等的用途。铝电解电容器存在由于反向电压、过电压和过电流而在内部产生氢气的情况,若产生大量氢气则有由于内部压力上升而使外壳破裂的担心。
因此,在通常的铝电解电容器中设置有具备特殊膜的安全阀。安全阀除了具有将电容器内部的氢气排出到外部的功能以外,还具有在电容器的内部压力急剧上升时自我破坏而使内部压力降低,防止电容器本身的破裂的功能。作为属于这种安全阀的构成构件的特殊膜,例如提出了如下特殊膜。
专利文献1中提出了一种具备箔带的压力调整膜,所述箔带由使钯中含有20wt%(19.8mol%)Ag的钯银(Pd-Ag)的合金构成。
另一方面,作为移动电话、笔记本电脑和汽车等的电池,广泛使用了锂离子电池。而且近些年,锂离子电池除了高容量化、提高循环特性之外,提高了对安全性的关注。特别是已知锂离子电池在单元内会产生气体,担心伴随内压上升的电池盒的膨胀、破裂。
在专利文献2中,作为选择性地透过在电池内产生的氢气的氢气选择透过性合金膜,公开了使用由锆(Zr)和镍(Ni)的合金形成的非晶质合金(例如,36Zr-64Ni合金)膜。
这种合金膜通常使用粘合剂或粘接剂等粘贴于保持构件等来使用,但存在如下问题:在电化学元件内大量地产生氢气而使氢气排出量变多、或者由于电化学元件的长时间的使用而导致合金膜从保持构件剥离、或者保持构件发生破坏、最坏的情况下电化学元件发生破坏。
现有技术文献
专利文献
专利文献1:专利第4280014号说明书
专利文献2:日本特开2003-297325号公报
发明内容
发明要解决的问题
本发明是鉴于上述问题点而完成的,其目的在于提供即使在电化学元件内大量地产生氢气而使氢气排出量变多、或者长时间使用电化学元件时也不会发生不良状况的氢气排出膜和氢气排出层叠膜。另外,目的在于提供具备该氢气排出膜或氢气排出层叠膜的电化学元件用安全阀、具备该安全阀的电化学元件。
用于解决问题的方案
本发明涉及一种氢气排出膜,其含有将Pd作为必要金属的合金,其特征在于,在50℃、氢分压0.01MPa的条件下进行测定时的贮氢量为0.4(H/M)以下。
使氢透过氢气排出膜时,则氢以穿过构成氢气排出膜的原子之间的缝隙的方式移动。即,氢暂时吸存在氢气排出膜中。另外,该移动中的氢与氢气排出膜中的原子发生替换并滞留于氢气排出膜中。即,可认为由于氢被蓄积于氢气排出膜中,氢气排出膜的体积变化,并由于该体积变化而产生前述不良状况。
本发明人基于前述见解进行了研究,结果发现,含有将Pd作为必要金属的合金的氢气排出膜的情况下,在50℃、氢分压0.01MPa的条件下进行测定时的贮氢量如果为0.4(H/M)以下,则能够有效地抑制由氢气蓄积导致的氢气排出膜的体积变化,因而即使在电化学元件内大量地产生氢气而使氢气排出量变多、或者在长时间使用电化学元件时,也不会产生氢气排出膜从保持构件上剥离、或者保持构件破坏等不良状况。
前述氢气排出膜在50℃、氢分压0.01MPa的条件下进行测定时的贮氢量优选为0.35(H/M)以下、更优选为0.2(H/M)以下,进一步优选为0.1(H/M)以下。
此处,贮氢量(H/M)用氢气排出膜中的氢(H)和金属(M)的摩尔比表示。另外,50℃、氢分压0.01MPa的测定条件是作为在电化学元件的通常使用环境中氢气排出膜最受物理影响的条件而采用的。
前述合金优选为含有20~65mol%第11族元素。另外,前述第11族元素优选为选自由金、银和铜组成的组中的至少1种。
含有Pd-第11族元素合金的氢气排出膜具有如下功能,即,在膜表面使氢分子解离为氢原子并将氢原子固溶于膜内,使固溶的氢原子由高压侧扩散至低压侧,在低压侧的膜表面再次将氢原子变换为氢分子并排出。在第11族元素的含量低于20mol%时,有合金的强度不充分、或者变得难以显现前述功能的倾向,在超过65mol%时有氢气透过速度降低的倾向。
前述氢气排出膜优选50℃下的氢气透过系数为1.0×10-13~2.0×10-9(mol·m-1·sec-1·Pa-1/2),且膜厚t和膜面积s满足下述式1:
〈式1〉
t/s<32.9m-1。
设置在电化学元件中的氢气排出膜要求压力的平方根为76.81Pa1/2(0.059bar)下的氢气透过量为10ml/天以上(4.03×10-4mol/天以上:根据SATP计算(温度25℃、气压1bar下的1mol的理想气体的体积为24.8L))。本发明的Pd-第11族元素合金中的第11族元素的含量为20~65mol%的氢气排出膜在50℃下的氢气透过系数为1.0×10-13~2.0×10-9(mol·m-1·sec-1·Pa-1/2)。此处,氢气透过系数根据下述式2求得。
〈式2〉氢气透过系数=(氢气摩尔数×膜厚t)/(膜面积s×时间×压力的平方根)
氢气透过量为10ml/天(4.03×10-4mol/天)且氢气透过系数为2.0×10-9(mol·m-1·sec-1·Pa-1/2)时,将各数值代入式2中时如下所述。
2.0×10-9=(4.03×10-4×膜厚t)/(膜面积s×86400×76.81)
2.0×10-9=6.08×10-11×膜厚t/膜面积s
膜厚t/膜面积s=32.9m-1
因此,使用50℃下的氢气透过系数为1.0×10-13~2.0×10-9(mol·m-1·sec-1·Pa-1/2)的氢气透过膜时,氢气透过量成为10ml/天以上(4.03×10-4mol/天以上)的条件是膜厚t/膜面积s<32.9m-1。
本发明的氢气排出层叠膜在前述氢气排出膜的单面或双面具有支撑体。支撑体为了防止氢气排出膜从安全阀脱落时掉落在电化学元件内而设置。另外,氢气排出膜需要具有作为在电化学元件的内部压力变为规定数值以上时自我破坏的安全阀的功能。氢气排出膜为薄膜时,由于氢气排出膜的机械强度低,因而有在电化学元件的内部压力变为规定数值之前自我破坏的担心,无法发挥作为安全阀的功能。因此,氢气排出膜为薄膜时,为了使机械强度提高而优选在氢气排出膜的单面或双面层叠支撑体。
支撑体优选为平均孔径100μm以下的多孔体。若平均孔径超过100μm,则多孔体的表面平滑性降低,因而在利用溅射法等制造氢气排出膜时,会变得难以在多孔体上形成膜厚均匀的氢气排出膜、或者会变得容易在氢气排出膜中产生针孔或裂纹。
从化学稳定和热稳定的观点出发,支撑体优选由选自由聚四氟乙烯、聚砜、聚酰亚胺、聚酰胺酰亚胺和芳族聚酰胺组成的组中的至少1种的聚合物形成。
另外,本发明涉及具备前述氢气排出膜或氢气排出层叠膜的电化学元件用安全阀和具有该安全阀的电化学元件。作为电化学元件,例如可列举出铝电解电容器和锂离子电池等。
发明的效果
本发明的氢气排出膜和氢气排出层叠膜具有如下特征:即使在电化学元件内大量地产生氢气而使氢气排出量变多、或者长时间使用电化学元件时也难以发生不良状况。另外,本发明的氢气排出膜和氢气排出层叠膜不仅能够迅速地仅将在电化学元件内部产生的氢气排出到外部,而且能够防止杂质由外部侵入电化学元件内部。另外,具备本发明的氢气排出膜和氢气排出层叠膜的安全阀在电化学元件的内部压力急剧上升时能够自我破坏而使内部压力降低,从而防止电化学元件本身的破裂。通过这些效果,能够长时间维持电化学元件的性能,能够实现电化学元件的长寿命化。
附图说明
图1是表示本发明的氢气排出层叠膜的结构的截面示意图。
图2是表示本发明的氢气排出层叠膜的其它结构的截面示意图。
具体实施方式
以下,针对本发明的实施方式进行说明。
作为本发明的氢气排出膜的原料,使用将Pd作为必要金属的合金。形成合金的其它金属没有特别限制,从容易将氢气排出膜的贮氢量调整为0.4(H/M)以下的观点出发,优选使用第11族元素、更优选为选自由金、银和铜组成的组中的至少1种、进一步优选为银或铜。前述合金优选含有20~65mol%第11族元素、更优选为30~65mol%、进一步优选为30~60mol%。另外,通过使用Ag含量为20mol%以上的Pd-Ag合金、或Cu含量为30mol%以上的Pd-Cu合金、Au含量为20mol%以上的Pd-Au合金来形成氢气排出膜,从而即使在50~60℃左右以下的低温区域,氢气排出膜也变得难以脆化。另外,前述合金在不损害本发明的效果的范围内也可以含有IB族和/或IIIA族的金属。
将Pd作为必要金属的合金的晶粒的大小优选为0.028μm以上、更优选为0.04μm以上、进一步优选为0.1μm以上、特别优选为0.4μm以上。若氢气被蓄积在氢气排出膜中,则氢气排出膜的体积发生变化,由于该体积变化而产生应力。晶粒越大,晶粒之间的界面相对越少,越可抑制应力向晶粒之间的界面集中。晶粒的大小越大则越难以发生龟裂等不良状况,因而晶粒的大小的上限值没有特别限制,从需要在电化学元件的内部压力急剧上升时自我破坏而使内部压力降低的观点出发,晶粒的大小优选为1000μm以下、更优选为600μm以下。晶粒的大小能够通过在制作氢气排出膜时进行温度调节而调整为目标大小。具体而言,在制作前述晶粒的氢气排出膜时的温度为50℃~合金熔化的温度。
本发明的氢气排出膜可以通过例如轧制法、溅射法、真空蒸镀法、离子镀法和镀覆法等来制造,但在制造膜厚度较厚的氢气排出膜时,优选使用轧制法,在制造膜厚度较薄的氢气排出膜时,优选使用溅射法。
轧制法既可为热轧,也可为冷轧的任意方法。轧制法是通过使一对或多对辊(roller)旋转,在辊之间一边施加压力一边使作为原料的Pd-Ag合金通过,从而加工成膜状的方法。
通过轧制法而得到的氢气排出膜的膜厚优选为5~50μm、更优选为10~30μm。在膜厚低于5μm时,在制造时变得容易产生针孔或裂纹、或者吸存氢气时变得容易变形。另一方面,若膜厚超过50μm,则由于透过氢气需要时间而使氢气排出性能降低、或者在成本方面差,故而不优选。
溅射法没有特别限定,能够使用平行平板型、单片型、通过型、DC溅射和RF溅射等溅射装置来进行。例如,在设置有Pd-Ag合金靶的溅射装置中安装基板后,对溅射装置内进行真空排气,将Ar气压调整为规定数值,对Pd-Ag合金靶接通规定的溅射电流,在基板上形成Pd-Ag合金膜。然后,从基板上剥离Pd-Ag合金膜而得到氢气排出膜。需要说明的是,作为靶,根据制造的氢气排出膜,可以使用单独一个或多个靶。
作为基板,例如可列举出玻璃板、陶瓷板、硅晶圆、铝和不锈钢等的金属板。
通过溅射法而得到的氢气排出膜的膜厚优选为0.01~5μm、更优选为0.05~2μm。在膜厚低于0.01μm时,不仅有可能形成针孔,而且难以获得所需的机械强度。另外,从基板上剥离时容易破损,剥离后的处理也变得困难。另一方面,若膜厚超过5μm,则制造氢气排出膜需要时间、成本方面差而不优选。
氢气排出膜的膜面积可以考虑氢气透过量和膜厚进行适当调整,但在用作安全阀的构成构件时为0.01~100mm2左右。需要说明的是,本发明中膜面积是氢气排出膜中实际排出氢气的部分的面积,不包括涂布了后述环状的粘接剂的部分。
也可以在氢气排出膜的单面或双面设置支撑体而制成氢气排出层叠膜。特别是通过溅射法而得到的氢气排出膜的膜厚度较薄,因此为了提高机械强度而优选在氢气排出膜的单面或双面层叠支撑体。
图1和2是表示本发明的氢气排出层叠膜1的结构的截面示意图。可以如图1的(a)或(b)所示那样在氢气排出膜2的单面或双面使用环状的粘接剂3层叠支撑体4,也可以如图2的(a)或(b)所示那样使用夹具5将支撑体4层叠在氢气排出膜2的单面或双面。
支撑体4只要是氢气透过性的、能支撑氢气排出膜2的物质就没有特别限定,既可为无孔体、也可为多孔体。另外,支撑体4也可为织布、无纺布。作为支撑体4的形成材料,例如可列举出聚乙烯和聚丙烯等聚烯烃、聚对苯二甲酸乙二酯和聚萘二甲酸乙二醇酯等聚酯、聚砜和聚醚砜等聚芳醚砜、聚四氟乙烯和聚偏氟乙烯等氟树脂、环氧树脂、聚酰胺、聚酰亚胺、聚酰胺酰亚胺、芳族聚酰胺等。这些中优选使用选自由化学稳定和热稳定的聚四氟乙烯、聚砜、聚酰亚胺、聚酰胺酰亚胺和芳族聚酰胺组成的组中的至少1种。
支撑体4的厚度没有特别限定,通常为5~1000μm左右、优选为10~300μm。
在用溅射法制造氢气排出膜2时,若使用支撑体4作为基板,则能够在支撑体4上直接形成氢气排出膜2,能够不使用粘接剂3或夹具5地制造氢气排出层叠膜1,因此从氢气排出层叠膜1的物性和制造效率的观点出发而优选。在此情况下,作为支撑体4,优选使用平均孔径100μm以下的多孔体、更优选为平均孔径5μm以下的多孔体、特别优选使用超滤膜(UF膜)。
本发明的氢气排出膜、复合氢气排出膜和氢气排出层叠膜的形状也可为大致圆形,也可为三角形、四角形、五角形等多角形。能够制成与后述用途相应的任意形状。
本发明的氢气排出膜和氢气排出层叠膜特别是作为铝电解电容器或锂离子电池的安全阀的构成构件是有用的。另外,本发明的氢气排出膜和氢气排出层叠膜也可以作为不同于安全阀的氢气排出阀设置在电化学元件中。
实施例
以下列举实施例对本发明进行说明,但本发明并不限定于这些实施例。
实施例1
〔利用轧制法的氢气排出膜(Ag含量20mol%)的制作〕
以铸锭中的Au含量为20mol%的方式分别称量Pd和Ag原料,投入具备水冷铜坩埚的电弧熔炼炉中,在大气压的Ar气体气氛中进行电弧熔炼。使用辊径100mm的二段轧机对得到的纽扣锭进行冷轧直至厚度为5mm而得到板材。然后,将轧制的板材放入玻璃管中,对玻璃管的两端进行密封。在室温下将玻璃管内部减压至5×10-4Pa,之后升温至700℃放置24小时,之后冷却至室温。通过该热处理,消除了合金中的Pd和Au的偏析。接着,使用辊径100mm的二段轧机对板材进行冷轧直至厚度为100μm,进一步使用辊径20mm的二段轧机对板材进行冷轧直至厚度为25μm。然后,将轧制的板材放入玻璃管中,对玻璃管的两端进行密封。在室温下将玻璃管内部减压至5×10-4Pa,之后升温至700℃放置1小时,之后冷却至室温。通过该热处理,去除了由轧制所产生的Pd-Ag合金内部的应变,制作了厚度25μm、Ag含量20mol%的Pd-Ag氢气排出膜。
实施例2
〔利用轧制法的氢气排出膜(Ag含量40mol%)的制作〕
以铸锭中的Ag含量为40mol%的方式分别使用了Pd和Ag原料,除此以外用与实施例1相同的方法制作了厚度t:25μm、Ag含量40mol%的Pd-Ag氢气排出膜。
实施例3
〔利用轧制法的氢气排出膜(Ag含量60mol%)的制作〕
以铸锭中的Ag含量为60mol%的方式分别使用了Pd和Ag原料,除此以外用与实施例1相同的方法制作了厚度t:25μm、Ag含量60mol%的Pd-Ag氢气排出膜。
实施例4
〔利用轧制法的氢气排出膜(Cu含量53mol%)的制作〕
以铸锭中的Cu含量为53mol%的方式分别使用了Pd和Cu原料,除此以外用与实施例1相同的方法制作了厚度t:25μm、Cu含量53mol%的Pd-Cu氢气排出膜。
实施例5
〔利用轧制法的氢气排出膜(Au含量20mol%)的制作〕
以铸锭中的Au含量为20mol%的方式分别使用了Pd和Au原料,除此以外用与实施例1相同的方法制作了厚度t:25μm、Au含量20mol%的Pd-Au氢气排出膜。
实施例6
〔利用轧制法的氢气排出膜(Au含量30mol%)的制作〕
以铸锭中的Au含量为30mol%的方式分别使用了Pd和Au原料,除此以外用与实施例1相同的方法制作了厚度t:25μm、Au含量30mol%的Pd-Au氢气排出膜。
实施例7
〔利用轧制法的氢气排出膜(Au含量40mol%)的制作〕
以铸锭中的Au含量为40mol%的方式分别使用了Pd和Au原料,除此以外用与实施例1相同的方法制作了厚度t:25μm、Au含量40mol%的Pd-Au氢气排出膜。
实施例8
〔利用溅射法的氢气排出层叠膜(Au含量30mol%)的制作〕
在安装有Au含量为30mol%的Pd-Au合金靶的RF磁控溅射装置(SanyuElectronics Co.,Ltd.制造)中安装作为支撑体的聚砜多孔片(日东电工株式会社制造、孔径0.001~0.02μm)。然后,对溅射装置内进行真空排气直至1×10-5Pa以下,在300℃、Ar气压1.0Pa下,对Pd-Au合金靶接通4.8A的溅射电流,在聚砜多孔片上形成厚度t:400nm的Pd-Au合金膜(Au含量30mol%),制作了氢气排出层叠膜。
实施例9
〔利用溅射法的氢气排出层叠膜(Au含量40mol%)的制作〕
使用Au含量为40mol%的Pd-Au合金靶,除此以外用与实施例8相同的方法形成厚度t:400nm的Pd-Au合金膜(Au含量40mol%)而制作了氢气排出层叠膜。
比较例1
〔利用轧制法的氢气排出膜(Ag含量19.8mol%)的制作〕
以铸锭中的Ag含量为19.8mol%的方式分别使用了Pd和Ag原料,除此以外用与实施例1相同的方法制作了厚度t:25μm、Ag含量19.8mol%的Pd-Ag氢气排出膜。
〔测定和评价方法〕
(贮氢量的测定)
PCT测定装置(JIS H 7201)是在某温度T下测定物质吸存、放出氢时的特性(压力P、贮氢量C)的装置。对于制作的氢气排出膜的各试验片而言,使用Suzuki Shokan Co.,Ltd.制造的PCT测定装置,求出了在50℃、氢分压0.01MPa的条件下进行测定时的贮氢量C(H/M)。
(晶粒的大小的测定)
使用光学显微镜(尼康株式会社制造、ECLIPSE ME600)以倍率50倍对制作的氢气排出膜的表面进行拍摄。并且,使用图像分析软件(美国国立卫生研究所[NIH]开放源代码、“Image J”)进行了拍摄图像的二值化。二值化中,晶粒用明部表示。然后,通过对亮度和对比度进行校正而使晶粒醒目,通过设定阈值而仅选择晶粒得到了二值化图像。接着,使用图像分析软件(Asahi Kasei Engineering Company制造、“A像くん”)分析了得到的二值化图像。需要说明的是,将二值化图像中的明部作为晶粒,从分析对象中排除了与矩形的分析范围(3mm×2mm)的外边缘重叠的晶粒。另外,二值化图像中,在聚集的晶粒的内侧有空隙时,未进行填埋空隙的处理。另外,二值化图像中,未进行使相互接触的晶粒分离的处理。将通过上述操作求得的圆当量直径作为晶粒径(晶粒的大小)。
(氢气透过系数的测定)
将制作的氢气排出膜安装在世伟洛克公司制造的VCR连接器中,在单侧安装SUS管,制作了密封的空间(63.5ml)。用真空泵对管内进行减压后,以氢气的压力成为0.15MPa的方式进行调整,监视了在50℃的环境下的压力变化。由于已知因压力变化而透过氢气排出膜或氢气排出层叠膜的氢气摩尔数,因此将其代入下述式2而计算出氢气透过系数。需要说明的是,用于测定的氢气排出膜的有效膜面积s为3.85×10-5m2。
〈式2〉氢气透过系数=(氢气摩尔数×膜厚t)/(膜面积s×时间×压力的平方根)
(氢气排出膜的不良状况的评价)
用双面粘合带(日东电工株式会社制造、No.5615)将制作的氢气排出膜粘贴于氢气罐而进行固定。然后,以氢气罐的氢分压为0.01MPa的方式进行调整,在50℃的环境下放置12小时。然后,以目视确认氢气排出膜的状态,利用下述基准进行了评价。
○:完全没有变化
×:氢气排出膜从双面粘合带上剥离。
[表1]
产业上的可利用性
本发明的氢气排出膜和氢气排出层叠膜适合用作设置在电池、电容器、电容器和传感器等电化学元件中的安全阀的构成构件。
附图标记说明
1:氢气排出层叠膜
2:氢气排出膜
3:粘接剂
4:支撑体
5:夹具
Claims (10)
1.一种氢气排出膜,其含有将Pd作为必要金属的合金,其特征在于,在50℃、氢分压0.01MPa的条件下测定时的贮氢量为0.4(H/M)以下。
2.根据权利要求1所述的氢气排出膜,其中,所述合金含有20~65mol%第11族元素。
3.根据权利要求2所述的氢气排出膜,其中,所述第11族元素为选自由金、银和铜组成的组中的至少1种。
4.根据权利要求2或3所述的氢气排出膜,其中,50℃的氢气透过系数为1.0×10-13~2.0×10-9(mol·m-1·sec-1·Pa-1/2),且膜厚t和膜面积s满足下述式1:
〈式1〉
t/s<32.9m-1。
5.一种氢气排出层叠膜,其在权利要求1~4中任一项所述的氢气排出膜的单面或双面具有支撑体。
6.根据权利要求5所述的氢气排出层叠膜,其中,所述支撑体为平均孔径100μm以下的多孔体。
7.根据权利要求5或6所述的氢气排出层叠膜,其中,所述支撑体的原料为选自由聚四氟乙烯、聚砜、聚酰亚胺、聚酰胺酰亚胺和芳族聚酰胺组成的组中的至少1种。
8.一种电化学元件用安全阀,其具备权利要求1~4中任一项所述的氢气排出膜、或权利要求5~7中任一项所述的氢气排出层叠膜。
9.一种电化学元件,其具备权利要求8所述的安全阀。
10.根据权利要求9所述的电化学元件,其中,所述电化学元件为铝电解电容器或锂离子电池。
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