CN102027630A - 具有锂介质的铁-空气蓄电池 - Google Patents
具有锂介质的铁-空气蓄电池 Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title description 10
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 38
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 29
- 239000011149 active material Substances 0.000 claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 23
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- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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Abstract
本发明涉及半蓄电池,其包含:(a)电极,其由电子集电极(3)和电化学活性材料(4)形成,所述电子集电极(3)包含周期表第4族至第12族的一种或多种过渡金属,所述电化学活性材料(4)在所述电子集电极的表面上被提供并以包含纳米粒子的纳米结构转化层的形式存在,所述纳米粒子的平均直径为1nm至1000nm,所述电化学活性材料包含在所述电子集电极中提供的所述过渡金属的至少一种化合物;以及(b)能够传导锂离子的固体电解质(5)的连续层,所述连续层为不透水和空气,并且完全覆盖在电极(a)的纳米结构活性材料的表面。本发明还涉及电化学发电机,其包含这样的半蓄电池优选在含LiOH的水性电解质存在下作为负极。
Description
本发明涉及新型电化学发电机,其包含由纳米结构的活性材料和锂离子导电固体电解质制成的负极,该固体电解质覆盖着所述电极的活性材料,所述发电机还包含水性电解质(aqueous electrolyte)(其包含锂离子)、空气电极以及氧发射电极(oxygen-emitting electrode)。
蓄电池的比能量密度(以Wh/kg表示)仍然是限制它们在诸如便携式电器或电动汽车等的便携式设备中使用的主要因素。这些蓄电池的有限能量与制备它们的材料的性能有很大关系。目前可用的负极材料通常具有的比容量为300Ah/kg至350Ah/kg。对于正极材料,该值仅为约100Ah/kg至150Ah/kg。
使用空气电极作为正极允许超过这样的上限,并由此提高了电池每单位质量的容量。
本申请人的法国专利申请FR2870639描述了用于锂离子或锂-金属电池的电极,该电极的特征在于,在电子集电极的表面上的包含纳米粒子的纳米结构电化学活性材料膜,所述纳米粒子由诸如形成所述电子集电极的金属的氧化物形成。电化学活性材料的特殊结构改善了关于动力和每单位质量的能量密度方面的性能。
本申请人的专利申请FR2901641涉及在FR2870639中描述的电极改进。这种改进存在于所述电极的织物结构中并导致了包含该织物结构的电池的每单位质量能量密度显著提高。织物结构的每根线优选为机织结构,所述机织织物结构是由金属中心部分(电子集电极)和纳米结构的表面转化膜(电化学活性材料)形成。
当本申请人试图将如在申请FR2870639和FR2901641中所述的负极的纳米结构电极与正空气电极相联系时,面临了负极不稳定的问题。这是因为空气电极的使用以水性电解质的存在为先决条件。如果负极与水性电解质的水接触,则水被还原为氢并且不可逆地腐蚀了负极。
因此,事实证明必须设计将在申请FR2870639和FR2901641中描述的那些类型的负极从含锂的水性电解质中有效分离的装置,所述装置对于正空气电极的运行是必不可少的。
使用以薄膜的形式沉积在纳米结构阳极上的锂离子导电固体电解质使这种分离成为可能。
因此,本发明的主题为半电池,其包含:
(a)电极,其由电子集电极和电化学活性材料形成,所述电子集电极包含元素周期表的第4族至第12族中的一种或多种过渡金属,所述电化学活性材料以包含纳米粒子的纳米结构转化膜的形式存在于电子集电极的表面上,所述纳米粒子的平均直径为1nm至1000nm,所述电化学活性材料包含存在于电子集电极中的过渡金属的至少一种化合物;以及
(b)锂离子导电固体电解质的连续膜,所述连续膜不透水和空气,并且以完全覆盖的方式直接沉积在所述电极(a)的纳米结构活性材料的表面上,固体电解质的所述连续膜的厚度为1μm至50μm。
本发明的另一主题是包含至少一个这样的半电池作为负极的电化学发电机。
如专利申请FR2870639所解释的,包含纳米粒子的纳米结构膜为转化膜,即通过形成通行集电极的金属材料表面的化学或电化学转化获得的膜,所述纳米粒子为存在于电子集电极中的过渡金属的至少一种化合物。特别地,这样的转化膜的已知优点是形成的表面膜的良好粘合性以及这样的膜可以通过对起始金属的简单处理来制备的巨大便利性。
在本发明的优选实施方案中,所述电极(a)具有由金属线和形成所述电极的活性材料的纳米结构表面转化膜形成的织物结构。
然后与电极的微细织物结构有关的特殊优点被加入到了转化膜的已知优点中。具体地,在电化学活性材料的形成过程中,保留了电极的织物结构,即织物上的开口或孔隙没有被活性材料的沉积阻塞的危险。这样的阻塞实际上将降低这样的织物结构的内在优势。由于开口小,这种阻塞织物中开口的风险自然更增加了。通过形成转化膜来制备活性材料限制了阻塞织物中开口的风险,这是由于从外部没有提供金属或其他材料,由此电极(电子集电极+活性材料)的微观尺寸(直径和线间距)基本上与所用的初始金属织物的微观尺寸相同。
用于形成本发明电极的金属线织物可以为机织织物、非机织织物或针织织物。优选为机织织物。
用于形成本发明电极的金属织物优选由很细的线制成,相互间隔较紧密。这是因为线越细,每单位面积的线的数量越多,因此电极的BET(Brunauer-Emmett-Teller)比表面积越大。
通常,形成初始织物的金属线或纤维的横截面或者覆盖活性材料转化膜的织物电极线的横截面的等效直径为3μm至1mm,优选为7μm至100μm,尤其是10μm至50μm。表达“等效直径”可理解为与线的横截面具有相同面积的圆的直径。
形成本发明电极的线的小等效直径有利地使电极的质量受到限制以便在蓄电池中使用。因此,有利地,由覆盖转化膜的电子集电极形成的本发明电极的每单位面积质量小于几何面积的1000g/m2,优选为几何面积的10g/m2至500g/m2,所述几何面积为微观尺寸上金属织物的面积。因此,这种几何面积独立于织物的微细结构。
优选地,电子集电极的过渡金属选自镍、钴、锰、铜、铬和铁。在这些金属中,铁是特别优选的。
在形成活性材料的转化膜的形成过程中,通过下文更详细描述的适当处理,将这些金属转换成所述过渡金属的化合物。有利地,这种化合物选自硫族元素和卤素,优选选自硫族元素(氧、硫、硒和碲),并且特别优选地,转化膜中存在的金属化合物为金属氧化物。
在本发明特别优选的实施方案中,金属氧化物符合通式:MxOy,其中1≤x≤3并且1≤y≤5,优选为1≤y≤4,并且M为至少一种过渡金属。优选地,这种化合物选自尖晶石结构AB2O4和/或选自倍半氧化物M’2O3,其中A为选自Fe、Mn、Cr、Ni、Co和Cu中的至少一种过渡金属,B为选自Fe、Cr和Mn中的至少一种金属,M’为选自Fe、Mn、Cr、Ni、Co和Cu中的至少一种过渡金属。
特别地,该过渡金属化合物为Cr2O3或者符合通式:Fex’Cry’Mnz’O4的化合物,其中0≤x’≤1,0≤z’≤1,且x’+y’+z’=3。
优选地,M的化合价等于2或3,特别是等于3。通式Fex’Cry’Mnz’O4的化合物包括诸如通式Fex’Cr1-x’Cr2O4的化合物(其中x’为如上所示的值)和通式Fex’Ni1-x’O4的化合物(其中x’为如上所示的值)。
如上所述,本发明所使用的织物电极的转化膜是“纳米结构”膜,其包含纳米粒子,所述纳米粒子的平均直径为1nm至1000nm,优选10nm至300nm。这样的纳米结构层的特征是粗糙多孔结构,并且包含至少50wt%的纳米粒子,优选至少70wt%的纳米粒子。
在织物电极的转化膜中,优选将纳米粒子重新组合并相互聚成集块,优选地,集块的平均大小为1nm至10,000nm,尤其是10nm至3000nm。例如可通过扫描电镜来证明纳米粒子集块的基本多孔结构。
优选地,转化膜(电化学活性材料)覆盖电子集电极的整个表面,并且优选地,所述转化膜的厚度为30nm至15,000nm,尤其是30nm至12,000nm。
根据一个特别有利的实施方案,电子集电极是由基于铁的合金形成的织物,所述合金可以被拉成很细的线,例如像316L钢的奥氏体钢。
在如上所述的纳米结构转化膜形成之后,基于能用作电池负极的过渡金属的金属织物是本领域已知的,并且是可商购的,例如以下列名称商购:方网眼平织、方网眼斜织、维重平织、维重斜织、经重平织以及经重斜织。
在申请FR2870639中描述了纳米结构转化膜的形成。在该文献中所使用的处理无需进一步的预措施或改进就可施用于上述的金属织物。例如,所述转化处理为在还原、中性或氧化的气氛中的高温热处理。对于本领域技术人员这些处理是已知的并且目前正在使用。
例如,所述处理可以是在氢中,在500℃至1000℃,优选600℃至800℃,例如接近700℃的温度下,持续时间为1min至16h的处理。
也可以是在空气中,在例如600℃至1200℃,优选800℃至1150℃,例如接近1000℃的温度下,持续时间为1min至16h的热处理。
由氧化或还原热处理形成的转化膜通常不具有所期望的确定的纳米结构。电极的最终纳米结构即纳米粒子的形成仅发生在电池的第一次放电过程中。当然织物电极可能在并入到锂蓄电池之前经历这样的放电。例如可通过将相对于的锂电极的织物电极在包含锂盐的有机电解质中,在还原电流密度(电极几何面积的0.05mA/cm2至0.5mA/cm2)高达相对于锂的20mV电势下还原,然后通过将所述织物电极在还原电流密度(电极几何面积的0.05mA/cm2至0.5mA/cm2)高达相对于锂的3000mV电势下氧化来发生这种第一次放电。
用锂离子导电固体电解质涂覆本发明中所用的负极遍及能够与液体电解质接触的所述负极的所有表面。这种固体电解质在电化学发电机的使用条件下必须是不透水和空气的。所述固体电解质直接沉积在电极的纳米结构转化膜上。
在本发明优选的实施方案中,所述锂离子导电固体电解质为陶瓷制品。
能够形成锂离子导电固体电解质的陶瓷制品本身是已知的。例如由Ohara出售的名称为LISICON(锂超离子导体)和LIC-GC的陶瓷制品。它们是具有如下组成的材料:Li1+x(M,Al,Ga)x(Ge1-yTiy)2-x(PO4)3或Li1+xAlxTi2-x(PO4)3。例如在J.Fu的文章,Solid State Ionics,96,(1997),第195-200页中描述了这些材料。可以通过电泳或通过反应溅射法来沉积这些材料的薄膜。
在另一实施方案中,通过沉积到负极上后吸收了含不可水解锂盐的疏水离子液体的疏水聚合物微孔膜或无孔膜来形成所述锂离子导电固体电解质。
例如可通过在由丙酮、碳酸丙烯酯和PVDF-HFP组成的溶液中浸涂负极,接着蒸发掉丙酮并随后在120℃下真空蒸发掉碳酸丙烯酯的来沉积这种疏水聚合物的微孔膜。
例如可通过诸如由PPG提供的Catolac ED 5000的胺改性环氧树脂的电透法(施加2秒至300秒的2V/cm至10V/cm的电场),然后使其交联(例如在150℃下持续15分钟)来沉积聚合物的无孔膜。
疏水离子液体的实例可以由1-乙基-3-甲基咪唑双(三氟甲磺酰基)亚胺(EMI TFSI)、1-丙基-3-甲基咪唑双(三氟甲磺酰基)亚胺(PMITFSI)、1-乙基-3-甲基咪唑双(五氟乙磺酰基)亚胺(EMI BETI)或1-丙基-3-甲基咪唑双(五氟乙磺酰基)亚胺(PMI BETI)或它们的混合物制成。此外,疏水离子液体还优选包含0.1M至1M的不可水解锂盐,所述不可水解锂盐例如双(三氟甲磺酰基)亚胺锂(LiTFSI)、双(五氟乙磺酰基)亚胺锂(LiBETI)或者双(氟磺酰基)亚胺锂(LiFSI)。
优选地,覆盖负极活性材料的锂离子导电固体电解质膜的厚度为1μm至50μm,尤其是1.5μm至30μm,并且理想为2μm至10μm。
当负极为织物电极时,在固体电解质沉积后电极的所述织物结构仍然明显不总是必需的。换言之,固体电解质可以部分地或甚至完全地填充负极中的开口或孔隙,然后具有连续片形式的半电池将所述织物电极围起来。
然而,在本发明的半电池的特殊实施方案中,锂离子导电固体电解质膜的厚度足够薄以至于电极织物结构中的孔隙是不闭合的,换言之,在固体电解质沉积后电极织物结构仍然清晰可见,并且半电池具有诸如方格的格状外观。在含一堆多个半电池的电化学发电机中,当导电方向垂直于堆砌的半电池的平面时,这种半电池的孔隙结构是有益的。
在纳米结构负极表面上沉积成薄膜的固体电解质必须符合负极有时可观的体积变化而不开裂。固体电解质的开裂实际上将导致负极的快速降解。固体电解质的陶瓷性质意味着其不具有足够的弹性来承受电极的体积变化。
为了解决该问题并且防止固体电解质开裂,将其沉积在被小空隙隔开的多个相互临近的区域中的负极的纳米结构表面上,随后将用不与液体电解质相容或渗透的材料填充所述小空隙,所述材料比固体电解质更可变形,更有可塑性或弹性。例如这样的材料可以为疏水有机聚合物,优选为交联有机聚合物。优选地,用所述疏水聚合物填充的空隙覆盖负极纳米结构表面的不足20%,更优选不足10%。
虽然本发明研究了“完全覆盖电极纳米结构活性材料表面的固体电解质的连续膜”,其还包括这种实施方案,其中在膜的某些区域中,用能够吸收电极体积变化的疏水聚合物代替固体电解质。优选地,通过电透法将该聚合物沉积在没有被陶瓷覆盖的间隙中。事实上本领域技术人员会理解,为了使发电机正确运行,水性液体电解质基本上不与负极接触并且能够阻止这种接触是必要的
-或者通过锂离子导电固体电解质的连续膜阻止这种接触,
-或者通过锂离子导电固体电解质以及对水性电解质不渗透的疏水聚合物的不连续沉积形成的连续膜阻止这种接触,这种疏水聚合物填充锂离子导电固体电解质间的空隙。
如介绍所述,本发明的主题还包括电化学发电机,其包含一个或多个如上所述的半电池。
除了如上所述的一个或多个半电池,这样的电化学发电机还包含:
-含LiOH的水性电解质,所述半电池浸渍在其中;
-空气电极,其与含LiOH的水性电解质接触;以及
-氧发射电极,其同样与含LiOH的水性电解质接触。
在发电机的放电(空气中的氧还原为氢氧离子)过程中,所述空气电极起正极的作用。空气电极是已知的。在本发明中,优选使用空气电极,所述空气电极包含(i)碳粉,其中已经分散了诸如二氧化锰、热解的钴卟啉(CoTMPP)、铂或银的催化剂的细粒子;(ii)疏水有机粘接剂,例如聚四氟乙烯;以及(iii)微孔隔离器,其作用为在允许水性电解质透过的同时,使氧发射电极与空气电极电隔离。这样的微孔隔离器的实例可由商购产品Celgard制成,Celgard为基于聚乙烯/聚丙烯的微孔材料。
适当的空气电极例如由E-Tek和Electric Fuel Ltd(Arotech公司)出售的合适的空气电极,以及例如在国际专利申请WO 2000/036676中描述的合适的空气电极。
在发电机的充电过程中,氧发射电极代替空气电极。所述氧发射电极由不被水性电解质腐蚀的金属制成,例如,所述金属为诸如316L钢的不锈钢。例如通过电泳或溅射热解可使催化剂沉积在所述电极表面上以便降低氧发射的超电势,例如,所述催化剂为诸如NiCo2O4的金属氧化物。
其中浸渍了一个或多个半电池、空气电极以及氧发射电极的水性电解质为氢氧化锂(LiOH)的水溶液。
本发明的电化学发电机的空气电极的每单位面积容量没有限制发电机的容量,这是由于氧没有被储存,而是取自空气。
与此相反,甚至当负极是织物电极时,其有限的每单位面积容量为0.5mAh/cm2至5mAh/cm2,最通常为1mAh/cm2至2mAh/cm2。
为了尽可能提高电化学发电机的容量,因此强烈推荐使用多个半电池(每一半电池由电极,优选织物电极形成,所述电极具有纳米结构转化膜并用锂离子导电固体电解质涂覆)。优选堆砌并平行电连接这些半电池。将由此获得的组合体浸渍在由LiOH水溶液形成的水性电解质中。当LiOH浓度处于最低时,可添加诸如KOH的载体盐(support salt)以确保水性电解质在充电循环结束时具有良好的离子电导性。当Li+阳离子的扩散方向垂直于堆砌的半电池平面时,重要的是半电池具有孔隙结构,这就是说固体电极已经被沉积成用于维护织物电极孔隙结构的足够薄的膜。这需要保证Li+离子和OH-离子的自由扩散并避免形成导致电池内阻升高的浓度梯度。
然而,如图1所示的,当锂离子的扩散路径平行于堆砌的半电池平面时,氢氧离子和锂离子能够通过分隔半电池的间隙自由地在这些半电池和空气电极或氧发射电极间迁移。
使用图1和图2所示的两个实施方案分别更详细地描述本发明。
图1显示含四个半电池1的本发明的电化学发电机。每一半电池由具有经线2a和纬线2b的机织织物电极10形成。每一经线和纬线由对应于电子集电极3的中心部分和对应于电化学活性材料4的周围部分组成。织物电极的横截面穿过两个相邻的经线,并由此电子集电极3仅在机织结构的纬线2b中是可见的。每一织物电极由固体电解质5围绕,所述固体电解质5完全包围织物电极以使该电极与浸渍了四个半电池1的水性液体电解质6隔离。这里,固体电解质5的沉积使得半电池具有填充结构,并且不具有反映所述固体电解质包围的电极10织物结构的孔隙网格型结构。
两个具有机织织物结构的氧发射电极7像纳米结构电极10(负极)一样也浸渍在水性液体电解质6(LiOH)中。氧发射电极7是由不锈钢形成的,但它与负极不同,其不包含纳米结构转化膜。电化学发电机还包含通过膜9与水性液体电解质6隔离的两个空气电极8,所述膜9可以为微孔隔离器或阴离子聚合物。在该实施方案中,导电方向通常平行于四个堆砌的半电池1的平面并且垂直于氧发射电极7的平面。因此,Li+和OH-离子可以在处于半电池1之间的空隙中的液态电解质中自由地迁移,并且不会被半电池不具有孔隙网格型结构的事实扰乱。氧发射电极7的织物结构保证了在放电过程中纳米结构电极10和空气电极8之间的阳离子和阴离子的自由流动。
图2显示了本发明的电化学发电机的另一实施方案。该实施方案与图1实施方案的主要区别在于各种不同电极的相对排列。在该实施方案中,将四个半电池1彼此平行放置。它们也平行于氧发射电极7和空气电极8。因此,这里Li+离子和OH-离子的扩散方向垂直于半电池的平面并且半电池必须具有孔隙结构,就是说固体电解质的沉积必须足够薄从而不堵塞负极10的织物结构中的开口。
Claims (12)
1.半电池,其包含:
(a)电极,其由电子集电极和电化学活性材料形成,所述电子集电极包含元素周期表第4族至第12族的一种或多种过渡金属,所述电化学活性材料以包含纳米粒子的纳米结构转化膜的形式存在于所述电子集电极的表面,所述纳米粒子的平均直径为1nm至1000nm,所述电化学活性材料包含存在于所述电子集电极中的所述过渡金属的至少一种化合物;以及
(b)锂离子导电固体电解质的连续膜,所述连续膜不透水和空气,并且以完全覆盖的方式直接沉积在所述电极(a)的所述纳米结构活性材料的表面上,所述固体电解质的连续膜的厚度为1μm至50μm。
2.如权利要求1所述的半电池,其特征在于,所述电极(a)具有由金属线和形成所述电极的活性材料的纳米结构表面转化膜形成的织物结构。
3.如权利要求1或2所述的半电池,其特征在于,所述织物结构为机织结构。
4.如权利要求2或3所述的半电池,其特征在于,由活性材料转化膜覆盖的所述金属线横截面的等效直径为3μm至1mm,优选7μm至100μm,尤其是10μm至50μm。
5.如前述权利要求中任一权利要求所述的半电池,其特征在于,所述锂离子导电固体电解质为陶瓷制品。
6.如权利要求1至4中任一权利要求所述的半电池,其特征在于,所述锂离子导电固体电解质为吸收了含不可水解锂盐的疏水离子液体的疏水聚合物膜。
7.如前述权利要求中任一权利要求所述的半电池,其特征在于,所述锂离子导电电解质膜(b)的厚度为1μm至50μm,优选1.5μm至30μm,尤其是2μm至10μm。
8.如权利要求2至7中任一权利要求所述的半电池,其特征在于,所述锂离子导电固体电解质膜(b)的厚度足够薄以至于由所述电极(a)形成的所述织物结构中的孔隙是不闭合的。
9.如前述权利要求中任一权利要求所述的半电池,其特征在于,所述电子集电极含有铁,并且形成所述活性材料的所述表面转化膜含有氧化铁。
10.电化学发电机,其包含至少一个如前述权利要求中任一权利要求所述的半电池。
11.如权利要求10所述的电化学发电机,其特征在于,所述电化学发电机还包含:
-含LiOH的水性电解质;
-空气电极,其与所述含LiOH的水性电解质接触;以及
-氧发射电极,其与所述含LiOH的水性电解质接触。
12.如权利要求11所述的电化学发电机,其特征在于,所述含LiOH的水性电解质为LiOH的水溶液。
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