CN102668171A - 具有离子捕获分子的碱性电池分隔体 - Google Patents
具有离子捕获分子的碱性电池分隔体 Download PDFInfo
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- CN102668171A CN102668171A CN2010800521600A CN201080052160A CN102668171A CN 102668171 A CN102668171 A CN 102668171A CN 2010800521600 A CN2010800521600 A CN 2010800521600A CN 201080052160 A CN201080052160 A CN 201080052160A CN 102668171 A CN102668171 A CN 102668171A
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- chelating agent
- battery separators
- polymer
- acetic acid
- ion
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Abstract
本发明公开了一种电池分隔体,所述电池分隔体包括含有固定化螯合剂的离子选择性聚合物膜、复合膜、或多层。
Description
技术领域
本发明涉及具有离子捕获分子的碱性电池分隔体。
背景技术
多种高能量密度和/或倍率性能的阴极化学物质(例如,铋氧化物、铜氧化物、高价态铁的氧化物、高价态锰的氧化物)在被配置到具有碱性电解质的电池中时由于自放电而表现出有限的储存寿命。此类电解质的实例包括氢氧化钾、氢氧化钠、氢氧化锂、或它们的组合。自放电有时能够在几天内使得包含化学物质的电池的电压变得不可取地低,或者使得电池容量变为可忽略的。
已试图利用常规的分隔体并利用经过离子选择性改进的分隔体来解决该问题,所述离子选择性即传导氢氧根离子而阻塞金属离子或金属离子络合物。改进的电池分隔体能够包括一个或多个离子捕获层。离子捕获层能够将可溶解的金属(例如,铋离子物质)转化为在电解质中具有降低的溶解性或流动性的铋金属或铋络合物质。该转化通过化学反应或离子键合发生。另一个实例涉及邻近两层分隔体的氧化银阴极,所述两层分隔体包括玻璃纸和非织造层。具有其表面官能度的玻璃纸层牺牲性地将Ag+或Ag+2还原为银金属,从而阻止传输至阳极。作为另外一种选择,离子捕获层可包含有机化合物,例如金属多价螯合剂、螯合剂和络合剂。此类化合物包括例如在碱性电解质溶液中稳定的环糊精化合物和直链多元醇,包括例如木糖醇。此类有机金属离子络合性化合物在一些情况下被接枝或换句话讲被键合到聚合物基质,所述聚合物基质在电解质中是稳定的且不溶解的。此类接枝聚合物已作为涂层而被涂覆到非织造层或可渗透或半渗透膜。
发明内容
本公开特征在于分隔体包含螯合剂以捕集阴极金属离子,从而改善包括分隔体的碱性电池的储存寿命。例如,本文所公开的分隔体对于遭受储存寿命限制的化学物质为有益的,所述限制归因于可电解质溶解的阴极,例如CuO、Bi2O3,以及包含五价铋的金属氧化物。
在一个方面,本公开特征在于包括聚合物膜和固定在聚合物膜内的螯合剂的电池分隔体。电池分隔体具有大于100,例如大于1,000的葛尔莱数。
在另一方面,本公开提供了包括两个纳米多孔层和介于两个纳米多孔层之间的螯合层的电池分隔体。螯合层可包含能够与阴极金属离子形成络合物的螯合剂。
在另一方面,本公开特征在于包括聚合物膜和固定在聚合物膜内的包含羟乙基乙二胺三乙酸的螯合剂的电池分隔体。
在另一方面,本公开提供一种制备电池分隔体的方法。所述方法包括将螯合剂固定在聚合物基质内,以及由所述包含螯合剂的聚合物基质形成膜。
在另一方面,本公开特征在于一种制备电池分隔体的方法。所述方法包括将包含螯合剂的层设置在两个纳米多孔层之间。
实施方案可包括下列一个或多个特征。
电池分隔体可对流体流是基本上不渗透的。
螯合剂可包括环糊精。
螯合剂可包括乙二胺四乙酸衍生物。例如,乙二胺四乙酸衍生物可选自环己烷二胺四乙酸、羟乙基乙二胺三乙酸、三亚乙基四胺六乙酸、乙二醇二乙醚二胺四乙酸、二亚乙基三胺五乙酸、次氮基三乙酸、以及它们的混合物。在一些实施方案中,乙二胺四乙酸衍生物为羟乙基乙二胺三乙酸。
聚合物膜中螯合剂的浓度可为每平方厘米的电池分隔体几何表面积至少0.1μg。
电池分隔体的聚合物可选自聚丙烯酸、聚乙烯醇、聚纤维素、聚苯乙烯磺酸盐、以及它们的混合物。
两个纳米多孔层可具有大于水合氢氧根离子的尺寸且小于螯合剂和络合物的尺寸的孔。
电池分隔体可包含浆液、溶液或悬浮液,并且浆液、溶液或悬浮液可包含载体中的螯合剂。
固定可包括将螯合剂与聚合物混合。
固定可包括使螯合剂与聚合物反应。
反应可包括将螯合剂共价键合到聚合物。
固定可包括首先使螯合剂与材料反应以形成反应产物,并且随后将所述反应产物与聚合物共混。
反应可包括将螯合剂键合到较大的基质分子。
可选择材料来增加螯合剂的水溶性。
所述方法还可包括通过在载体内形成螯合剂的溶液、分散体或浆液而形成螯合层。
本文所公开的分隔体可表现出下列一个或更多个优点。所述分隔体可表现出高碱度下的良好选择性,可还原金属离子的氧化状态,能够由溶液有效地捕集并保留金属离子,并且可在高度碱性电解质中保持其离子捕获能力。
本发明的一个或多个实施方案的细节示出于以下附图和说明中。通过该说明和附图并通过所述权利要求书,本发明的其它特征和优点将显而易见。
附图说明
图1为示出了包括分隔体层的电池的示意图,其中在所述分隔体层中金属离子螯合剂被捕集在纳米多孔层之间。
图1A为图1中圈出的分隔体部分的放大细部图。
图2示出了包含0.35mM(21ppm)Cu2+以及具有不同羟乙基乙二胺三乙酸浓度的1.8mM β-环糊精的0.9M KOH溶液(pH 13.9)的吸收光谱。
图3示出了包含1.9mM(100ppm)Cu2+、具有不同羟乙基乙二胺三乙酸浓度的9mM β-环糊精的5.1M KOH溶液的吸收光谱。
图4示出了包含3.4mM(160ppm)Cu2+、具有不同羟乙基乙二胺三乙酸浓度的16mM β-环糊精的9M KOH溶液的吸收光谱。
具体实施方式
以下描述了优选的离子选择性分隔体以及此类分隔体的制造方法。所述分隔体包含固定化螯合剂。在一些具体实施中,通过使聚合物与螯合剂反应和/或共混以产生包含固定化螯合剂的聚合物膜而形成分隔体。在某些具体实施中,螯合剂被固定在两个纳米多孔层之间。任选地,这些方法可被组合。在这两种情况中,螯合剂被有效地固定,同时保持螯合剂捕集金属离子的能力。
本文所公开的一些优选的分隔体包括连续层,例如具有高螯合剂浓度的相当低流动渗透性的连续层。
分隔体可通过其葛尔莱数或葛尔莱单元测定为具有低的流体流渗透性。即,高的葛尔莱数表明分隔体具有低的流动渗透性。与多孔纸材和非织造物(如美国专利公开6,613,703中所述)不同,本文所公开的连续(例如,基本上低流动渗透性)的分隔体层可具有大于100(例如大于1,000)的葛尔莱数。Gurley Precision Instruments(Troy,NY)已规定了步骤和仪器,例如4150型号。渗透性的葛尔莱单元标准定义于F.Cardarelli的Encyclopaedia of Scientific Units,Weights and Measures,第363页,Springer-Verlag(2003)中。不受理论的束缚,据信大体上连续的层可迫使金属离子处在邻近位于层中的螯合剂的分子尺度内。
一般来讲,螯合剂的浓度为至少0.1μg/cm2(以每分隔体几何表面积的螯合剂质量表示)。任选地,螯合剂的浓度为0.1g/cm2(以每分隔体几何表面积的螯合剂质量表示)。
所谓“离子选择性”是指本文所公开的分隔体能够与例如Cu2+和Bi3+的金属离子络合并降低金属离子的迁移,同时允许氢氧根离子透过。
存在多种方法来将螯合剂(例如环糊精)掺入到用于高能量碱性电池的分隔体中。螯合剂可与聚合物基质物理混合,或者化学反应以使得螯合剂以分子形式掺入到聚合物基质中。
物理混合物可通过例如将螯合剂与聚丙烯酸、聚乙烯醇、或通常用于碱性电池分隔体中的其它聚合物混合而实现。例如:环糊精、聚丙烯酸和乙酸纤维素在甲基乙基酮中的混合物可通过在室温下搅拌多个小时而被制备成均匀的溶液。可改变不同组分在混合物中的比率。其它聚合物(例如聚乙烯醇)也可与环糊精配制成溶液。聚乙烯醇和羟丙基-β-环糊精可在水溶液中于60至80℃下保持整夜而制备。可改变这两种组分的比率以适用于制备分隔体膜的合适粘度。
溶液可用于浇铸5至40密耳厚度的膜。所述膜随后可作为分隔体或与玻璃纸组合作为分隔体。
螯合剂以分子形式掺入到聚合物基质中,这可通过例如将螯合剂共价键合到一种或多种聚合物或单体来实现。例如聚合物(例如纤维素、聚丙烯酸和马来酸酐)可与环糊精共价键合。在乙二胺四乙酸衍生物的情况下,螯合剂可首先被反应到较大的固定基质。例如,螯合剂可共价键合到羧基功能化微球。大多数环糊精分子不是水溶性的。然而,环糊精与水溶性聚合物的组合在分隔体膜的制备中提供实际有益效果。环糊精掺入到聚合物基质中可产生更水溶性且更易制备的分隔体膜。任选地,较大的基质(微球)可通过例如纳米多孔膜的非键合方式包含在分隔体中。在一些实施方案中,可利用具有进一步键合功能的较大分子。然而,即使不键合,利用较大分子也可增加受纳米多孔膜限制的可能性。作为另外一种选择,为了保护用于螯合的所有亲核基团,可优选通过一个或多个碳原子共价键合到聚合物。在一些情况下,可能期望螯合剂与增加螯合剂的水溶解度的材料反应,以便反应产物随后能够与聚合物在水溶液中共混。
例如,环糊精可在氢氧化钠溶液中与环氧氯丙烷共价键合。该水溶性环糊精聚合物可进一步连结到聚乙烯醇以及聚丙烯酸。
共混的聚合物混合物或键合的聚合物基质可流铸或挤出成膜。通过例如控制溶液流铸或挤出的参数,和/或通过与其它层(例如非织造材料)层压,可获得不同厚度的分隔体。这些膜可被制备成例如5至40密耳的厚度。
离子选择性膜一般应于轻微压缩下存储在平坦的干燥表面(例如,加重的纸材)之间以避免膜发生卷绕的倾向。此外,为了避免吸收环境水分并变得粘稠的倾向,膜一般应存储在干燥环境中直至测试或插入电池中。
在一个实施方案中,离子选择性膜可利用β-环糊精(CD)作为螯合剂如下制备:(a)环糊精与聚合物溶液相混合,(b)将所得混合物流铸成分隔体膜,以及(c)干燥以除去溶剂。
现在将讨论合适螯合剂的实例。
螯合剂
A)环糊精
环糊精为由6、7或8个α-1,4-连接的葡萄糖单体组成的环状低聚物。环糊精在结构上为圆环形分子。环糊精分子内的腔体捕集能够被捕集的客体分子或金属离子,从而形成稳定的络合物。已充分证明β-环糊精能够强烈地络合碱性溶液中的金属离子,例如Cu2+、Pb2+、Co2+、Mn3+、Cd2+。其它环糊精(例如α和γ-环糊精)具有与β-环糊精极其相似的特性。环糊精可通过羟基与许多其它聚合物或分子衍生。衍生的环糊精可具有许多期望的化学特性和物理特性。例如,α-羟丙基-β-环糊精可为那些环糊精衍生物中的一种。其具有期望的特性,例如水溶性。
B)乙二胺四乙酸(EDTA)的衍生物
一类相似于乙二胺四乙酸(EDTA)的螯合剂也捕集强碱性溶液中的金属离子。该类中的一些螯合剂为:
反式-环己烷-1,2-二胺四乙酸(CDTA)
羟乙基乙二胺三乙酸(HEDTA)
三亚乙基四胺六乙酸(TTHA)
乙二醇二乙醚二胺四乙酸(EGTA)
二亚乙基三胺五乙酸(DTPA)
次氮基三乙酸(NTA)
乙二醇二乙醚二胺四乙酸和环己烷二胺四乙酸分别在直到pH 13.3和14.2时螯合Cu2+。就三亚乙基四胺六乙酸和羟乙基乙二胺三乙酸而言,检测到直至pH 14.3时螯合活性仍无限制。(例如,根据存在的附加离子,14.3的pH可由约2至3M OH-的溶液来产生。)
申请人已发现羟乙基乙二胺三乙酸在至多5M,可能至多9M的KOH浓度下捕集Cu+2金属离子。该发现的重要性在于此类高度碱性电解质对于显著数量的商业碱性电池是必要的。
将螯合剂限制于纳米多孔层中
螯合剂可被包含在分隔体内的多个层中。此类分隔体的实施方案示出于图1和1A中。此类分隔体可通过多种方法形成。例如,在一些具体实施中,溶液、悬浮液或浆液中的螯合剂层被夹置在两个纳米多孔层之间。水可用作载体。螯合剂的浓度可为例如0.1μg/cm2至0.1g/cm2(以每分隔体几何表面积的螯合剂质量表示)。含水碱性层内的螯合剂可尽可能浓缩同时维持传输OH-离子的能力。在一些实施方案中,所述层可为具有碱性溶液的固体螯合剂颗粒的(多孔)填充层(<0.1g/cm2)。在某些实施方案中,所述层可为溶解于碱性溶液中的螯合剂的饱和或不完全饱和均匀液体(>0.1ug/cm2)。一般来讲,纳米多孔层具有小于螯合剂分子尺寸的孔,所述孔可阻止螯合剂从纳米多孔层之间迁移出。水和氢氧化物可穿过层。螯合剂以及因此络合的金属离子通常将被限定在纳米多孔层内。“螯合层”包含作为固体或溶液中的螯合剂。
如图1A所示,纳米多孔层使得氢氧根离子(OH-)从阴极传输至阳极,但是阻止螯合剂和螯合金属离子络合物的传输。如图所示,来自阴极的金属离子络合物,M(OH)x n可渗透邻近阴极的纳米多孔层,但是其随后被捕集在螯合层内并阻止穿过邻近阳极的纳米多孔层。该方法优于含有固定化螯合剂的膜的优点可在于制备(制造)以及螯合剂的高密度。在一些情况下,螯合剂的该物理限制(尺寸排阻限制)可比共价键合到固定基质或分隔体聚合物上更容易(成本更少、更可靠)。螯合剂的密度为至多~0.1g/cm2,其为粉末状固体的密度。该高负载能够增强金属离子的容量及与螯合剂的接触。
纳米多孔层一般应具有大于氢氧根离子的尺寸且小于螯合剂和络合物的尺寸的孔,以及在高度碱性溶液中的稳定性。
具有期望的孔径范围以及高碱液稳定性的纳米多孔层可通过KochMembrane Systems(Wilmington,Massachusetts)和Somicon(Basel,Switzerland)商购获得。作为孔径的量度,层可根据允许渗透的分子的最大分子量进行分级。螯合剂羟乙基乙二胺三乙酸与β-环糊精各自具有278和1135g/mol的分子量。适当的是,Somicon提供对>200-250g/mol的尺寸是不渗透的并能够在60℃下经受15%的氢氧化钠的层。由Koch提供的膜也具有期望范围内的尺寸限制和高碱液稳定性。具体地讲,命名为MPF-34的产品排斥大于200g/mol的物质,具有大体10密耳的厚度(包括附加支撑层),以及通过至少pH 14的稳定性。就电池功能而言重要的是水(18g/mol)与水合氢氧根离子(~65g/mol)易于渗透这些商业纳米多孔层。要注意的是,孔径对于包含相对于水和氢氧化物较大的螯合分子可为重要的。孔隙率可为次要因素。一般来讲,为了有利于氢氧化物传输,较高的孔隙率可为优选的(例如>50%,例如>75%)。
实施例
实施例I
利用含水的制备方法将螯合剂(β-环糊精)聚合成膜。基本上不溶于水的β-环糊精最初与环氧氯丙烷反应以生成水溶性环糊精(CD)聚合物。β-环糊精在33%的氢氧化钠溶液中于室温下搅拌整夜。将环氧氯丙烷快速加入到搅拌的混合物中。在加入丙酮之前再次搅拌混合物多个小时。除去含水层之后,将混合物的pH调节至中性。经由过滤来收集白色的环糊精聚合物。环糊精与环氧氯丙烷的摩尔比可由1:5改变成1:15。接下来,为了产生可被膜流铸的共混聚合物,将环糊精溶液与苯乙烯磺酸盐-丙烯酸聚合物混合。将通过苯乙烯和丙烯酸的聚合而制备的聚苯乙烯磺酸盐和聚丙烯酸的溶液与由前述步骤获得的环糊精聚合物混合。聚丙烯酸、聚苯乙烯磺酸盐和环糊精的总比率可为50:30:20;40:40:20;20:30:50或22:40:40或其它比率。所述聚合物溶液随后被膜流铸,所得的为具有5至40密耳厚度的离子选择性膜。
在另一个实验中,将水溶性α-羟丙基β-环糊精与聚乙烯醇在水中被混合。一个实例为30%的α-羟丙基β-环糊精与7%的聚乙烯醇在水中于70至80℃下混合多个小时。所得的均匀溶液随后被膜流铸。由于该螯合剂的水溶性的缘故,不必最初使螯合剂反应以增加其溶解度。所得的膜具有5至40密耳的厚度。
实施例II
利用以上实施例I中所述的方法由与苯乙烯磺酸盐-丙烯酸聚合物共混的β-环糊精-环氧氯丙烷聚合物形成的分隔体展示出降低阴极金属离子迁移的能力。将具有15:50:35的PAA:PSS:CD比率的分隔体机械地夹紧到两个9M KOH高度碱性溶液隔室之间的扩散测试夹具中。类似于电解质可溶解的Bi2O3阴极的第一隔室包含饱和的Bi+3溶液而第二隔室最初不含Bi+3。每个隔室中的Bi+3浓度随时间推移的测量以及与仅仅含有苯乙烯磺酸盐-丙烯酸的相同实验的比较提供相对的选择性指示。几周之后从每个隔室取出等分试样的溶液量以用于Bi3+浓度测量。聚合β-环糊精的加入在三至五天的时段内降低Bi3+的迁移接近50%。
实施例III
该实施例展示出乙二胺四乙酸衍生物螯合剂与聚合物的混合。根据以下步骤来制备物理固定的螯合剂羟乙基乙二胺三乙酸的膜:
(1)按下列顺序将成分组合并缓慢搅拌以减少捕集的气泡:
1g羟乙基乙二胺三乙酸(为细粉),
4g聚乙烯醇溶液(水中7.5重量%),
1g 1M的KOH。
在20℃下用实验室搅拌棒(~0.5cm直径)以大致20rpm手动搅拌所述组分。
(2)将所得的浓稠混合物浇铸成膜并在室温(21℃)下存储整夜。所述膜大约30密耳厚且为白色不透明的,其具有可见的固定但不溶解的羟乙基乙二胺三乙酸细小颗粒。
实施例IV
在该实施例中,螯合剂未被固定在分隔体中。然而,该实施例展示羟乙基乙二胺三乙酸(乙二胺四乙酸的衍生物)在5M且可能9M KOH的高度碱性溶液中捕集金属离子的能力。
对于与羟乙基乙二胺三乙酸螯合的Cu2+的检测在各自大约1、5和9MKOH浓度的溶液中进行。首先,制备9M的KOH并使Cu+2饱和(为CuO)。利用Thermo Electron Intrepid II XSP电感耦合等离子体(ICP)光谱仪来测量Cu+2浓度。接下来,通过稀释来制备大约1M和5M的KOH混合物。最终,将β-环糊精和羟乙基乙二胺三乙酸溶解于每个KOH摩尔浓度的样本中以制备图2-4的标题中指示的组合物。利用紫外-可见(UV-Vis)分光光度计,具有1-cm石英比色杯的Agilent 8453系统进行螯合检测。当光谱随着增加的螯合剂量移动时,共同吸光度的波长(等吸收点)表明成功螯合,如对于羟乙基乙二胺三乙酸在图2(0.9M KOH)和图3(5.1M KOH)中所展示的那样。例如,在5M KOH情况下,Cu:HEDTA的浓度比范围为8.6至0.58。在9M KOH中,螯合暗示有可能的等吸收点(参见图4)。较高的Cu2+浓度可能已接近用紫外-可见光谱分析的应用极限。
其它实施方案
已描述了本发明的许多实施方案。然而应当理解,在不背离本发明精神和范围的条件下,可进行各种修改。
例如,可使用其它螯合剂。此外,螯合剂可利用不同于上述那些的技术掺入。
此外,任何期望的材料,包括常规用于电池分隔体中的任何材料和层,均可与本文所述的离子选择性层联合使用。此外,分隔体可具有通常用于一次碱性电池分隔体的任何设计。
例如,在一些实施方案中,分隔体可包括非织造、非膜材料层,例如,两个非织造、非膜材料层,每层各自具有约54克/平方米的基重、干燥时约5.4密耳的厚度以及润湿时约10密耳的厚度。这些层可基本上不含填充剂,例如无机颗粒。在一些实施方案中,分隔体可包含无机颗粒。
在其它实施方案中,分隔体可包括玻璃纸外层以及一个或多个非织造材料层。玻璃纸层可邻近阴极。
因此,其它实施方案在以下权利要求的范围之内。
Claims (15)
1.一种电池分隔体,所述电池分隔体包括:
聚合物膜;和
固定在所述聚合物膜中的螯合剂,
其中所述电池分隔体具有大于100的葛尔莱数。
2.如权利要求1所述的电池分隔体,其中所述电池分隔体具有大于1,000的葛尔莱数。
3.如权利要求1-2中的任一项所述的电池分隔体,其中所述电池分隔体对流体流是基本上不渗透的。
4.如权利要求1-3中的任一项所述的电池分隔体,其中所述螯合剂包括环糊精。
5.如权利要求1-3中的任一项所述的电池分隔体,其中所述螯合剂包括乙二胺四乙酸的衍生物。
6.如权利要求5所述的电池分隔体,其中所述乙二胺四乙酸衍生物选自由下列组成的组:环己烷二胺四乙酸、羟乙基乙二胺三乙酸、三亚乙基四胺六乙酸、乙二醇二乙醚二胺四乙酸、二亚乙基三胺五乙酸、次氮基三乙酸、以及它们的混合物。
7.如权利要求6所述的电池分隔体,其中所述乙二胺四乙酸衍生物为羟乙基乙二胺三乙酸。
8.如权利要求1-7中的任一项所述的电池分隔体,其中所述聚合物膜中的螯合剂浓度为每平方厘米所述电池分隔体几何表面积至少0.1μg。
9.如权利要求1-8中的任一项所述的电池分隔体,其中所述聚合物选自由下列组成的组:聚丙烯酸、聚乙烯醇、聚纤维素、聚苯乙烯磺酸盐、以及它们的混合物。
10.一种制造电池分隔体的方法,所述方法包括:
将螯合剂固定在聚合物基质中;以及
由包含所述螯合剂的聚合物基质形成膜。
11.如权利要求10所述的方法,其中固定包括将所述螯合剂与聚合物混合。
12.如权利要求10所述的方法,其中固定包括使所述螯合剂与聚合物反应。
13.如权利要求12所述的方法,其中反应包括将所述螯合剂共价键合到所述聚合物。
14.如权利要求10所述的方法,其中固定包括首先使所述螯合剂与材料反应以形成反应产物,并且随后将所述反应产物与聚合物共混。
15.如权利要求14所述的方法,其中反应包括将所述螯合剂键合到较大的基质分子。
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US10581117B2 (en) | 2017-07-07 | 2020-03-03 | GM Global Technology Operations LLC | Iron ion trapping van der Waals gripper additives for electrolyte systems in lithium-ion batteries |
US10581119B2 (en) | 2017-07-07 | 2020-03-03 | GM Global Technology Operations LLC | Polymeric ion traps for suppressing or minimizing transition metal ions and dendrite formation or growth in lithium-ion batteries |
CN108110193A (zh) * | 2017-12-22 | 2018-06-01 | 武汉惠强新能源材料科技有限公司 | 一种具备铁离子吸附功能的锂电池隔膜涂层及其制备方法 |
CN108110193B (zh) * | 2017-12-22 | 2021-03-02 | 武汉惠强新能源材料科技有限公司 | 一种具备铁离子吸附功能的锂电池隔膜涂层及其制备方法 |
CN108305974A (zh) * | 2018-01-05 | 2018-07-20 | 河南惠强新能源材料科技股份有限公司 | 一种基于静电纺丝法的功能型锂离子电池隔膜及其制备方法 |
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US20110117413A1 (en) | 2011-05-19 |
US20130130093A1 (en) | 2013-05-23 |
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EP2502294A1 (en) | 2012-09-26 |
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