CN105693566B - 用于制备用于电化学器件的新型单离子导电聚合物家族的新型交联剂以及所述聚合物 - Google Patents
用于制备用于电化学器件的新型单离子导电聚合物家族的新型交联剂以及所述聚合物 Download PDFInfo
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Abstract
本发明涉及将一种特定交联剂、碱金属二(苯乙烯磺酰基)亚胺单体用于合成单离子导电共聚物,该共聚物是非氟化的且非PEO基的。这类共聚物用作固体聚合物电解质(SPE)时满足安全和成本要求。它们是碱金属离子电池中的标准液体电解质的有希望的替代物,这是因为它们具有改进的安全和阻燃性能。所述共聚物为聚乙烯基磺酸盐或丙烯酸酯乙烯基磺酸盐嵌段共聚物。优选丙烯酸酯单体为甲基丙烯酸酯,优选乙烯基磺酸盐为苯乙烯磺酸盐。共聚物通过将乙烯基磺酸盐和交联剂以及任选丙烯酸酯自由基聚合,尤其是使用官能化二(酰基)膦氧化物(BAPO)作为光引发剂的自由基光聚合而制备。本发明还描述了这类共聚物在锂离子电池中作为固体聚合物电解质的用途。
Description
技术领域
本发明涉及适用于制备导电共聚物的交联剂以及所述共聚物,所述共 聚物适用于锂离子电池。
背景技术
全电和混合动力汽车的开发已经成为长期可持续发展的迫切需求[1]。 在不远的将来,最重要的挑战是找到安全、廉价且有效的电池技术,该技 术为电动汽车提供延长的驾驶里程(>300km)。相应的能量密度的增加要求 开发用于活性电极材料和电解质的新型化学物质[2]。金属锂为最终阳极并 且为补偿正空气(O2)或硫阴极以及利用这些阴极高比容量的唯一选择[3]。 然而,将金属锂与液体电解质接触使用导致重要的安全问题,所述问题与 再充电过程中形成不规则的金属锂电沉积相关。这会导致与爆炸危险有关 的树枝体的形成。为了满足电动汽车大宗市场的要求,锂离子电池必须改 进与热不稳定性[4],形成可燃性反应产物,可能的泄露,以及内部短路相 关的安全问题。固态电解质是缓和锂树枝生长的完美解决方案[5]。使用固 体聚合物电解质(SPE)(其中锂盐与极性聚合物基质相连)可解决大部分上 述安全问题。此外,还有与电池加工相关的其他优点,如层压(金属锂、电 解质、复合物、阴极)、堆叠和真空密封会变得更容易并且用聚合物电解质 会使得成本更有效。
在过去50年中,已经考虑将许多聚合物/锂盐体系用于替换锂离子电池 中液体电解质。开发合适聚合物材料的困难在于设计下述聚合物的能力, 该聚合物结合了高离子电导率和良好的机械性能[6]。最广泛研究和使用的 体系基于溶于聚氧乙烯(PEO)的非质子聚合物基质的氟化盐,所述聚合物 含有能够离解盐的醚配位点以及有助于离子传输的柔性大分子结构。然而, PEO结晶区域的存在干扰了离子传输(离子传输要求无定形相)[7]。在高温 下(大于65℃),大多数PEO基聚合物变为粘稠液体并失去它们的尺寸稳定 性[8]。此外,PEO-氟化盐体系中,锂离子运动仅携带了总离子电流的一小 部分(1/5),这在电池操作过程中导致有利于树枝生长的强浓度梯度,这限 制了功率释放[9]。为此,优选单离子聚合物,其中仅Li+迁移负责聚合物的 离子导电。
在过去数年中,将不同类型的聚合物共混或直接共聚广泛用于满足 SPE聚合物的离子电导率和机械性能相关的要求。共聚物路线的优点在于 可通过将结构单元官能化而设计机械性能如硬度/延展性,所述官能化可引 入新的聚合物单元。通过将不同功能的单元组合,可改进锂电导率和对抗 碱金属的电化学稳定性。聚合物链的可运动性可通过将聚合物与增塑剂结 合而改进,从而可避免聚合物致密堆积和结晶。
然而,到目前为止还未能提供令人满意的满足机械和电导率需求的导 电聚合物。因此,本发明的目的是提供单体、单体组合物和单离子固体共 聚物电解质,其具有改进的电导率和/或机械性能。
发明内容
因此,本发明总的目的是提供一种适合在单离子固体共聚物电解质的 制备中作为共聚单体的交联剂。
为了实现本发明的这些和其他目的(它们会随着说明书的展开而更变 得清晰),交联剂的特征在于其为二(苯乙烯基磺酰亚胺)碱金属盐,即如下 式(I)化合物:
其中M+为Li+或Na+。
本发明优选盐为锂盐。
该交联剂尤其适用于制备单离子导电聚合物(也称作(单离子)导电(共) 聚合物或(单离子)导体(共)聚合物,或如果用于电池应用,(单离子)导电(固 体)电解质或仅固体电解质)。
在单离子固体共聚物电解质的制备中,可使用任意自由基引发剂,即 热活化和UV活化自由基引发剂以及热活化和UV活化自由基引发剂的混合 物。这类热活化和/或UV活化引发剂可形成一个或优选两个自由基。
合适的光引发剂包括α-羟基酮、二苯甲酮、苄基衍生物、噻吨酮、乙 酰基膦或尤其是酰基膦氧化物。乙酰基膦,尤其是乙酰基膦氧化物允许在 较高材料深度下的高固化速率。本发明优选乙酰基膦类型或酰基膦氧化物 类型的光引发剂,它们例如描述于WO2006/056541、WO2011/003772和 WO2014/053455。此处引入这些文献的全文作为参考。
酰基膦氧化物类型的光引发剂的通式结构由下式(II)表示:
在该光引发剂中:
n为1-6,优选n等于1、2、3或4,更优选1或2,
m为1或2,
X为氧或硫,
R1为–C(R4)3,其中
如果n=1,
则所有R4相互独立地选自:
-H,
-芳族基团
-链烯基,和
-脂族基团,其中脂族基团可以是未支化或支化的,未被取代或被 一个或多个如下基团取代:芳族基团、杂芳族基团、杂环基团、醚(聚 乙二醇或聚氧乙烯)、硒化物(selenide)、羟基、硫醇基、酮、亚胺、羧 酸衍生物、砜、亚砜、硫酸根、锍、硫亚胺、亚砜亚胺、磺酰胺、胺、 铵盐、腈、硝基、脒、氨基甲酸酯、胍离子(guanidinium)、腙、酰肼、 肼、硅烷、硅氧烷、聚硅氧烷、亚膦酸酯、氧化膦或磷酸酯基团。
如果n>1,尤其是n为2-6,优选n为2、3或4,
则至少一个R4为2-6价的选自上文所列的取代基,其中上述烷基 也可在链中包含一个、两个或更多个上述基团,即脂族链可以被上述 官能基团间隔(或互联)一次、两次或更多次,或者被这些基团取代一次 或多次,其中所述基团不是连续的,即被至少一个CH2基团隔开,
R2为芳基,优选2,4,6-三甲基苯基(基)或2,6-二甲氧基苯基,和
R3为如上对R1所述的C(R4)3。
这些光引发剂可以与相同种类和/或与其他种类的光引发剂组合。优选 引发剂为双(酰基)膦氧化物(BAPO)。这类BAPO可以与补充BAPO固化性 能的引发剂,如α-羟基酮、二苯甲酮、苄基衍生物、噻吨酮或其他酰基膦 氧化物一起使用。
在本发明优选实施方案中,自由基引发剂为适合产生两个自由基的光 引发剂,尤其是上述式(II)光引发剂,其中:
n为1,
m为2,
X为O
R1为-CH2-CH2(Z),
Z为–(CH2)n1-NMe3X’+,其中n1为1-4,更优选1-3,以及X’为Cl、 Br或I,优选Br,
Z为酯-(CO)OR6,其中
R6为烷基,其在链中包含一个或多个-O-(如聚乙烯基团)或所述烷基链 被一个或多个-O-(如聚乙烯基团)间隔,或带有一个或多个甲硅烷氧基团如 –SiR7 y(OR8)3-y,其中y为0-3,或带有一个或多个铵盐基团如-N(R9)4+X’-, 其中X’如上所定义,其中
R7、R8和R9为烷基,优选C1-C4烷基,和
R2为基或2,6-二甲氧基苯基,更优选基,
或
n为2,
m为2,
R1为-(CO)O-(CH2-CH2-O)x-O(CO)-其中x为1-1000,优选1-100,最 优选x为约100,
R2为基或2,6-二甲氧基苯基,更优选基。
这些光引发剂被进一步称作BAPO(对于双(酰基)膦氧化物)。
BAPO光引发剂(BAPO-1和衍生物BAPO-2、BAPO-3、BAPO-4和 BAPO-5和BAPO-6)的合成可由专利 PCT/EP2013/070378(WO2014/053455)、WO2006/056541和 WO2011/003772得到。
如上所述,本发明优选使用的光引发剂包括或者R1为小官能团 (BAPO-1、BAPO-3和BAPO-6)或者接枝聚合物(BAPO-4和BAPO-5)。 BAPO-4为用聚硅氧烷大分子官能化的光引发剂(例如可通过聚合BAPO-2 得到),其中Mn为至多约2400,如对于用于本文的BAPO-4为2136。 BAPO-5为用在磷原子处键接的聚氧乙烯(PEO,Mn6000)在各末端(n=2) 官能化的。BAPO的性质可不仅经由连接的侧链,而且经由聚合活性影响 最终聚合物,导致具有不同机械和导电性能的聚合物。在下式中,Mes分 别为(mesitylene)或1,3,5-三甲基苯。
取决于所选的一种或多种自由基引发剂,本发明交联剂可与乙烯基磺 酸盐单体,优选苯乙烯磺酸盐单体一起使用以形成共聚物(CP),其中所述 乙烯基磺酸盐单体可以是单独的或与丙烯酸酯单体一起的,其中在加入丙 烯酸酯单体的情况下,共聚物也称作三嵌段共聚物(TBP)或在丙烯酸酯不 存在的情况下共聚物称作二嵌段共聚物(DBP)。对于锂离子电池,优选碱 金属为锂,对于钠电池优选钠。
使用上述那些交联剂和合适的自由基引发剂,可以制备非氟化单离子 共聚物电解质,其中任选使用丙烯酸酯作为其他共聚单体,优选甲基丙烯 酸酯,如丙烯酸烷基酯,如甲基丙烯酸甲酯。作为另一共聚单体,使用碱 金属磺酸盐乙烯基单体,优选碱金属苯乙烯磺酸盐单体,其中碱金属为钠 或锂。
使用BAPO-1至BAPO-5中的一种制备的甲基丙烯酸酯、交联剂和苯 乙烯磺酸锂单体的共聚物直至在190℃以上是热稳定的并且在60℃下的单 离子电导率在10-4S cm-1的范围,即比现有技术的单离子聚合物电解质[10] 高出了一个数量级。
如上所述,包含(甲基)丙烯酸酯的非氟化单离子导电共聚物电解质也 称作三嵌段聚合物(TBP),尽管由于缺乏溶解性使得无法测定它们的实际 结构。因此,本发明共聚物电解质可能是三嵌段共聚物仅是一个基于如下 事实的推测:已知丙烯酸酯如甲基丙烯酸酯均聚快以及基于固含量以及所 得聚合物的分离产率的推测。然而,本发明不应以任何方式受到该推测或 该术语的限制。
与TBP类似,乙烯基磺酸盐单体和交联剂的共聚物称作二嵌段(共)聚 合物(DBP),由于摩尔比的区别,至少存在聚乙烯基磺酸盐嵌段。
共聚物(TBP)适合在含水介质中通过自由基引发剂(尤其是光引发剂如 BAPO)促进下述化合物聚合而形成:丙烯酸酯,优选甲基丙烯酸酯,尤其 是甲基丙烯酸甲酯,碱金属乙烯基磺酸盐单体,优选苯乙烯磺酸盐,如苯 乙烯磺酸锂以及双官能乙烯基单体交联剂,即碱金属(二(苯乙烯磺酰基)酰 亚胺)(alkaline metal(bis(styrenesulfonyl)imide)),如锂(二(苯乙烯磺酰基) 酰亚胺)。通过使用BAPO 1-6中一种和优选单体获得的所得三嵌段或二嵌 段共聚物的通式结构如下所示。
聚合物CP-1或TBP-1:R=-CH2CH2CO(OCH2CH2)2OCH2CH3
聚合物CP-2或TBP-2:R=-CH2CH2CO2(CH2)3Si(OCH3)3
聚合物CP-3或TBP-3:R=-CH2CH2CO2(CH2)2NMe3 +Br-
聚合物CP-4或TBP-4:R=-CH2CH2CO2(CH2)3SiO3-
聚合物CP-5或TBP-5:R=-CH2CH2CO(OCH2CH2)nO2COCH2CH2-
聚合物CP-6或DBP-6(n=0):R=-CH2CH2CH2N(CH3)3Br
取决于所需特性,单体比例可以在一定范围内变化。对于电导率而言, 磺酰基单体是需要的,但是在某些实施方案中,取决于所用光引发剂,为 了机械稳定性而需要(甲基)丙烯酸酯。考虑到这些需求,乙烯基磺酸盐单 体与丙烯酸酯单体的比例为1:0-1:4。交联单体相对于其他单体(即丙烯酸酯 单体和乙烯基磺酸盐单体)可以以至多20摩尔%,优选约10摩尔%的量存 在。
在特定实施方案中,尤其是如果使用BAPO(其在R1中包含酯基,如 BAPO-1至BAPO-5)的话,碱金属乙烯基磺酸盐单体:丙烯酸酯单体的比例 可以从约1:4至约4:1(或反过来,丙烯酸酯单体:碱金属乙烯基磺酸盐单 体可以从约4:1至约1:4)变化,其中本发明优选约1:1的比例。因此,在本 发明优选实施方案中,(甲基)丙烯酸酯基团与磺酸根基团的摩尔比为约1, 优选(甲基)丙烯酸酯:乙烯基磺酸盐:二(苯乙烯磺酰基)酰亚胺的比例为约 1:1:0.2。
对于其他BAPO如BAPO-6,可无需丙烯酸酯。对于这类聚合物,乙 烯基磺酸盐:二(苯乙烯磺酰基)酰亚胺的比例可以从10:2-10:0.5变化,其 中优选10:1。
最佳的自由基引发剂量可以通过浓度系列容易地测定。然而,光引发 剂和/或热引发剂通常以总单体(即(甲基)丙烯酸酯和乙烯基磺酸盐和二(苯 乙烯磺酰基)酰亚胺)的约1摩尔%存在。
最终的交联聚合物网络结构促进了M+与阴离子结构的弱相互作用, 赋予了高的离解水平和高的通过基质的碱金属离子迁移率(在60℃下,对于 Li为10-4S cm-1)。用BAPO-1至BAPO-5聚合得到的是80-200nm尺寸 的聚合物颗粒乳液。用BAPO-6聚合得到的是水溶性离子导电聚合物。
在反应过程中,可加入含碱金属的表面活性剂(如十二烷基磺酸锂)从 而有效控制粒度和最终乳液的稳定性,其中粒度分布稳定数周。
二(酰基)膦氧化物与无机材料如金属氧化物连接(参见图1)。在单离子 导电聚合物的制备中使用这种联合引发剂的目的是为了获得锂离子或钠离 子活性材料与锂离子或钠离子导电聚合物之间的密切接触。作为概念的证 据,下文中描述了在有机溶剂中用与钒酸盐连接的BAPO聚合MMA(甲基 丙烯酸甲酯)。
含有硅氧烷基团的BAPO如BAPO-2可通过将试剂在合适有机溶剂如 THF中共悬浮并在惰性气体中回流合适时间,如在氩气中4小时而锚定至 材料,如电子活性材料如钒酸盐上。
本发明还涉及一种干燥方法,该方法允许将SPE乳液加工得到SPE 自立式膜。电化学电池可通过将该SPE自立式膜置于阳极和阴极之间而形 成,所述SPE自立式膜起到分隔器的作用。本发明还包括将SPE通过溶 液流延在电极上而直接沉积。
加入增塑剂也在本发明的范围内。分别取决于加入时间和量或比例, 聚合物膜的特性可以变化。通常而言,最小5重量%且最大20重量%的增 塑剂如四甘醇二甲醚(TEG)可以用于SPE分隔器中。
在另一方面,本发明涉及碱金属离子电池如锂离子电池,其中SPE膜 将金属锂制成的负电极和正电极分开,其中正电极通过将阴极活性(如 LiFePO4或LixHyV3O8,其中在该式中2<x+y<6.8和0<x<4和0.5<y<6) 或EP 2 755 259(A1)"石墨烯氧化物和H4V3O8的自组装复合材料"中所 述的钒酸盐/石墨烯复合材料)与导电碳添加剂和上述SPE混合而制备。在 所述构造中,SPE起到两个作用,即用作分隔器和用作电解质。
在该实施方案中,用于与阴极材料和导电碳混合的SPE可具有低机械 强度,但具有高电导率,以及自立式膜可具有较低电导率,但具有提高的 机械稳定性。
在另一实施方案中,SPE乳液可任选与无机填料如热解法二氧化硅、 二氧化钛、氧化铝、氧化锆、氧化硼等混合。这类无机纳米填料尤其用于 改进自立式SPE膜的机械特性。
在另一方法中,用单体和引发剂涂敷或混合活性阴极材料和导电碳, 然后引发聚合,或在另一方法中,将引发剂连接在活性阴极材料上,然后 在聚合引发之前与单体结合。由于单体扩散入多孔阴极材料和导电碳层中, 可能有利的是使用热活化的引发剂而非光引发剂。还是在该实施方案中, 可能需要施加SPE自立式膜作为(额外)分隔器。
也可以使用两步方法,即首先使用常用的粘合剂或SPE(如果需要获得 足够稳定的阴极)制备阴极,然后用SPE层涂敷该阴极。由于SPE层与阴 极层密切接触,与分开制备然后施加自立式层相比SPE层的稳定性得以改 进。
通过改变单体组成和填料,可以变化共聚物的特性,以及在很大程度 上适应电导率和机械性能方面的特别需求。如上所述,也可且经常优选使 用SPE(如高电导率和较差机械强度的一层)与较低电导率的自立式膜的组 合。
使用SPE层或自立式膜的优点在于防止树枝体的形成得以改进。
设计由SPE导电聚合物和活性阴极材料制成的复合膜从而确保电极和 SPE分隔器之间的最佳界面,以在设计全电池单元时提供额外优点。除了 层之间的良好机械接触之外,电解质聚合物也可提高电极内的局部离子导 电。
本发明的SPE不仅可以与阴极材料混合,而且可以与阳极材料混合。 分别适用上述内容。然而,目前更优选阳极为金属锂或钠。
相对于锂的电化学稳定性和电化学可行性已经通过使用标准阴极材 料,如铁锂磷酸盐(LFP),或新型活性材料,如钒酸锂(其为具有高吸引力 的下一代锂离子电池单元(battry cell)阴极材料,如描述于EP 2 755 259A1) 显示。三嵌段聚合物单离子导体(称作TBP)可以合适的通过在水中的光引 发剂引发的自由基聚合而合成。
因此,除了特定交联剂和用其产生的固体导电聚合物之外,本发明的 其他方面为包含活性电极材料、SPE和可能的导电填料如石墨烯、石墨、 导电碳及其组合的电极,以及使用本发明SPE作为电解质,优选与金属阳 极结合而产生的电池。这种电池可通过一种包括如下步骤的方法制备:用 活性电极材料和任选导电填料涂敷可剥离载体,如铝箔以形成阴极,然后 用本发明的固体导电聚合物涂料涂敷阴极。
附图简述
当考虑下文的详细描述时,本发明会更好理解,并且上文所述之外的 目的会变得更加清晰。该描述参考附图,其中
图1:合成光引发剂BAPO-钒酸盐
图2:与钒酸盐连接的光引发剂的31P NMR
图3:由BAPO-钒酸盐聚合得到的嵌入LixHyV3O8纤维的PMMA的 SEM图像
图4:膜聚合物TBP-1 1a(不用LiDS制备)和1b(用9mM LiDS制备) 的XRD谱图
图5:聚合物TBP-1在水中的粒度分布
图6:TBP-1的TGA(“A”)和DSC(“B”)曲线
图7:对于分别使用BAPO-1、BAPO-6作为光引发剂制备的三嵌段聚 合物(TBP-1至TBP-5以及DBP-6)的电导率的温度依赖性(对数绘制)
图8:在压缩之前和之后的LFP复合阴极膜(L1和L2)的SEM图象。
图9:钒酸盐复合阴极膜(V1)的SEM图像。
图10:使用聚合物TBP-1a的复合物L1在60℃和70℃下使用20mA/g 电流的循环寿命(C/8)。
图11:对于复合物L3的比容vs.循环
图12:对于复合物V1和V2的电势vs.比容
图13:对于复合物V1和V2的比容vs.循环
进行本发明的方式
如上所述,本发明涉及适用于合成单离子导电共聚物的交联剂,所述 共聚物为非氟化且非PEO基的。这类共聚物用作固体聚合物电解质(SPE) 时满足安全和成本要求。它们是锂离子电池或钠离子电池中的标准液体电 解质的有希望的替代物,这是因为它们具有改进的安全和阻燃性能。所述 共聚物为用碱金属聚乙烯基磺酰基,如碱金属聚磺酰基苯乙烯,如聚磺酰 基苯乙烯锂(LiPSS)官能化并通过使用本发明交联剂,即碱金属(如锂)二(苯乙烯磺酰基)酰亚胺(MBSSI如LiBSSI)单体交联的聚乙烯基磺酸盐或聚丙 烯酸酯,尤其是聚甲基丙烯酸酯,如聚甲基丙烯酸甲酯(PMMA)。本发明 共聚物可通过自由基聚合,尤其是自由基光聚合,优选使用官能化二(酰基) 膦氧化物(BAPO)作为光引发剂光聚合而制备。这类共聚物可在锂离子或钠 离子电池中用作固体聚合物电解质。
实验部分
1)市售起始材料
苯乙烯磺酸锂购自荷兰Tosoh Europe B.V.(>94%)并且在使用前通过 从二(2-甲氧基乙基)醚(DME)中再结晶并在真空下在100℃下干燥2天而提 纯。
甲基丙烯酸甲酯(MMA)购自Aldrich(>99%)并在使用之前蒸馏。四甘 醇二甲醚(TEG)通过蒸馏提纯并用分子筛储存。
2)合成交联剂:二(苯乙烯基磺酰亚胺)锂盐
i)4-乙烯基苯磺酰氯
将4-乙烯基苯磺酸钠盐(7.2g,35mmol,1当量)在二甲基甲酰胺 (DMF)(58ml)中的溶液冷却至0℃,然后滴加入亚硫酰氯(34.4g,21mL, 289mmol,8.3当量)。将亚硫酰氯经脱气但不经提纯而使用。在搅拌12小 时后,使混合物在-4℃下过夜,然后倒入冰水(100mL)中并用乙醚(3 x 50mL) 萃取。将溶液在减压下浓缩得到淡黄色油(4.4g,66%)。1H-NMR(500.2 MHz,CDCl3)δ=7.92(d,J=8.0Hz,2H,CHAr),7.56(d,J=7.5Hz,2H, CHAr),6.81(m,1H,CHolef),5.92(d,J=17.5Hz,1H,CHolef),5.47(d,J =11.0Hz,1H,CHolef)ppm。
13C{1H}NMR(75.5MHz,CDCl3):δ=144.9(CH2=CH-C),142.9 (CSO2Cl),135.0(CH2=CH),127.6(CHAr),127.2(CHAr),119.5 (CH2)ppm。
ii)4-乙烯基苯磺酰基酰胺
使4-乙烯基苯磺酰氯(2g,9.87mmol,1当量)与氨水溶液(100mL, (25%NH3))反应2h,然后用醚萃取、用MgSO4干燥并浓缩得到作为白色 固体的磺酰胺(1.11g,62%)。
熔点:141℃。
1H-NMR(500.2MHz,CDCl3):δ=7.95(d,J=8.0Hz,2H,CHAr), 7.58(d,J=8.5Hz,2H,CHAr),6.75(m,1H,CHolef),5.94(d,J=17.5Hz, 1H,CHolef),5.50(d,J=11.0Hz,1H,CHolef),3.08(s,2H,NH2)ppm。
iii)二(苯乙烯基磺酰亚胺)锂盐
将4-乙烯基苯磺酰氯(323mg,1.6mmol,1当量)、4-乙烯基苯磺酰基 酰胺(293mg,1.6mmol,1当量)和LiH(77mg,3.2mmol,2当量)在 THF(5mL)中的混合物在Ar和室温下搅拌12h,然后浓缩并用醚洗涤得到 白色固体。将该固体从MeOH中再结晶得到0.4g,71%产率。
熔点:>250℃
1H-NMR(500.2MHz,D2O):δ=7.61(m,4H,CHAr),7.46(m,4H, CHAr),6.76(m,2H,CHolef),5.91(d,J=17.5Hz,2H,CHolef),5.36(d,J= 11.0Hz,2H,CHolef)。
13C-NMR(75.5MHz,D2O):δ=141.9(CH2=CH-C),138.9(CSO2N), 135.4(CH2=CH),126.7(CHAr),125.8(CHAr),116.4(CH2)ppm。
7Li-MAS NMRδ=0ppm
ATR IR:λ-1(cm-1)=1626w,1494m,1424m,1200s,1137m,1093s, 989s,904m,839s,743m。
EA计算:C54.0%,H 4.0%;发现C53.4%,H4.1%
3)合成二(酰基)膦氧化物(BAPO)光引发剂
不同BAPO的一般合成描述于 PCT/EP2013/070378(WO2014/053455)、WO2011/003772和 WO2006/056541。对于BAPO-1例如参见WO2014/053455的实施例23, 对于BAPO-2例如参见WO2014/053455的实施例12a,对于BAPO-3例如 参见WO2014/053455的实施例27。BAPO-4使用BAPO-2制备并且方案 描述于WO2011/003772的实施例34,以及BAPO-5根据WO2014/053455 的实施例23使用聚乙二醇二丙烯酸酯Mn6000作为原料制备。
BAPO-6可溶于水并且如专利WO2006/056541的实施例1所述使用 3-溴丙基三甲基溴化铵在乙醇中将bisenolate Na[P(COMes)2]χDME}(步骤 d)烷基化而进行合成。
4)合成与钒酸盐连接的二(酰基)膦氧化物(BAPO)光引发剂并聚合 MMA。
将用硅氧烷基团官能化的二(酰基)膦氧化物(BAPO-2)连接于氧合氢氧 化物钒酸锂LixHyV3O8(其中2<x+y<6.8和0<x<4和0.5<y<6)(描述于 US20130157138 A1)(图1)。
BAPO与钒酸盐的连接在100mL的Schlenk烧瓶中在氩气氛下进行, 其中该烧瓶与回流冷凝器连接。向THF(30mL)中的LixHyV3O8(1g)悬浮 液中加入BAPO-2(0.05g,0.087mmol),并将混合物回流4h。在将混合物 冷却之后,将固体过滤、洗涤并在THF(20mL)中声处理2次(1分钟)。将 所得淡绿色固体在真空和50℃下干燥24h得到0.95g。对材料进行波谱分 析(MAS NMR)以确定在材料上存在二(酰基)膦氧化物光活性基团(31P NMR)(图2)。
5)通过使用与钒酸盐连接的光引发剂的自由基聚合合成PMMA
MMA的光引发的聚合在100mL Schlenk中在氩气氛下进行。制备连 接的光引发剂(0.95g)在THF(30mL)中的悬浮液,并向悬浮液中加入MMA (0.78g,7.8mmol)。在辐照之前将混合物剧烈搅拌5分钟。混合物的辐照 用水银UV灯在剧烈搅拌和室温下进行1h从而得到凝胶。将淡绿色固体悬 浮在50mL的THF中、声处理并过滤。将样品在真空下干燥得到0.87g淡绿色固体。通过SEM分析观察该固体的形态(图3)。
6)合成共聚物(CP-1至CP-6)
6a)合成三嵌段共聚物(TBP-1至TBP-5)
合成TBP-1的反应路径:
聚合物TBP-1(1b)的合成在100mL的Schlenk烧瓶中在氩气氛下进行。 向反应器中装入磺酸锂苯乙烯(4mmol,760mg),锂二(苯乙烯磺酰基)酰 亚胺(0.8mmol,284mg)和蒸馏水(30mL)。在氩气氛下向搅拌的混合物中缓 慢加入新鲜蒸馏的甲基丙烯酸甲酯(MMA)(4mmol,400mg,430μL)和溶 于DME(二甲氧基乙烷)(5mL)中的光引发剂BAPO-1 (R=CH2CH2CO(OCH2CH2)2OEt)(0.08mmol,42mg)。向反应混合物中加 入十二烷基硫酸锂(9mM)。将乳液脱氧20分钟,然后用中压水银UV灯 (254nm)在22℃下辐照1h,同时保持剧烈搅拌(1200rpm),得到白色悬浮 液。
将聚合物通过在真空(40℃,20毫巴)下除去溶剂而分离。将所得白色 粘性残留物用异丙醇(2 x 5mL)和四氢呋喃洗涤。将回收的聚合物在真空下 干燥过夜(25℃,0.1毫巴),得到945mg(71%产率)。
通过加入蒸馏水和5%(w/w)四甘醇二甲醚(TEG)而制备聚合物的稳定 悬浮液。TEG作为增塑剂加入以避免聚合物的致密堆积。
类似地进行TBP-2至TBP-5的合成。
6b)合成聚合物DBP-6
对于聚合物TBP-6,苯乙烯基磺酸锂与交联剂的优选比例为10:1,且 不使用丙烯酸酯和甲基丙烯酸酯。除了所述变化以及将BAPO-6加入含有 单体的水溶液中之外,其他根据用于TBP-1的程序。
7)由TBP的悬浮液制备SPE的自立式膜
聚合物电解质的自立式膜通过将TBP悬浮液流延在具有300-500μm 的圆形凹槽的Teflon板上而制备。这些圆形凹槽具有电导率和电池测试( 和17mm)所需的电解质膜的尺寸。将聚合物在室温和Ar下首先干燥 24h,然后在50℃和Ar下干燥4天,最后在50℃和真空下干燥24h。加工 得到200-700μm的均匀的自立式膜,将其在使用前在手套箱中储存2天。
8)三嵌段共聚物(TBP)的表征(在加工为自立式膜之后)
8a)所用方法
NMR
MAS NMR实验使用Bruker Avance 400MHz 9.4T波谱仪进行。7Li MAS NMR谱使用1.0s射频脉冲在155.50MHz下记录,循环延迟为2.0s, 瞬变数目为600,旋转速率为7.0kHz。
XRD
在配有锗单色器和CuKα1辐照的STOE Stadi P衍射仪上得到粉末X- 射线衍射谱图(在40kV,35mA下操作)。
SEM
扫描电子显微镜法(SEM)在Zeiss Gemini 1530上于1kV下进行,
TEM
透射电子显微镜法(TEM)在CM30ST(FEI;LaB6阴极)和TecnaiF30 显微镜(在300kV下操作且最大点分辨率为约)上进行。
离子电导率
阻抗测量在500kHz至1Hz的频率范围使用50mV的激励幅值(法国 VMP3,BiologicSAS)进行。从电解质膜切割17mm直径的圆盘并将样品 放置在两个不锈钢圆盘(1.8cm2)之间并用温度稳定的带密封以防空气和水 气。在Nyquist图中选择电解质弧和起始界面弧之间的最小值从而由所得 曲线计算体积电阻(R)。然后将聚合物的体积电阻R用于根据方程1计算 电导率(σ),其中d为样品厚度且A为在钢圆盘之间测量的样品面积。该方 法广泛描述用于测量不同温度下的SPE离子电导率[11]。
方程1
8b.三嵌段共聚物TBP-1的表征
7Li MAS NMRδ=-0.5ppm
ATR IR:ν(cm-1)=2350w,1724s,1456m,1248s,1149s,1085s,1030s, 985m,948m,892m,758m,638s
EA C 52.8%,H 4.0%,N 0.7%
使用XRD衍射时,没有发现TBP1有明显的结晶度,这与添加表面 活性剂(LiDS)无关。仅在10°-25°的2θ范围检测到非常宽的信号,表明聚 合物含有具有有序链的区域,但是从信号宽度来说,这些有序区域非常小 或者没有良好界定(图4)。
另一方面,LiDS的加入对聚合物粒度和分布有影响。未用LiDS制备 的聚合物表现出差的稳定性并且在数小时之后遭受到颗粒沉降。含有LiDS (9mM)的聚合物悬浮液的Zeta尺寸测量显示,围绕41nm的窄粒度分布(图 5)。在2周老化之后,尺寸分布保持不变并用于制备复合膜。
聚合物的热稳定性通过热重分析(TGA)评价。TBP1直至190℃热稳 定,具有可忽略的质量损失(1%)。在290℃存在增加的7.6%的质量损失。 聚合物的熔融行为使用差示扫描量热法(DSC)量化,聚合物1a的代表性曲 线呈现于图6并在290℃显示有吸热峰。
图7显示了TBP-1和使用上述不同BAPO光引发剂制备的类似聚合 物(TBP2、TBP3、TBP4、TBP5和DBP6)的相对于温度倒数(T-1)的电导 率。电导率的线性增加表明在测量温度范围内,导电机制保持相同。使用 含有聚硅氧烷(BAPO-4)的BAPO得到的聚合物在60℃下达到0.14mS/cm 的最大电导率。然而,该样品在对数电导率vs.T-1曲线上偏离了线性增加。 这表明,在较高温度下导电机制的变化,或者第二导电过程的影响。聚合 物膜对抗锂的化学稳定性通过在干氩气氛下将膜置于新鲜切割的锂上而测 试。在将聚合物膜以规则的时间间隔(长达3周)提起之后,聚合物/锂界面 保持不变。
9)用TBP-1制备复合阴极
9a)一步制备SPE/AM复合物
在第一步中,在玛瑙球磨机(300rpm,2 x 10分钟)中,将阴极活性材 料(AM)、碳涂覆的铁锂磷酸盐(LFP)(2μm,A1100,Alees,Taiwan)或者 氧合氢氧化物钒酸锂LixHyV3O8(其中2<x+y<6.8和0<x<4和0.5<y<6) (描述于US20130157138 A1)与碳黑导电添加剂(Super-P,Timcal)或者还 有石墨(SFG6或KS6,Timcal,瑞士)预混合。然后,加入浓度为0.16g/ml的聚合物TBP-1的含水悬浮液。取决于固含量,加入一些额外的去离子水 直至获得合适粘度浆料。分别将约18%和35%的最佳固含量用于制备LFP 和钒酸盐复合物(L1-L2和V1-V2)。为了防止在球磨过程中强烈发泡从而 导致阴极膜中产生洞,加入最小量的三丁基磷酸酯(>99.0%,Fluka Chemie AG,Buchs,瑞士)作为消泡剂。在球磨2 x 30分钟(300rpm,具有反相旋转)之后,获得均匀浆料。不同复合物的组成的重量百分数示于表 1。
表1.不同比例的LFP或LixHyV3O8复合物
将浆料通过刮刀流延在标准铝箔(15μm)上。将膜在室温和空气流下干 燥1小时,然后在氩气氛和50℃下干燥12小时,最终在真空和50℃下干 燥至少24小时,得到40-100μm厚的干膜。将膜压缩(15吨,5分钟)以减 少膜中的空隙并改进颗粒之间的接触。基于LFP的膜的微观结构示于图9, 基于钒酸盐的膜的相应微观结构示于图10。
9b)通过涂覆和渗透两步制备SPE/AM复合物
作为制备SPE/AM复合物的替代方式,首先将基于LFP的阴极通过绕 线棒刮涂于铝箔上,然后将SPE溶液下滴流延在阴极上。
涂覆的阴极具有如下组成:88%(LFP),6%(KS6)和4%(SuperP))。 为了确保与铝箔的粘合,使用2%的甲基纤维素钠(Na-CMC)作为粘合剂。 然后,将TBP1在水中的悬浮液(30重量%)下滴流延在LFP阴极上。将复 合阴极首先在室温和Ar下干燥24h,然后在50℃和Ar下干燥24h,最终 在真空(10毫巴)和50℃下干燥24h。所得阳极复合物(复合物L3)为100μm 厚且含有17.6mg聚合物/cm2阳极膜的负载。
10)电池制备
电化学性能在标准纽扣电池(CR2025,Renata,瑞士)中测试。将金属 锂盘用作阳极。随后从复合阳极膜切割13mm直径的盘。
对于通过一步路线制备的复合物(L1-L2和V1-V2),将来自自立式 SPE膜TBP1的SPE盘(直径17mm)置于阴极和阳极之间。将测试电池在 干Ar气氛(<0.1ppm H2O;<0.1ppmO2)中组装。对于恒电流实验,使用 20-25mA/g的电流(基于活性材料)。LFP电位窗口为3.0-3.9V且对于钒为 1.6-4.2V。
10a)LFP复合物(一步合成)的电化学性能
阳极L1(图10)显示,容量接近于理论值(在60℃下的首次循环中为 152Ah/kg),当用20mA/g(C/8)的电流循环时在该温度下测量的5次循环 是稳定的。在这5次循环之后,将电池转移至用于长期测量的另一测量装 置,并将温度升高至70℃。在该温度下,容量首先增加至167Ah/kg。在 20次循环之后,测得144Ah/kg。
10b)LFP复合物(两步合成)的电化学性能
在图11中,将复合物L3(其中将SPE下滴流延,参见8b)用20mA/g 的电流在70℃下在3.0-3.9V范围恒定电流循环。在最初的6次循环中,观 察到略微过载(overcapacity),第7次循环,再充电效率接近于100%。在 C/8率下,在第20次循环之后,仍然获得容量高于160mA/g的电池性能。
10c)钒酸盐复合物(一步合成)的电化学性能
图12显示了使用阳极V1和V2的电池在70℃下首次循环的电势(相 对于Li+/Li)(V)vs.比容(Ah/Kg)。在图13中,显示了两种复合物直至第 23次循环的容量对循环次数的依赖性。阴极复合物V1在首次循环中的容 量为398Ah/kg,这接近于理论值,在第23次循环之后下降到148Ah/Kg。 阴极复合物V2在首次循环中获得高达419Ah/kg的容量,在第23次循环 之后缓慢下降至150Ah/Kg。显然,与V2(仅有SuperP作为碳添加剂)相 比,复合物V2(SuperP和石墨)的充放电效率(columbic efficiency)得以改 进。
尽管已显示和描述了本发明目前优选的实施方案,应当清楚地理解, 本发明不限于所述实施方案,而是可在所附权利要求书的范围内以其他方 式具体实施和进行。
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Claims (33)
1.式(I)的二(苯乙烯基磺酰亚胺)盐作为交联单体在通过将所述二(苯乙烯基磺酰亚胺)盐与碱金属乙烯基磺酸盐单体和自由基引发剂以及任选丙烯酸酯单体共聚而制备固体导电聚合物中的用途,其中所述自由基引发剂为光引发剂,或热引发剂,或光引发剂和热引发剂的组合,
其中M+为Li+或Na+。
2.根据权利要求1的用途,其中M为锂。
3.式(I)的二(苯乙烯基磺酰亚胺)盐作为交联单体在通过将所述二(苯乙烯基磺酰亚胺)盐与碱金属乙烯基磺酸盐单体和自由基引发剂以及任选丙烯酸酯单体共聚而制备固体聚合物电解质中的用途,其中所述自由基引发剂为光引发剂,或热引发剂,或光引发剂和热引发剂的组合,
其中M+为Li+或Na+。
4.根据权利要求3的用途,其中M为锂。
5.通过将如权利要求1或2中所定义的二(苯乙烯基磺酰亚胺)盐作为交联单体与碱金属乙烯基磺酸盐单体和自由基引发剂以及任选丙烯酸酯单体共聚而制备的固体单离子导电聚合物,其中所述自由基引发剂为光引发剂,或热引发剂,或光引发剂和热引发剂的组合。
6.权利要求5的固体单离子导电聚合物,其中该聚合物为固体聚合物电解质。
7.权利要求5的固体单离子导电聚合物,其中使用丙烯酸酯单体。
8.权利要求7的固体单离子导电聚合物,其中所述丙烯酸酯单体为甲基丙烯酸酯单体。
9.权利要求8的固体单离子导电聚合物,其中所述丙烯酸酯单体为甲基丙烯酸甲酯。
10.权利要求5的固体单离子导电聚合物,其中所述乙烯基磺酸盐单体为苯乙烯磺酸盐。
11.权利要求5的固体单离子导电聚合物,其中所述自由基引发剂为光引发剂或光引发剂与热引发剂的组合。
12.权利要求5的固体单离子导电聚合物,其中所述自由基引发剂包括光引发剂,该光引发剂选自α-羟基酮、二苯甲酮、苄基衍生物、噻吨酮、乙酰基膦、烷氧基胺和酰基膦氧化物。
13.权利要求12的固体单离子导电聚合物,其中所述光引发剂由式(II)的酰基膦氧化物光引发剂组成或含有式(II)的酰基膦氧化物光引发剂:
其中
n为1-6,
m为1或2,
X为氧或硫,
R1为–C(R4)3,其中
如果n=1,
则所有R4相互独立地选自:
-H,
-芳族基团
-链烯基,和
-脂族基团,其中脂族基团可以是未支化或支化的,未被取代或被一个或多个如下基团取代:芳族基团、杂芳族基团、杂环基团、醚(聚乙二醇或聚氧乙烯)、硒化物、羟基、硫醇基、酮、亚胺、羧酸衍生物、砜、亚砜、硫酸根、锍、硫亚胺、亚砜亚胺、磺酰胺、胺、铵盐、腈、硝基、脒、氨基甲酸酯、胍离子、腙、酰肼、肼、硅烷、硅氧烷、聚硅氧烷、亚膦酸酯、氧化膦或磷酸酯基团,
如果n>1,
则至少一个R4为2-6价的选自上文所列的取代基,其中上述烷基也可在链中包含一个、两个或更多个上述基团,即脂族链可以被上述官能基团间隔(或互联)一次、两次或更多次,或者被这些基团取代一次或多次,其中所述基团被至少一个CH2基团隔开,
R2为芳基,和
R3为如上对R1所述的C(R4)3。
14.权利要求13的固体单离子导电聚合物,其中n为1、2、3或4。
15.权利要求14的固体单离子导电聚合物,其中n为1或2。
16.权利要求13的固体单离子导电聚合物,其中R2为2,4,6-三甲基苯基(基)。
17.权利要求13的固体单离子导电聚合物,其中R2为2,6-二甲氧基苯基。
18.权利要求13的固体单离子导电聚合物,其中所述光引发剂适于产生两个自由基。
19.权利要求13的固体单离子导电聚合物,其中所述光引发剂具有式(II)且其中
n为1,
m为2,
X为O,
R1为-CH2-CH2(Z),
Z为–(CH2)n1-NMe3X’+,其中n1为1-4,以及X’为Cl、Br或I,
Z为酯-(CO)OR6,其中
R6为烷基,其在链中包含一个或多个-O-(如聚乙烯基团)或所述烷基链被一个或多个-O-(如聚乙烯基团)间隔,或带有一个或多个甲硅烷氧基团如–SiR7 y(OR8)3-y,其中y为0-3,或带有一个或多个铵盐基团如-N(R9)4+X’-,其中
R7、R8和R9为烷基,和
R2为基或2,6-二甲氧基苯基,
或
n为2,
m为2,
R1为-(CO)O-(CH2-CH2-O)x-O(CO)-,其中x为1-1000,
R2为基或2,6-二甲氧基苯基。
20.权利要求19的固体单离子导电聚合物,其中n1为1-3。
21.权利要求19的固体单离子导电聚合物,其中R7、R8和R9为C1-C4烷基。
22.权利要求19的固体单离子导电聚合物,其中R2为基。
23.权利要求19的固体单离子导电聚合物,其中x为1-100。
24.权利要求13的固体单离子导电聚合物,其中所述光引发剂为下列中的一种:
25.权利要求10的固体单离子导电聚合物,其中碱金属苯乙烯磺酸盐:丙烯酸酯之比为约1:0至约1:4。
26.权利要求24的固体单离子导电聚合物,其中碱金属苯乙烯磺酸盐:丙烯酸酯之比为1:1。
27.权利要求7的固体单离子导电聚合物,其中交联单体相对于丙烯酸酯单体和磺酸盐单体的量以至多20摩尔%的比例存在。
28.权利要求13的固体单离子导电聚合物,其中R1为被酯基取代的烷基且其中丙烯酸酯:碱金属苯乙烯磺酸盐:交联单体之比为约1:1:0.2,或其中R1为被铵盐取代的脂族基团且其中丙烯酸酯:碱金属苯乙烯磺酸盐:交联单体之比为约0:10:1。
29.权利要求5的固体单离子导电聚合物,其中光引发剂和/或热引发剂以总单体的约1摩尔%存在。
30.权利要求5的固体单离子导电聚合物在锂离子或钠离子电池中作为电解质的用途。
31.包含权利要求5的固体单离子导电聚合物作为电解质的电池。
32.一种阴极或阳极,其中权利要求5的固体单离子导电聚合物与阳极或阴极电活性材料和任选石墨烯和/或导电碳或石墨密切混合。
33.一种制备权利要求31的电池的方法,包括用活性电极材料和任选导电填料涂敷可剥离载体以形成阴极,然后用权利要求5的固体单离子导电聚合物的涂料涂敷该阴极的步骤。
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KR20170140138A (ko) | 2017-12-20 |
KR20160070701A (ko) | 2016-06-20 |
US9771319B2 (en) | 2017-09-26 |
JP2016128562A (ja) | 2016-07-14 |
US20160168086A1 (en) | 2016-06-16 |
EP3031798A1 (en) | 2016-06-15 |
CN105693566A (zh) | 2016-06-22 |
JP6110928B2 (ja) | 2017-04-05 |
CA2914715A1 (en) | 2016-06-10 |
CA2914715C (en) | 2018-10-02 |
EP3031798B1 (en) | 2017-09-27 |
TW201638094A (zh) | 2016-11-01 |
KR102287715B1 (ko) | 2021-08-09 |
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