CN107093733B - 一种抑制锂枝晶增长的锂离子电池负极浆料的制备方法 - Google Patents
一种抑制锂枝晶增长的锂离子电池负极浆料的制备方法 Download PDFInfo
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Abstract
本发明公开了一种抑制锂枝晶增长的锂离子电池负极浆料的方法，首先制备出八乙烯基多面体低聚倍半硅氧烷和丙烯酸锂两种单体，接着将两种单体在氮气条件下引发自由基聚合，最后，将碳化后的聚丙烯酸锂/八乙烯基多面体低聚倍半硅氧烷星型交联聚合物制备成负极浆料。本方法流程简单，原料易得，制备出的锂离子电池负极浆料在较高的电流密度下的循环性能十分优异，锂离子电池的使用寿命较长。
Description
技术领域
本发明属于电池技术领域，具体为锂离子二次电池负极浆料的制备方法，主要涉及聚丙烯酸锂/八乙烯基多面体低聚倍半硅氧烷星型交联结构复合浆料作为抑制锂枝晶增长的锂离子电池负极浆料的制备方法。
背景技术
锂离子电池具有能量密度高、比容量大、质量轻等优异的性能，广泛用于储能系统和电动汽车等。锂金属因其较高的理论比容量3860mAh g-1(相比碳负极372mAh g-1)和较低的电化学电压成为很有吸引力的锂离子电池负极材料，然而在重复的充放电循环中形成了锂枝晶从而限制了锂金属负极的商业化应用。大量的学者探讨各种方法来抑制锂枝晶和改善锂负极表面的固体-电解质界面层的均匀性，因此，制备一个坚固的界面层能够容纳因锂沉积而引起的体积膨胀而不被破坏，且能够抑制枝晶增长而没有阻碍锂离子的传导，这将是一种非常有前景的方法。Chongwu Zhou等利用了具有大比表面积且电导率高的3D碳纳米纤维网格作为负极浆料，在充放电过程中，锂金属直接插入并沉积到碳纳米纤维上，最终观察到平坦的锂金属表面而没有观察到锂枝晶，该材料在1.0mAh·cm-2的电流密度下能够实现300圈循环后平均库伦效率达到99.9％(Nano Research,2016, 9(11),3428-3436)。
多面体低聚倍半硅氧烷包含大量的高能键，具有优异的热稳定性，且笼型无机结构相对稳定难以折叠，将八乙烯基多面体低聚倍半硅氧烷通过聚丙烯酸锂连接，形成星型交联结构复合浆料，经过碳化后涂布在铜箔上能够形成这样一层坚固、纳米多孔、灵活的界面层，成为能够抑制锂枝晶增长的负极浆料。
本发明的目的是将八乙烯基多面体低聚倍半硅氧烷通过聚丙烯酸锂连接形成星型交联结构复合材料，制备成负极浆料，锂离子直接沉积在碳化后的聚丙烯酸锂/八乙烯基多面体低聚倍半硅氧烷星型交联聚合物导电网格上，形成了平坦的锂金属表面，避免生成锂枝晶，且不阻碍锂离子传导，并在一定程度上释放锂离子。该复合浆料制备简单，原料廉价，制备的负极浆料在高电流密度下保持较高的库伦效率。
本发明提供的一种抑制锂枝晶增长的锂离子电池负极浆料的制备方法包括以下步骤：
(1)将乙醇、硅烷偶联剂、去离子水与盐酸按照体积比20:1:1:1在50～60℃条件下机械搅拌8～10h形成均一溶液，通过离心得到白色产物，再用乙醇洗涤6 次，将产物在40～60℃下干燥得到八乙烯基多面体低聚倍半硅氧烷；
(2)将氢氧化锂与丙烯酸按照摩尔比1:1.5～2溶解在甲醇中，磁力搅拌2～6h，将所得溶液与丙酮按照体积比3:20混合，形成沉淀，通过洗涤抽滤得到白色固体产物，然后经冷冻干燥得到丙烯酸锂粉末；
(3)取步骤(1)中制备的八乙烯基多面体低聚倍半硅氧烷与引发剂溶解在二甲基亚砜中，在超声波作用下得到均一溶液A，取步骤(2)中制备的丙烯酸锂与引发剂溶解在二甲基亚砜中，在超声波作用下得到均一溶液B，在氮气氛围下， 65～80℃条件下，将B溶液逐滴滴入到A溶液中，磁力搅拌12～24h，形成白色凝胶，用乙醇离心洗涤4次，在40～60℃条件下干燥得到聚丙烯酸锂/八乙烯基多面体低聚倍半硅氧烷星型交联共聚物；
(4)取步骤(3)中制备的聚丙烯酸锂/八乙烯基多面体低聚倍半硅氧烷星型交联共聚物在充满氩气的管式炉中450～600℃下焙烧2～3h进行碳化，自然冷却至室温，研磨均匀，得到粉末状产物；
(5)取步骤(4)中碳化后的粉末状产物、乙炔黑和聚偏氟乙烯按照质量比7:2:1，滴入N-甲基吡咯烷酮，用球磨机球磨2～4h后，将混合浆料涂布在铜箔上，真空下100～120℃干燥10～14h，得到负极浆料。
进一步的，所述步骤中的硅烷偶联剂为3-(异丁烯酰氯)丙基三甲氧基硅烷、乙烯基三乙氧基硅烷的至少一种。
进一步的，所述步骤中的引发剂为偶氮二异丁腈、偶氮二异庚腈的至少一种。
进一步的，所述步骤中的八乙烯基多面体低聚倍半硅氧烷与聚丙烯酸锂的摩尔比为1:24～40。
本发明的特点是：制备过程简单、流程短、生产成本低，该负极浆料的循环性能十分优异。
具体实施方式
下面结合具体实施方式对本发明作进一步说明。以下实施例旨在说明本发明而不是对本发明的进一步限定。
实施例1：
(1)将60ml乙醇、3ml 3-(异丁烯酰氯)丙基三甲氧基硅烷、3ml去离子水与 3ml盐酸在60℃条件下机械搅拌8h形成均一溶液，通过离心得到白色产物，再用乙醇洗涤6次，将产物在60℃下干燥得到八乙烯基多面体低聚倍半硅氧烷；
(2)将2.518g氢氧化锂与12.348g丙烯酸溶解在30ml甲醇中，磁力搅拌4h，将所得溶液倒入200ml丙酮中，形成沉淀，通过抽滤洗涤得到白色固体产物，然后经冷冻干燥得到丙烯酸锂粉末；
(3)取0.078g八乙烯基多面体低聚倍半硅氧烷与0.02g偶氮二异丁腈溶解在 10ml二甲基亚砜中，在超声波作用下得到均一溶液A，取0.435g丙烯酸锂与0.02g 偶氮二异丁腈溶解在10ml二甲基亚砜中，在超声波作用下得到均一溶液B，在氮气氛围中70℃条件下，将B溶液逐滴滴入A溶液中，磁力搅拌12h，形成白色凝胶，用乙醇离心洗涤4次，在40℃条件下干燥得到聚丙烯酸锂/八乙烯基多面体低聚倍半硅氧烷星型交联聚合物；
(4)取步骤(3)中制备的聚丙烯酸锂/八乙烯基多面体低聚倍半硅氧烷星型交联聚合物在充满氩气的管式炉中500℃焙烧2h进行碳化，自然冷却至室温，研磨均匀，得到粉末状产物；
(5)取0.035g步骤(4)中碳化后的粉末产物、0.01g乙炔黑和0.005g聚偏氟乙烯，滴入N-甲基吡咯烷酮，用球磨机球磨4h，将混合浆料涂布在铜箔上，真空下100℃干燥12h，得到负极浆料。
实施例2：(1)将60ml乙醇、3ml乙烯基三乙氧基硅烷、3ml去离子水与 3ml盐酸在50℃条件下机械搅拌10h形成均一溶液，通过离心得到白色产物，再用乙醇洗涤6次，将产物在40℃下干燥得到八乙烯基多面体低聚倍半硅氧烷；
(2)将2.414g氢氧化锂与14.456g丙烯酸溶解在30ml甲醇中，磁力搅拌6h，将所得溶液倒入200ml丙酮中，形成沉淀，通过抽滤洗涤得到白色固体产物，然后经冷冻干燥得到丙烯酸锂粉末；
(3)取0.087g八乙烯基多面体低聚倍半硅氧烷与0.02g偶氮二异庚腈溶解在 10ml二甲基亚砜中，在超声波作用下得到均一溶液A，取0.508g丙烯酸锂与0.02g 偶氮二异庚腈溶解在10ml二甲基亚砜中，在超声波作用下得到均一溶液B，在氮气氛围中75℃条件下，将B溶液逐滴滴入到A溶液中，磁力搅拌16h，形成白色凝胶，用乙醇离心洗涤4次，在50℃条件下干燥得到聚丙烯酸锂/八乙烯基多面体低聚倍半硅氧烷星型交联聚合物；
(4)取步骤(3)中制备的聚丙烯酸锂/八乙烯基多面体低聚倍半硅氧烷星型交联聚合物在充满氩气的管式炉中550℃焙烧3h进行碳化，自然冷却至室温，研磨均匀，得到粉末状产物；
(5)取0.0525g步骤(4)中碳化后的粉末状固体、0.015g乙炔黑和0.0075g聚偏氟乙烯，滴入N-甲基吡咯烷酮，用球磨机球磨4h，将混合浆料涂布在铜箔上，真空下110℃干燥10h，得到负极浆料。
实施例3：(1)将60ml乙醇、3ml乙烯基三乙氧基硅烷、3ml去离子水与 3ml盐酸在50℃条件下机械搅拌7h形成均一溶液，通过离心得到白色产物，再用乙醇洗涤6次，将产物在40℃下干燥得到八乙烯基多面体低聚倍半硅氧烷；
(2)将2.218g氢氧化锂与12.348g丙烯酸溶解在30ml甲醇中，磁力搅拌4h，将所得溶液倒入200ml丙酮中，形成沉淀，通过抽滤洗涤得到白色固体产物，然后经冷冻干燥得到丙烯酸锂粉末；
(3)取0.086g八乙烯基多面体低聚倍半硅氧烷与0.02g偶氮二异庚腈溶解在 10ml二甲基亚砜中，在超声波作用下得到均一溶液A，取0.476g丙烯酸锂与0.02g 偶氮二异庚腈溶解在10ml二甲基亚砜中，在超声波作用下得到均一溶液B，在氮气氛围中75℃条件下，将B溶液逐滴滴入到A溶液中，磁力搅拌12h，形成白色凝胶，用乙醇离心洗涤4次，在50℃条件下干燥得到聚丙烯酸锂/八乙烯基多面体低聚倍半硅氧烷星型交联聚合物；
(4)取步骤(3)中制备的聚丙烯酸锂/八乙烯基多面体低聚倍半硅氧烷星型交联聚合物在充满氩气的管式炉中550℃焙烧2h进行碳化，自然冷却至室温，研磨均匀，得到粉末状产物；
(5)取0.0525g步骤(4)中碳化后的粉末状固体、0.015g乙炔黑和0.0075g聚偏氟乙烯，滴入N-甲基吡咯烷酮，用球磨机球磨4h，将混合浆料涂布在铜箔上，真空下100℃干燥12h，得到负极浆料。
Claims (4)
1.一种抑制锂枝晶增长的锂离子电池负极浆料的制备方法，其特征在于，包括如下步骤：
(1)将乙醇、硅烷偶联剂、去离子水与盐酸按照体积比20:1:1:1在50～60℃条件下机械搅拌8～10h形成均一溶液，通过离心得到白色产物，再用乙醇洗涤6次，将产物在40～60℃下干燥得到八乙烯基多面体低聚倍半硅氧烷；
(2)将氢氧化锂与丙烯酸按照摩尔比1:1.5～2溶解在甲醇中，磁力搅拌2～6h，将所得溶液与丙酮按照体积比3:20混合，形成沉淀，通过洗涤抽滤得到白色固体产物，然后经冷冻干燥得到丙烯酸锂粉末；
(3)取步骤(1)中制备的八乙烯基多面体低聚倍半硅氧烷与引发剂溶解在二甲基亚砜中，在超声波作用下得到均一溶液A，取步骤(2)中制备的丙烯酸锂与引发剂溶解在二甲基亚砜中，在超声波作用下得到均一溶液B，在氮气氛围下，65～80℃条件下，将B溶液逐滴滴入到A溶液中，磁力搅拌12～24h，形成白色凝胶，用乙醇离心洗涤4次，在40～60℃条件下干燥得到聚丙烯酸锂/八乙烯基多面体低聚倍半硅氧烷星型交联共聚物；
(4)取步骤(3)中制备的聚丙烯酸锂/八乙烯基多面体低聚倍半硅氧烷星型交联共聚物在充满氩气的管式炉中，450～600℃焙烧2～3h进行碳化，自然冷却至室温，研磨均匀，得到粉末状产物；
(5)取步骤(4)中碳化后的粉末状产物、乙炔黑和聚偏氟乙烯按照质量比7:2:1，滴入N-甲基吡咯烷酮，用球磨机球磨2～4h后，将混合浆料涂布在铜箔上，真空下100～120℃干燥10～14h，得到负极浆料。
2.根据权利要求1所述的一种抑制锂枝晶增长的锂离子电池负极浆料，其特征在于：步骤(1)所述的硅烷偶联剂为3-(异丁烯酰氯)丙基三甲氧基硅烷、乙烯基三乙氧基硅烷的至少一种。
3.根据权利要求1所述的一种抑制锂枝晶增长的锂离子电池负极浆料，其特征在于：步骤(3)所述的引发剂为偶氮二异丁腈、偶氮二异庚腈的至少一种。
4.根据权利要求1所述的一种抑制锂枝晶增长的锂离子电池负极浆料，其特征在于：步骤(3)所述的八乙烯基多面体低聚倍半硅氧烷与聚丙烯酸锂的摩尔比为1:24～40。
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