CN111916690A - 一种锂离子电池硅碳负极制备方法 - Google Patents
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Abstract
一种锂离子电池硅碳负极制备方法:包括制浆、涂布、干燥、碾压、切片步骤,其中制浆过程中混合CMC溶液和SBR乳液作为粘结剂,并采用异丙醇溶液作为溶剂。本发明的方法具有所制备的硅碳负极比容量高、循环稳定性好、原材料价格便宜、工艺简单、环保等优点。
Description
技术领域
本发明涉及一种一种锂离子电池硅碳负极制备方法,属于锂离子电池技术领域。
背景技术
随着社会经济的高速发展,能源危机和环境问题日益加剧。锂离子电池因其具有能量密度高、功率密度高、循环寿命长、无记忆效应、自放电率低、工作温度范围宽、环境友好等优点,已经在便携式消费电子、电动工具、医疗电子等领域获得了广泛应用。在纯电动汽车、混合动力汽车以及储能等领域也显示了良好的应用前景。近年来,各个领域对电池能量密度的需求飞速提高,迫切需要开发出更高能量密度的锂离子电池。目前,商业化的锂离子电池主要是以石墨为负极材料,石墨的理论比容量为372mAh/g,而市场上的高端石墨材料已经可以达到360~365mAh/g,因此相应锂离子电池能量密度的提升空间已相当有限。
硅的氧化物负极因具有来源简单、高循环稳定性、成本低、比容量相对较高(约为1500mAh/g,远远高于石墨)等特点,近年来受到越来越多的关注。研究表明,氧化亚硅(SiO)基负极良好的循环稳定性主要来自于其特殊的反应机制,即在首周合金化过程中,氧化物首先与锂反应生成了电化学惰性的氧化锂、硅酸锂以及活性的纳米硅簇,随后均匀填埋于惰性组分中的纳米硅簇与锂发生进一步的合金化反应。由于惰性基质能够有效地缓冲纳米硅簇合金化和去合金化过程中的体积效应,改善了活性组分的循环稳定性。然而,由于氧化物和硅酸盐的形成为不可逆过程,氧化亚硅负极的首周效率较低。此外,纳米硅簇在循环过程中仍然存在团聚趋势,影响氧化亚硅基负极的循环稳定性。
已知工艺多用表面包覆的方式来缓冲氧化亚硅在充放电循环过程中的体积膨胀,制备工艺复杂,成本高。
发明内容
本发明的发明目的在于提供一种锂离子电池硅碳负极制备方法,以简单、经济、环保的制备工艺制备了SiO与碳的复合负极,该负极利用SiO与碳的复合,提高了SiO材料的导电性,缓冲了SiO材料的体积效应,并抑制了循环过程中SiO材料的团聚,显著提高了SiO的电化学性能。
本发明的技术方案如下:
一种锂离子电池硅碳负极制备方法:包括制浆、涂布、干燥、碾压、切片步骤,其中,
制浆步骤:
制浆用到的材料和试剂为:氧化亚硅,粒径<100μm;人工石墨;导电炭黑;羧甲基纤维素钠,使用前用水配置成4%重量比的溶液;固含量40.7%的丁苯橡胶乳液;异丙醇,使用前用水配置成10%(重量比)的溶液;
负极配方按固体含量计相对重量比为SiO/石墨/导电炭黑/CMC/SBR=18.4/73.6/2/3/3。实际制浆过程使用溶液,负极配方根据实际称量的溶液计算重量比例为SiO颗粒/石墨/导电炭黑/4%CMC溶液/10%异丙醇溶液/SBR乳液=294.4/1177.6/32/960/3000/117.9;
具体制浆过程为:将SiO颗粒/石墨/导电炭黑/4%CMC溶液/10%异丙醇溶液混合后,球磨6h让混合物混合均匀,之后加入SBR乳液,球磨过夜。
其中,具体涂布步骤为:将混合好的浆料用一个固定厚度为100μm的刀片涂布到铜箔上;
其中,具体干燥步骤为:将涂布好的电极在室温下自然干燥3h,之后在温度60℃、真空为10-2Torr下干燥24h;
其中,具体碾压步骤为:将干燥好的极片用40μm厚度的辊压机碾压;
其中,具体切片步骤为:碾压后的电极根据需要切割成面积合适的极片。
相对于现有的制备工艺,采用本发明的制备工艺至少具有以下有益效果:
(1)本工艺方法用石墨和氧化亚硅制备的复合材料负极有远远高于石墨的比容量,同时又有良好的循环稳定性;
(2)本工艺用到的都是水性的粘结剂,工艺中仅用无毒的异丙醇和水作溶剂,氧化亚硅容易制备,原材料价格便宜,工艺简单、环保。
附图说明
图1为本发明的锂离子电池硅碳负极制备方法的流程图;
图2为负极极片照片;其中a为制浆过程中未添加异丙醇的负极极片,b为制浆过程中添加了异丙醇的负极极片;
图3为按照本工艺流程涂布的负极极片扫描电镜图;
图4负极的循环容量;
图5为负极循环的库仑效率。
具体实施方式
图1示出了本发明的锂离子电池硅碳负极制备方法的流程图;利用锂离子电池硅碳负极制备方法:包括制浆、涂布、干燥、碾压、切片五个步骤。
制浆步骤为:
所用材料和试剂:制浆用到的材料和试剂为:氧化亚硅(SiO),粒径<100μm;人工石墨(SPG6);导电炭黑(TIMCAL SUPER C65);羧甲基纤维素钠(CMC)(平均分子量Mw 250000,取代度0.90),使用前用水配置成4%(重量比)的CMC溶液;丁苯橡胶(SBR)乳液(JSRTRD105A,固含量40.7%(重量比));异丙醇(分析纯),使用前用水配置成10%(重量比)的溶液;
负极配方按固体含量计为SiO/石墨/导电炭黑/CMC/SBR=18.4/73.6/2/3/3(重量比)。实际制浆过程中用到了溶液,负极配方根据实际称量的溶液计算为SiO颗粒/石墨/导电炭黑/4%CMC溶液/10%异丙醇溶液/SBR乳液=294.4/1177.6/32/960/3000/117.9(重量比)。
具体制浆过程如下:
将将纳米硅、石墨、导电炭黑、CMC、水混合在一起,球磨6h,之后加入SBR乳液,球磨过夜。
涂布步骤为:
混合好的浆料用一个固定厚度为100μm的刀片涂布到铜箔上。
干燥步骤为:
涂布好的电极在室温下自然干燥3h,之后在温度60℃、真空为10-2Torr下干燥24h。
碾压步骤为:
干燥好的极片用40μm厚度的辊压机碾压。
切片步骤为:
碾压后的电极根据需要切割成面积合适的极片。
需要说明的是,商业化石墨材料本身是不亲水的,很难在水中分散,使用CMC的一个作用就是作为分散剂,分散石墨和导电剂,另外CMC在水中会形成凝胶,使得浆料变稠(增稠剂),这样如果大规模涂覆时,因为凝胶结构的存在,既能保水份又能稳定浆料,在一定时间内能够保持浆料的均匀性,有利于大规模生产。但是CMC单独作为粘结剂时的粘性不强,且脆性大、柔顺性差,在碾压时活性物质易脱落,充放电循环时极片易龟裂。SBR乳液是溶于水的,SBR本身是柔性材料,具有较好的粘接性能,这样极片在高压实的情况下,极片不会掉粉,碾压后的极片粘接强度也高,因此,本工艺用CMC和SBR混合使用作为粘结剂。试验了CMC和SBR不同比例的效果,CMC和SBR比例在介于3:2和2:3(重量比)之间效果最佳,而CMC和SBR粘结剂总重量占负极总重量5-6%之间,效果最佳,因此,本方法最终确定CMC和SBR的比例为1:1(重量比),CMC和SBR的总重量占负极总重量的6%。经过反复试验,导电炭黑(导电剂)占负极总重量的2%可以达到最佳效果,导电炭黑太少,影响活性物质颗粒间的导电性,会导致循环性能不佳;导电炭黑太多,则会导致极片比容量下降。CMC和SBR都是水溶性粘结剂,在试验中发现,如果在制浆过程中只用水为溶剂,在涂布极片的时候,浆料会在铜箔表面团聚收缩,造成极片涂布不均匀并有大片铜箔暴露(图2中a);为了改进涂布工艺,经过反复试验,发现用10%异丙醇水溶液代替水为溶剂可以达到理想的涂布效果(图2中b)。按照本工艺流程涂布的负极极片扫描电镜图(图3)显示,负极极片颗粒致密,无裂缝和孔洞(图3中a),导电剂在颗粒间(图3中b)和颗粒表面(图3中c)分布均匀。负极极片的宏观形貌(图2中b)和微观形貌(图3)均表明负极极片涂布效果很好。
进一步的测试试剂包括:碳酸乙烯酯(EC),电池级;碳酸二乙酯(DEC),电池级;氟代碳酸乙烯酯(FEC),电池级。
将干燥碾压后的负极极片切割成面积为1.6cm2的圆形极片,用高纯锂片为对电极(阴极),以本发明负极极片作为阳极,聚丙烯多孔膜为隔膜,装配成标准2325扣式电池。其中,电解液为1.2M LiPF6的EC:DEC(质量比:1:2)溶液中添加2%(重量比)的FEC。电池的组装在充满高纯氩气的手套箱中进行。扣式电池的循环性能在Maccor电池测试系统上进行,测试电流密度为1/3C(200mA/g)。
测试结果表明,本发明负极极片的首圈比容量可达到约570mAh/g,在循环10圈之后,比容量仍保持在约500mAh/g(图4),远远高于石墨的理论比容量(372mAh/g)。
3批不同极片的循环比容量几乎完全相同,首圈库仑效率可达到73%以上,从第二圈开始,库仑效率超过97%,在循环10圈后更是达到99%以上(图5),说明本发明的工艺流程能保证制备出一致性好、比容量高、循环性能优异的负极极片。
以上所述,仅为本发明较佳具体实施方式,但本发明保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明披露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。因此本发明保护范围以权利要求书的保护范围为准。
Claims (6)
1.一种锂离子电池硅碳负极制备方法:包括制浆、涂布、干燥、碾压、切片步骤,其中,
制浆步骤:
制浆用到的材料和试剂为:氧化亚硅,粒径<100μm;人工石墨;导电炭黑;羧甲基纤维素钠,使用前用水配置成4%重量比的溶液;固含量40.7%的丁苯橡胶乳液;异丙醇,使用前用水配置成10%重量比的溶液;
负极配方按固体含量计相对比例为SiO/石墨/导电炭黑/CMC/SBR=18.4/73.6/2/3/3;实际制浆过程使用溶液,负极配方根据实际称量的溶液计算重量比例为SiO颗粒/石墨/导电炭黑/4%CMC溶液/10%异丙醇溶液/SBR乳液=294.4/1177.6/32/960/3000/117.9;
具体制浆过程为:将SiO颗粒/石墨/导电炭黑/4%CMC溶液/10%异丙醇溶液混合后,球磨6h让混合物混合均匀,之后加入SBR乳液,球磨过夜。
2.根据权利要求1所述的锂离子电池硅碳负极制备方法,其特征在于,具体涂布步骤为:将混合好的浆料用一个固定厚度为100μm的刀片涂布到铜箔上。
3.根据权利要求1所述的锂离子电池硅碳负极制备方法,其特征在于,具体干燥步骤为:将涂布好的电极在室温下自然干燥3h,之后在温度60℃、真空为10-2Torr下干燥24h。
4.根据权利要求1所述的锂离子电池硅碳负极制备方法,其特征在于,具体碾压步骤为:将干燥好的极片用40μm厚度的辊压机碾压。
5.根据权利要求1所述的锂离子电池硅碳负极制备方法,其特征在于,具体切片步骤为:碾压后的电极根据需要切割成面积合适的极片。
6.根据权利要求1所述的锂离子电池硅碳负极制备方法,其特征在于,羧甲基纤维素钠的平均分子量Mw 250000,取代度0.90。
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