CN116190651A - 锂离子电池负极浆料、负极极片的制备方法及负极极片 - Google Patents
锂离子电池负极浆料、负极极片的制备方法及负极极片 Download PDFInfo
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Abstract
本发明公开了一种锂离子电池负极浆料,主要组份为负极活性物质、导电剂、粘接剂、增塑剂;增塑剂为碳酸乙烯酯和/或碳酸丙烯酯;以主要组分的质量之和为100%计,增塑剂的质量百分比为0.5%~2.5%,所述锂离子电池负极浆料的25℃粘度不大于3000mpa.s。本发明锂离子电池负极浆料利用增塑剂抑制浆料涂层干燥过程中的粘接剂上浮,提高干燥后和冷压后浆料涂层与集流体的剥离强度,有效减少负极极片表面裂纹;该较低粘度的负极浆料适用于更高风速和温度的干燥工艺,利于提高负极极片的生产效率。本发明还公开了一种负极极片的制备方法及负极极片。
Description
技术领域
本发明涉及锂离子电池浆料技术领域,具体涉及锂离子电池负极浆料、负极极片的制备方法及负极极片。
背景技术
锂离子电池负极浆料的主要组份为石墨/碳硅复合材料、导电剂、粘接剂和溶剂。溶剂为水的基础上,浆料的粘度和加工性能主要取决于粘接剂的具体组成,粘接剂多为水基粘接剂羧甲基纤维素钠和丁苯胶乳的组合。
传统负极浆料与集流体的粘接力欠佳,干燥过程中负极浆料涂层内的粘接剂组分随溶剂上浮迁移并在涂层表面富集,涂覆负极浆料的集流体在烘烤后容易出现涂层开裂的问题,而充放电过程中负极的粉化裂纹会进一步导致锂离子电池的容量损失、电池内阻增加等问题。工艺角度的改进方法包括调整温度梯度、适当降低烘干温度。
另外,低粘度的负极浆料具有良好的流动性,但是干燥困难,涂布的干燥速率低,也会加剧涂层龟裂、浆料颗粒团聚、面密度一致性不好等问题,因此烘干温度的降低会进一步加剧涂层的缺陷。如何在优化极片抗开裂性能、电芯倍率放电性能的同时,提高负极极片的生产效率,是本领域亟待解决的技术问题之一。
发明内容
本发明的目的之一在于克服现有技术中存在的缺陷,提供一种锂离子电池负极浆料,通过在较低粘度的负极浆料中加入增塑剂,负极浆料的流平速度快,浆料涂层与集流体的剥离强度高。
为了实现上述目的,本发明的技术方案为:锂离子电池负极浆料,主要组份为负极活性物质、导电剂、粘接剂、增塑剂;增塑剂为碳酸乙烯酯和/或碳酸丙烯酯;
以主要组分的质量之和为100%计,增塑剂的质量百分比为0.5%~2.5%,所述锂离子电池负极浆料的25℃粘度不大于3000mpa.s。
优选的技术方案为,所述增塑剂的质量百分比为0.55%~1.5%。进一步的,增塑剂的质量百分比为0.68%~1.5%,具体可选0.68%、0.7%、0.8%、0.9%、1.0%、1.1%、1.2%、1.3%、1.4%、1.5%等点值或者两点值之间的区间值。
优选的技术方案为,所述锂离子电池负极浆料的25℃粘度为1900~2700mpa.s。进一步的,所述锂离子电池负极浆料的25℃粘度为1900~2500mpa.s,更进一步的,粘度为1900~2300mpa.s。具体可选1900mpa.s、1950mpa.s、2000mpa.s、2050mpa.s、2100mpa.s、2150mpa.s、2200mpa.s、2250mpa.s、2300mpa.s等点值或者两点值之间的区间值。
除主要组分外,锂离子电池负极浆料还包括溶剂。进一步的,溶剂为水,优选为去离子水。
优选的技术方案为,以主要组分的质量之和为100%计,负极活性物质的质量百分比为94.1%~97.0%,导电剂的质量百分比为0.8%~1.5%,粘接剂的质量百分比为1.5%~4%,增塑剂的质量百分比为0.55%~1.5%。进一步的,负极活性物质的质量百分比为94.3%~96.3%,导电剂的质量百分比为0.8%~1.2%,粘接剂的质量百分比为2.2%~3.3%,增塑剂的质量百分比为0.68%~1.5%。
优选的技术方案为,所述粘接剂的主要组份为羧甲基纤维素钠和SBR-PAA复合粘接剂;羧甲基纤维素钠的质量百分比不大于1.5%。
优选的技术方案为,羧甲基纤维素钠的质量百分比为0.8%~1.4%,SBR-PAA复合粘接剂的质量百分比为1.4%~2.2%。进一步的,羧甲基纤维素钠的质量百分比为0.9%~1.3%,SBR-PAA复合粘接剂的质量百分比为1.5%~2.0%。羧甲基纤维素钠的质量百分比具体可选0.9%、0.95%、1%、1.05%、1.1%、1.15%、1.2%、1.25%、1.3%等点值或者两点值之间的区间值;SBR-PAA复合粘接剂的质量百分比具体可选1.5%、1.55%、1.6%、1.65%、1.7%、1.75%、1.8%、1.85%、1.9%、1.95%、2.0%等点值或者两点值之间的区间值。
SBR为丁苯胶乳;PAA为聚丙烯酸粘接剂。
优选的技术方案为,所述导电剂中包含单壁碳纳米管。
优选的技术方案为,单壁碳纳米管的质量百分比为0.03%~0.15%。进一步的,单壁碳纳米管的质量百分比为0.03%~0.12%。
本发明的目的之二在于提供负极极片的制备方法,包括以下步骤:将上述的负极浆料涂布于集流体的表面,经干燥、冷压制得负极极片,烘箱干燥风速为10~15m/s,烘箱干燥温度为90~120℃。进一步的,烘箱干燥风速为11~15m/s,烘箱干燥温度为101~115℃,更进一步的,烘箱干燥风速13~15m/s,烘箱干燥温度为110~115℃,
本发明的目的之二在于提供负极极片,经由上述的负极极片的制备方法制得。
本发明的优点和有益效果在于:
本发明锂离子电池负极浆料通过配置合适的负极浆料粘度,加入碳酸乙烯酯和/或碳酸丙烯酯作为增塑剂,利用增塑剂抑制浆料涂层干燥过程中的粘接剂上浮,提高干燥后和冷压后浆料涂层与集流体的剥离强度,有效减少负极极片表面裂纹;
包含增塑剂负极浆料的粘度较低,流平性能良好,在确保无涂层开裂的基础上,该负极浆料适用于更高风速和温度的干燥工艺,利于提高负极极片的生产效率。
附图说明
图1是实施例1-1、实施例2-1和对比例1的电性能变化折线图;
图2是对比例1涂布后(左图)和冷压后(右图)的NG负极极片照片,椭圆弧圈出区域为裂纹位置;
图3是实施例3-2涂布后(左图)和冷压后(右图)的OK负极极片照片。
具体实施方式
下面结合实施例,对本发明的具体实施方式作进一步描述。以下实施例仅用于更加清楚地说明本发明的技术方案,而不能以此来限制本发明的保护范围。
负极活性物质、导电剂、粘接剂、增塑剂构成锂离子电池负极浆料的主要组分。进一步的,负极活性物质、导电剂、粘接剂、增塑剂的质量之和占锂离子电池负极浆料除溶剂外质量的98%以上,更进一步的,负极活性物质、导电剂、粘接剂、增塑剂的质量之和占锂离子电池负极浆料除溶剂外质量的99%以上,更进一步的,负极活性物质、导电剂、粘接剂、增塑剂的质量之和等于锂离子电池负极浆料除溶剂外的质量。
在水作为负极浆料溶剂的基础上,粘接剂优选为水性粘接剂。例如粘接剂为SBR、CMC、PAA中一种或者两种以上复合,更优选为三种复合。
负极活性物质为人造石墨、天然石墨、硅、硅氧活性物质和碳硅复合材料中的至少一种。
导电剂为炭黑、碳纳米管中的至少一种,进一步的,为炭黑和碳纳米管组合而成。更进一步的,碳纳米管为单臂碳纳米管。碳管的主要作用是为了提供导电网络,防止硅负极充放电过程中破碎。
在以下实施例和对比例中,所使用的试剂、材料如没有特殊说明,均可商购获得。SBR-PAA复合粘结剂为上海道赢实业有限公司型号为GD1346L的市售产品,其中固含量为40%,以下实施例中SBR-PAA复合粘结剂在负极浆料中的含量以加入胶乳干重的质量计算。
试样电池制备
1、正极极片的制备
正极浆料中主要组分的配方比例:LiNiCoMnO2(镍钴锰酸锂,NCM):Super-P(导电碳黑,导电剂):PVDF(聚偏氟乙烯)比例为98:1:1;正极极片制备方法如下:
S1:将NMP(N,N-二甲基吡咯烷酮)于PVDF混合且搅拌均匀得到胶液,然后按照配方比例设定固含量75%,将活性物质NCM与导电剂加入胶液中并搅拌均匀,得到粘度在3000mpa.s左右混合均匀的浆料;
S2:将浆料按照一定的宽度和厚度均匀涂布在12μm厚的正极集流体(铝箔)的两面,经过冷压、分切,制得正极极片。
2、负极极片的制备
按比例配置活性物质(碳硅复合材料)、导电剂(Super-P、SW-CNT)、粘结剂(CMC、SBR-PAA复合粘结剂)、实施例的增塑剂(EC)以及溶剂(去离子水),负极极片制备方法如下:
S1’:将去离子水与CMC混合且搅拌均匀得到胶液,然后按照配方比例设定固含量50%,将活物质硅碳复合材料、导电剂加入胶液中并搅拌均匀,结束后加入增塑剂搅拌均匀,然后加入SBR-PAA复合粘结剂搅拌均匀,得到粘度在2000mpa.s左右混合均匀的浆料;
S2’:将浆料按照一定的宽度和厚度涂布在6um厚的负极集流体(铜箔)的两面,经过干燥、冷压制得负极极片。
3、电池组装
将正负极极片与双面涂覆陶瓷隔膜(隔膜涂覆陶瓷层>2um)按照设定工艺参数进行卷绕,其中隔膜包覆负极>2mm,负极包覆正极>1mm;然后将极片隔膜卷绕制成圆柱体卷芯;
将卷芯组装至壳体,90℃烘烤除水分;将电解液注入到电芯中,制成圆柱电芯;按照化成工艺参数进行化成,高温搁置,分容制备出正极克容量发挥>195mAh/g,25℃循环>85%@800cyc的高性能4680圆柱电池。
一、增塑剂对负极极片涂层剥离强度、开裂现象和电性能的影响
实施例1
实施例1负极浆料中主要组分按照以下比例配置:碳硅复合材料:Super-P:SW-CNT(单壁碳纳米管):CMC:SBR-PAA复合粘结剂:碳酸乙烯酯按照质量之比为96:0.95:0.05:1.2:1.8:1;
以主要组分的质量之和为100%计,实施例1各主要组分的质量百分比分别为:95.05%的碳硅复合材料、0.94%的Super-P、0.0495%的SW-CNT、1.188%的CMC、1.782%的SBR-PAA复合粘结剂、0.99%的碳酸乙烯酯;
负极极片干燥工艺参数烘箱风速10m/s、烘箱加热温度90℃;冷压工艺参数:压力50吨,辊缝80μm;此工艺所得负极极片以及电池试样标记为实施例1-1。
实施例2
实施例2负极浆料中主要组分按照以下比例配置:碳硅复合材料:Super-P:SW-CNT(单壁碳纳米管):CMC:SBR-PAA复合粘结剂:碳酸乙烯酯按照质量之比为96:0.9:0.1:1.0:1.8:1.5;
以主要组分的质量之和为100%计,实施例1各主要组分的质量百分比分别为:94.77%的碳硅复合材料、0.888%的Super-P、0.099%的SW-CNT、0.987%的CMC、1.777%的SBR-PAA复合粘结剂、1.481%的碳酸乙烯酯;
负极极片干燥工艺同实施例1-1,所得负极极片以及电池试样标记为实施例2-1。
对比例1
对比例1负极浆料中主要组分按照以下比例配置:碳硅复合材料:Super-P:SW-CNT:CMC:SBR-PAA复合粘结剂质量之比为96:0.95:0.05:1.2:1.8;
以主要组分的质量之和为100%计,实施例1各主要组分的质量百分比分别为:96%的碳硅复合材料、0.95%的Super-P、0.05%的SW-CNT、1.2%的CMC、1.8%的SBR-PAA复合粘结剂;
对比例1负极极片干燥工艺同实施例1-1。
试样的检测(剥离强度、电性能均平行试验取平均值)
1、集流体表面涂布负极浆料,干燥后检测涂层和集流体的剥离强度,目检负极极片涂层的裂纹;
2、涂层干燥后的集流体经冷压处理,检测冷压后涂层和集流体的剥离强度,目检负极极片涂层的裂纹;
3、测试试样电池的电性能。
负极极片试样的目检质量评价
干燥后冷压前负极极片涂层出现裂纹,和/或冷压后负极极片涂层出现裂纹,均判定为NG,两次检测合格均判定为OK。
实施例1-1、实施例2-1和对比例1的负极极片试样剥离强度检测结果和目检质量评价见下表:
试样 | 干燥后剥离强度(N/m) | 冷压后剥离强度(N/m) | 极片质量评价 |
实施例1-1 | 9.93 | 22.9 | OK |
实施例2-1 | 12.1 | 26.1 | OK |
对比例1 | 6.2 | 18.1 | NG |
实施例1-1、实施例2-1和对比例1电池的电性能见附图1,与未加入增塑剂的对比例1相比,加入增塑剂的实施例1-1、实施例2-1浆料涂层与集流体剥离强度、包含负极极片的电池倍率放电能力均得到提升;
上表中,在增塑剂添加量小于1.5%时,随着增塑剂用量的增加,浆料涂层与集流体剥离强度逐渐增大;附图1中,在电池的倍率放电能力方面,实施例1-1的试样3C倍率放电能力较实施例2-1更高。二、增塑剂的加入量、干燥工艺参数对负极极片加工性能的影响
实施例1-2及实施例1-3
基于实施例1的负极浆料组成,实施例1-2中S2’的干燥工艺参数为:风速10.8m/s、加热温度95.5℃;冷压工艺参数同实施例1-1;
基于实施例1的负极浆料组成,实施例1-3中S2’的干燥工艺参数为风速14m/s、加热温度112.5℃;冷压工艺参数同实施例1-1。
实施例3
实施例3负极浆料中主要组分按照以下比例配置:碳硅复合材料:Super-P:SW-CNT(单壁碳纳米管):CMC:SBR-PAA复合粘结剂:碳酸乙烯酯按照质量之比为96:0.95:0.05:1.0:1.8:0.7;
以主要组分的质量之和为100%计,实施例1各主要组分的质量百分比分别为:95.52%的碳硅复合材料、0.945%的Super-P、0.0498%的SW-CNT、0.995%的CMC、1.791%的SBR-PAA复合粘结剂、0.697%的碳酸乙烯酯;
实施例3-1中S2’的干燥工艺参数:风速11.2m/s、加热温度101℃;冷压工艺参数同实施例1-1;
实施例3-2中S2’的干燥工艺参数:风速14m/s、加热温度112.5℃;冷压工艺参数同实施例1-1。
目检实施例1-2、1-3、实施例3-1的负极极片试样,并进行质量评价,结果如下:
试样 | 评价 | 烘箱风速/m/s | 烘箱温度/℃ | 备注 |
实施例3-1 | OK | 11.2 | 101 | |
实施例3-2 | OK | 14 | 112.5 | 临界,判定OK |
实施例1-2 | OK | 10.8 | 95.5 | |
实施例1-3 | OK | 14 | 112.5 |
由上表结果可知,实施例1负极浆料中增塑剂含量为0.99%,实施例3负极浆料中增塑剂含量为0.697%,烘箱风速提升至14m/s,烘箱温度提升至112.5℃均能制得无裂纹的负极极片;其中实施例3-2的“临界”指基本满足负极极片的不开裂指标。
实施例和对比例测试结果表明:负极浆料中负极活性物质、导电剂、粘接剂、增塑剂作为主要组成,增塑剂含量为0.69%~1.5%时,粘度较低(2000mpa.s)的负极浆料具有更优的加工性能,包含负极浆料涂层的负极极片适于更高的烘干效率,同时具有较高的倍率放电能力。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明技术原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.锂离子电池负极浆料,其特征在于,主要组份为负极活性物质、导电剂、粘接剂、增塑剂;增塑剂为碳酸乙烯酯和/或碳酸丙烯酯;
以主要组分的质量之和为100%计,增塑剂的质量百分比为0.5%~2.5%,所述锂离子电池负极浆料的25℃粘度不大于3000mpa.s。
2.根据权利要求1所述的锂离子电池负极浆料,其特征在于,所述增塑剂的质量百分比为0.55%~1.5%。
3.根据权利要求1所述的锂离子电池负极浆料,其特征在于,所述锂离子电池负极浆料的25℃粘度为1900~2700mpa.s。
4.根据权利要求1所述的锂离子电池负极浆料,其特征在于,以主要组分的质量之和为100%计,负极活性物质的质量百分比为94.1%~97.0%,导电剂的质量百分比为0.8%~1.5%,粘接剂的质量百分比为1.5%~4%,增塑剂的质量百分比为0.55%~1.5%。
5.根据权利要求1所述的锂离子电池负极浆料,其特征在于,所述粘接剂的主要组份为羧甲基纤维素钠和SBR-PAA复合粘接剂;羧甲基纤维素钠的质量百分比不大于1.5%。
6.根据权利要求5所述的锂离子电池负极浆料,其特征在于,羧甲基纤维素钠的质量百分比为0.8%~1.4%,SBR-PAA复合粘接剂的质量百分比为1.4%~2.2%。
7.根据权利要求1所述的锂离子电池负极浆料,其特征在于,所述导电剂中包含单壁碳纳米管。
8.根据权利要求1所述的锂离子电池负极浆料,其特征在于,单壁碳纳米管的质量百分比为0.03%~0.15%。
9.负极极片的制备方法,其特征在于,包括以下步骤:将权利要求1至8中任意一项所述的负极浆料涂布于集流体的表面,经干燥、冷压制得负极极片,烘箱干燥风速为10~15m/s,烘箱干燥温度为90~120℃。
10.负极极片,其特征在于,经由权利要求9所述的负极极片的制备方法制得。
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