CN115548456B - 一种原位聚合半固态电池的制备方法 - Google Patents
一种原位聚合半固态电池的制备方法 Download PDFInfo
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- CN115548456B CN115548456B CN202211505924.8A CN202211505924A CN115548456B CN 115548456 B CN115548456 B CN 115548456B CN 202211505924 A CN202211505924 A CN 202211505924A CN 115548456 B CN115548456 B CN 115548456B
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- lithium
- situ polymerization
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- solid battery
- aging
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明公开了一种原位聚合半固态电池的制备方法;包括如下步骤:装配:将正极片、隔膜和负极片装配入壳制成干电芯;一次注液:注入锂电池液态电解液;陈化,化成;二次注液:注入聚合物单体、增塑剂和引发剂的混合物;所述聚合物单体为碳酸亚乙烯酯和磷酸三丙炔酯的组合;陈化,在58‑65℃原位聚合进行凝胶化,即得所述低阻抗半固态电池。本发明的二次注液配方中含有立体结构单体,交联后可将液态电解液锁定在立体结构中,和链状聚合物相比,可使用较少的聚合物达到凝胶的效果,形成的凝胶结构也更加稳定,热稳定性更好,同时液体组分更高,阻抗更小,进而获得较低阻抗的半固态电池。
Description
技术领域
本发明涉及半固态电池技术领域,具体涉及一种原位聚合半固态电池的制备方法。
背景技术
随着人们对提高锂离子电池能量密度的日益迫切的要求,传统锂离子电池已经很难满足超高比能量的需求。当前商业化的锂电池负极材料主要为改性天然石墨和人造石墨,尽管制备技术已相当成熟,但石墨的理论比容量只有372 mAh g-1,难以满足市场对高能量密度锂离子电池的需求。于是,基于高能量密度电池的需求,具有超高比能量优势的负极材料成为研究热点。例如:硅负极、金属合金负极和金属锂负极。以硅负极材料为例,目前主要使用掺比一定量的硅材料以达到提升比容量的目的。以金属锂负极为例,其比容量为3860mAh g-1,电化学势为-3.04V (vs. 标准氢电极)。以这些负极材料制作的电池可以有效提升能量密度,甚至可以达到400Wh kg-1以上甚至更高。而中、高镍三元锂电池因其活性较高,搭配高比容量负极材料后,在提高比能量密度的同时,对于电池安全性的提升也是重中之重。
然而,基于传统锂离子电池体系,高能量密度电池材料目前仍有很多安全隐患。材料本身较大的体积膨胀,结构的改变,和与液态电解液搭配时的循环寿命与安全性隐患。液态电解液无法有效抑制硅负极的巨大膨胀,或锂金属负极结构的变化和金属枝晶的生长,且枝晶可能刺穿隔膜而引发电池内部的短路,引发更大的安全问题。
原位聚合半固态电池可以有效降低电池中液态电解液的使用量,在提升电池的能量密度的同时,也将液态电解液可能引发的安全隐患同步降低。另外,半固态凝胶电解质在一定程度上可以有效抑制负极结构的改变和金属枝晶的生长,在提升比能量的同时可以较大程度地提高电池的安全性。但半固态电池的电解质配方和生产制造方法都会对电池的阻抗有较大影响,尤其是常规的原位聚合的方法导致聚合物参与了负极SEI膜的构成,导致电池的阻抗大大增加。
发明内容
本发明的目的在于提供一种原位聚合半固态电池的制备方法。通过优选的电解质配方与用量、特殊的制作工序,降低半固态电池的阻抗,同时提升电池的能量密度以及大大改善电池的安全性。
本发明的目的通过以下技术方案来实现的:
本发明涉及一种原位聚合半固态电池的制备方法,所述方法包括如下步骤:
S1、装配:将正极片、隔膜和负极片装配入壳制成干电芯;
S2、一次注液:注入锂电池液态电解液;
S3、陈化,化成;
S4、二次注液:注入聚合物单体、增塑剂和引发剂的混合物;所述聚合物单体为碳酸亚乙烯酯和磷酸三丙炔酯的组合;
S5、陈化,在58-65℃原位聚合进行凝胶化,即得所述半固态电池。
作为一个实施方案,二次注液的总量为一次注液的总量的5-30 wt.%。优选为10-20 wt.%。
作为一个实施方案,聚合物单体占二次注液的总量的70-95 wt.%(例如70wt.%、72wt.%、74wt.%、76wt.%、78wt.%、80wt.%、82wt.%、84wt.%、86wt.%、88wt.%、90wt.%、92wt.%、94wt.%、95wt.%等),优选为80-90wt.%。增塑剂占二次注液的总量的4.8-29.8 wt.%(例如4.8wt.%、7wt.%、10wt.%、13wt.%、15wt.%、17wt.%、20wt.%、22wt.%、25wt.%、27wt.%、29wt.%、29.8wt.%等)。引发剂占二次注液的总量的0.01-0.4 wt.%(例如0.01wt.%、0.05wt.%、0.1wt.%、0.15wt.%、0.2wt.%、0.25wt.%、0.3wt.%、0.35wt.%、0.4wt.%等),优选为0.05-0.1wt.%。
作为一个实施方案,聚合物单体中碳酸亚乙烯酯(VC):磷酸三丙炔酯(TPP)的质量比为10:1-100:1,优选为20:1-50:1。VC为主要聚合物单体,TPP为辅助聚合物单体,TPP中含有磷酸结构,可以降低半固态电解质的阻抗。如果VC含量过高将会导致电池的阻抗明显增加;如果VC含量过低将会导致电解质难以凝胶,无法有效形成半固态电解质。
作为一个实施方案,所述增塑剂为硅酸四乙酯(TEOS)、环氧接枝化的笼型环氧多面体寡聚倍半硅氧烷(EP-POSS)、硼酸(BA)、四氯化硅(SiCl4)中的一种或几种。优选为环氧接枝化的笼型环氧多面体寡聚倍半硅氧烷(EP-POSS)。EP-POSS具有笼状结构,可以将液态电解液锁在笼状结构内,减少液态电解液的流动,提高安全性能。
作为一个实施方案,所述引发剂为2,2-偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁酸二甲酯、过氧化苯甲酰中的一种或几种。
作为一个实施方案,步骤S3中,陈化温度为20-50℃,陈化时间为22-26h。优选为陈化温度45-48℃,陈化24h。
作为一个实施方案,步骤S3中,化成的温度为40±5℃,化成的压力为2000N-4000N。
作为一个实施方案,步骤S5中,陈化温度为20-50℃,陈化时间为22-26h。优选为陈化温度45-48℃,陈化24h。
作为一个实施方案,步骤S5中,原位聚合的时间为1.25-3h。
作为一个实施方案,步骤S2中,锂电池液态电解液的锂盐为六氟磷酸锂(LiPF6)、双氟磺酰亚胺锂(LiFSI)、双三氟甲磺酰亚胺锂(LiTFSI)、三氟甲基磺酸锂(LiCF3SO3)、四氟硼酸锂(LiBF4)、双草酸硼酸锂(LiBOB)、二氟草酸硼酸锂(LiODFB)、二氟双草酸磷酸锂(LiDFBP)中的一种或几种。
作为一个实施方案,所述负极片采用掺硅石墨负极、锂金属负极,或金属合金负极;所述掺硅石墨负极中掺硅量为3-80 wt.%,优选为5-60 wt.%,进一步优选为8-30 wt.%。所述金属合金负极包括Ga-Sn、Ge-Se或Sn-Al合金负极。
作为一个实施方案,所述正极片的材料采用高镍材料(NCM811、Ni90)、NCM111、NCM532、NCM622、NCM712、镍锰铝材料(NCA)、磷酸锰铁锂(LMFP)或磷酸亚铁锂(LiFePO4);所述Ni90结构式LiNixCoyMnzO2,其中x≥0.8。
作为一个实施方案,正、负极极片中均需要混合导电剂,具体为炭黑(super P),乙炔黑,多壁碳纳米管(MWCNT),单壁碳纳米管(SWCNT)中的一种或几种。
作为一个实施方案,正、负极极片中均需要粘结剂,具体为PEO(聚氧化乙烯),PVDF(聚偏氟乙烯),CMC(羧甲基纤维素钠),PU(聚氨酯),SBR(丁苯橡胶),PVA(聚乙烯醇),PAA(聚丙烯酸),PAN(聚丙烯腈)中的一种或几种。
与现有技术相比,本发明具有如下有益效果:
1)本发明使用原位聚合方法制作及生产半固态电池的技术;通过先注入常规液态电解液、化成后再注入聚合物单体、原位聚合的制作流程,形成较低阻抗的半固态电池;
2)二次注液配方中含有立体结构单体,交联后可将液态电解液锁定在立体结构中,和链状聚合物相比,可使用较少的聚合物达到凝胶的效果,形成的凝胶结构也更加稳定,热稳定性更好,同时液体组分更高,阻抗更小;
3)本发明的方法简单,和现有常规液态电池生产工艺兼容;通过该方法制得的半固态电池,阻抗接近液态电池,大大改善了现有半固态电池阻抗大的缺点。
附图说明
通过阅读参照以下附图对非限制性实施例所作的详细描述,本发明的其它特征、目的和优点将会变得更明显:
图1为原位聚合半固态电池的制备流程图;
图2为实施例1半固态电池的25℃ 50%SOC 3C DCIR曲线图。
具体实施方式
本发明的原位聚合半固态电池的制备过程如下:
本发明的实施例及对比例中的干电芯的制备过程如下:
首先混合浆料,其中,正极浆料配比为,9系三元材料(NCM-Ni90):导电炭黑(SuperP):碳纳米管(CNT800):粘结剂(PVDF_1100)=97:1.1:0.8:1.1,均为质量百分比(wt.%);
负极浆料配比为,石墨(BF):硅氧材料(Si-O):导电炭黑(Super P):碳纳米管(CNT800):粘结剂(羧甲基纤维素钠CMC_500):粘结剂(丁苯橡胶SBR)=88.1:6.5:1.8:0.2:1.2:2.2,均为质量百分比(wt.%);
然后进行涂布,将正极浆料涂到铝箔上,负极浆料涂到铜箔上,进行烘干收卷。之后进行辊压,然后进行分切。之后进行极芯卷绕,使用制作的正、负极片和隔膜,隔膜采用PE隔膜(3μm PVDF胶层+9μm基膜+3μm Al2O3陶瓷层+3μm PVDF胶层)。将卷绕后的极芯热压后对顶盖进行焊接,然后装配入壳制成干电芯。
干电芯烘烤后进行注液。如图1所示,电池完成装配后,一次注液先注入一定量的常规锂电池液态电解液。电解液为常规锂电池液态电解液,含有锂盐(可以是六氟磷酸锂LiPF6,双氟磺酰亚胺锂LiFSI,双三氟甲磺酰亚胺锂LiTFSI,三氟甲基磺酸锂LiCF3SO3,四氟硼酸锂LiBF4,双草酸硼酸锂LiBOB,二氟草酸硼酸锂LiODFB,二氟双草酸磷酸锂LiDFBP中的一种或几种)。注液后进行陈化工艺,陈化温度为20-50℃,优选为45-48℃,陈化24h。陈化后进行常规化成工艺,化成的温度为40±5℃,压力为2000N。化成后进行二次注液(二次注液的总量为一次注液量的5-30 wt.%,优选为10-20 wt.%),注入的为聚合物单体、增塑剂和引发剂的混合物。聚合物单体占二次注液量的70-95 wt.%,优选为80-90 wt.%,成分为碳酸亚乙烯酯VC和磷酸三丙炔酯(TPP)的组合,VC:TPP的质量比为10:1-100:1,优选为20:1-50:1。增塑剂占二次注液量的4.8-29.8 wt.%,采用硅酸四乙酯(TEOS)、环氧接枝化的笼型环氧多面体寡聚倍半硅氧烷(EP-POSS)、硼酸(BA)、四氯化硅(SiCl4)中的一种或几种。优选环氧接枝化的笼型环氧多面体寡聚倍半硅氧烷(EP-POSS)。引发剂占二次注液量的0.01-0.4wt.%,优选为0.05-0.1 wt.%,采用2,2-偶氮二异丁腈AIBN、偶氮二异庚腈ABVN、偶氮二异丁酸二甲酯AIBME、过氧化苯甲酰BPO中的一种或几种。注液后进行陈化,陈化温度为20-50℃,优选为45-48℃,陈化24h。陈化后进行原位聚合的温度为58-65℃,原位聚合的时间为1.25-3h。电解液中一些添加剂在持续的长时间高温下会不稳定,容易与极片材料引发不理想的分解副反应。因此需要控制温度不能过高,且时间不能过长。之后可以进行正常的分容工序,产出成品电芯。
下面结合实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明,但不以任何形式限制本发明。应当指出的是,对本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干调整和改进。这些都属于本发明的保护范围。
实施例1
干电芯烘烤后进行一次注液,注入450g常规锂电池液态电解液,常规电解液采用碳酸乙烯酯EC:碳酸甲乙酯EMC:碳酸二乙酯DEC:六氟磷酸锂LiPF6:双氟磺酰亚胺锂LiFSI:二氟磷酸锂LiPO2F2 :氟代碳酸乙烯酯FEC:硫酸乙烯酯DTD=22:28.2:20:12:12:0.5:4.5:0.8,均为质量百分比(wt.%)。一次注液后进行陈化,陈化温度为45℃,陈化24h;然后电池在高温高压条件下(温度为40±5℃,压力通过夹具控制,为2000N)化成;化成后进行二次注液,二次注液量为50g,组分为碳酸亚乙烯酯VC:磷酸三丙炔酯TPP:环氧接枝化的笼型环氧多面体寡聚倍半硅氧烷EP-POSS:2,2-偶氮二异丁腈AIBN:过氧化苯甲酰BPO=87.1:2.9:9.9:0.08:0.02, 均为质量百分比(wt.%)。在25℃陈化24h后将电池放入60℃的高温环境中进行凝胶反应2h,引发电解液的凝胶聚合形成半固态凝胶电解质。最后在室温条件下进行分容,得到成品电芯。
图2为本实施例制得的半固态电池的25℃ 50%SOC 3C DCIR曲线图,具体方法是:电池调节至50%SOC后,放置于25℃烘箱内,以3C的电流对电池进行放电,放电时间为30s,以放电时间为横坐标,电压为纵坐标,即可得到曲线图。通过计算,该电池的阻抗为53.3mΩ,与液态电池阻抗相当。
实施例2-5
实施例2-5提供了一种原位聚合低阻抗半固态电池的制备方法,基本同实施例1,具体注液量以及电解液组成见表1。
对比例1
干电芯烘烤后注入500g的电解液(本实施例的电解液为:常规电解液和聚合物单体、增塑剂和引发剂的混合物),一次注液的电解液的组成为EC:EMC:DEC:LiPF6:LiFSI:LiPO2F2:FEC:DTD:VC:TPP:EP-POSS:AIBN:BPO=19.8:25.38:18:10.8:10.8:0.45:4.05:0.72:8.71:0.29:0.99:0.008:0.002, 均为质量百分比(wt.%)。注液后进行陈化,陈化温度为45℃,陈化24h;然后将电池放入60℃的高温环境中进行凝胶反应2h,引发电解液的凝胶聚合形成半固态凝胶电解质;然后电池在高温高压条件下(温度为40±5℃,压力通过夹具控制,为2000N)化成,在25℃条件下陈化,室温条件下进行分容,得到成品电芯。
对比例2
干电芯烘烤后注入450g常规锂电池液态电解液,常规电解液采用EC:EMC:DEC:LiPF6:LiFSI:LiPO2F2 :FEC:DTD=22:28.2:20:12:12:0.5:4.5:0.8,均为质量百分比(wt.%),一次注液后进行陈化,陈化温度为45℃,陈化24h;然后电池在高温高压条件下(温度为40±5℃,压力通过夹具控制,为2000N)化成;化成后进行二次注液,二次注液量为50g,组分为VC:TMC:EP-POSS:AIBN:BPO=87.1:2.9:9.9:0.08:0.02, 均为质量百分比(wt.%),在25℃陈化24h后将电池放入60℃的高温环境中进行凝胶反应2h,引发电解液的凝胶聚合形成半固态凝胶电解质。最后在室温条件下进行分容,得到成品电芯。
对比例3
干电芯烘烤后注入450g常规锂电池液态电解液,常规电解液采用EC:EMC:DEC:LiPF6:LiFSI:LiPO2F2 :FEC:DTD=22:28.2:20:12:12:0.5:4.5:0.8,均为质量百分比(wt.%),一次注液后进行陈化,陈化温度为45℃,陈化24h;然后电池在高温高压条件下(温度为40±5℃,压力通过夹具控制,为2000N)化成;化成后进行二次注液,二次注液量为50g,组分为VC:TPP:SN:AIBN:BPO=87.1:2.9:9.9:0.08:0.02, 均为质量百分比(wt.%),在25℃陈化24h后将电池放入60℃的高温环境中进行凝胶反应2h,引发电解液的凝胶聚合形成半固态凝胶电解质。最后在室温条件下进行分容,得到成品电芯。
对比例4
干电芯烘烤后注入450g常规锂电池液态电解液,常规电解液采用EC:EMC:DEC:LiPF6:LiFSI:LiPO2F2 :FEC:DTD=22:28.2:20:12:12:0.5:4.5:0.8,均为质量百分比(wt.%),一次注液后进行陈化,陈化温度为45℃,陈化24h;然后电池在高温高压条件下(温度为40±5℃,压力通过夹具控制,为2000N)化成;化成后进行二次注液,二次注液量为50g,组分为VC:EP-POSS:AIBN:BPO=90:9.9:0.08:0.02, 均为质量百分比(wt.%),在25℃陈化24h后将电池放入60℃的高温环境中进行凝胶反应2h,引发电解液的凝胶聚合形成半固态凝胶电解质。最后在室温条件下进行分容,得到成品电芯。
对比例5
干电芯烘烤后注入450g常规锂电池液态电解液,常规电解液采用EC:EMC:DEC:
LiPF6:LiFSI:LiPO2F2:FEC:DTD=22:28.2:20:12:12:0.5:4.5:0.8,均为质量百分比
(wt.%),一次注液后进行陈化,陈化温度为45℃,陈化24h;然后电池在高温高压条件下(温
度为40±5℃,压力通过夹具控制,为2000N)化成;化成后进行二次注液,二次注液量为50g,
组分为VC: 叔丁基过氧化物=99.5:0.5(质量百分比(wt.%)), 均为质量百分比(wt.%),在
25℃陈化24h后将电池放入60℃的高温环境中进行凝胶反应2h,引发电解液的凝胶聚合形
成半固态凝胶电解质。最后在室温条件下进行分容,得到成品电芯。叔丁基过氧化物结构式
为。
性能测试:将各个实施例和对比例得到的电池调节至50%SOC后,放置于25℃烘箱内,以3C的电流对电池进行放电,放电时间为30s,以放电时间为横坐标,电压为纵坐标,即可得到曲线图,通过计算,得到各个实施例和对比例电池的阻抗,具体阻抗值见表1。
表1
以上对本发明的具体实施例进行了描述。需要理解的是,本发明并不局限于上述特定实施方式,本领域技术人员可以在权利要求的范围内做出各种变形或修改,这并不影响本发明的实质内容。
Claims (7)
1.一种原位聚合半固态电池的制备方法,其特征在于,所述方法由如下步骤组成:
S1、装配:将正极片、隔膜和负极片装配入壳制成干电芯;
S2、一次注液:注入锂电池液态电解液;
S3、陈化,化成;
S4、二次注液:注入聚合物单体、增塑剂和引发剂的混合物;所述聚合物单体为质量比为10:1-100:1的碳酸亚乙烯酯和磷酸三丙炔酯的组合;所述增塑剂为硅酸四乙酯、环氧接枝化的笼型环氧多面体寡聚倍半硅氧烷、四氯化硅中的一种或几种;二次注液的总量为一次注液的总量的5-30 wt.%;聚合物单体占二次注液的总量的70-95 wt.%,增塑剂占二次注液的总量的4.8-29.8 wt.%,引发剂占二次注液的总量的0.01-0.4 wt.%;
S5、陈化,在58-65℃原位聚合进行凝胶化,即得所述半固态电池。
2.根据权利要求1所述原位聚合半固态电池的制备方法,其特征在于,所述引发剂为2,2-偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁酸二甲酯、过氧化苯甲酰中的一种或几种。
3.根据权利要求1所述原位聚合半固态电池的制备方法,其特征在于,步骤S3中,陈化温度为20-50℃,陈化时间为22-26h;化成的温度为40±5℃,化成的压力为2000N-4000N。
4.根据权利要求1所述原位聚合半固态电池的制备方法,其特征在于,步骤S5中,陈化温度为20-50℃,陈化时间为22-26h;原位聚合的时间为1.25-3h。
5.根据权利要求1所述原位聚合半固态电池的制备方法,其特征在于,步骤S2中,锂电池液态电解液中锂盐为六氟磷酸锂、双氟磺酰亚胺锂、双三氟甲磺酰亚胺锂、三氟甲基磺酸锂、四氟硼酸锂、双草酸硼酸锂、二氟草酸硼酸锂、二氟双草酸磷酸锂中的一种或几种。
6.根据权利要求1所述原位聚合半固态电池的制备方法,其特征在于,所述负极片采用掺硅石墨负极、锂金属负极或金属合金负极;所述掺硅石墨负极中掺硅量为3-80 wt.%,所述金属合金负极包括Ga-Sn、Ge-Se或Sn-Al合金负极。
7.根据权利要求1所述原位聚合半固态电池的制备方法,其特征在于,所述正极片的材料采用NCM811、Ni90、NCM111、NCM532、NCM622、NCM712、镍锰铝材料、磷酸锰铁锂或磷酸亚铁锂;所述Ni90结构式为LiNixCoyMnzO2,其中x≥0.8。
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