CN107910568B - 一种锂原电池 - Google Patents

一种锂原电池 Download PDF

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CN107910568B
CN107910568B CN201711133240.9A CN201711133240A CN107910568B CN 107910568 B CN107910568 B CN 107910568B CN 201711133240 A CN201711133240 A CN 201711133240A CN 107910568 B CN107910568 B CN 107910568B
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杨勇
徐良帆
李益孝
高军
何华锦
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Xiamen University
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Abstract

本发明公开了一种锂原电池，基于固‑液相串联耦合反应模式，包括可反应固体正极、可离子导电与同时能在电极固相反应之后可发生串联耦合反应的液态电解质、隔膜和锂负极，该液态电解质包括溶剂和电解质盐。本发明将亚硫酸酯类化合物作为锂原电池中液态电解质的组分，由于亚硫酸酯类化合物的还原电位低于氟化碳和二氧化锰，亚硫酸酯类化合物可以在传统的固态放电完成后充当液态正极发生电化学还原反应提供可观的额外容量，有效地降低了电池的非活性组分质量占比，使得锂原电池高比能量的优势得到进一步地体现。

Description

一种锂原电池
技术领域
本发明属于化学电池技术领域，具体涉及一种锂原电池。
背景技术
随着消费类电子设备电动汽车等产业的发展，作为其电源的锂离子电池受到了广泛的关注，目前商业化的锂离子电池能量密度可达250Wh/kg。但对于一些对能量密度要求特别高的消费电子装备，航空/航天、深海、医疗上的应用，包括无线射频识别装置、遥感装置和人造心脏起搏器等，它要求电源拥有更高的能量密度以满足长时间持续工作的要求。
相比可充的锂离子电池，原电池特别是锂原电池，包括Li-MnO2、Li-SO2、Li-SOCl2和Li-CFx电池等拥有更高的比容量和能量密度，可以更好地满足这些应用的要求，其中氟化碳的理论能量密度达2180Wh/kg，远超目前商业化的锂离子电池。
虽然氟化碳等原电池固体正极材料本身具有非常高的比能量，但在组装的电池中还会包括其他非活性组分，因此组装后的锂原电池相比固体正极本身比能量会大大的降低。在传统的锂原电池中，电解质起到主要起到传导锂离子的作用，但其在电池中的质量占比较高，是影响电池整体比能量的重要因素。锂原电池不需要考虑充电过程，电解质组分只需要在传统固体正极放电完成前保持稳定即可。因此，如果设想通过合理的设计与选择电解质中部分溶剂/盐组分能够在传统的固体正极放电完成后充当液态正极，而且在一个较高的电压区间放电的话可以提供额外的容量，如果这种电解质组分比容量比较高的话将大大提升锂原电池的能量密度。
田艳艳等(Enhanced electrochemical performance of fluorinated carbonnanotube as cathode for Li-O-2primary batteries；Electrochimica Acta，2013，90，186-193)曾报道了一种氟化碳与氧电极联用的电化学反应体系，在1A/g电流密度下，正极材料的放电容量仍可高达676mAh/g，远高于单纯氟化碳材料的188mAh/g的容量。US20150295241(A1)公开了β-Li3PS4应用于锂氟化碳电池可提供额外放电容量，但其技术方案使用的是全固态电解质，受离子扩散速度影响，要实现活性材料的全利用非常困难。CN104577201A公开了一种含硫基团化合物作为锂原电池的液态电解质溶剂，但该技术方案仅对其能够改善液态电解质和氟化碳的相容性进行了描述。目前尚无使用固-液液相串联耦合反应模式的原电池及其电池结构及其配方的专利与文献报道。
发明内容
本发明的目的在于克服现有技术缺陷，提供一种锂原电池。
本发明的锂原电池的工作原理可以分为两个步骤：在3.2V～2.4V区间，固体正极的活性物质会首先参与放电反应，此时液态电解质主要起到传导锂离子的作用，不参与放电反应。随着放电的进行，固体正极的活性物质逐渐被耗尽，当电压下降到2.4V以下时，液态电解质中的亚硫酸酯类化合物可以以充当液态电极的形式参与放电。
本发明中的亚硫酸酯类化合物的放电反应可以用如下方程式表示：
Figure BDA0001469164590000021
本发明的技术方案如下：
一种锂原电池，基于固-液相串联耦合反应模式，包括可反应固体正极、可离子导电与同时能在电极固相反应之后可发生串联耦合反应的液态电解质、隔膜和锂负极，该液态电解质包括溶剂和电解质盐，电解质盐在液态电解质中的浓度为0.1～3mol/L，该溶剂中包括亚硫酸酯类化合物和有机溶剂，该亚硫酸酯类化合物在有机溶剂中的浓度为5～90wt％，该亚硫酸酯类化合物的结构式如下：
Figure BDA0001469164590000022
R为氢、氟、氯、溴、碘原子、通式为-CxH2x+1的烷基官能团或通式为-CH＝CxH2x的烯烃官能团，R’为氢、氟、氯、溴、碘原子、通式为-CxH2x+1的烷基官能团或通式为-CH＝CxH2x的烯烃官能团，其中，x为1～5的整数。
在本发明的一个优选实施方案中，所述有机溶剂为碳酸乙烯酯、碳酸丙烯酯、二甲基碳酸酯、二乙基碳酸酯、甲基乙基碳酸酯、甲基丙基碳酸酯、碳酸丁烯酯、乙二醇二甲醚、环丁砜和二甲基亚砜中的至少一种。
在本发明的一个优选实施方案中，所述电解质盐为六氟磷酸锂、四氟硼酸锂、双草酸硼酸锂、二氟草酸硼酸锂、六氟合砷(V)酸锂和高氯酸锂中的至少一种。
在本发明的一个优选实施方案中，所述可反应固体正极的材质为金属、非金属氟化物和金属氧化物中的一种。进一步优选的，所述非金属氟化物包括氟化碳，所述金属氧化物包括二氧化锰。
在本发明的一个优选实施方案中，所述锂负极的材质为金属锂或其合金。
在本发明的一个优选实施方案中，所述隔膜为聚合物隔膜、复合聚合物隔膜或无机材料隔膜。进一步优选的，所述聚合物隔膜包括聚丙烯隔膜和聚乙烯隔膜，所述复合聚合物隔膜包括涂覆或未涂覆无机/有机修饰层的复合聚丙烯/聚乙烯隔膜，所述无极材料隔膜包括玻璃纤维隔膜。
本发明的有益效果是：本发明将亚硫酸酯类化合物作为锂原电池中液态电解质的组分，由于亚硫酸酯类化合物的还原电位低于氟化碳和二氧化锰，亚硫酸酯类化合物可以在传统的固态放电完成后充当液态正极发生电化学还原反应提供可观的额外容量，有效地降低了电池的非活性组分质量占比，使得锂原电池高比能量的优势得到进一步地体现。
附图说明
图1为本发明实施例2中锂氟化石墨电池在使用含ES和不含ES两种电解质条件下的放电曲线比较图，其中，电流密度10mA/g。
图2为本发明实施例3中锂氟化石墨烯电池在使用含ES和不含ES两种电解质条件下的放电曲线比较图，其中，电流密度10mA/g。
图3为本发明实施例4中锂二氧化锰电池在使用含ES和不含ES两种电解质条件下的放电曲线比较图，其中，电流密度10mA/g。
具体实施方式
以下通过具体实施方式结合附图对本发明的技术方案进行进一步的说明和描述。
下述实施例中，配制亚硫酸乙烯酯(ES)质量百分数(5％-90％)的液态电解质，包括电解质盐、有机溶剂和ES组成的混合溶液。电解质盐浓度为0.1～3mol/L。有机溶剂为碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、二甲基碳酸酯(DMC)、二乙基碳酸酯(DEC)、甲基乙基碳酸酯(EMC)，乙二醇二甲醚(DME)中的至少一种。电解质盐为四氟硼酸锂(LiBF4)、六氟磷酸锂(LiPF6)、六氟合砷(V)酸锂(LiAsF6)、高氯酸锂(LiClO4)、双草酸硼酸锂(LiBOB)和二氟草酸硼酸锂(LiODFB)中的至少一种。
实施例1：
在充满氩气的室温手套箱内，配制不同的ES质量百分数的电解质1MLiPF6+EC+EMC+ES(x％)，其中EC∶EMC＝3∶7(质量比)。溶液充分混匀。
比较例
在充满氩气的室温手套箱内，配制不含ES的电解质1MLiPF6+EC+EMC，其中EC∶EMC＝＝3∶7(质量比)。溶液充分混匀。
实施例2：
制作锂-氟化石墨电池：
室温下将氟化石墨正极材料、导电剂乙炔黑、粘接剂聚偏二氟乙烯(PVDF)按照85∶5∶10的比例进行匀浆，溶剂为N-甲基-2-吡咯烷酮(NMP)，均匀涂覆在泡沫铜上，80℃真空干燥箱烘干，压制成型。得到氟化石墨电极。图1中1为不含ES的电解质条件下氟化石墨的放电曲线，2为电解质中含ES的质量百分数为63％条件下氟化石墨的放电曲线。与不含ES的条件相比，氟化石墨-ES复合电池体系的比容量和比能量分别提高了6.5％和6.7％。
实施例3：
制作锂-氟化石墨烯电池：
室温下将氟化石墨烯正极材料、导电剂乙炔黑、粘接剂聚偏二氟乙烯(PVDF)按照85∶5∶10的比例进行匀浆，溶剂为N-甲基-2-吡咯烷酮(NMP)，均匀涂覆在泡沫铜上，80℃真空干燥箱烘干，压制成型。得到氟化石墨烯电极。图2中1为不含ES的电解质条件下氟化石墨烯的放电曲线，2为电解质中含ES的质量百分数为44％条件下氟化石墨烯的放电曲线。与不含ES的条件相比，氟化石墨烯-ES复合电池体系的比容量和比能量分别提高了9.9％和8.5％。
实施例4：
制作锂-二氧化锰电池：
室温下将二氧化锰正极材料、导电剂乙炔黑、粘接剂聚偏二氟乙烯(PVDF)按照80∶10∶10的比例进行匀浆，溶剂为N-甲基-2-吡咯烷酮(NMP)，均匀涂覆在铝箔上，80℃真空干燥箱烘干，压制成型。得到二氧化锰电极。图3中1为不含ES的电解质条件下二氧化锰的放电曲线，2为电解质中含ES的质量百分数为44％条件下二氧化锰的放电曲线。与不含ES的条件相比，二氧化锰-ES复合电池体系的比容量和比能量分别提高了62.6％和45.2％。
实施例5：
以实施例2-4中的所准备的电极为正极，金属锂为负极，cellgard 2400为隔膜，分别以1M LiPF6的EC/EMC为电解质和含ES的1M LiPF6的EC/EMC为电解质，组装成2025扣式电池，在LAND电池测试***(武汉金诺电子有限公司提供)上进行恒电流放电性能测试，截止电压1.5V，电流密度为10mA/g，测试环境为25℃恒温，测试结果如图1至3。
本领域普通技术人员可知，本发明的技术方案在下述范围内变化时，仍然能够得到与上述实施例相同或相近的技术效果，仍然属于本发明的保护范围：
一种锂原电池，基于固-液相串联耦合反应模式，包括可反应固体正极、可离子导电与同时能在电极固相反应之后可发生串联耦合反应的液态电解质、隔膜和锂负极，该液态电解质包括溶剂和电解质盐，电解质盐在液态电解质中的浓度为0.1～3mol/L，该溶剂中包括亚硫酸酯类化合物和有机溶剂，该亚硫酸酯类化合物在有机溶剂中的浓度为5～90wt％，该亚硫酸酯类化合物的结构式如下：
Figure BDA0001469164590000051
R为氢、氟、氯、溴、碘原子、通式为-CxH2x+1的烷基官能团或通式为-CH＝CxH2x的烯烃官能团，R’为氢、氟、氯、溴、碘原子、通式为-CxH2x+1的烷基官能团或通式为-CH＝CxH2x的烯烃官能团，其中，x为1～5的整数。
所述可反应固体正极的材质为金属、非金属氟化物和金属氧化物中的一种。
所述锂负极的材质为金属锂或其合金。
所述隔膜为聚合物隔膜、复合聚合物隔膜或无机材料隔膜。进一步的，所述聚合物隔膜包括聚丙烯隔膜和聚乙烯隔膜，所述复合聚合物隔膜包括涂覆或未涂覆无机/有机修饰层的复合聚丙烯/聚乙烯隔膜，所述无极材料隔膜包括玻璃纤维隔膜。
以上所述，仅为本发明的较佳实施例而已，故不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖的范围内。

Claims (4)

1.一种锂原电池，其特征在于：基于固-液相串联耦合反应模式，包括可反应固体正极、可离子导电与同时能在电极固相反应之后可发生串联耦合反应的液态电解质、隔膜和锂负极，该液态电解质包括溶剂和电解质盐，电解质盐在液态电解质中的浓度为0.1～3mol/L，该溶剂中包括亚硫酸酯类化合物和有机溶剂，该亚硫酸酯类化合物在有机溶剂中的浓度为5～90wt％，该亚硫酸酯类化合物的结构式如下：
Figure FDA0002375837170000011
R为氟、氯、溴、碘原子、通式为-CxH2x+1的烷基官能团或通式为-CH＝CxH2x的烯烃官能团，R’为氟、氯、溴、碘原子、通式为-CxH2x+1的烷基官能团或通式为-CH＝CxH2x的烯烃官能团，其中，x为1～5的整数；
上述有机溶剂为碳酸乙烯酯、碳酸丙烯酯、二甲基碳酸酯、二乙基碳酸酯、甲基乙基碳酸酯、甲基丙基碳酸酯、碳酸丁烯酯、乙二醇二甲醚、环丁砜和二甲基亚砜中的至少一种；上述电解质盐为六氟磷酸锂、四氟硼酸锂、双草酸硼酸锂、二氟草酸硼酸锂、六氟合砷(V)酸锂和高氯酸锂中的至少一种；上述隔膜为聚合物隔膜、复合聚合物隔膜或无机材料隔膜，所述聚合物隔膜包括聚丙烯隔膜和聚乙烯隔膜，所述复合聚合物隔膜包括涂覆或未涂覆无机/有机修饰层的复合聚丙烯/聚乙烯隔膜，所述无机材料隔膜包括玻璃纤维隔膜。
2.如权利要求1所述的一种锂原电池，其特征在于：所述可反应固体正极的材质为金属、非金属氟化物和金属氧化物中的一种。
3.如权利要求2所述的一种锂原电池，其特征在于：所述非金属氟化物包括氟化碳，所述金属氧化物包括二氧化锰。
4.如权利要求1所述的一种锂原电池，其特征在于：所述锂负极的材质为金属锂或其合金。
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