CN110931843A - 一种新型的锂金属负极高电压正极的固液电池 - Google Patents

一种新型的锂金属负极高电压正极的固液电池 Download PDF

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CN110931843A
CN110931843A CN201911035198.6A CN201911035198A CN110931843A CN 110931843 A CN110931843 A CN 110931843A CN 201911035198 A CN201911035198 A CN 201911035198A CN 110931843 A CN110931843 A CN 110931843A
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positive electrode
electrolyte
solid
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lithium metal
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CN110931843B (zh
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许晓雄
崔言明
张秩华
黄园桥
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Zhejiang Feng Li Amperex Technology Ltd
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Priority to AU2020377021A priority patent/AU2020377021B2/en
Priority to CA3133860A priority patent/CA3133860C/en
Priority to PCT/CN2020/123624 priority patent/WO2021083074A1/zh
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Abstract

本发明公开了一种新型的锂金属负极高电压正极的固液混合电解质电池，包括正极和负极，所述负极由金属锂制成，所述正极和负极之间设置有固体电解质，且所述固体电解质与正极之间填充有酯类电解液，所述固体电解质与负极之间填充有醚类电解液。一方面在锂金属和固体电解质之间填充醚类电解液，这样有利于提高了锂金属的循环寿命；另一方面在正极和固体电解质之间填充酯类电解液，有利于提高了正极的选择空间，进而提高电池的能量密度；另外，通过填充电解液，这样可以降低固体电解质使用量，在保证利用固体电解质提高安全性的基础上，降低电池界面阻抗；再者，固体电解质的存在可以阻挡电解质溶出的金属离子迁移到金属锂表面后对负极性能的影响。

Description

一种新型的锂金属负极高电压正极的固液电池
技术领域
本发明涉及锂电池领域，特别涉及一种新型的锂金属负极高电压正极的固液电池。
背景技术
目前电解质有三大类，醚类电解液与酯类电解液以及固态电解质，其中锂负极在醚类电解液中的循环性能远高于酯类电解液，醚类电解液的锂金属库伦效率可高达99.9％以上，非常有利于锂金属作为负极的循环寿命。而为了获得高能量密度，正极需要充电到4.2V甚至5V以上，然而醚类电解液的耐压性能较差，一般仅在4.0V(vsLi+/Li)左右稳定，较高电压下会发生严重分解，导致电池胀气等影响全电池循环性能。
而若采用酯类电解液虽然耐压较高，但对锂金属的库伦效率大多在60％以下，锂金属的循环寿命严重限制。若全部采用固体电解质，固体电解质的高强度可以有效防止锂金属负极的枝晶短路，提高电池安全性，但一方面固体电解质的密度较高，会降低电池的能量密度，而且固体电解质与负极或者正极的固固界面相容性差，会增加电池工艺复杂性。
因此，有必要设计出一种以锂金属作为负极并由高电压材料作为正极的电池。
发明内容
本发明的目的是提供一种新型的锂金属负极高电压正极的固液电池，其既具有较高的库伦效率，又具有良好的循环性能。
本发明的上述发明目的是通过以下技术方案得以实现的：一种新型的锂金属负极高电压正极的固液电池，包括正极和负极，所述负极由金属锂制成，所述正极和负极之间设置有固体电解质，且所述固体电解质与正极之间填充有酯类电解液，所述固体电解质与负极之间填充有醚类电解液。
通过采用上述技术方案，一方面在锂金属和固体电解质之间填充醚类电解液，这样有利于提高了锂金属的循环寿命；另一方面在正极和固体电解质之间填充酯类电解液，其具有较高的耐压性能，从而有利于提高了正极的选择空间，尤其是可采用高电势电压的材料来作为正极，从而有利于提高电池的能量密度；
另外，通过填充电解液，这样可以降低固体电解质使用量，提高电池质量，在保证利用固体电解质提高安全性的基础上，还利用相容性更好的固-液界面替代固-固界面，降低电池界面阻抗；再者，固体电解质的存在可以完全阻挡高镍三元或者锰基富锂正极材料的电解质溶出的金属离子(镍离子或者锰离子)迁移到金属锂表面后对负极性能的影响，最终使得电池获得较高的循环寿命与能量密度。
优选为，所述正极包括高镍三元或者锰基富锂正极材料中的一种。
通过采用上述技术方案，高镍三元和锰基富锂具有较高的电压，其与锂金属材料能够组成较高的电势差，这样有利于提高电池的能量密度。
优选为，所述酯类电解液包括碳酸酯、锂盐和添加剂一，三者的质量比为(4～7)∶(2～5)∶1
优选为，所述碳酸酯为碳酸甲乙酯、碳酸二甲酯和碳酸乙烯酯中的一种。
通过采用上述技术方案，其有效地保证电池的各项性能都能够长时间良好的运行。
优选为，所述锂盐为LiBOB、LiODFB、LiFSI和LiTFSI中的一种
优选为，所述添加剂一为环己基苯和(β-氯甲基)磷酸酯混合物，且两者的摩尔比为1∶1。
通过采用上述技术方案，当锂离子电池体系过充电时，环己基苯和(β-氯甲基)磷酸酯协同作用，能够有效地抑制正极活性物质结构发生不可逆变化及电解液发生氧化分解反应，从而降低了负极发生过多的锂沉积。进而，也有利于避免负极材料结构的破坏，而在短时间内电池内部产生大量气体并放出大量的热量，使得电池的内压和温度迅速上升，而引发电解液的燃烧甚至电池的爆炸等安全隐患的发生。
优选为，所述醚类电解液包含有氟代醚、锂盐和添加剂二，三者的质量比为(3～6)∶(3～6)∶1。
优选为，所述氟代醚为甲基九氟正丁基醚、1，1，2，2-四氟乙基-2，2，3，3-四氟丙基醚和八氟戊基-四氟乙基醚的一种。
通过采用上述技术方案，甲基九氟正丁基醚、1，1，2，2-四氟乙基-2，2，3，3-四氟丙基醚和八氟戊基-四氟乙基醚均具有良好的耐氧化性，且在高电压4.4v左右具有较好的稳定性，并且能够降低电解液的粘度，有利于电解液的浸润和电池容量的发挥，还有助于电解液的阻燃。
优选为，所述添加剂二为氟代碳酸乙烯酯、三氟乙烯碳酸酯和三氟乙基丙烯酸酯中的一种。
通过采用上述技术方案，将氟代醚和氟酯进行混合使用，一方面不会增加溶液黏度，稳定性好，抗电化学氧化性强，介电常数高，能充分溶解有机物并且应用温度范围宽，还具有高闪电和高安全性，这些化合物使电池具有优异的耐电压性及充放电循环性能。
而且选用氟代碳酸乙烯酯、三氟乙烯碳酸酯和三氟乙基丙烯酸酯的氟取代的环状碳酸酯，在低温条件下，氟类碳酸酯的还原电位略高于EC的还原电位，添加剂就容易与溶剂共同还原而在SEI膜中引入含有C-F的基团，降低SEI膜的表面能，有利于Li+在SEI膜中扩散。
优选为，所述负极的金属锂表面带有一层氮化锂。
通过采用上述技术方案，将氮化锂作为保护层，能够有效地隔绝金属锂和电解液的直接接触，从而避免了两者之间在电池充放电过程中发生反应生产SEI膜，进而影响固态电池的正常使用
综上所述，本发明的有益技术效果为：
1、在负极锂金属和固体电解质之间填充醚类电解液，在正极和固体电解质之间填充酯类电解液，这样在延长锂金属的循环寿命的同时，也有利于提高电池的能量密度；
2、选用环己基苯和(β-氯甲基)磷酸酯作为添加剂一，这样可以在锂离子电池体系过充电时，起到保护作用，降低锂电池发生燃烧甚至爆炸概率；
3、选用氟代碳酸酯和氟代醚进行共同使用，一方面可使电池具有优异的耐电压性及充放电循环性能，另一方面降低SEI膜的表面能，有利于Li+在SEI膜中扩散。
具体实施方式
实施例一、
一种新型的锂金属负极高电压正极的固液电池的制备方法，包括如下步骤：
步骤一、将锂金属涂敷再铜箔上，然后将带有锂金属的铜箔置于氮气气氛中7小时，并且氮气的温度为45℃，且流速为4m/s，最终获得负极极片；
步骤二、将LiNi0.8Co0.1Mn0.1O2材料、导电炭黑和聚氧化乙烯-聚偏氟乙烯以质量比为90∶4∶6加入于四氢呋喃中充分混合，制得正极浆料；
步骤三、将正极浆料均匀涂敷于铝箔上，且涂敷厚度为25μm，并在温度为110℃～150℃下进行干燥，之后再经辊压及裁切后，制得正极极片；
步骤四、将锂镧锆氧、聚偏氟乙烯和双三氟甲烷磺酸亚胺以质量比为90∶5∶5进行熔融混合均匀，然后涂敷于PP膜的两侧，且两侧的涂敷厚度均为2.5μm；待冷却固化裁切后，得到固体电解质；
步骤五、将正极极片和负极极片分别叠放于固体电解质的两侧，之后向正极极片和固体电解质之间填充醚类电解液，向负极极片和固体电解质之间填充酯类电解液，得到电池芯；
步骤六、将电池芯进行包装，得打成品的固液电池。
其中，醚类电解液由碳酸甲乙酯、LiBOB和添加剂一以质量比为4∶2∶1进行混合，并且添加剂一由环己基苯和(β-氯甲基)磷酸酯混合，且两者的摩尔比为1∶1。而酯类电解液由甲基九氟正丁基醚、LiDFOB和氟代碳酸乙烯酯以质量比为3∶3∶1进行混合。
实施例二、
一种新型的锂金属负极高电压正极的固液电池的制备方法，与实施例一的区别仅在于，步骤二的正极浆料由LiNi0.5Mn1.5O4、导电炭黑和聚氧化乙烯-聚偏氟乙烯以质量比为45∶2∶3加入于四氢呋喃中混合得到。
实施例三、
一种新型的锂金属负极高电压正极的固液电池的制备方法，与实施例一的区别仅在于，醚类电解液由碳酸二甲酯、LiFSI和添加剂一以质量比为7∶5∶1进行混合，酯类电解液由1，1，2，2-四氟乙基-2，2，3，3-四氟丙基醚、LiTFSI和三氟乙烯碳酸酯以质量比为6∶6∶1进行混合。
实施例四、
一种新型的锂金属负极高电压正极的固液电池的制备方法，与实施例一的区别仅在于，醚类电解液由碳酸乙烯酯、LiODFB和添加剂一以质量比为5∶3∶1进行混合，酯类电解液由八氟戊基-四氟乙基醚、LiBOB和三氟乙基丙烯酸酯以质量比为4∶4∶1进行混合。
实施例五、
一种新型的锂金属负极高电压正极的固液电池的制备方法，与实施例一的区别仅在于，醚类电解液由碳酸二甲酯、LiTFSI和添加剂一以质量比为4∶5∶1进行混合，酯类电解液由1，1，2，2-四氟乙基-2，2，3，3-四氟丙基醚、LiFSI和氟代碳酸乙烯酯以质量比为4∶4∶1进行混合。
实施例六、
一种新型的锂金属负极高电压正极的固液电池的制备方法，与实施例一的区别仅在于，固体电解质化学式为Li6.4La3Zr1.4Ta0.6O12的纯无机陶瓷片。
对比例一、
与实施例一的区别仅在于，锂金属表面未在氮气气氛中进行处理。
对比例二、
与实施例一的区别仅在于，添加剂一仅含有环己基苯。
对比例三、
与实施例一的区别仅在于，添加剂一仅含有(β-氯甲基)磷酸酯。
对比例四、
与实施例一的区别仅在于，酯类电解液未添加氟代碳酸乙烯酯(添加剂二)。
对比例五、
与实施例二的区别仅在于，无酯类电解液。
对比例六、
与实施例二的区别仅在于，无醚类电解液。[使用测试]
以LiNi0.5Mn1.5O4或LiNi0.8Co0.1Mn0.1O2三元材料作为正极匹配组合体组装，使用金属锂作为负极，再在正负极上配置不锈钢集流体，并在集流体上附加引线。最后使用绝缘套，将绝缘外筒内部与外部气体气氛隔断密闭，由此制作了测试电池。对测试电池进行试运行。
[阻抗和循环性能测试]
将电池置于25℃恒温条件下，以相对于电池的理论容量为0.05C(20h，以正极计算，1C＝1mA)的电流值进行恒流充电，在电压为4.3V(正极为LiNi0.8Co0.1Mn0.1O2)或5V(正极为LiNi0.8Co0.1Mn0.1O2)时结束充电。接着，同样以0.05C倍率的电流放电，在电压为3.0V时结束放电。以此获得电池的库伦效率和放电容量，另通过测试电池EIS表征阻抗。
从第二周循环开始，以0.2C进行200次充放电循环，计算器容量保持率越高代表循环性能越好。
测试结果如表一所示
表一
Figure BDA0002250390950000061
Figure BDA0002250390950000071
从上述电池测试结果可以发现，相较于对比例，一方面在锂金属和固体电解质之间填充特定的醚类电解液，这样有利于提高了锂金属的循环寿命；另一方面在正极和固体电解质之间填充特定的酯类电解液，其具有较高的耐压性能，从而有利于提高了正极的选择空间，尤其是可采用高电势电压的材料来作为正极，从而有利于提高电池的能量密度；另外，通过填充耐高温电解液添加剂，在保证利用固体电解质提高安全性的基础上，还利用相容性更好的固-液界面替代固-固界面，降低电池界面阻抗，最终使得电池获得较高的循环寿命、能量密度、以及耐过充性能。
本具体实施例仅仅是对本发明的解释，其并不是对本发明的限制，本领域技术人员在阅读完本说明书后可以根据需要对本实施例做出没有创造性贡献的修改，但只要在本发明的权利要求范围内都受到专利法的保护。

Claims (10)

1.一种新型的锂金属负极高电压正极的固液电池，包括正极和负极，所述负极由金属锂制成，其特征在于：所述正极和负极之间设置有固体电解质，且所述固体电解质与正极之间填充有酯类电解液，所述固体电解质与负极之间填充有醚类电解液。
2.根据权利要求1所述的一种新型的锂金属负极高电压正极的固液电池，其特征在于：所述正极包括高镍三元或者锰基富锂正极材料中的一种。
3.根据权利要求1所述的一种新型的锂金属负极高电压正极的固液电池，其特征在于：所述酯类电解液包括碳酸酯、锂盐和添加剂一，三者的质量比为(4～7)∶(2～5)∶1。
4.根据权利要求3所述的一种新型的锂金属负极高电压正极的固液电池，其特征在于：所述碳酸酯为碳酸甲乙酯、碳酸二甲酯和碳酸乙烯酯中的一种。
5.根据权利要求3所述的一种新型的锂金属负极高电压正极的固液电池，其特征在于：所述锂盐为LiBOB、LiODFB、LiFSI和LiTFSI中的一种。
6.根据权利要求3所述的一种新型的锂金属负极高电压正极的固液电池，其特征在于：所述添加剂一为环已基苯和(β-氯甲基)磷酸酯混合物，且两者的摩尔比为1∶1。
7.根据权利要求1所述的一种新型的锂金属负极高电压正极的固液电池，其特征在于：所述醚类电解液包含有氟代醚、锂盐和添加剂二，三者的质量比为(3～6)∶(3～6)∶1。
8.根据权利要求7所述的一种新型的锂金属负极高电压正极的固液电池，其特征在于：所述氟代醚为甲基九氟正丁基醚、1，1，2，2-四氟乙基-2，2，3，3-四氟丙基醚和八氟戊基-四氟乙基醚的一种。
9.根据权利要求7所述的一种新型的锂金属负极高电压正极的固液电池，其特征在于：所述添加剂二为氟代碳酸乙烯酯、三氟乙烯碳酸酯和三氟乙基丙烯酸酯中的一种。
10.根据权利要求1所述的一种新型的锂金属负极高电压正极的固液电池，其特征在于：所述负极的金属锂表面带有一层氮化锂。
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