CN114006040B - 一种兼顾快充和超低温放电性能的电解液及锂离子电池 - Google Patents
一种兼顾快充和超低温放电性能的电解液及锂离子电池 Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 50
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 34
- 239000000654 additive Substances 0.000 claims abstract description 16
- 230000000996 additive effect Effects 0.000 claims abstract description 16
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims abstract description 14
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 13
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical group N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 13
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- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims abstract description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 57
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000011267 electrode slurry Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 11
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- 239000002033 PVDF binder Substances 0.000 claims description 10
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 9
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 6
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000013543 active substance Substances 0.000 claims description 3
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
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Abstract
本发明涉及锂离子电池技术领域,公开一种兼顾快充和超低温放电性能的电解液和锂离子电池。该电解液包括溶剂、电解质和添加剂,所述溶剂包括质量比为1:1:1:0.5的碳酸乙烯酯、碳酸二甲酯、碳酸甲乙酯和碳酸丙烯酯;所述电解质包括质量比为1:0.5的六氟磷酸锂和四氟硼酸锂,所述电解质的摩尔浓度为1mol/L;所述添加剂为氮化硅,所述氮化硅的质量浓度为0.1%。本发明的电解液中加入了添加剂氮化硅,能够提升电池耐热冲击能力,使电池在高、低温下保持性能稳定,从而兼顾快充和超低温放电性能。本发明的电池可以在15分钟内充满电,同时零下20℃放电效率大于80%,零下50℃放电效率大于60%,满足寒带地区的使用要求。
Description
技术领域
本发明涉及锂离子电池技术领域,具体地说是一种兼顾快充和超低温放电性能的电解液及锂离子电池。
背景技术
锂离子电池,以其能量高、电池电压高、工作温度范围宽、储存寿命长、无记忆效应、自放电率小、可快速充放电等优点,广泛应用于手机、笔记本电脑、数码相机等电子产品中,还作为动力型电池逐渐在电动自行车、航模、电动汽车上得到广泛使用。
传统锂离子电池在常温下充电速度最快在1小时左右,而低温下(负20℃)放电效率很低,在50%左右,而低温(负40℃)基本不能正常放电,从而限制了锂离子电池的应用范围。
基于上述情况,亟需开发一种兼顾快充和超低温放电性能的电解液及锂离子电池。
发明内容
针对上述存在的问题,本发明的目的在于提供一种兼顾快充和超低温放电性能的电解液及锂离子电池。本发明的电池可以在15分钟内充满电,同时零下20℃放电效率大于80%,零下50℃放电效率大于60%,满足寒带地区的使用要求。
本发明为实现上述目的,采取以下技术方案予以实现:
一种兼顾快充和超低温放电性能的电解液,包括溶剂、电解质和添加剂,所述溶剂包括质量比为1:1:1:0.5的碳酸乙烯酯、碳酸二甲酯、碳酸甲乙酯和碳酸丙烯酯;所述电解质包括质量比为1:0.5的六氟磷酸锂和四氟硼酸锂,所述电解质的摩尔浓度为1mol/L;所述添加剂为氮化硅,所述氮化硅的质量浓度为0.1%。
优选地,所述电解液通过以下方法制备而成:将溶剂、电解质和添加剂依次加入到反应釜中,加热搅拌,混合均匀后制得电解液。这里溶剂的水分及纯度要符合电解质的使用标准,否则应当预先进行提纯处理。
本发明的另一目的在于公开一种锂离子电池,包括正极片、负极片、隔膜和电解液,所述电解液是如上所述的电解液。
优选地,所述正极片通过以下步骤制得:
(1)将导电炭黑溶解于N-甲基吡络烷酮溶剂中,所述导电炭黑和N-甲基吡络烷酮溶剂的质量比为1:10,混合搅拌30分钟,搅拌线速度5~8m/s;
(2)加入聚偏氟乙烯,混合搅拌30分钟,搅拌线速度8~10m/s;
(3)将磷酸铁锂均匀分3次加入,每次搅拌10分钟,搅拌线速度8~10m/s;
(4)加入氮化铝,搅拌60分钟,搅拌线速度12~15m/s;
(5)加入石墨烯,搅拌240分钟,搅拌线速度12~18m/s;
(6)调整浆料粘度为8500cps,固含量为52%;
(7)真空静置60分钟,除气泡,得到正极浆料;
(8)将正极浆料均匀涂覆在铝箔上,制成正极片。
优选地,所述正极浆料包括质量百分比的以下组分:92~94%主活性物质、1~3%导电炭黑、0.5~1%石墨烯、0.5~1%氮化铝、2.5~4.5%聚偏氟乙烯。
优选地,所述主活性物质为磷酸铁锂。
优选地,所述正极浆料包括质量百分比的以下组分:93.5%磷酸铁锂、1.5%导电炭黑、0.5%石墨烯、0.5%氮化铝、4%聚偏氟乙烯。
优选地,所述负极片通过以下步骤制得:
(1)将导电炭黑溶解于水中,其中溶剂水的含量为45wt%,混合搅拌60分钟,搅拌线速度5~8m/s;
(2)加入羧甲基纤维素钠,混合搅拌30分钟,搅拌线速度6~10m/s;
(3)将石墨均匀分3次加入,每次搅拌30分钟,搅拌线速度8~10m/s;
(4)加入水性粘结剂,搅拌30分钟,搅拌线速度10~15m/s;
(5)调整浆料粘度为4000cps,固含量为50%;
(6)真空静置30分钟,除气泡,得到负极浆料;
(7)将负极浆料均匀涂覆在铜箔上,制成负极片。
优选地,所述负极浆料包括质量百分比的以下组分:95%石墨、1%导电炭黑、3.5%水性粘结剂、0.5%羧甲基纤维素钠。
优选地,所述调整浆料粘度具体是通过补充溶剂来调整浆料粘度。
与现有技术相比,本发明的有益效果如下:
本发明的电解液中加入了添加剂氮化硅,能够提升电池耐热冲击能力,使电池在高、低温下保持性能稳定,从而兼顾快充和超低温放电性能。
本发明的电解液采用四元溶剂,即质量比为1:1:1:0.5的碳酸乙烯酯、碳酸二甲酯、碳酸甲乙酯和碳酸丙烯酯,提升电池低温放电能力。
本发明的电解液采用质量比为1:0.5的六氟磷酸锂和四氟硼酸锂,提升电池低温放电能力。
本发明电池的正极片在制作过程中加入石墨烯及氮化铝材料,大幅提高正极的导电性及导热性,提升电池的快速充电能力。
本发明的电池可以在15分钟内充满电,同时零下20℃放电效率大于80%,零下50℃放电效率大于60%,满足寒带地区的使用要求。
具体实施方式
以下结合具体实施例来对本发明作进一步的说明。
实施例1
一种兼顾快充和超低温放电性能的电解液,包括溶剂、电解质和添加剂。
其中,溶剂包括质量比为1:1:1:0.5的碳酸乙烯酯、碳酸二甲酯、碳酸甲乙酯和碳酸丙烯酯。在原有三元溶剂的基础上加入了碳酸丙烯酯,变成四元溶剂。由于碳酸丙烯酯具有低熔点、大介电常数的特点,可以明显改善电池的低温性能。
电解质包括质量比为1:0.5的六氟磷酸锂和四氟硼酸锂,电解质的摩尔浓度为1mol/L。常用的锂离子电池的电解质为六氟磷酸锂,常温下六氟磷酸锂电化学性能稳定,易溶于有机溶剂,但是低温下生成的SEI膜阻抗过大限制了其在低温下的应用。而四氟硼酸锂具有热稳定性好、电荷转移阻抗小的特点,适合低温下应用。
添加剂采用氮化硅,氮化硅的质量浓度为0.1%。本发明的电解液中加入了添加剂氮化硅,能够提升电池耐热冲击能力,使电池在高、低温下保持性能稳定,从而兼顾快充和超低温放电性能。
电解液通过以下方法制备而成:将溶剂、电解质和添加剂依次加入到反应釜中,加热搅拌,混合均匀后制得电解液。这里溶剂的水分及纯度要符合电解质的使用标准,否则应当预先进行提纯处理。
实施例2
一种锂离子电池,包括正极片、负极片、隔膜和电解液,其中电解液如实施例1所述。
正极片制作:
正极浆料包括质量百分比的以下组分:92~94%主活性物质、1~3%导电炭黑、0.5~1%石墨烯、0.5~1%氮化铝、2.5~4.5%聚偏氟乙烯。主活性物质用于提供电池充放电容量;导电炭黑用于提高正极材料的导电性;石墨烯用于提高正极材料的超导能力;氮化铝用于提高正极材料的导热性能;聚偏氟乙烯用于提高正极材料的粘结性。主活性物质优选为磷酸铁锂。
本实施例采用的正极浆料包括质量百分比的以下组分:93.5%磷酸铁锂、1.5%导电炭黑、0.5%石墨烯、0.5%氮化铝、4%聚偏氟乙烯。应该注意的是,这里正极浆料中没有限定溶剂N-甲基吡络烷酮的用量,因为制备正极片过程中存在用溶剂N-甲基吡络烷酮调整浆料粘度的需求,溶剂N-甲基吡络烷酮的用量在实际应用中会有变化。
正极片通过以下步骤制得:
(1)将导电炭黑溶解于N-甲基吡络烷酮溶剂中,所述导电炭黑和N-甲基吡络烷酮溶剂的质量比为1:10,混合搅拌30分钟,搅拌线速度5~8m/s;
(2)加入聚偏氟乙烯,混合搅拌30分钟,搅拌线速度8~10m/s;
(3)将磷酸铁锂均匀分3次加入,每次搅拌10分钟,搅拌线速度8~10m/s;
(4)加入氮化铝,搅拌60分钟,搅拌线速度12~15m/s;
(5)加入石墨烯,搅拌240分钟,搅拌线速度12~18m/s;
(6)调整浆料粘度为8500cps,固含量为52%;
(7)真空静置60分钟,除气泡,得到正极浆料;
(8)将正极浆料均匀涂覆在铝箔上,制成正极片。
负极片制作:
本实施例的负极浆料包括质量百分比的以下组分:95%石墨、1%导电炭黑、3.5%水性粘结剂、0.5%羧甲基纤维素钠。应该注意的是,这里负极浆料中没有限定溶剂水的用量,因为制备负极片过程中存在用溶剂水调整浆料粘度的需求,溶剂水的用量在实际应用中会有变化。
负极片通过以下步骤制得:
(1)将导电炭黑溶解于水中,其中溶剂水的含量为45wt%,混合搅拌60分钟,搅拌线速度5~8m/s;
(2)加入羧甲基纤维素钠,混合搅拌30分钟,搅拌线速度6~10m/s;
(3)将石墨均匀分3次加入,每次搅拌30分钟,搅拌线速度8~10m/s;
(4)加入水性粘结剂,搅拌30分钟,搅拌线速度10~15m/s;
(5)调整浆料粘度为4000cps,固含量为50%;
(6)真空静置30分钟,除气泡,得到负极浆料;
(7)将负极浆料均匀涂覆在铜箔上,制成负极片。
对比例1:
本对比例1采用和实施例2相同的正极片、负极片和隔膜。电解液的其他组成和实施例2一样,区别在于电解液中不添加添加剂氮化硅。
实施例2和对比例1的性能对比:
按照实施例2和对比例1分别制作成5安时电芯,进行4c快充试验,低温负20℃,负50℃放电。结果如下表所示:
试验项目 | 实施例2 | 对比例1 |
4c快充效率 | 98% | 95% |
4c快充温升 | 5℃ | 9℃ |
负20℃1c放电效率 | 82% | 70% |
负50℃1c放电效率 | 63% | 无法放电 |
从上表可以看出:和对比例1相比,实施例2的电解液中加入了添加剂氮化硅,能够提升电池耐热冲击能力,使电池在高、低温下保持性能稳定,从而兼顾快充和超低温放电性能。
本发明的电池可以在15分钟内充满电,同时零下20℃放电效率大于80%,零下50℃放电效率大于60%,满足寒带地区的使用要求。
以上对本发明实施例所提供的技术方案进行了详细介绍,本文中应用了具体个例对本发明实施例的原理以及实施方式进行了阐述,以上实施例的说明只适用于帮助理解本发明实施例的原理;同时,对于本领域的一般技术人员,依据本发明实施例,在具体实施方式以及应用范围上均会有改变之处,综上所述,本说明书内容不应理解为对本发明的限制。
Claims (9)
1.一种兼顾快充和超低温放电性能的电解液,包括溶剂、电解质和添加剂,其特征在于,所述溶剂包括质量比为1:1:1:0.5的碳酸乙烯酯、碳酸二甲酯、碳酸甲乙酯和碳酸丙烯酯;所述电解质包括质量比为1:0.5的六氟磷酸锂和四氟硼酸锂,所述电解质的摩尔浓度为1mol/L;所述添加剂为氮化硅,所述氮化硅的质量浓度为0.1%;所述电解液通过以下方法制备而成:将溶剂、电解质和添加剂依次加入到反应釜中,加热搅拌,混合均匀后制得电解液。
2.一种锂离子电池,包括正极片、负极片、隔膜和电解液,其特征在于,所述电解液是如权利要求1所述的电解液。
3.根据权利要求2所述的一种锂离子电池,其特征在于,所述正极片通过以下步骤制得:
(1)将导电炭黑溶解于N-甲基吡络烷酮溶剂中,所述导电炭黑和N-甲基吡络烷酮溶剂的质量比为1:10,混合搅拌30分钟,搅拌线速度5~8m/s;
(2)加入聚偏氟乙烯,混合搅拌30分钟,搅拌线速度8~10m/s;
(3)将磷酸铁锂均匀分3次加入,每次搅拌10分钟,搅拌线速度8~10m/s;
(4)加入氮化铝,搅拌60分钟,搅拌线速度12~15m/s;
(5)加入石墨烯,搅拌240分钟,搅拌线速度12~18m/s;
(6)调整浆料粘度为8500cps,固含量为52%;
(7)真空静置60分钟,除气泡,得到正极浆料;
(8)将正极浆料均匀涂覆在铝箔上,制成正极片。
4.根据权利要求3所述的一种锂离子电池,其特征在于,所述正极浆料包括质量百分比的以下组分:92~94%主活性物质、1~3%导电炭黑、0.5~1%石墨烯、0.5~1%氮化铝、2.5~4.5%聚偏氟乙烯。
5.根据权利要求4所述的一种锂离子电池,其特征在于,所述主活性物质为磷酸铁锂。
6.根据权利要求5所述的一种锂离子电池,其特征在于,所述正极浆料包括质量百分比的以下组分:93.5%磷酸铁锂、1.5%导电炭黑、0.5%石墨烯、0.5%氮化铝、4%聚偏氟乙烯。
7.根据权利要求2所述的一种锂离子电池,其特征在于,所述负极片通过以下步骤制得:
(1)将导电炭黑溶解于水中,其中溶剂水的含量为45wt%,混合搅拌60分钟,搅拌线速度5~8m/s;
(2)加入羧甲基纤维素钠,混合搅拌30分钟,搅拌线速度6~10m/s;
(3)将石墨均匀分3次加入,每次搅拌30分钟,搅拌线速度8~10m/s;
(4)加入水性粘结剂,搅拌30分钟,搅拌线速度10~15m/s;
(5)调整浆料粘度为4000cps,固含量为50%;
(6)真空静置30分钟,除气泡,得到负极浆料;
(7)将负极浆料均匀涂覆在铜箔上,制成负极片。
8.根据权利要求7所述的一种锂离子电池,其特征在于,所述负极浆料包括质量百分比的以下组分:95%石墨、1%导电炭黑、3.5%水性粘结剂、0.5%羧甲基纤维素钠。
9.根据权利要求3或7所述的一种锂离子电池,其特征在于,所述调整浆料粘度具体是通过补充溶剂来调整浆料粘度。
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