CN114497728A - 一种电解液、电化学装置以及电子装置 - Google Patents
一种电解液、电化学装置以及电子装置 Download PDFInfo
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- CN114497728A CN114497728A CN202011258690.2A CN202011258690A CN114497728A CN 114497728 A CN114497728 A CN 114497728A CN 202011258690 A CN202011258690 A CN 202011258690A CN 114497728 A CN114497728 A CN 114497728A
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- -1 benzotriazine ketone compound Chemical class 0.000 claims abstract description 23
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- 239000008151 electrolyte solution Substances 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 10
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- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 8
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- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 229910001431 copper ion Inorganic materials 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
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- 125000003342 alkenyl group Chemical group 0.000 claims description 4
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- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
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- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- BTNXBLUGMAMSSH-UHFFFAOYSA-N octanedinitrile Chemical compound N#CCCCCCCC#N BTNXBLUGMAMSSH-UHFFFAOYSA-N 0.000 description 1
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- RXIMZKYZCDNHPG-UHFFFAOYSA-N pentane-1,3,5-tricarbonitrile Chemical compound N#CCCC(C#N)CCC#N RXIMZKYZCDNHPG-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
本申请提供了一种电解液以及包含该电解液的电化学装置和电子装置。本申请的电解液包括苯并三嗪酮类化合物。本发明将电解液包括苯并三嗪酮类化合物作为添加剂加入电解液中,可以吸附电解液中存在的水分,抑制LiPF6分解,避免生成HF,破坏铜箔和界面保护层,降低电池长期存储后的自放电现象。
Description
技术领域
本申请涉及电化学技术领域,具体地涉及一种包括苯并三嗪酮类化合物的电解液以及使用该电解液的电化学装置和电子装置。
背景技术
锂离子电池具有能量密度高、使用寿命长的优势,是现代商用电子产品常用电源,广泛应用于移动电子设备。在实际应用中,锂离子电池从形成成品到销售到客户手上,可能经过较长周期。客户在收到锂离子电池后,也经历长时间的使用过程,这一过程必然涉及荷电态发生变化的过程,因此锂离子电池在存储中的自放电性能显得尤为重要。研究发现,锂离子电池存储过程中的自放电与环境温度、荷电状态有关,并且受到正极、负极活性物质分解、集流体腐蚀、电解液分解以及界面副反应等因素的影响。当自放电恶化到一定程度时,往往伴随着电池内阻增加、倍率和安全性能恶化等现象。
电解液添加剂种类和用量的正确选择,可以有效地改善SEI和CEI的稳定性,改善对正负极活性物质保护,改善电池自放电的措施。因此,开发能够抑制氢氟酸(HF)对基材的腐蚀、同时具有改善正、负极界面保护的电解液,成为解决锂离子电池自放电的关键问题。
发明内容
鉴于背景技术中存在的问题,本申请的目的在于提供一种电解液及包括该电解液的电化学装置,以解决锂离子电池自放电中存在的问题。
本申请的一方面提供一种电解液,所述电解液包括苯并三嗪酮类化合物,所述苯并三嗪酮类化合物具有式(I)所示的结构:
其中,R1选自氢原子、取代或未取代的C1-C20烷基、烯基、炔基、芳基、烷氧基、烯氧基、炔氧基、芳氧基、羧基、烷基碳酰氧基、烯基碳酰氧基、炔基碳酰氧基、芳基碳酰氧基、烷硫基、烯硫基、炔硫基、芳硫基、氰基、氨基、N-取代的氨基、烷基碳酰胺基、N-取代的烷基碳酰胺基、烯基碳酰胺基、N-取代的烯基碳酰胺基、芳基碳酰胺基、N-取代的芳基碳酰胺基、含磷基团、含硫基团;其中,在取代或未取代的C1-C20烷基中,取代基为卤素原子;
Y表示O原子或S原子;
L表示单键或取代或未取代的C1-C6亚烷基;
R2选自取代或未取代的C1-C20烷基、烯基、炔基、芳基、亚氨基、烷氧基、烯氧基、炔氧基、芳氧基、羧基、烷基碳酰氧基、烯基碳酰氧基、炔基碳酰氧基、芳基碳酰氧基、烷硫基、烯硫基、炔硫基、芳硫基、氰基、氨基、N-取代的氨基、烷基碳酰胺基、N-取代的烷基碳酰胺基、烯基碳酰胺基、N-取代的烯基碳酰胺基、芳基碳酰胺基、N-取代的芳基碳酰胺基、含磷基团、含硫基团;在取代或未取代的C1-C20烷基中,取代基为卤素原子;
或者,R1选自式(II)表示的基团:
本申请通过在电解液中添加苯并三嗪酮类添加剂,可以解决锂离子电池自放电中存在的问题。一方面,苯并三嗪酮类添加剂可以吸附电解液中存在的水分,抑制LiPF6分解,避免生成HF,破坏铜箔和界面保护层,降低新鲜电池自放电。另一方面,苯并三嗪酮类添加剂可以在正、负极表面形成电解质膜,可以改善高电压的条件下的界面保护膜的稳定性,抑制钴的析出,降低长期存储后的自放电现象。
特别地,在本发明的苯并三嗪酮化合物中,羰基使三氮环具有强还原性,促进初始成膜阶段迅速形成含有N、O、S等元素的无机成分的负极保护层。
在本申请所述的电解液的一些实施例中,选自脲鎓、硫脲鎓、吡啶鎓、哌啶鎓、哌嗪鎓、吡嗪鎓、咪唑鎓、哒嗪鎓、噻唑鎓、噁唑鎓、三唑鎓、三(二甲基氨基)磷鎓、三吡咯烷磷鎓。正离子鎓盐具有夺电子能力,促进带电荷离子靠近负极材料,在初始成膜阶段发生多步还原反应,可能利于整体介电保护膜的成分分布,加强介电保护膜的稳定性。
在本申请所述的电解液的一些实施例中,选自BF4 -、PF6 -、AsF6 -、SO3CF3 -、N(SO2CF3)2 -、CO2CF3 -、N(SO2C2F5)2 -、N(SO2C4F9)2 -、C3N2(CN)2(CF3)-、C3N2(CN)2(C2F5)-。在这些阴离子中,从耐氧化性和离子离解性良好的观点考虑,优选BF4 -、PF6 -、AsF6 -。
在本申请所述的电解液的一些实施例中,所述苯并三嗪酮类化合物选自式(I-1)至式(I-17)所示的化合物中的至少一种:
在本申请所述的电解液的一些实施例中,所述电解液还包括多腈类化合物,所述多腈类化合物,所述多腈类化合物包括具有两个腈基的化合物和具有三个及三个以上腈基的化合物中的至少一种,所述具有两个腈基的化合物包括式(Ⅲ)化合物或式(Ⅳ)化合物中的至少一种,所述具有三个及三个以上腈基的化合物包括式(Ⅴ)化合物或式(Ⅵ)化合物中的至少一种:
其中,R5选自取代或未取代的C1-C12亚烷基或-(O-Ra)m-Rc-O-Rb,Ra和Rb各自独立地选自取代或未取代的C1-C3亚烷基,Rc选自单键或取代或未取代的C1-C3亚烷基,m选自0、1、2;
R6、R7各自独立地选自单键、取代或未取代的C1~12亚烷基;
R8、R9、R10各自独立地选自单键、取代或未取代的C1-C12亚烷基或取代或未取代的C1-C12亚烷氧基;
R11选自取代或未取代的C1-C12亚烷基、取代或未取代的C2-C12亚烯基、取代或未取代的C6-C26亚芳基或取代、或未取代的C2-C12亚杂环基;并且当R5、R6、R7、R8、R9、R10和R11中至少一者被取代时,取代基为卤素。
腈基吸附在正极过渡金属表面,有助于抑制高电位下过渡金属溶出,正极活性物质结构破坏,多腈类化合物较单腈基化合物吸附性更强,随着腈基增加,对高电压正极的保护性更强。
在本申请所述的电解液的一些实施例中,以电解液的总质量计,所述多腈类化合物在电解液中的质量分数为0.1%~12%,优选为0.5%~8%。这是因为多腈类化合物粘度普遍较大,含量过高可能严重影响电解液离子传输,电池阻抗过大;或多腈类人化合物的含量过低,则不能有效发挥保护正极的效果。
在本申请所述的电解液的一些实施例中,所述电解液的水分含量≤300ppm,优选≤200ppm。
在本申请所述的电解液的一些实施例中,所述电解液在化成之前的铜离子含量≤200ppm。
在本申请所述的电解液中,还包括有机溶剂、锂盐、其他常规添加剂。
在本申请所述的电解液中,对电解液中的有机溶剂没有特别的限定。例如,有机溶剂可以选自碳酸酯化合物、羧酸酯化合物的至少一种,其中,碳酸酯化合物可以是链状碳酸酯,也可以是环状碳酸酯。例如,有机溶剂可以是碳酸乙烯酯、碳酸丙烯酯、碳酸丁烯酯、氟代碳酸乙烯酯、碳酸甲乙酯、碳酸二甲酯、碳酸二乙酯、碳酸二丙酯、碳酸甲丙酯、碳酸乙丙酯、1,4-丁内酯、丙酸甲酯、丁酸甲酯、乙酸乙酯、丙酸乙酯、丁酸乙酯中的至少一种。
有机溶剂还可以选自丙烯酸甲酯、亚硫酸二甲酯、二乙基亚硫酸酯、酸酐、N-甲基吡咯烷酮、N-甲基甲酰胺、N-甲基乙酰胺、乙腈、N,N-二甲基甲酰胺、二甲亚砜、甲硫醚、四氢呋喃中的一种或几种。
在本申请的电解液中,对电解液中的锂盐没有特别的限定。例如,锂盐可以选自LiPF6、LiBF4、LiAsF6、LiClO4、LiB(C6H5)4、LiCH3SO3、LiCF3SO3、LiN(SO2CF3)2、LiC(SO2CF3)3、LiSiF6、LiBOB和LiDFOB中的一种或多种,优选LiPF6。
在本申请的电解液中,电解液的其他常规添加剂包括正极成膜添加剂、负极成膜添加剂。只要常规添加剂只要不导致电解液的性能劣化,则对常规添加剂的种类和含量没有特别限定。例如,负极成膜添加剂可能选自但不限于氟代碳酸乙烯酯(FEC)、1,3-丙烷磺内酯(PS)、碳酸亚乙烯酯(VC),正极添加剂包含多腈类化合物,例如:丙二腈、丁二腈、戊二腈、己二腈、庚二腈、辛二腈、癸二腈、3,3'-氧二丙腈、己-2-烯二腈、反丁烯二腈、2-戊烯二腈、甲基戊二腈、4-氰基庚二腈、(Z)-丁-2-烯二腈、2,2,3,3-四氟丁二腈、乙二醇双(丙腈)醚、1,3,5-戊三甲腈、1,3,6-己三甲腈、1,2,6-己三甲腈、1,2,3-三(2-氰氧基)丙烷、1,1,3,3-丙四甲腈、以及如下结构表示的多腈化合物:
本发明的另一方面提供了一种电化学装置,其包括正极、负极、设置在正极与负极之间的隔离膜、以及本发明所述的电解液。
本发明的又一方面还提供一种电子装置,所述电子装置包括如上所述的电化学装置。
本申请提供的技术方案可以达到以下有益效果:
本发明将苯并三嗪酮类化合物作为电解液的添加剂,可以吸附电解液中存在的水分,抑制LiPF6分解,避免生成HF,破坏铜箔和界面保护层,降低新鲜电池自放电。另一方面,苯并三嗪酮类化合物可以在正、负极表面形成电解质膜,可以改善高电压的条件下的界面保护膜的稳定性,抑制钴的析出,降低长期存储后的自放电现象。
具体实施方式
下面结合实施例,进一步阐述本申请。应理解,这些实施例仅用于说明本申请而不用于限制本申请的范围。
实施例以及对比例中的锂离子电池均按照下述方法进行制备:
(1)正极片制备
将正极活性材料钴酸锂(LiCoO2)、导电剂、粘结剂混合,加入N-甲基吡咯烷酮(NMP),在真空搅拌机作用下搅拌均匀,获得正极浆料;将正极浆料均匀涂覆于正极集流体铝箔上;将铝箔烘干,然后经过冷压、裁片、分切后,在真空条件下干燥,得到正极片。经激光清洗出极耳焊接空箔区。
(2)负极片制备
将负极活性材料人造石墨、导电剂、增稠剂、粘结剂混合,加入去离子水,在真空搅拌机作用下获得负极浆料;将负极浆料均匀涂覆在负极集流体铜箔上;将铜箔烘干,然后经过冷压、裁片、分切后,在真空条件下干燥,得到负极片。经激光清洗出极耳焊接空箔区。
(3)电解液制备
在干燥的氩气气氛手套箱中,将碳酸乙烯酯(EC):碳酸丙烯酯(PC):丙酸丙酯(PP)=1:3:6溶剂混合,接着加入苯并三嗪酮类添加剂和常规添加剂,本案中使用溶解并充分搅拌后加入锂盐LiPF6,混合均匀后获得电解液。
电解液中常规添加剂的种类及添加剂的具体种类以及含量如表1至表2所示,其中,表1中常规添加剂种类含量保持一致,参考表2实施例1-21所列。wt%均为基于电解液的总质量计算得到的质量百分数。
在对比例1-1至1-5、实施例1-1至1-42、实施例2-1至2-12,电解液水含量控制为20ppm,实施例3-1至3-5,水含量如表3所示。
(4)隔离膜的制备
将勃姆石与聚丙烯酸酯混合并将其溶入到去离子水中以形成涂层浆料。随后采用微凹涂布法将所述涂层浆料均匀涂布到多孔基材的两个表面上,经过干燥处理以获得所需隔离膜。
(5)锂离子电池的制备
将正极片、隔离膜、负极片按顺序叠好,使隔离膜处于正、负极片之间起到隔离的作用,然后卷绕得到裸电芯;焊接极耳后将裸电芯置于外包装箔铝塑膜中,将上述制备好的电解液注入到干燥后的裸电芯中,经过真空封装、静置、化成、整形、容量测试等工序,获得软包锂离子电池。
本申请中各参数的测试方法及测试条件如下:
锂离子电池的电性能测试:
(1)电解液中铜离子的检测
使用等离子发散光谱仪ICP-OES测试化成前离心电解液中铜元素含量。
(2)负极表面不可逆钴的检测
使用等离子发散光谱仪ICP-OES测试新鲜电池0%SOC拆解的阳极片上钴元素含量。
(3)K值测试
新鲜电池K值:容量后电池经45℃24小时、25℃24小时放置后,测试新鲜电池的初始电压OCV1。再经过25℃恒温放置48小时后测试自放电后的电压OCV2,通过下列公式计算获得K值(mV/h)。
其中,Time1为48(小时)。
存储6个月后K值:新鲜电池充电至50%SOC,经过25℃恒温放置6个月后测试自放电后的电压OCV3,通过下列公式计算获得K值(mV/h)。
其中,Time2为4320(小时)。
下面表1示出了苯并三嗪酮类化合物对电池性能的影响。
表1
其中,“/”表示未添加该物质。
表1中数据,通过分析对比例1-1至1-5、实施例1-3、1-4、1-9、1-10、1-15、1-16、1-21、1-22、1-27、1-28、1-31、1-32、1-35、1-36、1-41、1-42、1-45、1-46可知,苯并多氮化合物有改善HF腐蚀铜箔、降低电解液中铜离子含量的作用,其中苯并三氮唑、苯并三嗪酮类化合物含量效果优于苯并咪唑,式(Ⅰ-1)、(Ⅰ-4)、(Ⅰ-5)效果更好;新鲜电池的自放电程度与铜箔腐蚀相关度高,同样式(Ⅰ-4)、(Ⅰ-5)具有比苯并三氮唑更好的改善效果。一方面,三氮环络合铜离子后,在铜箔表面形成致密的保护层。另一方面,可能由于三嗪酮衍生物对H2O的吸附减弱HF生成,进一步抑制铜箔腐蚀。
同时,苯并多氮化合物具有保护正极、降低荷电态长期存储后过渡金属不可逆溶出的作用,苯并三嗪酮类化合物效果明显优于苯并三氮唑、这可能由于酮基和含N、P、S的衍生物基团加强了化合物络合过渡金属的能力,成膜更稳定。
通过分析实施例1-1至1-46,苯并三嗪酮类化合物用量增加,对新鲜电池和长期存储后的电池自放电改善均有提升,用量过低,改善效果不明显,用量过多,虽然不影响自放电改善,但可能影响电池其他性能,故优选0.1~1wt%。
表2表示常规添加剂与本申请的苯并三嗪酮类添加剂的交互作用。
表2
注:表2中,化合物4为1,3,6-己烷三腈;化合物5为1,2,3-三(2-氰氧基)丙烷;“/”表示未添加该物质。
从表2中数据,通过分析实施例1-21、实施例2-12可知,常规正负极保护添加剂FEC、VC、PS对铜箔腐蚀基本无影响,多腈类严重恶化铜箔腐蚀,这源于多氰基化合物络合铜离子后,无法形成有效的基材保护,持续的析出反应,进一步加速HF带来的的腐蚀。
但在荷电存储中,PS、多腈类对正极都具有显著的保护作用,改善长期存储后自放电。通过常规添加剂和多腈类的用量调控,难以同时改善铜箔腐蚀和正极保护不足造成的自放电。通过使用苯并三嗪酮类化合物,可明显改善化学微反应造成的自放电,结合正负极保护添加剂的调整,达到最优效果。
表3电解液中水分含量对电池性能的影响
其中,“/”表示未添加该物质。
基于表3数据,通过分析实施例1-21、实施例3-1至3-13可知,电解液中的水分含量直接造成铜箔腐蚀和严重的自放电。通过使用苯并三嗪酮类化合物,同时限定水含量低于300ppm,新鲜电池自放电可控制在0.2mV/h以下,无严重短路危险。优选地,需限定水分含量低于200ppm,新鲜电池K值≤0.05mV/h。
本发明通过将使用苯并三嗪酮类化合物作为添加剂添加到电解液中,可以吸附电解液中存在的水分,抑制LiPF6分解,避免生成HF,破坏铜箔和界面保护层,降低新鲜电池自放电。另外,苯并三嗪酮类化合物可以在正、负极表面形成电解质膜,可以改善高电压的条件下的界面保护膜的稳定性,抑制钴的析出,降低电池长期存储后的自放电现象。
根据上述说明书的揭示,本申请所属领域的技术人员还可以对上述实施方式进行适当的变更和修改。因此,本申请并不局限于上面揭示和描述的具体实施方式,对本申请的一些修改和变更也应当落入本申请的权利要求的保护范围内。
Claims (10)
1.一种电解液,其特征在于,所述电解液包括苯并三嗪酮类化合物,所述苯并三嗪酮类化合物具有式(I)所示的结构:
其中,R1选自氢原子、取代或未取代的C1-C20烷基、烯基、炔基、芳基、烷氧基、烯氧基、炔氧基、芳氧基、羧基、烷基碳酰氧基、烯基碳酰氧基、炔基碳酰氧基、芳基碳酰氧基、烷硫基、烯硫基、炔硫基、芳硫基、氰基、氨基、N-取代的氨基、烷基碳酰胺基、N-取代的烷基碳酰胺基、烯基碳酰胺基、N-取代的烯基碳酰胺基、芳基碳酰胺基、N-取代的芳基碳酰胺基、含磷基团、含硫基团;其中,在取代或未取代的C1-C20烷基中,取代基为卤素原子;
Y表示O原子或S原子;
L表示单键或取代或未取代的C1-C6亚烷基;
R2选自取代或未取代的C1-C20烷基、烯基、炔基、芳基、亚氨基、烷氧基、烯氧基、炔氧基、芳氧基、羧基、烷基碳酰氧基、烯基碳酰氧基、炔基碳酰氧基、芳基碳酰氧基、烷硫基、烯硫基、炔硫基、芳硫基、氰基、氨基、N-取代的氨基、烷基碳酰胺基、N-取代的烷基碳酰胺基、烯基碳酰胺基、N-取代的烯基碳酰胺基、芳基碳酰胺基、N-取代的芳基碳酰胺基、含磷基团、含硫基团;在取代或未取代的C1-C20烷基中,取代基为卤素原子;
或者,R1选自式(II)表示的基团:
5.根据权利要求1所述的电解液,其特征在于,所述电解液还包括多腈类化合物,所述多腈类化合物包括具有两个腈基的化合物和具有三个及三个以上腈基的化合物中的至少一种,所述具有两个腈基的化合物包括式(Ⅲ)化合物或式(Ⅳ)化合物中的至少一种,所述具有三个及三个以上腈基的化合物包括式(Ⅴ)化合物或式(Ⅵ)化合物中的至少一种:
其中,R5选自取代或未取代的C1-C12亚烷基或-(O-Ra)m-Rc-O-Rb,Ra和Rb各自独立地选自取代或未取代的C1-C3亚烷基,Rc选自单键或取代或未取代的C1-C3亚烷基,m选自0、1、2;
R6、R7各自独立地选自单键、取代或未取代的C1~12亚烷基;
R8、R9、R10各自独立地选自单键、取代或未取代的C1-C12亚烷基或取代或未取代的C1-C12亚烷氧基;
R11选自取代或未取代的C1-C12亚烷基、取代或未取代的C2-C12亚烯基、取代或未取代的C6-C26亚芳基或取代、或未取代的C2-C12亚杂环基;并且当R5、R6、R7、R8、R9、R10和R11中至少一者被取代时,取代基为卤素。
6.根据权利要求5所述的电解液,其特征在于,以电解液的总质量计,所述多腈类化合物在电解液中的质量分数为0.1%~12%,优选为0.5%~8%。
7.根据权利要求1所述的电解液,其特征在于,所述电解液的水分含量≤300ppm,优选≤200ppm。
8.根据权利要求1所述的电解液,其特征在于,所述电解液在化成之前的铜离子含量≤200ppm。
9.一种电化学装置,其包括:
正极、负极、设置在正极与负极之间的隔离膜、以及根据权利要求1至权利要求8任一项所述的电解液。
10.一种电子装置,包括权利要求9所述的电化学装置。
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