CN108370069A - 含聚多巴胺的电解液和包含所述电解液的锂硫电池 - Google Patents
含聚多巴胺的电解液和包含所述电解液的锂硫电池 Download PDFInfo
- Publication number
- CN108370069A CN108370069A CN201780004895.8A CN201780004895A CN108370069A CN 108370069 A CN108370069 A CN 108370069A CN 201780004895 A CN201780004895 A CN 201780004895A CN 108370069 A CN108370069 A CN 108370069A
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- Prior art keywords
- lithium
- electrolyte
- sulfur cell
- dopamine
- poly
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000003792 electrolyte Substances 0.000 title claims abstract description 54
- 229920001690 polydopamine Polymers 0.000 title claims abstract description 41
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 17
- -1 phosphotriester Chemical compound 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 5
- 159000000002 lithium salts Chemical class 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical class COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 3
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- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical class CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 2
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- 229910003253 LiB10Cl10 Inorganic materials 0.000 claims description 2
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 2
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- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
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- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 150000004862 dioxolanes Chemical class 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 2
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 claims description 2
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
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- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- HSFDLPWPRRSVSM-UHFFFAOYSA-M lithium;2,2,2-trifluoroacetate Chemical compound [Li+].[O-]C(=O)C(F)(F)F HSFDLPWPRRSVSM-UHFFFAOYSA-M 0.000 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 2
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- GLFAEFVIKYUOJK-UHFFFAOYSA-N [B].[Cl] Chemical compound [B].[Cl] GLFAEFVIKYUOJK-UHFFFAOYSA-N 0.000 claims 1
- 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 claims 1
- 229940017219 methyl propionate Drugs 0.000 claims 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical class [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 abstract description 24
- 238000006243 chemical reaction Methods 0.000 abstract description 13
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- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 14
- 239000005864 Sulphur Substances 0.000 description 13
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Abstract
本发明涉及包含聚多巴胺的电解液和包含所述电解液的锂硫电池，并且更具体地涉及包含在电解液中的聚多巴胺吸附从锂硫电池的正极溶出的多硫化锂的技术。当使用本发明的其中添加了聚多巴胺粒子的电解液时，分散在所述电解液中的所述聚多巴胺粒子起到吸附在充放电过程中从正极溶出的多硫化锂的作用，由此能够抑制其扩散，即抑制穿梭反应，从而改善所述锂硫电池的容量和寿命特性。
Description
技术领域
本申请要求于2016年5月2日向韩国知识产权局提交的韩国专利申请第10-2016-0054164号的优先权和权益，并通过引用的方式将其全部内容并入本文中。
本发明涉及包含聚多巴胺的电解液和包含所述电解液的锂硫电池，并且特别地涉及包含在电解液中的聚多巴胺吸附从锂硫电池的正极溶出的多硫化锂的技术。
背景技术
近年来，随着电子产品、电子设备、通信设备等快速地变得越来越小且越来越轻，并且考虑到环境问题而迫切需要电动车辆，因此对改善用作这些产品的电源的二次电池的性能的要求大大增加。其中，锂二次电池由于其高能量密度和高标准电极电位而作为高性能电池受到极大关注。
特别地，锂硫(Li-S)电池是使用具有硫-硫(S-S)键的硫系材料作为正极活性材料并使用锂金属作为负极活性材料的二次电池。作为正极活性材料的主要材料的硫具有资源非常丰富、无毒且原子量低的优势。此外，锂硫电池的理论放电容量为1675mAh/g-硫且理论能量密度为2600Wh/kg，这与目前研究的其他电池系统的理论能量密度(Ni-MH电池：450Wh/kg，Li-FeS电池：480Wh/kg，Li-MnO2电池：1000Wh/kg，Na-S电池：800Wh/kg)相比是非常高的，因此是迄今开发的电池中最有前景的电池。
在锂硫(Li-S)电池的放电反应期间，在负极(阳极)中发生锂的氧化反应，并且在正极(阴极)中发生硫的还原反应。硫在放电之前具有环状的S8结构，并且使用氧化还原反应来储存和产生电能，其中在还原反应(放电)期间S的氧化数随S-S键的断裂而降低，并且在氧化反应(充电)期间S的氧化数随S-S键的再次形成而升高。在这样的反应期间，通过还原反应将硫从环状的S8转化成线性结构的多硫化锂(Li2Sx，x＝8、6、4和2)，结果，当这样的多硫化锂被完全还原时最终产生硫化锂(Li2S)。通过还原成各种多硫化锂的过程，锂硫(Li-S)电池的放电行为显示出与锂离子电池不同的阶段性的放电电压。
在诸如Li2S8、Li2S6、Li2S4和Li2S2的多硫化锂中，具有高的硫氧化数的多硫化锂(Li2Sx，通常x>4)特别是容易溶解在亲水性电解液中。溶解在电解液中的多硫化锂由于浓度差而从生成了多硫化锂的正极扩散开。如上所述从正极溶出的多硫化锂被冲到正极反应区域之外，使得不能逐渐还原成硫化锂(Li2S)。换句话说，在正极和负极外部以溶解状态存在的多硫化锂不能参与电池的充放电反应，因此参与正极中的电化学反应的硫物质的量减少，结果，这成为引起锂硫电池的充电容量降低和能量减少的主要因素。
此外，除了漂浮在或浸入电解液中的多硫化锂之外，扩散到负极的多硫化锂直接与锂反应并以Li2S的形式固定在负极表面上，这导致腐蚀锂金属负极的问题。
为了使这样的多硫化锂的溶出最小化，一直在对改变用硫粒子填充各种碳结构的正极复合体的形态进行研究，然而，这样的方法在制备时是复杂的并且没有解决根本问题。
发明内容
技术问题
如上所述，锂硫电池的问题在于，由于多硫化锂从正极中溶出并扩散，因此电池容量和寿命特性随着充放电循环的进行而下降。
因此，本发明的一个方面提供抑制多硫化锂的溶出和扩散的锂硫电池用电解液。
本发明的另一个方面提供包含所述电解液的锂硫电池。
技术方案
根据本发明的一个方面，提供包含聚多巴胺的锂硫电池用电解液。
根据本发明的另一个方面，提供包含所述电解液的锂硫电池。
有益效果
当使用本发明一个方面的添加了聚多巴胺的电解液时，分散在电解液中的聚多巴胺粒子起到吸附在充放电期间从正极溶出的多硫化锂的作用，因此通过抑制多硫化锂的扩散即抑制穿梭反应，能够提高锂硫电池的容量和寿命特性。
附图说明
图1是本发明比较例1的用不含聚多巴胺粒子的电解液形成的锂硫电池的充放电曲线。
图2是本发明实施例1的用包含0.1重量％聚多巴胺粒子的电解液形成的锂硫电池的充放电曲线。
图3是本发明实施例2的用包含0.25重量％聚多巴胺粒子的电解液形成的锂硫电池的充放电曲线。
图4是本发明实施例3的用包含0.5重量％聚多巴胺粒子的电解液形成的锂硫电池的充放电曲线。
图5是本发明实施例4的用包含1.0重量％聚多巴胺粒子的电解液形成的锂硫电池的充放电曲线。
图6是显示本发明的比较例1和实施例1～4的锂硫电池的与循环相关的放电循环性能的图。
具体实施方式
下文中，将参考附图对本发明的实施方案进行详细说明，以便本领域技术人员能够容易地实现本发明。然而，本发明可以以各种不同的形式来实现，并且不限于下面说明的实施方案。
锂硫电池用电解液
本发明公开了包含聚多巴胺的锂硫电池用电解液。具体地，本发明的锂硫电池用电解液是包含聚多巴胺的非水电解液，并通过包含聚多巴胺、锂盐和非水液体成分而形成。
作为聚多巴胺的单体形式的多巴胺众所周知是神经递质，并且是在海中的贻贝中发现的3,4-二羟基-L-苯丙氨酸(L-DOPA)分子的仿制分子。特别地，通过多巴胺的氧化剂诱导的自聚合和电化学聚合而产生的聚多巴胺具有儿茶酚、胺和亚胺官能团，并且不仅在诸如生物材料或合成聚合物的有机物质中而且在诸如电池电极或隔膜的固体表面上形成非常强的键，因此可以实现表面重整、表面改性、自组装多层的形成、纳米复合薄膜的形成等。多巴胺的儿茶酚官能团在氧气存在下易于被氧化，并且可通过自聚合而形成聚多巴胺。
具体地，多巴胺以溶解在价格低廉且环境友好的蒸馏水基缓冲液(10mM的三羟甲基氨基甲烷缓冲液)中、而不是溶解在价格昂贵且对环境不利的普通有机溶剂中的方式进行使用，这是因为如下原因：溶液需要稳定地保持在弱碱性(例如pH8.5)状态下以使多巴胺通过自发聚合形成聚多巴胺(来源于贻贝的聚合物)。
在本发明中，这样的聚多巴胺优选以粒子形式包含在锂硫电池的电解液中。通过对其中溶解有多巴胺或其衍生物的混合溶液进行搅拌，然后对所得物进行洗涤并干燥，可以将这样的聚多巴胺粒子制备成粉末。
在此，制备的聚多巴胺的平均粒径可以通过调节包含多巴胺的混合溶液的pH进行控制。作为一个实例，通过添加三羟甲基氨基甲烷(NH2C(CH2OH)3)或氢氧化钠(NaOH)，可以将聚多巴胺制备成具有100nm～800nm的粒径。更优选地，使用具有200nm～600nm平均粒径的粒子作为引入到本发明的锂硫电池用电解液中的聚多巴胺。当平均粒径小于200nm时，工艺条件是复杂的，并且当平均粒径大于600nm时，能够吸附多硫化锂的表面积减小，导致吸附效率降低的问题。
基于全部电解液的总重量，优选包含0.1重量％～1.0重量％的聚多巴胺，当含量小于0.1重量％时，聚多巴胺吸附多硫化锂的效果可能得不到保证，而当含量大于1.0重量％时，聚多巴胺粒子起电阻的作用，导致电效率降低的问题。
本发明的锂盐是易于溶解在非水有机溶剂中的材料，并且其实例可以包括选自由如下构成的组中的一种或多种：LiCl、LiBr、LiI、LiClO4、LiBF4、LiB10Cl10、LiB(Ph)4、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、LiSO3CH3、LiSO3CF3、LiSCN、LiC(CF3SO2)3、LiN(CF3SO2)2、LiNO3、氯硼烷锂、低级脂族羧酸锂、四苯基硼酸锂和亚氨基锂。
根据各种因素如电解液混合物的精确组成、盐的溶解度、被溶解了的盐的电导率、电池的充放电条件、工作温度以及锂电池领域中已知的其他因素，锂盐的浓度可以为0.2M～4M，具体地为0.3M～2M，更具体地为0.3M～1.5M。当使用量小于0.2M时，电解液的电导率可能降低，导致电解液性能下降，并且当用量大于4M时，电解液的粘度增加，导致锂离子(Li+)迁移率降低。
非水有机溶剂需要易于溶解锂盐，且本发明的非水有机溶剂的实例可以包括非质子有机溶剂，如N-甲基-2-吡咯烷酮、碳酸亚丙酯、碳酸亚乙酯、碳酸亚丁酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、γ-丁内酯、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷、四氢呋喃、2-甲基四氢呋喃、二甲亚砜、1,3-二氧戊环、4-甲基-1,3-二烷、二乙醚、甲酰胺、二甲基甲酰胺、乙腈、硝基甲烷、甲酸甲酯、乙酸甲酯、磷酸三酯、三甲氧基甲烷、二氧戊环衍生物、环丁砜、甲基环丁砜、1,3-二甲基-2-咪唑烷酮、碳酸亚丙酯衍生物、四氢呋喃衍生物、醚、丙酸甲酯或丙酸乙酯，且有机溶剂可以单独或作为两种以上有机溶剂的混合物使用。
为了提高充放电性能、阻燃性等，可以向本发明的电解液添加例如吡啶、亚磷酸三乙酯、三乙醇胺、环醚、乙二胺、正甘醇二甲醚、六甲基磷酰三胺、硝基苯衍生物、硫、醌亚胺染料、N-取代的唑烷酮、N,N-取代的咪唑烷、乙二醇二烷基醚、铵盐、吡咯、2-甲氧基乙醇、三氯化铝等。在某些情况下，为了赋予阻燃性，还可以包含含卤素的溶剂如四氯化碳或三氟乙烯，另外可以包含二氧化碳气体以提高高温储存性能，并还可以包含氟代碳酸亚乙酯(FEC)、丙烯磺内酯(PRS)、氟代碳酸亚丙酯(FPC)等。
锂硫电池
本发明的正极为锂硫电池的正极，并且可以包含正极活性材料层和用于支撑所述正极活性材料层的正极集电器。
正极活性材料可以包括硫元素(S8)、硫系化合物或它们的混合物。硫系化合物可以具体为Li2Sn(n≥1)、有机硫化合物、碳-硫聚合物((C2Sx)n：x＝2.5～50，n≥2)等。由于单独的硫材料不具有导电性，因此这些物质可以作为与导体的复合物来使用。
导体可以是多孔的。因此，作为导体，可以没有限制地使用具有多孔性和导电性的物质，并且例如可以使用具有多孔性的碳基材料。作为这样的碳基材料，可以使用炭黑、石墨、石墨烯、活性炭、碳纤维等。另外，还可以使用：金属纤维如金属网；金属粉末如铜、银、镍和铝；或者有机导电材料如聚亚苯基衍生物。导电材料可以单独使用或作为混合物使用。
粘结剂可以包括热塑性树脂或热固性树脂。例如可以单独或作为混合物的形式使用：聚乙烯、聚丙烯、聚四氟乙烯(PTFE)、聚偏二氟乙烯(PVDF)、丁苯橡胶、四氟乙烯-全氟烷基乙烯基醚共聚物、偏二氟乙烯-六氟丙烯共聚物、偏二氟乙烯-氯三氟乙烯共聚物、乙烯-四氟乙烯共聚物、聚氯三氟乙烯、偏二氟乙烯-五氟丙烯共聚物、丙烯-四氟乙烯共聚物、乙烯-氯三氟乙烯共聚物、偏二氟乙烯-六氟丙烯-四氟乙烯共聚物、偏二氟乙烯-全氟甲基乙烯基醚-四氟乙烯共聚物、乙烯-丙烯酸共聚物等，然而，粘结剂不限于此，并且在本领域中能够用作粘结剂的那些粘结剂都可以使用。
作为正极集电器，能够用作本领域中的集电器的那些集电器都可以使用，且具体地，可以优选使用具有优异导电性的发泡铝、发泡镍等。
这样的正极可以使用普通方法来制备，具体地，可以通过将用于形成正极活性材料层的组合物涂布在集电器上并对所得物进行干燥，并选择性地将所得物在集电器上压缩成型以提高电极密度来制备，所述组合物通过将正极活性材料、导体和粘结剂混合在有机溶剂中而制备。在此，作为有机溶剂，优选使用能够均匀地分散正极活性材料、粘结剂和导体并容易蒸发的物质。具体地，可以包括乙腈、甲醇、乙醇、四氢呋喃、水、异丙醇等。
本发明的负极为锂硫电池的负极，并且包含负极活性材料层并且可以选择性地进一步包含用于支撑负极活性材料层的负极集电器。
负极可以使用如下物质作为负极活性材料：能够可逆地嵌入或脱嵌锂离子(Li+)的材料、能够通过与锂离子(Li+)反应而可逆地形成含锂化合物的材料、锂金属或锂合金。能够可逆地嵌入或脱嵌锂离子(Li+)的材料的实例可以包括结晶碳、无定形碳或其混合物。能够通过与锂离子(Li+)反应而可逆地形成含锂化合物的材料的实例可以包括氧化锡、硝酸钛或硅。锂合金的实例可以包括锂(Li)与选自由如下构成的组中的金属的合金：钠(Na)、钾(K)、铷(Rb)、铯(Cs)、镧(Fr)、铍(Be)、镁(Mg)、钙(Ca)、锶(Sr)、钡(Ba)、镭(Ra)、铝(Al)和锡(Sn)。
粘结剂起到将负极活性材料糊化、使活性材料彼此粘合、使活性材料和集电器粘合、并对活性材料的膨胀和收缩具有缓冲效果等作用。具体地，所述粘结剂与上述正极的粘结剂中的相同。
另外，负极可以是锂金属或锂合金。作为非限制性实例，负极还可以是锂金属的薄膜，或者可以是锂与选自由如下金属构成的组中的一种或多种金属的合金：Na、K、Rb、Cs、Fr、Be、Mg、Ca、Sr、Ba、Ra、Al和Sn。
负极集电器可以具体地选自由铜、不锈钢、钛、银、钯、镍、其合金及其组合构成的组。不锈钢可以用碳、镍、钛或银进行表面处理，并且可以将铝-镉合金用作所述合金。除此之外，还可以使用焙烧碳、表面用导体处理过的非导电聚合物、导电聚合物等。
可以在正极与负极之间设置普通的隔膜。隔膜是具有将电极物理隔开的功能的物理隔膜，且可以使用通常用作隔膜的那些隔膜而没有特别限制，特别地，具有优异的电解液保湿能力并同时对电解液的离子迁移具有低的阻力的隔膜是优选的。
另外，隔膜在使正极与负极彼此隔开并绝缘的同时能够使锂离子在正极与负极之间迁移。这样的隔膜可以由多孔的不导电或绝缘的材料形成。隔膜可以是诸如膜的独立构件，或者可以是附加到正极和/或负极的涂层。
具体地，可以单独地或作为其层压体使用多孔聚合物膜，例如用聚烯烃类聚合物如乙烯均聚物、丙烯均聚物、乙烯/丁烯共聚物、乙烯/己烯共聚物和乙烯/甲基丙烯酸酯共聚物制备的多孔聚合物膜，或者可以使用普通的多孔无纺布如由高熔点玻璃纤维或聚对苯二甲酸乙二醇酯纤维制成的无纺布，然而，隔膜不限于此。
包含在锂硫电池中的正极、负极和隔膜各自可以使用普通的成分和制备方法来制备，并且尽管没有特别限制于此，但是锂硫电池的外观可以包括圆柱型、方型、袋型、使用罐的硬币型等。
本发明的实施方式
下文中，为了具体说明本发明，将参考实例详细说明本发明。然而，本发明的实例可以修改为多种其他形式，并且本发明的范围不应解释为限于下面说明的实例。提供本发明的实例是为了更充分地向本领域普通技术人员说明本发明。
<实施例1>
1.电解液的制备
向在体积比为1:1的二甲氧基乙烷和1,3-二氧戊环中混合溶解有1M LiN(CF3SO2)2的溶液中添加0.1重量％的聚多巴胺粉末以制备电解液。在此，使用通过精制而具有400nm～500nm的粒径的聚多巴胺。
2.锂硫电池的制造
在通过将正极混合物添加到去离子水来制备正极浆料之后，将所得物涂布在铝集电器上以制备正极，所述正极混合物的组成为75重量％的硫/碳复合体(S/C复合体:硫+Super-P＝9:1)、20重量％的导电材料(超导电乙炔炭黑(Denka black))和5重量％的粘结剂(SBR:CMC＝1:1)。在此，在粘结剂中，SBR为丁苯橡胶且CMC为羧甲基纤维素。
作为负极，使用厚度约150μm的锂箔，且作为隔膜，使用厚度为20μm的聚丙烯膜，并通过注入100μl上述制备的含有聚多巴胺的电解液来制造钮扣状锂硫电池。
<实施例2>
除了使用包含0.25重量％的聚多巴胺粉末的电解液之外，以与实施例1中相同的方式制造了锂硫电池。
<实施例3>
除了使用包含0.5重量％的聚多巴胺粉末的电解液之外，以与实施例1中相同的方式制造了锂硫电池。
<实施例4>
除了使用包含1.0重量％的聚多巴胺粉末的电解液之外，以与实施例1中相同的方式制造了锂硫电池。
<比较例1>
除了使用不含聚多巴胺粉末的电解液之外，以与实施例1中相同的方式制造了锂硫电池。
<实验例1>
为了确定根据实施例1～4和比较例1制造的锂硫电池的穿梭抑制效果，使用1.5V～2.8V的截止电压和0.1C的C倍率，实施了充放电试验。在此，电池载荷为1.223mAh/cm2，且当以0.1C的倍率进行试验时，电流水平为0.188×10-6A，并将充放电试验的结果示于图1～图5中。
已经确认，如图1中所示，充电在2.3V～4V附近未完成，并且当发生穿梭反应时持续发生延迟反应，并且如图2～图5中所示，当穿梭反应受到抑制时，充电适当地完成，虽然程度有所不同。因此确认了，当使用包含聚多巴胺的电解液时，穿梭反应受到抑制。
<实验例2>
对于根据实施例1～4和比较例1制造的锂硫电池，分别在0.1C/0.1C下重复50个循环的充电/放电的同时，测量了各个电池的比放电容量。如图6所示，已经确认了，实施例1～4的锂硫电池比比较例1的锂硫电池具有更大的初始容量，并且还具有提高的寿命特性，且尤其已经确认了，实施例3的锂硫电池显示出最优异的性能。
产业实用性
本发明的锂硫电池稳定地显示优异的放电容量、输出特性和容量保持率，并且因此可用于便携式设备如移动电话、笔记本计算机、数码相机和摄像机以及诸如混合动力汽车(HEV)的电动车辆的领域中。
因此，根据本发明的另一个实施方案，提供包含所述锂硫电池作为单元电池的电池模块以及包含所述电池模块的电池组。所述电池模块或所述电池组可以用作如下一种或多种中型到大型装置的电源：电动工具；电动车辆，包括电动汽车(EV)、混合动力汽车和插电式混合动力汽车(PHEV)；或电力存储系统。
Claims (7)
1.一种锂硫电池用电解液，所述电解液包含聚多巴胺。
2.如权利要求1所述的锂硫电池用电解液，其中，
所述聚多巴胺具有平均粒径为200nm～600nm的粒子形式。
3.如权利要求1所述的锂硫电池用电解液，其中，
基于全部电解液的总重量，包含0.1重量％～1.0重量％的所述聚多巴胺。
4.如权利要求1所述的锂硫电池用电解液，其为非水电解液。
5.如权利要求1所述的锂硫电池用电解液，其包括选自由如下构成的组中的一种或多种锂盐：LiCl、LiBr、LiI、LiClO4、LiBF4、LiB10Cl10、LiB(Ph)4、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、LiSO3CH3、LiSO3CF3、LiSCN、LiC(CF3SO2)3、LiN(CF3SO2)2、LiNO3、氯硼烷锂、低级脂族羧酸锂、四苯基硼酸锂和亚氨基锂。
6.如权利要求1所述的锂硫电池用电解液，其包括选自由如下构成的组中的一种或多种有机溶剂：N-甲基-2-吡咯烷酮、碳酸亚丙酯、碳酸亚乙酯、碳酸亚丁酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、γ-丁内酯、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷、四氢呋喃、2-甲基四氢呋喃、二甲亚砜、1,3-二氧戊环、4-甲基-1,3-二烷、二乙醚、甲酰胺、二甲基甲酰胺、乙腈、硝基甲烷、甲酸甲酯、乙酸甲酯、磷酸三酯、三甲氧基甲烷、二氧戊环衍生物、环丁砜、甲基环丁砜、1,3-二甲基-2-咪唑烷酮、碳酸亚丙酯衍生物、四氢呋喃衍生物、醚、丙酸甲酯和丙酸乙酯。
7.一种锂硫电池，所述锂硫电池包含：
正极；
负极；
设置在所述正极与所述负极之间的隔膜；以及
浸渗在它们中的电解液，
其中所述电解液为权利要求1～6中任一项所述的电解液。
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| CN113314773A (zh) * | 2021-05-12 | 2021-08-27 | 江苏师范大学 | 一种水系锌离子电池电解质及其制备方法和应用 |
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| WO2017191883A1 (ko) | 2017-11-09 |
| EP3370297A4 (en) | 2018-09-05 |
| CN108370069B (zh) | 2021-01-12 |
| US20180331391A1 (en) | 2018-11-15 |
| US10573930B2 (en) | 2020-02-25 |
| EP3370297A1 (en) | 2018-09-05 |
| KR102006720B1 (ko) | 2019-08-02 |
| JP6664482B2 (ja) | 2020-03-13 |
| EP3370297B1 (en) | 2019-04-24 |
| JP2018533824A (ja) | 2018-11-15 |
| KR20170124362A (ko) | 2017-11-10 |
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