CN112020756A - 用于高温应用的能量存储设备 - Google Patents
用于高温应用的能量存储设备 Download PDFInfo
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- CN112020756A CN112020756A CN201980026716.XA CN201980026716A CN112020756A CN 112020756 A CN112020756 A CN 112020756A CN 201980026716 A CN201980026716 A CN 201980026716A CN 112020756 A CN112020756 A CN 112020756A
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- aqueous electrolyte
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Abstract
一种用于高温应用的能量存储设备,尤其是超级电容器,具有支撑由赝电容材料改性或掺杂的碳质基体的集电器元件,所述赝电容材料包括一种或多种过渡金属二硫属元素化物、过渡金属氧化物及其混合物,碳质基体与非水性电解质组合物接触,其中除了双电层机理以外,还可以利用感应机理作为储能原理。
Description
技术领域
本公开涉及一种用于在需要电能的装置中使用的设备,特别地公开的设备可以作为用于在极端环境条件下使用的能量存储设备使用。还公开了可以用于这种设备的电解质组合物。
背景技术
在许多技术领域中显然需要紧凑的能量存储器。由于现在要求许多设备能够独立于电网运行,因此在电荷存储设备的研究方面已经做出了很大的努力。
诸如“硬币”或“纽扣”大小的电池的设备具有有限的能量值,并且使用寿命相对较短。可以使用更大的电池单元,即所谓的“蓄电池”,其能够输出更多的电能或延长使用寿命,但是只能在不会导致部件材料(如电池或蓄电池功能所需的液体电解质)分解的条件下使用。
存储电荷的设备的另一种形式是电容器,其保持静电电荷,该电容器可以选择性地快速放电以完成有限的工作,例如,以激活门锁或触发警报系统。
尽管电池和电容器都具有相反极性的电极以与外部电路连接,但在内部它们却以不同的原理操作。电池通常在电池内的电极与电解质之间进行化学反应,随着化学反应的进行,电池会释放出电能。当化学反应接近完成时,电池将不再能够提供足够的电能,并被视为已耗尽。
相反,电容器具有在间隔开的导电板之间的内部非导体或介电材料,并且可以在介电材料上建立高静电荷。
因此,与这两种类型的设备相比,可以说,当前技术水平的电池倾向于缓慢充电,能够在有限的保质期内保持电荷,并且可以在预期的时间范围内传递可预测水平的电能。相反,电容器可以被重复快速地充电,并且在放电时机可以在瞬时时间段内传递强烈的能量爆发。因此,这些类型的电能存储设备趋于遵循不同的开发路径,但是出于某些目的已经考虑了混合装置。
本公开的主题的一个目的是提供一种在宽范围的操作条件下(包括常温和常压,例如在室温下)提供有用的操作特性和有利的特性的电能存储设备。
本公开的主题的另一个目的是提供一种电能存储设备,其可用于可能暴露在诸如在地下环境中遇到的极端温度和压力条件的装置或设备中。
本公开的主题的另一个目的是提供一种可以用于电能存储设备中的电解质组合物。
在该领域中已经认识到,当暴露于超过100℃的温度时,典型的电化学能量存储设备受到电解质和隔板的热诱导降解的限制。几种可商购的设备包含液体电解质(通常是具有低沸点的有机溶剂)。因此,目前,用于这种设备的商业上允许的最高温度设定为85℃。当前,在本领域中将50℃至100℃之间的温度范围视为“高温”暴露。
期望获得一种电化学能量存储设备,其也可以在超过当前“高温”曲线的条件下操作,例如期望甚至达到200℃或更高。
本公开涉及电容器类型的设备的开发,该设备在本领域中通常被称为“超级电容器(supercapacitor)”或“超电容器(ultracapacitor)”。超级电容器本身是已知的。超级电容器与基本电容器的不同之处在于,电容器具有被绝缘体隔开的导电金属板,而超级电容器还对导电金属板进行了改性,并且将这些板浸入电解质中以作为电极。而且,在电极和电解质之间的边界中形成了电荷双层。超级电容器中的每个导电金属板都涂覆有具有比板本身大的表面积的多孔材料,例如会增加在给定施加电压下可存储在超级电容器中的电荷的量(电容)的活性炭。
以下文档可以提供有助于理解本公开背景的信息:
(1)US 8,760,851 B2;(2)US 2012/0156528 A1;(3)US 2013/0342962 A1;(4)WO2013/067540 A1;(5)US 2014/057164 A1;(6)CN 2013/10570159;(7)CN 2015/10821905。
发明内容
在本公开中,描述了尤其用于高温应用的能量存储设备,其包括支撑由赝电容材料改性或掺杂的碳质基体的集电器元件,该碳质基体与非水性电解质组合物接触,其中提出了除了双电层机理以外,还可以利用感应机理作为储能原理。碳质基体可以由一种或多种选自硫属元素化物(chalcogenide)、氧化物及其混合物的过渡金属(Mt)化合物改性或掺杂。该设备可以包括过渡金属二硫属元素化物,并且任选地还包括过渡金属氧化物。改性的或掺杂的碳质基体用作活性材料,使得能够满足预期用途的关键功能要求。活性材料可以包括以下描述的材料。
过渡金属(Mt)可以选自元素周期表的第3至12族,在一些实施方案中,例如,可以是选自铝(Al)、钛(Ti)、钒(V)、铬(Cr)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、铜(Cu)、锌(Zn)、钼(Mo)、钯(Pa)、银(Ag)、镉(Cd)、钨(W)的一种或多种过渡金属,优选基于在氧化物[MtOx](其中x对应于金属M的可用化合价)或硫属元素化物形式[MtXc 2]时表现出的半导体性质来选择。
硫属元素(Xc),例如可以选自硫(S)、硒(Se)或碲(Te),其中硫可以最大的丰度方便地获得。
二硫属元素化物[MtXc 2],例如可以选自单独或以其各种组合的MoS2、MoSe2、WS2、WSe2、TeS2、TeSe2。以下是目前可能的用于该目的的部件材料:单独或以各种组合的TiS2、TaS2、ZrS2、Bi2S3、Bi2Se3、Bi2Te3、MoSe2、TaSe2、NbSe2、MoTe2、NiTe2、BiTe2、GeS2、GeSe2、GeTe、ZnS、ZnSe、EuSe、Ag2S、Ag2Se、Ag2Te、FeS2、Fe7S8、Fe3S4、FeSe2、Fe3Se4、β-FeSex、In2S3、SnS、SnS2、SnSe、SnTe、CuS、Cu2S、Cu2-xSe、Sb2S3、Sb2Te3、MnS、MnSe、CoS2、CoS3、CoTe、NiS、NiSe、NiTe、VS2。
集电器元件可以包括金属部件,其任选地支撑在诸如塑料、玻璃或陶瓷的其他材料上,并且可以通过电导体元件连接到其他部件以形成用于充电或放电目的的电路的一部分,其中该电路可以包括:电源或发电机。集电器元件可以被称为复合正极和复合负极。金属部件可以以各种物理形式构造,任选地以柔性形式构造,例如网、箔、泡沫、海绵、片、涡管、板、线圈、棒等,改性或掺杂的碳质基体组合物已被施加至其上,例如作为导电粘附层或连续涂层。
可以通过诸如表面改性的处理(例如以增加表面粗糙度)或通过利用电沉积在集电器基板上的树枝状铜箔来制备集电器,以增强活性材料的涂覆或负载。这样制备的集电器更容易接受涂料的浆液,并证明了预期涂层的改善的粘附力。
碳涂覆的金属集电器可以在设备中显示改善的性能,因为可以减少电解质与集电器表面之间的相互作用,而不会不利地影响跨该界面的电导。
在构建设备时,可以通过采用非对称结构来实现改善的性能,例如,其中第一电极是使用双电层材料(EDL)形成的,第二电极包括赝电容材料(PC),例如作为EDL/PC混合物。这种由两种不同电极材料组装而成的不对称设备可以提供宽的操作电压窗口,从而提高能量密度。
碳质基体可以是基于石墨烯,石墨烯是非常低密度/高表面积的碳形式。可以提供碳质基体用于所公开的作为石墨烯气凝胶或类似的低密度碳基基体的用途,其表现出大的表面积并用作支撑赝电容材料的支架。各种形式的高表面积碳是可商购的,并且包括活性炭、碳纤维,或石墨、碳纳米管、碳气凝胶或碳纤维织物或布或带,例如人造丝或粘胶纤维中的任何一种。碳质基体可以是多孔的、微孔的或纳米孔的,由此离子液体或电解质可以被吸附或渗透到碳质基体中。
可以通过根据所谓的“Hummers方法”(William S.Hummers Jr.,RichardE.Offeman,J.Am.Chem.Soc.,1958,80(6),第1339至1339页,DOI:10.1021/ja01539a017,公布日期:1958年3月)以获得可以分散在水中并经历水热反应的石墨氧化物(石墨烯氧化物),以便获得还原形式,其在冷冻干燥后以3D形式重排为高表面积形式的石墨烯。
获得石墨烯氧化物的可选方法可以是本领域中称为“Brodie方法”、“Staudenmaier方法”、“Hofmann方法”和“Tour方法”的方法之一。
为了向碳质基体引入由赝电容材料的所需改性或掺杂,通过Hummers方法获得的石墨烯基体,在水热处理之前,可以将用于预期的过渡金属硫属元素化物/过渡金属氧化物的前体引入石墨烯氧化物或水中的石墨烯氧化物分散体。例如,磷钼酸和L-半胱氨酸可以用于MoS2纳米片的共合成。
在可选实施方案中,可以通过其他诸如例如电沉积、化学气相沉积、溅射、原子层沉积等的湿法或干法技术将赝电容材料引入碳质基体。
本文公开的设备可以包括在选自高沸腾温度溶剂和离子液体的液体介质中的电解质,该电解质包括选自有机盐类和无机盐类的一种或多种盐。本文公开的设备特别使用非水性电解质组合物,并且该设备的优选实施方案设计为在可能的范围内排除有害湿气或有害水分进入。
实施方案可以采用液体、聚合物或凝胶形式的电解质组合物。
聚合物凝胶类型将包括聚合物基体;任选的增塑剂或粘度调节剂或非质子溶剂;和作为电解质的离子盐。这样形成用于镀覆或覆盖集电器或电极的合适的涂料组合物。
已经提出了用于凝胶电解质用途的各种聚合物,包括聚丙烯腈“PAN”、聚氧乙烯“PEO”、聚甲基丙烯酸甲酯“PMMA”、聚偏氟乙烯“PVDF”和聚(偏氟乙烯-共-六氟丙烯)(PVDF-HFP)。
作为用于聚合物制备的液体载体的溶剂和助溶剂可以包括例如丙酮、四氢呋喃“THF”、二甲基乙酰胺“DMAc”、二甲基甲酰胺“DMF”、N-甲基-2-吡咯烷酮“NMP”和其他非质子有机溶剂。
在实施方案中,例如,可以通过将诸如聚(偏氟乙烯-六氟丙烯)“PVDF-HFP”(溶解在溶剂中)的聚合物溶液与离子液体混合来获得凝胶聚合物型电解质,如在[Lu,Wen,等人“Incorporating ionic liquid electrolytes into polymer gels for solid-stateultracapacitors.”Journal of the Electrochemical Society 155.5(2008):A361-A367]中描述的。以此方式,可以避免使用隔板而增加装置的机械稳定性。聚合物电解质可以同时用作离子导体和隔板,以避免电极弯曲时发生短路,从而大大简化了设备的制造工艺。
任选地作为凝胶状材料实现的电解质可以包含介电颗粒材料,任选地为陶瓷或陶瓷复合材料,例如诸如氧化铝、二氧化钛、硅酸镁等的无机材料的纳米颗粒,或例如诸如膨润土、蒙脱土、高岭石、白土石、锂皂石粘土(laponite clay)中的任何一种的粘土,方便的是膨润土,或这些介电颗粒材料中任何一种的组合。
在本设备中有用的电解质包括非水性溶剂、阳离子和阴离子,它们可以是有机或无机盐类,其任选地与离子液体混合。
下表示出了被认为是适合用于本文公开的尤其是用于高温应用的设备的电解质组合物中使用的候选物的溶剂,因为直到达到至少150℃的温度,这些溶剂在正常(海平面)大气压下才经历到气态的变化。
这些溶剂可以用作本文公开的电解质组合物的稀释剂。
可以通过在非水性电解质组合物中包括至少一种季铵盐获得阳离子。可以从以下列表(i)中不受限制地选择合适的阳离子:
(i)四丁基铵、1-乙基3-甲基咪唑鎓、1-丁基-3-甲基咪唑鎓、1-(3-氰丙基)-3-甲基咪唑鎓、1,2-二甲基-3-丙基咪唑鎓、1,3-双(3-氰丙基)咪唑鎓、1,3-二乙氧基咪唑鎓、1-丁基-1-甲基哌啶鎓、1-丁基-2,3-二甲基咪唑鎓、1-丁基-4-甲基吡啶鎓、1-丁基吡啶鎓、1-癸基-3-甲基咪唑鎓、3-甲基-1-丙基吡啶鎓,单独或以其两种以上的组合使用。
可以通过在非水性电解质组合物中包含至少一种盐来获得阴离子。可以从以下列表(ii)中不受限制地选择合适的阴离子:
(ii)乙基硫酸盐、甲基硫酸盐、硫氰酸盐、乙酸盐、氯化物、甲磺酸盐、四氯铝酸盐、四氟硼酸盐、六氟磷酸盐、三氟甲磺酸盐、双(五氟乙磺酸盐)酰亚胺、三氟(三氟甲基)硼酸盐、双(三氟甲磺酸盐)酰亚胺、三(三氟甲3磺酸盐)甲基化物(tris(trifluoromethane 3sulfonate)methide,或称为三(三氟甲磺酰基)甲烷)、二氰胺,单独或以其两种以上的组合使用。
所提出的基于在有机电解质中包括无机盐类的非水性材料的电解质组合物是新颖的,并且其与由过渡金属二硫属元素化物改性或掺杂的碳质基体的复合材料形成的电极一起使用以形成电气设备具有高创新性,尤其用于电容式电能存储设备的高温应用。
在实施方案中,电能存储设备,尤其是“超级电容器”,包括具有至少一个表面的金属集电器,该表面覆盖有由赝电容材料改性或掺杂的碳质基体,赝电容材料诸如为过渡金属二硫属元素化物纳米结构,例如基于MoS2。
在一种方法中,碳质基体基于石墨烯,其可以通过按照所谓的Hummer方法或上述用于获得石墨烯氧化物的任何等效方法处理可以被氧化、膨胀和剥落的石墨粉末而获得。所得的石墨烯氧化物(GO)粉末可以容易地分散在水中,该溶液可用于水热反应,以便同时获得GO的还原(还原的石墨烯氧化物-rGO)和具有高表面积(冷冻干燥后)的3D排列–所谓的“气凝胶”。
为了由金属硫化物(MSx)或金属氧化物(MOx)改性或掺杂3D rGO气凝胶,其中x对应于金属M的可用化合价,在水热合成之前向GO分散体中简单添加合适的前体是足够的(例如使用磷钼酸和L-半胱氨酸来共合成MoS2纳米片)。
可以将获得的材料与溶解在合适的溶剂中的粘合剂(通常是聚合物,诸如PVDF、PTFE、聚噻吩、聚(2,3-二氢噻吩并-1,4-二噁烯)-聚(苯乙烯磺酸盐)(Poly(2,3-dihydrothieno-1,4-dioxin)-poly(styrenesulfonate))(即PEDOT:PSS)或任何其他能够承受高达200℃的温度而无有害降解的聚合物)混合获得浆液、糊,其具有适合于通过丝网印刷或滴涂(drop-casting)沉积到例如金属丝、箔、网、泡沫或海绵形状的集电器(可以是金属或碳基)上的粘度。
生产浆液的可选粘合剂可以是水基加工粘合剂,诸如苯乙烯丁二烯共聚物(SBR)、黄原胶、聚丙烯酸(PAA)并用Na-改性的粘合剂(NaPAA)、海藻酸钠、聚胺酰亚胺(PAI)、氟丙烯酸胶乳粘合剂和纤维素基粘合剂(羧甲基纤维素(CMC)并用锂盐(Li-CMC)、钠盐(Na-CMC)、聚氨酯(PU/CMC)、聚丙烯酸(PAA/CMC)、聚(丙烯酸钠)(NaPAA-g-CMC共聚物)改性的粘合剂,微纤化纤维素(MFC)并用聚吡咯(MFC/PPy)改性的粘合剂)。
如果选择平面构造,则可以将浆液沉积在集电器的两侧,以增加可用的表面积并因此增加设备的电容。
可以使用聚酰亚胺胶带(或任何其他能够承受高达200℃的温度而不会造成有害降解的聚合物-还考虑到用作隔板的材料)作为粘合层,可以在其上附接集电器,以方便后续的设备结构成型过程。
溶剂热蒸发后,可以将电极以平行构造组装,在电极之间夹有隔板。隔板可以是具有合适的热稳定性能的多孔聚合物(例如PTFE、PVDF、聚酰亚胺等),或者由玻璃棉或纤维或陶瓷制成。
集电器可以被切割成矩形形状且在集电器上具有突起用作电接触,或者可以被切割成任何其他形状。
所得的多层可以以卷绕(涡旋)形式卷成圆柱状,或保持为平面结构并用附加的聚酰亚胺胶带固定。涡旋设备可以通过将其浸入电解质溶液中以填充电解质,并对其进行真空处理,使得整个系统保持在低压(真空)环境中,从而允许隔板渗透和排空空气。可选地,可以将多层组装成“硬币”电池、“咖啡包”(袋)电池或任何其他结构。
在填充电解质之后,可以将该设备用一层可光固化树脂(优选是可紫外线固化树脂)涂覆,并用紫外线照射以使该树脂完全聚合,从而密封该设备。该步骤可以重复几次,以改善密封并获得连续且均匀的聚合物膜。
在组装设备时,应适当考虑选择用于高温应用的设备所选择结构的次要部件(例如O形圈或密封件),避免使用例如标准的聚丙烯材料,并替代高温操作特性之一,诸如聚四氟乙烯(PTFE)或全氟烷氧基共聚物(PFA)或乙烯四氟乙烯(ETFE)或氟化乙烯丙烯(FEP)的定制O形圈,或使用此类氟碳聚合物的O形圈的封装,或在适当情况下使用柔性高温工作范围石墨材料(例如)的密封件。
附图说明
为了示例性地进一步说明本公开,在下文中将参考这些附图,这些附图包括:
图1示出了用于包含掺杂有MoS2的还原的石墨烯氧化物的材料的设备在30mV/s的扫描速率下在30℃至200℃之间记录的循环伏安法的图示;
图2示出了热分析(TGA和DSC)的图示以评估所公开的掺杂有MoS2的石墨烯氧化物的高达220℃的最佳热稳定性;和
图3示意性地示出了超级电容器设备的组装。
具体实施方式
参考图1,在Shen,Baoshou,等人Journal of Materials Chemistry A 4.21(2016):8316-8327和Borges,Raquel S.,等人Scientific reports 3(2013)中讨论的材料与根据本公开的实施方案的比较揭示了此处公开的实施方案在200℃下表现出高达210F/g(对应于365mF/cm2)的电容值,电压窗口等于2.1V。这些值在比电容(重量和面密度)方面均优越。下表1中收集了在不同温度下记录的比电容值。
表1.不同温度下记录的电容值
温度(℃) | C<sub>s</sub>(F/G) | C<sub>s</sub>(mF/cm<sup>2</sup>) |
30 | 174,9 | 306,2 |
50 | 202,1 | 353,7 |
100 | 209,2 | 366,1 |
150 | 190,8 | 333,9 |
200 | 208,5 | 364,6 |
可以根据以下说明性程序组装设备,该设备代表了一种不受限制的可能的组装方法中一个可能的实施方案,并参考图3,其中在第一阶段,将金属集电器元件1通过从金属板切割或冲压形成所需的形状,可以任选地具有突出的导电连接器2。可以以受控的方式(例如,使用刮刀)将如上所述的浆液、凝胶或糊形式的且包括由赝电容材料改性或掺杂的碳质基体和聚合物粘合剂的活性材料施加到集电器元件1上,以在集电器元件1的至少一个表面上形成覆盖选定表面区域的沉积物3,以提供第一电极4。可以将电极安装在柔性支撑基板5上。可以重复相同的程序以提供第二电极8。可以在减压下对电极4、8进行热处理,以在任何后续组装步骤之前充分去除溶剂并最小化湿气的存在。电极3、8以面对隔开的关系定向且并置,并且在电极4、8之间引入具有适当热稳定性的多孔聚合物片状隔板6,以形成层状组件。任选地,层状组件可以涡旋至大致圆柱形的本体9中。涡旋圆柱形本体9可以例如通过浸入电解质浴中而被引入到电解质溶液中,并经历减压以促进隔板6被电解质溶液渗透并排空空气。填充电解质后,可以在圆柱形本体9上涂覆可光固化树脂层并进行紫外线(UV)照射以使树脂充分聚合,从而提供密封设备。可以重复树脂涂覆步骤,并且可以任选地进行其他涂装步骤,以提供具有连续且均匀的聚合物膜表面的密封设备。
所公开的方法、材料和设备的优点包括能够实现能够在地下(例如,井下)应用所需的工作温度(高达200℃或更高)下操作的设备的能力,该设备相对于已知产品,利用较低粘度和较高离子迁移率的电解质,其与能够传递电容值(高于单独利用碳同素异形体可获得的值)的复合电极(例如包含赝电容材料的3D石墨烯网络)结合。
Claims (20)
1.一种设备,包括集电器元件,每个所述集电器元件支撑碳质基体,所述碳质基体由赝电容材料改性或掺杂,并且与非水性电解质组合物接触。
2.根据权利要求1所述的设备,其中所述非水性电解质组合物包括在选自高沸腾温度溶剂和离子液体的液体介质中的阳离子和阴离子。
3.根据权利要求1或2所述的设备,其中所述非水性电解质组合物包括一种或多种选自有机盐类和无机盐类的盐。
4.根据前述权利要求任一项所述的设备,其中所述非水性电解质组合物包括至少一种季铵盐。
5.根据前述权利要求任一项所述的设备,其中所述非水性电解质组合物包括至少一种选自四丁基铵、1-乙基3-甲基咪唑鎓、1-丁基-3甲基咪唑鎓、1-(3-氰丙基)-3-甲基咪唑鎓、1,2-二甲基-3-丙基咪唑鎓、1,3-双(3-氰丙基)咪唑鎓、1,3-二乙氧基咪唑鎓、1-丁基-1-甲基哌啶鎓、1-丁基-2,3-二甲基咪唑鎓、1-丁基-4-甲基吡啶鎓、1-丁基吡啶鎓、1-癸基-3-甲基咪唑鎓、3-甲基-1-丙基吡啶鎓的阳离子。
6.根据前述权利要求任一项所述的设备,其中所述非水性电解质组合物包括至少一种选自乙基硫酸盐、甲基硫酸盐、硫氰酸盐、乙酸盐、氯化物、甲磺酸盐、四氯铝酸盐、四氟硼酸盐、六氟磷酸盐、三氟甲磺酸盐、双(五氟乙磺酸盐)酰亚胺、三氟(三氟甲基)硼酸盐、双(三氟甲磺酸盐)酰亚胺、三(三氟甲3磺酸盐)甲基化物、二氰胺的阴离子。
7.根据前述权利要求任一项所述的设备,其中所述非水性电解质组合物包括以下中的至少一种:甘油、乙二醇、二乙二醇、二乙二醇二甲醚(二甘醇二甲醚)、碳酸亚丙酯、六甲基磷酰胺(HMPA)、N-甲基-2-吡咯烷酮(NMP)、二甲基亚砜(DMSO)、二甲基甲酰胺(DMF)、六甲基磷三酰胺(HMPT)。
8.根据前述权利要求任一项所述的设备,其中所述碳质基体由所述赝电容材料通过选自电沉积、化学气相沉积(CVD)、溅射、原子层沉积的方法改性或掺杂。
9.根据前述权利要求任一项所述的设备,其中所述碳质基体由金属硫属元素化物改性或掺杂。
10.根据权利要求9所述的设备,其中所述碳质基体由金属氧化物改性或掺杂。
11.根据前述权利要求任一项所述的设备,其中所述赝电容材料包括过渡金属。
12.根据权利要求11所述的设备,其中所述赝电容材料包括至少一种过渡金属二硫属元素化物,和任选的至少一种过渡金属氧化物。
13.根据权利要求12所述的设备,其中所述赝电容材料包括MoS2、MoSe2、WS2、WSe2、TeS2、TeSe2、TiS2、TaS2、ZrS2、Bi2S3、Bi2Se3、Bi2Te3、MoSe2、TaSe2、NbSe2、MoTe2、NiTe2、BiTe2、GeS2、GeSe2、GeTeZn2、ZnSe、EuSe、Ag2S、Ag2Se、Ag2Te、FeS2、Fe7S8、Fe3S4、FeSe2、Fe3Se4、β-FeSex、In2S3、SnS、SnS2、SnSe、SnTe、CuS、Cu2S、Cu2-xSe、Sb2S3、Sb2Te3、MnS、MnSe、CoS2、CoS3、CoTe、NiS、NiSe、NiTe、VS2中的一种或多种,单独或以各种组合。
14.根据前述权利要求任一项所述的设备,其中所述集电器元件包括金属部件,其任选地支撑在塑料或陶瓷上,并构造为网、箔、泡沫、海绵、片、涡管、板、线圈或棒中的一种。
15.根据前述权利要求任一项所述的设备,其中所述碳质基体包括石墨烯、活性炭、碳纤维、人造丝或粘胶纤维、碳纳米管、碳气凝胶或碳纤维织物或布或带。
16.根据前述权利要求任一项所述的设备,其中所述碳质基体包括石墨烯气凝胶,并且所述赝电容材料包括二硫化钼。
17.根据前述权利要求任一项所述的设备,构造为超级电容器并且包括用作正极和负极的多个集电器元件,并具有用于将所述集电器元件连接到外部电路的电导体元件,所述多个集电器元件分别与限制在所述设备内的非水性电解质组合物接触,并且具有位于所述集电器元件之间的隔板,使得所述正极和所述负极分离。
18.根据权利要求17所述的设备,其中所述隔板包括热稳定的聚合物或陶瓷或玻璃并且是多孔的。
19.根据权利要求17或18所述的设备,其中所述设备构造为多层结构,填充有电解质并用聚合物或树脂密封,能够组装成“硬币”电池或“咖啡包”(袋)电池。
20.根据权利要求19所述的设备,其中所述设备使用可光固化树脂密封。
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CN114203453B (zh) * | 2021-11-18 | 2024-06-25 | 益阳市万京源电子有限公司 | 一种超级电容器的负极及制备方法 |
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CN110981527B (zh) * | 2019-11-28 | 2021-04-02 | 中国矿业大学(北京) | 一种柔性陶瓷集流层薄膜生坯 |
CN112700967B (zh) * | 2020-11-30 | 2021-12-03 | 电子科技大学 | 一种高比容量的Cu2-xSe超级电容器负极材料 |
CN115072777B (zh) * | 2022-07-22 | 2022-12-23 | 山东海化集团有限公司 | 通过钴掺杂和溶剂协同调控制备中空硫化铋的方法及由其制备的钾离子电池负极材料 |
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US11923139B2 (en) | 2024-03-05 |
EA202092496A1 (ru) | 2021-02-12 |
US20210375558A1 (en) | 2021-12-02 |
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