CN115490688B - 基于三氮杂蒄的二维导电金属有机框架材料及其制备方法与应用 - Google Patents
基于三氮杂蒄的二维导电金属有机框架材料及其制备方法与应用 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 32
- 239000013299 conductive metal organic framework Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- -1 2,3,6,7,10, 11-hexahydroxy-1, 5,9-triazacoronene Chemical compound 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 17
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- 238000003786 synthesis reaction Methods 0.000 claims description 16
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- ATVRUZHAFYWCAQ-UHFFFAOYSA-N 2,3,6,7,10,11-hexamethoxy-1,5,9-trinitrotriphenylene Chemical compound COc1cc2c(c(c1OC)[N+]([O-])=O)c1cc(OC)c(OC)c([N+]([O-])=O)c1c1cc(OC)c(OC)c([N+]([O-])=O)c21 ATVRUZHAFYWCAQ-UHFFFAOYSA-N 0.000 claims description 11
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- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 2
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
- C07D471/16—Peri-condensed systems
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/606—Polymers containing aromatic main chain polymers
- H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
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Abstract
本发明公开了基于三氮杂蒄的二维导电金属有机框架材料及其制备方法与应用,基于氮杂蒄的二维导电金属有机框架材料,简称Cu‑TAC MOF,其结构式由式(VI)所示:本发明的二维导电金属有机框架材料Cu‑TAC MOF是基于氮杂蒄的羟基单体构筑的,Cu‑TAC MOF材料具有良好的导电性和丰富的氧化还原活性位点,其作为锂离子负极材料展现出高的比容量、长的循环稳定性和良好的倍率性能。这项工作为设计新型二维导电金属有机框架材料及其锂电池电极材料提供了新思路。
Description
技术领域
本发明属于二维导电金属有机框架材料领域,特别是涉及一种基于三氮杂蒄的二维导电金属有机框架材料及制备方法与应用。
背景技术
二维导电金属有机框架(2D c-MOFs)是由多向邻位-NH2、-OH、-SH或-SeH取代的共轭构建块和电子未成对的过渡金属离子通过强配位键连接形成具有高平面内共轭和面外范德华相互作用的层叠MOFs。由于其独特的片状结构,大的比表面积、规则的孔通道、丰富的活性位点和良好的导电性等优点,在场效应晶体管、电催化、可充电电池、超级电容器、电化学传感等多个领域得到了广泛的关注。然而到目前为止,可用于构筑二维导电金属有机框架材料的配体非常有限,主要是基于苯、苯并菲、三亚萘、三聚茚、四苯并萘和酞菁等衍生的具有π共轭的平面配体。且已报道的二维导电金属有机框架活性位点单一,导致其应用受限。
因此,设计合成新型具有多活性位点的有机配体来构筑二维导电金属有机框架对于提升二维导电金属有机框架的性能以及研究其结构和性能的关系具有重要意义。
三氮杂蒄(1,5,9-triazacoronene,TAC)是一类具有独特电子结构和物理化学性质的大π共轭的多环芳烃,在有机半导体材料、场效应晶体管、光电二极管和光伏电池等方面有着广泛的应用。相比于苯、苯并菲、三亚萘、三聚茚等共轭构建块,三氮杂蒄具有更大的共轭平面,有助于构筑高导电性的二维导电金属有机框架材料。且其丰富的N杂原子可以调控配体的电子特性,并且可以作为某些反应的活性位点,因此,将具有三氮杂蒄结构的分子整合到二维导电金属有机框架中有利于电导率和性能的提升,但是,如何构筑基于三氮杂蒄的二维导电金属有机框架材料仍然是一个巨大的挑战。
发明内容
本发明的目的是克服当前现有技术的不足,提供合成一种基于三氮杂蒄的二维导电金属有机框架材料的羟基单体2,3,6,7,10,11-六羟基-1,5,9-三氮杂蒄。
本发明的第二个目的是提供2,3,6,7,10,11-六羟基-1,5,9-三氮杂蒄的制备方法。
本发明的第三个目的是提供一种三氮杂蒄的二维导电金属有机框架材料。
本发明的第四个目的是提供一种基于三氮杂蒄的二维导电金属有机框架料的制备方法。
本发明的第五个目的是提供一种基于三氮杂蒄的二维导电金属有机框架料制备锂离子电池电极的应用。
本发明的技术方案概述如下:
2,3,6,7,10,11-六羟基-1,5,9-三氮杂蒄,其结构如式(V)所示,简称:6OH-TAC
2,3,6,7,10,11-六羟基-1,5,9-三氮杂蒄的制备方法,包括如下步骤:
1)2,3,6,7,10,11-六甲氧基苯并菲I的合成:
将1.2-二甲氧基苯,无水三氯化铁和浓硫酸加入到二氯甲烷溶液中,然后通过缩合反应得到2,3,6,7,10,11-六甲氧基苯并菲I;
2)1,5,9-三硝基-2,3,6,7,10,11-六甲氧基苯并菲II的合成:
将2,3,6,7,10,11-六甲氧基苯并菲I和发烟硝酸在乙酸,乙醚和二氯甲烷混合溶剂中反应得到1,5,9-三硝基-2,3,6,7,10,11-六甲氧基苯菲II;
3)1,5,9-三氨基-2,3,6,7,10,11-六甲氧基苯并菲III的合成:
将1,5,9-三硝基-2,3,6,7,10,11-六甲氧基苯并菲和四水合醋酸镍溶解于四氢呋喃和无水甲醇的混合溶液中,加入硼氢化钠还原得到1,5,9-三氨基-2,3,6,7,10,11-六甲氧基苯并菲III;
4)2,3,6,7,10,11-六甲氧基-1,5,9-三氮杂蒄IV的合成:
将1,5,9-三氨基-2,3,6,7,10,11-六甲氧基苯并菲III和多聚甲醛在含有1%三氟甲磺酸的DMF溶液中反应,得到2,3,6,7,10,11-六甲氧基-1,5,9-三氮杂蒄IV;
5)2,3,6,7,10,11-六羟基-1,5,9-三氮杂蒄V的合成:
将2,3,6,7,10,11-六甲氧基-1,5,9-三氮杂蒄IV的在吡啶盐酸盐中反应,得到2,3,6,7,10,11-六羟基-1,5,9-三氮杂蒄V;
反应式如下:
一种基于三氮杂蒄的二维导电金属有机框架材料,简称M-TAC MOF,由式VI所示:
一种基于三氮杂蒄的二维导电金属有机框架材料的制备方法,包括如下步骤:将2,3,6,7,10,11-六羟基-1,5,9-三氮杂蒄V与二价金属铜离子置于水和N甲基吡咯烷酮(质量浓度1%-20%)混合溶液中,然后加入乙二胺和氨水提供碱性条件,反应,得到基于三氮杂蒄的二维导电金属有机框架材料VI,简称为Cu-TAC MOF。反应式如下:
一种基于三氮杂蒄的二维导电金属有机框架料制备锂离子电池电极的应用,包括如下步骤:
将制备得到的Cu-TAC和科琴黑、羧甲基纤维素钠粘结剂以适当比例混合研磨制成浆料,然后涂覆在铜箔上烘干,剪裁成直径为12mm负极片,以金属锂片为对电极,Celgard2400为隔膜,1MLiPF6的EC(碳酸乙烯酯)﹕DEC(碳酸二乙酯)﹕DMC(碳酸二甲酯)混合液(体积比1:1:1)为电解液,组装得到CR2032型扣式电池。
本发明的优点:
本发明首次将三氮杂蒄的羟基单体用于构筑二维导电金属有机框架材料M-TAC(M=Cu、Ni、Co、Fe等),因为三氮杂蒄的引入,M-TAC MOF(M=Cu、Ni、Co、Fe等)具有良好的导电性和丰富的氧化还原活性位点,用其制备的电池电极材料展现出高的比容量、长的循环稳定性和良好的倍率性能。这项工作为设计具有多个氧化还原位点的新型二维导电金属有机框架材料提供了思路,为开发基于二维导电金属有机框架材料的高性能锂离子电池电极材料开辟了新的前景。
附图说明
图1为式IV所示化合物的核磁共振氢谱图。
图2为式IV所示化合物的核磁共振碳谱图。
图3为式V所示化合物的核磁共振氢谱图。
图4为VI所述Cu-TAC MOF模拟和实测的X射线粉末衍射图(XRD)。
图5为VI所述Cu-TAC MOF的扫描电镜图(SEM)。
图6为VI所述Cu-TAC MOF的透射电镜图(TEM)。
图7为VI所述Cu-TAC MOF的电导率测试图。
图8为VI所述Cu-TAC MOF作为负极活性材料的锂离子电池在300mA g-1电流密度下的循环性能图。
图9为VI所述Cu-TAC MOF作为负极活性材料的锂离子电池在50-1500mA g-1电流密度下的倍率性能测试图。
具体实施方式
下面结合具体实施例对本发明作进一步的说明。
实施例1:
2,3,6,7,10,11-六羟基-1,5,9-三氮杂蒄的制备方法,包括如下步骤:
1)2,3,6,7,10,11-六甲氧基苯并菲I的合成:
将52.8g无水三氯化铁和175mL二氯甲烷加入到500mL单口圆底烧瓶中,在剧烈搅拌下加入0.8mL浓硫酸,然后在恒压滴液漏斗中加入13.8mL 1,2-二甲氧基苯和75mL二氯甲烷,以每秒3滴左右的速度滴入圆底烧瓶中。滴加完毕后将所得混合液在室温下搅拌5小时,然后缓慢加入150mL甲醇猝灭反应,直到反应液从黑色粘稠状变成黄色悬浮液。甲醇完全加入后将反应继续在室温下搅拌半小时,然后过滤,用甲醇洗涤(50mL×3次),然后在120度烘箱中干燥两小时,得到灰白色粉末2,3,6,7,10,11-六甲氧基苯并菲I13.8g(产率83%)。
2)1,5,9-三硝基-2,3,6,7,10,11-六甲氧基苯并菲II的合成:
将13.8g 2,3,6,7,10,11-六甲氧基苯并菲I,70mL乙酸,70mL乙醚和70mL二氯甲烷加入到500mL单口圆底烧瓶中,在剧烈搅拌下逐滴加入21mL发烟硝酸,然后将混合液在55℃下搅拌反应12小时,反应完成后蒸发除去低沸点溶剂,然后将析出的黄色固体倒入水中,过滤,用去离子水反复洗涤,120℃干燥6小时,得到黄色固体粗产物。所得粗产物用石油醚和二氯甲烷作为洗脱剂进行柱层析,真空干燥后得淡黄色粉末1,5,9-三硝基-2,3,6,7,10,11-六甲氧基苯并菲II 5.4g(产率30%)。
3)1,5,9-三氨基-2,3,6,7,10,11-六甲氧基苯并菲III的合成:
将5.4g 1,5,9-三硝基-2,3,6,7,10,11-六甲氧基苯并菲II和2.5g四水合醋酸镍溶解于220mL四氢呋喃和无水甲醇的混合溶液中(体积比4:1),室温搅拌10分钟待其完全溶解,然后分多次将5.6g硼氢化钠粉末加入到上述反应混合物中,立即产生黑色沉淀物,继续室温搅拌24小时。然后缓慢加入110mL水猝灭反应,过滤,溶剂减压蒸发,残渣由乙醚重结晶得到灰色固体1,5,9-三氨基-2,3,6,7,10,11-六甲氧基苯并菲III 4.2g(产率93%)。
4)2,3,6,7,10,11-六甲氧基-1,5,9-三氮杂蒄IV的合成:
将4.2g 1,5,9-三氨基-2,3,6,7,10,11-六甲氧基苯并菲III和5g多聚甲醛溶于50mL DMF溶液中,然后在剧烈搅拌下滴加500μL三氟甲磺酸溶液,将反应加热到100℃反应24小时。反应结束后将反应液逐滴加入到300mL去离子水中,边加边搅拌,然后用1M的NaOH溶液将其pH调至8-9。用150mL二氯甲烷萃取三次,收集有机相然后再用300mL饱和碳酸钠溶液洗涤。减压蒸馏,真空干燥得到粗产物。所得粗产物用二氯甲烷和甲醇作为洗脱剂进行柱层析,真空干燥后得到黄色固体2,3,6,7,10,11-六甲氧基-1,5,9-三氮杂蒄IV 0.48g(产率11%)。
5)2,3,6,7,10,11-六羟基-1,5,9-三氮杂蒄V的合成:
将0.48g 2,3,6,7,10,11-六甲氧基-1,5,9-三氮杂蒄IV和25g吡啶盐酸盐加入到50mL单口烧瓶中,所得混合物经冷冻脱气三次后,惰性氛围(充氩气)下加热至200℃回流4小时;待反应结束后,冷却至室温,然后将水加入混合物中,通过抽吸过滤收集黑色沉淀,用水清洗,真空干燥后得到黑色固体2,3,6,7,10,11-六羟基-1,5,9-三氮杂蒄V 0.36g(产率90%);
反应式如下:
图1为2,3,6,7,10,11-六甲氧基-1,5,9-三氮杂蒄IV的核磁共振氢谱图。
图2为2,3,6,7,10,11-六甲氧基-1,5,9-三氮杂蒄IV的核磁共振碳谱图。
图3为2,3,6,7,10,11-六羟基-1,5,9-三氮杂蒄V的核磁共振氢谱图。
实施例2:
一种基于三氮杂蒄的二维导电金属有机框架材料的制备方法,包括如下步骤:
将10mg 2,3,6,7,10,11-六羟基-1,5,9-三氮杂蒄V(6OH-TAC)和9.4mg三水合硝酸铜置于5ml质量浓度为20%的N甲基吡咯烷酮水溶液中(1mL N甲基吡咯烷酮和4mL去离子水),然后加入质量浓度为1%的乙二胺和氨水提供碱性条件。超声20分钟,在80℃烘箱中反应48小时,待冷却至室温后通过离心收集固体,用水和丙酮各洗涤三次。收集固体,真空干燥24小时,得到黑色基于三氮杂蒄的二维导电金属有机框架材料V(Cu-TAC MOF)12mg(产率98%)。
图4为Cu-TAC MOF模拟和实验测得的XRD图,从图4可知,实验测得的数据与模拟结构数据相吻合。
图5为Cu-TAC MOF的扫描电镜图,从图5可以看出Cu-TAC MOF的形貌为纳米棒。
图6为Cu-TAC MOF的透射电镜图,从图6可以看出明显的晶格条纹,其晶面间距为1.9nm,与模拟的Cu-TAC MOF一维孔通道大小相吻合。
图7为Cu-TAC MOF的电导率测试图,表明Cu-TAC具有良好的导电性。
反应式如下:
所述M为Cu。
用9.7mg四水合醋酸镍、9.7mg毫克四水合醋酸钴或7.8mg四水合氯化亚铁替代本实施例的9.4mg的三水合硝酸铜,用质量浓度1%-20%(如5%、10%或15%)的N甲基吡咯烷酮水溶液,替代本实施例的质量浓度为20%的N甲基吡咯烷酮水溶液水溶液,用质量浓度为0.5%-5%的乙二胺和氨水,替代本实施例的质量浓度为1%的乙二胺和氨水提供的碱性条件,其它同本实施例,可以制备出相应的基于三氮杂蒄的二维导电金属有机框架材料Ni-TAC MOF、Co-TAC MOF或Fe-TAC MOF。
实施例3:
基于三氮杂蒄的二维导电金属有机框架料制备锂离子电池电极的应用,包括如下步骤:
将实施例2制备得到的Cu-TAC和科琴黑、羧甲基纤维素钠粘结剂以质量比7﹕2﹕1混合,加入适量H2O混合搅拌形成均匀浆料。用100-150mm刮刀将浆料涂覆在铜箔上,80℃真空干燥12h,然后剪裁成直径为12mm负极片。以金属锂片为对电极,Celgard2400为隔膜,1MLiPF6的EC(碳酸乙烯酯)﹕DEC(碳酸二乙酯)﹕DMC(碳酸二甲酯)混合液(体积比1:1:1)为电解液,组装得到CR2032型扣式电池。
图8为Cu-TAC作为负极活性材料的锂离子电池在300mAg-1电流密度下的循环性能图,如图8所示,在300mAg-1电流密度下,以Cu-TAC作为负极活性材料的锂离子电池放电比容量最高可达710mAh g-1,并且在循环250次后依然可以提供600mAh g-1的容量,库伦效率保持接近100%,表明其具有良好的循环稳定性能。
图9为Cu-TAC作为负极活性材料的锂离子电池在50-1500mAg-1电流密度下的倍率性能测试图,如图9所示,当电流密度从1500mAg-1时恢复到50mA g-1时,能量密度能够迅速回到一开始的状态,表明其具有良好的倍率性能。
上述实施例仅为本发明实施方式中的举例说明,而非对本发明所作的其他形式的限制,任何未背离本发明的设计构筑原理和精神实质下所作的简单修改、替换、等同变化与改型都包含在本发明的保护范围之内。需要进一步说明的是,本发明基于三氮杂蒄的二维导电金属有机框架材料,其结构中M为Cu、Ni、Co或Fe,在通过实施例2对本发明技术方案的进一步说明中,仅以Cu对本发明技术方案做了说明,对M作为Ni、Co或Fe的选择实例,与本实施例2采用的技术方案相同,并具有相同的技术效果。
Claims (5)
1.2,3,6,7,10,11-六羟基-1,5,9-三氮杂蒄,其结构如式V所示,简称:6OH-TAC
2.权利要求1所述的2,3,6,7,10,11-六羟基-1,5,9-三氮杂蒄的制备方法,其特征是包括如下步骤:
1)2,3,6,7,10,11-六甲氧基苯并菲I的合成:
将1.2-二甲氧基苯,无水三氯化铁和浓硫酸加入到二氯甲烷溶液中,然后通过缩合反应得到2,3,6,7,10,11-六甲氧基苯并菲I;
2)1,5,9-三硝基-2,3,6,7,10,11-六甲氧基苯并菲II的合成:
将2,3,6,7,10,11-六甲氧基苯并菲I和发烟硝酸在乙酸,乙醚和二氯甲烷混合溶剂中反应得到1,5,9-三硝基-2,3,6,7,10,11-六甲氧基苯并菲II;
3)1,5,9-三氨基-2,3,6,7,10,11-六甲氧基苯并菲III的合成:
将1,5,9-三硝基-2,3,6,7,10,11-六甲氧基苯并菲II和四水合醋酸镍溶解于四氢呋喃和无水甲醇的混合溶液中,加入硼氢化钠还原得到1,5,9-三氨基-2,3,6,7,10,11-六甲氧基苯并菲III;
4)2,3,6,7,10,11-六甲氧基-1,5,9-三氮杂蒄IV的合成:
将1,5,9-三氨基-2,3,6,7,10,11-六甲氧基苯并菲III和多聚甲醛在含有1%三氟甲磺酸的DMF溶液中反应,得到2,3,6,7,10,11-六甲氧基-1,5,9-三氮杂蒄IV;
5)2,3,6,7,10,11-六羟基-1,5,9-三氮杂蒄V的合成:
将2,3,6,7,10,11-六甲氧基-1,5,9-三氮杂蒄IV在吡啶盐酸盐中反应,得到2,3,6,7,10,11-六羟基-1,5,9-三氮杂蒄V;
反应式如下:
3.一种基于三氮杂蒄的二维导电金属有机框架材料,简称Cu-TAC MOF,结构如式VI所示:
4.权利要求3所述的基于三氮杂蒄的二维导电金属有机框架材料的制备方法,其特征是包括如下步骤:将2,3,6,7,10,11-六羟基-1,5,9-三氮杂蒄V与二价金属铜离子置于质量浓度1%-20%的水和N甲基吡咯烷酮混合溶液中,然后加入乙二胺和氨水提供碱性条件,反应,得到基于三氮杂蒄的二维导电金属有机框架材料,简称为Cu-TAC MOF,反应式如下:
5.权利要求3所述的基于三氮杂蒄的二维导电金属有机框架料在制备锂离子电池电极方面的应用,其特征是包括如下步骤:
将制备得到的Cu-TAC和科琴黑、羧甲基纤维素钠粘结剂以适当比例混合研磨制成浆料,然后涂覆在铜箔上烘干,剪裁成直径为12mm的负极片,以金属锂片为对电极,Celgard2400为隔膜,1MLiPF6的碳酸乙烯酯EC﹕碳酸二乙酯DEC﹕碳酸二甲酯DMC体积比1:1:1的混合液为电解液,组装得到CR2032型扣式电池。
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