CN111554891B - 一种制备三维介孔生物碳制锂硫电池正极材料的方法 - Google Patents
一种制备三维介孔生物碳制锂硫电池正极材料的方法 Download PDFInfo
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Abstract
本发明公开了一种制备三维介孔生物碳制锂硫电池正极材料的方法,首先,将木醋杆菌移入配制好的生长液中,培养以获得BC产物,将其后续处理得到BC气凝胶;然后,把BC气凝胶和CoCl2·6H2O、Na2S2O3·5H2O与三聚氰胺水热合成,获得一系列不同含N比的CoS2/N‑BC;最终,将CoS2/N‑BC碳化后与一定质量比的硫在充满N2的管式炉中进行高温熔融载硫,得到由生物碳构成的三维介孔S@CoS2/N‑CNFs锂硫电池正极材料。本发明中BC不仅具有高比表面积、高孔隙率,而且其纤维表面富含‑OH官能团,有助于将CoS2和N原子均匀地负载至BC。N掺杂和CoS2纳米颗粒均提供了硫亲核位点,通过化学吸附多硫化锂(LiPSs)抑制电化学过程中的穿梭效应,增加电极材料的循环寿命。
Description
技术领域
本发明涉及一种锂硫电池正极材料的制备方法,尤其涉及一种三维介孔生物碳制锂硫电池正极材料的制备。
背景技术
可充电锂硫电池由于其低成本和高能量密度而成为储能应用的有前途的选择。然而,由于多硫化物溶解/穿梭引起的快速容量衰减以及由于活性材料的不良电导率导致的低比容量,硫阴极的电化学性能被大大损害。为解决这些问题,人们致力于优化各种主体材料的结构设计,特别是纳米碳材料。然而,由于非化学亲和性以至于不能在长期循环中有效锚定多硫化物。为了提高对中间多硫化物的锚定,无机极性材料(尤其是金属硫化物)由于其优异化学吸附作用,引起了极大的关注。其中,CoS2具有良好的热稳定性,电子导电性较好,其电阻率为0.002Ω·cm,且具有独特的多孔结构,较强的负载能力,是一种综合性能优越的LSB正极材料。但是,在充放电过程中,CoS2通常无法提供大的孔体积来存储硫物质,且具有明显的体积膨胀。
发明内容
针对上述现有技术,本发明提出一种制备三维介孔生物碳制锂硫电池正极材料的方法,采用自制的碳纳米纤维,用水热合成法得到S@CoS2/N-CNFs正极材料,以改善CoS2的电化学性能。本发明制备方法工艺简单、成本低廉,提供了一种具有优良电化学性能的锂硫电池正极材料。
为了解决上述技术问题,本发明提出的一种制备三维介孔生物碳制锂硫电池正极材料的方法,通过简便的水热方法,将金属硫化物与绿色环保的三维介孔氮掺杂细菌纤维素(BC)材料结合,不仅可以提高导电性,为存储硫和限制体质膨胀提供了所需要的空间,而且BC表面的-OH,可与硫和多硫化锂成键来有效吸附多硫化锂,提高电化学稳定性。目前,针对硫@二硫化钴/氮掺碳纳米管(S@CoS2/N-CNFs)的锂硫电池正极材料的制备未见报道。
本发明一种制备三维介孔生物碳制锂硫电池正极材料的方法,步骤如下:
步骤一、制备细菌纤维素气凝胶:将葡萄糖、酵母粉、蛋白胨和磷酸氢二钠按质量比为10:3:4:4依次加入到盛有超纯水的容器中,搅拌溶液至澄清后滴加冰醋酸至溶液的pH=4-5,得到细菌生长液;将盛有细菌生长液的容器放进高温灭菌箱中灭菌30分钟,空冷至室温后移入木醋杆菌的菌种,放入30℃的恒温箱中培养7天,得到淡黄色的细菌纤维素液凝胶;将淡黄色的细菌纤维素液凝胶在80℃的去离子水中浸泡5小时后,移入0.5摩尔/升的NaOH溶液中纯化至颜色变为乳白色;然后,将纯化后的细菌纤维素液凝胶用去离子水煮沸至pH=7,在叔丁醇中浸泡7天,置换出其中的水分子,最后将该细菌纤维素薄膜冷冻干燥,得到细菌纤维素气凝胶。
步骤二:制备由生物碳构成的CoS2/N-CNFs:将质量比为1:2的CoCl2·6H2O:Na2S2O3·5H2O和适量的三聚氰胺溶解在含有步骤一制备的细菌纤维素气凝胶的去离子水中,在130℃下进行水热合成12小时,得到氮掺杂量质量百分比为20%-60%的CoS2/N-BC水热产物;将上述水热产物用去离子水洗涤数次,并冷冻干燥3天;将干燥好的产物在400℃的氮气气氛下煅烧2小时,得到由生物碳构成的具有精细结构的CoS2/N-CNFs;其中,适量的三聚氰胺是根据不同氮掺杂量百分比来计算得出。
步骤三:制备高硫载量的S@CoS2/N-CNFs正极材料:将步骤二制得的CoS2/N-CNFs与硫按质量比为1:3混合,研磨为粉末后放入石英舟;将石英舟的粉末在155℃的氮气氛围下的管式炉中烧结6小时,得到三维介孔生物碳制锂硫电池正极材料,记为S@CoS2/N-CNFs。
与现有技术相比,本发明的有益效果是:
利用本发明方法所制备的电极材料S@CoS2/N-CNFs原料绿色环保,工艺简单,极大地避免了对生态系统的危害。本发明中BC具有超精细网络结构、超高比表面积和孔隙率、较小孔径。最重要的是,其纤维表面富含的-OH官能团,有助于将CoS2和N原子均匀地负载至BC;其具有精细网络结构的细菌纤维素作为模板,不仅可以提高导电性,而且为存储硫和限制体质膨胀提供了所需要的空间。而N掺杂和CoS2纳米颗粒协同作用,都提供了硫亲核位点,可以通过化学吸附LiPSs来抑制电化学过程中的穿梭效应,增加电极材料的循环寿命。故本发明制得的正极材料S@CoS2/N-CNFs具有较好的电化学优势。
附图说明
图1为实施例1中所制备CoS2/20%N-CNFs材料的X-射线衍射图谱;
图2是实施例1中CoS2/20%N-CNFs材料的扫描电镜形貌图;
图3为实施例1中S@CoS2/N-CNFs(20%)材料的倍率性能图;
图4为实施例2中所制备CoS2/40%N-CNFs材料的X-射线衍射图谱;
图5为实施例2中CoS2/40%N-CNFs材料的扫描电镜形貌图;
图6为实施例2中S@CoS2/N-CNFs(40%)材料的倍率性能图;
图7为实施例3中所制备CoS2/60%N-CNFs材料的X-射线衍射图谱;
图8为实施例3中CoS2/60%N-CNFs材料的扫描电镜形貌图;
图9为实施例3中S@CoS2/N-CNFs(60%)材料的倍率性能图。
具体实施方式
下面结合附图及具体实施例对本发明做进一步的说明,但下述实施例绝非对本发明有任何限制。
实施例1:一种制备三维介孔生物碳制锂硫电池正极材料的方法,具体如下步骤:
步骤一:将25克葡萄糖,7.5克酵母粉,10克蛋白胨,10克磷酸氢二钠依次加入到盛有超纯水的大烧杯中,搅拌溶液至澄清后滴加冰醋酸至pH=4-5,得到细菌生长液;
步骤二:将细菌生长液倒入锥形瓶中,放进155℃的高温灭菌箱中灭菌30分钟,将灭菌后的生长液空冷至室温后,移入木醋杆菌的菌种,在30℃的培养箱中培养7天,使其生成淡黄色的BC液凝胶;
步骤三:将淡黄色的BC液凝胶在80℃的去离子水中浸泡5小时,然后在0.5摩尔/升NaOH溶液中纯化至颜色变为乳白色。然后将BC液凝胶用去离子水煮沸至pH=7,在叔丁醇中浸泡7天,置换出其中的水分子。最后将BC液凝胶冷冻干燥,得到BC气凝胶;
步骤四:将0.2克CoCl2·6H2O、0.4克Na2S2O3·5H2O和0.025克三聚氰胺溶解在30毫升含有0.1克细菌纤维素气凝胶的去离子水中,并在130℃下进行水热合成12小时,得到质量百分比为50%CoS2下的氮掺杂量为质量百分比为20%水热产物,记为CoS2/20%N-BC;
步骤五:将水热产物用去离子水洗涤数次,并冷冻干燥72小时。
步骤六:将干燥好的产物在400℃下的氮气气氛下煅烧2小时,得到由生物碳构成的具有精细结构的CoS2/20%N-CNFs,图1,2分别为CoS2/20%N-CNFs的X-射线衍射图谱和扫描电镜形貌图;
步骤七:将CoS2/20%N-CNFs与硫单质按1:3的质量比研磨后,置于155℃的氮气氛围下的管式炉中烧结6小时,从而得到锂硫电池的正极材料S@CoS2/N-CNFs(20%)。
以本实施例1制得S@CoS2/N-CNFs(20%)作为活性物质,与Super P和聚(偏二氟乙烯)(PVDF)粘合剂按质量比为80:10:10混合分散在N-甲基吡咯烷酮(NMP)中,通过磁力搅拌16小时形成浆料。将浆料涂覆在铝箔上,在60℃下干燥6小时并将箔冲压成直径为12.0mm的正极片备用。在高纯氩气气氛的手套箱(相对湿度<2%)中进行装配。锂箔用作对电极,Celgard 2400聚丙烯膜用作隔板。电解液是1.0摩尔/升双(三氟甲磺酰基)酰亚胺锂(LiTFSI)溶解在1,3-二氧戊环(DOL)和DME(体积比=1/1)的混合溶剂中,其中1质量%的LiNO3作为添加剂。组装电池所用的上、下盖和垫片都要事先用酒精清洗干净后进行干燥。为除去所有东西表面吸附的空气和水分,装配电池之前,将所有东西置于手套箱中4小时以上。
电池的具体装配过程为:在相对湿度<2%的手套箱中将负极壳摆正,依次放入弹片、垫片、锂片,加入适量的电解液后放置隔膜再滴加电解液,然后用镊子把正极材料圆片放在中央位置,最后放入正极壳压紧,组装成模拟电池。将装好的模拟电池移出手套箱,在室温下放置24小时以达到平衡温度再进行电化学测试,图3为S@CoS2/N-CNFs(20%)做锂硫电池正极材料的倍率性能图。
图1表明实施例1中20%的N掺杂并未影响CoS2/N-CNFs的生成,图2为实施例1制得的CoS2/20%N-CNFs在100K和50K下放大的扫描电镜形貌图,从中可以看出,该电极材料成功的合成了直径为30-75nm的3D网络结构的碳纤维,可用于缓解充放电过程中多硫化锂和活性物质的体积膨胀。图3为实施例1中载硫后S@CoS2/N-CNFs(20%)材料在不同电流密度下的倍率曲线图,在0.1C(1C=1672mAg-1)电流密度下,材料的首次放电容量为833.6mAhg-1,在0.1C、0.2C、0.5C和1C的电流密度下,材料分别循环10圈放电比容量基本维持在616.9mAhg-1、387.4mAhg-1、197.9mAhg-1和81.0mAhg-1;当电流密度返回到0.1C时,放电比容量维持到602.5mAhg-1。
实施例2:制备三维介孔生物碳制S@CoS2/N-CNFs(40%)锂硫电池正极材料的方法,实施例2中,除了步骤四与实施例1中的步骤不同,其他步骤均相同。在步骤四中,将0.2克CoCl2·6H2O、0.4克Na2S2O3·5H2O和0.067克三聚氰胺溶解在30mL含有0.1克细菌纤维素气凝胶的去离子水中,并在130℃下进行水热合成12h,得到50%CoS2下的氮掺杂量为40%水热产物,记为CoS2/40%N-BC,从而制备得到锂硫电池的正极材料S@CoS2/N-CNFs(40%),并制备出对应正极材料的纽扣电池。
图4和图5分别为实施例2制得的CoS2/N-CNFs(40%)的X-射线衍射图谱和扫描电镜形貌图,图4表明实施例2中40%的N掺杂并未影响CoS2的生成,从图5中可以看出,该电极材料成功的合成了直径为20-60nm的3D网络结构的多孔细纤维。图6为实施例2中载硫后S@CoS2/N-CNFs(40%)材料在不同电流密度下的倍率曲线图,在0.1C(1C=1672mAg-1)电流密度下,材料的首次放电容量为926.2mAhg-1,在0.1C、0.2C、0.5C和1C的电流密度下,材料分别循环10圈放电比容量基本维持在713.8mAhg-1、560.6mAhg-1、369.0mAhg-1和196.5mAhg-1;当电流密度返回到0.1C,放电比容量维持到643.9mAhg-1。
实施例3:制备三维介孔生物碳制S@CoS2/N-CNFs(60%)锂硫电池正极材料的方法,实施例3中,除了步骤四与实施例1中的步骤不同,其他步骤均相同。在步骤四中,将0.2克CoCl2·6H2O、0.4克Na2S2O3·5H2O和0.15克三聚氰胺溶解在30毫升含有0.1克细菌纤维素气凝胶的去离子水中,并在130℃下进行水热合成12小时,得到50%CoS2下的氮掺杂量为60%水热产物,记为CoS2/60%N-BC,从而制备得到锂硫电池的正极材料S@CoS2/N-CNFs(60%),并制备出对应正极材料的纽扣电池。
图7和图8分别为实施例3制得的CoS2/N-CNFs(60%)的X-射线衍射图谱和扫描电镜形貌图,图7表明实施例3中60%的N掺杂并未影响CoS2的生成,从图8中可以看出,该电极材料成功的合成了直径为20-70nm的3D网络结构的碳纤维。图9为实施例3中载硫后S@CoS2/N-CNFs(60%)材料在不同电流密度下的倍率曲线图,在0.1C(1C=1672mAg-1)电流密度下,材料的首次放电容量为765.8mAhg-1,在0.1C、0.2C、0.5C和1C的电流密度下,材料分别循环10圈放电比容量基本维持在498.5mAhg-1、332.9mAhg-1、269.1mAhg-1和222.0mAhg-1;当电流密度返回到0.1C时,放电比容量返回到342.3mAhg-1。
本发明采用生物合成法制备了BC(碳纤维素的前体),原料低廉,工艺简便,绿色环保,可用于大批量生产。将BC氮化和极性无机材料优点相结合,可以物理-化学协同作用吸附LiPSs。适量的氮掺杂可以提高碳材料的电化学活性,结合电导率可观的CoS2为活性材料,最终通过水热合成具有良好电化学性能的S@CoS2/N-CNFs三维碳纳米纤维。从图2、图4和图8中可以看出,随着氮掺杂量的增加,碳纳米纤维结构的直径先变小再变大,当氮掺杂量为40%时,三维介孔碳纳米纤维的孔隙度最大,可最大程度地抑制多硫化锂和活性物质的体积膨胀。与之相对应,其倍率性能最佳,随电流密度的增大容量衰减低。当电流密度返回0.1C时,容量为643.9mAhg-1。而N掺杂量为20%和60%时,当电流密度返回0.1C,容量分别为602.5mAhg-1和342.3mAhg-1。
本发明方法所制备S@CoS2/N-CNFs电极材料具有精细的三维网络结构,其接种细菌制备的绿色环保的BC模板,不仅可充当稳固的碳支架,使硫化物和异质原子在水热过程中均匀地负载到材料中,而且CNFs网络结构可通过空间限制来容纳高硫负荷并缓冲体积变化;N掺杂和CoS2纳米粒子都提供了硫亲核位点以化学限制多硫化物,并且还具有电催化作用。利用结构设计和成分改性,实现对可溶性多硫化锂的物理化学协同吸附,改善了锂硫电池正极的电化学性能。
尽管上面结合附图对本发明进行了描述,但是本发明并不局限于上述的具体实施方式,上述的具体实施方式仅仅是示意性的,而不是限制性的,本领域的普通技术人员在本发明的启示下,在不脱离本发明宗旨的情况下,还可以做出很多变形,这些均属于本发明的保护之内。
Claims (1)
1.一种制备三维介孔生物碳制锂硫电池正极材料的方法,其特征在于,包括以下步骤:
步骤一、制备细菌纤维素气凝胶:
将葡萄糖、酵母粉、蛋白胨和磷酸氢二钠按质量比为10:3:4:4依次加入到盛有超纯水的容器中,搅拌溶液至澄清后滴加冰醋酸至溶液的pH=4-5,得到细菌生长液;
将盛有细菌生长液的容器放进高温灭菌箱中灭菌30分钟,空冷至室温后移入木醋杆菌的菌种,放入30℃的恒温箱中培养7天,得到淡黄色的细菌纤维素液凝胶;
将淡黄色的细菌纤维素液凝胶在80℃的去离子水中浸泡5小时后,移入0.5摩尔/升的NaOH溶液中纯化至颜色变为乳白色;然后,将纯化后的细菌纤维素液凝胶用去离子水煮沸至pH=7,在叔丁醇中浸泡7天,置换出其中的水分子,最后将得到的细菌纤维素薄膜冷冻干燥,得到细菌纤维素气凝胶;
步骤二:制备由生物碳构成的CoS2/N-CNFs:
将质量比为1:2的CoCl2·6H2O:Na2S2O3·5H2O和适量的三聚氰胺溶解在含有步骤一制备的细菌纤维素气凝胶的去离子水中,在130℃下进行水热合成12小时,得到氮掺杂量质量百分比为20%-60%的CoS2/N-BC水热产物,其中,氮掺杂量质量百分比20%-60%是由三聚氰胺的质量占三聚氰胺与细菌纤维素气凝胶总质量的质量百分比计算得到的;
将上述水热产物用去离子水洗涤数次,并冷冻干燥3天;
将冷冻干燥好的产物在400℃的氮气气氛下煅烧2小时,得到由生物碳构成的具有精细结构的CoS2/N-CNFs;
步骤三:制备高硫载量的S@CoS2/N-CNFs正极材料:
将步骤二制得的CoS2/N-CNFs与硫按质量比为1:3混合,研磨为粉末后放入石英舟;
将石英舟的粉末在155℃的氮气氛围下的管式炉中烧结6小时,得到三维介孔生物碳制锂硫电池正极材料,记为S@CoS2/N-CNFs。
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