CN113991098A - 一种α-Fe2O3树枝状单晶材料及其锂电池电极制备方法 - Google Patents
一种α-Fe2O3树枝状单晶材料及其锂电池电极制备方法 Download PDFInfo
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Abstract
一种α‑Fe2O3树枝状单晶材料及其锂电池电极制备方法;将一定量K3[Fe(CN)6]溶解在去离子水中,在常温下搅拌至澄清溶液后,转移水热釜中,在180~200℃下水热处理6~12h;将所得产物用去离子水和无水乙醇各洗涤三次,后放入110℃烘箱干燥12h得到α‑Fe2O3树枝状单晶材料;将所制备的α‑Fe2O3树枝状单晶、乙炔黑、CMC按一定质量比称取,加入适量去离子水搅拌10h;将搅拌好的电极浆料均匀粘附在泡沫镍上后,在80℃烘箱干燥12h,即得到粘有活性物质的泡沫镍电极。采用单一原料通过简单的水热法合成三维的α‑Fe2O3树枝状单晶材料,并将其作为负极材料引入锂离子电池。
Description
技术领域
本发明涉及锂电池应用领域,特别涉及一种α-Fe2O3树枝状单晶材料及其锂电池电极制备方法。
背景技术
随着现代经济的快速发展,石油、煤炭和天然气等化石原料被过度消耗,环境污染加重及全球气候变暖加剧,已广泛开发风能、太阳能和地热能等新能源系统。但这些可再生能源存在能量不稳定等问题,迫切需要寻求高容量、低成本及环境友好的能源存储系统。锂离子电池(LIBs)作为分散式独立储能系统具有电极电势极低、能量密度大、倍率电容高、低成本寿命长等优点。锂离子电池自1991年商业化以来,商业电池负极材料主要由石墨组成,虽然石墨负极制造工艺成熟、价格低廉,但理论容量仅为372mAh/g,已经无法满足现代高性能储能设备的需求,急需开发高性能的电极材料。氧化铁(Fe2O3)因其储量丰富、价格低廉、理论容量高(1007mAh/g)无毒等优点而受到广泛关注。然而,Fe2O3材料存在本身导电性能差、体积膨胀引起的循环性能不稳定和倍率性能低等问题。
众多研究显示,改变材料的微观结构、扩大比表面积和形成多孔结构能够有效缓解Fe2O3材料体积膨胀。以此为依据,研究者们合成了许多不同结构的Fe2O3材料,如:0维(粒子)、1维(棒、线、管)、2维(薄膜、片)、3维(花、树枝晶、球)等结构扩大比表面积缓解Fe2O3材料体积膨胀引起的循环性能不稳定和倍率性能低等问题。Sun等利用菠菜汁的生物分子作为生物模板和碳源,合成碳包覆的多孔Fe2O3纳米棒,在100mA/g的电流密度下经过100次循环比容量保持在581mAh/g。Xiang等以三氯化铁为原料合成直径为90nm,长度约300-400nm的Fe2O3纳米管,可有效提高电池的循环性能。Min等通过混合溶剂热法制备Cu掺杂的Fe2O3微球,在100Am/g的电流密度下经过120次循环比容量由初始的1287mAh/g先降低后增加稳定在665mAh/g。Zhao等通过原位静电纺丝和碳化法合成Fe2O3/rGO/CNFs纳米纤维,初始容量接近1400mAh/g,在100mA/g的电流密度下经过150次循环后比容量为811mAh/g。由此可见,调整材料微观结构与扩大比表面积能有效地改善电极体积膨胀和循环稳定性,但是还存在导电性差、过程繁琐、可控性差、成本高等问题。
为了进一步解决以上问题,提高Fe2O3电极的电化学性能,本发明通过简单水热法合成α-Fe2O3树枝状单晶材料。与其他方法相比,水热过程可以促进结晶产物形成,不需要退火或煅烧等后续处理;单晶材料相对于由多个小晶体团聚集合组成的多晶材料具有更大的优势,例如:结构完整性、高传导率性、高温稳定性及材料安全性等;三维树枝状及多孔结构可以为Li+存储提供更多的嵌锂空间和活性位点,同时缓解充放电过程中体积变化导致的结构崩塌,从而提高其在锂离子电池中的比容量和循环稳定性。
发明内容
为解决上述现有技术存在的问题,本发明的目的在于提供一种α-Fe2O3树枝状单晶材料及其锂电池电极制备方法;
为达到上述目的,本发明的技术方案为:
一种α-Fe2O3树枝状单晶电极材料,将一定量K3[Fe(CN)6]溶解在去离子水中,在常温下搅拌至澄清溶液后,转移水热釜中,在180~200℃下水热处理6~12h;将所得产物用去离子水和无水乙醇各洗涤三次,后放入110℃烘箱干燥12h得到α-Fe2O3树枝状单晶材料。
进一步的,所述K3[Fe(CN)6]与去离子水的质量体积比具体为0.326:65g/ml。
进一步的,转移水热釜中,在180℃下水热处理12h。
进一步的,转移水热釜中,在190℃下水热处理10h。
进一步的,转移水热釜中,在200℃下水热处理6h。
由上述α-Fe2O3树枝状单晶电极材料制备得到的α-Fe2O3树枝状单晶电极,将所制备的α-Fe2O3树枝状单晶材料、乙炔黑、CMC按一定质量比称取,加入适量去离子水搅拌10h;将搅拌好的电极浆料均匀粘附在泡沫镍上后,在80℃烘箱干燥12h,即得到。
进一步的,所述α-Fe2O3树枝状单晶、乙炔黑、CMC的质量比为8:1:1。
负极上述α-Fe2O3树枝状单晶电极的锂离子电池、锂硫电池。
根据上述的电极制备的锂离子半电池,所述半电池具体为:将上述电极在充满氩气的手套箱内组装电池,将粘有活性物质的泡沫镍电极作为锂离子电池正极,锂片作为电池负极,Gelgard2400为隔膜,滴加适量电解液,组装CR2032型扣式电池。
相对于现有技术,本发明的有益效果为:
一种α-Fe2O3树枝状单晶材料及其锂电池电极制备方法;采用单一原料进行简单的水热合成α-Fe2O3树枝状单晶,并将其作为负极材料引入到锂离子中。对电极材料表面微观形貌和电化学性能分析表明,α-Fe2O3树枝晶具有单晶体结构增加Fe2O3材料的导电性能,大比表面积和表面无规则孔洞可以为Li+存储提供更多的嵌锂空间和活性位点,同时缓解充放电的过程中体积变化的影响,进而提高负极材料的电化学性能,因此α-Fe2O3树枝状单晶电极材料的电化学性能优于多晶α-Fe2O3材料。所制备的α-Fe2O3树枝状单晶对比多晶Fe2O3表现出较好的电化学性能,其首圈放电容量为1497.4mAh/g,经过50次循环后,放电容量保持在866.5mAh/g远超多晶Fe2O3的361.5mAh/g。优异的电化学性能主要归功于单晶的高电导电性、三维树枝状结构大的表面积及枝晶叶片无规则孔洞,为负极材料提供更多的活性位点,同时有效缓解充放电过程中体积膨胀。
附图说明
图1试验例1铁源分别为K3[Fe(CN)6]和FeCl3.6H2O水热处理后样品的XRD对比图谱;
图2为试验例1不同放大倍率下铁源为K3[Fe(CN)6]所制备的α-Fe2O3树枝状单晶的SEM图;其中图2(a)为低倍率下α-Fe2O3树枝状单晶SEM图像;图2(b)为高倍率SEM图像;
图3试验例1α-Fe2O3树枝状单晶的TEM图像。其中图3(a)为低倍率下α-Fe2O3树枝状单晶TEM图像;图3(b)为α-Fe2O3树枝状单晶的单一树枝TEM图像;图3(c)为α-Fe2O3树枝状单晶叶片边缘的高倍率TEM图像;图3(d)为高倍率下α-Fe2O3树枝状单晶叶片对应的SAED衍射花样;
图4试验例1(a)为α-Fe2O3树枝状单晶电极的循环伏安(CV)曲线图;图4(b)为多晶α-Fe2O3电极的CV曲线图;
图5试验例1(a)为α-Fe2O3树枝状单晶电极充放电曲线图;图5(b)多晶α-Fe2O3电极的充放电曲线图;
图6试验例1为α-Fe2O3树枝状单晶电极和多晶α-Fe2O3电极的锂离子半电池的循环性能图;
图7试验例1α-Fe2O3树枝状单晶电极和多晶α-Fe2O3电极的倍率性能图;
图8试验例1α-Fe2O3树枝状单晶电极和多晶α-Fe2O3电极的阻抗测试曲线图。
图9试验例2铁源为K3[Fe(CN)6],水热温度为180℃,水热处理为12h条件下所制备的α-Fe2O3树枝状单晶的低倍SEM图
图10试验例2铁源为K3[Fe(CN)6],水热温度为180℃,水热处理为12h条件下所制备的α-Fe2O3树枝状单晶的高倍SEM图
具体实施方式
下面结合附图和具体实施方式对本发明技术方案做进一步详细描述:
如图1-10所示,
试验例1:
实验材料
六氰合铁(Ⅲ)酸钾(K3[Fe(CN)6])(国药集团化学试剂有限公司,分析纯),六水合氯化铁(FeCl3.6H2O)(国药集团化学试剂有限公司,分析纯),磷酸二氢铵(NH4H2PO4)(国药集团化学试剂有限公司,分析纯),无水硫酸钠(Na2SO4)(国药集团化学试剂有限公司,分析纯),无水乙醇(天津玉福泰化学试剂有限公司,分析纯),去离子水(实验室自制),电解液(六氟磷酸锂(LiPF6)/醋酸乙烯酯(EC)和碳酸乙二酯(DEC)和碳酸二甲酯(DMC)(V LiPF6/EC:VDEC:V DMC)=1:1:1)(赛博电化学材料网)),乙炔黑(深圳科晶),CMC(深圳科晶)。所有试剂均未经过进一步处理。
电极材料的制备
α-Fe2O3树枝状单晶的制备
将0.326g K3[Fe(CN)6]溶解在65ml的去离子水中,在常温下搅拌至澄清溶液后,转移水热釜中,在200℃下水热处理6h。将所得产物用去离子水和无水乙醇各洗涤三次,后放入110℃烘箱干燥12h得到α-Fe2O3树枝状单晶材料。
多晶α-Fe2O3的制备
将0.4325g的FeCl3.6H2O、0.0066g的NH4H2PO4和0.0063g的Na2SO4溶解于73mL去离子水中,超声30分钟,后置于磁力搅拌器上搅拌1h,得到橙黄色溶液转移至水热中,并在200℃下水热处理48h,将所得产物用去离子水和无水乙醇各洗涤三次,后放入60℃烘箱干燥12h得到多晶α-Fe2O3材料。
电极制作与电池组装
需要说明的是,因实验室条件限制,下述制作为半电池,实际的电池中,本申请材料作为电池负极;
将上述所制备的α-Fe2O3树枝状单晶电极或多晶α-Fe2O3、乙炔黑、CMC按8:1:1的质量比称取,加入适量去离子水搅拌10h。将搅拌好的电极浆料均匀粘附泡沫镍上后,在80℃烘箱干燥12h,即得到粘有活性物质的泡沫镍电极。在充满氩气的手套箱内组装电池,将粘有活性物质的泡沫镍电极作为锂离子电池正极,锂片作为电池负极,Gelgard2400为隔膜,滴加适量电解液,以CR2032型扣式电池壳组装电池并进行电化学测试。
试验例2:
其他同试验例1,转移水热釜中,在180℃下水热处理12h,得到α-Fe2O3树枝状单晶材料。所得α-Fe2O3树枝状单晶的SEM图如图9-10所示。
试验例3:
其他同试验例1,转移水热釜中,在190℃下水热处理10h,得到α-Fe2O3树枝状单晶材料。
材料表征与性能测试(下述测试以试验例1数据进行)
采用德国Bruker公司的X射线衍射仪(D8Advance)对材料的晶体结构进行分析。采用日本东京JEOL公司的扫描电子显微镜FE-SEM(JSM-6700F)对材料微观形貌和结构进行分析。采用日本电子株式会社的透射电子显微镜TEM(JEM-2010(HR))对材料的形态和微观结构进行分析。采用上海辰华仪器有限公司的CHI电化学分析仪(CHI660E),在电压区间为0.01-3V,扫描速率为0.1mV·s-1进行循环伏安测试(CV)和交流阻抗测试(EIS)。采用武汉蓝电电子有限公司的蓝电测试系统(CT2001A)进行锂离子电池恒流充放和倍率充放电测试,电池测试前须静置12h,充放电压区为0.005-3V。
材料表征
图1显示铁源分别为K3[Fe(CN)6]和FeCl3.6H2O水热处理后样品的XRD对比图谱。由图可以看出两个样品的XRD衍射峰与α-Fe2O3(卡片PDF No.33-0664)的衍射峰吻合,说明这两个样品均为为晶态α-Fe2O3。XRD图中出现了10个主要的衍射峰(24.1°、33.1°、35.6°、40.8°、49.4°、54.0°、57.4°、62.4°、63.9°、71.9°),分别对应(012),(104),(110),(113),(024),(116),(018),(214),(300)和(1010)晶面,这些衍射峰证明所制备的两个样品均为α-Fe2O3。同时可以明显看到铁源为K3[Fe(CN)6]制备的α-Fe2O3的衍射峰的峰强度远远高于铁源为FeCl3.6H2O所制备α-Fe2O3的衍射峰峰强,说明铁源为K3[Fe(CN)6]所制备α-Fe2O3样品的结晶度更好,纯度更高。
图2a为低放大倍率下的全景图可以清楚地看到大量长度为1-15μm树枝状结构。将倍率放大进一步观察(图2b),单个α-Fe2O3树枝状结构由中央主枝干、次级枝干和三级叶片组成。主次分支结构相同,由小菱形固体α-Fe2O3链接而成。次级分支之间彼此平行,均匀的生长在主枝干的两侧,且长度几百纳米到几微米不等。三级分支彼此紧密链接,均匀的生长在次级分支两侧。
图3a~c为不同放大倍率下α-Fe2O3树枝状晶体的TEM图像。图3a为低倍率下的α-Fe2O3树枝状晶体TEM图像,可以看到存在长度为1-15μm树枝晶结构,与SEM图像相对应。图3b为α-Fe2O3树枝状晶体的单一树枝TEM图像,可以清晰看到中央主枝干由多节小菱形构建块组成。图3c为α-Fe2O3树枝状晶体叶片边缘的高倍率TEM图像,可以看出次级枝干的颜色明显深于三级叶片,叶片边缘曲线呈平滑且叶片上存在大量不规则的孔洞。作为锂离子电池负极材料,树枝叶片结构可提供大的比较面积,叶片表面大量孔洞为锂离子的嵌入提供更多的活性位点,能有效缓解电池的体积膨胀问题。其对应的电子衍射图如图(3d),SAED衍射花样表示α-Fe2O3树枝晶在本质上属于单晶体。
电化学性能测试
图4为α-Fe2O3树枝状单晶电极和多晶α-Fe2O3电极的循环伏安(CV)曲线图。图aα-Fe2O3树枝状单晶电极在首圈循环中,在0.52V附近的还原峰是Li+插入Fe2O3中将Fe(Ⅲ)、Fe(Ⅱ)还原成Fe(0)和电解质不可逆分解形成固体电解质(SEI)膜所引起的,在1.6V处宽峰是由于Fe(0)先氧化成Fe(Ⅱ)再进一步氧化成Fe(Ⅲ)。第二个循环中还原峰偏移至0.86V,峰值强度显著降低,表明在第一次循环锂离子插入和脱离过程中发生容量损失和一些不可逆的过程,在1.3V附近的小峰可能是由于Li+插入Fe2O3树枝晶中将Fe(Ⅲ)还原成Fe(Ⅱ)。图b多晶α-Fe2O3的CV曲线与之前报道的结果类似。首圈循环中,在0.47V处有个还原峰,1.5V和2.1V处的氧化峰分别对应的将Fe(0)氧化成Fe(Ⅱ)再进一步氧化成Fe(Ⅲ),第二圈循环中,还原峰由于第一次循环SEI形成消耗电解质发生偏移。
图5a、b分别为α-Fe2O3树枝状单晶电极和多晶α-Fe2O3电极前5个循环的恒流充放电曲线。电极材料在100mA/g电流密度进行充放,α-Fe2O3树枝状单晶电极的首个放电比容量为1497.4mAh/g,多晶Fe2O3的首个放电比容量为1305mAh/g,它们的首次放电比容量相差无几。由图5可以明显看出在α-Fe2O3树枝状单晶电极和多晶α-Fe2O3电极第一个循环后都出现了容量的下降,这主要是因为第一个放电过程中电解质分解和SEI膜的形成。在α-Fe2O3树枝状单晶电极第五个循环的比容量与前几个循环保持稳定,但在多晶α-Fe2O3电极从第二个循环开始的比容量逐渐明显下降。
图6为α-Fe2O3树枝状单晶电极和多晶α-Fe2O3电极的锂离子半电池的循环性能图。α-Fe2O3树枝状单晶电极在100mA/g电流密度下经过50次充放电循环,比容量保持在866.5mAh/g。多晶α-Fe2O3经过50次充放电循环,比容量仅为361.6mAh/g。相比多晶α-Fe2O3电极,α-Fe2O3树枝状单晶电极具有更好的循环稳定性。多晶α-Fe2O3在充放电过程中存在较大的体积膨胀,导致容量急剧衰减,循环性能差。α-Fe2O3树枝状单晶电极具有单晶结构,可提高氧化铁材料的导电性能;大的比表面积、丰富的无规则孔洞等特点,在充放电的过程中,能为脱/嵌锂提供更多的活性位点,同时也能有效地缓解材料体积变化引起的结构崩塌,从而表现出比多晶α-Fe2O3电极更好的循环性能。
为了进一步探究α-Fe2O3树枝状单晶电极和多晶α-Fe2O3电极的锂离子存储性能差异,分别将α-Fe2O3树枝状单晶电极和多晶α-Fe2O3电极进行倍率循环性能测试。如图7所示,测试电池分别在100mA/g、200mA/g、500mA/g、1000mA/g和100mA/g的电流密度下的倍率充放性能。从图可以看出,树枝状Fe2O3单晶电极在1000mA/g的电流密度充放时的平均比容量为862.5mAh/g,在恢复到100mA/g电流密度充放时,比容量可恢复为1123.8mAh/g,后续循环中容量保持稳定,并且存在上升的趋势。而多晶α-Fe2O3电池在1000mA/g的电流密度充放时的平均比容量为424.3mAh/g,在恢复到100mA/g电流密度充放时,比容量仅回到674mAh/g,但后续循环中容量不断下降。这表明树枝状Fe2O3单晶作为锂离子电池负极材料具有更好的倍率循环性能。
为了进一步了解α-Fe2O3树枝状单晶电极良好的导电性能,分别对α-Fe2O3树枝状单晶电极和多晶α-Fe2O3电极进行电化学阻抗(EIS)测试。EIS分为高频半圆弧区域和低频直线区域组成,高频半圆弧区域与电荷转移电阻有关,低频直线区域与Li+的扩散阻抗有关。由图8可以很明显看出α-Fe2O3树枝状单晶电极在高频区域的半圆直径小于多晶态Fe2O3电极,说明α-Fe2O3树枝状单晶电极中单晶结构能很好地改善了电极材料的导电性能。
以上所述,仅为本发明的具体实施方式,但本发明的保护范围并不局限于此,任何不经过创造性劳动想到的变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应该以权利要求书所限定的保护范围为准。
Claims (9)
1.一种α-Fe2O3树枝状单晶电极材料,其特征在于:将一定量K3[Fe(CN)6]溶解在去离子水中,在常温下搅拌至澄清溶液后,转移水热釜中,在180~200℃下水热处理6~12h;将所得产物用去离子水和无水乙醇各洗涤三次,后放入110℃烘箱干燥12h得到α-Fe2O3树枝状单晶材料。
2.根据权利要求1所述的α-Fe2O3树枝状单晶电极材料,其特征在于:所述K3[Fe(CN)6]与去离子水的质量体积比具体为0.326:65g/ml。
3.根据权利要求2所述的α-Fe2O3树枝状单晶电极材料,其特征在于:转移水热釜中,在180℃下水热处理12h。
4.根据权利要求2所述的α-Fe2O3树枝状单晶电极材料,其特征在于:转移水热釜中,在190℃下水热处理10h。
5.根据权利要求2所述的α-Fe2O3树枝状单晶电极材料,其特征在于:转移水热釜中,在200℃下水热处理6h。
6.由权利要求3-5任一所述α-Fe2O3树枝状单晶电极材料制备得到的α-Fe2O3树枝状单晶电极,其特征在于:将所制备的α-Fe2O3树枝状单晶材料、乙炔黑、CMC按一定质量比称取,加入适量去离子水搅10h;将搅拌好的电极浆料均匀粘附在泡沫镍上后,在80℃烘箱干燥12h,即得到。
7.根据权利要求6所述的电极,其特征在于:所述α-Fe2O3树枝状单晶、乙炔黑、CMC的质量比为8:1:1。
8.负极采用权利要求7所述α-Fe2O3树枝状单晶电极的锂离子电池、锂硫电池。
9.根据权利要求7所述的电极制备的锂离子半电池,其特征在于:所述半电池具体为:将上述电极在充满氩气的手套箱内组装电池,将粘有活性物质的泡沫镍电极作为锂离子电池正极,锂片作为电池负极,Gelgard2400为隔膜,滴加适量电解液,组装CR2032型扣式电池。
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