CN110034286A - 制备三氧化二铁-铋金属碳纤维复合材料及方法 - Google Patents
制备三氧化二铁-铋金属碳纤维复合材料及方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 22
- -1 di-iron trioxide-bismuth Chemical compound 0.000 title claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 22
- 239000002184 metal Substances 0.000 title claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 19
- 239000000835 fiber Substances 0.000 title claims abstract description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 43
- 150000001621 bismuth Chemical class 0.000 claims abstract description 23
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 23
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 15
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 claims abstract description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 13
- 239000004917 carbon fiber Substances 0.000 claims abstract description 13
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- 239000002105 nanoparticle Substances 0.000 claims abstract description 9
- 229910016874 Fe(NO3) Inorganic materials 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000010935 stainless steel Substances 0.000 claims abstract description 6
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- 229910001416 lithium ion Inorganic materials 0.000 abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 229910052744 lithium Inorganic materials 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 6
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- 239000002134 carbon nanofiber Substances 0.000 abstract description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 11
- 229910001415 sodium ion Inorganic materials 0.000 description 11
- 239000011734 sodium Substances 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 239000007772 electrode material Substances 0.000 description 5
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- BDJYZEWQEALFKK-UHFFFAOYSA-N bismuth;hydrate Chemical compound O.[Bi] BDJYZEWQEALFKK-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
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- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及制备三氧化二铁‑铋金属碳纤维复合材料及方法。将聚丙烯腈加入到二甲基甲酰胺中,再将五水合硝酸铋和九水合硝酸铁加入到二甲基甲酰胺中,室温下搅拌得到含铋盐,铁盐的混合液。然后将含铋盐、铁盐的混合液加入到含聚丙烯腈的混合液中,搅拌后得到含聚丙烯腈、铋盐和铁盐的混合液。将所得混合液抽入到装有不锈钢针头的针筒之中缓慢泵出,通过静电纺丝法和退火处理得到三氧化二铁‑铋金属碳纤维复合材料。该复合材料是将铋和三氧化二铁纳米颗粒封装在碳纤维中形成的网状结构。将其用作锂/钠离子电池负极材料,一维碳纳米纤维在抑制体积膨胀的同时,构架高效的导电网络,使得材料表现出较高的电化学活性和稳定性。
Description
技术领域
本发明属于无机纳米材料合成领域。具体地,涉及制备三氧化二铁-铋金属碳纤维复合材料及方法。
背景技术
化石燃料的过度使用和其燃烧所带来的环境问题,使得人们对清洁能源的开发和利用广泛关注,二次电池因为适用范围广,成本低,转换效率高等特点满足其要求。锂离子电池以其高比能量、放电电压高、高循环寿命、无记忆效应、无污染等特点占据了便携式能源存储市场。但是锂资源不足且分布不均,使其失去用于大尺寸、静态能量存储的价格优势。钠和锂具有相似的物化性质,且钠资源储量丰富、分布均匀,被认为是今后在规模储能领域替代锂离子电池的最佳候选。电池的性能如容量和工作电压等很大程度上由电极材料的性能决定,由于钠离子电池的电化学反应与锂离子电池相似,因此钠离子电池电极材料的选择可参考已经较为成熟的锂离子电池电极材料。近二十年来,关于钠离子电池的正极材料研究已经在性能和机理两方面取得一定成绩,但在负极材料方面尚未取得较为满意的成果,仍待进一步研究。钠原子质量是锂的三倍,离子半径也比锂离子大,且Na+/Na标准电化学电位比Li+/Li高,因而钠离子电池能量密度很难与锂离子电池相媲美,如一些锂离子电池的负极材料作为钠离子电池负极使用时,表现一般甚至不具有活性。石墨就是其中一例,由于石墨碳层间距较小而不能有效嵌脱钠离子。考虑到钠离子电池未来的实际商业应用,寻找、研发有竞争力、高性能、循环稳定的新型电极材料至关重要。合金基材料具有较高的理论容量和多重电子转移能力,因此作为一种有发展前景的负极材料受到了广泛的关注。在众多合金基材料中,铋以其独特的层状晶体结构(沿c轴方向具有较大的层间距在充放电过程中易于离子扩散,成本低廉,无毒环保等优势,在锂/钠离子电池领域非常具有竞争力。从外观和结构上看,铋与石墨十分相似,呈灰白色褶皱片层状,是由六元环组成的晶体结构。Bi与Na反应生成Na3Bi,表现出385mAh g-1的理论容量,且铋工作电压高于钠枝晶形成的电压,可使其成为更安全的负极材料。但在合金化/脱合金化过程中,铋金属材料体积变化达352%,导致了活性材料的严重粉化,阻碍了铋金属作为钠离子电池负极的实际应用。近年来,通过设计新颖的纳米结构或复合导电性优异的碳材料制得的负极材料虽然具有较高容量,但其循环性能较差,容量衰减太快,尤其是在高倍率下的表现还远远不能令人满意。相较于复合石墨烯或组合成片层状材料,制备一维碳纳米结构更具有优势,在抑制体积膨胀的同时,构架高效的导电网络,使得材料表现出较高的电化学活性和稳定性。如Xue等将铋纳米棒封装在氮掺杂碳纳米管里制备出Bi nanorods@N-doped carbon nanotubes复合材料,将其应用在钠离子电池中,其独特的结构可以很好的适应铋金属在循环过程中的体积膨胀,稳定固体电解质相间层,提高电子导电性。三氧化二铁作为负极材料具有理论容量高(1007mAh g-1)、储量丰富、成本低、无毒性等优点,但是在充放电过程中也具有较大的体积膨胀(215%),且电极活性材料颗粒易团聚。因此通过设计合适的结构,制备三氧化二铁-铋金属碳纤维复合材料来同时提高材料的导电性和缓冲体积膨胀,是提高铋基材料作为锂/钠离子电池负极材料循环稳定性的有效措施之一。
发明内容
本发明的目的是采用静电纺丝法,通过调整聚丙烯腈(PAN)和铁/铋金属元素的比例,提供了一种制备三氧化二铁-铋金属碳纤维复合材料的方法。该复合材料是将铋和三氧化二铁纳米颗粒封装在碳纤维中形成的网状结构。将其用作锂/钠离子电池负极材料,一维碳纳米纤维在抑制体积膨胀的同时,构架高效的导电网络,使得材料表现出较高的电化学活性和稳定性。三氧化二铁纳米颗粒的引入有利于实现铋金属的纳米化,同时二者之间的界面提供了丰富的活性位点,并且铋金属和三氧化二铁纳米颗粒储锂/钠同时,均发生电化学体积膨胀,这种膨胀类似钉扎效应可以互相抑制维持电极的稳定,使材料表现出更好的电化学性能。
本发明的技术方案如下:
制备三氧化二铁-铋金属碳纤维复合材料;其复合材料是将铋和三氧化二铁纳米颗粒封装在碳纤维中形成的网状结构;通过调整聚丙烯腈和铁/铋金属元素的比例,使用静电纺丝法和退火处理得到三氧化二铁-铋金属碳纤维复合材料
本发明制备三氧化二铁-铋金属碳纤维复合材料的方法,包括如下步骤:
1).将聚丙烯腈(PAN)加入到二甲基甲酰胺(DMF)中,60-80℃下搅拌2-4h,制得聚丙烯腈均匀分散的混合液;
2).将五水合硝酸铋(Bi(NO3)3·5H2O)和九水合硝酸铁(Fe(NO3)3·9H2O)加入到二甲基甲酰胺(DMF)中,以200-400r/min搅拌20-40min,得到含铋盐,铁盐的混合液;
3).将步骤2)制得的含铋盐,铁盐的混合液加入到步骤1)制得的聚丙烯腈混合液中,搅拌10-30min,得到含聚丙烯腈,铋盐,铁盐的混合液;
4).将步骤3)制得的含聚丙烯腈,铋盐,铁盐的混合液抽入到装有不锈钢针头的针筒之中,经针头泵出并在针头和收集板之间加上9-11kV的高压,进行静电纺丝;如图4所示;
5).静电纺丝过程结束后,将收集板上的产物回收,在Ar气氛下,以2℃min-1升温至280℃保温2h,然后再以5℃min-1升温至700℃保温1h;
6).反应结束后,自然冷却至室温,取出反应物,得到三氧化二铁-铋金属碳纤维复合材料。
所述步骤1)所述步骤1)中聚丙烯腈浓度为133-200g/L。
所述步骤2)聚丙烯腈与五水合硝酸铋的质量比为1:0.61-1:1.82。
所述步骤2)聚丙烯腈与九水合硝酸铁的质量比为1:0.51-1:1.52。
所述步骤4)将针管中混合液经针头以0.2-0.4ml h-1的速度泵出。
所述步骤4)针头和收集板之间的距离为18-20cm。
本发明的效果是可制备出三氧化二铁-铋金属碳纤维复合材料。该复合材料是将铋和三氧化二铁纳米颗粒封装在碳纤维中形成的网状结构,将其用作锂/钠离子电池负极材料。一维碳纳米纤维在抑制体积膨胀的同时,构架高效的导电网络,使得材料表现出较高的电化学活性和稳定性。引入三氧化二铁纳米颗粒有利于实现铋金属的纳米化,同时二者之间的界面提供了丰富的活性位点,并且铋金属和三氧化二铁纳米颗粒储锂/钠同时,均发生电化学体积膨胀,这种膨胀类似钉扎效应可以互相抑制维持电极的稳定,使材料表现出更好的电化学性能。
附图说明
图1是实施例1,2,3所制备三氧化二铁-铋金属碳纤维复合材料的X射线衍射图,说明所制备的产品均由三氧化二铁和铋金属组成。
图2是实施例2所制备三氧化二铁-铋金属碳纤维复合材料的扫描电镜图片,从图中可以看出,产物是由纤维组成的网状结构。
图3是实施例3所制备三氧化二铁-铋金属碳纤维复合材料的透射电镜图片,从图中可以看出,铋金属和三氧化二铁以尺寸很小的纳米颗粒的形式存在于碳纤维中。
图4是静电纺丝装置示意图。静电纺丝装置由注射泵、喷丝头(针头)、高压电源和收集板组成,工作时在针头与收集板之间施加一个高压电场,聚合物溶液在强电场作用下经针头泵出进行喷射纺丝,静电纺丝过程结束后,将收集板上的产物回收。
具体实施方式
实施例1:
1).将0.8g聚丙烯腈(PAN)加入到4ml二甲基甲酰胺(DMF)中,60℃下搅拌2h,制得聚丙烯腈均匀分散的混合液,该混合液中聚丙烯腈浓度为200g/L;
2).将1mmol五水合硝酸铋(Bi(NO3)3·5H2O)和3mmol九水合硝酸铁(Fe(NO3)3·9H2O)加入到6ml二甲基甲酰胺(DMF)中,以200r/min搅拌20min,得到含铋盐,铁盐的混合液;
3).将步骤2)制得的含铋盐,铁盐的混合液加入到步骤1)制得的聚丙烯腈混合液中,搅拌10min,得到含聚丙烯腈,铋盐,铁盐(质量比为1:0.61:1.52)的混合液;
4).将步骤3)制得的含聚丙烯腈,铋盐,铁盐的混合液抽入到装有不锈钢针头的针筒之中,经针头以0.2ml h-1的速度泵出并在针头和收集板之间加上9kV的高压,针头和收集板之间的距离为18cm,进行静电纺丝;
5).静电纺丝过程结束后,将收集板上的产物回收,在Ar气氛下,以2℃min-1升温至280℃保温2h,然后再以5℃min-1升温至700℃保温1h;
6).反应结束后,自然冷却至室温,取出反应物,得到三氧化二铁-铋金属碳纤维复合材料;
如图1所示,说明制备的产物是由三氧化二铁-铋金属组成。用于锂离子电池中,在100mA g-1的电流密度下测试其性能,循环100次之后其比容量可达550mA h g-1以上。在1Ag-1的电流密度下测试其性能,循环1000次之后其比容量可达504mA h g-1以上。
实施例2:
1).将0.8g聚丙烯腈(PAN)加入到5ml二甲基甲酰胺(DMF)中,70℃下搅拌3h,制得聚丙烯腈均匀分散的混合液,该混合液中聚丙烯腈浓度为160g/L;
2).将2mmol五水合硝酸铋(Bi(NO3)3·5H2O)和2mmol九水合硝酸铁(Fe(NO3)3·9H2O)加入到5ml二甲基甲酰胺(DMF)中,以300r/min搅拌30min,得到含铋盐,铁盐的混合液;
3).将步骤2)制得的含铋盐,铁盐的混合液加入到步骤1)制得的聚丙烯腈混合液中,搅拌20min,得到含聚丙烯腈,铋盐,铁盐(质量比为1:1.215:1.015)的混合液;
4).将步骤3)制得的含聚丙烯腈,铋盐,铁盐的混合液抽入到装有不锈钢针头的针筒之中,经针头以0.3ml h-1的速度泵出并在针头和收集板之间加上10kV的高压,针头和收集板之间的距离为19cm,进行静电纺丝;
5).静电纺丝过程结束后,将收集板上的产物回收,在Ar气氛下,以2℃min-1升温至280℃保温2h,然后再以5℃min-1升温至700℃保温1h;
6).反应结束后,自然冷却至室温,取出反应物,得到三氧化二铁-铋金属碳纤维复合材料;
如图2所示,在扫描电镜下可以看到产物是由纤维组成的网状结构。用于钠离子电池中,在100mA g-1的电流密度下测试其性能,循环50次之后其比容量可达331mA h g-1以上。
实施例3:
1).将0.8g聚丙烯腈(PAN)加入到6ml二甲基甲酰胺(DMF)中,80℃下搅拌4h,制得聚丙烯腈均匀分散的混合液,该混合液中聚丙烯腈浓度为133g/L;
2).将3mmol五水合硝酸铋(Bi(NO3)3·5H2O)和1mmol九水合硝酸铁(Fe(NO3)3·9H2O)加入到4ml二甲基甲酰胺(DMF)中,以400r/min搅拌40min,得到含铋盐,铁盐的混合液;
3).将步骤2)制得的含铋盐,铁盐的混合液加入到步骤1)制得的聚丙烯腈混合液中,搅拌30min,得到含聚丙烯腈,铋盐,铁盐(质量比为1:1.82:0.51)的混合液;
4).将步骤3)制得的含聚丙烯腈,铋盐,铁盐的混合液抽入到装有不锈钢针头的针筒之中,经针头以0.4ml h-1的速度泵出并在针头和收集板之间加上11kV的高压,针头和收集板之间的距离为20cm,进行静电纺丝;
5).静电纺丝过程结束后,将收集板上的产物回收,在Ar气氛下,以2℃min-1升温至280℃保温2h,然后再以5℃min-1升温至700℃保温1h;
6).反应结束后,自然冷却至室温,取出反应物,得到三氧化二铁-铋金属碳纤维复合材料;
如图3所示,从透射电镜图中可以看出,铋金属和三氧化二铁以尺寸很小的纳米颗粒的形式存在于碳纤维中。
综上实施例的附图也可以明确看出,本发明所制备的产品为三氧化二铁-铋金属碳纤维复合材料。
Claims (7)
1.制备三氧化二铁-铋金属碳纤维复合材料;其特征是复合材料是将铋和三氧化二铁纳米颗粒封装在碳纤维中形成的网状结构。
2.权利要求1的制备三氧化二铁-铋金属碳纤维复合材料的方法,其特征是包括如下步骤:
1).将聚丙烯腈加入到二甲基甲酰胺中,60-80℃下搅拌2-4h,制得聚丙烯腈均匀分散的混合液;
2).将五水合硝酸铋和九水合硝酸铁加入到二甲基甲酰胺中,以200-400r/min搅拌20-40min,得到含铋盐、铁盐的混合液;
3).将步骤2)制得的含铋盐、铁盐的混合液加入到步骤1)制得的聚丙烯腈混合液中,搅拌10-30min,得到含聚丙烯腈、铋盐和铁盐的混合液;
4).将步骤3)制得的含聚丙烯腈、铋盐和铁盐的混合液抽入到装有不锈钢针头的针筒之中,经针头泵出并在针头和收集板之间加上9-11kV的高压,进行静电纺丝;
5).静电纺丝过程结束后,将收集板上的产物回收,在Ar气氛下,以2℃ min-1升温至280℃保温2h,然后再以5℃ min-1升温至700℃保温1h;
6).反应结束后,自然冷却至室温,取出反应物,得到三氧化二铁-铋金属碳纤维复合材料。
3.如权利要求2所述的方法,其特征是所述步骤1)中聚丙烯腈浓度为133-200g/L。
4.如权利要求2所述的方法,其特征是所述步骤2)聚丙烯腈与五水合硝酸铋的质量比为1:0.61-1:1.82。
5.如权利要求2所述的方法,其特征是所述步骤2)聚丙烯腈与九水合硝酸铁的质量比为1:0.51-1:1.52。
6.如权利要求2所述的方法,其特征是所述步骤4)将针管中混合液经针头以0.2-0.4mlh-1的速度泵出。
7.如权利要求2所述的方法,其特征是所述步骤4)针头和收集板之间的距离为18-20cm。
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