CN110586104A - 一种二氧化钛、氧化铜与钛酸钴复合物纳米纤维及其制备方法 - Google Patents
一种二氧化钛、氧化铜与钛酸钴复合物纳米纤维及其制备方法 Download PDFInfo
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 21
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 8
- LFSBSHDDAGNCTM-UHFFFAOYSA-N cobalt(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Co+2] LFSBSHDDAGNCTM-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 8
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 6
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 6
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- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 16
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 10
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005245 sintering Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- 229940011182 cobalt acetate Drugs 0.000 claims abstract description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 229910019096 CoTiO3 Inorganic materials 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 10
- UZJJFTNGFSFYTP-UHFFFAOYSA-L copper diacetate tetrahydrate Chemical compound O.O.O.O.[Cu++].CC([O-])=O.CC([O-])=O UZJJFTNGFSFYTP-UHFFFAOYSA-L 0.000 claims description 7
- 238000005859 coupling reaction Methods 0.000 claims description 7
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 7
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 2
- 239000003426 co-catalyst Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
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- 239000000243 solution Substances 0.000 description 28
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
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- 239000002245 particle Substances 0.000 description 4
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 description 3
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
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- 241000627951 Osteobrama cotio Species 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
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Abstract
本发明公开了一种二氧化钛、氧化铜与钛酸钴复合物纳米纤维及其制备方法,在本发明中将一定量的醋酸铜、醋酸钴、醋酸和钛酸四丁酯溶于一定体积的N,N‑二甲基甲酰胺和乙醇中,然后加入适量的聚乙烯吡咯烷酮,搅拌,得到前驱体混合物溶液;然后在一定的电压、流率及一定的温度下进行静电纺丝;然后放入马弗炉中进行烧结得到纳米纤维。物理化学性能测试结果显示,该复合物纳米纤维具有催化活性以及作为锂离子电池负极材料,循环性能好,其在能源存储材料领域有广阔的应用前景。在整个制备过程中,操作简单,原料成本低,投资少,适合批量生产。
Description
技术领域
本发明属于材料化学领域,具体涉及到一种二氧化钛(TiO2)、氧化铜(CuO)与钛酸钴(CoTiO3)复合物纳米纤维及其制备方法。
背景技术
随着当今社会的发展,人们对能源存储材料的质量要求越来越高。锂离子电池因其能量密度高成为许多设备首选的能量储存和转化装置,推动着社会朝着更加环保的方向迈进。锂离子电池相对于传统铅酸电池有着不可替代的优点,首先电池质量更轻,更容易携带;其次能量密度高,比容量大,循环使用寿命更长;第三,污染小,在使用过程中,几乎不产生有毒、污染环境的物质。锂离子电池已经成为手机和电脑不可或缺的一部分。锂电池电极材料对电池性能影响很大,尤其是负极材料很大程度上影响着电池的性能,普通的商用锂电池负极大多采用石墨材料,现在已经广泛的应用到通信、交通等领域。目前,锂电池还存在着一些不可避免的问题,如在使用过程中电极材料会产生体积膨胀,破坏电解质界面膜(SEI)造成严重的安全问题;锂电池的容量与人们的要求还存在一定差距。近年来,人们对锂离子电池负极材料研究的热度只增不减,钛基材料因其较小的体积变化和稳定的电化学性能有望成为替代石墨的优良负极材料。Yan-Jing Hao等人通过原位沉淀法利用SnO2与钛基复合而合成的负极材料,虽然在容量上比单一钛基材料略有提升,但循环稳定性能差,循环充放电后容量明显下降(Journal of Alloys and Compounds,2008,462,404-409)。王建涛、王耀等人利用碳硅等经济材料制备Si-O-C骨架的硅基负极材料,突出的优点是其高循环性能,在100周以后平均容量衰减0.12%(物理化学学报,2014,305-310),但由于硅碳结构的导电性能差,复合材料的导电性能还有待提高。不同元素化合物形成复合物是提高材料电化学性能的可选方法。钛基材料具有良好的充放电循环性能,通过与其他化合物的复合有望提高其比容量。另外,钴或铜的化合物纳米材料具有的催化性能,在钯催化的Suzuki碳碳键偶联反应中,钴或铜的化合物纳米材料可作为助催化剂或共催化剂,能够提高偶联反应的产率。
发明内容
本发明所要解决的技术问题是针对现有技术,利用静电纺丝合成技术,提供一种TiO2、CuO与CoTiO3复合物纳米纤维及其制备方法。
本发明解决上述技术问题所采取的技术方案为:一种二氧化钛(TiO2)、氧化铜(CuO)与钛酸钴(CoTiO3)复合物纳米纤维的制备方法,所述制备方法采用以钛酸四丁酯、乙酸钴、乙酸铜为主要原料,加入乙醇、N,N-二甲基甲酰胺(DMF)和乙酸为混合溶剂,加入高分子PVP为粘合剂,在高电压条件下利用静电纺丝技术,制备静电纺丝前驱体,随后在马弗炉中进行煅烧,得到一种TiO2、CuO与CoTiO3复合物纳米纤维,具体包括以下步骤:
(1)将一定量的乙酸铜四水合物(C4H6O4Cu·4H2O)和乙酸钴四水合物(C4H6O4Co·4H2O)溶于一定量的体积比为1:1的N,N-二甲基甲酰胺(DMF)和乙醇的混合溶剂中,搅拌0.5h,形成混合物溶液A;
(2)将适量的钛酸四丁酯(C16H36O4Ti)溶于上述混合物溶液A中,加入适量的冰醋酸,调节pH=1~2,搅拌0.5h,形成混合物溶液B;
(3)将适量的PVP加入到溶液B中,搅拌10h,形成溶液C;
(4)将溶液C在温度为32℃,电压为17~19kV,接收距离15~20cm和0.6~0.8mL h-1的流率条件下,进行静电纺丝;
(5)将得到的静电纺丝产物置于80℃下干燥12h,然后转移到马弗炉中,在750~900℃温度下,烧结4~6h,得所述的一种TiO2、CuO与CoTiO3复合物纳米纤维;
所述参加反应的物质、溶剂为化学纯或分析纯;
所述PVP的名称为K-90型聚乙烯吡咯烷酮;
所述溶液C中,乙酸铜、乙酸钴与钛酸四丁酯的摩尔比为1:1:2;
所述溶液C中,PVP与乙酸铜四水合物量的比为2~3g:1mmol。
本发明所制备的TiO2、CuO与CoTiO3复合物纳米纤维作为锂离子电池负极材料,充放电循环140圈,放电比容量为100mAh g-1以上,库伦效率保持在99%以上。
本发明所制备的的TiO2、CuO与CoTiO3复合物纳米纤维作为碳碳键偶联反应的助催化剂或共催化剂,在醋酸钯催化的Suzuki偶联反应中能够提高反应的产率。
与现有技术相比,本发明采用静电纺丝技术合成的复合物纳米纤维的特点如下:
(1)一维纳米纤维由小颗粒构成,颗粒的直径为100~150nm;
(2)充放电循环过程中体积膨胀效应小;
(3)所制备的纳米纤维作为锂离子电池负极材料,充放电循环使用寿命长,在100mA g-1的电流密度下,充放电循环140圈,库伦效率保持在99%以上;
(4)所制备的复合物纳米纤维作为碳碳键偶联反应的助催化剂或共催化剂,在醋酸钯催化的Suzuki偶联反应中能够提高反应的产率。
附图说明
图1为实施例1制得的TiO2、CuO与CoTiO3复合物纳米纤维的XRD图。
图2为实施例1制得的TiO2、CuO与CoTiO3复合物纳米纤维的SEM图。
图3为实施例1制得的TiO2、CuO与CoTiO3复合物纳米纤维作为锂离子电池负极材料,在100mA g-1的电流密度下电池的充放电循环和库伦效率图,。
具体实施方式
以下结合实施例对本发明作进一步详细描述,本发明技术方案不局限于以下所列举具体实施方式,还包括各具体实施方式间的任意组合。
实施例1
将1.0mmol(0.254g)乙酸铜四水合物和1.0mmol(0.249g)乙酸钴四水合物溶于20mL体积比为1:1的N,N-二甲基甲酰胺(DMF)和乙醇的混合溶剂中,搅拌0.5h,形成混合物溶液A;将2mmol(0.680g)钛酸四丁酯(C16H36O4Ti),加入到混合物溶液A中,添加冰醋酸,调节pH=1,搅拌0.5h,形成混合物溶液B;将2.0g K-90型聚乙烯吡咯烷酮(PVP)加入混合溶液B中,搅拌10h,形成溶液C;将溶液C在温度为32℃,电压为17kV,接收距离为15cm和流速为0.6mL h-1下,进行静电纺丝;将得到的静电纺丝产物放于80℃下干燥12h;将干燥后的静电纺丝产物转移到马弗炉中,在750℃烧结6h,得一种TiO2、CuO与CoTiO3复合物纳米纤维。
将得到的复合物纳米纤维进行粉末X射线衍射(XRD)测试,结果显示X射线衍射峰与TiO2、CuO与CoTiO3复合物的衍射峰相吻合(图1);扫描电镜(SEM)观测复合物的形貌为一维纳米纤维,该纤维是由小颗粒构成,颗粒的直径为100~150nm(图2);将得到的复合物纳米纤维作为锂离子电池负极材料进行电化学性能测试,结果显示在100mA g-1的电流密度下,充放电循环140圈后电池的放电比容量为100mAh g-1以上,库伦效率保持在99%以上(图3);
实施例2
将1.0mmol(0.254g)乙酸铜四水合物和1.0mmol(0.249g)乙酸钴四水合物溶于20mL体积比为1:1的N,N-二甲基甲酰胺(DMF)和乙醇的混合溶剂中,搅拌0.5h,形成混合物溶液A;将2mmol(0.680g)钛酸四丁酯(C16H36O4Ti),加入到混合物溶液A中,添加冰醋酸,调节pH=2,搅拌0.5h,形成混合物溶液B;将2.0g K-90型聚乙烯吡咯烷酮(PVP)加入混合溶液B中,搅拌10h,形成溶液C;将溶液C在温度为32℃,电压为19kV,接收距离为20cm和流速为0.8mL h-1下,进行静电纺丝;将得到的静电纺丝产物放于80℃下干燥12h;将干燥后的静电纺丝产物转移到马弗炉中,在900℃烧结4h,得一种TiO2、CuO与CoTiO3复合物纳米纤维。将得到的复合物纳米纤维进行XRD、SEM以及电化学性能测试分析和表征。
实施例3
将1.0mmol(0.254g)乙酸铜四水合物和1.0mmol(0.249g)乙酸钴四水合物溶于20mL体积比为1:1的N,N-二甲基甲酰胺(DMF)和乙醇的混合溶剂中,搅拌0.5h,形成混合物溶液A;将2mmol(0.680g)钛酸四丁酯(C16H36O4Ti),加入到混合物溶液A中,添加冰醋酸,调节pH=2,搅拌0.5h,形成混合物溶液B;将3.0g K-90型聚乙烯吡咯烷酮(PVP)加入混合溶液B中,搅拌10h,形成溶液C;将溶液C在温度为32℃,电压18kV,接收距离为17cm和流速为0.7mLh-1下,进行静电纺丝;将得到的静电纺丝产物放于80℃下干燥12h;将干燥后的静电纺丝产物转移到马弗炉中,在850℃烧结5h,得所述的一种TiO2、CuO与CoTiO3复合物纳米纤维。将得到的复合物纳米纤维进行XRD、SEM以及电化学性能测试分析和表征。
以实施例1、2和3所制备的复合物纳米纤维作为助催化剂或共催化剂,与醋酸钯化合物一起催化Suzuki碳碳键偶联反应,反应方程式如下:
使用上述实施例1制备的复合物纳米纤维0.05g置于25mL的三口烧瓶中,加入1.0mL浓度为1.0×10-3g/mL的醋酸钯水溶液,搅拌10min,然后加入1.0mmol(0.171g)的4-溴甲苯、1.2mmol苯硼酸和2.0mmol Na2CO3,加入2mL水、10mL乙醇,加热回流反应4h,产率为92%;在上述反应中,如果不添加0.05g的复合物纳米纤维,在其他条件相同的情况下,反应的产率为75%。
使用上述实施例2制备的复合物纳米纤维0.05g置于25mL的三口烧瓶中,加入1.0mL浓度为1.0×10-3g/mL的醋酸钯水溶液,搅拌10min,然后加入1.0mmol(0.171g)的4-溴甲苯、1.2mmol苯硼酸和2.0mmol Na2CO3,加入2mL水、10mL乙醇,加热回流反应4h,产率为90%;在上述反应中,如果没有添加0.05g的复合物纳米纤维,在其他条件相同的情况下,反应的产率为73%。
使用上述实施例2制备的复合物纳米纤维0.05g置于25mL的三口烧瓶中,加入1.0mL浓度为1.0×10-3g/mL的醋酸钯水溶液,搅拌10min,然后加入1.0mmol(0.171g)的4-溴甲苯、1.2mmol苯硼酸和2.0mmol Na2CO3,加入2mL水、10mL乙醇,加热回流反应4h,产率为91%;在上述反应中,如果没有添加0.05g的复合物纳米纤维,在其他条件相同的情况下,反应的产率为76%。
综上反应可见,复合物纳米纤维作为助催化剂或共催化剂,在反应中起着重要作用,其在醋酸钯催化的Suzuki碳碳键偶联反应中提高了反应的产率。
Claims (3)
1.一种二氧化钛、氧化铜与钛酸钴复合物纳米纤维的制备方法,其特征在于,所述制备方法包括以下步骤:
(1)将一定量的乙酸铜四水合物和乙酸钴四水合物溶于体积比为1:1的N,N-二甲基甲酰胺和乙醇的混合溶剂中,搅拌0.5h,形成混合物溶液A;
(2)将适量的钛酸四丁酯(C16H36O4Ti)溶于上述混合物溶液A中,加入适量的冰醋酸,调节pH=1~2,搅拌0.5h,形成混合物溶液B;
(3)将适量的PVP加入到溶液B中,搅拌10h,形成溶液C;
(4)将溶液C在温度为32℃,电压为17~19kV,接收距离15~20cm和0.6~0.8mL h-1的流率条件下,进行静电纺丝;
(5)将得到的静电纺丝产物置于80℃下干燥12h,然后转移到马弗炉中,在750~900℃温度下,烧结4~6h,得所述的一种TiO2、CuO与CoTiO3复合物纳米纤维;
所述参加反应的物质、溶剂为化学纯或分析纯;
所述PVP的名称为K-90型聚乙烯吡咯烷酮;
所述溶液C中,乙酸铜、乙酸钴与钛酸四丁酯的摩尔比为1:1:2。
PVP与乙酸铜四水合物量的比为2~3g:1mmol。
2.根据权利要求1所述的制备方法得到的一种二氧化钛、氧化铜与钛酸钴复合物纳米纤维,其特征在于,该复合物纳米纤维作为锂离子电池负极材料,在一定的电流密度下,充放电循环140圈,放电比容量为100mAh g-1以上,库伦效率保持在99%以上。
3.根据权利要求1所述的制备方法得到的一种二氧化钛、氧化铜与钛酸钴复合物纳米纤维,其特征在于,该复合物纳米纤维作为碳碳键偶联反应的助催化剂或共催化剂,在醋酸钯催化的Suzuki偶联反应中能够提高反应的产率。
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