CN112174220B - 二氧化钛包覆四氧化三钴蜂窝孔纳米线材料及其制备和应用 - Google Patents
二氧化钛包覆四氧化三钴蜂窝孔纳米线材料及其制备和应用 Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 95
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000002070 nanowire Substances 0.000 title claims abstract description 83
- 239000000463 material Substances 0.000 title claims abstract description 40
- 239000011148 porous material Substances 0.000 title claims abstract description 36
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 23
- HIYNGBUQYVBFLA-UHFFFAOYSA-D cobalt(2+);dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Co+2].[Co+2].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O HIYNGBUQYVBFLA-UHFFFAOYSA-D 0.000 claims abstract description 13
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 claims abstract description 13
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
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- 239000008367 deionised water Substances 0.000 claims description 14
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- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 claims description 8
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 7
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 7
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
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- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种二氧化钛包覆四氧化三钴蜂窝孔纳米线材料及其制备和应用。所述二氧化钛包覆四氧化三钴蜂窝孔纳米线材料中,四氧化三钴纳米线内部遍布微孔和介孔,呈蜂窝状多孔结构;二氧化钛包覆于四氧化三钴纳米线的表面,部分晶化。制备方法:首先合成碱式碳酸钴纳米线,然后在其表面包覆水合TiO2,最后对其煅烧。本发明可提高Co3O4的电化学活性、结构稳定性和循环稳定性,使Co3O4具有高的比容量和稳定的循环性能。TiO2包覆Co3O4蜂窝孔纳米线作为锂离子电池负极材料具有显著的应用价值。
Description
技术领域
本发明涉及锂离子电池技术领域,具体涉及一种二氧化钛包覆四氧化三钴蜂窝孔纳米线材料及其制备和应用。
背景技术
和传统的铅酸电池、镍镉电池相比,锂离子电池具有能量密度和功率密度高、循环寿命长、无记忆效应等优点,广泛用于电动汽车和移动电子设备。石墨是目前商品锂离子电池主要使用的负极材料,但是石墨的理论容量只有372mAh/g,而且还存在安全性能较差,倍率性能较低等问题,探索其它电极材料替代石墨已迫在眉睫。
过渡金属氧化物因其成本低,环境友善,储量丰富而被认为是石墨的理想替代者,其中,Co3O4理论容量达890mAh/g,是石墨的2.4倍,被国内外学者高度关注。但是,Co3O4在锂离子嵌入/脱出过程中体积变化较大,导致容量衰减很快,循环稳定性较差。
为改善Co3O4的锂离子电池性能,构建纳米结构是一个有效策略,这可以提高Co3O4的比表面积,加强其锂离子存储能力。迄今为止,已经报道了各种Co3O4纳米材料,如纳米球、纳米棒、纳米管、纳米线、纳米片等。公开号为CN110395771A的专利说明书公开了一种六棱柱状的Co3O4及其制备方法与锂离子电池应用。王捷等人报道了纳米颗粒组装三维Co3O4微米花材料及其储锂性能(王捷,李园,赵海雷,化工学报,71(04)(2020)1844-1850)。然而,常规纳米材料在使用中还存在一些明显缺点,比如,在充放电过程中纳米颗粒接触的损失,纳米材料极易团聚导致纳米效应显著下降。
发明内容
针对本领域存在的不足之处,本发明提供了一种二氧化钛包覆四氧化三钴蜂窝孔纳米线材料,它具有制备方法简单,成本低,性能优异等特点。
一种二氧化钛包覆四氧化三钴蜂窝孔纳米线材料,所述四氧化三钴纳米线内部遍布微孔和介孔,呈蜂窝状多孔结构;所述二氧化钛包覆于四氧化三钴纳米线的表面,部分晶化。
所述四氧化三钴纳米线具有各种尺寸的多孔结构,具有很大的比表面积。
作为优选,所述四氧化三钴纳米线的直径为20-350nm,长度为0.4-5μm;二氧化钛包覆层的厚度为5-50nm。
本发明还提供了所述的二氧化钛包覆四氧化三钴蜂窝孔纳米线材料的制备方法,包括步骤:
(1)将CoCl2·6H2O和尿素溶于去离子水,加热至30-50℃并保温,然后在搅拌下将预热至60-70℃的油胺加入到上述保温溶液中,混合均匀后将所得混合液于170-200℃进行溶剂热反应,所得固体产物经后处理即得碱式碳酸钴纳米线Co(OH)x(CO3)y,x>0,y>0,且x+2y=3;
(2)将步骤(1)得到的碱式碳酸钴纳米线Co(OH)x(CO3)y分散在乙醇中,加入钛酸异丙酯,搅拌混匀后滴加去离子水,继续搅拌30-60min后离心分离,将所得固体产物洗涤、干燥得到水合TiO2包覆碱式碳酸钴纳米线;
(3)将步骤(2)得到的水合TiO2包覆碱式碳酸钴纳米线于空气条件下以0.5-5℃/min的升温速率加热到350-450℃并保温30-120min,得到所述二氧化钛包覆四氧化三钴蜂窝孔纳米线材料。
作为优选,步骤(1)中,所述CoCl2·6H2O、尿素、去离子水和油胺的比例为0.356g:0.068g:37mL:2.25mL,所述保温的时间为30min,所述溶剂热反应的时间为1-24h,所述后处理包括:所得固体产物冷却至室温后,离心分离,用水和乙醇清洗三次,冷冻干燥。
作为优选,步骤(2)中,所述碱式碳酸钴纳米线Co(OH)x(CO3)y、乙醇、钛酸异丙酯、去离子水的比例为0.02g:30mL:0.01-0.2mL:0.1-2mL,所述搅拌混匀的时间为5min,所述洗涤具体为用水和乙醇清洗三次,所述干燥的温度为80℃。
进一步优选,步骤(2)中,所述钛酸异丙酯和去离子水的体积比为1:10。
本发明还提供了所述的二氧化钛包覆四氧化三钴蜂窝孔纳米线材料在锂离子电池负极材料中的应用。
在一优选例中,采用本发明的二氧化钛(TiO2)包覆四氧化三钴(Co3O4)蜂窝孔纳米线材料制作锂离子电池负极:分别称取质量比8:1:1的TiO2包覆Co3O4蜂窝孔纳米线材料、乙炔黑导电剂、聚偏氟乙烯(PVDF)粘结剂,将PVDF溶于适量的1-甲基-2-吡咯烷酮(NMP),搅拌至完全溶解,再将研磨均匀的活性材料和乙炔黑加入到上述溶液中,继续搅拌以保证浆料混合均匀。然后把浆料均匀涂覆在圆片铜箔上(直径12mm),在真空烘箱100℃烘干,最后在压片机上用10MPa的压强压平,即制得电极片。
在充满高纯氩气的手套箱内将制备的电极片与锂片、隔膜组装成CR2025纽扣型锂离子电池。电解液为1mol/L LiPF6的EC/DMC电解液,采用新威电池测试系统测试锂离子电池的充放电性能与循环稳定性。
本发明可提高Co3O4的电化学活性、结构稳定性和循环稳定性,使Co3O4具有高的比容量和稳定的循环性能。
本发明与现有技术相比,主要优点包括:
(1)通过碱式碳酸钴纳米线Co(OH)x(CO3)y受热分解释放出H2O和CO2,在纳米线内部产生大量微孔和介孔,形成独特的Co3O4蜂窝孔纳米线,蜂窝孔提高了材料的比表面积,增加了材料的电化学活性位点数量,进一步缩小了Co3O4的晶粒尺寸,缩短了锂离子扩散路径;此外,蜂窝孔不仅提供了内部空间存储电解液,满足了充放电电化学反应的需要,而且提高了材料强度,加强了Co3O4适应材料体积变化的能力,显著改善了Co3O4的循环稳定性。
(2)350-450℃煅烧使水合TiO2部分晶化成纳米晶TiO2分散于非晶TiO2的连续复合结构,这种结构具有较高的结构强度,能有效保护内部的Co3O4蜂窝孔纳米线,进一步提高Co3O4蜂窝孔纳米线的结构强度和循环稳定性,此外,TiO2也能参与储锂反应,避免拉低复合材料整体的平均容量。本发明特殊结构且部分晶化的TiO2在充放电反应中体积变化较小,结构稳定,适合作为包覆材料使用。
(3)纳米线的轴向大尺度能有效避免纳米材料团聚现象,径向小尺度有利于离子/电子快速传输。
附图说明
图1为实施例1制备的TiO2包覆Co3O4蜂窝孔纳米线的SEM照片;
图2为实施例1制备的TiO2包覆Co3O4蜂窝孔纳米线的TEM照片;
图3为实施例1制备的TiO2包覆Co3O4蜂窝孔纳米线材料在电流密度100mA/g的循环性能图;
图4为实施例1制备的TiO2包覆Co3O4蜂窝孔纳米线材料的倍率性能图。
具体实施方式
下面结合附图及具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的操作方法,通常按照常规条件,或按照制造厂商所建议的条件。
实施例1
(1)将0.356g CoCl2·6H2O和0.068g尿素溶于37mL去离子水,加热至40℃并保温30min。随后,在65℃烘箱中预热2.25mL油胺,在缓慢搅拌下加入到前述溶液中。搅拌均匀后将溶液转移到50mL高压反应釜内并加热至185℃反应12h。冷却至室温后,产物离心分离,用水和乙醇清洗三次,冷冻干燥得到碱式碳酸钴纳米线Co(OH)x(CO3)y,x>0,y>0,且x+2y=3;
(2)将步骤(1)得到的0.02g碱式碳酸钴纳米线分散在30mL乙醇中,滴加0.08mL钛酸异丙酯,搅拌5min后缓慢滴加0.8mL去离子水,继续搅拌40min后离心分离产物,用水和乙醇清洗三次,80℃烘干,得到水合TiO2包覆碱式碳酸钴纳米线;
(3)将步骤(3)得到的水合TiO2包覆碱式碳酸钴纳米线置于马弗炉中,在空气中以1℃/min的升温速率加热到400℃并保温30min,得到TiO2包覆Co3O4蜂窝孔纳米线。
图1是合成的TiO2包覆Co3O4蜂窝孔纳米线的SEM照片。纳米线表面粗糙,还黏附了一些纳米颗粒,是钛酸异丙酯水解产生的多余的TiO2纳米颗粒,纳米线直径大约50-150nm,长度从400-500nm至2-3μm。对纳米线进行TEM观察,如图2所示。可以看到有2条清晰的界线,是TiO2与Co3O4蜂窝孔纳米线的界面。界线以内区域是Co3O4纳米线,纳米线内遍布大量的微孔和介孔,使纳米线形成蜂窝状多孔结构,区别于传统的实心纳米线结构。界线以外区域是包覆的TiO2层,400℃煅烧没有使TiO2完全晶化,因此包覆层仍然保持连续致密的非晶态管壳层结构,在其内部分布有细小的纳米晶TiO2,TiO2包覆层厚度大约20nm。
采用本实施例的TiO2包覆Co3O4蜂窝孔纳米线制作锂离子电池负极:分别称取质量比8:1:1的TiO2包覆Co3O4蜂窝孔纳米线材料、乙炔黑导电剂、聚偏氟乙烯(PVDF)粘结剂,将PVDF溶于适量的1-甲基-2-吡咯烷酮(NMP),搅拌至完全溶解,再将研磨均匀的活性材料和乙炔黑加入到上述溶液中,继续搅拌以保证浆料混合均匀。然后把浆料均匀涂覆在圆片铜箔上(直径12mm),在真空烘箱100℃烘干,最后在压片机上用10MPa的压强压平,即制得电极片。
在充满高纯氩气的手套箱内将制备的电极片与锂片、隔膜组装成CR2025纽扣型锂离子电池。电解液为1mol/L LiPF6的EC/DMC电解液,采用新威电池测试系统测试锂离子电池的充放电性能与循环稳定性,充放电电流密度100mA/g,电压范围0.01~3.0V。
图3是TiO2包覆Co3O4蜂窝孔纳米线材料在电流密度100mA/g的循环性能图。首循环的放电容量是1239.6mAh/g,第4个循环下降到933.5mAh/g,之后放电容量表现平稳,到第200个循环时放电容量下降到793.6mAh/g。200个循环的平均放电容量847.5mAh/g。TiO2包覆Co3O4蜂窝孔纳米线的放电比容量和循环稳定性优于公开号为CN111162264A的专利技术和X.L.Tong等人(X.L.Tong,M.Zeng,J.Li,Z.J.Liu,Journal of Alloys and Compounds,723(2017)129-138.)的工作。
图4是TiO2包覆Co3O4蜂窝孔纳米线材料的倍率性能图。在电流密度100,200,500,1000和2000mA/g,TiO2包覆Co3O4蜂窝孔纳米线的平均放电容量分别是906.2,841.1,745.3,633.6和505.6mAh/g,高的比容量表明材料具有高的电化学活性。当电流密度回到100mA/g,平均放电比容量回到876.2mAh/g,恢复到初始100mA/g电流时的96.7%,显示材料具有高的循环稳定性和可逆性,能够进行较大电流的电化学反应。
TiO2包覆Co3O4蜂窝孔纳米线具有优秀的锂电池性能,包括高的放电比容量,稳定的循环性能和良好的倍率能力,这来源于蜂窝孔纳米线结构赋予Co3O4良好的电化学活性和结构稳定性,以及TiO2包覆材料提供的结构增强作用。
实施例2
(1)将0.356g CoCl2·6H2O和0.068g尿素溶于37mL去离子水,加热至40℃并保温30min。随后,在65℃烘箱中预热2.25mL油胺,在缓慢搅拌下加入到前述溶液中。搅拌均匀后将溶液转移到50mL高压反应釜内并加热至190℃反应20h。冷却至室温后,产物离心分离,用水和乙醇清洗三次,冷冻干燥得到碱式碳酸钴纳米线Co(OH)x(CO3)y,x>0,y>0,且x+2y=3;
后续工艺与实施例1相同。
产物TiO2包覆Co3O4蜂窝孔纳米线的结构与实施例1相似,主要区别是纳米线的直径变为100-200nm。
采用与实施例1相同的工艺制作锂离子电池负极,装配成锂离子电池,以电流密度100mA/g,0.01~3.0V的电压范围进行循环充放电测试。首循环放电容量是1152.4mAh/g,到第5个循环放电容量下降到910.2mAh/g,之后放电容量十分稳定,到第200个循环放电容量下降到776.1mAh/g。200个循环的平均放电容量是836.4mAh/g。
实施例3
(1)将0.356g CoCl2·6H2O和0.068g尿素溶于37mL去离子水,加热至40℃并保温30min。随后,在65℃烘箱中预热2.25mL油胺,在缓慢搅拌下加入到前述溶液中。搅拌均匀后将溶液转移到50mL高压反应釜内并加热至185℃反应12h。冷却至室温后,产物离心分离,用水和乙醇清洗三次,冷冻干燥得到碱式碳酸钴纳米线Co(OH)x(CO3)y,x>0,y>0,且x+2y=3;
(2)将步骤(1)得到的0.02g碱式碳酸钴纳米线分散在30mL乙醇中,滴加0.12mL钛酸异丙酯,搅拌5min后缓慢滴加1.2mL去离子水,继续搅拌40min后离心分离产物,用水和乙醇清洗三次,80℃烘干,得到水合TiO2包覆碱式碳酸钴纳米线;
后续工艺与实施例1相同。
产物TiO2包覆Co3O4蜂窝孔纳米线的结构与实施例1相似,主要区别是TiO2包覆层厚度变为29nm。
采用与实施例1相同的工艺制作锂离子电池负极,装配成锂离子电池,以电流密度100mA/g,0.01~3.0V的电压范围进行循环充放电测试。首循环放电容量是1001.6mAh/g,到第8个循环放电容量下降到754.3mAh/g,之后放电容量十分平稳,到第200个循环放电容量是728.6mAh/g。200个循环的平均放电容量740.3mAh/g。
此外应理解,在阅读了本发明的上述描述内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
Claims (5)
1.一种二氧化钛包覆四氧化三钴蜂窝孔纳米线材料,其特征在于,所述四氧化三钴纳米线内部遍布微孔和介孔,呈蜂窝状多孔结构;所述二氧化钛包覆于四氧化三钴纳米线的表面,部分晶化;
所述的二氧化钛包覆四氧化三钴蜂窝孔纳米线材料的制备方法包括步骤:
(1)将CoCl2·6H2O和尿素溶于去离子水,加热至30-50℃并保温,然后在搅拌下将预热至60-70℃的油胺加入到上述保温溶液中,混合均匀后将所得混合液于170-200℃进行溶剂热反应,所得固体产物经后处理即得碱式碳酸钴纳米线Co(OH)x(CO3)y,x>0,y>0,且x+2y=3;
所述后处理包括:所得固体产物冷却至室温后,离心分离,用水和乙醇清洗三次,冷冻干燥;
(2)将步骤(1)得到的碱式碳酸钴纳米线Co(OH)x(CO3)y分散在乙醇中,加入钛酸异丙酯,搅拌混匀后滴加去离子水,继续搅拌30-60min后离心分离,将所得固体产物洗涤、干燥得到水合TiO2包覆碱式碳酸钴纳米线;
(3)将步骤(2)得到的水合TiO2包覆碱式碳酸钴纳米线于空气条件下以0.5-5℃/min的升温速率加热到350-450℃并保温30-120min,得到所述二氧化钛包覆四氧化三钴蜂窝孔纳米线材料。
2.根据权利要求1所述的二氧化钛包覆四氧化三钴蜂窝孔纳米线材料,其特征在于,所述四氧化三钴纳米线的直径为20-350nm,长度为0.4-5μm;二氧化钛包覆层的厚度为5-50nm。
3.根据权利要求1所述的二氧化钛包覆四氧化三钴蜂窝孔纳米线材料,其特征在于,步骤(1)中,所述CoCl2·6H2O、尿素、去离子水和油胺的比例为0.356g:0.068g:37mL:2.25mL,所述保温的时间为30min,所述溶剂热反应的时间为1-24h。
4.根据权利要求1所述的二氧化钛包覆四氧化三钴蜂窝孔纳米线材料,其特征在于,步骤(2)中,所述碱式碳酸钴纳米线Co(OH)x(CO3)y、乙醇、钛酸异丙酯、去离子水的比例为0.02g:30mL:0.01-0.2mL:0.1-2mL,所述搅拌混匀的时间为5min,所述洗涤具体为用水和乙醇清洗三次,所述干燥的温度为80℃。
5.根据权利要求1~4任一项所述的二氧化钛包覆四氧化三钴蜂窝孔纳米线材料在锂离子电池负极材料中的应用。
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