CN107658433A - 氮掺杂镍钴氧纳米线阵列及其制备方法 - Google Patents
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Abstract
氮掺杂镍钴氧纳米线阵列及其制备方法,首先,在水热条件下,将硝酸钴、硝酸镍、氟化铵、尿素混合反应,于泡沫镍上生长镍钴氧前驱体纳米线阵列,其次,将镍钴氧前驱体纳米线阵列高温煅烧,合成NiCo2O4纳米线阵列,最后,将NiCo2O4纳米线阵列高温煅烧,对生长在泡沫镍上的NiCo2O4纳米线阵列进行氮掺杂,能够制备出生长在泡沫镍上的氮掺杂NiCo2O4纳米线阵列,提高NiCo2O4的导电率,从而提高其电池性能,具有操作简单、成本低廉、环保无污染的特点。
Description
技术领域
本发明涉及锂离子电池负极材料技术领域,特别涉及一种氮掺杂镍钴氧纳米线阵列及其制备方法。
背景技术
锂离子电池因其具有高能量密度和高输出电压,已经被广泛应用于便携式设备。为了满足动力汽车等大器件的储能需求,需要进一步提高其能量密度和比容量。多元金属氧化物具有这方面的潜力,因为多金属中心可以提供更多的氧化还原电位对,有利于提高电池容量。另外,当多元金属氧化物直接生长在泡沫镍上可以节约粘结剂和导电剂等材料,降低电池生产成本。
目前有多种方法制备NiCo2O4纳米线阵列,但是其锂电循环稳定性能差,经过几十个循环测试后,容量衰减严重。这是由于锂离子在多次嵌入脱出引起的应力积累导致结构被破坏,所以后期有效锂离子不能嵌入,从而出现容量减小现象。非金属掺杂能够缓解应力,改善循环稳定性,这种策略已经在其它材料上广泛应用,但是对于NiCo2O4没有报道。
发明内容
为了克服上述现有技术的缺点,本发明的目的在于提供一种氮掺杂镍钴氧纳米线阵列及其制备方法,能够制备出生长在泡沫镍上的氮掺杂NiCo2O4纳米线阵列,提高NiCo2O4的导电率,从而提高其电池性能,具有操作简单、成本低廉、环保无污染的特点。
为了达到上述目的,本发明采取的技术方案为:
氮掺杂NiCo2O4纳米线阵列的制备方法,其步骤如下:
步骤一:在水热条件下,将硝酸钴、硝酸镍、氟化铵、尿素混合反应,于泡沫镍上生长镍钴氧前驱体纳米线阵列;
步骤二:将镍钴氧前驱体纳米线阵列在空气气氛下煅烧,合成NiCo2O4纳米线阵列;
步骤三:将NiCo2O4纳米线阵列在氨气气氛下煅烧,对生长在泡沫镍上的NiCo2O4纳米线阵列进行氮掺杂。
所述氮掺杂NiCo2O4纳米线阵列长度为4-6μm,直径为15-25nm,在100mAg-1电流密度下,放电比容量达到1100-1300mAh g-1。
所述硝酸钴、硝酸镍、氟化铵、尿素的质量比为1:1:0.3:0.2。
所述步骤一水热温度为90-140℃,反应时间为8-10h。
所述步骤二煅烧温度为200-500℃,时间为3-5h。
所述步骤三煅烧温度为200-500℃,时间为1-3h。
本发明的有益效果为:
本发明采用尿素诱导生长镍钴氧前驱体纳米线阵列,再使其高温分解成为NiCo2O4纳米线,最后高温掺氮,利用本方法制备的氮掺杂NiCo2O4纳米线阵列可以显著提高NiCo2O4的电导率,从而提高其锂电性能,本发明制备方法具有可重复性强、成本低、对环境无污染的特点,易于规模化生产。
附图说明
图1为实施例一~四中制备的生长在泡沫镍上的氮掺杂NiCo2O4纳米线阵列的XRD图。其中,横坐标为角度;纵坐标为相对强度。
图2为实施例一~四中制备的生长在泡沫镍上的氮掺杂NiCo2O4纳米线阵列的SEM图。
图3为实施例一~四中制备的生长在泡沫镍上的氮掺杂NiCo2O4纳米线阵列的XPS氮精细谱图。
图4为实施例1中制备的生长在泡沫镍上的氮掺杂NiCo2O4纳米线阵列的充放电曲线图。
具体实施方式
下面结合附图和实施例对本发明作进一步详细说明。
实施例一
步骤一:在90℃水热条件下,将0.5g硝酸钴、0.5g硝酸镍、0.15g氟化铵、0.1g尿素混合反应10h,于2g泡沫镍上生长镍钴氧前驱体纳米线阵列;
步骤二:将镍钴氧前驱体纳米线阵列在200℃、空气气氛下煅烧4h,合成NiCo2O4纳米线阵列;
步骤三:将NiCo2O4纳米线阵列在200℃、氨气气氛下煅烧3h,对生长在泡沫镍上的NiCo2O4纳米线阵列进行氮掺杂。
图4为实施例一中制备的泡沫镍上生长镍钴氧前驱体纳米线阵列的充放电曲线图图,由图4可知,在100mAg-1电流密度下,放电比容量达到1300mAh g-1。
实施例二
步骤一:在110℃水热条件下,将0.3g硝酸钴、0.3g硝酸镍、0.09g氟化铵、0.06g尿素混合反应9h,于2g泡沫镍上生长镍钴氧前驱体纳米线阵列;
步骤二:将镍钴氧前驱体纳米线阵列在300℃、空气气氛下煅烧3h,合成NiCo2O4纳米线阵列;
步骤三:将NiCo2O4纳米线阵列在300℃、氨气气氛下煅烧2h,对生长在泡沫镍上的NiCo2O4纳米线阵列进行氮掺杂。
实施例三
步骤一:在120℃水热条件下,将0.4g硝酸钴、0.4g硝酸镍、0.12g氟化铵、0.08g尿素混合反应9.5h,于2g泡沫镍上生长镍钴氧前驱体纳米线阵列;
步骤二:将镍钴氧前驱体纳米线阵列在400℃、空气气氛下煅烧5h,合成NiCo2O4纳米线阵列;
步骤三:将NiCo2O4纳米线阵列在400℃、氨气气氛下煅烧1.5h,对生长在泡沫镍上的NiCo2O4纳米线阵列进行氮掺杂。
实施例四
步骤一:在140℃水热条件下,将0.3g硝酸钴、0.3g硝酸镍、0.09g氟化铵、0.06g尿素按照质量比1:1:0.3:0.2混合反应8h,于2g泡沫镍上生长镍钴氧前驱体纳米线阵列;
步骤二:将镍钴氧前驱体纳米线阵列在500℃、空气气氛下煅烧4.5h,合成NiCo2O4纳米线阵列;
步骤三:将NiCo2O4纳米线阵列在500℃、氨气气氛下煅烧1h,对生长在泡沫镍上的NiCo2O4纳米线阵列进行氮掺杂。
参见附图,图1为实施例一~四中制备的泡沫镍上生长镍钴氧前驱体纳米线阵列的XRD图。从图中看出镍的特征峰和NiCo2O4的特征峰。
图2为实施例一~四中制备的泡沫镍上生长镍钴氧前驱体纳米线阵列的SEM图。从图中可以看到尺寸均一的纳米线阵列。
图3为实施例一~四中制备的泡沫镍上生长镍钴氧前驱体纳米线阵列的XPS图,掺杂氮元素的精细谱。
Claims (6)
1.氮掺杂镍钴氧纳米线阵列,其特征在于,所述氮掺杂NiCo2O4纳米线阵列长度为4-6μm,直径为15-25nm,在100mAg-1电流密度下,放电比容量达到1100-1300mAh g-1。
2.氮掺杂镍钴氧纳米线阵列的制备方法,其特征在于,步骤如下:
步骤一:在水热条件下,将硝酸钴、硝酸镍、氟化铵、尿素混合反应,于泡沫镍上生长镍钴氧前驱体纳米线阵列;
步骤二:将镍钴氧前驱体纳米线阵列在空气气氛下煅烧,合成NiCo2O4纳米线阵列;
步骤三:将NiCo2O4纳米线阵列在氨气气氛下煅烧,对生长在泡沫镍上的NiCo2O4纳米线阵列进行氮掺杂。
3.根据权利要求2所述的氮掺杂镍钴氧纳米线阵列的制备方法,其特征在于,所述硝酸钴、硝酸镍、氟化铵、尿素的质量比为1:1:0.3:0.2。
4.根据权利要求2所述的氮掺杂镍钴氧纳米线阵列的制备方法,其特征在于,所述步骤一水热温度为90-140℃,反应时间为8-10h。
5.根据权利要求2所述的氮掺杂镍钴氧纳米线阵列的制备方法,其特征在于,所述步骤二煅烧温度为200-500℃,时间为3-5h。
6.根据权利要求2所述的氮掺杂镍钴氧纳米线阵列的制备方法,其特征在于,所述步骤三煅烧温度为200-500℃,时间为1-3h。
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CN110931769A (zh) * | 2019-11-27 | 2020-03-27 | 上海纳米技术及应用国家工程研究中心有限公司 | 泡沫镍原位生长三元正极材料的制备方法及产品和应用 |
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Cited By (4)
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WO2021051896A1 (zh) * | 2019-09-20 | 2021-03-25 | 中国科学院宁波材料技术与工程研究所 | 一种掺氮碳包裹四氧化三钴纳米线整体式催化剂及其制备方法 |
CN110931769A (zh) * | 2019-11-27 | 2020-03-27 | 上海纳米技术及应用国家工程研究中心有限公司 | 泡沫镍原位生长三元正极材料的制备方法及产品和应用 |
CN110931769B (zh) * | 2019-11-27 | 2022-09-02 | 上海纳米技术及应用国家工程研究中心有限公司 | 泡沫镍原位生长三元正极材料的制备方法及产品和应用 |
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