CN111244420A - 一种锂电池用NiCo2O4@Ni-B负极材料及其制备方法 - Google Patents
一种锂电池用NiCo2O4@Ni-B负极材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种锂电池用NiCo2O4@Ni‑B负极材料及其制备方法,包括如下步骤:将聚乙烯吡咯烷酮、镍盐和盐溶解在甘油/异丙醇的混合溶液中,搅匀,转移到反应釜中密闭恒温反应,离心干燥,收集粉末状产品;将上述产品在空气中热解,得到NiCo2O4;将NiCo2O4和六水合硝酸镍溶解在去离子水中,搅匀得混合盐溶液;将混合盐溶液脱气,加入硼氢化钠水溶液,搅拌离心;将上述所得沉淀在真空炉中冷冻干燥,即得。本发明通过采用原位溶液生长的方法将非晶化硼化镍(Ni‑B)引入多孔NiCo2O4纳米球中,包覆的Ni‑B组分不仅可以作为镍纳米球的锚点,而且还可以作为有效的电子传导桥梁,促进电子/电荷的快速转移,从而大大地提高了NiCo2O4的比容量、循环寿命、稳定性等电化学性能。
Description
技术领域
本发明属于电池材料技术领域,具体涉及一种锂电池用NiCo2O4@Ni-B负极材料及其制备方法。
背景技术
目前,锂离子电池已经成为便携式电子产品和电动汽车的主要电源,这就需要更高的能量密度、更低的成本和更环保的储能设备。不幸的是,目前商业化的石墨阳极在锂离子电池中具有低理论容量(372mAh·g-1),远远不能满足长续航里程和长寿命。因此,迫切需要开发其他非碳替代品以满足工业需求。
过渡金属氧化物作为新一代锂离子电池的负极材料,以其较高的能量密度、较低的成本和较好的生态友好性获得了广泛的研究兴趣。然而,它们在充放电过程中受低电导率和剧烈的体积变化的影响,使得实现自由空间性能良好的过渡金属氧化物负极面临着巨大的挑战。
发明内容
本发明旨在克服现有技术的不足,尤其是现有的锂离子电池负极材料充放电过程中低电导率和剧烈的体积变化等问题,提供一种锂电池用NiCo2O4@Ni-B负极材料及其制备方法。
本发明上述目的通过如下技术方案实现:
一种锂电池用NiCo2O4@Ni-B负极材料的制备方法,包括如下步骤:
步骤(1),将聚乙烯吡咯烷酮、可溶性镍盐和可溶性钴盐溶解在甘油/异丙醇的混合溶剂中,在磁力搅拌器上搅拌溶解均匀,得到透明的粉红色溶液,转移到反应釜中密闭恒温反应一段时间,所得产物经无水乙醇离心后干燥,收集粉末状产品;
步骤(2),将步骤(1)所得到的产品在空气中热解,得到NiCo2O4;
步骤(3),将步骤(2)所得到的NiCo2O4和六水合硝酸镍溶解在去离子水中,在磁力搅拌器上搅拌溶解均匀,得到混合盐溶液;
步骤(4),将步骤(3)所得到的混合盐溶液在惰性气氛下进行脱气,加入硼氢化钠水溶液,搅拌离心;
步骤(5),将步骤(4)所得沉淀在真空炉中冷冻干燥,即得NiCo2O4@Ni-B复合材料。
进一步地,步骤(1)中,所述聚乙烯吡咯烷酮为K90,平均分子量为1300000,质量分数为0.8%-1.0%;可溶性镍盐为六水合硝酸镍;可溶性钴盐为六水合硝酸钴。
进一步地,步骤(1)中,反应釜中反应温度为180℃,反应时间为6h;离心分离速率为 5000r/min,离心时间为5min。
进一步地,步骤(2)中,热解温度为400℃,热解时间为4h,升温速率为2℃/min。
进一步地,步骤(3)中,搅拌时间为0.5h-1h。
进一步地,步骤(3)所述混合盐溶液中,NiCo2O4的质量分数为0.09%-0.1%,六水合硝酸镍的质量分数为0.2%-0.3%。
进一步地,步骤(4)中,惰性气氛为氩气,脱气时间为0.5h。
进一步地,步骤(4)中,硼氢化钠水溶液的质量分数为0.2%-0.3%。
上述任一所述制备方法制备得到的NiCo2O4@Ni-B负极材料。
进一步地,所述NiCo2O4@Ni-B负极材料用作锂电池负极材料的用途。
有益效果:
本发明通过采用原位溶液生长的方法将非晶化硼化镍(Ni-B)引入多孔NiCo2O4纳米球中,包覆的Ni-B组分不仅可以作为镍纳米球的锚点,抑制其严重的体积膨胀,而且还可以作为有效的电子传导桥梁,促进电子/电荷的快速转移,从而大大地提高了NiCo2O4的比容量、循环寿命、稳定性等电化学性能。而且NiCo2O4@Ni-B负极中锂的存储大部分是由电容性电荷贡献的,这对快速电荷存储和长期循环非常有利。此外,NiCo2O4@Ni-B材料存在大量的4~10nm范围内孔道结构,可以有效抑制锂化/脱锂过程中严重的体积变化,克服了过渡金属氧化物在锂离子电池充放电过程中低电导率和剧烈的体积变化等问题。
本发明所得到的NiCo2O4@Ni-B复合材料,在0.2A·g-1的电流密度下具有1221mAh·g-1的高可逆容量,在0.5A·g-1时500次循环后具有865mAh·g-1的高可逆容量,显示出极佳的循环稳定性。此外,在高速率5A·g-1的情况下,还可以获得648mAh·g-1的容量,显示出良好的速率能力。
附图说明
图1为本发明实施例1制备的NiCo2O4和实施例2制备的NiCo2O4@Ni-B的扫描电镜图,其中(a)为NiCo2O4于500nm下的扫描电镜图,(b)为NiCo2O4@Ni-B于500nm下的扫描电镜图,(c)为NiCo2O4@Ni-B于200nm下的扫描电镜图;
图2为本发明实施例1制备的NiCo2O4和实施例2制备的NiCo2O4@Ni-B材料的X射线衍射图;
图3为本发明实施例1制备的NiCo2O4和实施例2制备的NiCo2O4@Ni-B材料制成电池在0.2A·g-1的电流密度下的性能曲线;
图4为本发明实施例1制备的NiCo2O4和实施例2制备的NiCo2O4@Ni-B材料制成电池在0.5A·g-1的电流密度经过500次循环的性能曲线。
具体实施方式
下面结合附图和实施例具体介绍本发明实质性内容,但并不以此限定本发明的保护范围。除有特别说明,本发明中用到的各种试剂、原料均为可以从市场上购买的商品或者可以通过公知的方法制得的产品。
实施例1:NiCo2O4材料的制备
一种用NiCo2O4作为锂离子电池负极材料的制备方法,包括如下步骤:
步骤(1),将聚乙烯吡咯烷酮和8mL甘油溶解在40mL异丙醇溶液中,在磁力搅拌器上以250r/min的速率搅拌溶解均匀,得到聚乙烯吡咯烷酮质量分数为0.8%-0.9%的透明粉红色溶液;
步骤(2),向所得的混合溶液中加入六水合硝酸镍和六水合硝酸钴,继续在磁力搅拌器上搅拌至溶解得到均匀溶液,其中六水合硝酸镍的质量分数为0.3%-0.4%,六水合硝酸钴的质量分数为1.0%-2.0%;
步骤(3),将所得的均匀溶液转移到反应釜中,密闭于180℃反应6h,所得产物经无水乙醇离心后干燥,收集粉末状产品;
步骤(4),将所得到的产品在空气中于400℃热解4h,升温速率为2℃·min-1,即得到 NiCo2O4锂离子电池负极材料。
实施例2:NiCo2O4@Ni-B负极材料的制备
一种NiCo2O4@Ni-B作为锂离子电池负极材料的制备方法,包括如下步骤:
步骤(1),将上述实施例1所得到的NiCo2O4材料和六水合硝酸镍溶解在100mL去离子水中,在磁力搅拌器上以500r/min的速率搅拌溶解均匀,得到混合盐溶液;
步骤(2),将所得到的混合盐溶液在氩气气氛下脱气0.5h,再加入质量分数为0.2%-0.3%的硼氢化钠水溶液,将所得产物进行搅拌离心;
步骤(3),将所得到的产品在真空炉中冷冻干燥过夜,即得到NiCo2O4@Ni-B复合材料。
其中,NiCo2O4材料和六水合硝酸镍质量比为1:3。
将上述实施例1和实施例2获得的材料进行表征和检测:以制备的NiCo2O4粉末和NiCo2O4@Ni-B复合材料粉末进行扫描电子显微镜分析,得到图1的表征结果;以制备的NiCo2O4粉末和NiCo2O4@Ni-B复合材料粉末进行X-射线衍射分析,得到图2的表征结果。
实施例3:性能测定
将上述实施例1和实施例2获得的材料进行电池性能测试,具体步骤如下:
以NiCo2O4或NiCo2O4@Ni-B粉末为活性物质、炭黑(Super P)为导电剂、羧甲基纤维素钠(CMC)为粘结剂,三者质量比为7:2:1,加入去离子水和少量乙醇,在球磨机上球磨 2h制成均匀浆料,涂敷在铝箔集流体上,制成电池的极片。以锂片为负极,聚乙烯隔膜,采用1M的LiPF6/EC+EMC(体积比为1:1)为电解液,在充满氩气的手套箱中,组装成纽扣型电池。经检测在0.2A·g-1的电流密度下,循环80次后,NiCo2O4放电比容量保持709mAh·g-1,NiCo2O4@Ni-B电极容量为在1221mAh·g-1(检测结果曲线如图3所示);在0.5A·g-1的电流密度下,循环500次后,NiCo2O4放电比容量保持在530mAh·g-1,NiCo2O4@Ni-B电极容量为865mAh·g-1(检测结果曲线如图4所示)。
本发明通过采用原位溶液生长的方法将非晶化硼化镍(Ni-B)引入多孔NiCo2O4纳米球中,包覆的Ni-B组分不仅可以作为镍纳米球的锚点,抑制其严重的体积膨胀,而且还可以作为有效的电子传导桥梁,促进电子/电荷的快速转移,从而大大地提高了NiCo2O4的比容量、循环寿命、稳定性等电化学性能。而且NiCo2O4@Ni-B负极中锂的存储大部分是由电容性电荷贡献的,这对快速电荷存储和长期循环非常有利。此外,NiCo2O4@Ni-B材料存在大量的4~10nm范围内孔道结构,可以有效抑制锂化/脱锂过程中严重的体积变化,克服了过渡金属氧化物在锂离子电池充放电过程中低电导率和剧烈的体积变化等问题。
本发明所得到的NiCo2O4@Ni-B复合材料,在0.2A·g-1的电流密度下具有1221mAh·g-1的高可逆容量,在0.5A·g-1时500次循环后具有865mAh·g-1的高可逆容量,显示出极佳的循环稳定性。此外,在高速率5A·g-1的情况下,还可以获得648mAh·g-1的容量,显示出良好的速率能力。
上述实施例的作用在于具体介绍本发明的实质性内容,但本领域技术人员应当知道,不应将本发明的保护范围局限于该具体实施例。
Claims (10)
1.一种锂电池用NiCo2O4@Ni-B负极材料的制备方法,其特征在于,包括如下步骤:
步骤(1),将聚乙烯吡咯烷酮、可溶性镍盐和可溶性钴盐溶解在甘油/异丙醇的混合溶剂中,在磁力搅拌器上搅拌溶解均匀,得到透明的粉红色溶液,转移到反应釜中密闭恒温反应一段时间,所得产物经无水乙醇离心后干燥,收集粉末状产品;
步骤(2),将步骤(1)所得到的产品在空气中热解,得到NiCo2O4;
步骤(3),将步骤(2)所得到的NiCo2O4和六水合硝酸镍溶解在去离子水中,在磁力搅拌器上搅拌溶解均匀,得到混合盐溶液;
步骤(4),将步骤(3)所得到的混合盐溶液在惰性气氛下进行脱气,加入硼氢化钠水溶液,搅拌离心;
步骤(5),将步骤(4)所得沉淀在真空炉中冷冻干燥,即得NiCo2O4@Ni-B复合材料。
2.根据权利要求1所述的制备方法,其特征在于:步骤(1)中,所述聚乙烯吡咯烷酮为K90,平均分子量为1300000,质量分数为0.8%-1.0%;可溶性镍盐为六水合硝酸镍;可溶性钴盐为六水合硝酸钴。
3.根据权利要求1所述的制备方法,其特征在于:步骤(1)中,反应釜中反应温度为180℃,反应时间为6h;离心分离速率为5000r/min,离心时间为5min。
4.根据权利要求1所述的制备方法,其特征在于:步骤(2)中,热解温度为400℃,热解时间为4h,升温速率为2℃/min。
5.根据权利要求1所述的制备方法,其特征在于:步骤(3)中,搅拌时间为0.5h-1h。
6.根据权利要求1所述的制备方法,其特征在于:步骤(3)所述混合盐溶液中,NiCo2O4的质量分数为0.09%-0.1%,六水合硝酸镍的质量分数为0.2%-0.3%。
7.根据权利要求1所述的制备方法,其特征在于:步骤(4)中,惰性气氛为氩气,脱气时间为0.5h。
8.根据权利要求1所述的制备方法,其特征在于:步骤(4)中,硼氢化钠水溶液的质量分数为0.2%-0.3%。
9.一种权利要求1~8任一所述制备方法制备得到的NiCo2O4@Ni-B负极材料。
10.权利要求9所述NiCo2O4@Ni-B负极材料用作锂电池负极材料的用途。
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CN113629254A (zh) * | 2021-10-12 | 2021-11-09 | 浙江帕瓦新能源股份有限公司 | 一种单晶类高镍低钴或无钴正极材料的制备方法 |
CN113629254B (zh) * | 2021-10-12 | 2021-12-14 | 浙江帕瓦新能源股份有限公司 | 一种单晶类高镍低钴或无钴正极材料的制备方法 |
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