CN112960663A - 一种LiFeXCo1-XPO4/N-C/CC复合材料的制备方法 - Google Patents
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
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Abstract
本发明公开了一种LiFeXCo1‑XPO4/N‑C/CC复合材料的制备方法,包括下述步骤:首先将醋酸锂、硝酸铁、硝酸钴和磷酸二氢铵溶解在去离子水中,水热反应,之后加入苯胺和乙二醇和十六烷基三甲基溴化铵,搅拌老化之后,再放入碳布,水热煅烧后得到LiFeXCo1‑XPO4/N‑C/CC复合材料,制备的LiFeXCo1‑XPO4/N‑C/CC复合材料应用于锂离子电池的正极材料,具有良好的电化学性能和稳定性。
Description
技术领域
本发明应用于锂离子电池的正极材料,具体涉及一种LiFeXCo1-XPO4/N-C/CC复合材料的制备方法。
背景技术
随着第二次工业革命以来,经济的发展突飞猛进,对能源的消耗也逐渐的膨胀,人类对自然资源的掠夺式开采导致不可再生资源消耗待竭,使得石油、煤矿、天然气等不可再生资源将在21世纪中叶接近枯竭。同时,环境污染问题伴随着能源危机迅速呈现出来,目前已经严重影响着人类的正常生活,为了缓解能源危机引发的各种社会问题,新型绿色能源的开发和利用越来越受到人们的重视。锂离子电池作为一种新型储能装置,其比容量大、循环寿命长、绿色环保、无记忆效应,被公认为是最理想的电池,也是目前的研究热点。锂离子电池的性能主要取决于正极材料。LiFePO4是目前最常用的正极材料,其具有循环稳定性高、比容量高、循环寿命长、充放电电压平稳和绿色无污染等优点,是目前国内市场主流的动力锂离子电池正极材料,但LiFePO4的能量密度较低,电子电导率低阻碍了其进一步发展。研究表明,将LiFePO4与碳基材料复合能够有效提升其性能,但粉末状LiFePO4/C需要与粘接剂混合制备成电极材料,这会带来额外的内部阻力,影响其性能。因此可以将LiFePO4/C材料负载在导电基底上,制成柔性电极,可以避免粘接剂的使用,提升其性能。同时利用杂原子掺杂改变C材料的表面结构,进一步增强其催化性能。
发明内容
本发明的目的在于提供一种LiFeXCo1-XPO4/N-C/CC复合材料的制备方法,所述的LiFeXCo1-XPO4/N-C/CC复合材料包括以下原料:硝酸铁、硝酸钴、醋酸锂、磷酸二氢铵和苯胺。其制备方法有以下步骤:
(1)碳布的预处理:将边长为2×3cm碳布放入硝酸和水体积比为1:3的混合溶液中,80-100℃水热反应2h;
(2)将醋酸锂、硝酸铁、硝酸钴和磷酸二氢铵加入去离子水中,磁力搅拌1h,将上述溶液转入聚四氟乙烯反应釜中,放入碳布,水热反应,冷却后用去离子水洗涤;
(3)将乙二醇和苯胺放入烧杯中,加入去离子水,搅拌1h,加入十六烷基三甲基溴化铵,继续搅拌10-12h,之后老化4-6h,反应结束后,用去离子水和乙醇清洗产物,放入干燥箱中干燥;
(4)将步骤(3)产物放入烧杯中,加入去离子水,超声1-2h,之后将混合溶液转入聚四氟乙烯反应釜中,放入步骤(2)产物,进行水热反应;
(5)将步骤(4)产物置于管式炉内,在氩气气氛下煅烧。
优选的,所述步骤(2)中,醋酸锂、硝酸铁、硝酸钴和磷酸二氢铵的摩尔比为1:(0-0.5):(0.5-1):1。
优选的,0.5≤x≤1。
优选的,所述步骤(2)中水热反应的温度为160-220℃,反应时间为10-14h。
优选的,所述步骤(3)中加入苯胺、十六烷基三甲基溴化铵、乙二醇和去离子水的质量体积比为1ml:(1-2)g:(4-5)ml:(50-60)ml。
优选的,所述步骤(4)中水热反应的温度为100-150℃,反应时间为6-10h。
优选的,所述步骤(5)中煅烧温度为700-900℃,煅烧时间为8-10h。
优选的,所述LiFeXCo1-XPO4/N-C/CC复合材料的制备方法制备的复合材料应用于锂离子电池的正极材料。
与现有技术相比,本发明具有的有益效果如下:
本发明提供了一种LiFeXCo1-XPO4/N-C/CC复合材料的制备方法,所述工艺非常简单,得到的LiFeXCo1-XPO4/N-C/CC复合材料具有优异的电催化性能。LiFeXCo1-XPO4/N-C/CC复合材料通过将LiFeXCo1-XPO4/N-C负载在碳布上,避免了粘接剂的使用,提升了其电催化性能,同时LiFeXCo1-XPO4三元材料相比传统二元材料提高了材料的使用寿命和容量,N元素的掺杂改变了C材料的的表面结构,降低了Li+的嵌入能量,提升了材料的催化性能,将LiFePO4/C材料负载在导电基底上,制成柔性电极,可以避免粘接剂的使用,提升其性能。本发明制备的LiFeXCo1-XPO4/N-C/CC复合材料成本低、处理方法简单,能用作锂离子电池的正极材料。
本发明原料简单,易于获取,并且对环境友好。
附图说明
图1为本发明实施例1制备的LiFeXCo1-XPO4/N-C/CC复合材料的扫描电子显微镜(SEM)图。
图2为本发明实施例1制备的LiFeXCo1-XPO4/N-C复合材料的透射电子显微镜(TEM)图。
图3为本发明实施例1-4制备的LiFeXCo1-XPO4/N-C/CC复合材料的循环伏安曲线(1:实施例1;2:实施例2;3:实施例3;4:实施例4)。
图4为本发明实施例1制备的LiFeXCo1-XPO4/N-C/CC复合材料的倍率性能图。
图5为本发明实施例1制备的LiFeXCo1-XPO4/N-C/CC复合材料的在0.1C条件下的循环性能图。
具体实施方案
实施例1:
一种LiFeXCo1-XPO4/N-C/CC复合材料,具体包括以下制备步骤:
(1)碳布的预处理:将边长为2×3的碳布放入100ml硝酸和水体积比为1:3的混合溶液中,在90℃水热反应2h;
(2)将0.03mol醋酸锂、0.015mol硝酸铁、0.015mol硝酸钴和0.03mol磷酸二氢铵加入60ml去离子水中,磁力搅拌1h,将上述溶液转入聚四氟乙烯反应釜中,放入碳布,在190℃水热反应12h,之后用去离子水洗涤;
(3)将5ml乙二醇和1ml苯胺放入烧杯中,加入55ml去离子水,搅拌1h,加入1.5g十六烷基三甲基溴化铵,继续搅拌11h,之后老化5h,反应结束后,用去离子水和乙醇清洗产物,放入干燥箱中干燥;
(4)将步骤(3)产物放入烧杯中,加入去离子水,超声1.5h,将混合溶液转入聚四氟乙烯反应釜中,放入步骤(2)产物,在120℃水热反应8h;
(5)将步骤(4)产物置于管式炉内,在氩气气氛下800℃煅烧9h。
性能测试:
将实施例1-4制备的复合材料在手套箱中组装成电池;
(1)循环伏安测试:
采用PARSTAT-4000高级电化学测试系统(PrincetonApplied Research)对组装成的电池进行循环伏安测试,并进行数据采集及分析。具体测试条件:环境温度为25℃,扫描电压范围为2.5-5.0V,扫描速度为0.1mV·s-1。
(2)倍率测试:
将实施例1-4制备的正极材料在不同倍率下(0.1C、0.5C、1C、5C、10C、20C)恒流放电至1.5V,再转入电流恒流充电至3V,搁置5min后,再以恒流放电至1.5V终止电压。每个倍率下循环3次。
从图1扫描电镜图可以看出,实施例1制备的LiFeXCo1-XPO4/N-C均匀负载在碳布表面上,从图2透射电镜图可以看出LiFeXCo1-XPO4/N-C为纳米颗粒状。测试实施例1-4制备的LiFeXCo1-XPO4/N-C/CC复合材料在室温条件下,扫描速率为0.02mV/s的循环伏安曲线,所测电池都经过0.1C(17mA/g)充放电循环三次的活化过程。从图3中可以看出所有样品均有两对氧化还原峰,分别为Fe2+/Fe3+和Co2+/Co3+氧化还原对应的峰,同时可以看出出氧化还原峰峰型一致、面积相当、极化电压较小,这表明实施例1-4所制备材料具有较好的可逆性,并且实施例1的峰电流最大,说明实施例1制备的LiFeXCo1-XPO4/N-C/CC复合材料的电池可逆性和快速充放电能力最好。从图4可以看出,实施例1制备的电极在电流密度0.1C,0.5C,1C,5C,10C,20C时平均放电容量为176.2mAh·g-1,165.4mAh·g-1,155.1mAh·g-1,140.5mAh·g-1,118.4mAh·g-1和86.7mAh·g-1。从图5可以看出实施例1制备的LiFeXCo1-XPO4/N-C/CC电极显示了非常稳定的循环性能,在100次充放电后的放电容量为最初放电容量的97.94%,表明其具有良好的可逆性和循环寿命。
实施例2:
一种LiFeXCo1-XPO4/N-C/CC复合材料,具体包括以下制备步骤:
(1)碳布的预处理:将边长为2×3的碳布放入100ml硝酸和水体积比为1:3的混合溶液中,在80℃水热反应2h;
(2)将0.03mol醋酸锂、0.01mol硝酸铁、0.02mol硝酸钴和0.03mol磷酸二氢铵加入60ml去离子水中,磁力搅拌1h,将上述溶液转入聚四氟乙烯反应釜中,放入碳布,在160℃水热反应10h,之后用去离子水洗涤;
(3)将4ml乙二醇和1ml苯胺放入烧杯中,加入50ml去离子水,搅拌1h,加入1g十六烷基三甲基溴化铵,继续搅拌10h,之后老化4h,反应结束后,用去离子水和乙醇清洗产物,放入干燥箱中干燥;
(4)将步骤(3)产物放入烧杯中,加入去离子水,超声1h,之后将混合溶液转入聚四氟乙烯反应釜中,放入步骤(2)产物,在100℃水热反应6h;
(5)将步骤(4)产物置于管式炉内,在氩气气氛下700℃煅烧8h。
实施例2制备的LiFeXCo1-XPO4/N-C/CC复合材料的电极在电流密度0.1C,0.5C,1C,5C,10C,20C时平均放电容量为164.7mAh·g-1,152.4mAh·g-1,139.1mAh·g-1,123.5mAh·g-1,108.7mAh·g-1和75.5mAh·g-1,性能与实施例1相近。
实施例3:
一种LiFeXCo1-XPO4/N-C/CC复合材料,具体包括以下制备步骤:
(1)碳布的预处理:将边长为2×3的碳布放入100ml硝酸和水体积比为1:3的混合溶液中,在100℃水热反应2h;
(2)将0.03mol醋酸锂、0.015mol硝酸铁、0.015mol硝酸钴和0.03mol磷酸二氢铵加入60ml去离子水中,磁力搅拌1h,将上述溶液转入聚四氟乙烯反应釜中,放入碳布,在190℃水热反应12h,之后用去离子水洗涤;
(3)将5ml乙二醇和1ml苯胺放入烧杯中,加入60ml去离子水,搅拌1h,加入2g十六烷基三甲基溴化铵,继续搅拌12h,之后老化6h,反应结束后,用去离子水和乙醇清洗产物,放入干燥箱中干燥;
(4)将步骤(3)产物放入烧杯中,加入去离子水,超声2h,之后将混合溶液转入聚四氟乙烯反应釜中,放入步骤(2)产物,在150℃水热反应10h;
(5)将步骤(4)产物置于管式炉内,在氩气气氛下900℃煅烧10h。
实施例3制备的LiFeXCo1-XPO4/N-C/CC复合材料的电极在电流密度0.1C,0.5C,1C,5C,10C,20C时平均放电容量为161.7mAh·g-1,149.7mAh·g-1,137.6mAh·g-1,115.4mAh·g-1,93.4mAh·g-1和64.2mAh·g-1,性能与实施例1相近。
实施例4:
一种LiFeXCo1-XPO4/N-C/CC复合材料,具体包括以下制备步骤:
(1)碳布的预处理:将边长为2×3的碳布放入100ml硝酸和水体积比为1:3的混合溶液中,在90℃水热反应2h;
(2)将0.03mol醋酸锂、0.005mol硝酸铁、0.025mol硝酸钴和0.03mol磷酸二氢铵加入60ml去离子水中,磁力搅拌1h,将上述溶液转入聚四氟乙烯反应釜中,放入碳布,在190℃水热反应12h,之后用去离子水洗涤;
(3)将5ml乙二醇和1ml苯胺放入烧杯中,加入55ml去离子水,搅拌1h,加入1.5g十六烷基三甲基溴化铵,继续搅拌11h,之后老化5h,反应结束后,用去离子水和乙醇清洗产物,放入干燥箱中干燥;
(4)将步骤(3)产物放入烧杯中,加入去离子水,超声1.5h,之后将混合溶液转入聚四氟乙烯反应釜中,放入步骤(2)产物,在120℃水热反应8h;
(5)将步骤(4)产物置于管式炉内,在氩气气氛下800℃煅烧9h。
实施例4制备的LiFeXCo1-XPO4/N-C/CC复合材料的电极在电流密度0.1C,0.5C,1C,5C,10C,20C时平均放电容量为150.4mAh·g-1,138.4mAh·g-1,121.3mAh·g-1,95.7mAh·g-1,74.9mAh·g-1和50.6mAh·g-1,性能与实施例1相近。
Claims (8)
1.一种LiFeXCo1-XPO4/N-C/CC复合材料的制备方法,其特征在于,所述复合材料的制备方法包括以下步骤:
(1)碳布的预处理:将边长为2×3cm碳布放入硝酸和水体积比为1:3的混合溶液中,80-100℃水热反应2h;
(2)将醋酸锂、硝酸铁、硝酸钴和磷酸二氢铵加入去离子水中,磁力搅拌1h,将上述溶液转入聚四氟乙烯反应釜中,放入碳布,水热反应,冷却后用去离子水洗涤;
(3)将乙二醇和苯胺放入烧杯中,加入去离子水,搅拌1h,加入十六烷基三甲基溴化铵,继续搅拌10-12h,之后老化4-6h,反应结束后,用去离子水和乙醇清洗产物,放入干燥箱中干燥;
(4)将步骤(3)产物放入烧杯中,加入去离子水,超声1-2h,之后将混合溶液转入聚四氟乙烯反应釜中,放入步骤(2)产物,进行水热反应;
(5)将步骤(4)产物置于管式炉内,在氩气气氛下煅烧。
2.如权利要求1所述的一种LiFeXCo1-XPO4/N-C/CC复合材料的制备方法,其特征在于,0.5≤x≤1。
3.如权利要求1所述的一种LiFeXCo1-XPO4/N-C/CC复合材料的制备方法,其特征在于,所述步骤(2)中,醋酸锂、硝酸铁、硝酸钴和磷酸二氢铵的摩尔比为1:(0-0.5):(0.5-1):1。
4.如权利要求1所述的一种LiFeXCo1-XPO4/N-C/CC复合材料的制备方法,其特征在于,所述步骤(2)中水热反应的温度为160-220℃,反应时间为10-14h。
5.如权利要求1所述的一种LiFeXCo1-XPO4/N-C/CC复合材料的制备方法,其特征在于,所述步骤(3)中加入苯胺、十六烷基三甲基溴化铵、乙二醇和去离子水的质量体积比为1ml:(1-2)g:(4-5)ml:(50-60)ml。
6.如权利要求1所述的一种LiFeXCo1-XPO4/N-C/CC复合材料的制备方法,其特征在于,所述步骤(4)中水热反应的温度为100-150℃,反应时间为6-10h。
7.如权利要求1所述的一种LiFeXCo1-XPO4/N-C/CC复合材料的制备方法,其特征在于,所述步骤(5)中煅烧温度为700-900℃,煅烧时间为8-10h。
8.如权利要求1-5任一项所述的一种LiFeXCo1-XPO4/N-C/CC复合材料的制备方法,其特征在于,所述LiFeXCo1-XPO4/N-C/CC复合材料的制备方法制备的复合材料应用于锂离子电池的正极材料。
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