CN110071269B - 一种在水相体系中制备磷酸锰锂/石墨烯纳米片的方法 - Google Patents
一种在水相体系中制备磷酸锰锂/石墨烯纳米片的方法 Download PDFInfo
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Abstract
本发明公开了一种在水相体系中制备磷酸锰锂/石墨烯纳米片的方法,具体过程为:以去离子水作为反应介质,以氢氧化锂、可溶性锰盐和磷酸为原料,在反应体系中加入少量烷基葡萄糖苷非离子表面活性剂(烷基的碳原子数≥6)和氧化石墨烯,在常压下于100℃回流反应25‑48h制得磷酸锰锂/石墨烯纳米片。本发明避免了溶剂热法需要高温高压的苛刻条件以及后续的高温纯化处理,工艺操作简单,反应条件温和,所用试剂为去离子水,绿色环保。
Description
技术领域
本发明属于锂离子电池正极材料磷酸锰锂的制备技术领域,具体涉及一种在水相体系中制备磷酸锰锂/石墨烯纳米片的方法。
背景技术
以锂离子电池为代表的化学储能电源因其安全、清洁和便捷的优点,不仅在手机和笔记本等便携式用电器上得到广泛使用,而且也逐渐在电动工具、电动车等大型用电器领域得到越来越多的应用。人们在享受锂离子电池作为动力的现代化通讯和交通的同时,也不得不承受生产这些电池材料所带来的环境污染。因此,在研究探索高能量、长寿命、高安全性和廉价电池材料的同时,研究选择对环境无污染的绿色合成工艺显得尤其重要。
LiMnPO4具有和LiFePO4相同的橄榄石结构,理论比容量相同,但是其工作电压为4.1V(相对于Li/Li+的电极电位),该电压正好位于现有锂离子电池电解液体系的电化学窗口。因此,由于较高的工作电压,LiMnPO4的理论比能量可以达到近700Wh/kg,比LiFePO4高出约20%。此外LiMnPO4具有原料资源丰富、价格廉价、环境友好、结构稳定、化学相容性好和安全性高等优点,被认为是一种极具发展前景的动力型锂离子电池正极材料。此外,LiMnPO4材料具有原料资源丰富、价格低廉、环境友好、结构稳定、化学相容性好和安全性高等优点,被认为是一种有发展前景的锂离子电池正极材料。然而,LiMnPO4的电子导电率和锂离子扩散系数非常低,基本属于绝缘体,因此合成能够可逆充放电的LiMnPO4非常困难,这也是目前为止,该材料尚未能实现产业化的主要原因。为了改善LiMnPO4材料的导电性能,通常采用方式是在颗粒表面包覆碳层以增加颗粒间的导电性能,体相掺杂其它金属离子以改善离子导电性能以及减小颗粒尺寸以缩短锂离子在固相的迁移距离,增加离子的扩散速度。为了达到上述目的,人们探索了不同的液相合成路线,比如溶胶-凝胶法、溶剂热法、多元醇法等,与传统的高温固相法相比,液相法由于晶核的形成与生长处于液相环境,更适合调控LiMnPO4的微纳米结构,制备具有特定形貌的纳米尺寸颗粒。但是,这些液相法大多使用有机溶剂,为环境造成二次污染。例如:Hung-Cuong Dinh等(RSC Advances., 2015, 5,100709)报道了一种利用溶剂热法制备LiMnPO4纳米材料的方法,需要使用和蒸发大量的有机溶剂,而且还要在高温高压条件下进行;专利申请号为201510097239.X的发明专利公开了一种利用乙二醇和水溶液体系在180℃反应10h制备LiMnPO4材料的方法,同时反应需要在高温高压的容器中进行。专利申请号为201410413701.8的发明专利公开了一种乙二醇溶剂热法,在高温高压下以KOH为矿化剂合成出由纳米棒聚集而成的微米级颗粒,在后续的覆碳工艺很难将碳层包覆在内部的纳米棒表面,直接影响了材料内部一次颗粒的导电性能。
多元醇法则直接采用高沸点有机溶剂作为反应介质。这些方法之所以使用有机溶剂是由于有机溶剂的表面张力明显小于水,有利于抑制晶核的生长。例如:专利申请号为201410232083.7的发明专利公开一种以聚乙二醇和二甲基甲酰胺为有机溶剂,以油酸为表面活性剂制备纳米LiMnPO4颗粒的方法,该方法也需要在高压水热反应釜中进行。但是,使用大量的有机溶剂不仅增加了生产成本,更重要的是对环境造成了严重污染。专利申请号为201410562468.X的发明专利公开了一种LiMnPO4纳米微球的制备方法,以乙二醇和水溶液为溶剂,在密闭的高压容器中经160-240℃的反应生成了由纳米棒团聚组成的微球。专利申请号为201410564186.3的发明专利采用同样的体系和方法合成出了直径200纳米、长度2微米的纳米棒聚集而成的微米花状LiMnPO4颗粒。专利申请号为201510928559.5的发明专利公开了一种利用可溶性锰盐在乙二醇和水混合溶液中添加葡萄糖,在常压较低温度下制备出纯相LiMnPO4颗粒的方法,但是反应体系仍然使用了大量的乙二醇有机溶剂。
由此可见,液相合成微纳米磷酸锰锂颗粒都要选用有机溶剂,并且大都需要在高压高温的容器内进行,操作复杂,成本高,势必对环境造成二次污染。因此,减少有机溶剂的使用量甚至在纯水体系中合成纳米级LMP电池材料具有重要的意义。
近几年,人们发现石墨烯具有超薄柔软和优异的导电性能,将其作为导电剂与LiMnPO4颗粒复合以提高颗粒间的导电性。例如,专利申请号为201410112130.4的发明专利公开了一种制备片状磷酸锰锂/石墨烯复合材料的方法,该方法采用的是喷雾干燥辅助高温烧结方法,合成出的是微米级球形颗粒。专利申请号为201310278122.2的发明专利公开了一种将石墨烯和有机碳源裂解性能的无定型碳形成导电网络改善LiMnPO4颗粒的导电性,但是该方法采用的方法是高温高压的水热反应,需要高的温度和压力,反应条件极其苛刻,难以实现产业化。
发明内容
本发明解决的技术问题是提供了一种在水相体系中制备磷酸锰锂/石墨烯纳米片的方法,该方法利用去离子水作为反应介质,添加少量的烷基葡萄糖苷非离子表面活性剂(APG)以降低水的表面张力,同时添加少量的氧化石墨烯(GO)用于构建颗粒表面的导电层,在常压和水正常沸点(100℃)的条件下制备出菱形片状磷酸锰锂/石墨烯纳米片,该磷酸锰锂/石墨烯纳米片可以用作锂离子电池正极材料。
本发明为解決上述技术问题采用如下技术方案,一种在水相体系中制备磷酸锰锂/石墨烯纳米片的方法,其特征在于具体过程为:
步骤S1:将氢氧化锂溶于去离子水中得到溶液A,将可溶性锰盐和磷酸加入到去离子水中,再加入氧化石墨烯并超声分散得到含有氧化石墨烯的溶液B,在搅拌的条件下依次将烷基葡萄糖苷非离子表面活性剂和溶液A加入到溶液B中,其中氢氧化锂、可溶性锰盐、磷酸、氧化石墨烯、烷基葡萄糖苷非离子表面活性剂与去离子水总量的投料配比为0.15-0.3mol:0.05-0.1mol:0.05-0.1mol:9.8-78.4mg:1-5mL:100mL,烷基葡萄糖苷非离子表面活性剂中烷基的碳原子数≥6;
步骤S2:将步骤S1得到的反应液置于带有回流装置的反应容器中,在N2保护下于100℃回流反应25-48h,所得沉淀物经离心、去离子水洗涤和真空干燥后制得厚度为50-100nm的菱形片状磷酸锰锂/石墨烯纳米片,该磷酸锰锂/石墨烯纳米片中磷酸锰锂为纯橄榄石相。
优选的,步骤S1中所述可溶性锰盐为氯化锰、硫酸锰、硝酸锰或乙酸锰。
优选的,步骤S1中所述烷基葡萄糖苷非离子表面活性剂中的烷基为C6-12烷基。
优选的,一种在水相体系中制备磷酸锰锂/石墨烯纳米片的方法,其特征在于具体步骤为:
步骤S1:将0.15mol氢氧化锂溶于30mL去离子水中得到溶液A,将0.05mol可溶性锰盐和0.05mol磷酸加入到去70mL离子水中,再加入19.6mg氧化石墨烯并超声分散得到含有氧化石墨烯的溶液B,在搅拌的条件下依次将烷基葡萄糖苷非离子表面活性剂APG06和溶液A加入到溶液B中;
步骤S2:将步骤S1得到的反应液置于带有回流装置的反应容器中,在N2保护下于100℃回流反应25h,所得沉淀物经8000r/min离心、去离子水洗涤和80℃真空干燥12h后制得厚度为50-100nm的菱形片状磷酸锰锂/石墨烯纳米片,该磷酸锰锂/石墨烯纳米片中磷酸锰锂为纯橄榄石相,石墨烯的含量为1wt%。
本发明与现有技术相比具有以下优点:
1、本发明采用常压液相法一步合成纯橄榄石相磷酸锰锂纳米片,采用去离子水作为反应介质,采用在常压下相对较低的反应温度100℃进行反应,避免了溶剂热法需要高温高压的苛刻条件以及后续的高温纯化处理过程,工艺操作简单,反应条件温和,所用试剂为去离子水,绿色环保;
2、本发明采用烷基葡萄糖苷非离子表面活性剂可以有效降低溶剂水的表面张力,促使纯橄榄石相LiMnPO4纳米晶核的形成和定向生长,由于烷基葡萄糖苷非离子表面活性剂的活性随烷基碳原子数的增加而增强,一定长度(烷基碳原子数≥6)的烷基葡萄糖苷非离子表面活性剂亲水端吸附在晶核表面,疏水端朝向水溶剂,可以有效阻隔溶剂水分子的直接作用,进而有助于形成纯相目标产物;
3、本发明合成的菱形片状磷酸锰锂/石墨烯纳米片有利于缩短锂离子在固相的传递距离,石墨烯可以构成导电网,从而大大增强了颗粒内部锂离子的扩散速率和颗粒间的电子导电性能。
附图说明
图1是实施例1制得的磷酸锰锂/石墨烯纳米片的XRD图;
图2是实施例1制得的磷酸锰锂/石墨烯纳米片的TEM图;
图3是对比例1制得的磷酸锰锂/石墨烯颗粒的XRD图。
具体实施方式
以下通过实施例对本发明的上述内容做进一步详细说明,但不应该将此理解为本发明上述主题的范围仅限于以下的实施例,凡基于本发明上述内容实现的技术均属于本发明的范围。
实施例1
步骤S1:将0.15mol氢氧化锂溶于30mL去离子水中得到溶液A,将0.05mol乙酸锰和0.05mol磷酸加入到去70mL离子水中,再加入19.6mg氧化石墨烯并超声分散得到含有氧化石墨烯的溶液B,在搅拌的条件下依次将1mL烷基葡萄糖苷非离子表面活性剂APG06和溶液A加入到溶液B中;
步骤S2:将步骤S1得到的反应液置于带有回流装置的反应容器中,在N2保护下于100℃回流反应25h,所得沉淀物经8000r/min离心、去离子水洗涤和80℃真空干燥12h后制得磷酸锰锂/石墨烯纳米片,该磷酸锰锂/石墨烯纳米片中石墨烯的含量为1wt%。
经XRD分析证明制得的目标产物中磷酸锰锂为纯橄榄石相LiMnPO4,如图1所示。扫描电镜显示制得的目标产品的形貌近似菱形片状,厚度约为50-100nm,如图2所示。
实施例2
步骤S1:将0.15mol氢氧化锂溶于30mL去离子水中得到溶液A,将0.05mol乙酸锰和0.05mol磷酸加入到去70mL离子水中,再加入9.8mg氧化石墨烯并超声分散得到含有氧化石墨烯的溶液B,在搅拌的条件下依次将3mL烷基葡萄糖苷非离子表面活性剂APG0810和溶液A加入到溶液B中;
步骤S2:将步骤S1得到的反应液置于带有回流装置的反应容器中,在N2保护下于100℃回流反应36h,所得沉淀物经8000r/min离心、去离子水洗涤和80℃真空干燥12h后制得磷酸锰锂/石墨烯纳米片,该磷酸锰锂/石墨烯纳米片中石墨烯的含量为0.5wt%。
经XRD分析证明制得的目标产物中磷酸锰锂为纯橄榄石相LiMnPO4。扫描电镜显示制得的目标产品的形貌近似菱形片状,厚度约为50-100nm。
实施例3
步骤S1:将0.3mol氢氧化锂溶于30mL去离子水中得到溶液A,将0.1mol氯化锰和0.1mol磷酸加入到去70mL离子水中,再加入19.6mg氧化石墨烯并超声分散得到含有氧化石墨烯的溶液B,在搅拌的条件下依次将2mL烷基葡萄糖苷非离子表面活性剂APG1214和溶液A加入到溶液B中;
步骤S2:将步骤S1得到的反应液置于带有回流装置的反应容器中,在N2保护下于100℃回流反应48h,所得沉淀物经8000r/min离心、去离子水洗涤和100℃真空干燥12h后制得磷酸锰锂/石墨烯纳米片,该磷酸锰锂/石墨烯纳米片中石墨烯的含量为0.5wt%。
经XRD分析证明制得的目标产物中磷酸锰锂为纯橄榄石相LiMnPO4。扫描电镜显示制得的目标产品的形貌近似菱形片状,厚度约为50-100nm。
实施例4
步骤S1:将0.15mol氢氧化锂溶于30mL去离子水中得到溶液A,将0.05mol硝酸锰和0.05mol磷酸加入到去70mL离子水中,再加入29.4mg氧化石墨烯并超声分散得到含有氧化石墨烯的溶液B,在搅拌的条件下依次将5mL烷基葡萄糖苷非离子表面活性剂APG0810和溶液A加入到溶液B中;
步骤S2:将步骤S1得到的反应液置于带有回流装置的反应容器中,在N2保护下于100℃回流反应36h,所得沉淀物经8000r/min离心、去离子水洗涤和100℃真空干燥12h后制得磷酸锰锂/石墨烯纳米片,该磷酸锰锂/石墨烯纳米片中石墨烯的含量为1.5wt%。
经XRD分析证明制得的目标产物中磷酸锰锂为纯橄榄石相LiMnPO4。扫描电镜显示制得的目标产品的形貌近似菱形片状,厚度约为50-100nm。
实施例5
步骤S1:将0.15mol氢氧化锂溶于30mL去离子水中得到溶液A,将0.05mol乙酸锰和0.05mol磷酸加入到去70mL离子水中,再加入78.4mg氧化石墨烯并超声分散得到含有氧化石墨烯的溶液B,在搅拌的条件下依次将2mL烷基葡萄糖苷非离子表面活性剂APG1214和溶液A加入到溶液B中;
步骤S2:将步骤S1得到的反应液置于带有回流装置的反应容器中,在N2保护下于100℃回流反应25h,所得沉淀物经8000r/min离心、去离子水洗涤和80℃真空干燥12h后制得磷酸锰锂/石墨烯纳米片,该磷酸锰锂/石墨烯纳米片中石墨烯的含量为4wt%。
经XRD分析证明制得的目标产物中磷酸锰锂为纯橄榄石相LiMnPO4。扫描电镜显示制得的目标产品的形貌近似菱形片状,厚度约为50-100nm。
对比例1
将实例1中的APG06换成乙二醇葡萄糖苷(烷基碳原子数为4),其余步骤相同。经XRD分析证明制得的目标产物含有杂相峰,并非纯橄榄石相的磷酸锰锂,如图3所示。
以上实施例描述了本发明的基本原理、主要特征及优点,本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明原理的范围下,本发明还会有各种变化和改进,这些变化和改进均落入本发明保护的范围内。
Claims (4)
1.一种在水相体系中制备磷酸锰锂/石墨烯纳米片的方法,其特征在于具体过程为:
步骤S1:将氢氧化锂溶于去离子水中得到溶液A,将可溶性锰盐和磷酸加入到去离子水中,再加入氧化石墨烯并超声分散得到含有氧化石墨烯的溶液B,在搅拌的条件下依次将烷基葡萄糖苷非离子表面活性剂和溶液A加入到溶液B中,其中氢氧化锂、可溶性锰盐、磷酸、氧化石墨烯、烷基葡萄糖苷非离子表面活性剂与去离子水总量的投料配比为0.15-0.3mol:0.05-0.1mol:0.05-0.1mol:9.8-78.4mg:1-5mL:100mL,烷基葡萄糖苷非离子表面活性剂中烷基的碳原子数≥6;
步骤S2:将步骤S1得到的反应液置于带有回流装置的反应容器中,在N2保护下于100℃回流反应25-48h,所得沉淀物经离心、去离子水洗涤和真空干燥后制得厚度为50-100nm的菱形片状磷酸锰锂/石墨烯纳米片,该磷酸锰锂/石墨烯纳米片中磷酸锰锂为纯橄榄石相。
2.根据权利要求1所述的在水相体系中制备磷酸锰锂/石墨烯纳米片的方法,其特征在于:步骤S1中所述可溶性锰盐为氯化锰、硫酸锰、硝酸锰或乙酸锰。
3.根据权利要求1所述的在水相体系中制备磷酸锰锂/石墨烯纳米片的方法,其特征在于:步骤S1中所述烷基葡萄糖苷非离子表面活性剂中的烷基为C6-12烷基。
4.根据权利要求1所述的在水相体系中制备磷酸锰锂/石墨烯纳米片的方法,其特征在于具体步骤为:
步骤S1:将0.15mol氢氧化锂溶于30mL去离子水中得到溶液A,将0.05mol可溶性锰盐和0.05mol磷酸加入到去70mL离子水中,再加入19.6mg氧化石墨烯并超声分散得到含有氧化石墨烯的溶液B,在搅拌的条件下依次将烷基葡萄糖苷非离子表面活性剂APG06和溶液A加入到溶液B中;
步骤S2:将步骤S1得到的反应液置于带有回流装置的反应容器中,在N2保护下于100℃回流反应25h,所得沉淀物经8000r/min离心、去离子水洗涤和80℃真空干燥后12h制得厚度为50-100nm的菱形片状磷酸锰锂/石墨烯纳米片,该磷酸锰锂/石墨烯纳米片中磷酸锰锂为纯橄榄石相,石墨烯的含量为1wt%。
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