CN110571431B - Li2FeSiO4@介孔碳锂离子电池正极材料及其制备方法 - Google Patents
Li2FeSiO4@介孔碳锂离子电池正极材料及其制备方法 Download PDFInfo
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- 229910009731 Li2FeSiO4 Inorganic materials 0.000 title claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000010406 cathode material Substances 0.000 title claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 17
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 10
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- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 14
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
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- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 3
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Abstract
本发明提供一种Li2FeSiO4@介孔碳锂离子电池正极材料及其制备方法,所述的制备方法包括以下步骤:步骤1、将一定量的酚、一水乙醛酸和表面活性剂溶于乙醇中;步骤2、按锂、铁、硅元素的摩尔比为1:1:2的比例,依次加入原料搅拌溶解;步骤3、所得混合物转移到培养皿内,在通风橱内室温蒸发溶剂后,烘干得到干凝胶;步骤4、将、干凝胶在惰性气氛或者还原气氛下升到600‑800℃,保温2‑4h。本发明的制备过程为液相混合,使得所得复合物中Li2FeSiO4纯度较高,达到为纳米级,在碳基体中均匀分散,优化电化学性能。由于加入了表面活性剂,所得碳基体为介孔结构,利于电解液的充分浸润,增加电极‑电解液的接触面积,加速离子和电子的扩散和转移,利于其电化学储锂性能的提高。
Description
技术领域
本发明涉及锂电池正极材料技术领域,具体而言涉及一种Li2FeSiO4@介孔碳锂离子电池正极材料及其制备方法。
背景技术
锂离子电池由于具有高的能量密度、功率密度、长的循环寿命等优点,其应用领域已经从便携电子设备逐渐拓展到电动汽车和电网存储领域。不过,要实现锂离子电池在电动汽车和电网存储方面更大规模的应用,其能量和功率密度还有待进一步提高。正极材料是发展下一代高能量密度锂离子电池的瓶颈。探索新型正极材料或对现有正极材料进行改性是提高锂离子电池能量密度的关键。
自从2005年Armand等人首次报道了Li2FeSiO4以来,Li2FeSiO4由于存在2个锂离子脱嵌的可能性,从而其理论容量接近330mAh g-1,理论能量密度在1000Wh kg-1以上,是极具潜力的动力电池用锂离子电池正极材料,近年来吸引了研究者们的广泛关注。
Li2FeSiO4除了理论容量高和安全性好以外,硅在地壳中储量丰富且分布广泛,其在成本方面具有潜在的商业优势。然而Li2FeSiO4的本征离子和电子导电性远远低于商业的正极材料,为了促进离子和电子传输,人们采取了各种措施,包括微纳米化、离子掺杂以及导电材料包覆等。与碳复合是Li2FeSiO4材料最常用的改性方法。
现有技术中,目前可见的文献报道的Li2FeSiO4/C复合物的典型制备方法有原位模板法、高温固相合成法、溶胶凝胶法和水热法等。在《Hierarchical porous Li2FeSiO4/Ccomposite with 2Li storage capacity and long cycle stability for advanced Li-ion batteries》(作者:H.X.Yang) 中分别以硝酸锂,硝酸铁和正硅酸乙酯为锂源、铁源和硅源,甲阶酚醛树脂为碳源,在表面活性剂F127的向导下,通过原位模板法合成了Li2FeSiO4/C复合物。该方法的缺点是复合物中 Li2FeSiO4分散性差,其中Li2FeSiO4粒径的只能达到微米级,团聚现象严重。
而在另外的现有技术中,例如《In situ generation of Li2FeSiO4 coating onMWNT as a high rate cathode material for lithium ion batteries》(作者:Y.Zhao)公开的方案中,将化学计量的 MWNT@SiO2,无水醋酸锂,草酸铁溶解于20mL乙醇,超声3h后,接着60℃搅拌蒸发乙醇,所得混合物研磨成粉,压片,最终惰性气氛下600℃煅烧5h。该方案中,通过该固态反应法制备获得复合物,除了包含单斜相的Li2FeSiO4,还伴有较多的非电化学活性杂质相,如Fe3O4和Li2SiO3,这些杂相严重影响了电化学储锂性能,是人们不希望看到的。
现有技术的Li2FeSiO4/C复合物普遍存在微观结构不尽理想和存在多种杂相的问题,从而影响其电化学储锂性能。
发明内容
本发明的目的在于解决现有制备的Li2FeSiO4/C复合物中纯度较低、Li2FeSiO4颗粒较大,在碳基质中分散性差的问题,而提供一种新型的锂离子电池用硅酸亚铁锂/碳正极材料的制备方法。
为了实现上述目的,本发明采用的技术方案:
一种Li2FeSiO4@介孔碳锂离子电池正极材料的制备方法,包括如下步骤:
步骤1、将一定量的酚、一水乙醛酸和表面活性剂溶于40-60mL乙醇中;
步骤2、按锂、铁、硅元素的摩尔比为1:1:2的比例,依次加入锂源化合物、铁源化合物、硅源化合物,搅拌溶解;
步骤3、所得混合物均匀地转移到4-6个培养皿内,在通风橱内室温蒸发溶剂后,接着在 60-100℃下烘干得到干凝胶;
步骤4、将所得干凝胶在流速为50-100mL/min的惰性气氛或者还原气氛下以1-3℃/min 升到600-800℃,保温2-4h得到Li2FeSiO4@介孔碳复合材料,其中Li2FeSiO4粒径为纳米级,分散在介孔碳基体中。
进一步地,本发明的制备方法步骤1中,所述的酚为苯酚,邻苯二酚,间苯二酚,对苯二酚,1,2,3-苯三酚,1,2,4-苯三酚以及间苯三酚中的一种。
进一步地,所述步骤1中,所述的表面活性剂为Pluronic P123,Pluronic P65,Pluronic P85, Pluronic F108,Pluronic F68,Pluronic F127,十六烷基三甲基溴化铵(CTAB),聚乙二醇以及聚乙烯醇中的一种。
进一步地,所述锂源化合物为醋酸锂、硝酸锂或者氢氧化锂中的一种。所述的铁源化合物为硝酸铁、柠檬酸铁、醋酸亚铁。所述的硅源化合物为正硅酸甲酯或正硅酸乙酯。
进一步地,步骤4中,所述的惰性气氛或者还原气氛为氩气、氮气、氦气、氖气、氩氢混合气、氮氢混合气,其中氩氢混合气中氢气的体积含量为1%~10%,氮氢混合气中氢气的体积含量为1%~10%。
与现有技术相比,本发明的显著优点在于:
1、碳源和锂源、铁源、硅源以溶液状态混合,是一种液相混合,从而可以使硅酸亚铁锂前驱体与碳前驱体在很短时间内实现分子水平的均匀性,干燥后形成干凝胶时,反应物之能是在分子水平上被均匀的混合,相应地,煅烧后,所得复合物中Li2FeSiO4纯度较高,为纳米级,且在碳基体中均匀分散。
2、由于在复合物合成过程中加入了表面活性剂,所得碳基体为介孔结构。此复合物微观结构有利于电解液的充分浸润,增加电极-电解液的接触面积,加速离子和电子的扩散和转移,从而有利于其电化学储锂性能的提高;
3、本发明的制备方法工艺简单、安全性高、煅烧温度低、保温时间短,有利于降低能耗,从而降低合成成本,易于实现产业化。
附图说明
图1实施例1中Li2FeSiO4@介孔碳材料的X-射线衍射图。
图2实施例1中Li2FeSiO4@介孔碳材料在空气气氛中的热重曲线。
图3实施例1中Li2FeSiO4@介孔碳材料的透射电镜图。
图4实施例1中Li2FeSiO4@介孔碳材料充放电曲线图,充放电倍率为C/20。
具体实施方式
为了更了解本发明的技术内容,特举具体实施例并配合所附图式说明如下。
在本公开中参照附图来描述本发明的各方面,附图中示出了许多说明的实施例。本公开的实施例不必定意在包括本发明的所有方面。应当理解,上面介绍的多种构思和实施例,以及下面更加详细地描述的那些构思和实施方式可以以很多方式中任意一种来实施。
下面结合实施例对本发明进行进一步阐述。下列实施例方案都只是举例说明,所有在本发明内或等同本发明的范围内的改变均被本发明包含。
【实施例1】
将0.82g间苯三酚、0.61g一水乙醛酸、1.61gF127溶于40mL乙醇中,依次加入1.2784 g硝酸锂,3.7451g九水硝酸铁,1.9312g正硅酸乙酯,搅拌溶解,所得混合溶液均匀地转移到4个培养皿内,在通风橱内室温蒸发溶剂后,接着在80℃下烘干得到干凝胶,将所得干凝胶在流速为50mL/min的氩氢气氛下以2℃/min升到800℃,保温2h,即可获得Li2FeSiO4@ 介孔碳复合材料。
【实施例2】
将0.82g间苯三酚、0.61g一水乙醛酸、1.61g F68溶于50mL乙醇中,依次加入1.8898 g醋酸锂,1.6130g醋酸亚铁,1.4111g正硅酸甲酯,搅拌溶解,所得混合溶液均匀地转移到5个培养皿内,在通风橱内室温蒸发溶剂后,接着在60℃下烘干得到干凝胶,将所得干凝胶在流速为100mL/min的氩气气氛下以3℃/min升到700℃,保温3h,即可获得Li2FeSiO4@ 介孔碳复合材料。
【实施例3】
将1.8358g苯酚、0.61g一水乙醛酸、1.61g P123溶于60mL乙醇中,依次加入1.2784g 硝酸锂,3.7451g九水硝酸铁,1.9312g正硅酸乙酯,搅拌溶解,所得混合溶液均匀地转移到6个培养皿内,在通风橱内室温蒸发溶剂后,接着在70℃下烘干得到干凝胶,将所得干凝胶在流速为60mL/min的氮氢气氛下以1℃/min升到600℃,保温4h,即可获得Li2FeSiO4@ 介孔碳复合材料。
【实施例4】
将1.0739g对苯二酚、0.61g一水乙醛酸、1.61g聚乙二醇溶于50mL乙醇中,依次加入 1.2784g硝酸锂,3.7451g九水硝酸铁,1.9312g正硅酸乙酯,搅拌溶解,所得混合溶液均匀地转移到6个培养皿内,在通风橱内室温蒸发溶剂后,接着在100℃下烘干得到干凝胶,将所得干凝胶在流速为90mL/min的氦气气氛下以1℃/min升到700℃,保温3h,即可获得Li2FeSiO4@介孔碳复合材料。
【实施例5】
将0.82g 1,2,3-苯三酚、0.61g一水乙醛酸、1.61g P65溶于60mL乙醇中,依次加入0.4441 g硝酸锂,2.4377g柠檬酸铁,1.9312g正硅酸乙酯,搅拌溶解,所得混合溶液均匀地转移到6个培养皿内,在通风橱内室温蒸发溶剂后,接着在90℃下烘干得到干凝胶,将所得干凝胶在流速为80mL/min的氮气气氛下以2℃/min升到800℃,保温3h,即可获得Li2FeSiO4@介孔碳复合材料。
下面结合附图所示,对实施例1所制备的Li2FeSiO4@介孔碳复合材料的性能测试结果进行进一步的说明。
如图所示,所得复合材料通过X-射线衍射分析,结果为正交晶系,空间群为Pmn21。由场发射透射电镜图可观察到,该复合物中Li2FeSiO4粒径达到纳米级,为几个纳米,且均匀分散在介孔碳基体中,通过这样更细粒径利于在基体中均匀分布,优化电化学性能。
同时,我们还进行热重分析,该复合物中碳含量达到21wt.%。
所得Li2FeSiO4@介孔碳复合材料的电化学性能按照下述方法进一步测定:首先取0.1g PVDF溶解于有机溶剂NMP中,然后依次加入0.8g Li2FeSiO4@介孔碳复合物、0.1g导电添加剂碳黑,充分搅拌成糊状物后,采用doctor-blade涂敷器涂敷于干净的铝箔上,厚度控制在 150μm左右,然后置于80℃真空干燥箱干燥12h,烘干后的膜片切成直径为16mm的电极片,将电极片转移至充满高纯氩气的手套箱中装配电池,手套箱中H2O和O2含量均低于1ppm。
以金属锂为对电极和参比电极,Celgard 2400为隔膜组装成CR2032型扣式电池,电解质为1M的LiPF6/(EC+DMC)溶液。采用恒流模式充放电,电极先放电再充电,电流密度为C/10,截至电压范围为2-4.2V。图4为该复合材料的首次充放电曲线,由图可见,所合成材料的首次充电容量高达120mAh/g,放电容量为94mAh/g,较传统的充放电性能都得到显著的提升。
虽然本发明已以较佳实施例揭露如上,然其并非用以限定本发明。本发明所属技术领域中具有通常知识者,在不脱离本发明的精神和范围内,当可作各种的更动与润饰。因此,本发明的保护范围当视权利要求书所界定者为准。
Claims (8)
1.一种Li2FeSiO4@介孔碳锂离子电池正极材料的制备方法,其特征在于,包括以下步骤:
步骤1、将一定量的酚、一水乙醛酸和表面活性剂溶于40-60mL乙醇中;
步骤2、按锂、铁、硅元素的摩尔比为1:1:2的比例,依次加入锂源化合物、铁源化合物、硅源化合物,搅拌溶解;
步骤3、所得混合物均匀地转移到4-6个培养皿内,在通风橱内室温蒸发溶剂后,接着在60-100℃下烘干得到干凝胶;
步骤4、将所得干凝胶在流速为50-100mL/min的惰性气氛或者还原气氛下以1-3℃/min升到600-800℃,保温2-4h得到Li2FeSiO4@介孔碳复合材料,其中Li2FeSiO4粒径为纳米级,分散在介孔碳基体中;
其中,所述Li2FeSiO4@介孔碳复合材料为正交晶系,空间群为Pmn21;
所述Li2FeSiO4@介孔碳复合材料中碳含量达到21wt.%。
2.根据权利要求1所述的Li2FeSiO4@介孔碳锂离子电池正极材料的制备方法,其特征在于,所述的酚为苯酚,邻苯二酚,间苯二酚,对苯二酚,1,2,3-苯三酚,1,2,4-苯三酚以及间苯三酚中的一种。
3.根据权利要求1所述的Li2FeSiO4@介孔碳锂离子电池正极材料的制备方法,其特征在于,所述的表面活性剂为Pluronic P123,Pluronic P65,Pluronic P85,Pluronic F108,Pluronic F68,Pluronic F127,十六烷基三甲基溴化铵(CTAB),聚乙二醇以及聚乙烯醇中的一种。
4.根据权利要求1所述的Li2FeSiO4@介孔碳锂离子电池正极材料的制备方法,其特征在于,所述锂源化合物为醋酸锂、硝酸锂或者氢氧化锂中的一种。
5.根据权利要求1所述的Li2FeSiO4@介孔碳锂离子电池正极材料的制备方法,其特征在于,所述的铁源化合物为硝酸铁、柠檬酸铁和醋酸亚铁中的一种。
6.根据权利要求1所述的Li2FeSiO4@介孔碳锂离子电池正极材料的制备方法,其特征在于,所述的硅源化合物为正硅酸甲酯或正硅酸乙酯。
7.根据权利要求1所述的Li2FeSiO4@介孔碳锂离子电池正极材料的制备方法,其特征在于,所述的惰性气氛或者还原气氛为氩气、氮气、氦气、氖气、氩氢混合气、氮氢混合气,其中氩氢混合气中氢气的体积含量为1%~10%,氮氢混合气中氢气的体积含量为1%~10%。
8.一种基于权利要求1-7中任意一项所述的Li2FeSiO4@介孔碳锂离子电池正极材料的制备方法所制得的Li2FeSiO4@介孔碳复合材料。
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