CN114914410B - 界面相互作用构建内建电场用于高性能锂离子存储 - Google Patents
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Abstract
本发明涉及锂离子电池存储技术领域,且公开了界面相互作用构建内建电场用于高性能锂离子存储,包括:S1样品合成,氧化石墨烯(GO)悬浮液是通过改进的Hummer制备方法,合成GaZnON@NG异质结构通常遵循以下步骤,用连续磁力搅拌器在Ga2(SO4)3和ZnSO4溶液中加入一定量的GO溶液,开发了界面相互作用和内建电场调节策略来构建氮掺杂石墨烯(NG)复合的GaZnON纳米颗粒(GaZnON@NG)简单易行的方法。先进的结构表征和密度泛函理论(DFT)分析揭示了强化学键(Ga–N/N–C)和GaZnON@NG的界面电荷转移。这种界面相互作用可以巧妙地调节界面电子状态,改善表面电子密度和电荷传输动力学,从而实现高效锂离子存储。
Description
技术领域
本发明涉及锂离子电池存储技术领域,具体为界面相互作用构建内建电场用于高性能锂离子存储。
背景技术
锂离子电池(LIB)被认为是高效的储能装置,尤其是清洁和可持续能源产生的电能,虽然实际能量密度足以使其在电动汽车中应用,但仍需进一步提高其能量/功率密度和循环稳定性,以扩展其在日常生活中的应用范围。但是,影响其应用前景的问题还包括成本、寿命和安全问题,这些问题大多与负极材料直接相关。因此,可以改性负极材料以提高能量/功率密度和循环稳定性,而目前商用石墨作负极的理论容量低,倍率性能较差,此外,石墨负极容易形成锂金属枝晶,这种枝晶可以穿透隔膜导致短路。因此,寻找合适且高效的负极活性材料已成为近年来研究的重点。为此,金属氮化物(例如Fe2N、Sn3N4、Ni3N、MoN、Ge3N4和Cu3N)因其较高的理论容量和能量密度而被作为替代负极材料得到广泛研究。然而,基于金属氮化物的负极在电化学反应过程中存在电荷传输缓慢和体积膨胀明显等问题。此外,传统金属氮化物负极发生的副反应也会导致库仑效率降低,导致容量衰减。因此,要实现高容量长寿命的电化学性能,需要探索具有快速电荷传输特性的负极材料。氮氧化物作为一种混合离子材料,由于其优异的化学/结构稳定性和低体积膨胀效应,展现出高的能量/功率密度,作为一种四元固溶体,GaZnON具有快速的电子迁移率和较低的电压窗口。因此,GaZnON比传统的金属氮化物具有更高的导电性和离子扩散性。此外,优良的结构和化学稳定性也有利于GaZnON在极端环境下作为LIB负极材料使用。因此,GaZnON基纳米材料作为一种具有潜在应用前景的负极材料引起人们的广泛关注。然而,由于循环容量较低,原始GaZnON的电化学性能仍然受到活性位点低的限制。此外,传统的氨化反应会导致GaZnON纳米颗粒形态和组分的不均匀。为解决上述问题,提高GaZnON负极的电化学性能,人们期望通过形态修饰和结构设计策略来提高GaZnON基负极的电化学性能,然而,这些策略并不能从本质上提高GaZnON基负极的离子扩散效率和电子导电性。此外,GaZnON和电解质之间缺乏界面相互作用会严重限制界面电荷扩散效率。界面工程作为一种可行的解决方案,它可以提高电极材料的比表面积,而GaZnON颗粒与石墨烯的复合可以产生界面相互作用和内建电场。然而,对于GaZnON基负极材料构建界面相互作用和内建电场还没有进行系统的研究。
发明内容
本发明的目的在于提供了界面相互作用构建内建电场用于高性能锂离子存储,解决了上述背景技术中的问题。
为实现上述目的,本发明提供如下技术方案:界面相互作用构建内建电场用于高性能锂离子存储,包括以下步骤:
S1样品合成,氧化石墨烯(GO)悬浮液是通过改进的Hummer制备方法,合成GaZnON@NG异质结构通常遵循以下步骤,用连续磁力搅拌器在制备的Ga2(SO4)3和ZnSO4溶液中加入一定量的GO溶液,在连续搅拌下,通过滴加氨(NH3·H2O)形成弱碱性溶液,氨水提供的OH-与Ga3+反应;
S2电池组装,通过组装CR2016型扣式电池进行研究,该电池组装在充氩手套箱中,水分和氧气浓度低于1ppm;
S3 GITT分析的细节,在GITT测量期间,恒定电流密度为0.1A g-1持续30分钟以获得闭路电压(CCV),再持续30分钟以收集准开路电压(QOCV),这种测量可以被认为是一个准静态过程,因此用来研究充放电过程中的反应电阻。
优选的,采用均匀沉淀法,通过GO表面官能团的吸附作用,将镓和锌的氢氧化物(GaZnOOH)沉积到GO片上,镓和锌的氢氧化物相对缓慢的沉淀速率有利于GO板上的异相成核。
优选的,冷冻干燥制备了复合材料(GaZnOOH/GO),干燥后的复合材料在氨气(NH3)气氛中以2℃的速率加热至1050℃。
优选的,将原始GaZnON和GaZnON@NG、80wt%的活性材料、10wt%的导电碳和10wt%的聚偏氟乙烯(PVDF)作为粘合剂混合在N-甲基-2-吡咯烷酮中,然后将充分混合的活性材料涂覆在铜箔上,然后在使用前在80℃下真空干燥。
优选的,活性物质的平均负载量约为1.9mg,直径为12mm的金属锂片用作正极,正极和负极由聚丙烯膜(Celgard 2320)进行分离,电解质溶液为碳酸乙烯酯/碳酸二甲酯/碳酸二乙酯(1:1:1vol%)中的LiPF6(1M),使用新威CT-3008W电池测量系统在不同电流密度下进行恒电流充放电试验。
优选的,截止电压为0.01~3.0V vs.Li+/Li,室温下,恒电流间歇滴定技术(GITT)也在新威电池测试仪上进行了测试,电池在0.2A g-1下放电5分钟,然后在0.01~2.8V的电压窗口内静置20分钟。
优选的,使用CHI660D电化学工作站在0.01~3.0V范围内,进行不同扫描速率下的循环伏安法(CV),电化学阻抗谱(EIS)测量频率范围为0.01Hz至1MHz,振幅扰动信号为5mV,无外加电压偏置。
优选的,为了排除SEI薄膜形成的影响,在首圈循环后进行GITT测量,根据菲克第二定律,通过GITT测量Li+固态扩散系数(DLi +)。
本发明提供了用于高性能锂离子存储的界面相互作用内建电场调节。该用于高性能锂离子存储的界面相互作用内建电场调节具备以下有益效果:
(1)本发明中:该用于界面相互作用构建内建电场用于高性能锂离子存储时,开发了界面相互作用和内建电场调节策略来构建氮掺杂石墨烯(NG)复合的GaZnON纳米颗粒(GaZnON@NG),先进的结构表征和密度泛函理论(DFT)分析揭示了强化学(Ga–N/N–C)和GaZnON@NG的界面电荷转移。这种界面相互作用可以巧妙地调节界面电子状态,改善表面电子密度和电荷传输动力学,从而实现高效锂离子存储;
(2)本发明中:该用于界面相互作用构建内建电场用于高性能锂离子存储时,GaZnON@NG异质结构负极在0.1A g-1电流密度下进行200次循环后,显示出1073.6mA h g-1的可逆存储容量。即使在5.0A g-1大电流密度下经2000圈循环后,可逆容量仍保持在338.6mA h g-1。对应的电化学动力学分析证实了该体系中赝电容贡献和增强的锂离子反应动力学;
(3)本发明中:该用于界面相互作用构建内建电场用于高性能锂离子存储时,对样品进行XRD和XPS分析后发现,可逆的锂离子插层机理是GaZnON@NG异质结构保持良好的结构稳定性和电化学性能的主要原因,DFT分析进一步表明GaZnON@NG异质结构负极具有较高的导电性和较低的锂离子吸附能及扩散能垒,这种界面交互策略可以为先进的储能应用和其他应用提供借鉴。
附图说明
图1为本发明原始纳米颗粒的SEM图;
图2为本发明样品的XRD图;
图3为本发明聚合物的结构图;
图4为本发明化学反应动力图;
图5为本发明电化学反应的非原位XRD图;
图6为本发明锂离子迁移途径结构示意图。
具体实施方式
如图1-6所示,本发明提供一种技术方案:界面相互作用构建内建电场用于高性能锂离子存储,包括以下步骤:
S1样品合成,氧化石墨烯(GO)悬浮液是通过改进的Hummer制备方法,合成GaZnON@NG异质结构通常遵循以下步骤,用连续磁力搅拌器在制备的Ga2(SO4)3和ZnSO4溶液中加入一定量的GO溶液,在连续搅拌下,通过滴加氨(NH3·H2O)形成弱碱性溶液,氨水提供的OH-离子与Ga3+反应;
S2电化学测量,原始GaZnON和GaZnON@NG的电化学行为通过组装CR2016型扣式电池进行研究,该电池组装在充氩手套箱中,水分和氧气浓度低于1ppm;
S3 GITT分析的细节,在GITT测量期间,恒定电流密度为0.1A g-1持续30分钟以获得闭路电压(CCV),再持续30分钟以收集准开路电压(QOCV),这种测量可以被认为是一个准静态过程,因此用来研究充放电过程中的反应电阻,采用均匀沉淀法,通过GO表面官能团的吸附作用,将镓和锌的氢氧化物(GaZnOOH)沉积到GO片上,镓和锌的氢氧化物相对缓慢的沉淀速率有利于GO板上的异相成核,冷冻干燥制备了复合材料(GaZnOOH/GO),干燥后的复合材料在氨气(NH3)气氛中以2℃的速率加热至1050℃,分别将原始GaZnON和GaZnON@NG、80wt%的活性材料、10wt%的导电碳和10wt%的聚偏氟乙烯(PVDF)作为粘合剂混合在N-甲基-2-吡咯烷酮中,然后将充分混合的活性材料涂覆在铜箔上,然后在使用前在80℃下真空干燥,活性物质的平均负载量约为1.9mg,直径为12mm的金属锂片用作正极,正极和负极由聚丙烯膜(Celgard 2320)进行分离,电解质溶液为碳酸乙烯酯/碳酸二甲酯/碳酸二乙酯(1:1:1vol%)中的LiPF6(1M),使用新威CT-3008W电池测量系统在不同电流密度下进行恒电流充放电试验,截止电压为0.01~3.0V vs.Li+/Li,室温下,恒电流间歇滴定技术(GITT)也在新威电池测试仪上进行了测试,电池在0.2A g-1下放电5分钟,然后在0.01~2.8V的电压窗口内静置20分钟,使用CHI660D电化学工作站在0.01~3.0V范围内进行不同扫描速率下的循环伏安法(CV)测试,电化学阻抗谱(EIS)测试频率范围为0.01Hz至1MHz,振幅扰动信号为5mV,无外加电压偏置,为了排除SEI薄膜形成的影响,在首圈循环后进行GITT测量,根据菲克第二定律,通过GITT测量Li+固态扩散系数(DLi +)。
该用于界面相互作用构建内建电场用于高性能锂离子存储时,通过扫描电子显微镜(SEM,Hitachi S-4800)对样品的形貌和微观结构进行了表征,然后进行能量色散光谱(EDS)元素扫描,使用(TEM和相应的HRTEM,进行形貌进行分析,利用XRD和拉曼光谱对晶体结构进行分析。XRD和XPS分析发现,良好的结构稳定性和可逆的锂离子插层机理是GaZnON@NG异质结构具有优异电化学性能的原因。,DFT分析进一步表明GaZnON@NG异质结构负极具有较高的导电性和较低的锂离子吸附能和扩散能垒。
Claims (8)
1.界面相互作用构建内建电场用于高性能锂离子存储,包括以下步骤:
S1样品合成,氧化石墨烯(GO)悬浮液是通过改进的Hummer制备方法,合成GaZnON@NG异质结构通常遵循以下步骤,用连续磁力搅拌器在制备的Ga2(SO4)3和ZnSO4溶液中加入一定量的GO溶液,在连续搅拌下,通过滴加氨水(NH3·H2O)形成弱碱性溶液,氨水用来提供OH-离子与Ga3+反应;
S2电化学测量,原始GaZnON和GaZnON@NG的电化学行为通过组装CR2016型扣式电池进行研究,该电池组装在充氩手套箱中,水分和氧气浓度低于1ppm;
S3 GITT分析的细节,在GITT测量期间,恒定电流密度为0.1Ag-1持续30分钟以获得闭路电压(CCV),再持续30分钟以收集准开路电压(QOCV),这种测量可以被认为是一个准静态过程,因此用来研究充放电过程中的反应电阻。
2.根据权利要求1所述的界面相互作用构建内建电场用于高性能锂离子存储,其特征在于:采用均匀沉淀法,通过GO表面官能团将镓和锌的氢氧化物GaZnOOH沉积到GO片上,镓和锌的氢氧化物相对缓慢的沉淀速率有利于GO片上的异相成核。
3.根据权利要求1所述的界面相互作用构建内建电场用于高性能锂离子存储,其特征在于:冷冻干燥制备了复合材料GaZnOOH@GO,干燥后的复合材料在氨气(NH3)气氛中以2℃的速率加热至1050℃。
4.根据权利要求1所述的界面相互作用构建内建电场用于高性能锂离子存储,其特征在于:将GaZnON@NG、80wt%的活性材料、10wt%的导电碳和10wt%的聚偏氟乙烯(PVDF)作为粘合剂混合在N-甲基-2-吡咯烷酮中,然后将充分混合的活性材料涂覆在铜箔上,然后在80℃下真空干燥。
5.根据权利要求4所述的界面相互作用构建内建电场用于高性能锂离子存储,其特征在于:活性物质的平均负载量约为1.9mg,直径为12mm的金属锂片用作正极,正极和负极由Celgard 2320聚丙烯膜进行分离,电解质溶液为碳酸乙烯酯、碳酸二甲酯、碳酸二乙酯混合溶剂中的LiPF6,所述碳酸乙烯酯、碳酸二甲酯、碳酸二乙酯混合溶剂体积比为1:1:1,所述LiPF6浓度为1mol/L,使用新威CT-3008W电池测量系统在不同电流密度下进行恒电流充放电试验。
6.根据权利要求5所述的界面相互作用构建内建电场用于高性能锂离子存储,其特征在于:截止电压为0.01~3.0V vs.Li+/Li,室温下,恒电流间歇滴定技术(GITT)也在新威电池测试仪上进行了测试,电池在0.2Ag-1下放电5分钟,然后在0.01~2.8V的电压窗口内静置20分钟。
7.根据权利要求1所述的界面相互作用构建内建电场用于高性能锂离子存储,其特征在于:使用CHI660D电化学工作站在0.01~3.0V范围内,使用不同扫描速率下进行循环伏安法(CV),电化学阻抗谱(EIS)测量频率范围为0.01Hz至1MHz,振幅扰动信号为5mV,无外加电压偏置。
8.根据权利要求7所述的界面相互作用构建内建电场用于高性能锂离子存储,其特征在于:为了排除SEI薄膜形成的影响,在首圈循环后进行GITT测量,根据菲克第二定律,通过GITT测量分析Li+固态扩散系数(DLi +)。
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