CN113013411A - 氧化亚钴分级介孔纳米球@二氧化钛@碳复合材料及其制备和应用 - Google Patents
氧化亚钴分级介孔纳米球@二氧化钛@碳复合材料及其制备和应用 Download PDFInfo
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Abstract
本发明公开了一种氧化亚钴分级介孔纳米球@二氧化钛@碳复合材料,氧化亚钴分级介孔纳米球由CoO纳米晶组装而成,氧化亚钴分级介孔纳米球的表面依次包覆有由TiO2纳米晶组成的TiO2包覆层和非晶态碳层。本发明还公开了所述氧化亚钴分级介孔纳米球@二氧化钛@碳复合材料的制备方法:首先合成Co甘油球,然后通过碳化和氧化形成CoO分级介孔纳米球,之后在其表面包覆一层TiO2和一层RF树脂,碳化煅烧后获得最终产物。本发明可提高CoO的电化学活性和结构稳定性,使其具有高的放电比容量和良好的循环性能、倍率性能。CoO分级介孔纳米球@TiO2@C复合材料作为锂离子电池负极材料具有重要的应用价值。
Description
技术领域
本发明涉及锂离子电池技术领域,具体涉及一种氧化亚钴(CoO)分级介孔纳米球@二氧化钛(TiO2)@碳(C)复合材料及其制备和应用。
背景技术
可充电锂离子电池(LIBs)已经成为便携式电子产品和电动汽车的主要电源。然而,石墨作为最常见的商业负极材料,由于其理论容量低、倍率性能差,已经限制了LIBs的进一步发展。为了满足人们对储能***日益增长的需求,开发高比容量、长寿命的先进负极材料已成为国内外研究的热点。在众多有前途的负极材料候选者中,CoO因其低成本、高理论容量(716mAh g-1)和环境友好性而受到广泛关注。然而,挑战依然存在。对于CoO,由于其电子导电性差、离子扩散动力学缓慢、Li+嵌入引起的体积膨胀大,导致其结构严重不稳定,容量衰减迅速,比容量低,速率性能差。
为了克服上述问题,提高CoO的锂存储性能,目前采取的策略主要是对CoO进行纳米化设计,同时复合高导电材料,如各类碳材料。类似的工作如公开号为CN105958060A的发明专利公开了一种Super P/CoO自组装多孔纳米棒状复合物,公开号为CN106654193A的发明专利公开了一种多孔CoO@氮掺杂碳同轴纳米棒。不过,对于CoO基复合材料而言,当CoO和复合对象的结合力较弱时,纳米CoO在反复充放电循环过程中很难避免自聚集。另外,对于常见的复合结构,CoO纳米材料在复合后很容易失去高比表面积的特性,或者由于碳在复合材料中使用过多导致复合材料整体比容量下降。因此,CoO基分级多孔组装结构成为替代CoO常规纳米复合材料的一个有重要发展潜力的新结构,不过,如何设计并构建新颖的CoO基分级多孔组装材料还有待深入研究。
发明内容
针对上述技术问题以及本领域存在的不足之处,本发明提供了一种氧化亚钴分级介孔纳米球@二氧化钛@碳复合材料。本发明可提高CoO的电化学活性和结构稳定性,使其具有高的放电比容量和良好的循环性能、倍率性能。CoO分级介孔纳米球@TiO2@C复合材料作为锂离子电池负极材料具有重要的应用价值。
一种氧化亚钴分级介孔纳米球@二氧化钛@碳复合材料,所述氧化亚钴分级介孔纳米球由CoO纳米晶组装而成,所述氧化亚钴分级介孔纳米球的表面依次包覆有由TiO2纳米晶组成的TiO2包覆层和非晶态碳层。
优选地,所述CoO纳米晶的尺寸为3-50nm,所述氧化亚钴分级介孔纳米球的直径为100-1000nm。
优选地,所述TiO2纳米晶的尺寸为1-20nm,所述TiO2包覆层的厚度为30-300nm。
优选地,所述非晶态碳层的厚度为3-100nm。
所述非晶态碳层优选由间苯二酚-甲醛(RF)树脂碳化形成。
本发明还提供了所述的氧化亚钴分级介孔纳米球@二氧化钛@碳复合材料的制备方法,包括步骤:
(1)将Co(NO3)2·6H2O溶解于异丙醇中,加入甘油,搅拌30min后于150-200℃溶剂热反应2-10h,反应结束后冷却、离心分离,固体产物用无水乙醇洗涤后于80℃烘干,得到Co甘油球;
(2)在氩气气氛中,将所述Co甘油球以1-5℃min-1的升温速率加热至400-600℃,保温1h,得到CoO-C球,然后在空气气氛中,将所述CoO-C球以1-5℃min-1的升温速率加热至400-600℃,保温2h,得到CoO分级介孔纳米球;
(3)将所述CoO分级介孔纳米球均匀分散于无水乙醇中,在搅拌下加入异丙醇钛,将所得混合液加热至60℃后,在搅拌下加入去离子水,继续搅拌反应1.5h后,离心收集固体产物,并用无水乙醇洗涤,80℃烘干,得到CoO分级介孔纳米球@TiO2;
(4)将所述CoO分级介孔纳米球@TiO2超声分散于无水乙醇和去离子水的混合溶液中,然后加入十六烷基三甲基溴化铵、间苯二酚、氢氧化铵和甲醛溶液,随后将所得混合体系加热至30-50℃并保温16h,将所得固体产物离心分离,经无水乙醇洗涤、80℃烘干后于氩气气氛中以1-5℃min-1的升温速率加热至400-700℃并保温2h,得到所述氧化亚钴分级介孔纳米球@二氧化钛@碳复合材料。
本发明制备方法首先合成Co甘油球,然后通过碳化和氧化形成CoO分级介孔纳米球,之后在其表面包覆一层TiO2和一层RF树脂,碳化煅烧后获得最终产物。
作为优选,步骤(1)中,相对于145.5mg Co(NO3)2·6H2O,所述异丙醇的用量为50mL,所述甘油的用量为10mL。
作为优选,步骤(3)中,相对于25mg所述CoO分级介孔纳米球,用于分散所述CoO分级介孔纳米球的无水乙醇的用量为50mL,所述异丙醇钛的用量为0.05-0.4mL,所述去离子水的用量为0.05-0.4mL。
作为优选,步骤(4)中,相对于40mg所述CoO分级介孔纳米球@TiO2,所述混合溶液由12.5mL无水乙醇和30mL去离子水混合得到,所述十六烷基三甲基溴化铵的用量为20-190mg,所述间苯二酚的用量为5-40mg,所述氢氧化铵的用量为0.05-0.5mL,所述甲醛溶液的用量为5-60μL,所述甲醛溶液的浓度为37wt%。
一种优选的制备方法,包括步骤:
(1)将145.5mg六水合硝酸钴(Co(NO3)2·6H2O)溶解于50mL异丙醇中,加入10mL甘油。搅拌30min后,溶液被转移到一个容积为100mL的聚四氟乙烯水热反应釜内,然后加热到150-200℃,保温2-10h。冷却至室温后离心分离产物,用无水乙醇洗3次,80℃烘干,得到Co甘油球;
(2)取步骤(1)制备的Co甘油球置于石英管炉内,在氩气气氛下,以1-5℃min-1的升温速率加热至400-600℃,保温1h,制备出CoO-C球。然后,将CoO-C球置于马弗炉内,以1-5℃min-1的升温速率加热至400-600℃,保温2h,得到CoO分级介孔纳米球;
(3)取步骤(2)制备的CoO分级介孔纳米球25mg,均匀分散于50ml无水乙醇中,在剧烈搅拌下加入0.05-0.4ml异丙醇钛(TIP)。将溶液加热至60℃后,在搅拌下加入0.05-0.4mL去离子水。搅拌反应1.5h后,离心收集产物,用无水乙醇洗涤3次,80℃烘干,得到CoO分级介孔纳米球@TiO2;
(4)取步骤(3)制备的CoO分级介孔纳米球@TiO2 40mg,超声分散在含有12.5mL无水乙醇和30mL去离子水的混合溶液中,然后分别加入20-190mg十六烷基三甲基溴化铵(CTAB)、5-40mg间苯二酚、0.05-0.5mL氢氧化铵和5-60μL浓度为37wt%的甲醛溶液。随后溶液快速加热至30-50℃并保温16h。将产物离心分离,用无水乙醇洗涤3次,80℃烘干。最后,将产物置于石英管式炉内,在Ar气氛下,以1-5℃min-1的升温速率加热至400-700℃并保温2h。所得产物为CoO分级介孔纳米球@TiO2@C复合材料。
本发明还提供了所述的氧化亚钴分级介孔纳米球@二氧化钛@碳复合材料在锂离子电池负极材料中的应用。
采用本发明的材料制作锂离子电池负极:分别称取质量比8:1:1的CoO分级介孔纳米球@TiO2@C复合材料、乙炔黑导电剂、聚偏氟乙烯(PVDF)粘结剂,将PVDF溶于适量的1-甲基-2-吡咯烷酮(NMP),搅拌至完全溶解,再将研磨均匀的活性材料和乙炔黑加入到上述溶液中,继续搅拌以保证浆料混合均匀。然后把浆料均匀涂覆在圆片铜箔上(直径12mm),在真空烘箱100℃烘干,最后在压片机上用10MPa的压强压平,即制得电极片。
在充满高纯氩气的手套箱内将制备的电极片与锂片、隔膜组装成CR2025纽扣型锂离子电池。电解液为1mol L-1LiPF6的EC/DMC电解液,采用新威电池测试***测试锂离子电池的充放电性能与循环稳定性。
本发明与现有技术相比,主要优点包括:
1)本发明材料中的CoO分级介孔纳米球具有丰富的内部孔隙空间,这有利于电解质的渗透,能够提供更多的可进入的活性位点,并提供足够的空隙空间来缓解CoO在充放电过程中的体积膨胀。同时,小尺寸的CoO纳米晶缩短了Li+离子和电子的扩散路径,改善了反应动力学。这些有利的结构因素能显著提高CoO的可逆容量。
2)钴甘油球是钴与碳质前驱物均匀混合的无机有机复合物,通过碳化处理,钴甘油球分解为CoO和非晶碳,生成的CoO和非晶碳同样在球内均匀混合分布。由于非晶碳的约束作用,CoO的形成只能被限制在一个个狭小的纳米空间内,导致了CoO纳米晶的形成。非晶碳可以通过在空气中直接氧化完全去除,于是留下了大量孔洞,这样就形成了由CoO纳米晶组装而成的CoO分级介孔纳米球,本合成方法简单、高效。
3)包覆的TiO2和非晶态碳具有较高的结构强度,可抑制CoO在充放电过程中的体积膨胀,对于提高CoO分级介孔纳米球在充放电循环中的稳定性具有重要作用;没有TiO2和非晶态碳的包覆,CoO分级介孔纳米球的放电容量衰减迅速,循环稳定性较差。TiO2和非晶态碳共同包覆比单一包覆具有更强的结构稳定效果,复合效应强烈。此外,最外面包覆的非晶态碳具有良好的导电能力,能显著提高CoO和TiO2的电导率,弥补单独包覆TiO2存在的导电能力不足的缺陷。
附图说明
图1为实施例1制备的Co甘油球的SEM照片;
图2为实施例1制备的CoO分级介孔纳米球的SEM照片;
图3为实施例1制备的CoO分级介孔纳米球的TEM照片;
图4为实施例1制备的CoO分级介孔纳米球@TiO2的SEM照片;
图5为实施例1制备的CoO分级介孔纳米球@TiO2@C的SEM照片;
图6为实施例1制备的CoO分级介孔纳米球@TiO2@C的TEM照片;
图7为实施例1制备的CoO分级介孔纳米球@TiO2@C复合材料在电流密度0.5Ag-1的循环性能图;
图8为实施例1制备的CoO分级介孔纳米球@TiO2@C复合材料的倍率性能图。
具体实施方式
下面结合附图及具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的操作方法,通常按照常规条件,或按照制造厂商所建议的条件。
实施例1
(1)将145.5mg六水合硝酸钴(Co(NO3)2·6H2O)溶解于50ml异丙醇中,加入10ml甘油。搅拌30min后,溶液被转移到一个容积为100ml的聚四氟乙烯水热反应釜内,然后加热到180℃保温6h。冷却至室温后离心分离产物,用无水乙醇洗涤3次,80℃烘干,得到Co甘油球;
(2)取步骤(1)制备的Co甘油球置于石英管炉内,在氩气气氛下,以2℃min-1的升温速率加热至450℃,保温1h,制备出CoO-C球。然后,将CoO-C球置于马弗炉内,以2℃min-1的升温速率加热至450℃,保温2h,得到CoO分级介孔纳米球;
(3)取步骤(2)制备的CoO分级介孔纳米球25mg,均匀分散于50ml无水乙醇中,在剧烈搅拌下加入0.2ml异丙醇钛(TIP)。将溶液加热至60℃后,在搅拌下加入0.2ml去离子水。搅拌反应1.5h后,离心收集产物,用无水乙醇洗涤3次,80℃烘干,得到CoO分级介孔纳米球@TiO2;
(4)取步骤(3)制备的CoO分级介孔纳米球@TiO2 40mg,超声分散在含有12.5ml无水乙醇和30ml去离子水的混合溶液中,然后分别加入75mg十六烷基三甲基溴化铵(CTAB)、16mg间苯二酚、0.2ml氢氧化铵和22.6μl浓度为37wt%的甲醛溶液。随后溶液快速加热至35℃并保温16h。将产物离心分离,用无水乙醇洗涤3次,80℃烘干。最后,将产物置于石英管式炉内,在Ar气氛下,以2℃min-1的升温速率加热至500℃并保温2h。所得产物为CoO分级介孔纳米球@TiO2@C复合材料。
图1是制备的Co甘油球的SEM照片,Co甘油球尺寸均匀,表面光滑无粘连。图2是制备的CoO分级介孔纳米球的SEM照片,在小球的表面可见大量的纳米颗粒,颗粒间的介孔甚至也可看见;图3是其TEM照片,证实了这些小球确实是由大量纳米颗粒组装而成,纳米颗粒尺寸范围10-30nm,颗粒间的空隙清晰可见。如图2、3所示,制备的CoO分级介孔纳米球的直径为350nm。图4是制备的CoO分级介孔纳米球@TiO2的SEM照片,小球表面变得十分光滑,表面明显包覆了一层新物质。图5是制备的CoO分级介孔纳米球@TiO2@C的SEM照片,小球表面变得略为粗糙,许多小球被TiO2和非晶态碳粘连在一起;图6是其TEM照片,可以清楚地发现里面有三个CoO分级介孔纳米球。在CoO分级介孔纳米球外是一层较厚的超微小TiO2纳米晶和一层薄碳膜。包覆的TiO2层最厚处大约100nm,TiO2晶粒尺寸大约5nm。包覆的碳层更均匀更薄,厚度约为19nm。
采用本实施例的材料制作锂离子电池负极:分别称取质量比8:1:1的CoO分级介孔纳米球@TiO2@C、乙炔黑导电剂、聚偏氟乙烯(PVDF)粘结剂,将PVDF溶于适量的1-甲基-2-吡咯烷酮(NMP),搅拌至完全溶解,再将研磨均匀的活性材料和乙炔黑加入到上述溶液中,继续搅拌以保证浆料混合均匀。然后把浆料均匀涂覆在圆片铜箔上(直径12mm),在真空烘箱100℃烘干,最后在压片机上用10MPa的压强压平,即制得电极片。
在充满高纯氩气的手套箱内将制备的电极片与锂片、隔膜组装成CR2025纽扣型锂电池。电解液为1mol L-1LiPF6的EC/DMC电解液,采用新威电池测试***测试锂电池的充放电性能与循环稳定性,充放电电流密度0.5Ag-1,电压范围0.01~3.0V。
图7是CoO分级介孔纳米球@TiO2@C复合材料在电流密度0.5Ag-1的循环性能图。首循环放电容量是986mAh g-1。在最初的13个循环后,放电容量迅速下降到874mAh g-1。在接下来的循环中,放电容量缓慢增加。在第200个循环时,CoO@TiO2@C的放电容量高达1136mAhg-1。CoO分级介孔纳米球@TiO2@C的放电容量和循环性能超过了CN106654193B和D.Saikia(D.Saikia,J.R.Deka,C.W.Lin,Y.H.Lai,Y.H.Zeng,P.H.Chen,H.M.Kao,Y.C.Yang,Insightinto the superior lithium storage properties of ultrafine CoO nanoparticlesconfined in a 3D bimodal ordered mesoporous carbon CMK-9anode,Chemsuschem2020,13,2952-2965.)等的工作。
图8是CoO分级介孔纳米球@TiO2@C复合材料的倍率性能图。CoO@TiO2@C在电流密度为0.5、1、2、3、4、5Ag-1的情况下,平均放电容量分别为928、758、628、562、508和493mAh g-1。即使在5Ag-1的高电流密度下,CoO@TiO2@C仍能产生相当大的放电容量,表现出优越的高速率充放电能力。当电流下降到0.5Ag-1时,放电容量可恢复到910mAh g-1,容量恢复率高达98%,表现出极佳的稳定性。这说明本发明的CoO分级介孔纳米球@TiO2@C复合材料能承受连续的高倍率充放电反应,不出现明显的结构退化。
实施例2
(1)将145.5mg六水合硝酸钴(Co(NO3)2·6H2O)溶解于50ml异丙醇中,加入10ml甘油。搅拌30min后,溶液被转移到一个容积为100ml的聚四氟乙烯水热反应釜内,然后加热到180℃保温6h。冷却至室温后离心分离产物,用无水乙醇洗3次,80℃烘干,得到Co甘油球;
(2)取步骤(1)制备的Co甘油球置于石英管炉中,在氩气气氛下,以2℃min-1的升温速率加热至450℃,保温1h,制备出CoO-C球。然后,将CoO-C球置于马弗炉内,以2℃min-1的升温速率加热至450℃,保温2h,得到CoO分级介孔纳米球;
(3)取步骤(2)制备的CoO分级介孔纳米球25mg,均匀分散于50ml无水乙醇中,在剧烈搅拌下加入0.1ml异丙醇钛(TIP)。将溶液加热至60℃后,在搅拌下加入0.1ml去离子水。搅拌反应1.5h后,离心收集产物,用无水乙醇洗涤3次,80℃烘干,得到CoO分级介孔纳米球@TiO2;
后续工艺与实施例1相同。
产物CoO分级介孔纳米球@TiO2@C复合材料的结构与实施例1相似,主要区别是TiO2包覆层的厚度变为45-55nm。
采用与实施例1相同的工艺制作锂离子电池负极,装配成锂离子电池,以电流密度0.5Ag-1,0.01~3.0V电压范围进行循环充放电测试。首循环放电容量1232mAh g-1。在最初的11次循环后,放电容量迅速下降到786mAh g-1。在接下来的循环中,放电容量缓慢增加。在第200个循环时,CoO@TiO2@C的放电容量是817mAh g-1。
实施例3
(1)将145.5mg六水合硝酸钴(Co(NO3)2·6H2O)溶解于50ml异丙醇中,加入10ml甘油。搅拌30min后,溶液被转移到一个容积为100ml的聚四氟乙烯水热反应釜内,然后加热到180℃保温6h。冷却至室温后离心分离产物,用无水乙醇洗3次,80℃烘干,得到Co甘油球;
(2)取步骤(1)制备的Co甘油球置于石英管炉中,在氩气气氛下,以2℃min-1的升温速率加热至450℃,保温1h,制备出CoO-C球。然后,将CoO-C球置于马弗炉内,以2℃min-1的升温速率加热至450℃,保温2h,得到CoO分级介孔纳米球;
(3)取步骤(2)制备的CoO分级介孔纳米球25mg,均匀分散于50ml无水乙醇中,在剧烈搅拌下加入0.2ml异丙醇钛(TIP)。将溶液加热至60℃后,在搅拌下加入0.2ml去离子水。搅拌反应1.5h后,离心收集产物,用无水乙醇洗涤3次,80℃烘干,得到CoO分级介孔纳米球@TiO2;
(4)取步骤(3)制备的CoO分级介孔纳米球@TiO2 40mg,超声分散在含有12.5ml无水乙醇和30ml去离子水的混合溶液中,然后分别加入112mg十六烷基三甲基溴化铵(CTAB)、24mg间苯二酚、0.3ml氢氧化铵和33.9μl浓度为37wt%的甲醛溶液。随后溶液快速加热至35℃并保温16h。将产物离心分离,用无水乙醇洗涤3次,80℃烘干。最后,将产物置于石英管式炉内,在Ar气氛下,以2℃min-1的升温速率加热至500℃并保温2h。所得产物为CoO分级介孔纳米球@TiO2@C复合材料。
产物CoO分级介孔纳米球@TiO2@C复合材料的结构与实施例1相似,主要区别是碳包覆层的厚度变为大约30nm。
采用与实施例1相同的工艺制作锂离子电池负极,装配成锂离子电池,以电流密度0.5Ag-1,0.01~3.0V电压范围进行循环充放电测试。首循环放电容量877mAh g-1。在初始14次循环后,放电容量迅速下降到794mAh g-1。在接下来的循环中,放电容量缓慢增加。在第200个循环时,CoO@TiO2@C的放电容量是860mAh g-1。
此外应理解,在阅读了本发明的上述描述内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
Claims (7)
1.一种氧化亚钴分级介孔纳米球@二氧化钛@碳复合材料,其特征在于,所述氧化亚钴分级介孔纳米球由CoO纳米晶组装而成,所述氧化亚钴分级介孔纳米球的表面依次包覆有由TiO2纳米晶组成的TiO2包覆层和非晶态碳层。
2.根据权利要求1所述的氧化亚钴分级介孔纳米球@二氧化钛@碳复合材料,其特征在于,所述CoO纳米晶的尺寸为3-50nm,所述氧化亚钴分级介孔纳米球的直径为100-1000nm;
所述TiO2纳米晶的尺寸为1-20nm,所述TiO2包覆层的厚度为30-300nm;
所述非晶态碳层的厚度为3-100nm,由间苯二酚-甲醛树脂碳化形成。
3.根据权利要求1或2所述的氧化亚钴分级介孔纳米球@二氧化钛@碳复合材料的制备方法,其特征在于,包括步骤:
(1)将Co(NO3)2·6H2O溶解于异丙醇中,加入甘油,搅拌30min后于150-200℃溶剂热反应2-10h,反应结束后冷却、离心分离,固体产物用无水乙醇洗涤后于80℃烘干,得到Co甘油球;
(2)在氩气气氛中,将所述Co甘油球以1-5℃min-1的升温速率加热至400-600℃,保温1h,得到CoO-C球,然后在空气气氛中,将所述CoO-C球以1-5℃min-1的升温速率加热至400-600℃,保温2h,得到CoO分级介孔纳米球;
(3)将所述CoO分级介孔纳米球均匀分散于无水乙醇中,在搅拌下加入异丙醇钛,将所得混合液加热至60℃后,在搅拌下加入去离子水,继续搅拌反应1.5h后,离心收集固体产物,并用无水乙醇洗涤,80℃烘干,得到CoO分级介孔纳米球@TiO2;
(4)将所述CoO分级介孔纳米球@TiO2超声分散于无水乙醇和去离子水的混合溶液中,然后加入十六烷基三甲基溴化铵、间苯二酚、氢氧化铵和甲醛溶液,随后将所得混合体系加热至30-50℃并保温16h,将所得固体产物离心分离,经无水乙醇洗涤、80℃烘干后于氩气气氛中以1-5℃min-1的升温速率加热至400-700℃并保温2h,得到所述氧化亚钴分级介孔纳米球@二氧化钛@碳复合材料。
4.根据权利要求3所述的制备方法,其特征在于,步骤(1)中,相对于145.5mg Co(NO3)2·6H2O,所述异丙醇的用量为50mL,所述甘油的用量为10mL。
5.根据权利要求3所述的制备方法,其特征在于,步骤(3)中,相对于25mg所述CoO分级介孔纳米球,用于分散所述CoO分级介孔纳米球的无水乙醇的用量为50mL,所述异丙醇钛的用量为0.05-0.4mL,所述去离子水的用量为0.05-0.4mL。
6.根据权利要求3所述的制备方法,其特征在于,步骤(4)中,相对于40mg所述CoO分级介孔纳米球@TiO2,所述混合溶液由12.5mL无水乙醇和30mL去离子水混合得到,所述十六烷基三甲基溴化铵的用量为20-190mg,所述间苯二酚的用量为5-40mg,所述氢氧化铵的用量为0.05-0.5mL,所述甲醛溶液的用量为5-60μL,所述甲醛溶液的浓度为37%。
7.根据权利要求1或2所述的氧化亚钴分级介孔纳米球@二氧化钛@碳复合材料在锂离子电池负极材料中的应用。
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